TWI704382B - Display device and manufacturing method of display device - Google Patents

Abstract

Translated fromChinese

本發明之課題為提供，提高在具有藉由著色劑或量子點(Quantum dot)所構成的彩色濾光器層之彩色濾光器方式的顯示裝置中之光提取效率，且提高耐光性及耐濕熱性之高品質的顯示裝置，與故障缺陷較少而生產效率提高的顯示裝置之製造方法。本發明之顯示裝置為具備彩色濾光器單元之顯示裝置，其特徵為前述彩色濾光器單元為至少由基材、彩色濾光器層及平坦化層所構成，前述彩色濾光器層或前述平坦化層的至少1層為含有具有下述一般式(1)所示結構的有機金屬氧化物者；

。The subject of the present invention is to provide an improvement in light extraction efficiency in a color filter type display device having a color filter layer composed of colorants or quantum dots, and to improve light resistance and durability A high-quality display device with moist heat and a manufacturing method for a display device with fewer defects and improved production efficiency. The display device of the present invention is a display device provided with a color filter unit, characterized in that the color filter unit is composed of at least a substrate, a color filter layer, and a planarization layer, and the color filter layer or At least one layer of the aforementioned planarization layer contains an organometallic oxide having a structure represented by the following general formula (1);

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Description

Translated fromChinese

顯示裝置及顯示裝置之製造方法Display device and manufacturing method of display device

本發明係關於顯示裝置及顯示裝置的製造方法，更詳細為有關於提高具有藉由著色劑或量子點所構成的彩色濾光器層之彩色濾光器方式的顯示裝置之光提取效率，且提高耐光性及耐濕熱性之高品質的顯示裝置，與故障缺陷少而提高生產效率之顯示裝置的製造方法。The present invention relates to a display device and a method of manufacturing the display device, and more specifically to improving the light extraction efficiency of a color filter type display device having a color filter layer composed of colorants or quantum dots, and A high-quality display device with improved light resistance and humidity resistance, and a manufacturing method for a display device with fewer defects and improved production efficiency.

對於產業界，以電晶體及二極管作為代表的多數電子產品構件會因水或氧而引起劣化，故施予稱為密封加工或鈍化處理(鈍化)之加工。特別為將電子傳導由有機化合物來承擔的顯示裝置，例如有機薄膜電晶體或有機薄膜太陽電池、有機電致發光元件(以下稱為「有機EL元件」)等，對水分子特別敏感，故需要極高度之密封技術。In the industry, most electronic product components represented by transistors and diodes are degraded by water or oxygen, so processing called sealing processing or passivation (passivation) is applied. Especially for display devices where the conduction of electrons is undertaken by organic compounds, such as organic thin-film transistors or organic thin-film solar cells, organic electroluminescence elements (hereinafter referred to as "organic EL elements"), etc., which are particularly sensitive to water molecules, so they need Extremely high sealing technology.

顯示裝置之一的有機EL顯示器與液晶顯示裝置相比較，因具有視野角依賴性較少，對比較高，且可薄膜化等利點，故受到注目，而正進行著各種檢討。另外，大型電視已經投入市場中，平板顯示器加速擴大市場。Compared with the liquid crystal display device, the organic EL display, which is one of the display devices, has the advantages of less viewing angle dependence, higher contrast, and thin film thickness, so it is attracting attention and various reviews are being conducted. In addition, large-scale TVs have been put into the market, and flat-panel displays have accelerated their market expansion.

且，對於有機EL顯示器，由擴大適用領域的自由度之觀點來看，使用以樹脂薄膜等所構成的具備柔軟性之可撓性基材的有機EL顯示器之開發正受到重視。藉由對於有機EL顯示器等使用可撓性基材，除要求輕量化及大型化以外，具有可實現滾動再滾動之生產適性、提高形狀自由度、可曲面顯示等優點，取代重量重而容易裂開，且大面積化困難之玻璃基材而廣泛被利用。In addition, with regard to organic EL displays, from the viewpoint of expanding the degree of freedom in the field of application, the development of organic EL displays using flexible and flexible substrates made of resin films or the like is attracting attention. By using flexible substrates for organic EL displays, in addition to requiring lighter weight and larger size, it has the advantages of realizing roll-and-rolling production suitability, improved shape freedom, and curved display. It replaces heavy weight and easily cracks. It is widely used as a glass substrate which is difficult to open and enlarge the area.

然而，可撓性基材相對於玻璃基材，有著氣體阻隔性不佳的問題。例如，作為有機EL元件用之基材使用可撓性基材時，因水蒸氣透過性或氧透過性高，適用於對水分或氧較為弱的有機EL元件時，作為氣體阻隔性可說是不充分，所構成的有機功能層等會因水分或氧而劣化，引起像素收縮或亮度降低等，成為損失耐久性的要因。However, the flexible substrate has the problem of poor gas barrier properties compared to the glass substrate. For example, when a flexible substrate is used as a substrate for an organic EL element, it has high water vapor permeability or oxygen permeability and is suitable for organic EL elements that are weak to moisture or oxygen. Insufficient, the constituted organic functional layer and the like will be degraded by moisture or oxygen, causing shrinkage of pixels or reduction in brightness, etc., which will be a cause of loss of durability.

作為解決上述問題的方法之一，使用具備具有高氣體阻隔性的氣體阻隔層之可撓性基材，形成含有電極及發光層之有機功能層的可撓性有機EL顯示器之檢討正進行著(例如參照專利文獻1)。As one of the methods to solve the above-mentioned problems, the use of a flexible substrate with a gas barrier layer with high gas barrier properties to form an organic functional layer containing electrodes and a light-emitting layer is currently under review ( For example, refer to Patent Document 1).

另一方面，對於顯示裝置之開發，由製造成本之減低、大畫面TV之產率提高、製造步驟之簡便化等觀點來看，例如作為發光構件，使用白色發光方式之有機EL元件，配置於光提取側由著色劑所構成的彩色濾光器，使RGB發光之方式的檢討正被進行。進一步作為彩色濾光器之構成，對於RGB塗分法亦由於使用蒸鍍掩膜的製造精度或蒸鍍所造成的影子之影響，所顯示的彩色圖像之高精細化有著極限，作為進一步高精細化的嘗試，作為彩色濾光器，使用含有量子點而色變換發光的彩色濾光器之含有量子點的有機發光元件(以下亦稱為「QD-OLED」)之檢討正被檢討著(例如參照專利文獻2及3)。On the other hand, for the development of display devices, from the viewpoints of reducing manufacturing costs, increasing the yield of large-screen TVs, and simplifying manufacturing steps, for example, as a light-emitting member, an organic EL element of a white light-emitting method is used and arranged in The color filter made of coloring agent on the light extraction side is being reviewed for the way that RGB emits light. Furthermore, as the structure of the color filter, for the RGB coating method, due to the manufacturing accuracy of the vapor deposition mask or the influence of the shadow caused by vapor deposition, there is a limit to the high definition of the color image displayed. Attempts to refine, as a color filter, the use of a color filter containing quantum dots and color-converted light-emitting organic light-emitting devices containing quantum dots (hereinafter also referred to as "QD-OLED") is being reviewed ( For example, refer toPatent Documents 2 and 3).

然而，使用上述著色劑的彩色濾光器方式，或使用量子點的彩色濾光器方式中，於形成彩色濾光器單元時，因必須設置平坦化層，而折射率小，且進一步有著與彩色濾光器層的折射率差變大等問題，提取光的損失為高，藉著彩色濾光器單元所顯示的發光性能會降低，欲不要降低作為發光裝置之發光亮度，作為該對應，提高發光層自體之發光效率成為必要，所望的光提取特性，例如發光亮度的確保盡力努力達成。又，於形成彩色濾光器後所填充的填充劑，因藉由有機聚合物所成的透明樹脂層而構成，藉此亦有透過率至少降低1%以上的問題。另外，彩色濾光器容易吸收水分，藉由自密封後的彩色濾光器釋出水分，導致接近經配置的有機EL元件之有機功能層等的劣化，有著密封缺陷所引起的產率降低之問題。[先前技術文獻][專利文獻]However, in the color filter method using the above-mentioned colorant or the color filter method using quantum dots, when the color filter unit is formed, a flattening layer must be provided, and the refractive index is small, and it is further The color filter layer has a large refractive index difference, and the loss of extracted light is high. The luminous performance displayed by the color filter unit will be reduced. If you want to reduce the luminous brightness of the light-emitting device, as a countermeasure, It is necessary to improve the luminous efficiency of the light-emitting layer itself, and the desired light extraction characteristics, such as the guarantee of the luminous brightness, are tried hard to achieve. In addition, the filler filled after the color filter is formed is composed of a transparent resin layer made of an organic polymer, which also has a problem that the transmittance is reduced by at least 1%. In addition, the color filter easily absorbs moisture, and the moisture is released from the sealed color filter, resulting in deterioration of the organic functional layer close to the configured organic EL element, and the reduction in yield caused by sealing defects problem.[Prior Technical Literature][Patent Literature]

[專利文獻1]日本特開2011-156752號公報[專利文獻2]日本特開2016-80811號公報[專利文獻3]日本特開2017-26796號公報[Patent Document 1] Japanese Patent Application Publication No. 2011-156752[Patent Document 2] JP 2016-80811 A[Patent Document 3] JP 2017-26796 A

[發明所解決的問題][Problem Solved by Invention]

本發明為有鑑於上述問題而成者，該解決課題為提供，提高在具有藉由著色劑或量子點(Quantum dot)所構成的彩色濾光器層之彩色濾光器方式的顯示裝置中之光提取效率，且提高耐光性及耐濕熱性之高品質的顯示裝置，與故障缺陷較少而生產效率提高的顯示裝置之製造方法。[解決課題的手段]The present invention was made in view of the above-mentioned problems, and the problem to be solved is to provide an improvement in the display device of a color filter method having a color filter layer composed of a colorant or a quantum dot (Quantum dot) A high-quality display device with improved light extraction efficiency and improved light resistance and humidity resistance, and a method for manufacturing a display device with fewer defects and improved production efficiency.[Means to solve the problem]

本發明者有鑑於上述課題而進行詳細檢討之結果，發現具備彩色濾光器單元之顯示裝置，其為前述彩色濾光器單元為至少由基材、彩色濾光器層及平坦化層所構成，前述彩色濾光器層或前述平坦化層的至少1層因含有以下有機金屬氧化物，可得到作為水分透過之密封膜的功能之有機薄膜，其結果，可提高作為彩色濾光器單元的光提取效率之同時，可實現提高耐光性及耐濕熱性之高品質的顯示裝置，而完成本發明；上述有機金屬氧化物為具有下述一般式(1)所示結構者，該結構係由含有含氟原子的金屬烷氧化物或金屬羧酸酯之組成物所形成者。The inventor of the present invention conducted a detailed review in view of the above-mentioned problems, and found that a display device with a color filter unit is composed of at least a substrate, a color filter layer, and a planarization layer. At least one layer of the color filter layer or the flattening layer contains the following organometallic oxides, so that an organic thin film that functions as a sealing film for moisture transmission can be obtained. As a result, the color filter unit can be improved At the same time of light extraction efficiency, a high-quality display device with improved light resistance and humidity resistance can be realized, thus completing the present invention; the above-mentioned organometallic oxide has a structure represented by the following general formula (1), which is composed of It is formed by a composition containing a fluorine atom-containing metal alkoxide or metal carboxylate.

即，本發明者們對於克服如前述的種種問題之目的，實施可實現如以下的現象的技術創作。That is, for the purpose of overcoming various problems as described above, the inventors implemented technical creations that can realize the following phenomena.

(I)具有與水分子反應的乾燥性(desiccant)者。(I) Those with desiccant to react with water molecules.

(II)作為與水反應的功能為釋出具有不接近水的性質之物質者。(II) The function of reacting with water is to release substances with properties not close to water.

(III)可在大氣壓下的塗布成膜者。(III) Those that can be coated and formed under atmospheric pressure.

若可構築同時具有此三項要素之材料與技術，可有效果地防止於電子裝置之心臟部的水分子透過，又藉由對應透過的水分量而生成撥水性物質，可成為與過去的水蒸氣阻隔性為完全相異的新穎技術思想之阻止水蒸氣透過的方法，且若可進行在大氣壓下的塗布(塗布)，則變的可便宜且可進行大面積之密封，面對即將到來的IoT時代，實際上有潛力地可以一次解決成為製造成本的瓶頸之隱藏課題，即便宜且有效果地密封加工之問題。If we can construct materials and technologies that have these three elements at the same time, it can effectively prevent the penetration of water molecules in the heart of electronic devices, and generate water-repellent substances corresponding to the amount of water that penetrates, which can become the water of the past. The vapor barrier property is a completely different novel technical idea to prevent the transmission of water vapor, and if coating (coating) under atmospheric pressure can be performed, it can be cheap and can be sealed in a large area, facing the upcoming In the IoT era, it actually has the potential to solve the hidden problem that has become the bottleneck of the manufacturing cost at one time, that is, the problem of cheap and effective sealing processing.

即，有關本發明的上述課題，可藉由以下手段進行解決。That is, the above-mentioned problems related to the present invention can be solved by the following means.

1.一種顯示裝置，其為具備彩色濾光器單元的顯示裝置，其特徵為前述彩色濾光器單元至少由基材、彩色濾光器層及平坦化層所構成，前述彩色濾光器層或前述平坦化層的至少1層含有具有下述一般式(1)所示結構的有機金屬氧化物者；

(式中，R表示氫原子、碳數1個以上的烷基、烯基、芳基、環烷基、醯基、烷氧基或雜環基。但R亦可為含有作為取代基的氟原子之碳鏈。M表示金屬原子。OR₁表示氟化烷氧基。x表示金屬原子的價數，y表示1與x之間的任意整數。n各表示聚縮合度)。1. A display device comprising a color filter unit, characterized in that the color filter unit is at least composed of a substrate, a color filter layer, and a planarization layer, and the color filter layer Or at least one layer of the aforementioned planarization layer contains an organometallic oxide having a structure represented by the following general formula (1);

(In the formula, R represents a hydrogen atom, an alkyl group, alkenyl group, aryl group, cycloalkyl group, acyl group, alkoxy group or heterocyclic group with 1 or more carbon atoms. However, R may also contain fluorine as a substituent A carbon chain of atoms. M represents a metal atom. OR₁ represents a fluorinated alkoxy group. x represents the valence of the metal atom, and y represents any integer between 1 and x. Each n represents the degree of polycondensation).

2.將具有發光層者作為特徵之第1項所記載的顯示裝置。2. The display device described inItem 1 characterized by having a light-emitting layer.

3.以對於前述彩色濾光器層或前述平坦化層所含有的前述有機金屬氧化物的碳原子與氟原子之總數而言的氟原子之比的值為滿足下述式(a)所規定的條件為特徵的第1項或第2項所記載的顯示裝置。

3. The value of the ratio of fluorine atoms to the total number of carbon atoms and fluorine atoms of the organic metal oxide contained in the color filter layer or the planarization layer satisfies the following formula (a) The condition is the display device described initem 1 oritem 2.

4.以前述有機金屬氧化物所含有的金屬原子(M)為Ti、Zr、Sn、Ta、Fe、Zn或Al為特徵之第1項至第3項為止中任一項所記載的顯示裝置。4. The display device described in any one ofitems 1 to 3 up to the feature that the metal atom (M) contained in the aforementioned organometallic oxide is Ti, Zr, Sn, Ta, Fe, Zn, or Al .

5.以前述平坦化層的折射率為1.6～1.9的範圍內者為特徵的第1項至第4項為止中任一項所記載的顯示裝置。5. The display device described in any one ofitems 1 to 4, characterized by having a refractive index of the aforementioned planarization layer in the range of 1.6 to 1.9.

6.以前述平坦化層與前述彩色濾光器層的折射率差之絕對值為未達0.1者為特徵的第1項至第5項為止中任一項所記載的顯示裝置。6. The display device described in any one ofitems 1 to 5, characterized by the absolute value of the refractive index difference between the planarization layer and the color filter layer being less than 0.1.

7.以前述彩色濾光器單元為含有量子點者為特徵的第1項至第6項為止中任一項所記載的顯示裝置。7. The display device described in any one ofitems 1 to 6 up to the feature that the color filter unit contains quantum dots.

8.以顯示裝置為有機發光元件、無機發光元件或彩色電子紙者為特徵的第1項至第7項為止中任一項所記載的顯示裝置。8. The display device described in any one ofitems 1 to 7 up to the feature that the display device is an organic light-emitting element, an inorganic light-emitting element, or a color electronic paper.

9.以前述有機發光元件為有機電致發光元件或含有量子點的有機發光元件者為特徵的第8項所記載的顯示裝置。9. The display device described initem 8 characterized in that the aforementioned organic light-emitting element is an organic electroluminescence element or an organic light-emitting element containing quantum dots.

10.以前述無機發光元件為含有量子點的無機發光元件或微型LED者為特徵的第8項所記載的顯示裝置。10. The display device described initem 8 characterized in that the inorganic light-emitting element is an inorganic light-emitting element containing quantum dots or a micro LED.

11.一種顯示裝置之製造方法，其為製造如第1項至第10項為止中任一項所記載的具備彩色濾光器單元的顯示裝置之方法，其特徵為將構成前述彩色濾光器單元的彩色濾光器層，使用金屬烷氧化物或金屬羧酸酯，與氟化醇的混合液而形成者。11. A method of manufacturing a display device, which is a method of manufacturing a display device equipped with a color filter unit as described in any one ofitems 1 to 10, characterized in that the color filter is constructed The color filter layer of the unit is formed by using a mixture of metal alkoxide or metal carboxylate and fluorinated alcohol.

12.以將前述彩色濾光器層藉由濕式塗布法所形成者為特徵的第11項所記載的顯示裝置之製造方法。12. The method of manufacturing the display device described inItem 11 characterized by forming the aforementioned color filter layer by a wet coating method.

13.以前述濕式塗布法為噴墨印刷法為特徵的第12項所記載的顯示裝置之製造方法。[發明之效果]13. The method for manufacturing the display device described inItem 12 characterized by the wet coating method being an inkjet printing method.[Effects of Invention]

依據本發明可提供，可提高在具有著色劑或量子點所構成的彩色濾光器層之彩色濾光器方式的顯示裝置之光提取效率，且提高耐光性及耐濕熱性之高品質的顯示裝置，與故障缺陷較少且生產效率提高的顯示裝置之製造方法。According to the present invention, it is possible to provide a high-quality display that can improve the light extraction efficiency of a color filter type display device having a color filter layer composed of a colorant or a quantum dot, and improve the light resistance and humidity resistance Device, and manufacturing method of display device with fewer defects and improved production efficiency.

由以本發明所規定的構成所成的面發光面板之技術特徵與該效果之表現機構可由以下做推察。The technical characteristics of the surface light-emitting panel formed by the configuration specified in the present invention and the performance mechanism of the effect can be inferred as follows.

在本發明中提供一種構成膜，其為對於具備彩色濾光器單元的顯示裝置，於構成彩色濾光器單元的彩色濾光器層或前述平坦化層的至少1層上，藉由含有具有前述一般式(1)所示結構的有機金屬氧化物，含有該有機金屬氧化物之構成層作為化學反應型的水分之吸氣劑而作用，且僅釋出與水分的反應之份量的撥水性或疏水性物質，具備如此對於水分透過的新穎吸濕特性或密封特性的構成膜者。In the present invention, there is provided a constituent film, which is, for a display device having a color filter unit, on at least one of the color filter layer constituting the color filter unit or the aforementioned planarization layer, by containing The organometallic oxide of the structure represented by the aforementioned general formula (1), the constituent layer containing the organometallic oxide acts as a getter of chemically reactive water, and only releases the water repellency of the amount of the reaction with the water Or a hydrophobic substance, which has such novel moisture absorption properties or sealing properties for water penetration.

即，具有前述一般式(1)所示結構的有機金屬氧化物藉由水解，而生成與經淬火的水分子等莫耳之氟化醇，因此具有撥水功能或疏水功能，可防止此以上的水侵入者。因此，比起過去的化學反應型的吸濕劑，水分的侵入防止效果極高，除對於單一組成膜具有乾燥性，亦可發揮藉由與水分之反應而加成撥水功能等的相乘效果(協同作用效果)，具有在過去的吸濕劑及有機薄膜不具有的特徵之革新性技術。That is, the organometallic oxide having the structure represented by the general formula (1) is hydrolyzed to generate a molar fluorinated alcohol such as quenched water molecules. Therefore, it has a water-repellent function or a hydrophobic function, which can prevent this. Water invaders. Therefore, compared with the conventional chemical reaction type moisture absorption agent, the moisture intrusion prevention effect is extremely high. In addition to the drying property for a single composition film, it can also play a multiplier with the addition of water repellent function by reaction with moisture. Effect (synergistic effect), innovative technology with characteristics that were not available in the past moisture absorbents and organic films.

又，含有具有本發明有關一般式(1)所示結構之有機金屬氧化物的彩色濾光器層或前述平坦化層為採用以下方法形成，該方法為，將金屬烷氧化物溶液作為原料，一般稱為溶膠･凝膠法的藉由金屬烷氧化物之水解與接續進行的聚縮合反應而合成有機無機雜合化合物(Organic inorganic bismuth compound)，形成該構成層的方法。In addition, the color filter layer containing the organometallic oxide having the structure represented by the general formula (1) of the present invention or the aforementioned planarization layer is formed by the following method, which uses a metal alkoxide solution as a raw material, The method of synthesizing organic inorganic bismuth compound (Organic inorganic bismuth compound) through the hydrolysis of metal alkoxide and subsequent polycondensation reaction, which is generally called the sol-gel method, to form the constituent layer.

作為將無機氧化物以塗布方式進行成膜的常規手段，已有溶膠･凝膠法廣泛被知道。該方法為，一般將金屬烷氧化物溶液作為原料，以藉由金屬烷氧化物之水解，與接續進行的聚縮合反應而形成無機氧化物的方法，將金屬烷氧化物的一部分非作為烷氧基而係作為烷基或芳基時，該基在溶膠･凝膠反應後亦可被保持，故可形成將無機氧化物作為基底的有機無機雜合化合物膜。As a conventional method for forming a film of an inorganic oxide by a coating method, the sol-gel method is widely known. This method generally uses a metal alkoxide solution as a raw material to form an inorganic oxide through the hydrolysis of the metal alkoxide and subsequent polycondensation reactions. A part of the metal alkoxide is not used as an alkoxide. When the group is an alkyl group or an aryl group, the group can be retained after the sol-gel reaction, so that an organic-inorganic hybrid compound film with an inorganic oxide as a base can be formed.

基本上，可進行烷氧基化的所有金屬元素雖可適用於該溶膠･凝膠法，但實際上，在大氣中作為溶液時會引起凝膠化，而幾乎皆成為無法塗布的情況，具有實用價值者僅限於矽(四烷氧基矽烷)。該理由為，金屬元素為鈦或鋯之情況時，因該烷氧化物化合物本身為路易氏酸，水解反應後的脫水聚縮合之反應會以觸媒方式加速，會馬上引起凝膠化之故。Basically, all metal elements that can be alkoxylated can be applied to the sol/gel method, but in fact, when used as a solution in the atmosphere, gelation occurs, and almost all of them cannot be applied. The practical value is limited to silicon (tetraalkoxysilane). The reason is that when the metal element is titanium or zirconium, since the alkoxide compound itself is Lewis acid, the dehydration polycondensation reaction after the hydrolysis reaction will be accelerated by a catalyst, which will immediately cause gelation. .

又，鹼金屬或鹼土類金屬之情況時，即使為烷氧化物，因成為鹼性，最初的水解反應非常快，另一方面，因脫水聚縮合反應較為慢，難得到有機金屬氧化物。但因具有該中間性質者為矽烷氧化物，對於藉由溶膠･凝膠法的有機金屬氧化物合成或有機金屬氧化物薄膜形成中僅可使用此為現狀。In the case of an alkali metal or alkaline earth metal, even if it is an alkoxide, the initial hydrolysis reaction is very fast because it becomes alkaline. On the other hand, the dehydration polycondensation reaction is relatively slow, making it difficult to obtain an organometallic oxide. However, since the intermediate property is a silanoxide, it is the current state that it can only be used in organometallic oxide synthesis or organometallic oxide thin film formation by the sol-gel method.

相對於此，將金屬烷氧化物溶解於過剩醇(A)時，由化學平衡來看金屬的烷氧化物會被取代為醇(A)，而生成該醇(A)之金屬烷氧化物，但此時，將醇(A)作為以氟原子取代的醇時，所生成的金屬氟化烷氧基化合物(以下亦稱為「金屬氟化烷氧化物」)可使前述溶膠･凝膠反應速度緩和。On the other hand, when metal alkoxide is dissolved in excess alcohol (A), the metal alkoxide will be replaced with alcohol (A) from the chemical equilibrium, and the metal alkoxide of alcohol (A) will be generated. However, in this case, when alcohol (A) is used as an alcohol substituted with a fluorine atom, the produced metal fluorinated alkoxy compound (hereinafter also referred to as "metal fluorinated alkoxide") can react with the aforementioned sol/gel The speed slows down.

此雖為藉由氟原子的電子吸引效果而降低金屬元素上的電子密度而加速水分子的求核反應者，但藉由氟原子的水之排除效果更大，因水分子不會接近金屬元素，故所謂的頻度因子會大大降低，作為結果，水解速度會變慢，例如，鈦或鋯，進一步為存在空d軌道的過渡金屬(例如4價釩或4價鎢等)之烷氧化物化合物為路易氏酸，故可表現酸觸媒的效果，因加入脫水聚縮合或脫醇聚縮合反應，而為具有容易生成高分子量之有機金屬氧化物的特長者。Although this is the one that accelerates the nuclear reaction of water molecules by reducing the electron density on the metal element by the electron attracting effect of fluorine atoms, the water removal effect by the fluorine atom is greater because water molecules will not approach the metal element. Therefore, the so-called frequency factor will be greatly reduced. As a result, the hydrolysis rate will be slower. For example, titanium or zirconium, and further alkoxide compounds of transition metals with empty d orbitals (such as tetravalent vanadium or tetravalent tungsten) are Lewis acid can exhibit the effect of an acid catalyst. It is easy to generate high molecular weight organometallic oxide due to the addition of dehydration polycondensation or dealcoholization polycondensation reaction.

藉此該效果，可滿足前述(I)具有與水分子進行反應的乾燥性者、(II)作為與水反應的功能，具有釋放不接近水的性質之物質者，及(III)可在大氣壓下塗布成膜者等全部，特別在(III)所記載的要件，對於一般的金屬烷氧化物藉由進行凝膠化的處理在實質上並未能達成者，卻可在氟化醇的存在下，使其成為可能，對於所形成的構成層施予紫外線或電漿照射、微波照射等高能量後，於薄膜表面上形成連續性高密度的有機金屬氧化物膜，結果該薄膜具有(I)之乾燥性，且因未反應的金屬氟化烷氧化物會殘存於內部，故進入的水分子會與此進行反應，可發揮生成排斥水的氟化醇的(II)之效果，作為結果，形成同時具有(I)與(II)之效果的新穎薄膜成為可能。With this effect, it is possible to satisfy the requirements of (I) those with drying properties that react with water molecules, (II) those with the function of reacting with water, those with properties that release substances that are not close to water, and (III) those capable of working at atmospheric pressure In particular, the requirements described in (III) can not be achieved substantially by the gelation treatment of general metal alkoxides. However, it can be used in the presence of fluorinated alcohols. In order to make it possible to apply high energy such as ultraviolet rays, plasma irradiation, microwave irradiation to the formed constituent layer, a continuous and high-density organometal oxide film is formed on the surface of the film. As a result, the film has (I ) Is dry, and because the unreacted metal fluorinated alkoxide will remain inside, the ingressed water molecules will react with it, and the effect of (II) generating fluorinated alcohol that repels water can be exerted, as a result , It becomes possible to form a novel film with both (I) and (II) effects.

又，以氟化醇取代的金屬烷氧化物中，異種金屬烷氧化物彼此反應或鹽形成亦因藉由氟原子之排除效果而使頻度因子降低，故可有效果地抑制，亦可將2種或複數種的金屬烷氧化物作為金屬氟化烷氧化物而於溶液中共存，由該溶液所得之薄膜亦可賦予混合無機氧化物薄膜。In addition, in the metal alkoxides substituted with fluorinated alcohols, dissimilar metal alkoxides react with each other or form a salt because the frequency factor is reduced due to the elimination effect of fluorine atoms, so it can be effectively suppressed, and 2 One or more kinds of metal alkoxides coexist as metal fluorinated alkoxides in the solution, and the thin film obtained from the solution can also be given to the mixed inorganic oxide thin film.

例如，對於通常會成為路易氏酸/路易斯鹼對而凝膠化的鈦四異丙氧化物與鋇二丁氧化物，即使將各自以大量過剩的四氟丙醇(TFPO)進行稀釋後混合亦不會引起凝膠化，可直接進行塗布並經溶膠･凝膠法而形成薄膜，將該薄膜以紫外線等高能量照射下，亦可形成混合有機金屬氧化物皮膜。For example, for titanium tetraisopropoxide and barium dibutoxide, which usually become a Lewis acid/Lewis base pair and gelled, even if each is diluted with a large excess of tetrafluoropropanol (TFPO) and mixed It does not cause gelation, and can be directly coated and formed into a thin film by the sol/gel method. The thin film can be irradiated with high energy such as ultraviolet rays to form a mixed organic metal oxide film.

進一步本發明可藉由溶膠･凝膠法(以下亦稱為「溶膠･凝膠反應」)製造出有機金屬氧化物。Furthermore, in the present invention, organometallic oxides can be produced by the sol-gel method (hereinafter also referred to as "sol-gel reaction").

如前述，藉由使用使溶膠･凝膠反應速度變緩和的金屬烷氧化物溶液，可將溶液穩定性之提高及成膜時的處理性變得容易。另一方面，雖由形成的膜形成高密度的有機金屬酸化膜時變得需要高能量，但因藉由氧分子或氮分子被吸收，故有溶膠･凝膠反應留置於膜表面，而不會進行至內部的情況等問題。As mentioned above, by using a metal alkoxide solution that slows the sol-gel reaction rate, the stability of the solution and the handling during film formation can be improved. On the other hand, although high energy is required to form a high-density organometallic acidified film from the formed film, oxygen molecules or nitrogen molecules are absorbed, so sol-gel reaction remains on the surface of the film instead of Will progress to internal issues and other issues.

相對於此，在本發明中，藉由進行金屬烷氧化物的溶膠･凝膠反應，解決膜形成前後之相反課題者為本發明之特徵。In contrast, in the present invention, it is a feature of the present invention to solve the opposite problems before and after the film formation by performing the sol-gel reaction of the metal alkoxide.

即，有關本發明的有機金屬氧化物，並非僅停留在欲得到生成撥水性或疏水性化合物的吸濕功能之組成物，可使過去難以共存的複數種金屬烷氧化物在穩定下存在，作為該結果所得之混合有機金屬氧化物薄膜本身亦在此範圍中。此在過去似乎可實現，但實際上其為並未能實現的技術，欲使其實現，對於各式各樣的適用領域中，期待可發揮至今未有的功能，故本發明對產業界有著非常大的好影響。In other words, the organometallic oxide of the present invention does not only remain in the composition to obtain the moisture absorption function of generating water-repellent or hydrophobic compounds, but can make it possible to stably exist in a plurality of metal alkoxides that were difficult to coexist in the past. The resultant mixed organometal oxide film itself is also within this range. This seems to be achievable in the past, but in fact it is a technology that has not been achieved. To achieve this, it is expected that it can perform functions that have not been available until now in various applicable fields. Therefore, the present invention is useful for the industry. Very big good influence.

因此，本發明與過去藉由使用金屬烷氧化物的溶膠･凝膠法之薄膜形成為概念相異，且所形成的薄膜之功能亦相異，更實現了至今不可能達成的混合有機金屬氧化物薄膜，故本發明為可與類似的過去技術做區分者。Therefore, the present invention is different in concept from the past film formation by the sol-gel method using metal alkoxides, and the function of the formed film is also different, and realizes the hybrid organometallic oxidation that has not been possible so far. Therefore, the present invention is distinguishable from similar past technologies.

[實施發明的形態][The form of implementing the invention]

本發明之顯示裝置為具備彩色濾光器單元的顯示裝置，前述彩色濾光器單元為至少由基材、彩色濾光器層及平坦化層所構成，前述彩色濾光器層或前述平坦化層的至少1層為含有具有前述一般式(1)所示結構的有機金屬氧化物者為特徵。該特徵為有關下述各實施形態之發明的共通技術特徵。The display device of the present invention is a display device provided with a color filter unit. The color filter unit is composed of at least a substrate, a color filter layer, and a planarization layer. The color filter layer or the planarization layer At least one of the layers is characterized by containing an organometallic oxide having a structure represented by the aforementioned general formula (1). This feature is a common technical feature related to the inventions of the following embodiments.

對於由上述構成所成的本發明之顯示裝置，使用氟化醇溶劑，可藉由適用所望金屬種類，而取代由外部進入的分子，將水分藉由水解反應吸收、取代及成為具有羥基的化學鍵結狀態成為可能，其結果可得到吸濕功能優良的彩色濾光器單元，將由外部侵入或由彩色濾光器層擴散的水分以平坦化層吸水，或彩色濾光器層本身即可吸收水分，故可實現顯示裝置的構成層，特別是抑制對有機功能層群的水分擴散，而具有水分耐性的高信賴性之顯示裝置。For the display device of the present invention composed of the above-mentioned structure, a fluorinated alcohol solvent is used. By applying the desired metal species, the molecules entering from the outside can be replaced, and the water can be absorbed and replaced by the hydrolysis reaction, and the chemical bond with the hydroxyl group can be absorbed. The junction state becomes possible, and as a result, a color filter unit with excellent moisture absorption function can be obtained. The water invaded from the outside or diffused by the color filter layer is absorbed by the flattening layer, or the color filter layer itself can absorb water Therefore, it is possible to realize the constituent layers of the display device, in particular, a highly reliable display device with moisture resistance by suppressing the diffusion of moisture to the organic functional layer group.

作為本發明之實施形態，由可進一步表現作為本發明之目的的效果之觀點來看，藉由使用於具有對於水分的耐性低的發光層之顯示裝置，可顯著地提高該發光層的耐久性，實現信賴性高的顯示裝置。As an embodiment of the present invention, from the viewpoint that the effect of the object of the present invention can be further expressed, the durability of the light-emitting layer can be significantly improved by being used in a display device having a light-emitting layer with low moisture resistance , Realize a highly reliable display device.

又，將對於彩色濾光器層或前述平坦化層所含有的前述有機金屬氧化物之碳原子與氟原子的總數之氟原子的比值[F/(C+F)]設定在0.05～1.00之範圍內時，可控制溶劑的氟化醇之含有量，並可形成表現所望吸濕效果的彩色濾光器層。In addition, the ratio [F/(C+F)] of fluorine atoms to the total number of carbon atoms and fluorine atoms of the organic metal oxide contained in the color filter layer or the planarization layer is set at 0.05 to 1.00 When it is within the range, the content of the fluorinated alcohol in the solvent can be controlled, and a color filter layer that exhibits the desired moisture absorption effect can be formed.

又，將有機金屬氧化物所含有的金屬原子(M)設定為Ti、Zr、Sn、Ta、Fe、Zn或Al時，在適用的構成層可得到高折射率，並可得到可增加光提取效率的金屬烷氧化物。In addition, when the metal atom (M) contained in the organometallic oxide is set to Ti, Zr, Sn, Ta, Fe, Zn, or Al, a high refractive index can be obtained in the applicable constituent layer, and light extraction can be increased. Efficiency of metal alkoxides.

又，藉由將平坦化層的折射率設定在1.6～1.9的範圍內時，可將自發光層射出的光之光提取效率在該平坦化層提高，該結果為可達到作為顯示裝置的亮度提高，及此可使構成顯示裝置的發光元件壽命之延命化。In addition, when the refractive index of the planarization layer is set in the range of 1.6 to 1.9, the light extraction efficiency of the light emitted from the light-emitting layer can be improved in the planarization layer, and the result is that the brightness as a display device can be achieved This improves the life of the light-emitting element constituting the display device.

又，藉由適宜地選擇由對應所望折射率的金屬種所構成的有機金屬氧化物，可使平坦化層與彩色濾光器層的折射率差之絕對值成為未達0.1，該結果可達成藉由平坦化層與彩色濾光器層之折射率差所產生的光折射之光損失的減低、顯示裝置之亮度提高，與構成顯示裝置的發光元件壽命之延命化。In addition, by appropriately selecting an organometallic oxide composed of a metal species corresponding to the desired refractive index, the absolute value of the refractive index difference between the planarization layer and the color filter layer can be less than 0.1. This result can be achieved The light loss of light refraction caused by the difference in refractive index between the planarization layer and the color filter layer is reduced, the brightness of the display device is improved, and the life of the light emitting element constituting the display device is prolonged.

又，藉由將本發明之彩色濾光器方式的顯示裝置適用於有機發光元件、無機發光元件或彩色電子紙時，可實現光提取效率的提高，且耐光性及耐濕熱性提高的高品質之顯示裝置，亦可使元件壽命延命化，並可抑制由大型電視化所造成的密封缺陷，故可使品質提高，且可使產率提高。In addition, when the color filter type display device of the present invention is applied to organic light-emitting elements, inorganic light-emitting elements, or color electronic paper, high quality with improved light extraction efficiency and improved light resistance and humidity resistance can be achieved The display device can also prolong the life of the components, and can suppress the sealing defects caused by the large-scale television, so it can improve the quality and increase the yield.

又，本發明之顯示裝置之製造方法為，製造具備本發明之彩色濾光器單元的顯示裝置之顯示裝置之製造方法，其特徵為將構成前述彩色濾光器單元之彩色濾光器層使用金屬烷氧化物或金屬羧酸酯，與氟化醇的混合液而形成者。In addition, the method of manufacturing a display device of the present invention is a method of manufacturing a display device of a display device equipped with the color filter unit of the present invention, characterized by using the color filter layer constituting the color filter unit A mixture of metal alkoxides or metal carboxylates and fluorinated alcohols.

又，對於本發明之顯示裝置之製造方法，可提供將彩色濾光器層藉由濕式塗布法形成時，具有高折射率與吸濕能力，且對於有機功能層群不會造成損傷之製造方法，又大型設備變得不必要，可對局所部位以高精度方式進行塗布，且所形成的層厚之控制變得可能，可將對光提取的最佳光路長在精度良好下形成變得可能，可使光提取效率最大化的觀點來看為佳。In addition, the manufacturing method of the display device of the present invention can provide a manufacturing method that has high refractive index and moisture absorption capacity when the color filter layer is formed by a wet coating method, and does not cause damage to the organic functional layer group. The method and large-scale equipment become unnecessary, the site can be coated with high precision, and the thickness of the formed layer can be controlled, and the optimal optical path length for light extraction can be formed with good accuracy. Possibly, it is preferable from the viewpoint of maximizing light extraction efficiency.

上述濕式塗布法為噴墨印刷法時，由可進一步表現上述效果之觀點來看為佳。When the above-mentioned wet coating method is an inkjet printing method, it is preferable from the viewpoint that the above-mentioned effects can be further expressed.

本發明中，將第1基材、TFT單元、第1電極～第2密封層為止的構成稱為發光顯示單元或有機EL元件單元。In the present invention, the structure including the first substrate, the TFT unit, and the first electrode to the second sealing layer is referred to as a light-emitting display unit or an organic EL element unit.

又，將第1電極～第2密封層為止的構成稱為有機EL元件(OLED)。In addition, the structure from the first electrode to the second sealing layer is called an organic EL element (OLED).

又，將由基材、彩色濾光器層及平坦化層所構成的構成稱為彩色濾光器單元。In addition, the structure composed of the substrate, the color filter layer, and the planarization layer is called a color filter unit.

以下藉由圖而詳細說明本發明之具有彩色濾光器單元的顯示裝置之構成，與該構成要素。且，對於本案，表示數值範圍為「～」時，將記載於其前後的數值作為下限值及上限值之意思而使用。Hereinafter, the structure of the display device with the color filter unit of the present invention and the components will be described in detail with reference to the drawings. In this case, when the numerical value range is "~", the numerical values described before and after it are used as the meaning of the lower limit and the upper limit.

《顯示裝置之基本構成》本發明之顯示裝置之特徵為具備彩色濾光器單元，並且該彩色濾光器單元至少由基材、彩色濾光器層及平坦化層所構成。"Basic Composition of Display Device"The display device of the present invention is characterized by having a color filter unit, and the color filter unit is composed of at least a substrate, a color filter layer, and a planarization layer.

本發明之顯示裝置的代表性構成，例如於基材上配置具有薄層電晶體(Thin film transistor，以下簡稱為「TFT」)等的TFT單元，與於該上部含有發光層之發光元件，例如有機EL元件(OLED)，進而形成發光顯示單元D。另一方面，於前述基材的背面側上，形成有關本發明之彩色濾光器單元，於該最外面側上配置偏光板。發光元件裝置若為有機EL元件時，作為偏光板則適用圓偏光板(λ/4偏光板)。對於具備彩色濾光器單元的本發明之顯示裝置，構成發光元件的發光層使用白色發光形態之元件者為佳。The representative structure of the display device of the present invention includes, for example, a TFT unit having a thin film transistor (hereinafter referred to as "TFT") on a substrate, and a light-emitting element containing a light-emitting layer on the upper part, such as An organic EL element (OLED), which in turn forms a light-emitting display unit D. On the other hand, on the back side of the aforementioned substrate, the color filter unit according to the present invention is formed, and a polarizing plate is arranged on the outermost side. When the light-emitting element device is an organic EL element, a circular polarizing plate (λ/4 polarizing plate) is used as the polarizing plate. For the display device of the present invention provided with a color filter unit, it is preferable to use a white light-emitting element for the light-emitting layer constituting the light-emitting element.

又，對於具備本發明之彩色濾光器單元之顯示裝置為，將發光光線自對於基材配置發光元件裝置的表面側進行取出的「頂部發光型(Top emission type)」或自夾著基材而配置彩色濾光器單元的背面取出發光光線的「底部發光型(Bottom emission type)」中任一種皆可。In addition, a display device equipped with the color filter unit of the present invention is a "top emission type" in which light emitted from the substrate is taken out from the surface side where the light-emitting element device is arranged on the substrate, or the substrate is sandwiched On the back of the color filter unit, any of the "bottom emission type" in which light is emitted can be extracted.

對於有關本發明之彩色濾光器單元，作為彩色濾光器層，主要分類為以著色劑所構成的形態A，與適用量子點的形態B。With regard to the color filter unit of the present invention, as the color filter layer, it is mainly classified into a form A composed of a colorant and a form B applicable to quantum dots.

本發明之代表性顯示裝置的構成藉由圖而做說明，但以下所示構成僅為其中一例子，在本發明並未限定於此等例示的構成者。且，對於各圖說明，於構成要素的末尾所記載的數字表示各圖中之符號。The configuration of the representative display device of the present invention is described with reference to the drawings, but the configuration shown below is only one example, and the present invention is not limited to the exemplified configuration. In addition, for the description of each figure, the numbers described at the end of the constituent elements indicate the symbols in each figure.

圖1表示具備作為彩色濾光器層以著色劑所構成的形態A之彩色濾光器單元，發光裝置為有機EL方式之顯示裝置的一例概略截面圖。FIG. 1 shows a schematic cross-sectional view of an example of a color filter unit having a form A composed of a coloring agent as a color filter layer, and a light-emitting device of an organic EL type display device.

圖1所示的顯示裝置1中，位置於中央的第1基材2，較佳為於具備氣體阻隔層(未圖示)的第1基材2之上部上，配置以引出電極6及TFT4所配置的TFT單元3及有機EL元件(OLED)所構成的有機EL單元D。In thedisplay device 1 shown in FIG. 1, thefirst substrate 2 positioned in the center is preferably arranged on the upper portion of thefirst substrate 2 provided with a gas barrier layer (not shown) to draw out theelectrodes 6 and TFT4 The configuredTFT unit 3 and an organic EL element (OLED) constitute an organic EL unit D.

有關TFT4，並非必須要件，例如並非在被動矩陣形態之顯示用途上為必要。使用TFT時，亦可為非晶質Si形態或氧化物系，或LTPS(低溫聚矽)、HTPS(高溫聚矽)或OTFT(有機薄層電晶體)。使用可撓性基板時，較佳為於具有塗料或聚醯亞胺等高溫耐性之可撓性基材上形成氣體阻隔層，於該上面形成TFT。對於這些可撓性基板形成TFT的方法，例如可參考日本特開2016-162535號公報等所記載之方法。Regarding TFT4, it is not necessary, for example, it is not necessary for display purposes in the form of a passive matrix. When using TFT, it can also be in the form of amorphous Si or oxide system, or LTPS (low temperature polysilicon), HTPS (high temperature polysilicon) or OTFT (organic thin layer transistor). When a flexible substrate is used, it is preferable to form a gas barrier layer on a flexible substrate having high temperature resistance such as paint or polyimide, and to form a TFT on the flexible substrate. Regarding the method of forming TFTs on these flexible substrates, for example, the method described in JP 2016-162535 A, etc. can be referred to.

其次，於TFT單元3之上部配置OLED。Next, an OLED is placed on the upper part of theTFT unit 3.

OLED為，於對應構成彩色濾光器的各色著色濾器之位置上，第1電極5以離間方式被配置。於第1電極5上，配置含有發光層的有機功能層群7、第2電極8，於該上面，作為密封結構形成第1密封層9與第2密封層10。在圖1中，例示作為第2密封層之構成，隔著第1接著層11，配置由保護薄膜14與鋁箔13所構成的ALPET12之構成。在圖1中表示有機功能層群7及第2電極8為共通構成，但視必要，與第1電極5同樣地，亦可作為對應各著色濾器之獨立構成。In the OLED, thefirst electrodes 5 are arranged in a discrete manner at positions corresponding to the color filters of each color constituting the color filter. On thefirst electrode 5, an organicfunctional layer group 7 containing a light-emitting layer and asecond electrode 8 are arranged, and on this top surface, afirst sealing layer 9 and asecond sealing layer 10 are formed as a sealing structure. In FIG. 1, as an example of the configuration of the second sealing layer, a configuration in which ALPET 12 composed of aprotective film 14 and analuminum foil 13 is arranged via the firstadhesive layer 11 is shown. 1 shows that the organicfunctional layer group 7 and thesecond electrode 8 have a common configuration, but if necessary, the same as thefirst electrode 5, it may be an independent configuration corresponding to each colored filter.

對於OLED，第1電極5、含有發光層的有機功能層群7與第2電極8的所有位置之區域成為發光區域LA。For the OLED, the area at all positions of thefirst electrode 5, the organicfunctional layer group 7 containing the light-emitting layer, and thesecond electrode 8 becomes the light-emitting area LA.

另一方面，於與第1基材2的OLED之配置面為反側的面上，有關本發明之彩色濾光器單元16A隔著第2接著層15而配置。彩色濾光器單元16A為，於第2基材17上，配置含有紅色著色劑之紅色彩色濾光器CF_R1、含有綠色著色劑之綠色彩色濾光器CF_G1、含有藍色著色劑之藍色彩色濾光器CF_B1於各離間位置進行配置的彩色濾光器層18。各彩色濾光器CF之寬設定為比OLED之發光區域LA更為廣。On the other hand, thecolor filter unit 16A according to the present invention is arranged on the surface opposite to the arrangement surface of the OLED of thefirst substrate 2 with the secondadhesive layer 15 interposed therebetween. Thecolor filter unit 16A is arranged on thesecond substrate 17 with a red color filter CF_R1 containing a red colorant, a green color filter CF_G1 containing a green colorant, and a blue containing blue colorant. Thecolor filter layer 18 in which the color filter CF_B1 is arranged at each discrete position. The width of each color filter CF is set to be wider than the light-emitting area LA of the OLED.

其次，於彩色濾光器層18的上部，配置平坦化層19，隔著第2接著層15，貼合於第1基材2之背面。對於本發明的特徵為，彩色濾光器層18或平坦化層19的至少1層為含有具有有關本發明之一般式(1)所示結構的有機金屬氧化物者。Next, on the upper part of thecolor filter layer 18, theplanarization layer 19 is arranged, and the secondadhesive layer 15 is interposed, and it is bonded to the back surface of thefirst base material 2. The feature of the present invention is that at least one of thecolor filter layer 18 or theplanarization layer 19 contains an organometallic oxide having a structure represented by the general formula (1) related to the present invention.

最後於彩色濾光器單元16A之外側，配置偏光板20。Finally, thepolarizing plate 20 is arranged outside thecolor filter unit 16A.

對於顯示裝置1，將有機EL元件以白色發光形態進行設計，將白色光通過各彩色濾光器後，紅色發光光線L_R、綠色發光光線L_G、藍色發光光線L_B以底部發射方式取出。With thedisplay device 1, the organic EL element designed to form white light, the white light passes through the respective color filters, the red light emitting light L_R, the green luminescent light L_G, L_B blue luminescent light taken out in the bottom emission type .

藉由如圖1所示構成，彩色濾光器層18或平坦化層19的至少1層，藉由含有具有有關本發明的一般式(1)所示結構之有機金屬氧化物，將由彩色濾光器單元所產生的水分，或自背面側浸入的水分或氧進行捕集的吸濕等功能，或藉由與水分進行反應而表現撥水功能，可防止對有機功能層群等影響。By being constituted as shown in FIG. 1, at least one of thecolor filter layer 18 or theplanarization layer 19 contains an organometallic oxide having the structure shown in the general formula (1) related to the present invention, and the color filter layer The moisture generated by the optical unit, or the moisture or oxygen infiltrated from the back side has functions such as moisture absorption, or reacts with the moisture to exhibit a water repellent function, which can prevent the influence on the organic functional layer group.

圖2表示具備作為彩色濾光器層的以量子點所構成的形態B之彩色濾光器單元，發光裝置為有機EL方式的顯示裝置之一例概略截面圖。FIG. 2 shows a schematic cross-sectional view of an example of a color filter unit including a form B composed of quantum dots as a color filter layer, and the light-emitting device is an organic EL type display device.

圖2所示顯示裝置1中，彩色濾光器層18以外的構成與上述圖1所示的顯示裝置之構成相同。In thedisplay device 1 shown in FIG. 2, the structure other than thecolor filter layer 18 is the same as the structure of the display device shown in FIG.

在圖2所示的彩色濾光器單元16B中，構成的紅色彩色濾光器CF_R2、綠色彩色濾光器CF_G2、藍色彩色濾光器CF_B2為含有各紅色發光之量子點QD_R、綠色發光之量子點QD_G、藍色發光之量子點QD_B而構成。In thecolor filter unit 16B shown in FIG. 2, the red color filter CF_R2 , the green color filter CF_G2 , and the blue color filter CF_B2 are composed of quantum dots QD_R containing red light emission. , Green luminous quantum dots QD_G and blue luminous quantum dots QD_B.

其次，對於本發明之顯示裝置的各構成要素之詳細內容依序說明。Next, the detailed content of each component of the display device of the present invention will be described in order.

《彩色濾光器單元》對於有關本發明的彩色濾光器單元，至少由基材、彩色濾光器層及平坦化層所構成。"Color Filter Unit"The color filter unit according to the present invention is composed of at least a base material, a color filter layer, and a planarization layer.

[具有一般式(1)所示結構之有機金屬氧化物]對於本發明，其特徵為彩色濾光器層或平坦化層的至少1層為含有具有下述一般式(1)所示結構之有機金屬氧化物者。[Organic metal oxide with the structure shown in general formula (1)]The present invention is characterized in that at least one of the color filter layer or the planarization layer contains an organometallic oxide having a structure represented by the following general formula (1).

對於上述一般式(1)，R表示氫原子、碳數1個以上的烷基、烯基、芳基、環烷基、醯基、烷氧基或雜環基。但，R亦可為含有作為取代基的氟原子之碳鏈。M表示金屬原子。OR₁表示氟化烷氧基。x表示金屬原子之價數，y表示1與x之間的任意整數。n各表示聚縮合度。

Regarding the above general formula (1), R represents a hydrogen atom, an alkyl group, alkenyl group, aryl group, cycloalkyl group, acyl group, alkoxy group or heterocyclic group having 1 or more carbon atoms. However, R may also be a carbon chain containing a fluorine atom as a substituent. M represents a metal atom. OR₁ represents a fluorinated alkoxy group. x represents the valence of the metal atom, and y represents any integer between 1 and x. Each n represents the degree of polycondensation.

以下對於具有一般式(1)所示結構的有機金屬氧化物之詳細內容做說明。The details of the organometallic oxide having the structure represented by the general formula (1) are described below.

有關本發明之有機金屬氧化物為，將金屬烷氧化物在過剩的醇之存在下進行醇分解，經醇取代的有機金屬氧化物或有機金屬氧化物之聚縮合體。此時，藉由使用於羥基的β位由氟原子所取代的長鏈醇，可成為含有氟化烷氧化物之有機金屬氧化物，表現有關本發明之吸濕功能。The organometallic oxide related to the present invention is an organometallic oxide or a polycondensate of an organometallic oxide substituted with an alcohol by alcohol decomposition of a metal alkoxide in the presence of excess alcohol. In this case, by using a long-chain alcohol substituted with a fluorine atom at the β position of the hydroxyl group, it can become an organometallic oxide containing a fluorinated alkoxide, which exhibits the hygroscopic function related to the present invention.

另一方面，前述有機金屬氧化物為藉由燒結或照射紫外線，促進溶膠･凝膠反應，可形成聚縮合體。此時有著下述特徵，於前述羥基的β位，若使用以氟原子進行取代的長鏈醇時，藉由氟原子之撥水效果，可減少存在於金屬烷氧化物中之金屬周圍的水分之頻度因子，進而減少水解速度，藉由利用該現象，可抑制3次元之聚合反應，可形成含有所望有機金屬氧化物的均勻且稠密之有機薄膜的特徵。On the other hand, the aforementioned organometallic oxide can be sintered or irradiated with ultraviolet rays to promote the sol-gel reaction to form a polycondensate. In this case, it has the following characteristics. If a long-chain alcohol substituted with a fluorine atom is used at the β-position of the aforementioned hydroxyl group, the water repellent effect of the fluorine atom can reduce the water surrounding the metal in the metal alkoxide The frequency factor reduces the rate of hydrolysis. By taking advantage of this phenomenon, the three-dimensional polymerization reaction can be suppressed, and a uniform and dense organic thin film containing the desired organic metal oxide can be formed.

具有有關本發明的吸濕功能之有機金屬氧化物為顯示以下反應流程I者。且，對於燒結後的有機金屬氧化物之聚縮合體的結構式，「O-M」部之「M」為可進一步具有取代基但於此省略。The organometallic oxide having the hygroscopic function related to the present invention is one that shows the following reaction scheme I. In addition, for the structural formula of the polycondensate of the sintered organometal oxide, the "M" in the "O-M" part may further have a substituent but is omitted here.

上述有機金屬氧化物為，藉由燒結或紫外線照射而進行聚縮合所形成的有機薄膜，藉由以下反應流程II，以自系統外的水分(H₂O)進行水解，釋出撥水性或疏水性物質之氟化醇(R’-OH)。藉由該氟化醇，可進一步防止水分對電子裝置內部的透過。The above-mentioned organometallic oxide is an organic film formed by polycondensation by sintering or ultraviolet irradiation. Through the following reaction process II, the water (H₂ O) outside the system is hydrolyzed to release water repellency or hydrophobicity. Fluorinated alcohol (R'-OH) of sexual substance. The fluorinated alcohol can further prevent the penetration of moisture into the electronic device.

即，具有有關本發明的吸濕功能之有機金屬氧化物，因藉由水解所生成的氟化醇為撥水性或疏水性，故除原本的乾燥性以外，加成有藉由與水分之反應的撥水功能，對密封性可發揮相乘效果(協同作用效果)之在過去的吸濕劑未具有的特徵。That is, the organometallic oxide having the hygroscopic function of the present invention is water-repellent or hydrophobic due to the fluorinated alcohol produced by hydrolysis. Therefore, in addition to the original dryness, the addition is caused by the reaction with moisture The water repellent function of the product can exert a synergistic effect (synergistic effect) on the sealing performance, which is not a feature of the previous moisture absorbent.

且，對於下述結構式，「O-M」部的「M」為可進一步具有取代基但於此省略。In addition, in the following structural formula, the "M" of the "O-M" part may further have a substituent, but is omitted here.

有關本發明的有機金屬化合物係以含有將具有前述一般式(1)所示結構的有機金屬氧化物作為主成分者為佳。本發明中所謂的「主成分」表示，於前述吸濕劑之全體質量中，70質量%以上為釋出疏水性物質的前述有機金屬氧化物者為佳，較佳為80質量%以上，特佳為90質量%以上。The organometallic compound according to the present invention preferably contains an organometallic oxide having a structure represented by the general formula (1) as a main component. The term "main component" in the present invention means that, in the total mass of the moisture absorbent, 70% by mass or more is preferably the organic metal oxide that releases the hydrophobic substance, and preferably 80% by mass or more. Preferably, it is 90% by mass or more.

有關本發明的有機金屬氧化物，若為使用溶膠･凝膠法而可製作者即可，並無特別限制，例如可將含有選自「溶膠-凝膠法之科學」P13、P20中所介紹的金屬、鋰、鈉、銅、鈣、鍶、鋇、鋅、硼、鋁、鎵、釔、矽、鍺、鉛、磷、銻、釩、鉭、鎢、鑭、釹、鈦、鋯的1種以上之金屬所成的金屬氧化物作為例子而舉出。較佳的前述M所示金屬原子為選自鈦(Ti)、鋯(Zr)、錫(Sn)、鉭(Ta)、鐵(Fe)、鋅(Zn)、矽(Si)及鋁(Al)，由可得到本發明之效果的觀點來看為佳。The organometallic oxide of the present invention can be produced by the sol-gel method, and there is no particular limitation. For example, the organometallic oxide can be selected from those described in "Science of the Sol-Gel Method" P13 and P20 Of metals, lithium, sodium, copper, calcium, strontium, barium, zinc, boron, aluminum, gallium, yttrium, silicon, germanium, lead, phosphorus, antimony, vanadium, tantalum, tungsten, lanthanum, neodymium, titanium, zirconium1 Metal oxides composed of more than one metal are listed as examples. Preferably, the metal atom represented by M is selected from titanium (Ti), zirconium (Zr), tin (Sn), tantalum (Ta), iron (Fe), zinc (Zn), silicon (Si) and aluminum (Al). ), from the viewpoint of obtaining the effects of the present invention.

對於上述一般式(1)，OR₁表示氟化烷氧基。For the above general formula (1), OR₁ represents a fluorinated alkoxy group.

R₁表示由至少一個氟原子所取代的烷基、芳基、環烷基、醯基、烷氧基或雜環基。各取代基之具體例子如後述。R₁ represents an alkyl group, an aryl group, a cycloalkyl group, an acyl group, an alkoxy group, or a heterocyclic group substituted with at least one fluorine atom. The specific example of each substituent is mentioned later.

R表示氫、碳數1個以上的烷基、烯基、芳基、環烷基、醯基、烷氧基或雜環基。或亦可為將各基的氫之至少一部分由鹵素所取代者。又，亦可為聚合物。R represents hydrogen, an alkyl group, alkenyl group, aryl group, cycloalkyl group, acyl group, alkoxy group, or heterocyclic group having 1 or more carbon atoms. Or, at least a part of the hydrogen of each group may be substituted by halogen. Moreover, it may be a polymer.

烷基雖為取代或未取代者，但作為具體例子為甲基、乙基、丙基、丁基、sec-丁基、tert-丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基、十三烷基、十四烷基、十五烷基、十六烷基、十七烷基、十八烷基、十九烷基、二十烷基、二十一烷基、二十二烷基等，較佳為碳數為8以上者。又亦可為這些之寡聚物、聚合物。Although alkyl is substituted or unsubstituted, specific examples are methyl, ethyl, propyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, and nonyl , Decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, two Decayl, icosyl, behenyl, etc., preferably having 8 or more carbon atoms. It can also be these oligomers and polymers.

烯基為取代或未取代者，作為具體例子為乙烯基、烯丙基、丁烯基、戊烯基、己烯基等，較佳為碳數為8以上者。又亦可為這些之寡聚物、聚合物。The alkenyl group is substituted or unsubstituted, and specific examples include vinyl, allyl, butenyl, pentenyl, hexenyl, etc., preferably having 8 or more carbon atoms. It can also be these oligomers and polymers.

芳基為取代或未取代者，作為具體例子為，苯基、甲苯基、4-氰苯基、聯苯基、o,m,p-三聯苯、萘基、蒽基、菲基、芴基、9-苯基蒽基、9,10-二苯基蒽基、芘基等，較佳為碳數為8以上者。又亦可為這些的寡聚物或聚合物。Aryl is substituted or unsubstituted, as specific examples are phenyl, tolyl, 4-cyanophenyl, biphenyl, o,m,p-terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl , 9-phenylanthryl, 9,10-diphenylanthryl, pyrenyl, etc., preferably having 8 or more carbon atoms. It may also be these oligomers or polymers.

作為取代或未取代的烷氧基之具體例子，有甲氧基、n-丁氧基、tert-丁氧基、三氯甲氧基、三氟甲氧基等，較佳為碳數為8以上者。又亦可為這些的寡聚物、聚合物。As specific examples of the substituted or unsubstituted alkoxy group, there are methoxy, n-butoxy, tert-butoxy, trichloromethoxy, trifluoromethoxy, etc., preferably having 8 carbon atoms. The above. It may also be these oligomers and polymers.

作為取代或未取代的環烷基之具體例子，其為環戊基、環己基、降冰片烷基、金剛烷基、4-甲基環己基、4-氰基環己基等，較佳為碳數為8以上者。又亦可為這些的寡聚物或聚合物。As specific examples of substituted or unsubstituted cycloalkyl groups, they are cyclopentyl, cyclohexyl, norbornyl, adamantyl, 4-methylcyclohexyl, 4-cyanocyclohexyl, etc., preferably carbon The number is 8 or more. It may also be these oligomers or polymers.

作為取代或未取代的雜環基之具體例子，其為吡咯基、吡咯啉基、吡唑基、吡唑啉基、咪唑基、三唑基、吡啶基、噠嗪基、嘧啶基、吡嗪基、三嗪基、吲哚基、苯並咪唑基、嘌呤基、喹啉基、異喹啉基、噌啉基、喹喔啉基、苯並喹啉基、芴酮基、二氰基芴酮基、咔唑基、噁唑基、噁二唑基、噻唑基、噻二唑基、苯並噁唑基、苯並噻唑基、苯並三唑基、雙苯並噁唑基、雙苯並噻唑基、雙苯並咪唑基等。又亦可為這些之寡聚物、聚合物。As specific examples of substituted or unsubstituted heterocyclic groups, pyrrolyl, pyrrolinyl, pyrazolyl, pyrazolinyl, imidazolyl, triazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazine Group, triazinyl, indolyl, benzimidazolyl, purinyl, quinolinyl, isoquinolinyl, cinnolinyl, quinoxalinyl, benzoquinolinyl, fluorenone, dicyanofluorene Keto, carbazolyl, oxazolyl, oxadiazolyl, thiazolyl, thiadiazolyl, benzoxazolyl, benzothiazolyl, benzotriazolyl, bisbenzoxazolyl, biphenyl And thiazolyl, bisbenzimidazolyl, etc. It can also be these oligomers and polymers.

作為取代或未取代的醯基之具體例子，其為甲醯基、乙醯基、丙醯基、丁醯基、異丁醯基、香草基、異香草基、新戊醯基、月桂醯基、肉荳蔻醯基、棕櫚醯基、硬脂醯基、草醯基、丙二醯基、琥珀醯基、戊二醯基、己二醯基、庚二醯基、辛二醯基、壬二醯基、癸二醯基、丙烯醯基、丙炔醯基、甲基丙烯醯基、巴豆醯基、異巴豆醯基、油醯基、反油酸醯基、馬來醯基、富馬醯基、檸康醯基、中康醯基、樟腦醯基、苯甲醯基、鄰苯二甲醯基、異鄰苯二甲醯基、對苯二甲醯基、萘甲醯基、甲苯醯基、氫阿托醯基、阿托醯基、肉桂醯基、呋喃基、噻吩甲醯基、煙醯基、異煙醯基、乙醇醯基、乳糖醯基、甘油醯基、丙醇二醯基、蘋果醯基、酒石醯基、托品醯基、二苯羥乙醯基、水楊醯基、茴香醯基、香草醯基、藜蘆醯基、胡椒醯基、原兒茶油基、沒食子醯基、乙醛醯基、丙酮醯基、乙醯乙醯基、中草醯基、中草醯乙基、丁酮二醯基、丁酮二醯基、乙醯丙醯基，這些醯基可由氟、氯、溴或碘等取代。較佳為醯基的碳數為8以上者。又亦可為這些的寡聚物或聚合物。As specific examples of substituted or unsubstituted acyl groups, they are formyl, acetyl, propyl, butyl, isobutyl, vanillyl, isovanillyl, neopentyl, lauryl, myristyl Alkyl, palmitoyl, stearyl, oxalyl, malonyl, succinyl, glutaryl, adipyl, pimelic acid, suberyl, azelayl, decane Diacyl, acrylic, propargyl, methacrylic, crotonyl, isocrotonyl, oleyl, elaidic, maleic, fumaric, citraconic, medium Cantinyl, camphoryl, benzoyl, phthaloyl, isophthaloyl, p-phthaloyl, naphthoyl, tolyl, hydroatroyl, atto Alkyl, cinnamyl, furanyl, thienyl, nicotinyl, isonicotinyl, ethanolyl, lactosyl, glyceryl, propanol diacyl, apple acyl, tartaric, torto Pinyl, diphenylhydroxyacetin, salicyl, fennel, vanillin, veratrum, piperonyl, protocatechu oil, gallate, acetaldehyde, acetone Acetyl, acetyl acetyl, meso glycan, meso glycan ethyl, butanone diacetate, butanone diacetate, acetonitrile propyl group, these radicals can be substituted by fluorine, chlorine, bromine or iodine . Preferably, the carbon number of the acyl group is 8 or more. It may also be these oligomers or polymers.

前述金屬烷氧化物、金屬羧酸酯與氟化醇(R’-OH)為藉由以下反應流程III，成為有關本發明的有機金屬氧化物。其中，作為(R’-OH)例示出以下F-1～F-16的結構。The aforementioned metal alkoxides, metal carboxylates and fluorinated alcohols (R'-OH) become organometallic oxides related to the present invention through the following reaction scheme III. Among them, the following structures of F-1 to F-16 are illustrated as (R'-OH).

有關本發明的金屬烷氧化物或金屬羧酸酯，例示以下M(OR)_n或M(OCOR)_n所示化合物，有關本發明的有機金屬氧化物，藉由與前述(R’-OH：F-1～F-16)之組合，成為具有下述例示化合物號碼1～135之結構的化合物(參照下述例示化合物I、II及III)。有關本發明的有機金屬氧化物並未限定於此。Regarding the metal alkoxide or metal carboxylate of the present invention, the following compounds represented by M(OR)_n or M(OCOR)_{n are} exemplified. Regarding the organometallic oxide of the present invention, by combining with the aforementioned (R'-OH: The combination of F-1 to F-16) becomes a compound having the structure of the followingexemplary compound numbers 1 to 135 (refer to the following exemplary compounds I, II, and III). The organometallic oxide related to the present invention is not limited to this.

製造有關本發明的有機金屬氧化物之有機金屬氧化物之製造方法，其特徵為使用金屬烷氧化物與氟化醇之混合液而製造。The method for producing the organometallic oxide of the organometallic oxide according to the present invention is characterized by using a mixed solution of a metal alkoxide and a fluorinated alcohol.

作為反應之一例子，以下表示例示化合物號碼1之反應流程IV及適用於有機薄膜時的有機金屬氧化物之結構。As an example of the reaction, the following shows the reaction scheme IV ofcompound number 1 and the structure of the organometallic oxide when applied to an organic thin film.

且，對於下述結構式，「O-Ti」部之「Ti」為可進一步具有取代基但於此省略。In addition, for the following structural formula, the "Ti" of the "O-Ti" part may further have a substituent, but is omitted here.

有關本發明之有機金屬氧化物之製造方法，可舉出於金屬烷氧化物或金屬羧酸酯中加入氟化醇作為混合液，於進行攪拌混合後，視必要添加水與觸媒，在所定溫度下使其反應的方法。Regarding the production method of the organometallic oxide of the present invention, fluorinated alcohol is added to the metal alkoxide or metal carboxylate as a mixed liquid. After stirring and mixing, water and a catalyst are added as necessary. Method of making it react at temperature.

使進行溶膠･凝膠反應時，在促進水解･聚縮合反應的目的下，可加入可成為如下述所示的水解･聚合反應之觸媒者。作為溶膠･凝膠反應之水解･聚合反應的觸媒而使用者為，於「藉由最新溶膠-凝膠法之功能性薄膜製作技術」(平島碩著，總合技術中心股份有限公司，P29) 或「溶膠-凝膠法之科學」(作花濟夫著，Agne Seifusha，P154)等記載的一般溶膠･凝膠反應中所使用的觸媒。例如酸觸媒中可舉出鹽酸、硝酸、硫酸、磷酸、乙酸、草酸、酒石酸、甲苯磺酸等無機及有機酸類等。When the sol/gel reaction is carried out, for the purpose of accelerating the hydrolysis/polycondensation reaction, a catalyst that can become the hydrolysis/polymerization reaction shown below may be added. As a catalyst for the hydrolysis and polymerization of the sol/gel reaction, it is used as a catalyst for "functional film production technology by the latest sol-gel method" (Hiroshima Hirashima, Total Technology Center Co., Ltd., P29 ) Or "Science of the Sol-Gel Method" (by Kajio, Agne Seifusha, P154) and other catalysts used in general sol-gel reactions. For example, the acid catalyst includes inorganic and organic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetic acid, oxalic acid, tartaric acid, and toluenesulfonic acid.

作為較佳觸媒之使用量，對於成為有機金屬氧化物之原料的金屬烷氧化物或金屬羧酸酯1莫耳而言為2莫耳當量以下，更佳為1莫耳當量以下。As a preferable usage amount of the catalyst, 1 mole of metal alkoxide or metal carboxylate used as a raw material of the organometallic oxide is 2 mole equivalent or less, more preferably 1 mole equivalent or less.

使其進行溶膠･凝膠反應時，較佳的水之添加量為，對於成為有機金屬氧化物之原料的金屬烷氧化物或金屬羧酸酯1莫耳而言為40莫耳當量以下，較佳為10莫耳當量以下，更佳為5莫耳當量以下。When making it undergo a sol-gel reaction, the preferred amount of water added is 40 mol equivalent or less for 1 mol of the metal alkoxide or metal carboxylate that is the raw material of the organometallic oxide. It is preferably 10 mol equivalent or less, more preferably 5 mol equivalent or less.

對於本發明，較佳的溶膠･凝膠反應之反應濃度、溫度、時間，因與使用的金屬烷氧化物或金屬羧酸酯之種類或分子量的各條件有著相互關係，故無法一概而論。即，烷氧化物或金屬羧酸酯之分子量較高時，或反應濃度較高時，設定較高反應溫度，或不使反應時間過度長時，水解、聚縮合反應所造成的反應生成物之分子量會提高，有著高黏度化或凝膠化之可能性。但，通常的較佳反應濃度為，大致溶液中之固體成分的質量%濃度為1～50%之範圍內，5～30%之範圍內為較佳。又，反應溫度雖依反應時間而不同，通常為0～150℃之範圍內，以1～100℃為佳，較佳為20～60℃之範圍內，反應時間以1～50小時程度為佳。For the present invention, the preferred reaction concentration, temperature, and time of the sol-gel reaction are related to the type or molecular weight of the metal alkoxide or metal carboxylate used, and therefore cannot be generalized. That is, when the molecular weight of the alkoxide or metal carboxylate is high, or when the reaction concentration is high, the reaction temperature is set higher, or when the reaction time is not too long, the reaction product caused by the hydrolysis and polycondensation reaction The molecular weight will increase, and there is a possibility of high viscosity or gelation. However, in general, the preferred reaction concentration is that the mass% concentration of the solid content in the solution is generally in the range of 1-50%, preferably in the range of 5-30%. In addition, although the reaction temperature differs depending on the reaction time, it is usually in the range of 0 to 150°C, preferably 1 to 100°C, preferably in the range of 20 to 60°C, and the reaction time is preferably about 1 to 50 hours. .

前述有機金屬氧化物之聚縮合體形成有機薄膜，藉由以下反應流程V，吸收水分而釋出疏水性物質的氟化醇。The polycondensate of the aforementioned organometal oxide forms an organic film, and the fluorinated alcohol, which is a hydrophobic substance, is released by the following reaction process V by absorbing moisture.

且對於下述結構式，「O-Ti」部之「Ti」為可進一步具有取代基但於此省略。And for the following structural formula, the "Ti" in the "O-Ti" part may further have a substituent, but is omitted here.

[第2基材]作為可適用於有關本發明之彩色濾光器單元的第2基材，以具有充分強度、平坦性、耐熱性、光透過性等者為佳，例如作為通常彩色濾光器之基材使用的透明之樹脂薄膜、無鹼玻璃或蘇打玻璃等薄膜玻璃基板可舉出。[Second base material]As the second base material applicable to the color filter unit of the present invention, it is preferable to have sufficient strength, flatness, heat resistance, light transmittance, etc., for example, it is used as a base material of a general color filter Thin film glass substrates such as transparent resin film, alkali-free glass, soda glass, etc. can be cited.

作為透明樹脂薄膜基材，例如可舉出由聚乙烯對苯二甲酸酯(簡稱：PET)、聚乙烯萘二甲酸酯(簡稱：PEN)、聚甲基甲基丙烯酸酯(簡稱：PMMA)、聚碳酸酯(簡稱：PC)、聚碸、聚醚碸(簡稱：PES)、聚環烯烴(簡稱：COP)、丙烯酸系交聯性樹脂、環氧系交聯性樹脂交聯性樹脂、不飽和聚酯系交聯性樹脂、具有高溫耐性之塗料或經醯亞胺化的聚醯亞胺等所構成的薄膜基材。As the transparent resin film substrate, for example, polyethylene terephthalate (abbreviation: PET), polyethylene naphthalate (abbreviation: PEN), polymethylmethacrylate (abbreviation: PMMA) ), polycarbonate (abbreviation: PC), polysulfite, polyether sulfite (abbreviation: PES), polycyclic olefin (abbreviation: COP), acrylic crosslinkable resin, epoxy crosslinkable resin, crosslinkable resin , Unsaturated polyester-based cross-linkable resin, high-temperature resistant coating or film substrate composed of imidized polyimide.

[彩色濾光器層]構成有關本發明之彩色濾光器單元的彩色濾光器層，作為複數種彩色濾光器，紅･綠･藍(RGB)或黃色･洋紅色･藍綠色(YMC)之組合，該混合系以外，亦可適用欲進行亮度調整的透明畫素。對於複數種彩色濾光器上，欲使其平坦化等而形成平坦化層。[Color filter layer]The color filter layer constituting the color filter unit of the present invention, as a plurality of color filters, is a combination of red, green, blue (RGB) or yellow, magenta, cyan (YMC), and the hybrid system In addition, transparent pixels to be adjusted for brightness can also be applied. For plural kinds of color filters, a planarization layer is formed in order to planarize them.

又，對於有關本發明之彩色濾光器層或前述平坦化層，適用具有前述一般式(1)所示結構之有機金屬氧化物時，對於彩色濾光器層所含有的前述有機金屬氧化物之碳原子與氟原子的總數，氟原子數之比值滿足下述式(a)所規定的條件者為佳。In addition, when the organic metal oxide having the structure represented by the general formula (1) is applied to the color filter layer or the flattening layer of the present invention, the organic metal oxide contained in the color filter layer The total number of carbon atoms and fluorine atoms, and the ratio of the number of fluorine atoms satisfies the conditions specified in the following formula (a).

式(a)之測定意義為，以數值表示藉由溶膠･凝膠法所製作的有機薄膜需要一定量以上的氟原子。上述式(a)之F及C各表示氟原子及碳原子之濃度。

The measurement meaning of formula (a) is that the organic film produced by the sol-gel method requires a certain amount of fluorine atoms in numerical value. F and C in the above formula (a) each represent the concentration of fluorine atoms and carbon atoms.

作為式(a)的較佳範圍，其為0.2≦F/(C+F)≦0.6之範圍。As a preferable range of formula (a), it is a range of 0.2≦F/(C+F)≦0.6.

上述氟比率為，將使用於有機薄膜形成的溶膠･凝膠液於矽晶圓上進行塗布而製作出薄膜後，將該薄膜藉由SEM･EDS(Energy Dispersive X-ray Spectoroscopy：能量分散型X線分析裝置)進行元素分析，可求得各氟原子及碳原子之濃度。作為SEM･EDS裝置之一例子，可舉出JSM-IT100(日本電子公司製)。The above-mentioned fluorine ratio is that the sol/gel solution used in the formation of organic thin films is coated on a silicon wafer to form a thin film, and then the thin film is subjected to SEM･EDS (Energy Dispersive X-ray Spectoroscopy: Energy Dispersive X-ray Spectoroscopy). Line analyzer) performs elemental analysis to obtain the concentration of each fluorine atom and carbon atom. As an example of SEM and EDS devices, JSM-IT100 (manufactured by JEOL Ltd.) can be cited.

SEM･EDS分析具有在高速、高感度下可精度良好地檢測元素之特徵。SEM･EDS analysis has the characteristic of detecting elements accurately at high speed and high sensitivity.

作為彩色濾光器之形成方法，可舉出使用著色劑而形成的形態A，與使用量子點而形成的形態B。As a method of forming a color filter, form A formed using a coloring agent and form B formed using quantum dots can be mentioned.

(形態A：著色劑構成)＜著色劑＞可適用於彩色濾光器之形成的代表性著色劑如以下列舉者。(Form A: Colorant composition)＜Colorant＞Typical colorants applicable to the formation of color filters are as listed below.

欲形成紅色彩色濾光器(CF_R1)的紅色著色劑中，例如可使用C.I.Pigment Red 7、9、14、41、48：1、48：2、48：3、48：4、81：1、81：2、81：3、97、122、123、146、149、168、177、178、179、180、184、185、187、192、200、202、208、210、215、216、217、220、223、224、226、227、228、240、242、246、254、255、264、269、272、279等紅色顏料。紅色著色劑中可併用黃色顏料、橙色顏料。For the red colorant to form the red color filter (CF_R1 ), for example,CIPigment Red 7, 9, 14, 41, 48:1, 48:2, 48:3, 48:4, 81:1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220,223,224,226,227,228,240,242,246,254,255,264,269,272,279 and other red pigments. Yellow pigment and orange pigment can be used in combination with the red colorant.

作為黃色顏料，可舉出C.I.Pigment Yellow 1、2、3、4、5、6、10、12、13、14、15、16、17、18、20、24、31、32、34、35、35：1、36、36：1、37、37：1、40、42、43、53、55、60、61、62、63、65、73、74、77、81、83、86、93、94、95、97、98、100、101、104、106、108、109、110、113、114、115、116、117、118、119、120、123、125、126、127、128、129、137、138、139、144、146、147、148、150、151、152、153、154、155、156、161、162、164、166、167、168、169、170、171、172、173、174、175、176、177、179、180、181、182、185、187、188、193、194、199、213、214等。Examples of yellow pigments includeCIPigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137,138,139,144,146,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, etc.

作為橙色顏料，可舉出C.I.Pigment Orange 36、43、51、55、59、61、71、73等。As an orange pigment, C.I.Pigment Orange 36, 43, 51, 55, 59, 61, 71, 73, etc. are mentioned.

於欲形成綠色彩色濾光器(CF_G1)的綠色著色劑中，例如可使用C.I.Pigment Green 7、36、58等綠色顏料。綠色著色組成物中可併用與紅色著色組成物相同的黃色顏料。For the green colorant to be formed into the green color filter (CF_G1 ), for example, green pigments such asCIPigment Green 7, 36, and 58 can be used. The green coloring composition may use the same yellow pigment as the red coloring composition in combination.

於欲形成藍色彩色濾光器(CF_B1)之藍色著色劑中，例如可組合使用C.I.Pigment Blue 15：3、15：4之藍色顏料、C.I.Pigment Violet 23之紫色顏料以外，亦可組合使用適宜的其他顏料。In the blue colorant to be formed into the blue color filter (CF_B1 ), for example, CIPigment Blue 15:3, 15:4 blue pigments andCIPigment Violet 23 purple pigments can be used in combination. Other suitable pigments.

又，與上述有機顏料進行組合，欲取得彩度與明度之平衡下而可確保良好塗布性、感度、顯影性等時，視必要可組合無機顏料而使用。作為無機顏料，可舉出黃色鉛、鋅黃、胭脂(紅色氧化鐵(III))、鎘紅、群藍、紺藍、氧化鉻綠、鈷綠等金屬氧化物粉、金屬硫化物粉、金屬粉等。進一步欲調色且不會降低耐液晶性、耐熱性之範圍內可含有染料。In addition, when it is combined with the above-mentioned organic pigments to achieve a balance of chroma and lightness to ensure good coatability, sensitivity, developability, etc., inorganic pigments can be used in combination as necessary. As inorganic pigments, metal oxide powders such as yellow lead, zinc yellow, carmine (red iron oxide (III)), cadmium red, ultramarine blue, cyan, chromium oxide green, cobalt green, etc., metal sulfide powder, metal Powder etc. Further, dyes may be included in the range of color adjustment without reducing liquid crystal resistance and heat resistance.

(形態B：量子點構成)適用於有關本發明之彩色濾光器的形態B之量子點，其為以半導體結晶所構成，且具有表現量子點效果之所定粒徑的粒子狀之材料。量子點的能量準位E，在一般狀況下，將普朗克的常數以「h」表示，將電子的有效質量以「m」表示，將微粒子之半徑以「R」表示時，如下式(I)所示。(Form B: Quantum dot composition)The quantum dots of form B suitable for the color filter of the present invention are made of semiconductor crystals and have a particle-like material with a predetermined particle size that exhibits the effect of quantum dots. For the energy level E of quantum dots, under normal conditions, Planck’s constant is represented by "h", the effective mass of electrons is represented by "m", and the radius of the particle is represented by "R", as follows ( I) shown.

如式(I)所示，量子點之帶間隙為，對於「R^-2」之比例變大，而得到量子點效果。如此，藉由控制及規定量子點之粒子徑，可控制量子點之帶間隙值。即，藉由控制及規定量子點之粒子的粒子徑，可其具有通常分子中未具有的多樣性。因此，藉由經光使其激起，對於含有量子點的有機EL元件輸入電壓，於量子點封閉電子與洞而使其再結合後，可將電能量變換為所望波長之光而射出。在有關本發明之彩色濾光器中，將表現如此量子點效果之粒子狀材料作為量子點使用。

As shown in formula (I), the band gap of quantum dots is such that the ratio of "R^-2 "becomes larger, and the quantum dot effect is obtained. In this way, by controlling and specifying the particle diameter of the quantum dot, the band gap value of the quantum dot can be controlled. That is, by controlling and regulating the particle diameter of the particles of quantum dots, it is possible to have diversity not found in ordinary molecules. Therefore, by being excited by light, a voltage is input to an organic EL device containing quantum dots, and after the quantum dots confine the electrons and holes and recombine them, the electric energy can be converted into light of a desired wavelength and emitted. In the color filter of the present invention, a particulate material exhibiting such a quantum dot effect is used as a quantum dot.

量子點之粒子徑為對應所望發光光線譜的適宜值，其為較佳1～20nm之範圍內，更佳為1～10nm之範圍內。具體而言，量子點之粒子徑在將發光色設定為紅色時，設定在3.0～20nm之範圍內，將發光色設定在綠色時，設定在1.5～10nm之範圍內。且，如此粒子徑之範圍若為量子點之平均粒子徑含於此等範圍者即可。The particle diameter of the quantum dot is an appropriate value corresponding to the desired luminescence light spectrum, which is preferably in the range of 1-20 nm, more preferably in the range of 1-10 nm. Specifically, the particle diameter of the quantum dots is set within the range of 3.0-20 nm when the emission color is set to red, and within the range of 1.5-10 nm when the emission color is set to green. In addition, the range of such particle diameters is only necessary if the average particle diameter of the quantum dots is included in these ranges.

量子點之平均粒子徑可利用公知測定方法而進行測定。例如可舉出藉由透過型電子顯微鏡(TEM)進行量子點材料之粒子觀察，由此可藉由粒子徑分布求得數平均粒子徑之方法，或藉由動態光散射法之粒徑測定裝置，例如使用「ZETASIZER Nano Series Nano-ZS」(Malvern公司製)進行測定之方法，或由藉由X線小角散射法而得之光譜使用量子點之粒子徑分布模擬計算而導出粒子徑分布之方法等。The average particle diameter of the quantum dot can be measured by a known measurement method. For example, a method of observing the particles of quantum dot materials by a transmission electron microscope (TEM), which can obtain the number average particle diameter from the particle diameter distribution, or a particle size measuring device by the dynamic light scattering method For example, a method of measuring using "ZETASIZER Nano Series Nano-ZS" (manufactured by Malvern), or a method of deriving particle diameter distribution from the spectrum obtained by the small-angle X-ray scattering method using quantum dot particle diameter distribution simulation calculations Wait.

量子點之添加量，對於所要添加之彩色濾光器的全構成物質100質量份而言，以0.01～50質量份之範圍內者為佳，以0.05～25質量份之範圍內者為佳，以0.1～20質量份之範圍內者為特佳。若量子點之添加量為0.01質量份以上時，將發光層之摻合物材料的發光作為適宜的波長，藉由調節量子點材料之吸收能量，可得到顯著量子點效果，可容易穩定取出之光亮度或色度。又，量子點之添加量若為50質量份以下時，可充分地確保經分散的量子點之粒子間距離，故可確實地發揮藉由經添加的量子點之量子點效果。The amount of quantum dots to be added is preferably within the range of 0.01-50 parts by mass, preferably within the range of 0.05-25 parts by mass, with respect to 100 parts by mass of the total constituent material of the color filter to be added. It is particularly preferable that it is within the range of 0.1-20 parts by mass. If the added amount of quantum dots is 0.01 parts by mass or more, the light emission of the blend material of the light-emitting layer is taken as the appropriate wavelength. By adjusting the absorption energy of the quantum dot material, a significant quantum dot effect can be obtained, which can be easily and stably taken out Luminance or chromaticity. In addition, if the added amount of the quantum dots is 50 parts by mass or less, the distance between the dispersed quantum dots can be sufficiently ensured, so the quantum dot effect by the added quantum dots can be reliably exhibited.

作為量子點之構成材料，例如可舉出由碳、矽、鍺、錫等周期表第14族元素之單體、磷(黑磷)等周期表第15族元素之單體、硒、碲等周期表第16族元素之單體、碳化矽(SiC)等複數之周期表第14族元素所成的化合物、氧化錫(IV)(SnO₂)、硫化錫(II、IV)(Sn(II)Sn(IV)S₃)、硫化錫(IV)(SnS₂)、硫化錫(II)(SnS)、硒化錫(II)(SnSe)、碲化錫(II)(SnTe)、硫化鉛(II)(PbS)、硒化鉛(II)(PbSe)、碲化鉛(II)(PbTe)等周期表第14族元素與周期表第16族元素之化合物、氮化硼(BN)、磷化硼(BP)、砷化硼(BAs)、氮化鋁(AlN)、磷化鋁(AlP)、砷化鋁(AlAs)、銻化鋁(AlSb)、氮化鎵(GaN)、磷化鎵(GaP)、砷化鎵(GaAs)、銻化鎵(GaSb)、氮化銦(InN)、磷化銦(InP)、砷化銦(InAs)、銻化銦(InSb)等周期表第13族元素與周期表第15族元素之化合物(或III-V族化合物半導體)、硫化鋁(Al₂S₃)、硒化鋁(Al₂Se₃)、硫化鎵(Ga₂S₃)、硒化鎵(Ga₂Se₃)、碲化鎵(Ga₂Te₃)、氧化銦(In₂O₃)、硫化銦(In₂S₃)、硒化銦(In₂Se₃)、碲化銦(In₂Te₃)等周期表第13族元素與周期表第16族元素之化合物、氯化鉈(I)(TlCl)、溴化鉈(I)(TlBr)、碘化鉈(I)(TlI)等周期表第13族元素與周期表第17族元素之化合物、氧化鋅(ZnO)、硫化鋅(ZnS)、硒化鋅(ZnSe)、碲化鋅(ZnTe)、氧化鎘(CdO)、硫化鎘(CdS)、硒化鎘(CdSe)、碲化鎘(CdTe)、硫化水銀(HgS)、硒化水銀(HgSe)、碲化水銀(HgTe)等周期表第12族元素與周期表第16族元素之化合物(或II-VI族化合物半導體)、硫化砷(III)(As₂S₃)、硒化砷(III)(As₂Se₃)、碲化砷(III)(As₂Te₃)、硫化銻(III)(Sb₂S₃)、硒化銻(III)(Sb₂Se₃)、碲化銻(III) (Sb₂Te₃)、硫化鉍(III)(Bi₂S₃)、硒化鉍(III)(Bi₂Se₃)、碲化鉍(III)(Bi₂Te₃)等周期表第15族元素與周期表第16族元素之化合物、氧化銅(I)(Cu₂O)、硒化銅(I)(Cu₂Se)等周期表第11族元素與周期表第16族元素之化合物、氯化銅(I) (CuCl)、溴化銅(I)(CuBr)、碘化銅(I)(CuI)、氯化銀(AgCl)、溴化銀(AgBr)等周期表第11族元素與周期表第17族元素之化合物、氧化鎳(II)(NiO)等周期表第10族元素與周期表第16族元素之化合物、氧化鈷(II)(CoO)、硫化鈷(II)(CoS)等周期表第9族元素與周期表第16族元素之化合物、四氧化三鐵(Fe₃O₄)、硫化鐵(II)(FeS)等周期表第8族元素與周期表第16族元素之化合物、氧化錳(II)(MnO)等周期表第7族元素與周期表第16族元素之化合物、硫化鉬(IV)(MoS₂)、氧化鎢(IV)(WO₂)等周期表第6族元素與周期表第16族元素之化合物、氧化釩(II)(VO)、氧化釩(IV) (VO₂)、氧化鉭(V)(Ta₂O₅)等周期表第5族元素與周期表第16族元素之化合物、氧化鈦(TiO₂、Ti₂O₅、Ti₂O₃、Ti₅O₉等)等周期表第4族元素與周期表第16族元素之化合物、硫化鎂(MgS)、硒化鎂(MgSe)等周期表第2族元素與周期表第16族元素之化合物、氧化鎘(II)鉻(III)(CdCr₂O₄)、硒化鎘(II)鉻(III)(CdCr₂Se₄)、硫化銅(II)鉻(III)(CuCr₂S₄)、硒化水銀(II)鉻(III)(HgCr₂Se₄)等硫屬尖晶石類、鋇鈦酸鹽(BaTiO₃)等。The constituent materials of quantum dots include, for example, monomers ofgroup 14 elements of the periodic table such as carbon, silicon, germanium, and tin, monomers ofgroup 15 elements of the periodic table such as phosphorus (black phosphorus), selenium, tellurium, etc. The monomer of the 16th group of the periodic table, silicon carbide (SiC) and other compounds of the 14th group of the periodic table, tin (IV) oxide (SnO₂ ), tin sulfide (II, IV) (Sn(II) )Sn(IV)S₃ ), tin sulfide (IV) (SnS₂ ), tin sulfide (II) (SnS), tin selenide (II) (SnSe), tin telluride (II) (SnTe), lead sulfide (II) (PbS), lead selenide (PbSe), lead telluride (II) (PbTe) and other compounds of group 14 elements of the periodic table and group 16 elements of the periodic table, boron nitride (BN), Boron phosphide (BP), boron arsenide (BAs), aluminum nitride (AlN), aluminum phosphide (AlP), aluminum arsenide (AlAs), aluminum antimonide (AlSb), gallium nitride (GaN), phosphorus Gallium (GaP), gallium arsenide (GaAs), gallium antimonide (GaSb), indium nitride (InN), indium phosphide (InP), indium arsenide (InAs), indium antimonide (InSb) and other periodic tables Compounds of group 13 elements and group 15 elements of the periodic table (or III-V compound semiconductors), aluminum sulfide (Al₂ S₃ ), aluminum selenide (Al₂ Se₃ ), gallium sulfide (Ga₂ S₃ ) , Gallium selenide (Ga₂ Se₃ ), gallium telluride (Ga₂ Te₃ ), indium oxide (In₂ O₃ ), indium sulfide (In₂ S₃ ), indium selenide (In₂ Se₃ ), tellurium Indium (In₂ Te₃ ) and other periodic table group 13 elements and periodic table group 16 elements, thallium chloride (I) (TlCl), thallium bromide (I) (TlBr), thallium iodide (I) ) (TlI) and other compounds of group 13 elements of the periodic table and group 17 elements of the periodic table, zinc oxide (ZnO), zinc sulfide (ZnS), zinc selenide (ZnSe), zinc telluride (ZnTe), cadmium oxide ( CdO), cadmium sulfide (CdS), cadmium selenide (CdSe), cadmium telluride (CdTe), mercury sulfide (HgS), mercury selenide (HgSe), mercury telluride (HgTe) and other elements of group 12 of the periodic table Compounds of elements of group 16 of the periodic table (or II-VI compound semiconductors), arsenic (III) sulfide (As₂ S₃ ), arsenic selenide (III) (As₂ Se₃ ), arsenic telluride (III) ( As₂ Te₃ ), antimony sulfide (III) (Sb₂ S₃ ), antimony selenide (III) (Sb₂ Se₃ ), antimony telluride (III) (Sb₂ Te₃ ), bismuth sulfide (III) ( Bi₂ S₃ ), bismuth (III) selenide (Bi₂ Se₃ ), bismuth (III) telluride (Bi₂ Te₃ ) and other compounds of the 15th group of the periodic table and the 16th group of the periodic table, copper (I) (Cu₂ O), copper selenide (I) (Cu₂ Se) and the 11th group of the periodic table. Compounds of elements of group 16 of the periodic table, copper (I) chloride (CuCl), copper bromide (I) (CuBr), copper iodide (I) (CuI), silver chloride (AgCl), silver bromide ( AgBr) and other compounds of the 11th group of the periodic table and the 17th group of the periodic table, nickel(II) (NiO) and other compounds of the 10th group of the periodic table and the 16th group of the periodic table, cobalt(II)( CoO), cobalt sulfide (II) (CoS) and other compounds of the 9th group of the periodic table and the 16th group of the periodic table, triiron tetroxide (Fe₃ O₄ ), iron sulfide (II) (FeS) and other periodic table Compounds of group 8 elements and group 16 elements of the periodic table, manganese oxide (II) (MnO) and other compounds of group 7 elements of the periodic table and group 16 elements of the periodic table, molybdenum sulfide (IV) (MoS₂ ), oxidation Compounds of elements of group 6 of the periodic table such as tungsten (IV) (WO₂ ) and group 16 elements of the periodic table, vanadium (II) (VO), vanadium (IV) (VO₂ ), tantalum (V) ( Ta₂ O₅ ) and other periodic table group 5 elements and periodic table group 16 elements, titanium oxide (TiO₂ , Ti₂ O₅ , Ti₂ O₃ , Ti₅ O_9, etc.), etc. Compounds of elements and group 16 elements of the periodic table, magnesium sulfide (MgS), magnesium selenide (MgSe) and other compounds ofgroup 2 elements of the periodic table and group 16 elements of the periodic table, cadmium (II) chromium (III) ( CdCr₂ O₄ ), cadmium selenide (II) chromium (III) (CdCr₂ Se₄ ), copper (II) chromium (III) (CuCr₂ S₄ ), mercury selenide (II) chromium (III) ( HgCr₂ Se₄ ) and other chalcogen spinels, barium titanate (BaTiO₃ ), etc.

作為構成量子點之物質，此等中亦以SnS₂、SnS、SnSe、SnTe、PbS、PbSe、PbTe等周期表第14族元素與周期表第16族元素之化合物、GaN、GaP、GaAs、GaSb、InN、InP、InAs、InSb等III-V族化合物半導體、Ga₂O₃、Ga₂S₃、Ga₂Se₃、Ga₂Te₃、In₂O₃、In₂S₃、In₂Se₃、In₂Te₃等周期表第13族元素與周期表第16族元素之化合物、ZnO、ZnS、ZnSe、ZnTe、CdO、CdS、CdSe、CdTe、HgO、HgS、HgSe、HgTe等II-VI族化合物半導體、As₂O₃、As₂S₃、As₂Se₃、As₂Te₃、Sb₂O₃、Sb₂S₃、Sb₂Se₃、Sb₂Te₃、Bi₂O₃、Bi₂S₃、Bi₂Se₃、Bi₂Te₃等周期表第15族元素與周期表第16族元素之化合物、MgS、MgSe等周期表第2族元素與周期表第16族元素之化合物為佳，其中亦以Si、Ge、GaN、GaP、InN、InP、Ga₂O₃、Ga₂S₃、In₂O₃、In₂S₃、ZnO、ZnS、CdO、CdS為較佳。這些物質因未含毒性高的陰性元素，故耐環境污染性或對生物的安全性為優良，又在可見光區域可純粹地穩定光譜，故有利於發光元件之形成。這些材料之中，以CdSe、ZnSe、CdS由發光穩定性的觀點來看為佳。由發光效率、高折射率、安全性之經濟性觀點來看以ZnO、ZnS之量子點為佳。As the material that constitutes quantum dots, among them, SnS₂ , SnS, SnSe, SnTe, PbS, PbSe, PbTe and other compounds of the 14th group of the periodic table and the 16th group of the periodic table, GaN, GaP, GaAs, GaSb , InN, InP, InAs, InSb and other III-V compound semiconductors, Ga₂ O₃ , Ga₂ S₃ , Ga₂ Se₃ , Ga₂ Te₃ , In₂ O₃ , In₂ S₃ , In₂ Se₃ , In₂ Te₃ and other compounds of the 13th group of the periodic table and the 16th group of the periodic table, ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, HgO, HgS, HgSe, HgTe and other II-VI groups Compound semiconductor, As₂ O₃ , As₂ S₃ , As₂ Se₃ , As₂ Te₃ , Sb₂ O₃ , Sb₂ S₃ , Sb₂ Se₃ , Sb₂ Te₃ , Bi₂ O₃ , Bi₂ S₃ , Bi₂ Se₃ , Bi₂ Te₃ and otherperiodic table group 15 elements and periodic table group 16 elements, compounds ofperiodic table group 2 elements such as MgS, MgSe and periodic table group 16 elements are preferred Among them, Si, Ge, GaN, GaP, InN, InP, Ga₂ O₃ , Ga₂ S₃ , In₂ O₃ , In₂ S₃ , ZnO, ZnS, CdO, CdS are also preferred. These substances do not contain highly toxic negative elements, so they are excellent in environmental pollution resistance or biological safety, and they can purely stabilize the spectrum in the visible light region, so they are beneficial to the formation of light-emitting elements. Among these materials, CdSe, ZnSe, and CdS are preferable from the viewpoint of luminescence stability. From the economic point of view of luminous efficiency, high refractive index, and safety, quantum dots of ZnO and ZnS are preferred.

構成量子點之這些物質，可單獨使用1種，亦可組合2種以上使用。即，在前述發光光線譜或粒子徑之範圍下，可含有1種量子點之粒子，亦可含有2種以上之量子點的粒子。又，這些物質以外，於量子點中可視必要地摻合作為雜質的微量各種元素。藉由摻合微量各種元素，可大大地提高藉由量子點之發光特性。These substances constituting quantum dots may be used alone or in combination of two or more kinds. That is, within the range of the aforementioned emission light spectrum or particle diameter, one kind of quantum dot particles may be contained, or two or more kinds of quantum dot particles may be contained. In addition to these substances, the quantum dots can optionally be mixed with trace elements as impurities. By blending trace elements of various elements, the luminescence characteristics of quantum dots can be greatly improved.

量子點可作為具有核心/外殼型之結構的粒子。即，可將量子點以達成量子點效果之核心部，與惰性無機物或有機配位子所成的外殼部而構成。又，以核心部與外殼部無相異物質所構成，於核心部與外殼部之間可形成梯度結構(傾斜結構)。使用如此核心/外殼型之量子點時，可抑制量子點之凝集，進而可提高分散性。然後欲容易進行發光亮度或色度調整，可得到穩定的發光特性。外殼部之厚度以0.1～10nm之範圍內為較佳，較佳為0.1～5nm之範圍內。Quantum dots can be used as particles with a core/shell structure. That is, the quantum dot can be composed of a core part that achieves the quantum dot effect and an outer shell part formed by an inert inorganic substance or an organic ligand. In addition, the core part and the shell part are composed of no different substances, and a gradient structure (inclined structure) can be formed between the core part and the shell part. When using such core/shell type quantum dots, the aggregation of the quantum dots can be suppressed, and the dispersion can be improved. Then, if you want to easily adjust the brightness or chromaticity of light emission, you can obtain stable light emission characteristics. The thickness of the outer shell is preferably in the range of 0.1 to 10 nm, and more preferably in the range of 0.1 to 5 nm.

量子點進一步可作為經表面修飾的粒子。經表面修飾的粒子可由，於如此量子點之單體的粒子表面，或核心/外殼型之量子點的外殼部之表面上附著表面修飾劑而得。使用經表面修飾的量子點時，可提高經表面修飾的量子點之相溶性，於形成彩色濾光器之塗布液中可良好地分散。又，於量子點製造時，可容易使所望粒子徑之量子點成長。Quantum dots can further be used as surface-modified particles. The surface-modified particles can be obtained by attaching a surface modifier to the surface of the single particle of such a quantum dot or the surface of the outer shell of a core/shell type quantum dot. When the surface-modified quantum dots are used, the compatibility of the surface-modified quantum dots can be improved, and they can be dispersed well in the coating solution for forming the color filter. In addition, when manufacturing quantum dots, it is easy to grow quantum dots with a desired particle diameter.

作為表面修飾劑，例如可舉出聚氧乙烯月桂基醚、聚氧乙烯硬脂基醚、聚氧乙烯油基醚等聚氧乙烯烷基醚類，或三丙基膦、三丁基膦、三己基膦、三辛基膦等三烷基膦類，或聚氧乙烯n-辛基苯基醚、聚氧乙烯n-壬基苯基醚等聚氧乙烯烷基苯基醚類，或三(n-己基)胺、三(n-辛基)胺、三(n-癸基)胺等第3級胺類，或三丙基膦氧化物、三丁基膦氧化物、三己基膦氧化物、三辛基膦氧化物、十三烷基膦氧化物等有機磷化合物，或聚乙二醇二丁二月桂酸鹽、聚乙二醇二硬脂酸酯等聚乙二醇二酯類，或吡啶、盧剔啶、可力丁、喹啉類之含氮芳香族化合物等有機氮化合物，或己基胺、辛基胺、癸基胺、十二烷基胺、十四烷基胺、十六烷基胺、十八烷基胺等胺基烷烴類，或二丁基硫化物等二烷基硫化物類，或二甲基亞碸或二丁基亞碸等二烷基亞碸類，或噻吩等含硫芳香族化合物等有機硫化合物，或棕櫚酸、硬脂酸、油酸等高級脂肪酸，或醇類，或山梨糖醇脂肪酸酯類，或脂肪酸變性聚酯類，或3級胺變性聚胺基甲酸酯類，或聚乙烯亞胺類等。作為表面修飾劑，此等由製造於高溫液相中配位於量子點微粒子上而使其穩定化之物質的觀點來看為佳，具體以三烷基膦類、有機磷化合物、胺基烷烴類、第3級胺類、有機氮化合物、二烷基硫化物類、二烷基亞碸類、有機硫化合物、高級脂肪酸、醇類為佳。Examples of surface modifiers include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether, or tripropyl phosphine, tributyl phosphine, Trialkyl phosphines such as trihexyl phosphine and trioctyl phosphine, or polyoxyethylene alkyl phenyl ethers such as polyoxyethylene n-octyl phenyl ether, polyoxyethylene n-nonyl phenyl ether, or three (n-hexyl)amine, tri(n-octyl)amine, tri(n-decyl)amine and other tertiary amines, or tripropylphosphine oxide, tributylphosphine oxide, trihexylphosphine oxide Organic phosphorus compounds such as trioctyl phosphine oxide and tridecyl phosphine oxide, or polyethylene glycol diesters such as polyethylene glycol dibutyl dilaurate and polyethylene glycol distearate , Or organic nitrogen compounds such as pyridine, lutidine, collidine, quinoline and other nitrogen-containing aromatic compounds, or hexylamine, octylamine, decylamine, dodecylamine, tetradecylamine, Amino alkanes such as hexadecylamine and octadecylamine, or dialkyl sulfides such as dibutyl sulfide, or dialkyl sulfides such as dimethyl sulfide or dibutyl sulfide , Or organic sulfur compounds such as sulfur-containing aromatic compounds such as thiophene, or higher fatty acids such as palmitic acid, stearic acid, and oleic acid, or alcohols, or sorbitol fatty acid esters, or fatty acid denatured polyesters, or tertiary Amine modified polyurethanes, or polyethylene imines, etc. As surface modifiers, these are preferably manufactured from the viewpoint of stabilizing the quantum dot particles in a high-temperature liquid phase. Specifically, trialkylphosphines, organophosphorus compounds, and aminoalkanes are used. , Tertiary amines, organic nitrogen compounds, dialkyl sulfides, dialkyl sulfides, organic sulfur compounds, higher fatty acids, alcohols are preferred.

量子點可由公知方法而製造。具體而言，例如可使用分子束外延法、CVD法、液相合成法等。作為液相合成法，例如可舉出對於n-庚烷、n-辛烷、異辛烷等烷烴類，或苯、甲苯、二甲苯等芳香族烴等非極性有機溶劑中，形成原料水溶液之反膠束(Reverse micelle)，在該反膠束相內使結晶成長的反膠束法、將熱分解性原料注入於高溫液相有機媒體中使其結晶成長的熱皂法(Hot soap method)、在低溫下以酸鹼反應使其結晶成長的溶液反應法等。Quantum dots can be manufactured by known methods. Specifically, for example, molecular beam epitaxy, CVD, liquid phase synthesis, etc. can be used. As a liquid phase synthesis method, for example, a raw material aqueous solution is formed in a non-polar organic solvent such as n-heptane, n-octane, and isooctane, or aromatic hydrocarbons such as benzene, toluene, and xylene. Reverse micelle, a reverse micelle method in which crystals grow in the reverse micelle phase, and a hot soap method in which thermally decomposable materials are injected into a high-temperature liquid organic medium to grow crystals , The solution reaction method to grow crystals by acid-base reaction at low temperature, etc.

(彩色濾光器形成用黏合劑)作為保持上述各著色劑或量子點，欲形成彩色濾光器而可適用之黏合劑，除使用彩色濾光器層或平坦化層的至少1層為含有具有上述說明的有關本發明之一般式(1)所示結構的有機金屬氧化物以外，不損害本發明之目的效果的範圍下，亦可使用以下各種樹脂材料。(Adhesive for forming color filter)As a binder that can be used to form a color filter for holding each of the above-mentioned colorants or quantum dots, at least one layer except the color filter layer or the planarization layer contains the general formula of the present invention described above (1) In addition to the organometallic oxide of the structure shown, the following various resin materials can also be used within a range that does not impair the intended effect of the present invention.

作為熱可塑性樹脂，例如可舉出縮丁醛樹脂、苯乙烯-馬來酸共聚物、氯化聚乙烯、氯化聚丙烯、聚氯乙烯、氯化乙烯基-乙酸乙烯基共聚物、聚乙酸乙烯基、聚胺基甲酸酯系樹脂、聚酯樹脂、丙烯酸系樹脂、醇酸樹脂、聚苯乙烯、聚醯胺樹脂、橡膠系樹脂、環化橡膠系樹脂、纖維素類、聚乙烯、聚丁二烯、聚醯亞胺樹脂等。Examples of thermoplastic resins include butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, chlorinated vinyl-acetic acid vinyl copolymers, and polyacetic acid. Vinyl, polyurethane resin, polyester resin, acrylic resin, alkyd resin, polystyrene, polyamide resin, rubber resin, cyclized rubber resin, cellulose, polyethylene, Polybutadiene, polyimide resin, etc.

又，作為熱硬化性樹脂，例如可舉出環氧樹脂、苯並胍胺樹脂、松香變性馬來酸樹脂、松香變性富馬酸樹脂、三聚氰胺樹脂、尿素樹脂、酚樹脂等。In addition, examples of thermosetting resins include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

作為感光性樹脂，可使用具有羥基、羧基、胺基等反應性取代基的於線狀高分子具有異氰酸酯基、醛基、環氧基等反應性取代基之(甲基)丙烯酸化合物或使肉桂酸進行反應，將(甲基)丙烯醯基、苯乙烯基等光交聯性基導入於該線狀高分子之樹脂。又亦可使用將苯乙烯-馬來酸酐共聚物或α-烯烴-馬來酸酐共聚物等含有酸酐之線狀高分子藉由具有羥基烷基(甲基)丙烯酸酯等羥基之(甲基)丙烯酸化合物進行半酯化者。As the photosensitive resin, a (meth)acrylic compound having reactive substituents such as a hydroxyl group, a carboxyl group, and an amine group, or a linear polymer having reactive substituents such as an isocyanate group, an aldehyde group, and an epoxy group, or cinnamon can be used. The acid reacts to introduce a photocrosslinkable group such as a (meth)acryloyl group and a styryl group into the resin of the linear polymer. It is also possible to use linear polymers containing acid anhydrides, such as styrene-maleic anhydride copolymers or α-olefin-maleic anhydride copolymers, by (meth) having hydroxyl groups such as hydroxyalkyl (meth)acrylates. Acrylic compounds are semi-esterified.

對於含有有關本發明的著色劑之彩色濾光器的形成，可含有溶劑。作為溶劑，例如可舉出環己酮、乙基溶纖劑乙酸酯、丁基溶纖劑乙酸酯、1-甲氧基-2-丙基乙酸酯、二乙二醇二甲基醚、乙基苯、乙二醇二乙基醚、二甲苯、乙基溶纖劑、甲基-n戊基酮、丙二醇單甲基醚甲苯、甲基乙基酮、乙酸乙酯、甲醇、乙醇、異丙醇、丁醇、異丁基酮、石油系溶劑等，這些可單獨使用或者混合使用。For the formation of the color filter containing the coloring agent related to the present invention, a solvent may be contained. As the solvent, for example, cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, Ethyl benzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n-pentyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone, ethyl acetate, methanol, ethanol, Isopropanol, butanol, isobutyl ketone, petroleum-based solvents, etc. can be used alone or in combination.

[平坦化層]有關本發明之平坦化層，除使用具有有關本發明之一般式(1)所示結構的有機金屬氧化物以外，亦可使用有機單體、寡聚物、聚合物等有機樹脂者為佳。這些有機樹脂以具有聚合性基或交聯性基者為佳，以含有這些有機樹脂，視必要由含有聚合起始劑或交聯劑等有機樹脂組成物塗布液進行塗布形成的層上，施予光照射處理或熱處理而使其硬化者為佳。此所謂的「交聯性基」表示，藉由以光照射處理或熱處理所引起的化學反應，可使黏合劑聚合物進行交聯的基。若為具有如此功能之基，該化學結構並無特別限定，例如作為可進行加成聚合的官能基，可舉出乙烯性不飽和基、環氧基/氧雜環丁烷基等環狀醚基。又，亦可為藉由光照射成為自由基的官能基，作為如此交聯性基，例如可舉出硫醇基、鹵素原子、鎓鹽結構等。其中亦以乙烯性不飽和基為佳，含有日本特開2007-17948號公報之段落0130～0139所記載的官能基。[Planarization layer]Regarding the planarization layer of the present invention, in addition to the organometallic oxide having a structure represented by the general formula (1) related to the present invention, it is also preferable to use organic resins such as organic monomers, oligomers, and polymers. These organic resins preferably have a polymerizable group or a cross-linkable group, and if they contain these organic resins, if necessary, they are coated on a layer formed by applying a coating solution containing an organic resin composition such as a polymerization initiator or a cross-linking agent. It is better to harden by irradiation treatment or heat treatment. The so-called "crosslinkable group" refers to a group that can crosslink the binder polymer by a chemical reaction caused by light irradiation treatment or heat treatment. If it is a group having such a function, the chemical structure is not particularly limited. For example, the functional group that can undergo addition polymerization includes cyclic ethers such as ethylenically unsaturated groups and epoxy groups/oxetanyl groups. base. Moreover, it may be a functional group which becomes a radical by light irradiation, and as such a crosslinkable group, a thiol group, a halogen atom, an onium salt structure, etc. are mentioned, for example. Among them, an ethylenically unsaturated group is also preferable, and contains the functional group described in paragraphs 0130 to 0139 of JP 2007-17948 A.

作為具體的有機樹脂組成物，例如可舉出含有具有自由基反應性不飽和化合物之丙烯酸酯化合物的樹脂組成物、含有具有丙烯酸酯化合物與硫醇基之巰基化合物的樹脂組成物、將環氧丙烯酸酯、胺基甲酸酯丙烯酸酯、聚酯丙烯酸酯、聚醚丙烯酸酯、聚乙二醇丙烯酸酯、甘油甲基丙烯酸酯等多官能丙烯酸酯單體經溶解的樹脂組成物等。又，亦可使用如上述樹脂組成物之任意混合物，若為含有分子內具有1個以上光聚合性不飽和鍵之反應性單體的感光性樹脂即可，並無特別限制。As a specific organic resin composition, for example, a resin composition containing an acrylate compound having a radically reactive unsaturated compound, a resin composition containing a mercapto compound having an acrylate compound and a thiol group, and epoxy A resin composition in which polyfunctional acrylate monomers such as acrylate, urethane acrylate, polyester acrylate, polyether acrylate, polyethylene glycol acrylate, and glycerol methacrylate are dissolved. In addition, any mixtures of the above-mentioned resin compositions can also be used, and as long as it is a photosensitive resin containing a reactive monomer having one or more photopolymerizable unsaturated bonds in the molecule, it is not particularly limited.

作為於分子內具有1個以上該光聚合性不飽和鍵之反應性單體，可舉出甲基丙烯酸酯、乙基丙烯酸酯、n-丙基丙烯酸酯、異丙基丙烯酸酯、n-丁基丙烯酸酯、異丁基丙烯酸酯、tert-丁基丙烯酸酯、n-戊基丙烯酸酯、n-己基丙烯酸酯、2-乙基己基丙烯酸酯、n-辛基丙烯酸酯、n-癸基丙烯酸酯、羥基乙基丙烯酸酯、羥基丙基丙烯酸酯、烯丙基丙烯酸酯、苯甲基丙烯酸酯、丁氧基乙基丙烯酸酯、丁氧基乙二醇丙烯酸酯、環己基丙烯酸酯、二環戊基丙烯酸酯、2-乙基己基丙烯酸酯、甘油丙烯酸酯、縮水甘油基丙烯酸酯、2-羥基乙基丙烯酸酯、2-羥基丙基丙烯酸酯、異冰片基丙烯酸酯、異癸基丙烯酸酯、異辛基丙烯酸酯、月桂基丙烯酸酯、2-甲氧基丙烯酸酯、甲氧基乙二醇丙烯酸酯、苯氧基乙基丙烯酸酯、硬脂基丙烯酸酯、乙二醇二丙烯酸酯、二乙二醇二丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,5-戊烷二醇二丙烯酸酯、1,6-六二醇二丙烯酸酯、1,3-丙烷二醇丙烯酸酯、1,4-環己二醇二丙烯酸酯、2,2-二羥甲基丙烷二丙烯酸酯、甘油二丙烯酸酯、三丙二醇二丙烯酸酯、甘油三丙烯酸酯、三羥甲基丙烷三丙烯酸酯、聚氧乙基三羥甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、環氧乙烷變性季戊四醇三丙烯酸酯、環氧乙烷變性季戊四醇四丙烯酸酯、環氧丙烷變性季戊四醇三丙烯酸酯、環氧丙烷變性季戊四醇四丙烯酸酯、三乙二醇二丙烯酸酯、聚氧丙基三羥甲基丙烷三丙烯酸酯、丁二醇二丙烯酸酯、1,2,4-丁二醇三丙烯酸酯、2,2,4-三甲基-1,3-戊二醇二丙烯酸酯、二烯丙基富馬酸酯、1,10-癸烷二醇二甲基丙烯酸酯、季戊四醇六丙烯酸酯及將上述丙烯酸酯由甲基丙烯酸酯所取代者、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、1-乙烯基-2-吡咯啶酮等。上述反應性單體可作為1種或2種以上之混合物，或亦可作為與其他化合物之混合物使用。Examples of the reactive monomer having one or more of the photopolymerizable unsaturated bond in the molecule include methacrylate, ethacrylate, n-propyl acrylate, isopropyl acrylate, n-butyl Acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate Ester, hydroxyethyl acrylate, hydroxypropyl acrylate, allyl acrylate, benzyl methacrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, bicyclic Amyl acrylate, 2-ethylhexyl acrylate, glycerin acrylate, glycidyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, isodecyl acrylate , Isooctyl acrylate, lauryl acrylate, 2-methoxy acrylate, methoxy glycol acrylate, phenoxy ethyl acrylate, stearyl acrylate, ethylene glycol diacrylate, Diethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6-hexadiol diacrylate, 1,3-propanediol acrylic acid Esters, 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, tripropylene glycol diacrylate, glycerol triacrylate, trimethylolpropane triacrylate Ester, polyoxyethyl trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene oxide modified pentaerythritol triacrylate, ethylene oxide modified pentaerythritol tetraacrylate, propylene oxide modified pentaerythritol Triacrylate, propylene oxide modified pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyoxypropyl trimethylolpropane triacrylate, butanediol diacrylate, 1,2,4-butanediol Triacrylate, 2,2,4-trimethyl-1,3-pentanediol diacrylate, diallyl fumarate, 1,10-decanediol dimethacrylate, pentaerythritol hexa Acrylic esters and those substituted by methacrylates, γ-methacryloxypropyltrimethoxysilane, 1-vinyl-2-pyrrolidone, and the like. The above-mentioned reactive monomers can be used as a mixture of one type or two or more types, or as a mixture with other compounds.

前述感光性樹脂的組成物含有光聚合起始劑。作為光聚合起始劑，可舉出二苯甲酮、o-苯甲醯基安息香酸甲基、4,4-雙(二甲基胺)二苯甲酮、4,4-雙(二乙基胺)二苯甲酮、α-胺基･苯乙酮、4,4-二氯二苯甲酮、4-苯甲醯基-4-甲基二苯基酮、二苯甲基酮、芴酮、2,2-二乙氧基苯乙酮、2,2-二甲氧基-2-苯基苯乙酮、2-羥基-2-甲基苯丙酮、p-tert-丁基二氯苯乙酮、噻噸酮、2-甲基硫基呫噸酮、2-氯噻噸酮、2-異丙基硫基呫噸酮、二乙基硫基呫噸酮、苯甲基二甲基縮酮、苯甲基甲氧基乙基縮醛、安息香甲基醚、安息香丁基醚、蒽醌、2-tert-丁基蒽醌、2-戊基蒽醌、β-氯蒽醌、蒽酮、苯並蒽酮、二苯並環庚酮、伸甲基蒽酮、4-疊氮化物苯甲基苯乙酮、2,6-雙(p-疊氮化物亞苯甲基)環己烷、2,6-雙(p-疊氮化物亞苯甲基)-4-甲基環己酮、2-苯基-1,2-丁二酮-2-(o-甲氧基羰基)肟、1-苯基-丙烷二酮-2-(o-乙氧基羰基)肟、1,3-二苯基-丙烷三酮-2-(o-乙氧基羰基)肟、1-苯基-3-乙氧基-丙烷三酮-2-(o-苯甲醯基)肟、米氏酮、2-甲基[4-(甲基硫基)苯基]-2-嗎啉代-1-丙烷、2-苯甲基-2-二甲基胺基-1-(4-嗎啉代苯基)-丁酮-1、萘磺醯基氯化物、喹啉磺醯基氯化物、n-苯基硫基吖啶酮、4,4-偶氮二異丁腈、二苯基二硫化物、苯並噻唑二硫化物、三苯基膦、樟腦醌、四溴化碳、三溴苯基碸、過氧化安息香、伊紅、伸甲基藍等光還原性色素與抗壞血酸、三乙醇胺等還原劑之組合等，這些光聚合起始劑可使用1種或組合2種以上後使用。The composition of the aforementioned photosensitive resin contains a photopolymerization initiator. As the photopolymerization initiator, benzophenone, o-benzylbenzoic acid methyl, 4,4-bis(dimethylamine)benzophenone, 4,4-bis(diethyl) Base amine) benzophenone, α-amino·acetophenone, 4,4-dichlorobenzophenone, 4-benzyl-4-methylbenzophenone, benzophenone, Fluorenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyl two Chloroacetophenone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, diethylthioxanthone, benzyl bis Methyl ketal, benzyl methoxy ethyl acetal, benzoin methyl ether, benzoin butyl ether, anthraquinone, 2-tert-butylanthraquinone, 2-pentylanthraquinone, β-chloroanthraquinone , Anthrone, Benzoanthrone, Dibenzocycloheptanone, Ethylanthrone, 4-azide benzylacetophenone, 2,6-bis(p-azide benzyl) Cyclohexane, 2,6-bis(p-azide benzylidene)-4-methylcyclohexanone, 2-phenyl-1,2-butanedione-2-(o-methoxy Carbonyl) oxime, 1-phenyl-propanedione-2-(o-ethoxycarbonyl)oxime, 1,3-diphenyl-propanetrione-2-(o-ethoxycarbonyl)oxime, 1 -Phenyl-3-ethoxy-propanetrione-2-(o-benzyl)oxime, Michler’s ketone, 2-methyl[4-(methylsulfanyl)phenyl]-2-methyl Lino-1-propane, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, naphthalenesulfonyl chloride, quinolinesulfonyl Chloride, n-phenylthioacridone, 4,4-azobisisobutyronitrile, diphenyl disulfide, benzothiazole disulfide, triphenylphosphine, camphorquinone, carbon tetrabromide Combinations of photoreducible pigments such as, tribromophenyl sulfonium, benzoin peroxide, eosin, ethylene blue, and reducing agents such as ascorbic acid and triethanolamine. These photopolymerization initiators can be used singly or in combination of two or more After use.

[彩色濾光器單元之形成方法]對於由有關本發明的上述說明之第2基材17、彩色濾光器層18及平坦化層19所構成的彩色濾光器單元16之形成方法做說明。[Method of forming color filter unit]The method of forming the color filter unit 16 composed of thesecond base material 17, thecolor filter layer 18, and theplanarization layer 19 described above regarding the present invention will be described.

彩色濾光器單元16如圖1及圖2所示，對於在後述TFT形成步驟或有機EL裝置形成步驟所使用的第1基材2，在其之對面位置上配置第2基材17。於該第2基材17上，作為有關本發明之彩色濾光器層18，將射出紅･綠･藍之特定波長區域的光之複數種彩色濾光器，使用含有顯示這些顏色的著色材料(著色劑或量子點)之感光性樹脂材料，以濕式塗布法等配置形成為短冊狀。As shown in FIG. 1 and FIG. 2, the color filter unit 16 has asecond substrate 17 on the opposite side of thefirst substrate 2 used in the TFT formation step or the organic EL device formation step described later. On thesecond substrate 17, as thecolor filter layer 18 related to the present invention, a plurality of color filters that emit light in a specific wavelength region of red, green, and blue are used, and a coloring material containing these colors is used The photosensitive resin material (colorant or quantum dot) is arranged into a short book shape by a wet coating method or the like.

各彩色濾光器之厚度為，依據所選擇的種類或空腔結構之形成的有無而可進行適宜設定，通常形成為0.5～2μm之範圍內的厚度。雖可具有與鄰接各色彩色濾光器部分性重疊的部分，但以形成使用感光性聚醯亞胺等的隔壁層為佳，欲使各色濾器進行分離下形成紅･綠･藍之彩色濾光器。隔壁層或彩色濾光器可為正形態或負形態任一種。隔壁層可藉由所關連的彩色濾光器之厚度進行調整，亦可形成0.5～5μm之範圍內的厚度。特別為在紅･綠･藍之彩色濾光器的膜厚為相異時，使用隔壁時更可以抑制端部的厚度所引起的透過率變動，故適用此為佳。The thickness of each color filter can be appropriately set according to the selected type or the presence or absence of the cavity structure, and it is usually formed to a thickness in the range of 0.5-2 μm. Although it may have a part that overlaps with the adjacent color filters of each color, it is better to form a partition layer using photosensitive polyimide, etc., and to separate the color filters to form a red, green, and blue color filter Device. The barrier layer or the color filter may be in either a positive form or a negative form. The barrier layer can be adjusted by the thickness of the color filter to which it is connected, and can also be formed to have a thickness in the range of 0.5-5 μm. Especially when the film thicknesses of the red, green, and blue color filters are different, it is better to apply this because it is better to suppress the change in the transmittance caused by the thickness of the end when the partition wall is used.

其次，於形成紅･綠･藍之彩色濾光器(CF_R、CF_G、CF_B)後，欲進行平坦化處理，形成平坦化層19。平坦化層19對於鄰接層的第2接著層15必須具有充分的密著性，且使用於平坦化處理上。Next, after forming the red, green, and blue color filters (CF_R , CF_G , and CF_B ), a planarization process is to be performed to form aplanarization layer 19. Theplanarization layer 19 must have sufficient adhesion to the secondadhesive layer 15 of the adjacent layer, and be used for planarization processing.

且，對於彩色濾光器單元之形成方法的詳細情況，例如可參照日本特開2001-66414號公報、日本特開2001-66415號公報、WO2013/146903號等。In addition, for details of the method of forming the color filter unit, for example, Japanese Patent Application Publication No. 2001-66414, Japanese Patent Application Publication No. 2001-66415, WO2013/146903, etc. can be referred to.

[濕式塗布法]對於有關本發明的彩色濾光器單元之形成，可使用濕式塗布法，至少將彩色濾光器層藉由濕式塗布法而形成者為較佳態樣。[Wet coating method]For the formation of the color filter unit related to the present invention, a wet coating method can be used, and it is preferable that at least the color filter layer is formed by a wet coating method.

作為可適用於本發明的濕式塗布法，例如可舉出旋轉塗布法、澆鑄法、絲網印刷法、模塗法、刮刀塗布法、輥塗布法、噴霧塗布法、幕式塗布法、LB法(Langue-Brojet method)、噴墨印刷法等，由容易得到均質之薄膜且高生產性的觀點來看為佳。As the wet coating method applicable to the present invention, for example, spin coating method, casting method, screen printing method, die coating method, knife coating method, roll coating method, spray coating method, curtain coating method, LB Method (Langue-Brojet method), inkjet printing method, etc., are preferable from the viewpoint of easy obtaining of a homogeneous film and high productivity.

(噴墨印刷法)有關本發明，對於局部性區域，可形成高精度且均質之層厚的觀點來看，以噴墨印刷法為佳。(Inkjet printing method)Regarding the present invention, the inkjet printing method is preferred from the viewpoint that a highly accurate and uniform layer thickness can be formed for a local area.

以下對於噴墨印刷法之概要做說明。The outline of the inkjet printing method is explained below.

對於有關本發明之彩色濾光器單元的形成，以至少於彩色濾光器層的形成上使用噴墨印刷法者為特佳。Regarding the formation of the color filter unit of the present invention, it is particularly preferable to use an inkjet printing method for the formation of the color filter layer.

以下對於使用於噴墨印刷法的噴墨頭、水墨液滴之射出條件、噴墨記錄方法與記錄裝置及具體面發光面板之噴墨印刷法的製造程序，附上圖式說明。The following is a description of the inkjet head used in the inkjet printing method, the ejection conditions of the ink droplets, the inkjet recording method and the recording device, and the manufacturing process of the inkjet printing method of the specific surface-emitting panel.

＜噴墨頭＞作為使用於噴墨印刷法的噴墨頭，可為按需方法亦可為連續性方法。又，作為吐出方式，可將電氣-機械變換方式(例如單腔型、雙腔型、彎管機類型、活塞型、分享模式型、共享壁型等)、電-熱變換方式(例如，熱噴墨型、泡沫噴射(註冊商標)型等)、靜電吸引方式(例如，電場控制型、狹縫噴射型等)、放電方式(例如火花噴射型等)等作為具體例子而舉出，但所有吐出方式皆可使用。又，作為印字方式，可無限制下使用串行頭方式、線頭方式等。＜Inkjet head＞The inkjet head used in the inkjet printing method may be an on-demand method or a continuous method. In addition, as the discharge method, electrical-mechanical conversion methods (such as single-chamber type, double-chamber type, pipe bender type, piston type, sharing mode type, shared wall type, etc.), electrical-heat conversion methods (such as thermal Inkjet type, bubble jet (registered trademark) type, etc.), electrostatic attraction method (e.g., electric field control type, slit jet type, etc.), discharge method (e.g., spark jet type, etc.) are given as specific examples, but all Both spit out methods can be used. In addition, as a printing method, a serial head method, a thread head method, etc. can be used without limitation.

＜墨液滴尺寸＞對於彩色濾光器層之形成，自噴墨頭所射出的墨液滴之體積以設定為0.5～100pL之範圍內者為佳。以彩色濾光器層之塗布不均為少，且可使印字速度高速化的觀點來看，其為2～20pL之範圍者為較佳。且，墨液滴之體積可藉由外加電壓之調整等，適宜地調整至所望條件。＜Ink droplet size＞For the formation of the color filter layer, the volume of the ink droplets emitted from the inkjet head is preferably set to be in the range of 0.5-100 pL. From the viewpoint that the coating unevenness of the color filter layer is small and the printing speed can be increased, it is preferably in the range of 2 to 20 pL. In addition, the volume of the ink droplets can be appropriately adjusted to desired conditions by adjusting the applied voltage.

＜印字方法＞對於藉由噴墨印刷法之印字方法，有一遍打印方法與多遍打印方法。一遍打印方法為於所定印字區域上固定配置複數個噴墨頭，以1次頭部掃描方式進行印字的方法。相對於此，多遍打印方法(亦稱為串行打印方法)為將所定印字區域以複數次的頭部掃描進行印字的方法。＜Printing method＞For the printing method by the inkjet printing method, there is a one-pass printing method and a multi-pass printing method. The one-pass printing method is a method in which a plurality of inkjet heads are fixedly arranged on a predetermined printing area, and printing is performed by a head scan method. In contrast, the multi-pass printing method (also referred to as the serial printing method) is a method of printing a predetermined printing area by scanning the head in multiple times.

在一遍打印方法中，在作為所望的塗布圖型之寬度以上的寬度下，使用並列噴嘴的廣寬噴頭者為佳。於同一基材上，形成彼此圖型未連續的獨立複數塗布圖型時，至少使用各塗布圖型的寬度以上的廣寬噴頭即可。In the one-pass printing method, it is better to use a wide nozzle with parallel nozzles at a width greater than the width of the desired coating pattern. When forming a plurality of independent coating patterns that are not continuous with each other on the same substrate, at least a wide nozzle with a width of at least the width of each coating pattern may be used.

圖3表示使用一遍打印方法的噴墨印刷法之彩色濾光器的形成方法之一例概略圖。FIG. 3 is a schematic diagram showing an example of a method of forming a color filter by an inkjet printing method using a one-pass printing method.

圖3表示使用具備噴墨頭30的噴墨印表機，於第2基材17上，依序吐出含有構成彩色濾光器層18的複數彩色濾光器CF之形成材料(例如著色劑、量子點、黏合劑等)的墨液，形成複數獨立形態之彩色濾光器CF的方法之一例子。3 shows the use of an inkjet printer equipped with aninkjet head 30, on thesecond substrate 17, the formation material containing a plurality of color filters CF constituting the color filter layer 18 (for example, coloring agent, Quantum dots, adhesives, etc.) inks are an example of a method of forming a plurality of independent color filters CF.

如圖3所示，一邊將第2基材17以連續方式搬送下，藉由噴墨頭30將含有彩色濾光器形成材料的墨液，以水墨液滴方式依序射出，形成由所望彩色濾光器CF群所構成的彩色濾光器層18。As shown in FIG. 3, while thesecond substrate 17 is continuously conveyed, the ink containing the color filter forming material is sequentially ejected by theinkjet head 30 in the form of ink droplets to form the desired color Acolor filter layer 18 composed of a group of filters CF.

於噴墨頭30中，連接著射出用墨液之供給機構等。水墨液的供給係藉由槽38A進行。將噴墨頭30內之水墨液壓力始終保持恆定下，在此示例中，槽液面保持在恆定狀態。作為該方法，將水墨液自槽38A溢出，於槽38B自然流下而回歸。自槽38B至槽38A的水墨液之供給為藉由幫浦31而進行，配合射出條件下，控制至穩定下槽38A之液面呈現恆定狀態。Theinkjet head 30 is connected with a supply mechanism of ink for ejection and the like. The supply of ink is carried out through thetank 38A. The ink pressure in theinkjet head 30 is always kept constant. In this example, the liquid level of the tank is kept at a constant state. As this method, the ink overflows from thetank 38A, flows down naturally in thetank 38B, and returns. The supply of the ink from thetank 38B to thetank 38A is performed by thepump 31, and the liquid level of thetank 38A is controlled to be stable under the conditions of injection.

且，自幫浦31至槽38A將水墨液回歸時，通過濾器32後進行。如此，在水墨液供給於噴墨頭30前，至少通過絕對過濾精度或準絕對過濾精度為0.05～50μm之濾材1次者為佳。In addition, when the ink is returned from thepump 31 to thetank 38A, it passes through thefilter 32 and is performed. In this way, before the ink is supplied to theinkjet head 30, it is preferable to pass the filter medium with an absolute filtration accuracy or a quasi-absolute filtration accuracy of 0.05 to 50 μm at least once.

又，為了實施噴墨頭30的洗淨作業或液體填充作業等，藉由幫浦39對噴墨頭30從槽36強制性供給水墨液，從槽37強制性供給洗淨溶劑。對於噴墨頭30，如此槽幫浦類亦可分為複數個，或亦可使用管道之分支，又亦可為此等組合。在圖3中，使用管道分支33。且，又可欲充分地除去噴墨頭30內之空氣，從槽36以幫浦39對噴墨30進行水墨液的強制性送液下，自排氣管排出水墨液而送至廢水槽34者。In addition, in order to perform the cleaning operation or liquid filling operation of theinkjet head 30, theinkjet head 30 is forcibly supplied with ink from thetank 36 by thepump 39, and a cleaning solvent is forcibly supplied from thetank 37. For theinkjet head 30, such groove pumps can also be divided into a plurality of types, or branching of pipes can also be used, or combinations of these can also be used. In Figure 3, thepipe branch 33 is used. In addition, it is possible to sufficiently remove the air in theinkjet head 30. Under the forced delivery of ink from thetank 36 to theinkjet 30 by thepump 39, the ink is discharged from the exhaust pipe and sent to thewaste water tank 34. By.

作為適用於本發明的噴墨頭，例如可適宜地選擇使用如日本特開2012-140017號公報、日本特開2013-010227號公報、日本特開2014-058171號公報、日本特開2014-097644號公報、日本特開2015-142979號公報、日本特開2015-142980號公報、日本特開2016-002675號公報、日本特開2016-002682號公報、日本特開2016-107401號公報、日本特開2017-109476號公報、日本特開2017-177626號公報等記載的構成所成的噴墨頭。As an inkjet head suitable for the present invention, for example, Japanese Patent Application Publication No. 2012-140017, Japanese Patent Application Publication No. 2013-010227, Japanese Patent Application Publication No. 2014-058171, and Japanese Patent Application Publication No. 2014-097644 can be suitably selected and used. No. 2015-142979, No. 2015-142980, No. 2016-002675, No. 2016-002682, No. 2016-107401, No. 2016-107401, No. 2015-142979, No. 2015-142980, No. 2016-002675, No. 2016-002682, No. 2016-107401, No. The inkjet head is composed of the structure described in Japanese Patent Application Publication No. 2017-109476 and Japanese Patent Application Publication No. 2017-177626.

[第2接著層]對於本發明之顯示裝置，在上述方法所製作的彩色濾光器單元16如圖1及圖2所示，於構成有機EL單元D之第1基材2的背面上，隔著第2接著層15而貼合。[Second second floor]For the display device of the present invention, the color filter unit 16 produced by the above method is shown in FIGS. 1 and 2, on the back of thefirst substrate 2 constituting the organic EL unit D, with a second adhesive layer therebetween. 15 and fit.

作為形成第2接著層的接著材料(黏著劑量)，例如可舉出於環氧系熱硬化樹脂中分散無機、有機、混合(Hybrid)等填充物的熱硬化形態，或含有光起始劑並且在UV光下可進行硬化的形態、以聚丙烯酸系黏著劑作為代表的親水性丙烯酸聚合物系黏著劑、聚乙烯縮醛系黏著劑、聚乙烯醇系黏著劑、聚乙烯醇系黏著劑、乙酸乙烯基系黏著劑、橡膠系黏著劑(例如天然橡膠、合成橡膠、苯乙烯-異戊二烯-苯乙烯嵌段共聚物、異戊二烯橡膠、聚異丁烯(PIB)、苯乙烯-丁二烯-苯乙烯嵌段共聚物、苯乙烯-丁二烯橡膠、聚丁烯等)。As the adhesive material (adhesive amount) forming the second adhesive layer, for example, a thermosetting form in which inorganic, organic, and hybrid fillers are dispersed in an epoxy-based thermosetting resin, or containing a photoinitiator and A form that can be cured under UV light, hydrophilic acrylic polymer adhesives represented by polyacrylic adhesives, polyvinyl acetal adhesives, polyvinyl alcohol adhesives, polyvinyl alcohol adhesives, Vinyl acetate adhesive, rubber adhesive (e.g. natural rubber, synthetic rubber, styrene-isoprene-styrene block copolymer, isoprene rubber, polyisobutylene (PIB), styrene-butadiene Diene-styrene block copolymer, styrene-butadiene rubber, polybutene, etc.).

藉由接著材料所形成的第2接著層之厚度並無特別限制，選自0.1～10μm的範圍內者為佳。The thickness of the second adhesive layer formed by the adhesive material is not particularly limited, but it is preferably selected from the range of 0.1-10 μm.

《TFT單元》作為可適用於TFT單元的TFT，如前述所示，可適用非晶質Si形態或氧化物系，或LTPS(低溫聚矽)、HTPS(高溫聚矽)或OTFT(有機薄層電晶體)等。"TFT Unit"As the TFT that can be applied to TFT unit, as mentioned above, it can be applied to amorphous Si form or oxide system, or LTPS (low temperature polysilicon), HTPS (high temperature polysilicon) or OTFT (organic thin layer transistor), etc. .

對於在第1基材2上的TFT之形成方法，例如可參照如銳利技法 第99號(2007年11月)，或日本特開平6-202150號公報、日本特開2011-211003號公報、日本特開2014-078730號公報、日本特開2014-146823號公報、日本特開2014-168063號公報、日本特開2016-162535號公報等所記載的方法。For the method of forming the TFT on thefirst substrate 2, for example, refer to Sharp Technology No. 99 (November 2007), or Japanese Patent Application Publication No. 6-202150, Japanese Patent Application Publication No. 2011-211003, Japan Methods described in Japanese Patent Application Publication No. 2014-078730, Japanese Patent Application Publication No. 2014-146823, Japanese Patent Application Publication No. 2014-168063, Japanese Patent Application Publication No. 2016-162535, and the like.

例如，可舉出於基材上形成柵電極後，形成柵絕緣層，於該上面形成源電極、漏電極，於該源電極、漏電極間之柵絕緣層上形成有機半導體材料層而形成底閘型之有機TFT的方法，或於基材上形成柵電極後，形成柵絕緣層，於該上面形成有機半導體材料層後，進一步形成源電極、漏電極而形成有機TFT的方法等。For example, after forming a gate electrode on a substrate, a gate insulating layer is formed, a source electrode and a drain electrode are formed on the top surface, and an organic semiconductor material layer is formed on the gate insulating layer between the source electrode and the drain electrode to form a bottom A method of gate-type organic TFT, or a method of forming a gate insulating layer after forming a gate electrode on a substrate, forming an organic semiconductor material layer thereon, and further forming a source electrode and a drain electrode to form an organic TFT.

於TFT單元3上，除配置TFT4以外，配置構成有機EL元件OLED之自第1電極5的引出電極6。On theTFT unit 3, in addition to the TFT 4, theextraction electrode 6 from thefirst electrode 5 constituting the organic EL element OLED is arranged.

《發光元件單元》對於本發明之顯示裝置，例如於具備氣體阻隔層的第1基材2上，形成TFT單元3後，於該上面形成發光元件，例如形成有機EL元件之OLED，構成發光顯示單元D。"Light-emitting element unit"For the display device of the present invention, for example, theTFT unit 3 is formed on thefirst substrate 2 provided with a gas barrier layer, and then a light-emitting element, such as an OLED with an organic EL element, is formed thereon to form a light-emitting display unit D.

以下對於作為發光元件使用有機EL元件的例子做說明。Hereinafter, an example of using an organic EL element as a light-emitting element will be described.

[有機EL元件之基本構成]圖4表示，於本發明之顯示裝置上作為發光元件可適用的有機EL元件的代表性概略截面圖。[Basic structure of organic EL device]4 shows a representative schematic cross-sectional view of an organic EL element applicable as a light-emitting element in the display device of the present invention.

圖4所表示的有機EL元件OLED中，其中表示第1電極5～第2電極9為止的構成，省略該上的密封結構之記載。In the organic EL element OLED shown in FIG. 4, the structure up to thefirst electrode 5 to thesecond electrode 9 is shown, and the description of the sealing structure is omitted.

在圖4中，於第1基材2及TFT單元3上，於第1電極5及其延長線上具有引出電極6。In FIG. 4, on thefirst substrate 2 and theTFT unit 3, there is alead electrode 6 on thefirst electrode 5 and its extension.

於第1電極5上，層合有機功能層群7。有機功能層群7之構成，除至少具有發光層以外，可使用種種構成。On thefirst electrode 5, an organicfunctional layer group 7 is laminated. The organicfunctional layer group 7 has various constitutions other than having at least a light-emitting layer.

於圖4表示代表性有機功能層群之代表性構成，於第1電極5(陽極)上，依序層合電洞注入層22、電洞輸送層23、發光層24、電子輸送層25、電子注入層26，構成有機功能層群7，於該上面配置第2電極8(陰極)。4 shows a representative structure of a representative organic functional layer group. On the first electrode 5 (anode), ahole injection layer 22, ahole transport layer 23, a light emitting layer 24, anelectron transport layer 25, Theelectron injection layer 26 constitutes the organicfunctional layer group 7, and the second electrode 8 (cathode) is arranged on the upper surface.

[有機EL元件之構成材料]以下對於適用於本發明的顯示裝置之發光元件的有機EL元件之構成做詳細說明。[Material of organic EL device]The structure of the organic EL element suitable for the light-emitting element of the display device of the present invention will be described in detail below.

作為除有關本發明的有機EL元件之第1基材、TFT單元、密封部以外的構成，在圖4所示構成以外，可將下述構成作為一例子而舉出。且，適用於本發明的發光層係以由藍色發光層、綠色發光層及紅色發光層所成白色發光方式之發光層為佳。As a structure other than the first base material, TFT unit, and sealing portion of the organic EL element of the present invention, in addition to the structure shown in FIG. 4, the following structure can be cited as an example. Moreover, the light-emitting layer suitable for the present invention is preferably a light-emitting layer in a white light-emitting mode formed by a blue light-emitting layer, a green light-emitting layer and a red light-emitting layer.

(i)第1電極/有機功能層群(發光層/電子輸送層)/第2電極(ii)第1電極/有機功能層群(電洞輸送層/發光層/電子輸送層)/第2電極(iii)第1電極/有機功能層群(電洞輸送層/發光層/電洞阻擋層/電子輸送層)/第2電極(iv)第1電極/有機功能層群(電洞輸送層/發光層/電洞阻擋層/電子輸送層/第2電極緩衝液層)/第2電極(v)第1電極/有機功能層群(陽極緩衝液層/電洞輸送層/發光層/電洞阻擋層/電子輸送層/第2電極緩衝液層)/第2電極等可舉出。(i) First electrode/organic functional layer group (light emitting layer/electron transport layer)/second electrode(ii) The first electrode/organic functional layer group (hole transport layer/light emitting layer/electron transport layer)/second electrode(iii) The first electrode/organic functional layer group (hole transport layer/light emitting layer/hole blocking layer/electron transport layer)/second electrode(iv) The first electrode/organic functional layer group (hole transport layer/light emitting layer/hole blocking layer/electron transport layer/second electrode buffer layer)/second electrode(v) The first electrode/organic functional layer group (anode buffer layer/hole transport layer/light-emitting layer/hole blocking layer/electron transport layer/second electrode buffer layer)/second electrode, etc. may be mentioned.

其次，對於有機EL元件之各構成要素做說明。Next, each component of the organic EL device will be explained.

(第1基材)適用於有關本發明的有機EL元件之第1基材，以具有柔軟性的可折疊之可撓性樹脂基材者為佳。(First base material)The first substrate suitable for the organic EL device of the present invention is preferably a flexible foldable flexible resin substrate.

作為適用於本發明的樹脂基材，例如可舉出聚乙烯對苯二甲酸酯(簡稱：PET)、聚乙烯萘二甲酸酯(簡稱：PEN)等聚酯、聚乙烯、聚丙烯、賽璐玢(Cellophane)、纖維素二乙酸酯、纖維素三乙酸酯(簡稱：TAC)、纖維素乙酸酯丁酸酯、纖維素乙酸酯丙酸酯(簡稱：CAP)、纖維素乙酸酯鄰苯二甲酸酯、硝酸纖維素等纖維素酯類及此等衍生物、聚偏二氯乙烯、聚乙烯醇、聚乙烯乙烯基醇、間規聚苯乙烯、聚碳酸酯(簡稱：PC)、降冰片烯樹脂、聚甲基戊烯、聚醚酮、聚醯亞胺、聚醚碸(簡稱：PES)、聚伸苯基硫化物、聚碸類、聚醚醯亞胺、聚醚酮醯亞胺、聚醯胺、氟樹脂、尼龍、聚甲基甲基丙烯酸酯、丙烯酸及聚芳酯類、ARTON(商品名JSR公司製)及Appell(商品名三井化學公司製)等環烯烴系樹脂等。Examples of resin substrates suitable for the present invention include polyesters such as polyethylene terephthalate (abbreviation: PET) and polyethylene naphthalate (abbreviation: PEN), polyethylene, polypropylene, Cellophane (Cellophane), cellulose diacetate, cellulose triacetate (abbreviation: TAC), cellulose acetate butyrate, cellulose acetate propionate (abbreviation: CAP), fiber Cellulose esters such as cellulose acetate phthalate, nitrocellulose and these derivatives, polyvinylidene chloride, polyvinyl alcohol, polyvinyl vinyl alcohol, syndiotactic polystyrene, polycarbonate (Abbreviation: PC), norbornene resin, polymethylpentene, polyether ketone, polyimide, polyether sulfide (abbreviation: PES), polyphenylene sulfide, poly sulfide, polyether sulfide Amine, polyetherketimide, polyamide, fluororesin, nylon, polymethacrylate, acrylic acid and polyarylate, ARTON (trade name manufactured by JSR), and Appell (trade name manufactured by Mitsui Chemicals) ) And other cycloolefin resins.

這些樹脂基材中，由成本或獲得容易性的觀點來看，使用聚乙烯對苯二甲酸酯(簡稱：PET)、聚丁烯對苯二甲酸酯、聚乙烯萘二甲酸酯(簡稱：PEN)、聚碳酸酯(簡稱：PC)等薄膜作為可撓性樹脂基材而較佳。Among these resin substrates, polyethylene terephthalate (abbreviation: PET), polybutylene terephthalate, polyethylene naphthalate (polyethylene naphthalate) are used from the viewpoint of cost or availability. Films such as PEN (abbreviation: PEN) and polycarbonate (abbreviation: PC) are preferable as the flexible resin substrate.

對於本發明，作為樹脂基材之厚度，可設定為3～200μm之範圍內，以10～100μm之範圍內為佳，較佳為20～50μm之範圍內。For the present invention, the thickness of the resin substrate can be set in the range of 3 to 200 μm, preferably in the range of 10 to 100 μm, and preferably in the range of 20 to 50 μm.

有關本發明的第1基材亦可作為有機EL元件之密封構件(透明基材)使用而較佳。又，上述樹脂基材可為未延伸薄膜，亦可為延伸薄膜。The first substrate according to the present invention can also be used as a sealing member (transparent substrate) of an organic EL device, and is preferably used. In addition, the above-mentioned resin substrate may be an unstretched film or a stretched film.

可適用於本發明的樹脂基材，可藉由過去公知的一般製膜方法而製造。例如將作為材料的樹脂藉由押出機進行熔融，藉由環狀模具或T型模頭進行押出並急冷後，實質上可製造出未以非晶態進行配向的未延伸樹脂基材。又，將未延伸的樹脂基材藉由一軸延伸、拉幅式逐次二軸延伸、拉幅式同時二軸延伸、管狀式同時二軸延伸等公知方法，往樹脂基材之搬送方向(縱軸方向、MD方向)，或往與樹脂基材之搬送方向為直角的方向(橫軸方向、TD方向)進行延伸後，可製造出延伸樹脂基材。此時的延伸倍率可配合成為樹脂基材之原料的樹脂而做適宜選擇，對於縱軸方向及橫軸方向各以2～10倍範圍內者為佳。The resin substrate applicable to the present invention can be produced by conventionally known general film forming methods. For example, the resin as a material is melted by an extruder, extruded by a ring die or T-die and quenched, and an unstretched resin substrate that is not aligned in an amorphous state can be produced substantially. In addition, the unstretched resin base material is transferred to the conveying direction of the resin base material (vertical axis) by known methods such as uniaxial extension, tenter type successive two-axis extension, tenter type simultaneous two-axis extension, tubular type simultaneous two-axis extension, etc. Direction, MD direction), or in a direction (horizontal axis direction, TD direction) at right angles to the conveying direction of the resin substrate to produce a stretched resin substrate. The stretching ratio at this time can be appropriately selected according to the resin used as the raw material of the resin base material, and it is preferably within the range of 2 to 10 times in the vertical axis direction and the horizontal axis direction.

＜氣體阻隔層＞於有關本發明之第1基材上，可設置氣體阻隔層。作為氣體阻隔層，僅具有氣體或水分等遮斷效果即可，並無特別限制，可適宜地選擇過去公知的氣體阻隔層。＜Gas barrier layer＞A gas barrier layer can be provided on the first substrate related to the present invention. As the gas barrier layer, it is only necessary to have a shielding effect such as gas or moisture, and is not particularly limited, and conventionally known gas barrier layers can be appropriately selected.

氣體阻隔層並非僅為無機材料被膜，可為由與有機材料的複合材料所成的被膜或層合此等被膜之混合(Hybrid)被膜。作為氣體阻隔層之性能，依據JIS(日本工業規格)-K7129(2008年)，水蒸氣透過度(環境條件：25± 0.5℃，相對濕度(90±2)%)約0.01g/m²･24h以下，以JIS-K7126(2006年)為準，欲使氧透過度約0.01mL/m²･24h･atm以下，電阻率為1×10¹²Ω･cm以上，光線透過率在可見光區域下約80%以上，以具有氣體阻隔性及光透過性的絕緣膜者為佳。The gas barrier layer is not only an inorganic material film, but may be a film made of a composite material with an organic material or a hybrid film formed by laminating these films. As the performance of the gas barrier layer, according to JIS (Japanese Industrial Standards)-K7129 (2008), the water vapor permeability (environmental conditions: 25±0.5℃, relative humidity (90±2)%) is about 0.01g/m² ･ Below 24h, according to JIS-K7126 (2006), the oxygen permeability is about 0.01mL/m² ･24h･atm or less, the resistivity is 1×10¹² Ω･cm or more, and the light transmittance is in the visible light region About 80% or more, preferably an insulating film with gas barrier properties and light permeability.

作為氣體阻隔層之形成材料，若為可抑制導致有機EL元件的劣化，例如可抑制水或氧等氣體對有機EL元件的浸入之材料即可，可使用任意材料。As the material for forming the gas barrier layer, any material may be used as long as it can suppress the deterioration of the organic EL element, for example, the infiltration of gas such as water or oxygen into the organic EL element.

例如可為由氧化矽、氮化矽、氮氧化矽、碳化矽、碳氧化矽、氧化鋁、氮化鋁、氧化鈦、氧化鋯、氧化鈮、氧化鉬等無機材料所成的被膜所構成，以將氮化矽或氧化矽等矽化合物作為主原料之構成為佳。For example, it can be composed of a film made of inorganic materials such as silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, aluminum oxide, aluminum nitride, titanium oxide, zirconium oxide, niobium oxide, molybdenum oxide, etc. It is better to use silicon compounds such as silicon nitride or silicon oxide as the main raw material.

作為氣體阻隔層之形成方法，可使用適宜地選自過去公知的成膜方法，例如可使用真空蒸鍍法、濺射法、磁控管濺射法、分子束外延法、團簇離子束法、離子電鍍法、電漿聚合法、大氣壓電漿聚合法(參照日本特開2004-68143號公報)、電漿CVD(Chemical Vapor Deposition)法、雷射CVD法、熱CVD法、ALD(原子層堆積)法又聚矽氮烷等濕式塗布法為適用。As a method of forming the gas barrier layer, a film-forming method suitably selected from conventionally known film formation methods can be used. For example, a vacuum vapor deposition method, a sputtering method, a magnetron sputtering method, a molecular beam epitaxy method, and a cluster ion beam method can be used. , Ion plating method, plasma polymerization method, atmospheric piezoelectric plasma polymerization method (refer to JP 2004-68143), plasma CVD (Chemical Vapor Deposition) method, laser CVD method, thermal CVD method, ALD (atomic layer) Stacking) method and wet coating method such as polysilazane are suitable.

(第1電極：陽極)作為構成有關本發明之有機EL元件的第1電極，可舉出Ag、Au等金屬或將金屬作為主成分的合金、CuI，或銦-錫的複合氧化物(ITO)、SnO₂及ZnO等金屬氧化物，但以金屬或將金屬作為主成分的合金者為佳，更佳為銀或將銀作為主成分之合金。(First electrode: anode) As the first electrode constituting the organic EL element of the present invention, metals such as Ag and Au, alloys containing metals as the main component, CuI, or indium-tin composite oxides (ITO ), SnO₂ and ZnO and other metal oxides, but preferably metals or alloys containing metals as the main component, and more preferably silver or alloys containing silver as the main component.

當第1電極為透明電極時，將銀作為主成分而構成，作為銀之純度，以99%以上者為佳。又，欲確保銀的穩定性，亦可添加鈀(Pd)、銅(Cu)及金(Au)等。When the first electrode is a transparent electrode, it is composed of silver as the main component, and the purity of silver is preferably 99% or more. In addition, in order to ensure the stability of silver, palladium (Pd), copper (Cu), gold (Au), etc. may be added.

第1電極雖為將銀作為主成分而構成的層，但具體可單獨由銀所形成，或亦可由含有銀(Ag)的合金而構成。作為如此合金，例如可舉出銀-鎂(Ag-Mg)、銀-銅(Ag-Cu)、銀-鈀(Ag-Pd)、銀-鈀-銅(Ag-Pd-Cu)、銀-銦(Ag-In)等。Although the first electrode is a layer composed of silver as a main component, specifically, it may be composed of silver alone, or may be composed of an alloy containing silver (Ag). As such alloys, for example, silver-magnesium (Ag-Mg), silver-copper (Ag-Cu), silver-palladium (Ag-Pd), silver-palladium-copper (Ag-Pd-Cu), silver- Indium (Ag-In) and so on.

(中間電極)對於有關本發明之有機EL元件，於陽極(第1電極)與陰極(第2電極)之間，具有層合2個以上有機功能層單元的結構，將二個以上有機功能層單元間，可設計為藉由具有欲電連接的獨立連接端子之中間電極層單元而分離的結構。(Middle electrode)For the organic EL element of the present invention, there is a structure in which two or more organic functional layer units are laminated between the anode (first electrode) and the cathode (second electrode). Designed as a structure separated by intermediate electrode layer units with independent connection terminals to be electrically connected.

(有機功能層群7)其次，對於構成有機功能層群之各層，依據電荷注入層、發光層、電洞輸送層、電子輸送層及阻擋層的順序進行說明。(Organic functional layer group 7)Next, the layers constituting the organic functional layer group will be described in the order of the charge injection layer, the light emitting layer, the hole transport layer, the electron transport layer, and the barrier layer.

＜電荷注入層＞可適用於本發明的電荷注入層，因欲使驅動電壓降低或使發光亮度提高，其為設置於電極與發光層之間的層，於「有機EL元件與該工業化最前線(1998年11月30日NTS公司發行)」之第2編第2章「電極材料」(123～166頁)中有詳細記載，有電洞注入層與電子注入層。＜Charge injection layer＞The charge injection layer applicable to the present invention is a layer provided between the electrode and the light-emitting layer in order to reduce the driving voltage or increase the light-emitting brightness. It was used in "Organic EL Devices and the Forefront of Industrialization (November 1998). Issued by NTS Corporation on the 30th)"Chapter 2 "Electrode Materials" (pages 123 to 166) of "Volume 2" contains detailed descriptions of hole injection layer and electron injection layer.

作為電荷注入層，一般而言，若為電洞注入層，可存在於陽極與發光層或電洞輸送層之間，若為電子注入層，可存在於第2電極與發光層或電子輸送層之間，但對於本發明，以鄰接於透明電極而配置電荷注入層者為特徵。又，在中間電極使用時，鄰接的電子注入層及電洞注入層之至少一方僅滿足本發明之要件者即可。As a charge injection layer, generally speaking, if it is a hole injection layer, it can exist between the anode and the light emitting layer or hole transport layer, and if it is an electron injection layer, it can exist between the second electrode and the light emitting layer or electron transport layer. However, the present invention is characterized by a charge injection layer arranged adjacent to the transparent electrode. In addition, when the intermediate electrode is used, at least one of the adjacent electron injection layer and hole injection layer only needs to satisfy the requirements of the present invention.

有關本發明之電洞注入層，欲使驅動電壓降低或使發光亮度提高，其為鄰接於作為第1電極的陽極而配置的層，於「有機EL元件與該工業化最前線(1998年11月30日NTS公司發行)」之第2編第2章「電極材料」(123～166頁)中有詳細記載。The hole injection layer of the present invention is a layer arranged adjacent to the anode as the first electrode in order to reduce the driving voltage or increase the luminescence brightness. It was published in "Organic EL Devices and the Frontline of Industrialization (November 1998) The 30th NTS company issued)"Chapter 2 "Electrode Materials" (123 ~ 166) in the second chapter.

有關電洞注入層亦於日本特開平9-45479號公報、同9-260062號公報、同8-288069號公報等有詳細記載，作為使用於電洞注入層的材料，例如可舉出卟啉衍生物、酞菁衍生物、噁唑衍生物、噁二唑衍生物、三唑衍生物、咪唑衍生物、吡唑啉衍生物、吡唑啉酮衍生物、伸苯二胺衍生物、腙衍生物、芪衍生物、聚芳基烷烴衍生物、三芳基胺衍生物、咔唑衍生物、吲哚並咔唑衍生物、異吲哚衍生物、蒽或萘等並苯(Acene)系衍生物、芴衍生物、芴酮衍生物及聚乙烯咔唑、將芳香族胺導入於主鏈或側鏈的高分子材料或寡聚物、聚矽烷、導電性聚合物或寡聚物(例如PEDOT(聚乙烯二氧噻吩)：PSS(聚苯乙烯磺酸)、苯胺系共聚物、聚苯胺、聚噻吩等)等。The hole injection layer is also described in detail in Japanese Patent Laid-Open No. 9-45479, No. 9-260062, No. 8-288069, etc. As a material used for the hole injection layer, for example, porphyrin Derivatives, phthalocyanine derivatives, oxazole derivatives, oxadiazole derivatives, triazole derivatives, imidazole derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, hydrazone derivatives Compounds, stilbene derivatives, polyarylalkane derivatives, triarylamine derivatives, carbazole derivatives, indolocarbazole derivatives, isoindole derivatives, anthracene or naphthalene and other acene derivatives , Fluorene derivatives, fluorenone derivatives and polyvinyl carbazole, high molecular materials or oligomers that introduce aromatic amines into the main chain or side chains, polysilane, conductive polymers or oligomers (such as PEDOT( Polyethylenedioxythiophene): PSS (polystyrene sulfonic acid), aniline copolymer, polyaniline, polythiophene, etc.).

作為三芳基胺衍生物，可舉出α-NPD(4,4’-雙[N-(1-萘)-N-苯基胺基]聯苯基)做代表的聯苯胺型，或MTDATA(4,4’,4”-參[N-(3-甲基苯基)-N-苯基胺基]三苯基胺)做代表的星爆型，於三芳基胺連結核心部具有芴或蒽之化合物等。Examples of triarylamine derivatives include benzidine type represented by α-NPD (4,4'-bis[N-(1-naphthalene)-N-phenylamino]biphenyl), or MTDATA( 4,4',4”-[N-(3-methylphenyl)-N-phenylamino]triphenylamine) represented by starburst type, with fluorene or Anthracene compounds, etc.

又，如日本特表2003-519432號公報或日本特開2006-135145號公報等所記載的六氮雜三亞苯衍生物亦同樣地可作為電洞輸送材料使用。Furthermore, hexaazatriphenylene derivatives as described in Japanese Patent Application Publication No. 2003-519432 or Japanese Patent Application Publication No. 2006-135145 can also be used as hole transport materials in the same way.

電子注入層為，欲使驅動電壓降低或使發光亮度提高，設置於第2電極與發光層之間的層，第2電極若為以有關本發明的透明電極所構成時，設置在鄰接該透明電極上，於「有機EL元件與該工業化最前線(1998年11月30日NTS公司發行)」之第2編第2章「電極材料」(123～166頁)有詳細記載。The electron injection layer is a layer provided between the second electrode and the light-emitting layer in order to lower the driving voltage or increase the light-emitting brightness. If the second electrode is composed of the transparent electrode according to the present invention, it is provided adjacent to the transparent electrode. The electrode is described in detail inChapter 2 "Electrode Materials" (Pages 123 to 166) inChapter 2 of "Organic EL Elements and the Forefront of Industrialization (published by NTS Corporation on November 30, 1998)".

電子注入層亦於日本特開平6-325871號公報、同9-17574號公報、同10-74586號公報等有詳細記載，作為使用於電子注入層的較佳材料之具體例子，可舉出鍶或鋁等作為代表的金屬、氟化鋰、氟化鈉、氟化鉀等作為代表的鹼金屬化合物、氟化鎂、氟化鈣等作為代表的鹼金屬鹵化物層、氟化鎂作為代表的鹼土類金屬化合物層、氧化鉬、氧化鋁等作為代表的金屬氧化物、鋰8-羥基喹啉鹽(Liq)等作為代表的金屬錯合物等。又，本發明中之透明電極為第2電極時，使用金屬錯合物等有機材料為特佳。電子注入層以非常薄的膜者為佳，雖取決於構成材料，但該層厚以1nm～10μm之範圍為佳。The electron injection layer is also described in detail in Japanese Patent Laid-Open No. 6-325871, No. 9-17574, No. 10-74586, etc. As a specific example of a preferred material for the electron injection layer, strontium can be cited. Or metals such as aluminum, lithium fluoride, sodium fluoride, potassium fluoride, etc. as representative alkali metal compounds, magnesium fluoride, calcium fluoride, etc. as representative alkali metal halide layers, and magnesium fluoride as representative Alkaline earth metal compound layers, metal oxides represented by molybdenum oxide, aluminum oxide, and the like, metal complexes represented by lithium 8-quinolinolate (Liq), and the like. Furthermore, when the transparent electrode in the present invention is the second electrode, it is particularly preferable to use an organic material such as a metal complex. The electron injection layer is preferably a very thin film. Although it depends on the constituent material, the thickness of the layer is preferably in the range of 1 nm to 10 μm.

對於本發明，作為電子注入層之形成方法，例如可舉出使用塗布法、噴墨法、塗敷法、浸漬法等濕式塗布法，或使用蒸鍍法(抵抗加熱、EB法等)、濺射法、CVD法等乾式製程的方法等可舉出，但對於本發明之圖像顯示構件之製造方法，於所形成的隔壁(bank)內使用濕式塗布法而形成的方法為佳，以濕式塗布法為噴墨印刷法者為更佳。In the present invention, as a method of forming the electron injection layer, for example, wet coating methods such as coating method, inkjet method, coating method, dipping method, etc., or vapor deposition method (heat resistance, EB method, etc.) are used, The sputtering method, CVD method and other dry process methods can be exemplified, but for the method of manufacturing the image display member of the present invention, a method of forming a bank using a wet coating method is preferred. It is better to use the wet coating method as the inkjet printing method.

＜發光層＞構成有關本發明的有機EL元件之有機功能層單元的發光層，以含有作為發光材料之磷光發光化合物的構成為佳。＜Light-emitting layer＞The light-emitting layer constituting the organic functional layer unit of the organic EL device of the present invention preferably contains a phosphorescent light-emitting compound as a light-emitting material.

該發光層為，由電極或電子輸送層所注入的電子，與由電洞輸送層所注入的電洞進行再結合而發光的層，發光部分為發光層之層內，亦可為與發光層鄰接的層之界面。The light-emitting layer is a layer that recombines electrons injected from the electrode or the electron transport layer with the holes injected from the hole transport layer to emit light. The light-emitting part is in the layer of the light-emitting layer, or it can be combined with the light-emitting layer. The interface of adjacent layers.

作為如此發光層，若所含的發光材料能滿足發光要件，對於該構成並無特別限制。又，具有相同的發光光線譜或發光極大波長的層可為複數層。此時，於各發光層間具有非發光性之中間層者為佳。As such a light-emitting layer, if the contained light-emitting material satisfies the light-emitting requirements, there is no particular restriction on the composition. In addition, the layers having the same emission light spectrum or maximum emission wavelength may be plural layers. In this case, it is preferable to have a non-luminous intermediate layer between the light-emitting layers.

發光層之厚度總和以1～100nm之範圍內者為佳，因可得到較低驅動電壓，故在1～30nm之範圍內者為更佳。且，所謂發光層之厚度總和表示，在於發光層間存在非發光性之中間層時，其為亦含有該中間層之厚度。經層合的複數發光層若對應各藍、綠及紅之發光色時，對於藍、綠及紅之各發光層的厚度關係並無特別限制。The total thickness of the light-emitting layer is preferably in the range of 1-100 nm, and since a lower driving voltage can be obtained, it is more preferably in the range of 1-30 nm. In addition, the total thickness of the light-emitting layer means that when a non-luminescent intermediate layer exists between the light-emitting layers, it is the thickness that also includes the intermediate layer. When the laminated plural light-emitting layers correspond to the respective blue, green, and red light-emitting colors, there is no particular limitation on the thickness relationship of the blue, green, and red light-emitting layers.

如以上所示，發光層為將後述的發光材料或主體化合物，例如可藉由真空蒸鍍法、旋轉塗布法、澆鑄法、LB法(Langmuir Blodgett噴射法)及噴墨印刷法等公知方法而形成，但對於本發明之圖像顯示構件之製造方法，以於所形成的隔壁(bank)內使用濕式塗布法而形成發光層的方法為佳，以濕式塗布法為噴墨印刷法者為更佳。As shown above, the light-emitting layer is a light-emitting material or host compound described later, for example, it can be formed by a known method such as a vacuum evaporation method, a spin coating method, a casting method, an LB method (Langmuir Blodgett spray method), and an inkjet printing method. However, for the manufacturing method of the image display member of the present invention, a wet coating method is preferably used to form a light emitting layer in the formed bank, and the wet coating method is the inkjet printing method. For better.

又，發光層可為混合複數種發光材料，亦可將磷光發光材料與螢光發光材料(亦稱為螢光摻合物、螢光性化合物)在同一發光層中進行混合後使用。作為發光層之構成，含有主體化合物(亦稱為發光主體等)及發光材料(亦稱為發光摻合物)，藉由發光材料使其發光者為佳。In addition, the light-emitting layer may be a mixture of multiple types of light-emitting materials, or a phosphorescent light-emitting material and a fluorescent light-emitting material (also referred to as a fluorescent blend or a fluorescent compound) may be mixed in the same light-emitting layer. As the structure of the light-emitting layer, it contains a host compound (also called a light-emitting host, etc.) and a light-emitting material (also called a light-emitting blend), and it is preferable to use a light-emitting material to make it emit light.

＜主體化合物＞作為含於發光層的主體化合物，以在室溫(25℃)中之磷光發光的磷光量子產率未達0.1的化合物為佳。磷光量子產率未達0.01者為更佳。又，在含於發光層的化合物之中，在該層中的體積比以50%以上者為佳。＜Host compound＞As the host compound contained in the light-emitting layer, a compound whose phosphorescence quantum yield of phosphorescence at room temperature (25°C) is less than 0.1 is preferred. It is better if the phosphorescence quantum yield is less than 0.01. In addition, among the compounds contained in the light-emitting layer, the volume ratio in the layer is preferably 50% or more.

作為主體化合物，可單獨使用公知的主體化合物，或亦可使用複數種主體化合物。藉由使用複數種主體化合物，可調整電荷之移動，可使有機電場發光元件高效率化。又，藉由使用後述複數種發光材料，相異發光的混合變得可能，藉此可得到任意發光色。As the host compound, a known host compound may be used alone, or a plurality of host compounds may also be used. By using a plurality of host compounds, the movement of charges can be adjusted, and the efficiency of the organic electroluminescent device can be improved. In addition, by using a plurality of types of luminescent materials described later, it is possible to mix different luminescence, thereby obtaining arbitrary luminous colors.

作為使用於發光層的主體化合物，可為過去公知的低分子化合物，亦可為具有重複單元的高分子化合物，又亦可為具有如乙烯基或環氧基的聚合性基的低分子化合物(蒸鍍聚合性發光主體)。The host compound used in the light-emitting layer may be a conventionally known low-molecular compound, a high-molecular compound having a repeating unit, or a low-molecular compound having a polymerizable group such as a vinyl group or an epoxy group ( Evaporation of polymerizable light-emitting host).

作為可適用於本發明的主體化合物，例如可舉出日本特開2001-257076號公報、同2002-308855號公報、同2001-313179號公報、同2002-319491號公報、同2001-357977號公報、同2002-334786號公報、同2002-8860號公報、同2002-334787號公報、同2002-15871號公報、同2002-334788號公報、同2002-43056號公報、同2002-334789號公報、同2002-75645號公報、同2002-338579號公報、同2002-105445號公報、同2002-343568號公報、同2002-141173號公報、同2002-352957號公報、同2002-203683號公報、同2002-363227號公報、同2002-231453號公報、同2003-3165號公報、同2002-234888號公報、同2003-27048號公報、同2002-255934號公報、同2002-260861號公報、同2002-280183號公報、同2002-299060號公報、同2002-302516號公報、同2002-305083號公報、同2002-305084號公報、同2002-308837號公報、美國專利公開第2003/0175553號說明書、美國專利公開第2006/0280965號說明書、美國專利公開第2005/0112407號說明書、美國專利公開第2009/0017330號說明書、美國專利公開第2009/0030202號說明書、美國專利公開第2005/238919號說明書、國際公開第2001/039234號、國際公開第2009/021126號、國際公開第2008/056746號、國際公開第2004/093207號、國際公開第2005/089025號、國際公開第2007/063796號、國際公開第2007/063754號、國際公開第2004/107822號、國際公開第2005/030900號、國際公開第2006/114966號、國際公開第2009/086028號、國際公開第2009/003898號、國際公開第2012/023947號、日本特開2008-074939號公報、日本特開2007-254297號公報、歐洲專利第2034538號說明書等所記載的化合物。As the host compound applicable to the present invention, for example, Japanese Patent Laid-Open No. 2001-257076, No. 2002-308855, No. 2001-313179, No. 2002-319491, No. 2001-357977 can be cited. , Same as 2002-334786, same 2002-8860, same 2002-334787, same 2002-15871, same 2002-334788, same 2002-43056, same 2002-334789, Same as 2002-75645, same 2002-338579, same 2002-105445, same 2002-343568, same 2002-141173, same 2002-352957, same 2002-203683, same 2002-363227, same 2002-231453, same 2003-3165, same 2002-234888, same 2003-27048, same 2002-255934, same 2002-260861, same 2002 -280183, the same 2002-299060, the same 2002-302516, the same 2002-305083, the same 2002-305084, the same 2002-308837, the specification of U.S. Patent Publication No. 2003/0175553, U.S. Patent Publication No. 2006/0280965 Specification, U.S. Patent Publication No. 2005/0112407 Specification, U.S. Patent Publication No. 2009/0017330 Specification, U.S. Patent Publication No. 2009/0030202 Specification, U.S. Patent Publication No. 2005/238919 Specification, International Publication No. 2001/039234, International Publication No. 2009/021126, International Publication No. 2008/056746, International Publication No. 2004/093207, International Publication No. 2005/089025, International Publication No. 2007/063796, International Publication No. 2007/063754, International Publication No. 2004/107822, International Publication No. 2005/030900, International Publication No. 2006/114966, International Publication No. 2009/086028, International Publication No. 2009/003898, International Publication No. 2012 /023947, Japanese Patent Application Publication No. 2008-074939, Japanese Patent Application Publication No. 2007-254297, European Patent No. 2034538, etc.

＜發光材料＞作為可在本發明使用的發光材料，可舉出磷光發光性化合物(亦稱為磷光性化合物、磷光發光材料或磷光發光摻合物)及螢光發光性化合物(亦稱為螢光性化合物或螢光發光材料)。＜Luminescent material＞As the luminescent material that can be used in the present invention, a phosphorescent compound (also called a phosphorescent compound, a phosphorescent luminescent material, or a phosphorescent blend) and a fluorescent compound (also called a fluorescent compound or Fluorescent materials).

＜磷光發光性化合物＞所謂磷光發光性化合物為，觀測到由激起三重態之發光的化合物，具體為在室溫(25℃)下使磷光發光的化合物，被定義為磷光量子產率在25℃時為0.01以上的化合物者，較佳為磷光量子產率為0.1以上者。＜Phosphorescent compound＞The so-called phosphorescent compound is a compound in which luminescence from a triplet state is observed, specifically, a compound that causes phosphorescence to emit light at room temperature (25°C), and is defined as a phosphorescent quantum yield of 0.01 or more at 25°C The compound is preferably a phosphorescent quantum yield of 0.1 or more.

上述磷光量子產率可藉由第4版實驗化學講座7之分光II的398頁(1992年版、丸善)所記載的方法進行測定。在溶液中之磷光量子產率，可使用種種溶劑而測定，但對於本發明，使用磷光發光性化合物時，對於所有任意溶劑，作為上述磷光量子產率可達成0.01以上者即可。The aforementioned phosphorescence quantum yield can be measured by the method described on page 398 (1992 edition, Maruzen) of Spectroscopy II ofLecture 7 of Experimental Chemistry, 4th Edition. The phosphorescence quantum yield in the solution can be measured using various solvents. However, in the present invention, when the phosphorescence light-emitting compound is used, for any arbitrary solvent, the phosphorescence quantum yield can be 0.01 or more.

磷光發光性化合物為可使用適宜地選自使用於一般有機EL元件的發光層之公知者，較佳為含有在元素的周期表中的8～10族之金屬的錯合物系化合物，更佳為銥化合物、鋨化合物、鉑化合物(鉑錯合物系化合物)或稀土類錯合物，其中最佳為銥化合物。The phosphorescent light-emitting compound is a known one that can be suitably selected from the light-emitting layer used in general organic EL devices, and is preferably a complex compound containing a metal ofgroups 8 to 10 in the periodic table of the elements, more preferably It is an iridium compound, an osmium compound, a platinum compound (platinum complex compound) or a rare earth complex compound, of which the iridium compound is the best.

對於本發明，至少一個發光層含有二種以上磷光發光性化合物亦可，於發光層中之磷光發光性化合物的濃度比會因發光層的厚度方向而變化之態樣亦可。In the present invention, at least one light-emitting layer may contain two or more phosphorescent compounds, and the concentration ratio of the phosphorescent compound in the light-emitting layer may vary depending on the thickness direction of the light-emitting layer.

作為可使用於本發明的公知磷光發光性化合物之具體例子，可舉出以下文獻所記載的化合物等。Specific examples of known phosphorescent compounds that can be used in the present invention include compounds described in the following documents and the like.

Nature 395, 151 (1998)、Appl. Phys. Lett. 78, 1622 (2001)、Adv. Mater. 19, 739 (2007)、Chem. Mater. 17, 3532 (2005)、Adv. Mater. 17, 1059 (2005)、國際公開第2009/100991號、國際公開第2008/101842號、國際公開第2003/040257號、美國專利公開第2006/835469號說明書、美國專利公開第2006/0202194號說明書、美國專利公開第2007/0087321號說明書、美國專利公開第2005/0244673號說明書等所記載的化合物可舉出。Nature 395, 151 (1998), Appl. Phys. Lett. 78, 1622 (2001), Adv. Mater. 19, 739 (2007), Chem. Mater. 17, 3532 (2005), Adv. Mater. 17, 1059 (2005), International Publication No. 2009/100991, International Publication No. 2008/101842, International Publication No. 2003/040257, U.S. Patent Publication No. 2006/835469 Specification, U.S. Patent Publication No. 2006/0202194 Specification, U.S. Patent The compounds described in Publication No. 2007/0087321, U.S. Patent Publication No. 2005/0244673, etc. can be cited.

又，可舉出Inorg. Chem. 40, 1704 (2001)、Chem. Mater. 16, 2480 (2004)、Adv. Mater. 16, 2003 (2004)、Angew. Chem. lnt. Ed. 2006, 45, 7800、Appl. Phys. Lett. 86, 153505 (2005)、Chem. Lett. 34, 592 (2005)、Chem. Commun. 2906 (2005)、Inorg. Chem. 42, 1248 (2003)、國際公開第2009/050290號、國際公開第2002/015645號、國際公開第2009/000673號、美國專利公開第2002/0034656號說明書、美國專利第7332232號說明書、美國專利公開第2009/0108737號說明書、美國專利公開第2009/0039776號、美國專利第6921915號、美國專利第6687266號說明書、美國專利公開第2007/0190359號說明書、美國專利公開第2006/0008670號說明書、美國專利公開第2009/0165846號說明書、美國專利公開第2008/0015355號說明書、美國專利第7250226號說明書、美國專利第7396598號說明書、美國專利公開第2006/0263635號說明書、美國專利公開第2003/0138657號說明書、美國專利公開第2003/0152802號說明書、美國專利第7090928號說明書等所記載的化合物。Also, Inorg. Chem. 40, 1704 (2001), Chem. Mater. 16, 2480 (2004), Adv. Mater. 16, 2003 (2004), Angew. Chem. lnt. Ed. 2006, 45, 7800, Appl. Phys. Lett. 86, 153505 (2005), Chem. Lett. 34, 592 (2005), Chem. Commun. 2906 (2005), Inorg. Chem. 42, 1248 (2003), International Publication No. 2009 /050290, International Publication No. 2002/015645, International Publication No. 2009/000673, U.S. Patent Publication No. 2002/0034656 Specification, U.S. Patent No. 7332232 Specification, U.S. Patent Publication No. 2009/0108737 Specification, U.S. Patent Publication No. 2009/0039776, U.S. Patent No. 6921915, U.S. Patent No. 6687266 Specification, U.S. Patent Publication No. 2007/0190359 Specification, U.S. Patent Publication No. 2006/0008670 Specification, U.S. Patent Publication No. 2009/0165846 Specification, U.S. Patent Publication No. 2008/0015355 Specification, U.S. Patent No. 7250226 Specification, U.S. Patent No. 7396598 Specification, U.S. Patent Publication No. 2006/0263635 Specification, U.S. Patent Publication No. 2003/0138657 Specification, U.S. Patent Publication No. 2003/0152802 No. specification, US Patent No. 7090928 specification, etc.

對於本發明，作為較佳磷光發光性化合物，可舉出含有將Ir作為中心金屬的有機金屬錯合物。更佳為含有金屬-碳鍵結、金屬-氮鍵結、金屬-氧鍵結、金屬-硫鍵結之至少一個配位樣式的錯合物。In the present invention, as a preferred phosphorescent compound, an organometallic complex containing Ir as a central metal can be cited. More preferably, it is a complex containing at least one coordination pattern of metal-carbon bonding, metal-nitrogen bonding, metal-oxygen bonding, and metal-sulfur bonding.

上述說明的磷光發光性化合物(亦稱為磷光發光性金屬錯合物)，例如可使用如Organic Letter誌、vol3、No.16、2579～2581頁(2001)、Inorganic Chemistry,第30卷、第8號、1685～1687頁(1991年)、J. Am. Chem. Soc., 123卷、4304頁(2001年)、Inorganic Chemistry，第40卷、第7號、1704～1711頁(2001年)、Inorganic Chemistry，第41卷、第12號、3055～3066頁(2002年)、New Journal of Chemistry.，第26卷、1171頁(2002年)、European Journal of Organic Chemistry，第4卷、695～709頁(2004年)，以及這些文獻中所記載的參考文獻等所揭示的方法而進行合成。The phosphorescent compounds (also called phosphorescent metal complexes) described above can be used, for example, Organic Letters, vol3, No. 16, pages 2579-2581 (2001), Inorganic Chemistry, Vol. 30, No. No. 8, pages 1685-1687 (1991), J. Am. Chem. Soc., Volume 123, pages 4304 (2001), Inorganic Chemistry, Volume 40, No. 7, pages 1704-1711 (2001) , Inorganic Chemistry, Volume 41, No. 12, 3055-3066 pages (2002), New Journal of Chemistry.,Volume 26, pages 1171 (2002), European Journal of Organic Chemistry, Volume 4, 695- 709 pages (2004), and the methods disclosed in the references in these documents.

＜螢光發光性化合物＞作為螢光發光性化合物，可舉出香豆素系色素、吡喃系色素、花菁系色素、克酮酸鹽系色素、季鎓鹽系色素、氧代苯並蒽系色素、熒光素色素、羅丹明系色素、吡喃鎓系色素、苝系色素、芪系色素、聚噻吩系色素或稀土類錯合物系螢光體等。＜Fluorescent compounds＞Examples of fluorescent compounds include coumarin-based pigments, pyran-based pigments, cyanine-based pigments, croconate-based pigments, quaternary onium salt-based pigments, oxobenzoanthracene-based pigments, and fluorescein pigments. , Rhodamine pigments, pyrylium pigments, perylene pigments, stilbene pigments, polythiophene pigments, or rare earth complex phosphors.

＜電洞輸送層＞所謂電洞輸送層表示由具有輸送電洞的功能之電洞輸送材料所成，廣泛意思為，電洞注入層及電子阻擋層亦具有電洞輸送層之功能。可設置單層或複數層的電洞輸送層。＜Hole transport layer＞The so-called hole transport layer refers to a hole transport material that has the function of transporting holes, and broadly means that the hole injection layer and the electron blocking layer also have the function of the hole transport layer. A single layer or multiple layers of hole transport layer can be set.

作為電洞輸送材料，其為具有電洞的注入或輸送、電子的障壁性中任一種者，有機物、無機物中任一種皆可。例如可舉出三唑衍生物、噁二唑衍生物、咪唑衍生物、聚芳基烷烴衍生物、吡唑啉衍生物、吡唑啉酮衍生物、伸苯二胺衍生物、芳基胺衍生物、胺基取代查耳酮衍生物、噁唑衍生物、苯乙烯蒽衍生物、芴酮衍生物、腙衍生物、芪衍生物、矽氮烷衍生物、苯胺系共聚物、導電性高分子寡聚物及噻吩寡聚物等。As the hole transport material, it can be any one of hole injection or transport, and electron barrier properties, and it may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives Compounds, amine substituted chalcone derivatives, oxazole derivatives, styrene anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, conductive polymers Oligomers and thiophene oligomers, etc.

作為電洞輸送材料，可使用上述者，亦可使用卟啉化合物、芳香族第3級胺化合物及苯乙烯胺化合物，特別以使用芳香族第3級胺化合物者為佳。As the hole transport material, the above-mentioned ones can be used, and porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds can also be used, and it is particularly preferable to use aromatic tertiary amine compounds.

作為芳香族第3級胺化合物及苯乙烯胺化合物的代表例，可舉出N,N,N’,N’-四苯基-4,4’-二胺基苯基、N,N’-二苯基-N,N’-雙(3-甲基苯基)-[1,1’-聯苯基]-4,4’-二胺(簡稱：TPD)、2,2-雙(4-二-p-甲苯胺基苯基)丙烷、1,1-雙(4-二-p-甲苯胺基苯基)環己烷、N,N,N’,N’-四-p-甲苯-4,4’-二胺基聯苯基、1,1-雙(4-二-p-甲苯胺基苯基)-4-苯基環己烷、雙(4-二甲基胺基-2-甲基苯基)苯基甲烷、雙(4-二-p-甲苯胺基苯基)苯基甲烷、N,N’-二苯基-N,N’-二(4-甲氧基苯基)-4,4’-二胺基聯苯基、N,N,N’,N’-四苯基-4,4’-二胺基二苯基醚、4,4’-雙(二苯基胺基)四聯苯基(Quadriphenyl)、N,N,N-三(p-甲苯)胺、4-(二-p-甲苯胺基)-4’-[4-(二-p-甲苯胺基)苯乙烯]芪、4-N,N-二苯基胺基-(2-二苯基乙烯基)苯、3-甲氧基-4’-N,N-二苯基胺基乙基苯及N-苯基咔唑等。Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N,N,N',N'-tetraphenyl-4,4'-diaminophenyl, N,N'- Diphenyl-N,N'-bis(3-methylphenyl)-[1,1'-biphenyl]-4,4'-diamine (abbreviation: TPD), 2,2-bis(4 -Di-p-tolylphenyl)propane, 1,1-bis(4-di-p-tolylphenyl)cyclohexane, N,N,N',N'-tetra-p-toluene -4,4'-diaminobiphenyl, 1,1-bis(4-di-p-tolylinylphenyl)-4-phenylcyclohexane, bis(4-dimethylamino- 2-methylphenyl)phenylmethane, bis(4-bis-p-tolylphenyl)phenylmethane, N,N'-diphenyl-N,N'-bis(4-methoxy Phenyl)-4,4'-diaminobiphenyl, N,N,N',N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis( Diphenylamino) tetrabiphenyl (Quadriphenyl), N,N,N-tris(p-toluene)amine, 4-(di-p-tolylamine)-4'-[4-(di-p -Tolyl)styrene)stilbene, 4-N,N-diphenylamino-(2-diphenylvinyl)benzene, 3-methoxy-4'-N,N-diphenylamine Base ethylbenzene and N-phenylcarbazole, etc.

作為電洞輸送層之形成方法，例如可舉出塗布法、噴墨印刷法、塗布法、浸漬法等之濕式塗布法，或蒸鍍法(抵抗加熱、EB法等)、濺射法、CVD法等使用乾式製程的方法等，對於本發明之圖像顯示構件之製造方法，對於所形成的隔壁(bank)內使用濕式塗布法而形成的方法為佳，以濕式塗布法為噴墨印刷法者為更佳。Examples of methods for forming the hole transport layer include wet coating methods such as coating method, inkjet printing method, coating method, dipping method, etc., or vapor deposition method (heat resistance, EB method, etc.), sputtering method, The CVD method and other methods that use a dry process, etc. For the manufacturing method of the image display member of the present invention, it is preferable to use a wet coating method in the formed bank. The wet coating method is a spray method. The ink printing method is better.

對於電洞輸送層之層厚並無特別限制，通常為5nm～5μm程度，較佳為5～200nm之範圍。該電洞輸送層亦可為由上述材料的一種或二種以上所成的1層結構。The thickness of the hole transport layer is not particularly limited, and it is usually about 5 nm to 5 μm, preferably in the range of 5 to 200 nm. The hole transport layer may also have a one-layer structure composed of one or two or more of the aforementioned materials.

又，藉由於電洞輸送層的材料摻合雜質，亦可提高p性。作為該例子，可舉出日本特開平4-297076號公報、日本特開2000-196140號公報、同2001-102175號公報及J. Appl. Phys., 95, 5773(2004)等所記載者。In addition, the p property can also be improved by mixing impurities with the material of the hole transport layer. As this example, those described in Japanese Patent Laid-Open No. 4-297076, Japanese Patent Laid-Open No. 2000-196140, 2001-102175, J. Appl. Phys., 95, 5773 (2004), etc. can be cited.

如此，藉由提高電洞輸送層的p性，可製造低消費電力的元件故較佳。In this way, by improving the p property of the hole transport layer, it is preferable to manufacture a device with low power consumption.

＜電子輸送層＞電子輸送層係由具有輸送電子的功能之材料所構成，廣泛意思為電子注入層、電洞阻擋層亦含於電子輸送層。電子輸送層設置為單層結構或複數層的層合結構。＜Electron transport layer＞The electron transport layer is composed of materials that have the function of transporting electrons, which broadly means that the electron injection layer and the hole blocking layer are also included in the electron transport layer. The electron transport layer is provided in a single-layer structure or a laminated structure of multiple layers.

對於單層結構之電子輸送層及層合結構的電子輸送層，作為構成鄰接於發光層的層部分的電子輸送材料(兼作電洞阻止材料)，僅具有將藉由陰極被注入的電子傳達至發光層的功能者即可。作為如此材料，可選自過去公知化合物之中的任意者而使用。例如可舉出硝基取代芴衍生物、二苯基醌衍生物、硫代吡喃二氧化物衍生物、碳二亞胺、亞芴甲烷衍生物、蒽醌二甲烷、蒽酮衍生物及噁二唑衍生物等。且對於上述噁二唑衍生物，將噁二唑環的氧原子由硫原子所取代的噻二唑衍生物、具有作為電子吸引基而已知的喹喔啉環之喹喔啉衍生物亦可作為電子輸送層的材料而使用。且可使用將這些材料導入於高分子鏈的高分子材料，或將這些材料作為高分子的主鏈之高分子材料。For the electron transport layer of the single-layer structure and the electron transport layer of the laminated structure, as the electron transport material (also serving as the hole blocking material) constituting the layer portion adjacent to the light-emitting layer, only the electrons injected by the cathode are transmitted to The function of the light-emitting layer is sufficient. As such a material, any one selected from conventionally known compounds can be used. For example, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorene methane derivatives, anthraquinone dimethane, anthrone derivatives, and oxaquinone derivatives can be cited. Diazole derivatives and so on. For the above-mentioned oxadiazole derivatives, thiadiazole derivatives in which the oxygen atom of the oxadiazole ring is replaced by a sulfur atom, and quinoxaline derivatives having a quinoxaline ring known as an electron attracting group can also be used as Used as the material of the electron transport layer. In addition, a polymer material in which these materials are introduced into the polymer chain, or a polymer material in which these materials are used as the main chain of the polymer can be used.

又，8-羥基喹啉衍生物之金屬錯合物，例如參(8-羥基喹啉)鋁(簡稱：Alq₃)、參(5,7-二氯-8-羥基喹啉)鋁、參(5,7-二溴-8-羥基喹啉)鋁、參(2-甲基-8-羥基喹啉)鋁、參(5-甲基-8-羥基喹啉)鋁、雙(8-羥基喹啉)鋅(簡稱：Znq)等及此等金屬錯合物的中心金屬取代為In、Mg、Cu、Ca、Sn、Ga或Pb的金屬錯合物亦可作為電子輸送層之材料使用。In addition, metal complexes of 8-hydroxyquinoline derivatives, such as ginseng (8-hydroxyquinoline) aluminum (abbreviation: Alq₃ ), ginseng (5,7-dichloro-8-hydroxyquinoline) aluminum, ginseng (5,7-Dibromo-8-hydroxyquinoline) aluminum, ginseng (2-methyl-8-hydroxyquinoline) aluminum, ginseng (5-methyl-8-hydroxyquinoline) aluminum, bis(8- Hydroxyquinoline) zinc (abbreviation: Znq), etc. and metal complexes in which the central metal of these metal complexes is replaced with In, Mg, Cu, Ca, Sn, Ga or Pb can also be used as materials for the electron transport layer .

電子輸送層為，將上述材料，例如藉由含有真空蒸鍍法、旋轉塗布法、澆鑄法、噴墨印刷法的印刷法及LB法等公知方法，使其薄膜化而可形成，但對於本發明之圖像顯示構件之製造方法，於所形成的隔壁(bank)內使用濕式塗布法而形成電子輸送層的方法為佳，以濕式塗布法為噴墨印刷法者為更佳。The electron transport layer can be formed by thinning the above-mentioned material, for example, by a known method including a vacuum vapor deposition method, a spin coating method, a casting method, an inkjet printing method, and a LB method. In the method of manufacturing the image display member of the invention, a wet coating method is preferably used to form an electron transport layer in the formed bank, and the wet coating method is more preferably an inkjet printing method.

對於電子輸送層之層厚並無特別限制，通常為5nm～5μm程度，較佳為5～200nm之範圍內。電子輸送層亦可為由1種或2種以上的上述材料所成的單一結構。The thickness of the electron transport layer is not particularly limited, and is usually about 5 nm to 5 μm, preferably in the range of 5 to 200 nm. The electron transport layer may also have a single structure composed of one or more of the aforementioned materials.

＜阻擋層＞作為阻擋層，可舉出電洞阻擋層及電子阻擋層，除上述說明的有機功能層單元3之各構成層以外，視必要而設置的層。例如可舉出於日本特開平11-204258號公報、同11-204359號公報，及「有機EL元件與該工業化最前線(1998年11月30日NTS公司發行)」的第237頁等所記載的電洞阻止(Hall block)層等。＜Barrier layer＞Examples of the barrier layer include a hole barrier layer and an electron barrier layer, and layers provided as necessary in addition to the constituent layers of the organicfunctional layer unit 3 described above. For example, it can be cited as described in Japanese Patent Laid-Open No. 11-204258, No. 11-204359, and "Organic EL Elements and the Forefront of Industrialization (issued by NTS Corporation on November 30, 1998)" on page 237. The hole blocking (Hall block) layer and so on.

所謂電洞阻擋層，其廣泛意義為具有電子輸送層之功能。電洞阻擋層為，由具有輸送電子的功能，同時輸送電洞的能力為顯著小的電洞阻止材料所成，藉由輸送電子，同時阻擋電洞而可提高電子與電洞之再結合機率。又，將電子輸送層的構成對應需要，可作為電洞阻擋層使用。電洞阻擋層以設置在鄰接發光層者為佳。The so-called hole blocking layer has a broad meaning as having the function of an electron transport layer. The hole blocking layer is made of a hole blocking material that has the function of transporting electrons and the ability to transport holes at the same time. By transporting electrons while blocking holes, the probability of recombination of electrons and holes can be improved. . In addition, the structure of the electron transport layer can be used as a hole blocking layer according to needs. The hole blocking layer is preferably provided adjacent to the light-emitting layer.

另一方面，所謂電子阻擋層，其廣泛意義為具有電洞輸送層之功能。電子阻擋層為，由具有輸送電洞的功能，同時輸送電子的能力為顯著小的材料所成，藉由輸送電洞，同時阻擋電子而可提高電子與電洞之再結合機率確率。又，將電洞輸送層的構成對應需要，可作為電子阻擋層使用。On the other hand, the so-called electron blocking layer has a broad meaning as having the function of a hole transport layer. The electron blocking layer is made of a material that has the function of transporting holes and has a significantly smaller ability to transport electrons. By transporting holes while blocking electrons, the probability of recombination of electrons and holes can be improved. In addition, the structure of the hole transport layer can be used as an electron blocking layer according to needs.

有關本發明的各阻擋層，例如可藉由含有真空蒸鍍法、旋轉塗布法、澆鑄法、噴墨印刷法之印刷法及LB法等公知方法，使其薄膜化而形成，但對於本發明之圖像顯示構件之製造方法，於所形成的隔壁(bank)內使用濕式塗布法而形成阻擋層的方法為佳，以濕式塗布法為噴墨印刷法者為更佳。Each barrier layer of the present invention can be formed by thinning it into a thin film by a known method including a vacuum vapor deposition method, spin coating method, casting method, inkjet printing method, and LB method. In the method of manufacturing the image display member, a wet coating method is preferably used to form a barrier layer in the formed bank, and a wet coating method is more preferably an inkjet printing method.

作為適用於本發明的電洞阻擋層之層厚，以3～100nm之範圍內為佳，更佳為5～30nm之範圍內。The layer thickness of the hole blocking layer suitable for the present invention is preferably in the range of 3 to 100 nm, and more preferably in the range of 5 to 30 nm.

(陰極：第2電極)陰極(第2電極)為，具有欲於有機功能層單元供給電洞的功能之電極膜，使用金屬、合金、有機或無機的導電性化合物，或者這些混合物。具體可舉出金、鋁、銀、鎂、鋰、鎂/銅混合物、鎂/銀混合物、鎂/鋁混合物、鎂/銦混合物、銦、鋰/鋁混合物、稀土類金屬、ITO、ZnO、TiO₂及SnO₂等氧化物半導體等。(Cathode: Second electrode) The cathode (second electrode) is an electrode film having a function of supplying holes to the organic functional layer unit, and uses a metal, alloy, organic or inorganic conductive compound, or a mixture of these. Specific examples include gold, aluminum, silver, magnesium, lithium, magnesium/copper mixture, magnesium/silver mixture, magnesium/aluminum mixture, magnesium/indium mixture, indium, lithium/aluminum mixture, rare earth metals, ITO, ZnO, TiO₂ and SnO₂ and other oxide semiconductors.

第2電極為，將這些導電性材料藉由蒸鍍或濺射等方法形成薄膜而製作。又，作為第2電極的片電阻以數百Ω/sq.以下為佳，膜厚通常為5nm～5μm，以選自5～200nm之範圍內者為佳。The second electrode is produced by forming a thin film of these conductive materials by methods such as vapor deposition or sputtering. In addition, the sheet resistance of the second electrode is preferably several hundred Ω/sq. or less, and the film thickness is usually 5 nm to 5 μm, preferably selected from the range of 5 to 200 nm.

且，有機EL元件在自第2電極側取出發光光線L的頂部發射方式之情況時，選擇如在第1電極所記載的光透過性良好的形成材料，形成第2電極即可。Furthermore, in the case of the organic EL element in the case of the top emission method in which the luminous light L is taken out from the second electrode side, it is sufficient to select a forming material with good light permeability as described in the first electrode to form the second electrode.

[密封構件]其次，對於構成本發明之發光裝置的密封構件做說明。[Sealing member]Next, the sealing member constituting the light emitting device of the present invention will be described.

在圖1及圖2所示第1密封層9及第2密封層10中，發光層因藉由水分會形成暗點或收縮等非發光部，故使用於阻斷水分或氧的功能層。發光層為藉由底部發光型(Bottom emission type)或頂部發光型(Top emission type)，於密封構件所要求的透過率等光學特性會起變化。In thefirst sealing layer 9 and thesecond sealing layer 10 shown in FIGS. 1 and 2, the light-emitting layer is used as a functional layer that blocks moisture or oxygen because it forms dark spots or shrinks and other non-light-emitting parts due to moisture. The light-emitting layer is of a bottom emission type or a top emission type, and optical characteristics such as transmittance required for the sealing member will change.

通常作為密封層之性能，水蒸氣透過度(環境條件：25±0.5℃、相對濕度(90±2)%RH)約0.01g/(m²･day) 以下，氧透過度約0.01cm³/(m²･day･atm)以下，電阻率為1×10¹²Ω･cm以上，具有氣體阻隔性的透明絕緣膜者為佳。特別以氧透過度成為0.0001cm³/(m²･day･atm)以下之值，且水蒸氣透過度成為約0.0001g/(m²･day)以下的值之高阻隔性多層膜所構成者為佳。且，所謂「水蒸氣透過度」為，依據JIS(日本工業規格)-K7129(1992年)，藉由紅外傳感器法所測定的值，所謂「氧透過度」表示依據JIS-K7126 (1987年)藉由庫侖分析法所測定的值。Generally used as the performance of the sealing layer, the water vapor permeability (environmental conditions: 25±0.5℃, relative humidity (90±2)%RH) is below 0.01g/(m² ･day), and the oxygen permeability is about 0.01cm³ / (m² ･day･atm) or less, a resistivity of 1×10¹² Ω･cm or more, and a transparent insulating film with gas barrier properties is preferred. In particular, it is composed of a high-barrier multilayer film whose oxygen permeability is less than 0.0001cm³ /(m² ･day･atm) and water vapor transmission is less than about 0.0001g/(m² ･day) Better. In addition, the so-called "water vapor permeability" is a value measured by infrared sensor method in accordance with JIS (Japanese Industrial Standards)-K7129 (1992), and the so-called "oxygen permeability" means a value in accordance with JIS-K7126 (1987) The value determined by coulometric analysis.

作為上述密封層的形成材料，對於導致有機發光層的劣化之例如水或氧等氣體，可抑制其對有機發光層的浸入之材料即可，可使用任意材料。As a material for the formation of the above-mentioned sealing layer, any material may be used that can inhibit gas such as water or oxygen that causes deterioration of the organic light-emitting layer into the organic light-emitting layer.

例如，作為第1密封層之構成，例如可由氧化矽、氮化矽、氮氧化矽、碳化矽、碳氧化矽、氧化鋁、氮化鋁、氧化鈦、氧化鋯、氧化鈮、氧化鉬等無機材料所成的被膜所構成。對於有機發光層，考慮到氣體阻隔性或透明性、分割時的割斷性等，以密封層由將氮化矽或氧化矽等矽化合物作為主原料的無機材料被膜所構成者為佳。For example, as the composition of the first sealing layer, for example, silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, silicon oxycarbide, aluminum oxide, aluminum nitride, titanium oxide, zirconium oxide, niobium oxide, molybdenum oxide and other inorganic The material is made of a film. For the organic light-emitting layer, in consideration of gas barrier properties, transparency, and severability during division, the sealing layer is preferably composed of an inorganic material film mainly composed of silicon compounds such as silicon nitride or silicon oxide.

且，欲改良密封層之脆弱性，不僅為上述無機材料被膜，可為由與有機材料的複合材料所成的被膜，或亦可為合併層合這些被膜的混合(Hybrid)被膜而構成。此時，由無機材料所成的無機層，及由有機材料所成的有機層之層合順序可為任意，但對於作為有機層/無機層的構成，亦可為將有機層及無機層以交互方式進行複數層合的構成。Moreover, to improve the fragility of the sealing layer, not only the above-mentioned inorganic material film, but also a film made of a composite material with an organic material, or a hybrid film obtained by laminating these films together. At this time, the order of the lamination of the inorganic layer made of inorganic materials and the organic layer made of organic materials can be arbitrary, but for the composition as an organic layer/inorganic layer, the organic layer and the inorganic layer may be The structure of multiple layers is performed interactively.

藉此，可得到具有可迴避有機發光層因水分或氧所造成的損傷之良好阻隔功能的密封層。Thereby, it is possible to obtain a sealing layer with a good barrier function that can avoid damage to the organic light-emitting layer due to moisture or oxygen.

作為圖1及圖2所示第2密封層10，於上述第1密封層9的上層，可進一步設置可施予阻斷水分的第2密封層10。特別在底部發光型(Bottom emission type)之有機EL面板的情況，因於與光的射出方向呈對向的位置上設置有具備防濕性的彩色濾光器層，故形成不需要考慮到金屬箔(例如ALPET等)等光學特性之構成的第2密封層10者為佳。又，金屬層可舉出鋁箔、杜拉鋁(duralumin)箔、鈦箔、銅箔、磷青銅箔、SUS304箔、殷鋼箔、鎂合金箔，又可舉出此等混合箔等。通常這些金屬箔若過薄時有著針孔等缺陷，故使其變厚時可防止這些密封缺陷。較佳的厚度為5～50μm之範圍內，而使準備除去金屬箔的針孔或缺陷的箔片成為可能。As thesecond sealing layer 10 shown in FIGS. 1 and 2, asecond sealing layer 10 capable of blocking moisture can be further provided on the upper layer of the above-mentionedfirst sealing layer 9. Especially in the case of bottom emission type (Bottom emission type) organic EL panels, since a moisture-proof color filter layer is provided at a position opposite to the light emission direction, there is no need to consider metal for formation. Thesecond sealing layer 10 composed of optical properties such as foil (for example, ALPET, etc.) is preferable. In addition, examples of the metal layer include aluminum foil, duralumin foil, titanium foil, copper foil, phosphor bronze foil, SUS304 foil, Invar foil, and magnesium alloy foil, and other mixed foils such as these. Usually these metal foils have defects such as pinholes if they are too thin, so these sealing defects can be prevented when they are thickened. The preferred thickness is in the range of 5-50 μm, which makes it possible to prepare the foil for removing pinholes or defects of the metal foil.

如圖1及圖2所示，作為第2密封層10可適用ALPET12。ALPET12為在保護薄膜14上設置鋁箔13的構成。As shown in FIGS. 1 and 2,ALPET 12 can be applied as thesecond sealing layer 10.ALPET 12 has a configuration in which analuminum foil 13 is provided on aprotective film 14.

作為可適用於本發明的鋁13經蒸鍍的聚乙烯對苯二甲酸酯薄膜之ALPET12，例如可舉出亞洲鋁公司製的ALPET12/34、Panac公司製的9-100(鋁箔：9μm、PET：100μm)、9-125K(鋁箔：9μm、PET：125μm)、10-75(鋁箔：10μm、PET：75μm)、12-50(鋁箔：12μm、PET：50 μm)、12-188(鋁箔：12μm、PET：188μm)、20-75(鋁箔：20μm、PET：75μm)、20-100(鋁箔：20μm、PET：100 μm)、30-188(鋁箔：30μm、PET：188μm)、東海東洋鋁販賣公司製「ALPET1N30」、福田金屬公司製「ALPET3025」、大同化工公司製「ALPET1025」等。Examples of ALPET12 that can be applied to the vapor-deposited polyethylene terephthalate film ofaluminum 13 of the present invention include ALPET12/34 manufactured by Asia Aluminum Corporation and 9-100 manufactured by Panac (aluminum foil: 9μm, PET: 100μm), 9-125K (aluminum foil: 9μm, PET: 125μm), 10-75 (aluminum foil: 10μm, PET: 75μm), 12-50 (aluminum foil: 12μm, PET: 50 μm), 12-188 (aluminum foil : 12μm, PET: 188μm), 20-75 (aluminum foil: 20μm, PET: 75μm), 20-100 (aluminum foil: 20μm, PET: 100 μm), 30-188 (aluminum foil: 30μm, PET: 188μm), Tokai Toyo "ALPET1N30" manufactured by Aluminum Sales Company, "ALPET3025" manufactured by Fukuda Metal Co., Ltd., "ALPET1025" manufactured by Datong Chemical Co., Ltd., etc.

[表面保護薄膜]又，對於本發明，於第2密封層10上，以確保在第1密封層9之對向方向的電絕緣性或外傷防止之目的下，可配置具有絕緣性的保護薄膜者為佳。[Surface protection film]Furthermore, in the present invention, it is preferable to arrange an insulating protective film on thesecond sealing layer 10 for the purpose of ensuring electrical insulation in the opposing direction of thefirst sealing layer 9 or preventing external injuries.

具體以具有可撓性的樹脂薄膜為佳，例如可舉出由聚乙烯或聚丙烯、環狀烯烴共聚物(COP)等聚烯烴、聚醯胺、聚醯亞胺、聚乙烯對苯二甲酸酯(PET)、聚乙烯萘二甲酸酯(PEN)等聚酯、賽璐玢(Cellophane)、纖維素二乙酸酯、纖維素乙酸酯丁酸酯、纖維素乙酸酯丙酸酯(CAP)、三乙醯纖維素(TAC)、硝酸纖維素等纖維素酯類、聚偏二氯乙烯、聚乙烯醇、聚乙烯乙烯基醇共聚物(EVOH)、間規聚苯乙烯、聚碳酸酯、降冰片烯樹脂、聚甲基戊烯、聚醚酮、聚醯亞胺、聚醚碸(PES)、聚伸苯基硫化物、聚碸類、聚醚醯亞胺、聚醚酮醯亞胺、氟樹脂、聚甲基甲基丙烯酸酯(PMMA)等丙烯酸樹脂、聚芳酯類等材料與這些衍生物所構成的樹脂薄膜。進一步可使用例如稱為ARTON(註冊商標：JSR公司製)或Appell(註冊商標：三井化學公司製)的環烯烴系樹脂。Specifically, a flexible resin film is preferred. Examples include polyolefins such as polyethylene, polypropylene, cyclic olefin copolymers (COP), polyamides, polyimides, and polyethylene terephthalate. Polyester (PET), polyethylene naphthalate (PEN) and other polyesters, cellophane (Cellophane), cellulose diacetate, cellulose acetate butyrate, cellulose acetate propionate Cellulose esters (CAP), triacetyl cellulose (TAC), nitrocellulose, polyvinylidene chloride, polyvinyl alcohol, polyvinyl vinyl alcohol copolymer (EVOH), syndiotactic polystyrene, Polycarbonate, norbornene resin, polymethylpentene, polyetherketone, polyimide, polyether sulfide (PES), polyphenylene sulfide, polysulfide, polyetherimide, polyether A resin film composed of ketoximine, fluororesin, polymethylmethacrylate (PMMA) and other acrylic resins, polyarylates and other materials and these derivatives. Furthermore, for example, a cycloolefin-based resin called ARTON (registered trademark: manufactured by JSR Corporation) or Appell (registered trademark: manufactured by Mitsui Chemicals Corporation) can be used.

又，第2密封層10與第1密封層9以隔著第1接著層11而連接者為佳，可舉出熱硬化型樹脂或紫外線硬化型樹脂等，但於第2密封層10使用ALPET等金屬箔時，以熱硬化型樹脂為佳，且因有由同接著層體積之水分侵入，故以同接著劑為含有如可延遲水分擴散的材料或填充物等材料者為佳。In addition, thesecond sealing layer 10 and thefirst sealing layer 9 are preferably connected via the firstadhesive layer 11. Examples include thermosetting resins or ultraviolet curing resins, but ALPET is used for thesecond sealing layer 10. For metal foils, thermosetting resins are preferred, and since moisture invades from the same volume of the adhesive layer, it is better to use the same adhesive as a material that can delay the diffusion of moisture or fillers.

《偏光板》有機EL元件為由於電極的功函數，且因有效率地將發光的光子輸出於外部，特別為在底部發光型(Bottom emission type)之有機EL元件，於第2電極使用Al或Ag或合金、層壓等金屬材料者為多，又對於頂部發光型(Top emission type)，於陽極的ITO等下層形成TFT時，欲使光子可有效率地輸出於外部而形成反射電極。因此，有機EL面板形成時，因會有外光反射，故貼上圓偏光板，使外光反射消失，表現非發光部之黑色為一般情況。對於本發明之顯示裝置，於彩色濾光器單元16的外側上貼合圓偏光板20，進行黑色顯示。"Polarizer"The organic EL element is due to the work function of the electrode, and because it efficiently outputs the light-emitting photons to the outside, especially in the bottom emission type (bottom emission type) organic EL element, the second electrode uses Al, Ag or alloy, There are many metal materials such as laminates. For the top emission type (Top emission type), when forming a TFT underneath the anode, such as ITO, it is necessary to efficiently output photons to the outside to form a reflective electrode. Therefore, when the organic EL panel is formed, external light will be reflected, so a circular polarizing plate is attached to make the external light reflection disappear, and it is normal to express the black of the non-light emitting part. For the display device of the present invention, thecircular polarizer 20 is attached to the outer side of the color filter unit 16 to perform black display.

圓偏光板僅含有λ/4板放入即可，可為液晶形態或薄膜形態，並非受到限定者。圓偏光板為藉由光學接著劑而貼合於彩色濾光器單元。The circularly polarizing plate only needs to contain a λ/4 plate and can be in the form of liquid crystal or film, and it is not limited. The circular polarizing plate is attached to the color filter unit through an optical adhesive.

對於可適用於本發明的偏光板之詳細內容，例如可參照記載於日本特開2013-097279號公報、特2013-156391號公報、日本特開2014-240906號公報、日本特開2016-018021號公報、日本特開2017-111264號公報等內容。For the details of the polarizing plate applicable to the present invention, for example, refer to those described in Japanese Patent Application Publication No. 2013-097279, Japanese Patent Application Publication No. 2013-156391, Japanese Patent Application Publication No. 2014-240906, Japanese Patent Application Publication No. 2016-018021 Bulletin, Japanese Patent Application Publication No. 2017-111264, etc.

《顯示裝置之各構成單元的貼合》彩色濾光器單元與發光顯示單元D為隔著第2接著層15進行貼合。第2接著層15例如為有於環氧系的熱硬化樹脂中分散無機、有機、混合(Hybrid)等填充物的熱硬化形態，或含有光起始劑並且以UV光進行硬化的形態，兩者皆可使用。厚度通常為1～30μm程度，可由黏度或所含有的填充物之尺寸來調整。又，因使其變薄，可壓抑自邊緣的水分侵入，可不損害密封功能下進行貼合故較佳。"Lamination of the various components of the display device"The color filter unit and the light-emitting display unit D are bonded via the secondadhesive layer 15. For example, the secondadhesive layer 15 has a thermosetting form in which fillers such as inorganic, organic, and hybrid are dispersed in an epoxy-based thermosetting resin, or a form in which a photoinitiator is contained and cured by UV light. Both can be used. The thickness is usually about 1-30μm, which can be adjusted by the viscosity or the size of the filler. In addition, since it is made thinner, it is possible to suppress the intrusion of moisture from the edge, and it is preferable to perform bonding without impairing the sealing function.

在本發明之顯示裝置中，製作底部發光型(Bottom emission type)之有機EL形態的發光顯示單元，顯示裝置1為各別製造彩色濾光器單元16與發光顯示單元D，作為第2接著層15使用熱硬化型接著劑而貼合。In the display device of the present invention, a bottom emission type (Bottom emission type) organic EL type light-emitting display unit is produced, and thedisplay device 1 is separately produced with a color filter unit 16 and a light-emitting display unit D as the second adhesive layer 15Use a thermosetting adhesive for bonding.

由防止自端部的水分侵入之觀點來看，第2接著層15為使用熱硬化型接著劑，以含有填充物等可耐水分抑制擴散的構成為佳，在本案發明為使用適用此等之熱硬化型接著劑。From the standpoint of preventing the intrusion of moisture from the end, the secondadhesive layer 15 uses a thermosetting adhesive, and preferably contains fillers and other components that are resistant to moisture and inhibit diffusion. In this case, the invention is suitable for use Thermosetting adhesive.

又，在頂部發光型(Top emission type)等，將密封層以CVD法等形成後，可直接將彩色濾光器單元形成於密封層正上面。此時，於密封層上層，將彩色濾光器層例如以噴墨法進行製圖塗布，其後以旋轉法或噴墨法等形成有關本發明之平坦化層後，形成彩色濾光器單元。此時，因無須藉由熱硬化接著劑，故可容易判斷出可預測到信賴性的進一步提高。In addition, in the top emission type, etc., after the sealing layer is formed by a CVD method or the like, the color filter unit can be formed directly on the sealing layer. At this time, on the top layer of the sealing layer, the color filter layer is pattern-coated by, for example, the inkjet method, and then the planarization layer according to the present invention is formed by the spin method or the inkjet method, and then the color filter unit is formed. In this case, since there is no need to use a thermosetting adhesive, it can be easily judged that the reliability can be further improved.

《顯示裝置》作為本發明之顯示裝置，作為上述代表例而說明的使用有機EL元件之有機發光元件以外，亦可使用無機發光元件或彩色電子紙之構成。"Display Device"As the display device of the present invention, in addition to the organic light-emitting element using the organic EL element described as the representative example, an inorganic light-emitting element or a configuration of colored electronic paper may also be used.

且，有機發光元件中，以上述說明的有機電致發光元件，或含有量子點的有機發光元件者為較佳態樣。Furthermore, among the organic light-emitting elements, the organic electroluminescence element described above or the organic light-emitting element containing quantum dots is a preferable aspect.

又，作為無機發光元件，以含有量子點的無機發光元件，或微型LED者為較佳態樣。In addition, as the inorganic light-emitting element, an inorganic light-emitting element containing quantum dots or a micro LED is preferable.

對於本發明，有關作為發光元件具備有機EL元件的顯示裝置之詳細內容已說明，作為其他顯示裝置中，作為含有量子點的有機發光元件(QD-OLED)，例如可參照日本特開2014-077046號公報、日本特開2014-078380號公報、日本特開2014-078381號公報、日本特開2017-101128號公報等記載的構成。Regarding the present invention, the details of the display device including the organic EL element as the light-emitting element have been described. As an organic light-emitting element (QD-OLED) containing quantum dots among other display devices, for example, refer to Japanese Patent Application Publication No. 2014-077046 No., Japanese Patent Application Publication No. 2014-078380, Japanese Patent Application Publication No. 2014-078381, Japanese Patent Application Publication No. 2017-101128, etc.

又，作為含有量子點的無機發光元件(QLED)，例如可參照日本特開2015-156367號公報、日本特開2018-078279號公報所記載的內容。In addition, as an inorganic light emitting element (QLED) containing quantum dots, for example, the contents described in Japanese Patent Application Publication No. 2015-156367 and Japanese Patent Application Publication No. 2018-078279 can be referred to.

又，作為微型LED(μLED)，參考如日本特表2014-500562號公報、日本特表2017-535966號公報、日本特開2018-014481號公報等所記載的構成。In addition, as a micro LED (μLED), refer to the structure described in Japanese Patent Application No. 2014-500562, Japanese Patent Application Publication No. 2017-535966, Japanese Patent Application Publication No. 2018-014481, and the like.

又，作為彩色電子紙，可參照如日本特開2016-170260號公報、日本特開2016-170313號公報、特表2016-167295號公報、日本特開2017-073554號公報、日本特開2018-059998號公報等所記載的構成。[實施例]Also, as color electronic paper, refer to, for example, Japanese Patent Application Publication No. 2016-170260, Japanese Patent Application Publication No. 2016-170313, Japanese Patent Application Publication No. 2016-167295, Japanese Patent Application Publication No. 2017-073554, Japanese Patent Application Publication No. 2018- 059998 Bulletin, etc.[Example]

以下舉出實施例來具體說明本發明，但本發明並未限定於此等。且，對於實施例，使用「份」或「%」之表示方式，若無特別說明則表示「質量份」或「質量%」。Examples are given below to specifically illustrate the present invention, but the present invention is not limited to these. In addition, for the examples, the expression "parts" or "%" is used, and unless otherwise specified, it means "parts by mass" or "% by mass".

《顯示裝置之製作》[顯示裝置1之製作]依據下述方法，在底部發光型(Bottom emission type)之有機EL發光面板，彩色濾光器層係由著色劑所形成，製作出具備以下彩色濾光器單元1的顯示裝置1(本發明)，該彩色濾光器單元1為，將具有有關本發明之一般式(1)所示結構的有機金屬氧化物添加於平坦化層的構成。"Production of Display Device"[Production of display device 1]According to the following method, in a bottom emission type (Bottom emission type) organic EL light-emitting panel, the color filter layer is formed of a coloring agent, and adisplay device 1 having the followingcolor filter unit 1 is produced (this invention) Thecolor filter unit 1 has a structure in which an organic metal oxide having a structure represented by the general formula (1) related to the present invention is added to a planarization layer.

[有機EL單元之製作](第1基材之製作)作為第1基材2，作為30cm×40cm之具有可撓性的薄膜基材，於t=0.7mm之載體玻璃上，進行旋塗至厚度為50μm的塗料，其次在200℃進行20分鐘的後烘烤後製作出第1基材。[Production of organic EL unit](Production of the first base material)As thefirst substrate 2, a 30cm×40cm flexible film substrate was spin-coated to a thickness of 50μm on a carrier glass of t=0.7mm, followed by a 20-minute post-treatment at 200°C. After baking, the first substrate is produced.

其次，於塗料基板上，將下述含有聚矽氮烷的塗布液，使用線棒(Wire bar)，塗布至乾燥後的平均膜厚成為300nm，在溫度85℃，濕度55%RH之環境下，進行1分鐘加熱處理後使其乾燥。其次，在溫度25℃，濕度10%RH(露點溫度-8℃)之環境下保持10分鐘，進行除濕處理，於塗料基板上形成含有聚矽氮烷的層。Next, apply the following polysilazane-containing coating solution on the coating substrate using a wire bar, and apply it until the average film thickness after drying becomes 300nm, in an environment with a temperature of 85°C and a humidity of 55%RH , And dry it after heating for 1 minute. Next, hold for 10 minutes in an environment with a temperature of 25°C and a humidity of 10%RH (dew point temperature of -8°C) for dehumidification treatment to form a polysilazane-containing layer on the coating substrate.

其次，將形成含有聚矽氮烷的層之塗料基板，固定於準分子照射裝置MECL-M-1-200(Num Dy Com股份有限公司製)之操作臺上，以下述改質處理條件1下進行改質處理，作為氣體阻隔層，形成層厚300nm之聚矽氮烷改質層，製作出附有氣體阻隔層之第1基材。Next, the coating substrate on which the polysilazane-containing layer is formed is fixed on the console of the excimer irradiation device MECL-M-1-200 (manufactured by Num Dy Com Co., Ltd.), and the modifiedtreatment condition 1 is as follows The modification treatment is performed to form a 300nm-thick polysilazane modified layer as a gas barrier layer, and a first substrate with a gas barrier layer is produced.

＜含有聚矽氮烷的塗布液之準備＞作為含有聚矽氮烷的塗布液，準備全氫聚矽氮烷(AQUAMICA NN120-10，無觸媒形態，Merck(股)製)之10質量%二丁基醚溶液。＜Preparation of coating solution containing polysilazane＞As a coating solution containing polysilazane, a 10% by mass dibutyl ether solution of perhydropolysilazane (AQUAMICA NN120-10, non-catalyst form, manufactured by Merck Co., Ltd.) was prepared.

＜改質處理條件＞照射波長：172nm燈充滿氣體：Xe準分子燈光強度：130mW/cm²(172nm)含有聚矽氮烷的層與光源的距離：1mm臺加熱溫度：70℃照射裝置內之氧濃度：0.5體積%準分子燈照射時間：5秒＜第1基材之清潔＞繼續，將上述製作的附有氣體阻隔層的第1基材藉由濕洗法進行清潔。<Modification treatment conditions> Irradiation wavelength: 172nm Lamp filled with gas: Xe Excimer lamp intensity: 130mW/cm² (172nm) Distance between polysilazane-containing layer and light source: 1mm Heating temperature: 70℃ Inside the irradiation device Oxygen concentration: 0.5% by volume. Excimer lamp irradiation time: 5 seconds. <Cleaning of the first substrate> Continue to clean the first substrate with a gas barrier layer produced above by a wet cleaning method.

將稀釋鹼洗劑至5質量%的洗劑溶液加熱至60℃，於60℃的洗劑溶液浸漬第1基材，對於第1基材實施擦洗，除去附著於第1基材的異物。繼續，對於第1基材，依序實施超音波洗淨處理、純水輕洗(rinse)、氮氣吹入及IR(Infra Red)乾燥。其次，對於第1基材，實施UV(Ultra Violet)照射，除去附著於第1基材表面的有機物。繼續使用烤箱使第1基材乾燥。The detergent solution diluted to 5% by mass of the alkaline detergent is heated to 60°C, the first substrate is immersed in the 60°C lotion solution, and the first substrate is scrubbed to remove foreign matter adhering to the first substrate. Continuing, for the first substrate, ultrasonic cleaning treatment, pure water rinse, nitrogen blowing, and IR (Infra Red) drying are sequentially performed. Next, the first substrate is irradiated with UV (Ultra Violet) to remove organic matter adhering to the surface of the first substrate. Continue to use the oven to dry the first substrate.

(TFT之形成)首先，於底層將SiO膜以CVD形成，形成柵電極後，將柵極絕緣膜、作為通道層的a-Si：H膜及n⁺a-Si：H膜以隨時CVD法形成。(Formation of TFT) First, a SiO film is formed on the bottom layer by CVD. After the gate electrode is formed, the gate insulating film, the a-Si:H film and the n⁺ a-Si:H film as the channel layer are formed by the CVD method. form.

其次，以乾蝕刻進行加工至所望形狀圖型。Next, dry etching is used to process the pattern to the desired shape.

其次，形成源電極及漏電極後，形成鈍化膜，將電極寬100μm，厚度200nm，且通道寬度W=3mm，通道長度L=20μm之a-Si的TFT，形成於對應後述彩色濾光器層的各彩色濾光器之位置上。Next, after forming the source and drain electrodes, a passivation film is formed. The a-Si TFT with an electrode width of 100μm, a thickness of 200nm, channel width W=3mm and channel length L=20μm is formed on the color filter layer which will be described later The position of each color filter.

同時將第1電極的引出電極，使用ITO而形成，製作出TFT單元。At the same time, the lead electrode of the first electrode was formed using ITO to produce a TFT unit.

(有機EL元件之形成)其次，於第1基材及TFT單元上，形成白色串聯有機EL元件。(Formation of organic EL element)Next, a white tandem organic EL element is formed on the first substrate and the TFT unit.

對於TFT單元之製作，作為有機EL元件用之引出電極使用ITO而形成，在有機EL元件(OLED)將同ITO作為第1電極(陽極)而形成。For the production of the TFT unit, ITO is used as the lead electrode for the organic EL element, and ITO is used as the first electrode (anode) in the organic EL element (OLED).

其次，依據在日本特開2015-201508號公報之實施例的段落(0201)～同(0219)所記載的方法，形成由第1電洞輸送層/第1發光層/第1電子輸送層/中間連接器層/第2電洞輸送層/第2發光層/第2電子輸送層所構成的有機功能層群(7)。Next, according to the method described in paragraphs (0201) to (0219) of the embodiment of Japanese Patent Application Laid-Open No. 2015-201508, the first hole transport layer/first light-emitting layer/first electron transport layer/ An organic functional layer group (7) consisting of an intermediate connector layer/second hole transport layer/second light-emitting layer/second electron transport layer.

其次，將鋁蒸鍍至150nm的厚度，形成第2電極(陰極)。所製作的有機EL元件為，適宜地調整發光層，使在未藉由有關本發明的彩色濾光器而發光的條件下的發光層之CIE色度，成為與D65標準光源之同樣發光條件。又，作為構成有機EL元件的上述各層之形成方法，可使用圖3所記載的噴墨印刷法而形成。Next, aluminum was vapor-deposited to a thickness of 150 nm to form a second electrode (cathode). The produced organic EL device has a light-emitting layer suitably adjusted so that the CIE chromaticity of the light-emitting layer under the condition of not emitting light by the color filter of the present invention becomes the same light-emitting condition as the D65 standard light source. In addition, as a method of forming the above-mentioned layers constituting the organic EL element, the inkjet printing method described in FIG. 3 can be used.

(第1密封層之形成)其次，於第2電極上，作為密封層，在50Pa之製膜壓力條件下，供給矽烷氣體與氨氣體，以電漿CVD法進行製膜為厚度500nm的氮化矽膜，將此作為第1密封層。(Formation of the first sealing layer)Next, on the second electrode, as a sealing layer, silane gas and ammonia gas were supplied under a film forming pressure of 50 Pa, and the plasma CVD method was used to form a silicon nitride film with a thickness of 500 nm. This was referred to as the first Sealing layer.

具體而言，將形成至第2電極上的第1基材，放入於減壓至1×10^-4Pa以下的真空室，將第1基材的溫度調整為約70℃，作為上述反應氣體，將SiH₄氣體與NH₃氣體、H₂氣體以2：1：4的比例導入於真空室內，在減壓至50Pa中，以具有13.56MHz的高頻率電源之電漿CVD法進行製膜。於製膜時雖上升第1基材之溫度，但一邊將第1基材的冷卻控制至70℃，一邊製膜。藉此，形成由厚度500 nm之SiN所構成的第1密封層。Specifically, the first substrate formed on the second electrode is placed in a vacuum chamber whose pressure is reduced to 1×10^-4 Pa or less, and the temperature of the first substrate is adjusted to about 70°C as the reaction Gas, SiH₄ gas, NH₃ gas, and H₂ gas are introduced into the vacuum chamber at a ratio of 2:1:4, and the film is formed by the plasma CVD method with a high-frequency power supply of 13.56MHz at a reduced pressure of 50 Pa . Although the temperature of the first substrate was raised during film formation, the film was formed while controlling the cooling of the first substrate to 70°C. Thereby, the first sealing layer made of SiN with a thickness of 500 nm was formed.

(第2密封層之形成)其次，形成第2密封層。於上述所形成的第1密封層上貼合賦予熱硬化性接著劑的AlPET。因AlPET為可防止對構成上述第1密封層的SiN膜之水分攻擊者。對於該貼合，藉由進行30分鐘的100℃之加熱處理，使熱硬化性接著劑進行硬化後形成有機EL單元。(Formation of the second sealing layer)Next, a second sealing layer is formed. On the first sealing layer formed as described above, AlPET provided with a thermosetting adhesive was bonded. Because AlPET can prevent moisture attack on the SiN film constituting the first sealing layer. For this bonding, heat treatment at 100°C for 30 minutes is performed to cure the thermosetting adhesive to form an organic EL unit.

[彩色濾光器單元1之製作](第2基材之準備)作為第2基材，將0.5mm的玻璃基板(康寧公司製 EagleXG)，以與適用於上述第1基材的製作時同樣的洗淨方法進行鹼洗淨，其次將感光性聚醯亞胺(默克公司製)以旋轉塗布法進行塗布，進行在60℃之120秒的預烘烤。其次以光處理進行圖型曝光，以氫氧化四甲基銨(簡稱：TMAH)進行顯像、純粹輕洗(rinse)，形成將彩色濾光器形成部作為開口部而具有的隔壁。[Making of Color Filter Unit 1](Preparation of the second base material)As the second base material, a 0.5 mm glass substrate (EagleXG manufactured by Corning Incorporated) was alkali-cleaned using the same cleaning method as that applied to the production of the first base material. Next, photosensitive polyimide ( (Merck Co.) Coating was performed by a spin coating method, and pre-baked at 60°C for 120 seconds. Next, pattern exposure is performed by light processing, and development is performed with tetramethylammonium hydroxide (abbreviation: TMAH), and a clean rinse (rinse) is performed to form a partition wall having a color filter forming portion as an opening.

(彩色濾光器層1之製作)其次，將於上述製作的隔壁(bank)內以下述方法所調製的含有各著色劑之水墨液以噴墨印刷法賦予，製作出具有紅、綠、藍之各彩色濾光器的彩色濾光器層1。(Production of color filter layer 1)Next, the ink containing the respective colorants prepared in the bank prepared above by the following method is applied by inkjet printing to produce a color filter with red, green, and blue color filters器Layer 1.

1)著色劑含有墨液之調製於二乙二醇單乙基醚乙酸酯(沸點210℃)中，調製出將紅色顏料(C.I.Pigment Red 177)以固體成分20%進行混練的分散液。於該分散液30份中，混合三聚氰胺樹脂(MW-22，三和化學製)15份、二乙二醇單乙基醚乙酸酯55份，調製出紅色彩色濾光器形成用墨液。同樣地使用藍色顏料(Pigment Blue 15)、綠色顏料(Pigment Green 7)，調製出藍色彩色濾光器形成用墨液、綠色彩色濾光器形成用墨液。1) Preparation of ink containing colorantIn diethylene glycol monoethyl ether acetate (boiling point 210°C), a dispersion liquid in which a red pigment (C.I. Pigment Red 177) was kneaded at a solid content of 20% was prepared. In 30 parts of this dispersion, 15 parts of melamine resin (MW-22, manufactured by Sanwa Chemical Co., Ltd.) and 55 parts of diethylene glycol monoethyl ether acetate were mixed to prepare an ink for forming a red color filter. Similarly, a blue pigment (Pigment Blue 15) and a green pigment (Pigment Green 7) were used to prepare a blue color filter forming ink and a green color filter forming ink.

2)彩色濾光器層之形成於形成前述複數的隔壁的玻璃基板上，藉由吐出量12pL，載持噴嘴解像度180dpi之噴墨頭(Seiko Instruments Inc.公司製)的噴墨印刷裝置，使用前述含有各色之著色劑的墨液，吐出各色水墨液滴，形成紅色、綠色及藍色彩色濾光器，製作出彩色濾光器層1。2) Formation of color filter layerOn the glass substrate forming the plurality of partition walls, an inkjet printing device with an inkjet head (manufactured by Seiko Instruments Inc.) with a discharge volume of 12pL and a nozzle resolution of 180dpi is used, and the ink containing the colorants of each color is used. , Spit out ink droplets of various colors to form red, green, and blue color filters to create acolor filter layer 1.

各色彩色濾光器之折射率為依據後述方法所測定的結果，任一折射率皆為1.7。The refractive index of each color filter is the result measured according to the method described later, and any refractive index is 1.7.

(平坦化層1之形成)其次，於彩色濾光器層1上，形成含有具有有關本發明之一般式(1)所示結構的有機金屬氧化物之平坦化層1。(Formation of planarization layer 1)Next, on thecolor filter layer 1, aplanarization layer 1 containing an organometallic oxide having a structure represented by the general formula (1) related to the present invention is formed.

具體而言，在水分濃度為1ppm以下的乾燥氮環境下之手套箱內，調製出鈦四異丙氧化物(Ti(OiPr)₄)之10質量%脫水四氟丙醇(例示化合物F-1)溶液，於濕度30%之大氣中開放1分鐘，將馬上回到手套箱內之溶液作為溶膠･凝膠液1。將溶膠･凝膠液1中之式(a)所示F/(C+F)藉由下述方法進行測定的結果為0.20。Specifically, a 10% by mass dehydrated tetrafluoropropanol of titanium tetraisopropoxide (Ti(OiPr)₄ ) was prepared in a glove box under a dry nitrogen environment with a moisture concentration of 1 ppm or less (exemplary compound F-1 ) The solution is left open for 1 minute in the atmosphere with a humidity of 30%, and the solution immediately returned to the glove box will be used as a sol/gel solution 1. The F/(C+F) represented by the formula (a) in the sol/gel solution 1 was measured by the following method and the result was 0.20.

下述表示溶膠･凝膠液1之F/(C+F)的測定方法。The following shows the method of measuring F/(C+F) of sol/gel liquid 1.

首先，將溶膠･凝膠液1塗布於矽晶圓上，形成薄膜。將所形成的薄膜以藉由SEM･EDS(Energy Dispersive X-ray Spectoroscopy：能量分散型X線分析裝置)的元素分析，測定碳原子與氟原子之原子數，求得下述式(a)之值。SEM･EDS裝置為使用JSM-IT100(日本電子公司製)。First, the sol/gel solution 1 is applied on a silicon wafer to form a thin film. The formed thin film is analyzed by SEM･EDS (Energy Dispersive X-ray Spectoroscopy: Energy Dispersive X-ray Spectoroscopy: energy dispersive X-ray analyzer) to determine the atomic number of carbon atoms and fluorine atoms, and the following formula (a) is obtained value. SEM･EDS device uses JSM-IT100 (manufactured by JEOL).

其次，將同溶膠･凝膠液1以噴墨印刷法在使乾膜厚成為10μm之條件下進行塗布，在60℃下進行2分鐘的預烘烤後，其次，在110℃進行30分鐘的後烘烤，進行10分鐘的低壓水銀燈之照射後，形成平坦化層1，製作出彩色濾光器單元1。上述所形成的平坦化層1之折射率為1.9。

Next, apply the same sol/gel solution 1 by inkjet printing under the condition that the dry film thickness is 10μm, and after pre-baking at 60°C for 2 minutes, and then at 110°C for 30 minutes After post-baking and irradiating with a low-pressure mercury lamp for 10 minutes, aplanarization layer 1 is formed, and acolor filter unit 1 is produced. The refractive index of theplanarization layer 1 formed as described above is 1.9.

且，彩色濾光器層1及平坦化層1之折射率為，以與成為對象的各層之形成條件之相同方法而形成另外構成層，製作出折射率測定用之試樣。其次，使用分光光度計U-4100(島津製作所製)，對於各層法線方向，將入射光之入射角設定在5˚之正反射率，並在波長560nm進行測定。其次，使用西格瑪光機公司製的薄膜計算軟體「Essential Macleod」，測定折射率。In addition, the refractive index of thecolor filter layer 1 and theplanarization layer 1 is such that another constituent layer is formed by the same method as the formation conditions of each target layer, and a sample for refractive index measurement is produced. Secondly, using a spectrophotometer U-4100 (manufactured by Shimadzu Corporation), for the normal direction of each layer, the incident angle of the incident light was set at a specular reflectance of 5˚, and the measurement was performed at a wavelength of 560nm. Next, the thin film calculation software "Essential Macleod" manufactured by Sigma Koki Co., Ltd. was used to measure the refractive index.

[彩色濾光器單元1與有機EL單元之貼合]其次，於上述製作的彩色濾光器單元1之平坦化層1上，使用在有機EL單元的第2密封層之形成上所使用的熱硬化型接著劑，形成第2接著層後，將有機EL單元的第1基材之載體玻璃藉由雷射照射使其剝離後，露出塗料面的有機EL單元的第1基材面與彩色濾光器單元1進行貼合，在100℃施予30分鐘的加熱處理，貼合彩色濾光器單元1與有機EL單元。[Lamination ofcolor filter unit 1 and organic EL unit]Next, on theplanarization layer 1 of thecolor filter unit 1 produced above, use the thermosetting adhesive used in the formation of the second sealing layer of the organic EL unit to form the second adhesive layer, and then the organic After the carrier glass of the first substrate of the EL unit is peeled off by laser irradiation, the first substrate surface of the organic EL unit exposed to the paint surface is bonded to thecolor filter unit 1, and applied at 100°C for 30 Minutes of heat treatment, bonding thecolor filter unit 1 and the organic EL unit.

[圓偏光板之賦予]其次，依據WO2014/091759號公報之段落(0165)～(0167)所記載的方法，製作出光學薄膜後，依據下述方法，製作出圓偏光板。[Endowment of circular polarizer]Next, after producing an optical film according to the method described in paragraphs (0165) to (0167) of WO2014/091759, a circular polarizing plate is produced according to the following method.

(偏光子之製作)將厚度120μm的長尺狀聚乙烯醇薄膜，在延伸溫度110℃，延伸倍率5倍之條件下進行一軸延伸。將所得之薄膜於由碘0.075g、碘化鉀5g、水100g所成的水溶液中進行浸漬60秒後，於由碘化鉀6g、硼酸7.5g、水100g所成的68℃的水溶液中進行浸漬。將所得之薄膜經水洗、乾燥後，得到厚度20μm之長尺狀偏光子。(Making of Polaron)A long-length polyvinyl alcohol film with a thickness of 120 μm was stretched uniaxially at a stretching temperature of 110°C and a stretching ratio of 5 times. The resulting film was immersed in an aqueous solution of 0.075 g of iodine, 5 g of potassium iodide, and 100 g of water for 60 seconds, and then immersed in an aqueous solution of 6 g of potassium iodide, 7.5 g of boric acid, and 100 g of water at 68°C. After the obtained film is washed with water and dried, a long-length polarizer with a thickness of 20 μm is obtained.

(圓偏光板之製作)將在上述方法所製作的光學薄膜之與偏光子的貼合面進行鹼皂化處理。其次，於長尺狀偏光子的一面上，將光學薄膜藉由作為接著劑的完全皂化型聚乙烯醇5%水溶液進行貼合。貼合為藉由對齊偏光子之縱向方向與光學薄膜之縱向方向，將偏光子的透過軸與光學薄膜的遲相軸成45˚下進行。(Production of circular polarizing plate)The bonding surface of the optical film produced by the above method and the polarizer is subjected to alkali saponification treatment. Secondly, on one side of the long-length polarizer, the optical film is laminated with a fully saponifiedpolyvinyl alcohol 5% aqueous solution as an adhesive. The lamination is performed by aligning the longitudinal direction of the polarizer with the longitudinal direction of the optical film, so that the transmission axis of the polarizer and the slow axis of the optical film are at 45˚.

另一方面，準備Konica Minolta Tack薄膜KC4UA(Konica Minolta(股)製)，將與該偏光子的貼合面進行鹼皂化處理。然後於偏光子的另一面上，與前述同樣地，將KC4UA(Konica Minolta(股)製)藉由完全皂化型聚乙烯醇5%水溶液進行貼合。藉此得到圓偏光板。On the other hand, Konica Minolta Tack film KC4UA (manufactured by Konica Minolta Co., Ltd.) was prepared, and the bonding surface with the polarizer was subjected to alkali saponification. Then, on the other side of the polarizer, KC4UA (manufactured by Konica Minolta Co., Ltd.) was bonded with a fully saponifiedpolyvinyl alcohol 5% aqueous solution in the same manner as described above. Thus, a circular polarizing plate is obtained.

將上述製作的圓偏光板，隔著接著層貼合於構成彩色濾光器單元之第2基材的背面，製作出顯示裝置1。The circularly polarizing plate produced as described above was bonded to the back surface of the second base material constituting the color filter unit via an adhesive layer to produce thedisplay device 1.

[顯示裝置2之製作]對於上述顯示裝置1之製作，取代彩色濾光器單元1而使用下述方法所製作的彩色濾光器單元2以外，其他同樣地製作出顯示裝置2。[Production of display device 2]For the production of the above-mentioneddisplay device 1, instead of thecolor filter unit 1, thedisplay device 2 was produced in the same manner except that thecolor filter unit 2 produced by the following method was used.

[彩色濾光器單元2之製作]對於前述所製作彩色濾光器單元1，將彩色濾光器層1變更為下述彩色濾光器層2，且將平坦化層1變更為下述平坦化層2以外，其他同樣地製作出彩色濾光器單元2。[Making of Color Filter Unit 2]For thecolor filter unit 1 produced above, thecolor filter layer 1 was changed to thecolor filter layer 2 described below, and theplanarization layer 1 was changed to theplanarization layer 2 described below, and everything else was made in the same wayColor filter unit 2.

(彩色濾光器層2之製作)在水分濃度1ppm以下的乾燥氮環境下之手套箱內，調製出鈦四異丙氧化物(Ti(OiPr)₄)之10質量%脫水四氟丙醇(例示化合物F-1)溶液，於濕度30%之大氣下開放1分鐘，將馬上回到手套箱內之溶液作為溶膠･凝膠液1。(Production of color filter layer 2) In a glove box under a dry nitrogen environment with a moisture concentration of 1 ppm or less, a 10% by mass dehydrated tetrafluoropropanol (Ti(OiPr)₄ ) of titanium tetraisopropoxide (Ti(OiPr)₄ ) was prepared. Exemplary compound F-1) solution is left open for 1 minute in the atmosphere with a humidity of 30%, and the solution immediately returned to the glove box is referred to as sol/gel solution 1.

其次，於上述溶膠･凝膠液1，將於二乙二醇單乙基醚乙酸酯(沸點210℃)中混練有紅色顏料(C.I.Pigment Red 177)固體成分20%的分散液，以10.0質量%的固體成分濃度下添加，調製出含有著色劑的紅色彩色濾光器層形成用溶膠･凝膠液。Next, in the above-mentioned sol/gel solution 1, a dispersion of 20% of the solid content of the red pigment (CIPigment Red 177) was kneaded in diethylene glycol monoethyl ether acetate (boiling point 210°C) to 10.0 It is added at a solid content concentration of mass% to prepare a sol/gel solution for forming a red color filter layer containing a colorant.

同樣地，於上述溶膠･凝膠液1，作為著色劑使用藍色顏料(Pigment Blue 15)、綠色顏料(Pigment Green 7)，調製出含有著色劑的藍色彩色濾光器形成用溶膠･凝膠液、含有著色劑的綠色彩色濾光器形成用溶膠･凝膠液。Similarly, in the above sol/gel solution 1, blue pigment (Pigment Blue 15) and green pigment (Pigment Green 7) were used as colorants to prepare a sol for forming a blue color filter containing a colorant. Condensate Glue solution, sol/gel solution for forming green color filter containing colorant.

其次，將上述各溶膠･凝膠液藉由噴墨印刷法，於第2基材上射出成如圖1所記載的圖型，形成彩色濾光器層2。Next, each of the above-mentioned sol/gel liquids was ejected on the second substrate into a pattern as shown in FIG. 1 by an inkjet printing method to form acolor filter layer 2.

具體而言，首先將含有著色劑的藍色彩色濾光器層形成用溶膠･凝膠液，依據圖3所示噴墨印刷法，射出於第2基材上，實施在60℃的2分鐘預烘烤後，進行在110℃的30分鐘後烘烤，藉由將低壓水銀燈進行10分鐘照射後，形成層厚5μm的含有藍色著色劑之彩色濾光器CF_B1。其次，將含有著色劑的綠色彩色濾光器層形成用溶膠･凝膠液，欲使其不在前述形成的含有藍色著色劑的彩色濾光器(CF_B1)之端部上重疊而設置0.5μm的空間，以噴墨印刷法進行塗布，同樣地實施在60℃的2分鐘之預烘烤後，其次實施在110℃的30分鐘之後烘烤，其次，照射低壓水銀燈10分鐘後，形成層厚6μm的含有綠色著色劑之彩色濾光器CF_G1。同樣地形成層厚7μm的含有紅色著色劑的彩色濾光器CF_R1，形成彩色濾光器層2。Specifically, first, the sol/gel solution for forming a blue color filter layer containing a colorant is sprayed onto the second substrate according to the inkjet printing method shown in Fig. 3, and the process is performed at 60°C for 2 minutes After the pre-baking, post-baking was performed at 110°C for 30 minutes, and a low-pressure mercury lamp was irradiated for 10 minutes to form a color filter CF_B1 containing a blue colorant with a layer thickness of 5 μm. Next, the sol/gel solution for forming a green color filter layer containing a colorant is set so as not to overlap the end of the blue colorant-containing color filter (CF_B1 ) formed above and set 0.5 The space of μm is coated by inkjet printing method, and after pre-baking at 60°C for 2 minutes, then baking at 110°C for 30 minutes, and then irradiating a low-pressure mercury lamp for 10 minutes to form a layer 6μm thick color filter CF_G1 containing green colorant. In the same manner, a color filter CF_R1 containing a red colorant with a layer thickness of 7 μm was formed to form acolor filter layer 2.

上述形成的含有各著色劑之彩色濾光器的各折射率為1.90。Each refractive index of the color filter containing each coloring agent formed above was 1.90.

(平坦化層2之製作)其次，於上述形成的彩色濾光器層2上，使用聚酯丙烯酸酯樹脂，將折射率1.60之平坦化層2，藉由旋轉塗布法在使乾燥後的層厚成為5μm之條件下進行塗布、乾燥，形成平坦化層2，製作出彩色濾光器單元2。(Production of planarization layer 2)Next, on thecolor filter layer 2 formed as described above, a polyester acrylate resin is used to coat theplanarization layer 2 with a refractive index of 1.60 by a spin coating method under the condition that the layer thickness after drying becomes 5μm. , Drying, forming aplanarization layer 2, and fabricating acolor filter unit 2.

[顯示裝置3之製作]對於上述顯示裝置2的製作，取代彩色濾光器單元2而使用下述方法所製作的彩色濾光器單元3以外，其他同樣地製作出顯示裝置3。[Production of display device 3]For the production of thedisplay device 2 described above, thedisplay device 3 was produced in the same manner except for thecolor filter unit 3 produced by the following method instead of thecolor filter unit 2.

[彩色濾光器單元3之製作]對於前述製作的彩色濾光器單元2，將彩色濾光器層2變更為下述彩色濾光器層3以外，其他同樣地製作出彩色濾光器單元3。[Making of Color Filter Unit 3]For thecolor filter unit 2 produced above, except that thecolor filter layer 2 was changed to thecolor filter layer 3 described below, thecolor filter unit 3 was produced in the same manner.

(彩色濾光器層3之製作)在水分濃度1ppm以下的乾燥氮環境下之手套箱內，調製出鈦四異丙氧化物(Ti(OiPr)₄)之10質量%脫水四氟丙醇(例示化合物F-1)溶液，於濕度30%的大氣中開放1分鐘，將馬上回到手套箱內的溶液作為溶膠･凝膠液1。溶膠･凝膠液1中之前述式(a)所示F/(C+F)為0.20。(Production of color filter layer 3) In a glove box under a dry nitrogen environment with a moisture concentration of 1 ppm or less, prepare titanium tetraisopropoxide (Ti(OiPr)₄ ) with 10% by mass dehydrated tetrafluoropropanol ( The exemplified compound F-1) solution was left in the atmosphere with a humidity of 30% for 1 minute, and the solution immediately returned to the glove box was referred to as the sol/gel solution 1. The F/(C+F) represented by the aforementioned formula (a) in the sol/gel solution 1 is 0.20.

其次，於上述溶膠･凝膠液1，將作為紅色發光的量子點之由InP/ZnS所成的核心･外殼型半導體量子點，以10.0質量%之固體成分濃度下添加，調製出含有量子點的紅色彩色濾光器層形成用溶膠･凝膠液。Next, in the above-mentioned sol/gel solution 1, a core/shell semiconductor quantum dot made of InP/ZnS, which is a red-emitting quantum dot, is added at a solid content concentration of 10.0% by mass to prepare a quantum dot containing Sol･gel solution for forming the red color filter layer.

同樣地，於上述溶膠･凝膠液1中，添加作為綠色發光之量子點的由InP/GaP/ZnS所成的核心･外殼型半導體量子點10.0質量%，與作為表面修飾劑的三-n-辛基膦氧化物(簡稱：TOPO，關東化學公司製)0.1質量%，調製出含有量子點的綠色彩色濾光器層形成用溶膠･凝膠液。Similarly, in the above-mentioned sol/gel solution 1, 10.0% by mass of InP/GaP/ZnS core and shell semiconductor quantum dots as green light-emitting quantum dots, and tri-n as a surface modifier are added -Octylphosphine oxide (abbreviation: TOPO, manufactured by Kanto Chemical Co., Ltd.) 0.1% by mass to prepare a sol/gel solution for forming a green color filter layer containing quantum dots.

同樣地，於上述溶膠･凝膠液1中，添加作為藍色發光的量子點之由CdS/ZnS所成的核心･外殼型半導體量子點10.0質量%，與作為表面修飾劑的TOPO0.1質量%，調製出含有量子點的藍色彩色濾光器層形成用溶膠･凝膠液。Similarly, in the above-mentioned sol/gel solution 1, 10.0% by mass of CdS/ZnS core and shell type semiconductor quantum dots as blue-emitting quantum dots are added, and TOPO0.1 mass as a surface modifier %, prepared a sol/gel solution for forming a blue color filter layer containing quantum dots.

其次，將上述各溶膠･凝膠液藉由噴墨印刷法，射出於第2基材上成為圖2所記載的圖型。Next, each of the above-mentioned sol/gel liquids was projected onto the second substrate by the inkjet printing method to form the pattern shown in FIG. 2.

具體而言，首先將含有量子點的藍色彩色濾光器層形成用溶膠･凝膠液，依據圖3所示的噴墨印刷法，射出於第2基材上，實施在60℃的2分鐘預烘烤後，在110℃進行30分鐘的後烘烤，其次照射低壓水銀燈10分鐘後，形成層厚5μm的含有藍色發光之量子點QD_B的彩色濾光器CF_B2。其次，將含有量子點的綠色彩色濾光器層形成用溶膠･凝膠液，欲不要在前述形成的含有藍色發光之量子點QD_B的彩色濾光器CF_B2之端部上重疊而設置0.5μm的空間，以噴墨印刷法進行塗布，同樣地實施在60℃的2分鐘預烘烤後，其次在110℃實施30分鐘的後烘烤，其次照射低壓水銀燈10分鐘，形成層厚6μm的含有綠色發光之量子點QD_G的彩色濾光器CF_G2。同樣地形成層厚7μm的含有紅色發光之量子點QD_R的彩色濾光器CF_R2，且形成彩色濾光器層3。Specifically, first, the sol/gel solution for forming a blue color filter layer containing quantum dots is sprayed onto the second substrate according to the inkjet printing method shown in FIG. After 30 minutes of pre-baking, post-baking at 110°C for 30 minutes, and then irradiating a low-pressure mercury lamp for 10 minutes, a color filter CF_B2 containing blue light-emitting quantum dots QD_B with a layer thickness of 5 μm is formed. Next, the sol/gel solution for forming a green color filter layer containing quantum dots is installed without overlapping the end of the color filter CF_B2 containing blue light-emitting quantum dots QD_B formed above. The 0.5μm space is coated by inkjet printing. The same applies after pre-baking at 60°C for 2 minutes, followed by post-baking at 110°C for 30 minutes, followed by low-pressure mercury lamp irradiation for 10 minutes to form a layer thickness of 6μm The color filter CF_G2 containing green light-emitting quantum dots QD_G. Likewise forming a color filter CF_R2 thickness of 7μm containing the red light emitting quantum dot QD_R, and thecolor filter layer 3 is formed.

上述形成的含有各量子點的彩色濾光器之各折射率為1.90。The refractive index of the above-formed color filter containing each quantum dot is 1.90.

[顯示裝置4之製作]對於上述顯示裝置3之製作，取代彩色濾光器單元3而使用下述方法所製作的彩色濾光器單元4以外，其他同樣地製作出顯示裝置4。[Production of display device 4]For the production of the above-mentioneddisplay device 3, the display device 4 was produced in the same manner except for the color filter unit 4 produced by the following method instead of thecolor filter unit 3.

[彩色濾光器單元4之製作]對於使用於上述顯示裝置3的製作之彩色濾光器單元3，將平坦化層2，變更為使用於彩色濾光器單元1之製作上的平坦化層1以外，其他同樣地製作出將具有有關本發明的一般式(1)所示結構的有機金屬氧化物含於彩色濾光器層與平坦化層的彩色濾光器單元4。[Making of Color Filter Unit 4]For thecolor filter unit 3 used in the production of the above-mentioneddisplay device 3, theplanarization layer 2 is changed to theplanarization layer 1 used in the production of thecolor filter unit 1. The organic metal oxide of the structure represented by the general formula (1) related to the present invention is contained in the color filter unit 4 of the color filter layer and the planarization layer.

對於上述彩色濾光器單元4，可形成彩色濾光器層之折射率與平坦化層之折射率皆為1.9，且使藍色的吸收峰波長460nm與綠色的吸收峰波長550nm、紅色的吸收峰波長640nm之光各彼此加強的光提取效率達到最大之彩色濾光器層。For the above-mentioned color filter unit 4, the refractive index of the color filter layer and the refractive index of the flattening layer are both 1.9, and the blue absorption peak wavelength is 460nm, the green absorption peak wavelength is 550nm, and the red absorption The color filter layer where the light with a peak wavelength of 640nm each enhances the light extraction efficiency to the maximum.

[顯示裝置5之製作]對於上述顯示裝置4之製作，取代彩色濾光器單元4而使用在下述方法所製作的彩色濾光器單元5以外，其他同樣地製作出顯示裝置5。[Production of display device 5]For the production of the above-mentioned display device 4, instead of the color filter unit 4, except for using thecolor filter unit 5 produced by the following method, thedisplay device 5 was produced in the same manner.

[彩色濾光器單元5之製作]對於上述彩色濾光器單元4之製作，除將形成在彩色濾光器層3及平坦化層1使用的具有一般式(1)所示結構的有機金屬氧化物之溶膠･凝膠液，變更為鈦四異丙氧化物(Ti(OiPr)₄)之10質量%脫水八氟丙醇(例示化合物F-5)溶液(溶膠･凝膠液2)以外，其他同樣地製作出彩色濾光器單元5。[Production of color filter unit 5] For the production of the above-mentioned color filter unit 4, the organic metal having the structure shown in general formula (1) will be formed on thecolor filter layer 3 and theplanarization layer 1 Oxide sol/gel solution, changed to titanium tetraisopropoxide (Ti(OiPr)₄ ) 10% by mass dehydrated octafluoropropanol (exemplary compound F-5) solution (sol/gel solution 2) , And othercolor filter units 5 are produced in the same manner.

將溶膠･凝膠液2中之F/(C+F)以前述方法進行測定的結果為0.42，所形成的各層之折射率為1.70。The F/(C+F) in the sol/gel solution 2 was measured by the aforementioned method and the result was 0.42, and the refractive index of each layer formed was 1.70.

又，前述溶膠･凝膠液1的折射率為1.9，上述溶膠･凝膠液2的折射率為1.7，折射率可由醇溶劑之氟量做自由控制得到確認。In addition, the refractive index of the aforementioned sol/gel solution 1 is 1.9, and the refractive index of the aforementioned sol/gel solution 2 is 1.7, and it is confirmed that the refractive index can be freely controlled by the amount of fluorine in the alcohol solvent.

[顯示裝置6之製作]依據下述方法，製作出作為發光顯示單元具備液晶顯示裝置之顯示裝置6。[Production of display device 6]According to the following method, adisplay device 6 including a liquid crystal display device as a light-emitting display unit was manufactured.

[彩色濾光器單元6之製作]對於前述彩色濾光器單元1之製作，除將彩色濾光器層6以下述方法製作以外，其他同樣地製作出彩色濾光器單元6。[Making of Color Filter Unit 6]For the production of the aforementionedcolor filter unit 1, except that thecolor filter layer 6 is produced by the following method, thecolor filter unit 6 is produced in the same manner.

(彩色濾光器層6之製作)作為第2基材，於0.5mm的玻璃基板(康寧公司製 EagleXG)上，除將黑色矩陣以光刻法而形成以外，其他同樣地製作出彩色濾光器層5。(Production of color filter layer 6)As the second base material, on a 0.5 mm glass substrate (EagleXG manufactured by Corning Incorporated), thecolor filter layer 5 was produced in the same manner except that the black matrix was formed by photolithography.

於黑色矩陣材料，使用凸版印刷公司製的黑色矩陣材料而形成。將同黑色矩陣材料塗布於第2基材上，在預烘烤溫度100℃下進行2分鐘的暫時乾燥後，以光處理進行光製圖。The black matrix material is formed using a black matrix material manufactured by Toppan Printing. Coating the same black matrix material on the second substrate, and temporarily drying it at a pre-baking temperature of 100°C for 2 minutes, and then performing photo-patterning by light treatment.

其後，以3質量%的氫氧化四甲基銨(簡稱：TMAH)進行顯像，進行純水輕洗(rinse)。其次，將後烘烤在250℃下進行45分鐘後，形成約3μm厚的黑色矩陣。After that, development was performed with 3% by mass of tetramethylammonium hydroxide (abbreviation: TMAH), and rinsed with pure water. Next, after the post-baking was performed at 250°C for 45 minutes, a black matrix with a thickness of about 3 μm was formed.

其次，於上述製作的黑色矩陣將含有著色劑的水墨液以噴墨印刷法賦予，製作出含有紅、綠、藍之各彩色濾光器的彩色濾光器層6。Next, an ink containing a colorant is applied to the black matrix produced above by an inkjet printing method to produce acolor filter layer 6 containing red, green, and blue color filters.

1)著色劑含有墨液之調製調製出於二乙二醇單乙基醚乙酸酯(沸點210℃)中，將紅色顏料(C.I.Pigment Red 177)以固體成分20%進行混練的分散液。混合該分散液30份、三聚氰胺樹脂(MW-22，三和化學製)15份、二乙二醇單乙基醚乙酸酯55份，調製出紅色彩色濾光器形成用墨液。同樣地，使用藍色顏料(Pigment Blue 15)、綠色顏料(Pigment Green 7)，調製出藍色彩色濾光器形成用墨液、綠色彩色濾光器形成用墨液。1) Preparation of ink containing colorantA dispersion liquid obtained by kneading a red pigment (C.I. Pigment Red 177) with a solid content of 20% in diethylene glycol monoethyl ether acetate (boiling point 210°C) was prepared. 30 parts of this dispersion, 15 parts of melamine resin (MW-22, manufactured by Sanwa Chemical Co., Ltd.), and 55 parts of diethylene glycol monoethyl ether acetate were mixed to prepare an ink for forming a red color filter. Similarly, a blue pigment (Pigment Blue 15) and a green pigment (Pigment Green 7) were used to prepare a blue color filter forming ink and a green color filter forming ink.

2)彩色濾光器層之形成於形成前述複數隔壁的玻璃基板上，藉由吐出量12 pL，載持噴嘴解像度180dpi之噴墨頭(Seiko Instruments Inc.公司製)的噴墨印刷裝置，使用前述之含有各色著色劑的墨液，吐出各色水墨液滴，形成彩色濾光器，製作出彩色濾光器層6。2) Formation of color filter layerOn the glass substrate forming the plurality of partition walls, an inkjet printing device with a discharge volume of 12 pL and an inkjet head (manufactured by Seiko Instruments Inc.) with a nozzle resolution of 180 dpi is used, and the aforementioned inks containing colorants of each color are used , Spit out ink droplets of various colors to form a color filter, and make acolor filter layer 6.

(液晶顯示裝置之製作)依據日本特開2012-230154號公報之實施例的段落(0232)～(0261)所記載的方法，藉由構成SONY公司製BRAVIA KDL-46HX800的液晶單元，剝離彩色濾光器，取代之，安裝上述製作的彩色濾光器單元6以外，其他同樣地製作出顯示裝置6。(Production of liquid crystal display device)According to the method described in paragraphs (0232) to (0261) of the embodiment of Japanese Patent Application Laid-Open No. 2012-230154, by forming the liquid crystal cell of BRAVIA KDL-46HX800 manufactured by SONY Corporation, peeling off the color filter, replacing it, and installing Except for thecolor filter unit 6 produced as described above, thedisplay device 6 was produced in the same manner.

[顯示裝置7之製作]對於上述顯示裝置1之製作，取代彩色濾光器單元1而使用下述方法所製作的彩色濾光器單元7以外，其他同樣地製作出比較例的顯示裝置7(有機EL顯示器裝置)。[Production of display device 7]For the production of thedisplay device 1 described above, a display device 7 (organic EL display device) of a comparative example was produced in the same manner except for thecolor filter unit 7 produced by the following method instead of thecolor filter unit 1.

(彩色濾光器單元7之製作)對於使用於上述顯示裝置1之製作的彩色濾光器單元1，將平坦化層1變更為使用於彩色濾光器單元2的製作之平坦化層2以外，其他同樣地製作出由各未含有具有有關本發明的一般式(1)所示結構之有機金屬氧化物的彩色濾光器層與平坦化層所構成的彩色濾光器單元7。(Production of color filter unit 7)For thecolor filter unit 1 used in the production of the above-mentioneddisplay device 1, theplanarization layer 1 was changed to theplanarization layer 2 used in the production of thecolor filter unit 2, and the others were produced in the same manner. Thecolor filter unit 7 is composed of a color filter layer and a planarization layer of an organometal oxide having a structure represented by the general formula (1) related to the present invention.

[顯示裝置8之製作]對於上述顯示裝置6之製作，取代彩色濾光器單元6而使用上述製作的彩色濾光器單元7以外，其他同樣地製作出由各未含有具有有關本發明的一般式(1)所示結構之有機金屬氧化物的彩色濾光器層與平坦化層所構成的彩色濾光器單元7，且製作出使用此的比較例之顯示裝置8(液晶顯示裝置)。[Production of display device 8]For the production of thedisplay device 6 described above, instead of using thecolor filter unit 6 and using thecolor filter unit 7 produced above, other things were made in the same way. The structure shown in general formula (1) related to the present invention was not included. Acolor filter unit 7 composed of a color filter layer of an organic metal oxide and a planarization layer was fabricated, and a display device 8 (liquid crystal display device) of a comparative example using this was fabricated.

《顯示裝置之評估》對於上述製作之各顯示裝置，進行下述各評估。"Evaluation of Display Devices"For each display device manufactured above, the following evaluations were performed.

[初期外觀之評估]對於各顯示裝置，在輸入電流至初期發光亮度成為300cd/m²的狀態下，目視觀察有無亮度、像素收縮或暗點的產生，依據下述基準進行初期外觀之評估。[Evaluation of Initial Appearance] For each display device, under the input current until the initial emission brightness reaches 300 cd/m² , visually observe whether there is brightness, pixel shrinkage, or dark spots, and evaluate the initial appearance according to the following criteria.

且，發光亮度的測定為使用分光放射亮度計CS2000(Konica Minolta公司製)而進行。In addition, the measurement of emission brightness was performed using a spectroradiometer CS2000 (manufactured by Konica Minolta).

○：高亮度且完全未確認到像素收縮或暗點之產生△：發光亮度稍微低，在一部分確認到微弱像素收縮或暗點之產生，但未有實用上的問題×：發光亮度為低，又確認到像素收縮或暗點之產生，在實用上有問題[初期亮度之測定]對於各顯示裝置，使用分光放射亮度計CS2000 (Konica Minolta公司製)，在23℃之環境下，測定正面亮度，以將顯示裝置7的正面亮度作為1.00的相對亮度做表示，且依據下述評估等級，評估初期亮度。○: High brightness and no pixel shrinkage or dark spots have been confirmed△: The emission brightness is slightly low, and weak pixel shrinkage or dark spots are observed in some parts, but there is no practical problem×: The luminous brightness is low, and the occurrence of pixel shrinkage or dark spots is confirmed, which is problematic in practice[Measurement of initial brightness]For each display device, a spectroradiometer CS2000 (manufactured by Konica Minolta) was used to measure the front brightness under an environment of 23°C, and the front brightness of thedisplay device 7 was expressed as a relative brightness of 1.00, and the following evaluation was used Level, evaluate the initial brightness.

◎：初期亮度值與通常設計值比較為+10%以上之亮度值○：初期亮度值與通常設計值比較為+5%以上且未達+10%之亮度值-：初期亮度值與通常設計值比較為300cd/m²以上且未達+5%之亮度值×：初期亮度值與通常設計值比較為未達300cd/m²之亮度值[耐光性之評估]耐光性試驗為，在試樣數3(n=3)下，依據以JIS D 0205為準的方法，在黑色面板溫度65℃，且55%RH之環境下進行碳弧試驗，藉由UV光照射使自彩色濾光器單元的水分擴散下，會對發光元件造成損傷，故目視觀察發光時的發光不均或亮點、滅點、暗點之有無等，依據下述基準進行耐光性之評估。◎: The initial brightness value is more than +10% brightness value compared with the normal design value ○: The initial brightness value is more than +5% and less than +10% brightness value compared with the normal design value -: The initial brightness value is compared with the normal design value The value comparison is 300cd/m² or more and less than +5% brightness value×: The initial brightness value is less than 300cd/m² brightness value compared with the usual design value [Evaluation of light resistance] The light resistance test is under test With sample number 3 (n=3), the carbon arc test is carried out in an environment with a black panel temperature of 65°C and 55% RH according to JIS D 0205, and the self-color filter is irradiated by UV light The diffusion of moisture in the cell will cause damage to the light-emitting element. Therefore, visually observe the uneven light emission or the presence or absence of bright spots, dark spots, and dark spots during light emission, and evaluate the light resistance based on the following criteria.

◎：在所有n=3中，完全未確認到所有發光不均、亮點、暗點之產生○：在n=2中，完全未確認到所有發光不均、亮點、暗點之產生△：在n=2中，對於發光不均、亮點、暗點之中，稍微確認到其中1項目的產生，但在實用上沒有問題×：在n=1以上之試樣，對於發光不均、亮點、暗點之中，強烈確認到2個以上項目的產生，在實用上有問題[高溫高濕耐性之評估]將各顯示裝置，在試樣數3(n=3)，且在60℃且90%RH之高溫高濕環境下放置500小時後，以目視觀察發光時之發光不均或亮點、滅點、暗點之有無等，依據下述基準，進行高溫高濕耐性之評估。◎: In all n=3, the occurrence of uneven light emission, bright spots and dark spots has not been confirmed at all○: In n=2, no uneven light emission, bright spots, and dark spots have been confirmed at all△: In n=2, among the uneven luminescence, bright spots, and dark spots, the occurrence of one of them is slightly confirmed, but there is no practical problem×: For samples with n=1 or more, the occurrence of two or more items among uneven luminescence, bright spots, and dark spots is strongly confirmed, which is problematic in practice[Evaluation of resistance to high temperature and humidity]After placing each display device in a sample number of 3 (n=3), and placed in a high temperature and high humidity environment of 60°C and 90%RH for 500 hours, visually observe the uneven luminescence, bright spots, vanishing spots, and The presence or absence of dark spots is evaluated based on the following criteria for high temperature and high humidity resistance.

◎：在所有n=3中，完全未確認到所有發光不均、亮點、暗點之產生○：在n=2中，完全未確認到所有發光不均、亮點、暗點之產生△：在n=2中，對於發光不均、亮點、暗點之中，稍微確認到其中1項目的產生，但在實用上沒有問題×：在n=1以上之試樣，對於發光不均、亮點、暗點之中，強烈確認到2個以上項目的產生，在實用上有問題將由以上所得之結果表示於表I。◎: In all n=3, the occurrence of uneven light emission, bright spots and dark spots has not been confirmed at all○: In n=2, no uneven light emission, bright spots, and dark spots have been confirmed at all△: In n=2, among the uneven luminescence, bright spots, and dark spots, the occurrence of one of them is slightly confirmed, but there is no practical problem×: For samples with n=1 or more, the occurrence of two or more items among uneven luminescence, bright spots, and dark spots is strongly confirmed, which is problematic in practiceThe results obtained from the above are shown in Table 1.

由表I所記載的結果得知，對於作為顯示裝置的有關基本品質之初期發光特性，任一顯示元件皆無問題。From the results described in Table I, it is known that there is no problem with any display element regarding the initial light-emitting characteristics related to the basic quality of the display device.

又，得知以初期亮度作為代表的亮度提高為，對於比較品之顯示裝置7，本發明之顯示裝置1～5中任一者的初期亮度為高，可藉由高折射率來提高光提取效率。又，亦可確認對於液晶顯示裝置形態之顯示裝置6，對於作為比較的顯示裝置8，可確認到亮度提高，且由對比的觀點來看，亦可得到1.1倍以上之對比。In addition, it is known that the brightness improvement represented by the initial brightness is that for thedisplay device 7 of the comparative product, the initial brightness of any one of thedisplay devices 1 to 5 of the present invention is high, and the light extraction can be improved by the high refractive index. effectiveness. In addition, it can be confirmed that thedisplay device 6 in the form of a liquid crystal display device, and thedisplay device 8 as a comparison, can confirm that the brightness is improved, and from the viewpoint of contrast, a contrast of 1.1 times or more can also be obtained.

又，對於本評估，雖未進行作為顯示裝置之壽命試驗的實施，但亦可理解因提高光提取效率時，在相同亮度下的發光元件之壽命本身亦可提高。In addition, for this evaluation, although the implementation of the life test as a display device was not carried out, it can be understood that when the light extraction efficiency is improved, the life of the light-emitting element under the same brightness can also be improved.

在耐光性之評估中，在比較例之顯示裝置7中會產生暗點，此推測為對於阻隔密封具有缺陷，因由同部位會有水分侵入而產生DS。對於顯示裝置7，作為暗點產生率，發光面積與DS面積比率約2%程度，故得知產生同程度的缺陷。過去的彩色濾光器或過去的平坦化膜為含有大量水分，藉由耐光性試驗而釋出該水分，經由同缺陷將水分擴展到發光元件。又，在液晶顯示方式之顯示裝置8，確認到收縮及暗點之產生。In the evaluation of light resistance, dark spots were generated in thedisplay device 7 of the comparative example. This is presumed to be a defect in the barrier seal, and DS was generated due to moisture intrusion from the same part. As for thedisplay device 7, the ratio of the light-emitting area to the DS area is about 2% as the dark dot generation rate, so it is known that the same degree of defects are generated. The conventional color filter or the conventional flattening film contains a large amount of water, and the water is released by the light resistance test, and the water is spread to the light-emitting element through the same defect. In addition, in thedisplay device 8 of the liquid crystal display method, the occurrence of shrinkage and dark spots was confirmed.

雖在本實施例無記載，對於頂部發光型(Top emission type)亦相同，缺陷原因主要為由外來附著物所成的異物之情況為多，無論基板還是密封皆為大概相同的產生率，推測最近的密封技術的TFE亦具有同樣缺陷產生率。因此，可推測發光方式無論為底部發射還是頂部發射，藉由同樣缺陷所引起的水分所造成的品質不良，可藉由分子轉換所產生之水分子的捕集功能予以改善。Although there is no description in this example, it is the same for the top emission type. The defect is mainly caused by foreign matter formed by foreign matter. The generation rate of both the substrate and the seal is approximately the same. The latest sealing technology TFE also has the same defect generation rate. Therefore, it can be inferred that whether the light emission method is bottom emission or top emission, the poor quality caused by the moisture caused by the same defect can be improved by the trapping function of water molecules generated by molecular conversion.

其次作為彩色濾光器單元所保持的水分引起的強制損傷評估，實施在60℃之90%RH的高溫高濕試驗，本評估中，在比較例之顯示裝置6中產生暗點。具體為在顯示裝置6，將試樣數設定為3時，對於所有試樣，在面內約3%前後之面積產生暗點。Next, as a forced damage evaluation caused by moisture retained in the color filter unit, a high temperature and high humidity test at 60° C. and 90% RH was performed. In this evaluation, dark spots were generated in thedisplay device 6 of the comparative example. Specifically, when the number of samples is set to 3 in thedisplay device 6, dark spots are generated in the area around 3% in the plane for all samples.

同樣地，在顯示裝置7中產生收縮，推測為自彩色濾光器亦有水分傳送，自光學接著劑或彩色濾光器的平坦化膜之面板端部會有水分浸透，未被水分過飽和的彩色濾光器捕集到，水分往基板方向擴散而產生收縮。Similarly, shrinkage occurs in thedisplay device 7, and it is presumed that moisture is also transmitted from the color filter, and the end of the panel of the optical adhesive or the flattening film of the color filter will be saturated with moisture, which is not supersaturated with moisture. When the color filter is trapped, the moisture diffuses toward the substrate and shrinks.

相對於此，得知使用由在本發明規定的構成所成的彩色濾光器單元之顯示裝置1～5(有機EL面板)中，因彩色濾光器或平坦化膜會吸收水分，水分不會到達發光層，進而得到不會產生收縮的有機EL面板。又，對於光提取效率，亦可比比較例更提高亮度，並可控制折射率。On the other hand, it is known that in thedisplay devices 1 to 5 (organic EL panels) using the color filter unit formed by the configuration specified in the present invention, the color filter or the flattening film absorbs water, and the water does not Will reach the light-emitting layer, and then obtain an organic EL panel that does not shrink. In addition, with regard to light extraction efficiency, brightness can be improved more than the comparative example, and the refractive index can be controlled.

對於本發明之顯示裝置，自彩色濾光器層所產生的水分可考慮為1000ppm以上之水分，含有具有一般式(1)所示結構的有機金屬氧化物之彩色濾光器層或平坦化層進行分子變換，吸收水分子，故考慮到防止對有機發光層之水分浸透成為可能。For the display device of the present invention, the moisture generated from the color filter layer can be considered to be 1000 ppm or more moisture, and the color filter layer or the planarization layer containing the organometallic oxide having the structure represented by the general formula (1) It performs molecular transformation and absorbs water molecules, so it is possible to prevent the penetration of water into the organic light-emitting layer.

又，對於顯示裝置3，可確認適用量子點，對於具有含有一般式(1)所示結構之有機金屬氧化物的彩色濾光器層，亦可顯示製作出具有分子變換功能的彩色濾光器層，藉此即使使用耐水性劣位的量子點之彩色濾光器材料，亦可抑制劣化，可製造出品質提高的彩色濾光器單元。In addition, for thedisplay device 3, it can be confirmed that quantum dots are applicable, and for a color filter layer containing an organometallic oxide structure represented by the general formula (1), a color filter with a molecular conversion function can also be produced. In this way, even if a color filter material of quantum dots with inferior water resistance is used, deterioration can be suppressed, and a color filter unit with improved quality can be manufactured.

又，對於上述實施例，對於主要使用有機EL面板及液晶顯示裝置進行評估檢證，得知對於其他方式的顯示裝置，特別對於使用有機材料的電子裝置亦可得到相同的效果，例如得知對於QD-OLED或QLED、使用OTFT的電子裝置、使用微膠囊的電子紙或電子裝置、使用彩色濾光器的微型LED等亦有效。[產業上可利用性]In addition, for the above-mentioned embodiments, the evaluation and verification of organic EL panels and liquid crystal display devices are performed, and it is known that the same effects can be obtained for other display devices, especially for electronic devices using organic materials. QD-OLED or QLED, electronic devices using OTFT, electronic paper or electronic devices using microcapsules, and micro LEDs using color filters are also effective.[Industrial availability]

本發明之顯示裝置為光提取效率高，且耐光性及耐濕熱性提高的高品質顯示裝置，可適合利用於有機發光元件、無機發光元件、彩色電子紙等。The display device of the present invention is a high-quality display device with high light extraction efficiency and improved light resistance and moisture resistance, and can be suitably used in organic light-emitting elements, inorganic light-emitting elements, color electronic paper, and the like.

1:顯示裝置2:第1基材3:TFT單元4:TFT5:第1電極6:引出電極7:有機功能層群8:第2電極9:第1密封層10:第2密封層11:第1接著層12:ALPET13:鋁箔14:保護薄膜15:第2接著層16、16A、16B:彩色濾光器單元17:第2基材18:彩色濾光器層19:平坦化層20:偏光板22:電洞注入層23:電洞輸送層24:發光層25:電子輸送層26:電子注入層31、39:幫浦32:濾光器33:管道分支34:廢水槽35:控制部36、37、38A、38B:槽CF_R1、CF_G1、CF_B1、CF_R2、CF_G2、CF_B2、F:彩色濾光器D:發光顯示單元、有機EL單元LA:發光區域L_R、L_G、L_B:發光光線OLED:有機EL元件QD_R、QD_G、QD_B:量子點TFT:TFT單元1: Display device 2: First substrate 3: TFT unit 4: TFT 5: First electrode 6: Leading electrode 7: Organic functional layer group 8: Second electrode 9: First sealing layer 10: Second sealing layer 11 : First adhesive layer 12: ALPET 13: aluminum foil 14: protective film 15: secondadhesive layer 16, 16A, 16B: color filter unit 17: second base material 18: color filter layer 19: planarization layer 20: Polarizing plate 22: Electric hole injection layer 23: Electric hole transport layer 24: Light emitting layer 25: Electron transport layer 26:Electron injection layer 31, 39: Pump 32: Filter 33: Pipe branch 34: Waste water tank 35 :Control part 36, 37, 38A, 38B: Groove CF_R1 , CF_G1 , CF_B1 , CF_R2 , CF_G2 , CF_B2 , F: Color filter D: Light-emitting display unit, organic EL unit LA: Light-emitting area L_R , L_G , L_B : Luminous light OLED: Organic EL element QD_R , QD_G , QD_B : Quantum dot TFT: TFT unit

[圖1]表示具備彩色濾光器單元的有機EL方式之顯示裝置的一例概略截面圖[圖2]表示具備彩色濾光器單元的有機EL方式之顯示裝置的其他一例概略截面圖[圖3]表示濕式塗布方式的一例之噴墨印刷法的構成概略圖[圖4]表示構成顯示裝置的有機EL元件之代表性構成一例概略截面圖[FIG. 1] A schematic cross-sectional view showing an example of a display device of an organic EL system equipped with a color filter unit[FIG. 2] A schematic cross-sectional view showing another example of a display device of an organic EL method equipped with a color filter unit[Figure 3] A schematic diagram showing the structure of an inkjet printing method as an example of a wet coating method[FIG. 4] A schematic cross-sectional view showing an example of a representative structure of an organic EL element constituting a display device

1:顯示裝置1: display device

2:第1基材2: The first substrate

3:TFT單元3: TFT unit

4:TFT4: TFT

5:第1電極5: The first electrode

6:引出電極6: Lead electrode

7:有機功能層群7: Organic functional layer group

8:第2電極8: 2nd electrode

9:第1密封層9: The first sealing layer

10:第2密封層10: The second sealing layer

11:第1接著層11: The first subsequent layer

12:ALPET12: ALPET

13:鋁箔13: aluminum foil

14:保護薄膜14: Protective film

15:第2接著層15: Second next layer

16A:彩色濾光器單元16A: Color filter unit

17:第2基材17: The second substrate

18:彩色濾光器層18: Color filter layer

19:平坦化層19: Planarization layer

20:偏光板20: Polarizing plate

CF_R1、CF_G1、CF_B1:彩色濾光器CF_R1 , CF_G1 , CF_B1 : Color filter

D:發光顯示單元、有機EL單元D: Light-emitting display unit, organic EL unit

LA:發光區域LA: luminous area

L_R、L_G、L_B:發光光線L_R , L_G , L_B : luminous light

OLED:有機EL元件OLED: organic EL element

Claims (13)

Translated fromChinese

一種顯示裝置，其為具備彩色濾光器單元之顯示裝置，其特徵為前述彩色濾光器單元至少由基材、彩色濾光器層及平坦化層所構成，前述彩色濾光器層或前述平坦化層的至少1層含有具有下述一般式(1)所示結構的有機金屬氧化物者；一般式(1) R-〔M(OR₁)_y(O-)_x-y〕_n-R(式中，R表示氫原子、碳數1個以上的烷基、烯基、芳基、環烷基、醯基、烷氧基或雜環基；但，R亦可為含有作為取代基的氟原子之碳鏈；M表示金屬原子；OR₁表示氟化烷氧基；x表示金屬原子的價數，y表示1與x之間的任意整數；n分別表示聚縮合度)。A display device, which is a display device with a color filter unit, characterized in that the color filter unit is at least composed of a substrate, a color filter layer, and a planarization layer, and the color filter layer or the foregoing At least one layer of the planarization layer contains an organometallic oxide having a structure represented by the following general formula (1); general formula (1) R-[M(OR₁ )_y (O-)_xy ]_n -R( In the formula, R represents a hydrogen atom, an alkyl group, alkenyl group, aryl group, cycloalkyl group, acyl group, alkoxy group or heterocyclic group with 1 or more carbon atoms; however, R may also contain fluorine as a substituent A carbon chain of atoms; M represents a metal atom; OR₁ represents a fluorinated alkoxy group; x represents the valence of the metal atom, y represents any integer between 1 and x; n represents the degree of polycondensation respectively).如請求項1之顯示裝置，其為具有發光層者。Such as the display device of claim 1, which has a light-emitting layer.如請求項1或請求項2之顯示裝置，其中對於前述彩色濾光器層或前述平坦化層所含有的前述有機金屬氧化物之碳原子與氟原子的總數而言，氟原子的比值為滿足下述式(a)所規定之條件；式(a) 0.05≦F/(C+F)≦1.00。The display device of claim 1 or claim 2, wherein for the total number of carbon atoms and fluorine atoms of the organic metal oxide contained in the color filter layer or the planarization layer, the ratio of fluorine atoms satisfies The conditions specified by the following formula (a); formula (a) 0.05≦F/(C+F)≦1.00.如請求項1或請求項2之顯示裝置，其中前述有機金屬氧化物所含有的金屬原子(M)為Ti、Zr、Sn、Ta、Fe、Zn或Al。Such as the display device of claim 1 or claim 2, wherein the metal atoms (M) contained in the aforementioned organic metal oxide are Ti, Zr, Sn, Ta, Fe, ZnOr Al.如請求項1或請求項2之顯示裝置，其中前述平坦化層的折射率在1.6~1.9之範圍內。Such as the display device of claim 1 or claim 2, wherein the refractive index of the aforementioned planarization layer is in the range of 1.6 to 1.9.如請求項1或請求項2之顯示裝置，其中前述平坦化層與前述彩色濾光器層之折射率差的絶對值未達0.1。Such as the display device of claim 1 or claim 2, wherein the absolute value of the refractive index difference between the planarization layer and the color filter layer is less than 0.1.如請求項1或請求項2之顯示裝置，其中前述彩色濾光器單元為含有量子點者。Such as the display device of claim 1 or claim 2, wherein the aforementioned color filter unit contains quantum dots.如請求項1或請求項2之顯示裝置，其中顯示裝置為有機發光元件、無機發光元件或彩色電子紙。Such as the display device of claim 1 or claim 2, wherein the display device is an organic light-emitting element, an inorganic light-emitting element, or color electronic paper.如請求項8之顯示裝置，其中前述有機發光元件為有機電致發光元件或含有量子點的有機發光元件。The display device of claim 8, wherein the aforementioned organic light-emitting element is an organic electroluminescence element or an organic light-emitting element containing quantum dots.如請求項8之顯示裝置，其中前述無機發光元件為含有量子點的無機發光元件或微型LED。The display device according to claim 8, wherein the aforementioned inorganic light-emitting element is an inorganic light-emitting element containing quantum dots or a micro LED.一種顯示裝置之製造方法，其為製造如請求項1至請求項10中任一項之具備彩色濾光器單元的顯示裝置之方法，其特徵為將構成前述彩色濾光器單元的彩色濾光器層，使用金屬烷氧化物或金屬羧酸酯，與氟化醇的混合液而形成。A method of manufacturing a display device, which is a method of manufacturing a display device provided with a color filter unit as in any one of claim 1 to claim 10, characterized in that the color filter constituting the color filter unit Vessel layer, using metal alkoxide or metal carboxylate, mixed with fluorinated alcoholAnd formed.一種如請求項11之顯示裝置之製造方法，其中將前述彩色濾光器層藉由濕式塗布法而形成。A method of manufacturing a display device according to claim 11, wherein the color filter layer is formed by a wet coating method.一種如請求項12之顯示裝置之製造方法，其中前述濕式塗布法為噴墨印刷法。A method of manufacturing a display device according to claim 12, wherein the wet coating method is an inkjet printing method.

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