CN103048880B - Colouring agent, coloured composition, colour filter and display element - Google Patents

Abstract

Translated fromChinese

本发明提供着色剂、着色组合物、滤色器和显示元件，所述着色组合物使用染料作为着色剂时可形成良好的着色层，含有以下成分：（A）含有下述式（1）表示的染料的着色剂、（B）粘结剂树脂和（C）交联剂；〔式（1）中，X^－表示阴离子，a是使得该化合物为电中性而确定的整数，m为0～5的整数，R¹～R⁴各自独立地表示碳原子数6～10的1价芳香族烃基等，R⁵各自独立地表示－SO₃^－等，R⁶表示1价饱和烃基等，R⁷表示1价烃基等，R⁸和R⁹各自独立地表示1价饱和脂肪族烃基等，R¹⁰表示1价烃基等，R¹¹表示1价烃基等，Q表示碳原子数6～10的1价芳香族烃基等，M表示钠原子等。该化合物满足特定的必要条件。The present invention provides a colorant, a coloring composition, a color filter and a display element. The coloring composition can form a good coloring layer when a dye is used as a coloring agent, and contains the following components: (A) contains the following components represented by the following formula (1): The coloring agent of the dye, (B) binder resin and (C) cross-linking agent; [in the formula (1), X^- represents an anion, a is an integer determined to make the compound electrically neutral, and m is 0 is an integer of ∼5, R¹ to R⁴ each independently represent a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, etc., R⁵ each independently represents -SO₃^- , etc., R⁶ represents a monovalent saturated hydrocarbon group, etc., R⁷ represents a monovalent hydrocarbon group, etc., R⁸ and R⁹ each independently represent a monovalent saturated aliphatic hydrocarbon group, etc., R¹⁰ represents a monovalent hydrocarbon group, etc., R¹¹ represents a monovalent hydrocarbon group, etc., and Q represents 1 with 6 to 10 carbon atoms. valent aromatic hydrocarbon group, etc., and M represents a sodium atom, etc. The compound satisfies certain prerequisites.

Description

Translated fromChinese

着色剂、着色组合物、滤色器和显示元件Colorant, coloring composition, color filter and display element

技术领域technical field

本发明涉及着色剂、着色组合物、滤色器和显示元件，更详细的涉及适合在用于透射型或反射型的彩色液晶显示元件、固体摄像元件、有机EL显示元件、电子纸张等的滤色器的制造中使用的着色剂、含有该着色剂的着色组合物、具备使用该着色组合物形成的着色层的滤色器、以及具备该滤色器的显示元件。The present invention relates to a coloring agent, a coloring composition, a color filter, and a display element, and more specifically relates to filters suitable for use in transmissive or reflective color liquid crystal display elements, solid-state imaging elements, organic EL display elements, electronic paper, etc. A coloring agent used in the manufacture of a color device, a coloring composition containing the coloring agent, a color filter including a colored layer formed using the coloring composition, and a display element including the color filter.

背景技术Background technique

就使用了着色放射线敏感性组合物的滤色器的制造而言，已知在基板上涂布颜料分散型的着色放射线敏感性组合物并干燥后，对干燥涂膜照射放射线（以下称为“曝光”）使之显影成所希望的图案形状，从而得到各色的像素的方法（专利文献1～2）。另外，还已知利用分散有炭黑的光聚合性组合物形成黑矩阵的方法（专利文献3）。另外，还已知利用颜料分散型的着色树脂组合物通过喷墨方式得到各色像素的方法（专利文献4）。In the manufacture of a color filter using a colored radiation-sensitive composition, it is known to apply a pigment-dispersed colored radiation-sensitive composition on a substrate and dry it, and then irradiate the dried coating film with radiation (hereinafter referred to as "" Exposure") to develop it into a desired pattern shape to obtain pixels of each color (Patent Documents 1 to 2). Moreover, the method of forming a black matrix using the photopolymerizable composition in which carbon black was dispersed is also known (patent document 3). In addition, a method of obtaining pixels of each color by an inkjet method using a pigment-dispersed colored resin composition is also known (Patent Document 4).

近年来，强烈需要液晶显示元件的高对比度化、固体摄像元件的高精细化，为了实现这些，正在研究作为着色剂的染料的应用。例如，在专利文献5中，提出了特定的呫吨系染料的使用。In recent years, high contrast of liquid crystal display elements and high definition of solid-state imaging elements are strongly required, and in order to realize these, the application of dyes as colorants has been studied. For example, Patent Document 5 proposes the use of a specific xanthene-based dye.

专利文献1：日本特开平2－144502号公报Patent Document 1: Japanese Patent Application Laid-Open No. 2-144502

专利文献2：日本特开平3－53201号公报Patent Document 2: Japanese Patent Application Laid-Open No. 3-53201

专利文献3：日本特开平6－35188号公报Patent Document 3: Japanese Patent Application Laid-Open No. 6-35188

专利文献4：日本特开2000－310706号公报Patent Document 4: Japanese Patent Laid-Open No. 2000-310706

专利文献5：日本特开2010－254964号公报Patent Document 5: Japanese Patent Laid-Open No. 2010-254964

发明内容Contents of the invention

但是，如果使用专利文献5中提出的染料，则存在像素的对比度降低的问题。另一方面，如果使用染料，则滤色器的电压保持率、耐热性恶化的问题大量产生。因此，强烈要求适合能够兼顾良好的电压保持率、高对比度和高耐热性的滤色器的制作的着色组合物的开发。However, if the dye proposed in Patent Document 5 is used, there is a problem that the contrast of the pixels is lowered. On the other hand, when a dye is used, many problems arise that the voltage retention and heat resistance of the color filter deteriorate. Therefore, the development of a coloring composition suitable for the production of a color filter capable of achieving both good voltage retention, high contrast, and high heat resistance has been strongly demanded.

因此，本发明的课题是提供使用染料作为着色剂时能够形成能够兼顾良好的电压保持率、高对比度和高耐热性的着色层的着色组合物，以及提供可适用于该着色组合物的着色剂。另外，本发明的课题是提供具备由上述着色组合物形成的着色层而成的滤色器、以及具备该滤色器的显示元件。Therefore, an object of the present invention is to provide a coloring composition capable of forming a colored layer capable of achieving both good voltage retention, high contrast, and high heat resistance when a dye is used as a colorant, and to provide a coloring composition applicable to the coloring composition. agent. Moreover, the subject of this invention is providing the display element provided with the color filter provided with the coloring layer which consists of the said coloring composition, and this color filter.

鉴于该实际情况，本发明的发明人进行深入研究，结果发现通过将具有特定构造的染料作为着色剂使用，从而能够解决上述课题，完成了本发明。In view of this fact, the inventors of the present invention conducted intensive research and found that the above-mentioned problems can be solved by using a dye having a specific structure as a colorant, and completed the present invention.

即，本发明提供一种着色组合物，其特征在于，含有以下成分（A）、（B）和（C）：That is, the present invention provides a coloring composition characterized by containing the following components (A), (B) and (C):

（A）含有由下述式（1）表示的染料的着色剂，(A) a coloring agent containing a dye represented by the following formula (1),

（B）粘结剂树脂、和(B) binder resin, and

（C）交联剂。(C) Cross-linking agent.

〔式（1）中，[In formula (1),

X^-表示阴离子；X^- represents an anion;

a是使该化合物为电中性而确定的整数；a is an integer determined to make the compound electrically neutral;

m表示0～5的整数。其中，m为2以上的整数时，多个R⁵可以相同，也可以不同；m represents an integer of 0-5. Wherein, when m is an integer more than 2, multiple R⁵ can be the same or different;

R¹～R⁴各自独立地表示氢原子、－R⁶或碳原子数为6～10的1价芳香族烃基（该芳香族烃基所含的氢原子可以被卤素原子、－R⁶、－OH、－OR⁶、－SO₃^－、－SO₃H、－SO₃M、－CO₂H、－CO₂R⁶、－SO₃R⁶、－SO₂NH₂、－SO₂NHR⁸、－SO₂NR⁸R⁹、－SO₂－O－N＝CR⁷R¹⁰、－SO₂NHNHR⁷、－SO₂SR⁷或－SO₂NHSO₂R¹¹所取代）；R¹ to R⁴ each independently represent a hydrogen atom, -R⁶ or a monovalent aromatic hydrocarbon group with 6 to 10 carbon atoms (the hydrogen atom contained in the aromatic hydrocarbon group can be replaced by a halogen atom, -R⁶ , -OH , -OR⁶ , -SO₃^- , -SO₃ H, -SO₃ M, -CO₂ H, -CO₂ R⁶ , -SO₃ R⁶ , -SO₂ NH₂ , -SO₂ NHR⁸ , - SO₂ NR⁸ R⁹ , -SO₂ -O-N=CR⁷ R¹⁰ , -SO₂ NHNHR⁷ , -SO₂ SR⁷ or -SO₂ NHSO₂ R¹¹ replaced);

R⁵各自独立地表示－SO₃^－、－SO₃H、－SO₃M、－CO₂H、－CO₂R⁶、－SO₃R⁶、－SO₂NHR⁸、－SO₂NR⁸R⁹、－SO₂－O－N＝CR⁷R¹⁰、－SO₂NHNHR⁷、－SO₂SR⁷或－SO₂NHSO₂R¹¹；R⁵ each independently represents -SO₃^- , -SO₃ H, -SO₃ M, -CO₂ H, -CO₂ R⁶ , -SO₃ R⁶ , -SO₂ NHR⁸ , -SO₂ NR⁸ R^9. -SO₂ -O-N=CR⁷ R¹⁰ , -SO₂ NHNHR⁷ , -SO₂ SR⁷ or -SO₂ NHSO₂ R¹¹ ;

R⁶表示1价饱和烃基（该饱和烃基所含的氢原子可以被卤素原子所取代，该饱和烃基所含的－CH₂－可以被－O－、－CO－或－NR⁷－所取代）；R⁶ represents a monovalent saturated hydrocarbon group (the hydrogen atom contained in the saturated hydrocarbon group can be replaced by a halogen atom, and the -CH₂ - contained in the saturated hydrocarbon group can be replaced by -O-, -CO- or -NR⁷ -) ;

R⁷表示1价烃基（该烃基所含的氢原子可以被卤素原子或－R¹¹所取代，该烃基可以用－O－或－CO－连结）；R⁷ represents a monovalent hydrocarbon group (the hydrogen atom contained in the hydrocarbon group can be replaced by a halogen atom or -R¹¹ , and the hydrocarbon group can be linked by -O- or -CO-);

R⁸和R⁹各自独立地表示1价饱和脂肪族烃基（该饱和脂肪族烃基所含的氢原子可以被－OH、卤素原子、－Q、－CH＝CH₂或－CH＝CHR⁶所取代，该饱和脂肪族烃基所含的－CH₂－可以被－O－、－S－、－CO－、－NH－或－NR⁶－所取代）；R⁸ and R⁹ each independently represent a monovalent saturated aliphatic hydrocarbon group (the hydrogen atom contained in the saturated aliphatic hydrocarbon group can be replaced by -OH, halogen atom, -Q, -CH=CH₂ or -CH=CHR⁶ , the -CH₂ - contained in the saturated aliphatic hydrocarbon group can be replaced by -O-, -S-, -CO-, -NH- or -NR⁶ -);

R¹⁰表示氢原子、1价烃基（该烃基所含的氢原子可以被卤素原子或－R¹¹所取代，该烃基可以用－O－或－CO－连结）或－R¹¹；R¹⁰ represents a hydrogen atom, a monovalent hydrocarbon group (the hydrogen atom contained in the hydrocarbon group can be replaced by a halogen atom or -R¹¹ , and the hydrocarbon group can be linked by -O- or -CO-) or -R¹¹ ;

R¹¹表示可以具有取代基的1价烃基；R¹¹ represents a monovalent hydrocarbon group which may have a substituent;

Q表示碳原子数为6～10的1价芳香族烃基或碳原子数为3～10的1价杂环基（该芳香族烃基和该杂环基所含的1个以上的氢原子被选自－R⁶、－OR⁶和－CH＝CHR⁶中的至少1种所取代，该芳香族烃基和该杂环基所含的其余的氢原子可以被－OH、－NO₂、－CH＝CH₂或卤素原子所取代）；Q represents a monovalent aromatic hydrocarbon group with 6 to 10 carbon atoms or a monovalent heterocyclic group with 3 to 10 carbon atoms (one or more hydrogen atoms contained in the aromatic hydrocarbon group and the heterocyclic group are selected Since at least one of -R⁶ , -OR⁶ and -CH=CHR⁶ is substituted, the remaining hydrogen atoms contained in the aromatic hydrocarbon group and the heterocyclic group can be replaced by -OH, -NO₂ , -CH= CH₂ or halogen atoms replaced);

M表示钠原子或钾原子。M represents a sodium atom or a potassium atom.

其中，该化合物满足下述（i）～（vi）中的1种以上的必要条件。However, the compound satisfies at least one of the following requirements (i) to (vi).

（i）R¹～R⁴中的1个以上为具有选自－SO₂－O－N＝CR⁷R¹⁰、－SO₂NHNHR⁷、－SO₂SR⁷和－SO₂NHSO₂R¹¹中的至少1种取代基的芳香族烃基。(i) One or more of R¹ to R⁴ is selected from the group consisting of -SO₂ -O-N=CR⁷ R¹⁰ , -SO₂ NHNHR⁷ , -SO₂ SR⁷ and -SO₂ NHSO₂ R¹¹ An aromatic hydrocarbon group of at least one substituent.

（ii）R¹～R⁴中的1个以上为具有选自－SO₂NHR⁸和－SO₂NR⁸R⁹中的至少1种取代基的芳香族烃基。其中，由R⁸、R⁹表示的1价饱和脂肪族烃基的碳原子数为11以上。(ii) One or more of R¹ to R⁴ is an aromatic hydrocarbon group having at least one substituent selected from —SO₂ NHR⁸ and —SO₂ NR⁸ R⁹ . However, the monovalent saturated aliphatic hydrocarbon group represented by R⁸ and R⁹ has 11 or more carbon atoms.

（iii）R¹～R⁴中的1个以上为－R⁶、或具有选自－R⁶、－OR⁶、－CO₂R⁶和－SO₃R⁶中的至少1种取代基的芳香族烃基。其中，由R⁶表示的1价饱和烃基的碳原子数为11以上。(iii) One or more of R¹ to R⁴ is -R⁶ , or an aromatic compound having at least one substituent selected from -R⁶ , -OR⁶ , -CO₂ R⁶ and -SO₃ R⁶ family of hydrocarbon groups. Among them, the monovalent saturated hydrocarbon group represented by R⁶ has 11 or more carbon atoms.

（iv）具有m个的R⁵中的1个以上为－SO₂－O－N＝CR⁷R¹⁰、－SO₂NHNHR⁷、－SO₂SR⁷或－SO₂NHSO₂R¹¹。(iv) One or more of m R⁵ is -SO₂ -O-N=CR⁷ R¹⁰ , -SO₂ NHNHR⁷ , -SO₂ SR⁷ or -SO₂ NHSO₂ R¹¹ .

（v）具有m个的R⁵中的1个以上为－SO₂NHR⁸或－SO₂NR⁸R⁹。其中，由R⁸、R⁹表示的1价饱和脂肪族烃基的碳原子数为11以上。(v) One or more of m R⁵ is -SO₂ NHR⁸ or -SO₂ NR⁸ R⁹ . However, the monovalent saturated aliphatic hydrocarbon group represented by R⁸ and R⁹ has 11 or more carbon atoms.

（vi）具有m个的R⁵中的1个以上为－CO₂R⁶或－SO₃R⁶。其中，由R⁶表示的1价饱和烃基的碳原子数为11以上。〕(vi) One or more of m R⁵ is -CO₂ R⁶ or -SO₃ R⁶ . Among them, the monovalent saturated hydrocarbon group represented by R⁶ has 11 or more carbon atoms. 〕

另外，本发明提供具备利用该着色组合物形成的着色层而成的滤色器、以及具备该滤色器的显示元件。在这里，“着色层”意味着用于滤色器的各色像素、黑矩阵、黑间隔件等。Moreover, this invention provides the display element provided with the color filter provided with the colored layer formed from this colored composition, and this color filter. Here, "colored layer" means pixels of each color for a color filter, a black matrix, a black spacer, and the like.

另外，本发明提供由上述式（1）表示的染料。In addition, the present invention provides a dye represented by the above formula (1).

利用本发明的着色组合物，则能够形成电压保持率、对比度和耐热性优异的着色层。因此，本发明的着色组合物极其适用于以显示元件用滤色器、固体摄像元件的色分解用滤色器、有机EL显示元件用滤色器、电子纸张用滤色器为代表的各种滤色器的制作。The colored composition of the present invention can form a colored layer excellent in voltage retention, contrast, and heat resistance. Therefore, the coloring composition of the present invention is extremely suitable for use in various color filters represented by color filters for display devices, color resolution filters for solid-state imaging devices, color filters for organic EL display devices, and color filters for electronic paper. Fabrication of color filters.

具体实施方式Detailed ways

以下，对本发明详细说明。Hereinafter, the present invention will be described in detail.

着色组合物coloring composition

以下，对本发明的着色组合物的构成成分进行说明。Hereinafter, the constituent components of the coloring composition of the present invention will be described.

－（A）着色剂－－(A) Coloring agent－

本发明的着色组合物含有由上述式（1）表示的染料（以下称为“染料（a1）”）作为（A）着色剂。The coloring composition of the present invention contains a dye represented by the above formula (1) (hereinafter referred to as “dye (a1)”) as (A) colorant.

在式（1）中，作为X^－，可举出例如卤素离子、硼阴离子、磷酸阴离子、羧酸阴离子、硫酸阴离子、有机磺酸阴离子、氮阴离子、甲基化物阴离子等。In formula (1), examples of X⁻ include halide ions, boron anions, phosphate anions, carboxylic acid anions, sulfate anions, organic sulfonic acid anions, nitrogen anions, methide anions, and the like.

作为R¹～R⁴和Q中的碳原子数为6～10的1价芳香族烃基，优选碳原子数为6～10的1价芳基，更具体而言，可举出苯基、苄基、邻甲苯基、间甲苯基、对甲苯基、萘基等。另外，作为在上述芳香族烃基上可取代的卤素原子，可举出例如氟原子、氯原子和溴原子。The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R¹ to R⁴ and Q is preferably a monovalent aryl group having 6 to 10 carbon atoms, more specifically, phenyl, benzyl Base, o-tolyl, m-tolyl, p-tolyl, naphthyl, etc. In addition, examples of the halogen atom which may be substituted on the aromatic hydrocarbon group include a fluorine atom, a chlorine atom and a bromine atom.

R⁶中的1价饱和烃基可以是饱和脂肪族烃基和饱和脂环式烃基中的任一种。另外，饱和脂肪族烃基可以是直链状和支链状中的任一形态。作为上述饱和脂肪族烃基，优选碳原子数为1～20的饱和脂肪族烃基，具体而言，可举出碳原子数为1～20的烷基，可举出例如甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、己基、庚基、辛基、2－乙基己基、壬基、癸基、十一烷基、1－甲基癸基、2－甲基癸基、十二烷基、1－甲基十一烷基、1－乙基癸基、十三烷基、十四烷基、叔十二烷基、十五烷基、1－庚基辛基、十六烷基、十八烷基、十九烷基、二十烷－1－基等。该1价饱和烃基所含的－CH₂－可以被－O－、－CO－或－NR⁷－所取代，作为1价饱和烃基所含的－CH₂－被取代为－O－的基团，可举出例如甲氧基丙基、乙氧基丙基、甲氧基己基、乙氧基丙基、2－乙基己氧基丙基等。The monovalent saturated hydrocarbon group in R⁶ may be any of a saturated aliphatic hydrocarbon group and a saturated alicyclic hydrocarbon group. In addition, the saturated aliphatic hydrocarbon group may be either straight-chain or branched. As the above-mentioned saturated aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable, specifically, an alkyl group having 1 to 20 carbon atoms is mentioned, for example, methyl, ethyl, propyl, etc. Base, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, 1-methyl Decyl, 2-methyldecyl, dodecyl, 1-methylundecyl, 1-ethyldecyl, tridecyl, tetradecyl, tert-dodecyl, pentadecyl Base, 1-heptyl octyl, hexadecyl, octadecyl, nonadecyl, eicosan-1-yl, etc. The -CH₂ - contained in the monovalent saturated hydrocarbon group may be substituted by -O-, -CO- or -NR⁷ -, as a group in which the -CH₂ - contained in the monovalent saturated hydrocarbon group is replaced by -O- , for example, a methoxypropyl group, an ethoxypropyl group, a methoxyhexyl group, an ethoxypropyl group, a 2-ethylhexyloxypropyl group, etc. are mentioned.

另外，作为上述饱和脂环式烃基，优选碳原子数为3～30的饱和脂环式烃基，具体而言，可举出碳原子数为3～30的环烷基、饱和稠合多环烃基、饱和桥联环烃基、饱和螺烃基等。更具体而言，可举出环丙基、环丁基、环戊基、环己基、叔丁基环己基、环庚基、环辛基、三环癸基、十氢－2－萘基、三环[5.2.1.0^2,6]癸烷－8－基、五环十五烷基、异冰片基、金刚烷基等。其中，优选碳原子数为3～12的饱和脂环式烃基，更优选碳原子数为3～8的饱和脂环式烃基。In addition, the above-mentioned saturated alicyclic hydrocarbon group is preferably a saturated alicyclic hydrocarbon group having 3 to 30 carbon atoms, specifically, a cycloalkyl group having 3 to 30 carbon atoms, a saturated condensed polycyclic hydrocarbon group, , saturated bridged cyclic hydrocarbon group, saturated spiro hydrocarbon group, etc. More specifically, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, tert-butylcyclohexyl, cycloheptyl, cyclooctyl, tricyclodecanyl, decahydro-2-naphthyl, tricyclic [5.2.1.0^2,6 ]decane-8-yl, pentacyclopentadecyl, isobornyl, adamantyl, etc. Among them, a saturated alicyclic hydrocarbon group having 3 to 12 carbon atoms is preferable, and a saturated alicyclic hydrocarbon group having 3 to 8 carbon atoms is more preferable.

另外，作为可以在上述饱和烃基上取代的卤素原子，可举出与上述相同的卤素原子。In addition, examples of the halogen atom which may be substituted on the above-mentioned saturated hydrocarbon group include the same halogen atom as above.

作为－CO₂R⁶，可举出例如甲基氧羰基、乙基氧羰基、丙基氧羰基、异丙基氧羰基、丁基氧羰基、异丁基氧羰基、戊基氧羰基、异戊基氧羰基、新戊基氧羰基、环戊基氧羰基、己基氧羰基、环己基氧羰基、庚基氧羰基、环庚基氧羰基、辛基氧羰基、2－乙基己基氧羰基、环辛基氧羰基、壬基氧羰基、癸基氧羰基、三环癸基氧羰基、甲氧基丙基氧羰基、乙氧基丙基氧羰基、己氧基丙基氧羰基、2－乙基己氧基丙基氧羰基、甲氧基己基氧羰基、十一烷基羰基、十二烷基羰基、十四烷基羰基、叔十二烷基羰基、十六烷基羰基、十八烷基羰基等。Examples of -CO₂ R⁶ include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, isobutyloxycarbonyl, pentyloxycarbonyl, and isopentyloxycarbonyl. oxycarbonyl, neopentyloxycarbonyl, cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, cyclo Octyloxycarbonyl, nonyloxycarbonyl, decyloxycarbonyl, tricyclodecanyloxycarbonyl, methoxypropyloxycarbonyl, ethoxypropyloxycarbonyl, hexyloxypropyloxycarbonyl, 2-ethyl Hexyloxypropyloxycarbonyl, methoxyhexyloxycarbonyl, undecylcarbonyl, dodecylcarbonyl, tetradecylcarbonyl, tert-dodecylcarbonyl, hexadecylcarbonyl, octadecyl Carbonyl etc.

作为－SO₃R⁶，可举出例如甲磺酰基、乙磺酰基、己磺酰基、癸磺酰基、十一烷基磺酰基、十二烷基磺酰基、十四烷基磺酰基、叔十二烷基磺酰基、十六烷基磺酰基、十八烷基磺酰基等。Examples of -SO₃ R⁶ include methylsulfonyl, ethylsulfonyl, hexylsulfonyl, decanylsulfonyl, undecylsulfonyl, dodecylsulfonyl, tetradecylsulfonyl, t-decylsulfonyl, Dialkylsulfonyl, hexadecylsulfonyl, octadecylsulfonyl and the like.

R⁷、R¹⁰和R¹¹中的1价烃基可以是脂肪族烃基、脂环式烃基和芳香族烃基中的任一种。另外，脂肪族烃基可以是直链状和支链状中的任一形态。脂肪族烃基和脂环式烃基可以是饱和烃基，也可以是不饱和烃基。应予说明，不饱和烃基的不饱和键的位置可以是分子链内和分子链末端中的任意位置，可以在任意位置具有。另外，在R⁷中，作为用－O－或－CO－连结的1价烃基，可举出烷氧基、苯氧基、烷基羰基、苯甲酰基等。The monovalent hydrocarbon group in R⁷ , R¹⁰ and R¹¹ may be any of aliphatic hydrocarbon group, alicyclic hydrocarbon group and aromatic hydrocarbon group. In addition, the aliphatic hydrocarbon group may be in either straight-chain or branched form. The aliphatic hydrocarbon group and the alicyclic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. It should be noted that the position of the unsaturated bond of the unsaturated hydrocarbon group may be any position within the molecular chain or at the end of the molecular chain, and may be present at any position. In addition, in R⁷ , examples of the monovalent hydrocarbon group linked by -O- or -CO- include alkoxy, phenoxy, alkylcarbonyl, benzoyl and the like.

作为R¹¹中的1价烃基的取代基，可举出例如卤素原子、碳原子数为1～20的烷基、三氟甲基、氨基、硝基等。取代基的位置和数量为任意，具有2个以上取代基时，该取代基可以相同，也可以不同。再有，作为在烃基上可取代的卤素原子和碳原子数为1～20的烷基的具体例，可以举出与上述相同的基团。Examples of the substituent of the monovalent hydrocarbon group in R¹¹ include a halogen atom, an alkyl group having 1 to 20 carbon atoms, a trifluoromethyl group, an amino group, and a nitro group. The position and number of substituents are arbitrary, and when there are two or more substituents, the substituents may be the same or different. In addition, specific examples of the halogen atom and the alkyl group having 1 to 20 carbon atoms which may be substituted on the hydrocarbon group include the same groups as above.

作为上述脂肪族烃基，优选碳原子数为1～20的脂肪族烃基，具体而言，可举出碳原子数为1～20的烷基、碳原子数为2～16的烯基、碳原子数为2～12的炔基。作为烷基的具体例，可以举出与上述相同的基团。另外，作为烯基，可举出例如乙烯基、1－丙烯基、1－丁烯基、1，3－丁二烯基、1－戊烯基、2－戊烯基、1－己烯基、2－乙基－2－丁烯基、2－辛烯基、（4－乙烯基）－5－己烯基、2－癸烯基等。作为炔基，可举出例如乙炔基、1－丙炔基、1－丁炔基、1－戊炔基、3－戊炔基、1－己炔基、2－乙基－2－丁炔基、2－辛炔基、（4－乙炔基）－5－己炔基、2－癸炔基等。The above-mentioned aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, specifically, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 16 carbon atoms, a carbon atom An alkynyl group whose number is 2-12. Specific examples of the alkyl group include the same groups as those described above. In addition, examples of the alkenyl group include vinyl, 1-propenyl, 1-butenyl, 1,3-butadienyl, 1-pentenyl, 2-pentenyl, 1-hexenyl , 2-ethyl-2-butenyl, 2-octenyl, (4-vinyl)-5-hexenyl, 2-decenyl, etc. Examples of the alkynyl group include ethynyl, 1-propynyl, 1-butynyl, 1-pentynyl, 3-pentynyl, 1-hexynyl, 2-ethyl-2-butynyl base, 2-octynyl, (4-ethynyl)-5-hexynyl, 2-decynyl, etc.

作为上述脂环式烃基，优选碳原子数为3～30的脂环式烃基，具体而言，可举出碳原子数为3～18的环烷基、环烯基、稠合多环烃基、桥联环烃基、螺烃基、环状萜烯烃基等。作为这些具体例，除了与上述相同的以外，还可举出二环戊烯基、三环戊烯基等。The above-mentioned alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 3 to 30 carbon atoms, specifically, a cycloalkyl group having 3 to 18 carbon atoms, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, Bridged cyclic hydrocarbon group, spiro hydrocarbon group, cyclic terpene hydrocarbon group, etc. As these specific examples, in addition to the same as above, dicyclopentenyl, tricyclopentenyl, etc. are mentioned.

作为上述芳香族烃基，优选碳原子数为6～30的芳香族烃基，具体而言，可以举出与上述相同的基团。As the above-mentioned aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 30 carbon atoms is preferable, and specific examples thereof include the same groups as above.

另外，作为可以在上述烃基上取代的卤素原子，可以举出与上述相同的卤素原子。In addition, examples of the halogen atom which may be substituted on the above-mentioned hydrocarbon group include the same halogen atom as above.

其中，作为R⁷，优选脂肪族烃基、芳香族烃基，更优选碳原子数为1～20的烷基、碳原子数为6～30的芳香族烃基，进一步优选碳原子数为1～15的烷基、碳原子数为6～10的芳香族烃基。作为该芳香族烃基，还优选用－O－或－CO－连结的芳香族烃基。Among them, R⁷ is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, more preferably an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, and even more preferably an alkyl group having 1 to 15 carbon atoms. An alkyl group, an aromatic hydrocarbon group having 6 to 10 carbon atoms. As the aromatic hydrocarbon group, an aromatic hydrocarbon group linked by —O— or —CO— is also preferable.

另外，作为R¹⁰，优选脂肪族烃基，更优选碳原子数为1～10的烷基，进一步优选碳原子数为1～4的烷基，作为R¹¹，优选芳香族烃基，更优选碳原子数为6～10的芳基。In addition, R¹⁰ is preferably an aliphatic hydrocarbon group, more preferably an alkyl group having 1 to 10 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms, and R¹¹ is preferably an aromatic hydrocarbon group, more preferably a carbon atom group. An aryl group whose number is 6-10.

R⁸和R⁹中的1价饱和脂肪族烃基可以是直链状和支链状中的任一形态。作为上述饱和脂肪族烃基，优选碳原子数为1～24的饱和脂肪族烃基，作为具体例，除了上述R⁶中的碳原子数为1～20的烷基以外，可举出二十一烷－1－基、二十二烷－1－基、二十三烷－1－基、二十四烷－1－基等。作为可以在上述饱和脂肪族烃基上取代的卤素原子，可以举出与上述相同的卤素原子。The monovalent saturated aliphatic hydrocarbon group in R⁸ and R⁹ may be in any form of straight chain or branched chain. As the above-mentioned saturated aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group having 1 to 24 carbon atoms is preferred. As a specific example, in addition to the alkyl group having 1 to 20 carbon atoms in the above-mentioned R⁶ , eicosane -1-yl, docosane-1-yl, tricosane-1-yl, tetracosane-1-yl, etc. Examples of the halogen atom which may be substituted on the saturated aliphatic hydrocarbon group include the same halogen atoms as those described above.

作为－SO₂NHR⁸，可举出甲基氨磺酰基、乙基氨磺酰基、丙基氨磺酰基、异丙基氨磺酰基、丁基氨磺酰基、异丁基氨磺酰基、戊基氨磺酰基、异戊基氨磺酰基、新戊基氨磺酰基、己基氨磺酰基、庚基氨磺酰基、辛基氨磺酰基、2－乙基己基氨磺酰基、壬基氨磺酰基、癸基氨磺酰基、十一烷基氨磺酰基、1－甲基癸基、2－甲基癸基氨磺酰基、十二烷基氨磺酰基、1－甲基十一烷基氨磺酰基、1－乙基癸基氨磺酰基、十三烷基氨磺酰基、十四烷基氨磺酰基、叔十二烷基氨磺酰基、十五烷基氨磺酰基、1－庚基辛基氨磺酰基、十六烷基氨磺酰基、十八烷基氨磺酰基、二十二烷－1－基氨磺酰基等。Examples of -SO₂ NHR⁸ include methylsulfamoyl, ethylsulfamoyl, propylsulfamoyl, isopropylsulfamoyl, butylsulfamoyl, isobutylsulfamoyl, pentyl Sulfamoyl, isopentylsulfamoyl, neopentylsulfamoyl, hexylsulfamoyl, heptylsulfamoyl, octylsulfamoyl, 2-ethylhexylsulfamoyl, nonylsulfamoyl, Decylsulfamoyl, Undecylsulfamoyl, 1-Methyldecyl, 2-Methyldecylsulfamoyl, Dodecylsulfamoyl, 1-Methylundecylsulfamoyl , 1-ethyldecylsulfamoyl, tridecylsulfamoyl, tetradecylsulfamoyl, tert-dodecylsulfamoyl, pentadecylsulfamoyl, 1-heptyloctyl Sulfamoyl group, hexadecylsulfamoyl group, octadecylsulfamoyl group, docosan-1-ylsulfamoyl group, etc.

作为Q中的碳原子数为3～10的1价杂环基，可举出例如吡咯烷基、咪唑烷基基、吡唑烷基、哌啶基、哌啶子基、哌嗪基、高哌嗪基、吗啉基、硫代吗啉基等脂环式杂环基，吡啶基、吡嗪基、嘧啶基、哒嗪基、喹啉基、异喹啉基、酞嗪基、萘啶基、喹喔啉基、噻嗯基、呋喃基、吡喃基、吡咯基、咪唑基、吡唑基、三唑基、四唑基、噻唑基、唑基、吲哚基、吲唑基、苯并咪唑基、嘌呤基等芳香族杂环基。作为可以在上述杂环基上取代的卤素原子，可举出与上述相同的卤素原子。Examples of the monovalent heterocyclic group having 3 to 10 carbon atoms in Q include pyrrolidinyl, imidazolidinyl, pyrazolidinyl, piperidinyl, piperidino, piperazinyl, Piperazinyl, morpholinyl, thiomorpholinyl and other alicyclic heterocyclic groups, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, quinolinyl, isoquinolinyl, phthalazinyl, naphthyridine Base, quinoxalinyl, thienyl, furyl, pyryl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, thiazolyl, Aromatic heterocyclic groups such as azolyl, indolyl, indazolyl, benzimidazolyl, and purinyl. Examples of the halogen atom that may be substituted on the above-mentioned heterocyclic group include the same halogen atoms as those described above.

m为0～5的整数，优选为0～3，更优选为1或2。m is an integer of 0-5, Preferably it is 0-3, More preferably, it is 1 or 2.

M为钠原子或钾原子。M is a sodium atom or a potassium atom.

另外，染料（a1）需要满足下述（i）～（vi）中的1种以上的必要条件。In addition, the dye (a1) needs to satisfy at least one requirement among the following (i) to (vi).

（i）R¹～R⁴中的1个以上为具有选自－SO₂－O－N＝CR⁷R¹⁰、－SO₂NHNHR⁷、－SO₂SR⁷和－SO₂NHSO₂R¹¹中的至少1种取代基的芳香族烃基。(i) One or more of R¹ to R⁴ is selected from the group consisting of -SO₂ -O-N=CR⁷ R¹⁰ , -SO₂ NHNHR⁷ , -SO₂ SR⁷ and -SO₂ NHSO₂ R¹¹ An aromatic hydrocarbon group of at least one substituent.

（ii）R¹～R⁴中的1个以上为具有选自－SO₂NHR⁸和－SO₂NR⁸R⁹中的至少1种取代基的芳香族烃基。其中，由R⁸、R⁹表示的1价饱和脂肪族烃基的碳原子数为11以上。(ii) One or more of R¹ to R⁴ is an aromatic hydrocarbon group having at least one substituent selected from —SO₂ NHR⁸ and —SO₂ NR⁸ R⁹ . However, the monovalent saturated aliphatic hydrocarbon group represented by R⁸ and R⁹ has 11 or more carbon atoms.

（iii）R¹～R⁴中的1个以上为－R⁶、或具有选自－R⁶、－OR⁶、－CO₂R⁶和－SO₃R⁶中的至少1种取代基的芳香族烃基。其中，由R⁶表示的1价饱和烃基的碳原子数为11以上。(iii) One or more of R¹ to R⁴ is -R⁶ , or an aromatic compound having at least one substituent selected from -R⁶ , -OR⁶ , -CO₂ R⁶ and -SO₃ R⁶ family of hydrocarbon groups. Among them, the monovalent saturated hydrocarbon group represented by R⁶ has 11 or more carbon atoms.

（iv）具有m个的R⁵中的1个以上为－SO₂－O－N＝CR⁷R¹⁰、－SO₂NHNHR⁷、－SO₂SR⁷或－SO₂NHSO₂R¹¹。(iv) One or more of m R⁵ is -SO₂ -O-N=CR⁷ R¹⁰ , -SO₂ NHNHR⁷ , -SO₂ SR⁷ or -SO₂ NHSO₂ R¹¹ .

（v）具有m个的R⁵中的1个以上为－SO₂NHR⁸或－SO₂NR⁸R⁹。其中，由R⁸、R⁹表示的1价饱和脂肪族烃基的碳原子数为11以上。(v) One or more of m R⁵ is -SO₂ NHR⁸ or -SO₂ NR⁸ R⁹ . However, the monovalent saturated aliphatic hydrocarbon group represented by R⁸ and R⁹ has 11 or more carbon atoms.

（vi）具有m个的R⁵中的1个以上为－CO₂R⁶或－SO₃R⁶。其中，由R⁶表示的1价饱和烃基的碳原子数为11以上。(vi) One or more of m R⁵ is -CO₂ R⁶ or -SO₃ R⁶ . Among them, the monovalent saturated hydrocarbon group represented by R⁶ has 11 or more carbon atoms.

再有，染料（1a）满足必要条件（i）、（ii）和（iv）～（vi）中的1个以上时，并不一定需要必要条件（iii）的－R⁶、－OR⁶、－CO₂R⁶、－SO₃R⁶中的由R⁶表示的1价饱和烃基的碳原子数为11以上。In addition, when the dye (1a) satisfies one or more of the requirements (i), (ii) and (iv) to (vi), the -R⁶ , -OR⁶ , The monovalent saturated hydrocarbon group represented by R⁶ in —CO₂ R⁶ and —SO₃ R⁶ has 11 or more carbon atoms.

另外，染料（1a）满足必要条件（i）～（v）中的1个以上时，并不一定需要必要条件（vi）的－CO₂R⁶、－SO₃R⁶中由R⁶表示的1价饱和烃基的碳原子数为11以上。In addition, when the dye (1a) satisfies one or more of the requirements (i) to (v), the dye represented by R⁶ among -CO₂ R⁶ and -SO₃ R⁶ in the requirement (vi) is not necessarily required. The monovalent saturated hydrocarbon group has 11 or more carbon atoms.

在这种情况下，由R⁶表示的1价饱和烃基优选碳原子数为1～8的烷基，更优选碳原子数为1～6的烷基，进一步优选碳原子数为1～4的烷基。In this case, the monovalent saturated hydrocarbon group represented by R is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to⁶ carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms. alkyl.

另外，染料（1a）满足必要条件（i）和（iii）～（vi）中的1个以上时，并不一定需要必要条件（ii）的－SO₂NHR⁸、－SO₂NR⁸R⁹中的由R⁸、R⁹表示的1价饱和脂肪族烃基的碳原子数为11以上。In addition, when the dye (1a) satisfies one or more of the requirements (i) and (iii) to (vi), the requirements (ii) -SO₂ NHR⁸ , -SO₂ NR⁸ R⁹ are not necessarily required. The number of carbon atoms of the monovalent saturated aliphatic hydrocarbon group represented by R⁸ and R⁹ in is 11 or more.

另外，染料（1a）满足必要条件（i）～（iv）和（vi）中的1个以上时，并不一定需要必要条件（v）的－SO₂NHR⁸、－SO₂NR⁸R⁹中的由R⁸、R⁹表示的1价饱和脂肪族烃基的碳原子数为11以上。In addition, when the dye (1a) satisfies one or more of the requirements (i) to (iv) and (vi), -SO₂ NHR⁸ and -SO₂ NR⁸ R⁹ of the requirement (v) are not necessarily required. The number of carbon atoms of the monovalent saturated aliphatic hydrocarbon group represented by R⁸ and R⁹ in is 11 or more.

在这种情况下，由R⁸、R⁹表示的1价饱和脂肪族烃基优选碳原子数为1～12的烷基，更优选碳原子数为1～8的烷基，进一步优选碳原子数为1～6的烷基。In this case, the monovalent saturated aliphatic hydrocarbon group represented by R⁸ and R⁹ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and still more preferably an alkyl group having 1 to 8 carbon atoms. It is an alkyl group of 1-6.

在式（1）中，a为使染料（a1）为电中性而确定的整数，a为0的染料（a1）是R¹～R⁴中的1个被－SO₃^－所取代的芳香族烃基、或具有m个的R⁵中的1个为－SO₃^-。具体而言，可以由下述式（1－1）表示。另一方面，a为1的染料（a1）在R¹～R⁴中的1个以上为具有取代基的碳原子数为6～10的1价芳香族烃基时，该芳香族烃基具有－SO₃^－以外的取代基作为取代基，并且R⁵不是－SO₃^-。具体而言，可以由下述式（1－2）表示。In the formula (1), a is an integer determined to make the dye (a1) electrically neutral, and the dye (a1) where a is 0 is an aromatic dye in which one of R¹ to R⁴ is substituted by -SO₃^- Group hydrocarbon group, or one of m R⁵ is -SO₃^- . Specifically, it can be represented by the following formula (1-1). On the other hand, in the dye (a1) where a is 1, when one or more of R¹ to R⁴ is a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms having a substituent, the aromatic hydrocarbon group has -SO A substituent other than₃^- is used as a substituent, and R⁵ is not -SO₃^- . Specifically, it can be represented by the following formula (1-2).

〔式（1－1）中，[In formula (1-1),

R¹～R⁵和m分别与上述式（1）中的R¹～R⁵和m为相同意思。其中，R¹～R⁴中的1个为被－SO₃^－取代的芳香族烃基、或具有m个的R⁵中的1个为－SO₃^－。〕R¹ to R⁵ and m have the same meanings as R¹ to R⁵ and m in the above formula (1), respectively. However, one of R¹ to R⁴ is an aromatic hydrocarbon group substituted by -SO₃^- , or one of m R⁵ is -SO₃^- . 〕

〔式（1－2）中，[In formula (1-2),

X^－、R¹～R⁵和m分别与上述式（1）中的X^－、R¹～R⁵和m为相同意思。其中，R¹～R⁴中的1个以上为具有取代基的碳原子数为6～10的1价芳香族烃基时，该芳香族烃基具有－SO₃^－以外的取代基作为取代基，并且R⁵不是－SO₃^-。〕X⁻ , R¹ to R⁵ and m have the same meanings as X⁻ , R¹ to R⁵ and m in the above formula (1), respectively. Wherein, when one or more of R¹ to R⁴ is a monovalent aromatic hydrocarbon group having a substituent and having 6 to 10 carbon atoms, the aromatic hydrocarbon group has a substituent other than -SO₃^- as a substituent, and R⁵ is not -SO₃^- . 〕

另外，作为更优选的方式，可举出由下述式（2）表示的化合物。Moreover, the compound represented by following formula (2) is mentioned as a more preferable aspect.

〔式（2）中，[In formula (2),

R^1a～R^4a各自独立地表示氢原子、－R⁶或碳原子数为6～10的1价芳香族烃基（该芳香族烃基所含的氢原子可以被卤素原子、－R⁶、－OH、－OR⁶、－SO₃H、－SO₃M、－CO₂H、－CO₂R⁶、－SO₃R⁶、－SO₂NH₂、－SO₂NHR⁸、－SO₂NR⁸R⁹、－SO₂－O－N＝CR⁷R¹⁰、－SO₂NHNHR⁷、－SO₂SR⁷或－SO₂NHSO₂R¹¹所取代）；R^1a to R^4a each independently represent a hydrogen atom, -R⁶ or a monovalent aromatic hydrocarbon group with 6 to 10 carbon atoms (the hydrogen atom contained in the aromatic hydrocarbon group can be replaced by a halogen atom, -R⁶ , -OH , -OR⁶ , -SO₃ H, -SO₃ M, -CO₂ H, -CO₂ R⁶ , -SO₃ R⁶ , -SO₂ NH₂ , -SO₂ NHR⁸ , -SO₂ NR⁸ R⁹ , -SO₂ -O-N=CR⁷ R¹⁰ , -SO₂ NHNHR⁷ , -SO₂ SR⁷ or -SO₂ NHSO₂ R¹¹ replaced);

R^5a各自独立地表示－SO₃H、－SO₃M、－CO₂H、－CO₂R⁶、－SO₃R⁶、－SO₂NHR⁸、－SO₂NR⁸R⁹、－SO₂－O－N＝CR⁷R¹⁰、－SO₂NHNHR⁷、－SO₂SR⁷或－SO₂NHSO₂R¹¹；R^5a each independently represents -SO₃ H, -SO₃ M, -CO₂ H, -CO₂ R⁶ , -SO₃ R⁶ , -SO₂ NHR⁸ , -SO₂ NR⁸ R⁹ , -SO₂ -O-N=CR⁷ R¹⁰ , -SO₂ NHNHR⁷ , -SO₂ SR⁷ or -SO₂ NHSO₂ R¹¹ ;

R⁶表示1价饱和烃基（该饱和烃基所含的氢原子可以被卤素原子所取代，该饱和烃基所含的－CH₂－可以被－O－、－CO－或－NR⁷－所取代）；R⁶ represents a monovalent saturated hydrocarbon group (the hydrogen atom contained in the saturated hydrocarbon group can be replaced by a halogen atom, and the -CH₂ - contained in the saturated hydrocarbon group can be replaced by -O-, -CO- or -NR⁷ -) ;

R⁷表示1价烃基（该烃基所含的氢原子可以被卤素原子或－R¹¹所取代，该烃基可以用－O－或－CO－连结）；R⁷ represents a monovalent hydrocarbon group (the hydrogen atom contained in the hydrocarbon group can be replaced by a halogen atom or -R¹¹ , and the hydrocarbon group can be linked by -O- or -CO-);

R⁸和R⁹各自独立地表示1价饱和脂肪族烃基（该饱和脂肪族烃基所含的氢原子可以被－OH、卤素原子、－Q、－CH＝CH₂或－CH＝CHR⁶所取代，该饱和脂肪族烃基所含的－CH₂－可以被－O－、－S－、－CO－、－NH－或－NR⁶－所取代）；R⁸ and R⁹ each independently represent a monovalent saturated aliphatic hydrocarbon group (the hydrogen atom contained in the saturated aliphatic hydrocarbon group can be replaced by -OH, halogen atom, -Q, -CH=CH₂ or -CH=CHR⁶ , the -CH₂ - contained in the saturated aliphatic hydrocarbon group can be replaced by -O-, -S-, -CO-, -NH- or -NR⁶ -);

R¹⁰表示氢原子、1价烃基（该烃基所含的氢原子可以被卤素原子或－R¹¹所取代，该烃基可以用－O－或－CO－连结）或－R¹¹；R¹⁰ represents a hydrogen atom, a monovalent hydrocarbon group (the hydrogen atom contained in the hydrocarbon group can be replaced by a halogen atom or -R¹¹ , and the hydrocarbon group can be linked by -O- or -CO-) or -R¹¹ ;

R¹¹表示可以具有取代基的1价烃基；R¹¹ represents a monovalent hydrocarbon group which may have a substituent;

Q表示碳原子数为6～10的1价芳香族烃基或碳原子数为3～10的1价杂环基（该芳香族烃基和该杂环基所含的1个以上的氢原子被选自－R⁶、－OR⁶和－CH＝CHR⁶中的至少1种所取代，该芳香族烃基和该杂环基所含的其余的氢原子可以被－OH、－NO₂、－CH＝CH₂或卤素原子所取代）；Q represents a monovalent aromatic hydrocarbon group with 6 to 10 carbon atoms or a monovalent heterocyclic group with 3 to 10 carbon atoms (one or more hydrogen atoms contained in the aromatic hydrocarbon group and the heterocyclic group are selected Since at least one of -R⁶ , -OR⁶ and -CH=CHR⁶ is substituted, the remaining hydrogen atoms contained in the aromatic hydrocarbon group and the heterocyclic group can be replaced by -OH, -NO₂ , -CH= CH₂ or halogen atoms replaced);

M表示钠原子或钾原子。M represents a sodium atom or a potassium atom.

N表示0～4的整数。其中，n为2以上的整数时，多个R^5a可以相同，也可以不同；N represents an integer of 0-4. Wherein, when n is an integer of 2 or more, multiple R^5a can be the same or different;

其中，该化合物满足下述（i）～（vi）中的1个以上的必要条件。However, the compound satisfies one or more requirements of the following (i) to (vi).

（i）R^1a～R^4a中的1个以上为具有选自－SO₂－O－N＝CR⁷R¹⁰、－SO₂NHNHR⁷、－SO₂SR⁷和－SO₂NHSO₂R¹¹中的至少1种取代基的芳香族烃基。(i) One or more of R^1a to R^4a is selected from the group consisting of -SO₂ -O-N=CR⁷ R¹⁰ , -SO₂ NHNHR⁷ , -SO₂ SR⁷ and -SO₂ NHSO₂ R¹¹ An aromatic hydrocarbon group of at least one substituent.

（ii）R^1a～R^4a中的1个以上为具有选自－SO₂NHR⁸和－SO₂NR⁸R⁹中的至少1种取代基的芳香族烃基。其中，由R⁸、R⁹表示的1价饱和脂肪族烃基的碳原子数为11以上。(ii) One or more of R^1a to R^4a is an aromatic hydrocarbon group having at least one substituent selected from —SO₂ NHR⁸ and —SO₂ NR⁸ R⁹ . However, the monovalent saturated aliphatic hydrocarbon group represented by R⁸ and R⁹ has 11 or more carbon atoms.

（iii）R^1a～R^4a中的1个以上为－R⁶、或具有选自－R⁶、－OR⁶、－CO₂R⁶和－SO₃R⁶中的至少1种取代基的芳香族烃基。其中，由R⁶表示的1价饱和烃基的碳原子数为11以上。(iii) One or more of R^1a to R^4a is -R⁶ , or an aromatic having at least one substituent selected from -R⁶ , -OR⁶ , -CO₂ R⁶ and -SO₃ R⁶ family of hydrocarbon groups. Among them, the monovalent saturated hydrocarbon group represented by R⁶ has 11 or more carbon atoms.

（iv）具有n个的R^5a中的1个以上为－SO₂－O－N＝CR⁷R¹⁰、－SO₂NHNHR⁷、－SO₂SR⁷或－SO₂NHSO₂R¹¹。(iv) One or more of the n R^5a is -SO₂ -O-N=CR⁷ R¹⁰ , -SO₂ NHNHR⁷ , -SO₂ SR⁷ or -SO₂ NHSO₂ R¹¹ .

（v）具有n个的R^5a中的1个以上为－SO₂NHR⁸或－SO₂NR⁸R⁹。其中，由R⁸、R⁹表示的1价饱和脂肪族烃基的碳原子数为11以上。(v) One or more of the n R^5a is -SO₂ NHR⁸ or -SO₂ NR⁸ R⁹ . However, the monovalent saturated aliphatic hydrocarbon group represented by R⁸ and R⁹ has 11 or more carbon atoms.

（vi）具有n个的R^5a中的1个以上为－CO₂R⁶或－SO₃R⁶。其中，由R⁶表示的1价饱和烃基的碳原子数为11以上。〕(vi) One or more of the n R^5a is -CO₂ R⁶ or -SO₃ R⁶ . Among them, the monovalent saturated hydrocarbon group represented by R⁶ has 11 or more carbon atoms. 〕

在式（2）中，R^1a～R^4a中的碳原子数为6～10的1价芳香族烃基与上述R¹～R⁴中的碳原子数为6～10的1价芳香族烃基为相同意思，具体方式与上述说明相同。另外，R⁶～R¹¹、Q和M的具体方式也与上述说明相同。In formula (2), the monovalent aromatic hydrocarbon groups with 6 to 10 carbon atoms in R^1a to R^4a and the monovalent aromatic hydrocarbon groups with 6 to 10 carbon atoms in R¹ to R⁴ above are The same meaning, and the specific method is the same as the above description. In addition, specific aspects of R⁶ to R¹¹ , Q and M are also the same as those described above.

另外，－SO₃^－优选在苯基的邻位或对位，更优选在邻位。In addition, -SO₃^- is preferably at the ortho or para position of the phenyl group, more preferably at the ortho position.

染料（a1）可以通过适当方法制造，可举出例如与日本特开2010－254964号公报的实施例相同的方法。这样得到的染料（a1）在以环己酮等酮为代表的各种有机溶剂中可溶，另外具有优异的耐热性。The dye (a1) can be produced by an appropriate method, for example, the same method as in the Example of Unexamined-Japanese-Patent No. 2010-254964 is mentioned. The dye (a1) thus obtained is soluble in various organic solvents represented by ketones such as cyclohexanone, and has excellent heat resistance.

在本发明中，染料（a1）可以单独使用或将2种以上混合使用。In this invention, dye (a1) can be used individually or in mixture of 2 or more types.

本发明的着色组合物可以与染料（a1）一同进一步含有其他着色剂（以下也称为“着色剂（a2）”）作为着色剂。作为着色剂（a2），没有特别限定，可以根据用途适当选择色彩、材质。The coloring composition of the present invention may further contain another coloring agent (hereinafter also referred to as "coloring agent (a2)") as a coloring agent together with the dye (a1). The colorant (a2) is not particularly limited, and the color and material can be appropriately selected according to the application.

作为其他着色剂（a2），可以使用颜料、除了染料（a1）以外的染料和天然色素中的任意着色剂，但在得到亮度和色纯度高的像素的意义上，优选有机颜料、有机染料，特别优选有机颜料。As the other coloring agent (a2), any of pigments, dyes other than the dye (a1), and natural coloring agents can be used, but organic pigments and organic dyes are preferable in terms of obtaining pixels with high brightness and color purity, Particular preference is given to organic pigments.

作为上述有机颜料，可举出例如颜料索引（C.I.；The Society of Dyers andColourists公司发行）中被分类为颜料的化合物，其中，优选日本特开2001－081348号公报、日本特开2010－026334号公报、日本特开2010－191304号公报、日本特开2010－237384号公报、日本特开2010－237569号公报、日本特开2011－006602号公报、日本特开2011－145346号公报等记载的色淀颜料、C.I.颜料红166、C.I.颜料红177、C.I.颜料红224、C.I.颜料红242、C.I.颜料红254、C.I.颜料绿7、C.I.颜料绿36、C.I.颜料绿58、C.I.颜料蓝15：6、C.I.颜料蓝80、C.I.颜料黄83、C.I.颜料黄138、C.I.颜料黄139、C.I.颜料黄150、C.I.颜料黄180、C.I.颜料黄211、C.I.颜料橙38、C.I.颜料紫23等色淀颜料以外的有机颜料。另外，在色淀颜料中，优选三芳基甲烷系色淀颜料、呫吨系色淀颜料、偶氮系色淀颜料，更优选三芳基甲烷系色淀颜料和呫吨系色淀颜料。Examples of the above-mentioned organic pigments include compounds classified as pigments in the Pigment Index (C.I.; published by The Society of Dyers and Colourists, Inc.). Among them, Japanese Patent Application Laid-Open No. 2001-081348 and Japanese Patent Laid-Open No. 2010-026334 are preferred. , Japanese Patent Application Publication No. 2010-191304, Japanese Patent Application Publication No. 2010-237384, Japanese Patent Application Publication No. 2010-237569, Japanese Patent Application Publication No. 2011-006602, Japanese Patent Application Publication No. 2011-145346, etc. Pigment, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Blue 15:6, C.I. Pigment Blue 80, C.I. Pigment Yellow 83, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180, C.I. Pigment Yellow 211, C.I. Pigment Orange 38, C.I. pigment. In addition, among lake pigments, triarylmethane-based lake pigments, xanthene-based lake pigments, and azo-based lake pigments are preferable, and triarylmethane-based lake pigments and xanthene-based lake pigments are more preferable.

本发明的着色组合物优选用于蓝色像素的形成。此时，作为（A）着色剂，优选含有选自蓝色颜料、蓝色染料、紫色颜料和紫色染料中的至少1种作为其他着色剂与本着色剂一同使用。此时，本着色剂的含有比例在总着色剂中优选为0.1～80质量%、更优选为1～80质量%、进一步优选为5～60质量%、特别优选为10～40质量%。The coloring composition of the present invention is preferably used for the formation of blue pixels. In this case, as (A) coloring agent, it is preferable to contain at least 1 sort(s) selected from the group consisting of a blue pigment, a blue dye, a purple pigment, and a purple dye as another coloring agent and use it together with this coloring agent. In this case, the content of the colorant is preferably 0.1 to 80% by mass, more preferably 1 to 80% by mass, still more preferably 5 to 60% by mass, and particularly preferably 10 to 40% by mass in the total colorant.

在本发明中使用颜料作为着色剂（a2）时，也可以通过重结晶法、再沉淀法、溶剂洗涤法、升华法、真空加热法或它们的组合将颜料进行精制而使用。另外，颜料可以根据需要用树脂对其粒子表面改性而使用。作为将颜料的粒子表面改性的树脂，可以举出例如日本特开2001－1088147号公报中记载的展色料树脂、或市售的各种颜料分散用的树脂。作为炭黑表面的树脂被覆方法，可以采用例如日本特开平9－71733号公报、日本特开平9－95625号公报、日本特开平9－124969号公报等中记载的方法。另外，有机颜料优选通过所谓的盐磨法将一次粒子微细化而使用。作为盐磨法可以采用例如日本特开平08－179111号公报中公开的方法。When a pigment is used as the colorant (a2) in the present invention, the pigment may be purified and used by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, or a combination thereof. In addition, the pigment can be used by modifying the surface of its particles with a resin as needed. As the resin for modifying the particle surface of the pigment, for example, the vehicle resin described in JP-A-2001-1088147 or various commercially available resins for dispersing pigments may be mentioned. As the resin coating method on the surface of carbon black, for example, methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969, etc. can be employed. In addition, the organic pigment is preferably used by making primary particles finer by the so-called salt milling method. As the salt milling method, for example, the method disclosed in JP-A-08-179111 can be employed.

在本发明中使用颜料作为着色剂（a2）时，还可以进一步含有公知的分散剂和分散助剂。作为公知的分散剂，可举出例如聚氨酯系分散剂、聚乙烯亚胺系分散剂、聚氧乙烯烷基醚系分散剂、聚氧乙烯烷基苯基醚系分散剂、聚乙二醇二酯系分散剂、山梨糖醇酐脂肪酸酯系分散剂、聚酯系分散剂、丙烯酸系分散剂等，作为分散助剂可举出颜料衍生物等。When a pigment is used as the colorant (a2) in the present invention, it may further contain known dispersants and dispersion aids. Examples of known dispersants include polyurethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene alkylphenyl ether-based dispersants, polyethylene glycol Ester-based dispersants, sorbitan fatty acid ester-based dispersants, polyester-based dispersants, acrylic-based dispersants, and the like, and pigment derivatives and the like are exemplified as dispersing aids.

这样的分散剂可以从商业上获得，例如，作为丙烯酸系分散剂，可举出Disperbyk－2000、Disperbyk－2001、BYK－LPN6919、BYK－LPN21116、BYK－LPN21324（以上为BYK公司制）等，作为聚氨酯系分散剂，可举出Disperbyk－161、Disperbyk－162、Disperbyk－165、Disperbyk－167、Disperbyk－170、Disperbyk－182（以上为BYK公司制）、Solsperse76500（LUBRIZOL株式会社制）等，作为聚乙烯亚胺系分散剂，可以举出Solsperse24000（LUBRIZOL株式会社制）等，作为聚酯系分散剂，可举出Adisper PB821、Adisper PB822、Adisper PB880、Adisper PB881（以上由AJINOMOTO FINE TECHNO株式会社制）等。Such a dispersant can be obtained commercially, and for example, as an acrylic dispersant, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (manufactured by BYK Corporation) etc. are mentioned, as Examples of polyurethane-based dispersants include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (the above are manufactured by BYK), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), and the like. Examples of ethyleneimine-based dispersants include Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), and examples of polyester-based dispersants include Adisper PB821, Adisper PB822, Adisper PB880, and Adisper PB881 (the above are manufactured by AJINOMOTO FINE TECHNO Co., Ltd.). Wait.

另外，作为上述颜料衍生物，具体而言，可举出铜酞菁、二酮吡咯并吡咯、喹酞酮的磺酸衍生物等。Moreover, specific examples of the above-mentioned pigment derivatives include copper phthalocyanine, diketopyrrolopyrrole, sulfonic acid derivatives of quinophthalone, and the like.

在本发明中，着色剂（a2）可以单独使用或将2种以上混合使用。In this invention, a coloring agent (a2) can be used individually or in mixture of 2 or more types.

从形成亮度高且色纯度优异的像素、或形成遮光性优异的黑矩阵的方面考虑，（A）着色剂的含有比例通常在着色组合物的固体成分中为5～70质量%、优选为5～60质量%。在这里，固体成分是后述的溶剂以外的成分。From the viewpoint of forming pixels with high brightness and excellent color purity, or forming a black matrix with excellent light-shielding properties, the content ratio of (A) the colorant is usually 5 to 70% by mass in the solid content of the coloring composition, preferably 5% by mass. ~60% by mass. Here, the solid content refers to components other than the solvent described later.

－（B）粘结剂树脂－-(B) Binder resin-

作为本发明中的（B）粘结剂树脂，并无特别限制，优选是具有羧基、酚性羟基等酸性官能团的树脂。其中，优选具有羧基的聚合物（以下称为“含有羧基的聚合物”），可举出例如具有1个以上的羧基的乙烯性不饱和单体（以下称为“不饱和单体（b1）”）和其他可共聚的乙烯性不饱和单体（以下称为“不饱和单体（b2）”）的共聚物。The (B) binder resin in the present invention is not particularly limited, and is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, polymers having carboxyl groups (hereinafter referred to as "carboxyl group-containing polymers") are preferred, and examples include ethylenically unsaturated monomers having one or more carboxyl groups (hereinafter referred to as "unsaturated monomers (b1) ”) and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as “unsaturated monomer (b2)”).

作为上述不饱和单体（b1），可以列举例如（甲基）丙烯酸、马来酸、马来酸酐、琥珀酸单［2－（甲基）丙烯酰氧基乙基］酯、ω－羧基聚己内酯单（甲基）丙烯酸酯、对乙烯基苯甲酸等。Examples of the unsaturated monomer (b1) include (meth)acrylic acid, maleic acid, maleic anhydride, succinic acid mono[2-(meth)acryloyloxyethyl]ester, ω-carboxypoly Caprolactone mono(meth)acrylate, p-vinylbenzoic acid, etc.

这些不饱和单体（b1）可以单独使用或者将2种以上混合使用。These unsaturated monomers (b1) can be used individually or in mixture of 2 or more types.

另外，作为上述不饱和单体（b2），可以举出例如：In addition, examples of the unsaturated monomer (b2) include:

N－苯基马来酰亚胺、N－环己基马来酰亚胺之类的N－取代马来酰亚胺；苯乙烯、α－甲基苯乙烯、对羟基苯乙烯、对羟基－α－甲基苯乙烯、对乙烯基苄基缩水甘油醚、苊烯之类的芳香族乙烯基化合物；N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α - Aromatic vinyl compounds such as methyl styrene, p-vinyl benzyl glycidyl ether, acenaphthylene;

（甲基）丙烯酸甲酯、（甲基）丙烯酸正丁酯、（甲基）丙烯酸2－乙基己酯、（甲基）丙烯酸2－羟基乙酯、（甲基）丙烯酸烯丙酯、（甲基）丙烯酸苄酯、聚乙二醇（聚合度2～10）甲醚（甲基）丙烯酸酯、聚丙二醇（聚合度2～10）甲醚（甲基）丙烯酸酯、聚乙二醇（聚合度2～10）单（甲基）丙烯酸酯、聚丙二醇（聚合度2～10）单（甲基）丙烯酸酯、（甲基）丙烯酸环己酯、（甲基）丙烯酸异冰片酯、三环［5.2.1.0^2,6］癸烷－8－基（甲基）丙烯酸酯、二环戊烯基（甲基）丙烯酸酯、甘油单（甲基）丙烯酸酯、（甲基）丙烯酸4－羟基苯酯、对枯烯基苯酚的环氧乙烷改性（甲基）丙烯酸酯、（甲基）丙烯酸缩水甘油酯、（甲基）丙烯酸3,4－环氧环己基甲酯、3－［（甲基）丙烯酰氧基甲基］氧杂环丁烷、3－［（甲基）丙烯酰氧基甲基］－3－乙基氧杂环丁烷之类的（甲基）丙烯酸酯；Methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, ( Benzyl meth)acrylate, polyethylene glycol (polymerization degree 2-10) methyl ether (meth)acrylate, polypropylene glycol (polymerization degree 2-10) methyl ether (meth)acrylate, polyethylene glycol ( Polymerization degree 2~10) mono(meth)acrylate, polypropylene glycol (polymerization degree 2~10) mono(meth)acrylate, (meth)cyclohexyl acrylate, (meth)isobornyl acrylate, three Cyclo[5.2.1.0^2,6 ]decane-8-yl (meth)acrylate, dicyclopentenyl (meth)acrylate, glycerol mono(meth)acrylate, (meth)acrylate 4- Hydroxyphenyl ester, ethylene oxide modified (meth)acrylate of p-cumenylphenol, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3- (Meth)acrylic acid such as [(meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3-ethyloxetane ester;

环己基乙烯基醚、异冰片基乙烯基醚、三环［5.2.1.0^2,6］癸烷－8－基乙烯基醚、五环十五烷基乙烯基醚、3－（乙烯基氧甲基）－3－乙基氧杂环丁烷之类的乙烯基醚；Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0^2,6 ]decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3-(vinyloxymethyl base) - vinyl ethers such as 3-ethyloxetane;

聚苯乙烯、聚（甲基）丙烯酸甲酯、聚（甲基）丙烯酸正丁酯、聚硅氧烷之类的聚合物分子链的末端具有单（甲基）丙烯酰基的大分子单体等Polymers such as polystyrene, polymethyl(meth)acrylate, poly(n-butylmeth)acrylate, polysiloxane, etc. Macromonomers with a single (meth)acryloyl group at the end of their molecular chains, etc.

这些不饱和单体（b2）可以单独使用或者将2种以上混合使用。These unsaturated monomers (b2) can be used individually or in mixture of 2 or more types.

在不饱和单体（b1）与不饱和单体（b2）的共聚物中，该共聚物中的不饱和单体（b1）的共聚比例优选为5～50质量%，更优选为10～40质量%。通过在这样的范围使不饱和单体（b1）共聚，能够得到碱性显影性和保存稳定性优异的着色组合物。In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. quality%. By copolymerizing the unsaturated monomer (b1) in such a range, a colored composition excellent in alkali developability and storage stability can be obtained.

作为不饱和单体（b1）与不饱和单体（b2）的共聚物的具体例，可举出例如日本特开平7－140654号公报、日本特开平8－259876号公报、日本特开平10－31308号公报、日本特开平10－300922号公报、日本特开平11－174224号公报、日本特开平11－258415号公报、日本特开2000－56118号公报、日本特开2004－101728公报等中公开的共聚物。Specific examples of copolymers of unsaturated monomers (b1) and unsaturated monomers (b2) include, for example, Japanese Patent Application Laid-Open No. 7-140654, Japanese Patent Laid-Open No. 8-259876, Japanese Patent Laid-Open No. 10- 31308, JP-A-10-300922, JP-11-174224, JP-11-258415, JP-2000-56118, JP-2004-101728, etc. of copolymers.

另外，在本发明中，还可以例如如日本特开平5－19467号公报、日本特开平6－230212号公报、日本特开平7－207211号公报、日本特开平09－325494号公报、日本特开平11－140144号公报、日本特开2008－181095号公报等中公开那样使用侧链具有（甲基）丙烯酰基等聚合性不饱和键的含有羧基的聚合物作为粘结剂树脂。In addition, in the present invention, for example, Japanese Patent Application Publication No. 5-19467, Japanese Patent Application Publication No. 6-230212, Japanese Patent Application Publication No. 7-207211, Japanese Patent Application Publication No. 09-325494, Japanese Patent Application Publication No. As disclosed in JP-A-11-140144 and JP-A-2008-181095, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth)acryloyl group in a side chain is used as a binder resin.

本发明中的粘结剂树脂采用凝胶渗透色谱（以下简称为GPC）（溶出溶剂：四氢呋喃）测定的聚苯乙烯换算重均分子量（Mw）通常为1000～100000，优选为3000～50000。如果Mw过小，有可能得到的被膜的残膜率等降低，图案形状、耐热性等受损，而且电特性恶化，另一方面，如果过大，有可能析像度降低，或图案形状受损，而且采用狭缝喷嘴方式的涂布时容易产生干燥异物。The binder resin in the present invention has a polystyrene-equivalent weight-average molecular weight (Mw) as measured by gel permeation chromatography (hereinafter referred to as GPC) (elution solvent: tetrahydrofuran), usually 1,000 to 100,000, preferably 3,000 to 50,000. If Mw is too small, the remaining film ratio of the obtained film may decrease, the pattern shape, heat resistance, etc. may be damaged, and the electrical characteristics may deteriorate. On the other hand, if it is too large, the resolution may decrease, or the pattern shape may be damaged. Damaged, and dry foreign matter tends to be generated when applying the slit nozzle method.

另外，本发明中的粘结剂树脂的重量平均分子量（Mw）与数均分子量（Mn）之比（Mw/Mn）优选为1.0～5.0、更优选为1.0～3.0。应予说明，在这里所说的Mn是指采用GPC（溶出溶剂：四氢呋喃）测定的聚苯乙烯换算的数均分子量。In addition, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3.0. In addition, Mn mentioned here means the polystyrene-equivalent number average molecular weight measured by GPC (elution solvent: tetrahydrofuran).

本发明中的粘结剂树脂可以采用公知的方法制造，也可以采用例如日本特开2003－222717号公报、日本特开2006－259680号公报、国际公开第07/029871号小册子等中公开的方法，控制其结构、Mw、Mw/Mn。The binder resin in the present invention can be produced by a known method, and for example, those disclosed in JP-A-2003-222717, JP-A-2006-259680, International Publication No. 07/029871, etc. can be used. method to control its structure, Mw, Mw/Mn.

本发明中，粘结剂树脂可以单独使用或者将2种以上混合使用。In this invention, binder resin can be used individually or in mixture of 2 or more types.

本发明中，粘结剂树脂的含量，相对于（A）着色剂100质量份，通常为10～1000质量份，优选为20～500质量份。如果粘结剂树脂的含量过少，例如，有可能碱显影性降低，得到的着色组合物的保存稳定性降低，另一方面，如果过多，相对地着色剂浓度降低，实现作为薄膜的目标色浓度有可能变得困难。In this invention, content of binder resin is 10-1000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts. If the content of the binder resin is too small, for example, the alkali developability may decrease, and the storage stability of the obtained coloring composition may decrease. On the other hand, if it is too large, the concentration of the colorant may decrease relatively, and the target as a film may be achieved. Color density can become difficult.

－（C）交联剂－－(C) Crosslinking agent－

在本发明中，所谓的（C）交联剂是指具有2个以上的可聚合基团的化合物。作为可聚合基团，可以举出例如乙烯性不饱和基团、环氧乙基、氧杂环丁基、N－烷氧基甲基氨基等。在本发明中，作为（C）交联剂，优选具有2个以上的（甲基）丙烯酰基的化合物、或者具有2个以上的N－烷氧基甲基氨基的化合物。In the present invention, the (C) crosslinking agent refers to a compound having two or more polymerizable groups. As a polymerizable group, an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, N-alkoxymethylamino group etc. are mentioned, for example. In this invention, as (C) crosslinking agent, the compound which has 2 or more (meth)acryloyl groups, or the compound which has 2 or more N-alkoxymethylamino groups is preferable.

作为上述具有2个以上的（甲基）丙烯酰基的化合物的具体例子，可以举出使脂肪族多羟基化合物与（甲基）丙烯酸反应而得到的多官能（甲基）丙烯酸酯、己内酯改性的多官能（甲基）丙烯酸酯、烯基氧化物改性的多官能（甲基）丙烯酸酯、使具有羟基的（甲基）丙烯酸酯与多官能异氰酸酯反应而得到的多官能聚氨酯（甲基）丙烯酸酯、使具有羟基的（甲基）丙烯酸酯与酸酐反应而得到的具有羧基的多官能（甲基）丙烯酸酯等。Specific examples of the compound having two or more (meth)acryloyl groups include polyfunctional (meth)acrylates obtained by reacting aliphatic polyhydroxy compounds with (meth)acrylic acid, caprolactone Modified polyfunctional (meth)acrylates, alkenyl oxide modified polyfunctional (meth)acrylates, polyfunctional polyurethanes obtained by reacting hydroxyl-containing (meth)acrylates with polyfunctional isocyanates ( A meth)acrylate, a polyfunctional (meth)acrylate having a carboxyl group obtained by reacting a (meth)acrylate having a hydroxyl group with an acid anhydride, and the like.

在这里，作为上述脂肪族多羟基化合物，例如可以举出乙二醇、丙二醇、聚乙二醇、聚丙二醇之类的2元的脂肪族多羟基化合物，甘油、三羟甲基丙烷、季戊四醇、二季戊四醇之类的3元以上的脂肪族多羟基化合物。作为上述具有羟基的（甲基）丙烯酸酯，可以举出例如（甲基）丙烯酸2－羟基乙基酯、三羟甲基丙烷二（甲基）丙烯酸酯、季戊四醇三（甲基）丙烯酸酯、二季戊四醇五（甲基）丙烯酸酯、甘油二甲基丙烯酸酯等。作为上述多官能异氰酸酯，例如可以举出甲苯二异氰酸酯、六亚甲基二异氰酸酯、二苯基亚甲基二异氰酸酯、异佛尔酮二异氰酸酯等。作为酸酐，可以举出例如琥珀酸酐、马来酸酐、戊二酸酐、衣康酸酐、邻苯二甲酸酐、六氢邻苯二甲酸酐之类的二元酸的酐，均苯四甲酸酐、联苯四羧酸二酐、二苯甲酮四羧酸二酐之类的四元酸二酐。Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, An aliphatic polyol compound having a valence of three or more, such as dipentaerythritol. Examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, Dipentaerythritol penta(meth)acrylate, glycerin dimethacrylate, etc. As said polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, etc. are mentioned, for example. Examples of acid anhydrides include anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, pyromellitic anhydride, Tetrabasic acid dianhydrides such as biphenyltetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride.

另外，作为上述己内酯改性的多官能（甲基）丙烯酸酯，可以举出例如日本特开平11－44955号公报的〔0015〕～〔0018〕段记载的化合物。作为上述烯基氧化物改性的多官能（甲基）丙烯酸酯，可举出由选自双酚A的环氧乙烷和双酚A的环氧丙烷中的至少1种改性的二（甲基）丙烯酸酯、由选自三聚异氰酸的环氧乙烷和三聚异氰酸的环氧丙烷中的至少1种改性的三（甲基）丙烯酸酯、由选自三羟甲基丙烷的环氧乙烷和三羟甲基丙烷的环氧丙烷中的至少1种改性的三（甲基）丙烯酸酯、由选自季戊四醇的环氧乙烷和季戊四醇的环氧丙烷中的至少1种改性的三（甲基）丙烯酸酯、由选自季戊四醇的环氧乙烷和季戊四醇的环氧丙烷中的至少1种改性的四（甲基）丙烯酸酯、由选自二季戊四醇的环氧乙烷和二季戊四醇的环氧丙烷中的至少1种改性的五（甲基）丙烯酸酯、由选自二季戊四醇的环氧乙烷和二季戊四醇的环氧丙烷中的至少1种改性的六（甲基）丙烯酸酯等。In addition, examples of the caprolactone-modified polyfunctional (meth)acrylate include compounds described in paragraphs [0015] to [0018] of JP-A-11-44955. Examples of the polyfunctional (meth)acrylate modified by the above-mentioned alkenyl oxide include di( Meth)acrylate, tri(meth)acrylate modified by at least one selected from ethylene oxide of isocyanuric acid and propylene oxide of isocyanuric acid, trihydroxy Tri(meth)acrylate modified by at least one of ethylene oxide of methylpropane and propylene oxide of trimethylolpropane, selected from ethylene oxide of pentaerythritol and propylene oxide of pentaerythritol At least one modified tri(meth)acrylate, tetra(meth)acrylate modified by at least one selected from ethylene oxide of pentaerythritol and propylene oxide of pentaerythritol, tetra(meth)acrylate modified by at least one selected from two Penta(meth)acrylate modified by at least one of ethylene oxide of pentaerythritol and propylene oxide of dipentaerythritol, at least 1 of ethylene oxide of dipentaerythritol and propylene oxide of dipentaerythritol A modified hexa(meth)acrylate, etc.

另外，作为上述具有2个以上的N－烷氧基甲基氨基的化合物，可以举出例如具有三聚氰胺结构、苯鸟粪胺结构、脲结构的化合物等。应予说明，所谓的三聚氰胺结构、苯鸟粪胺结构是指具有1个以上的三嗪环或苯基取代三嗪环作为基本骨架的化学结构，是也包括三聚氰胺、苯鸟粪胺或它们的缩合物的概念。作为具有2个以上的N－烷氧基甲基氨基的化合物的具体例子，可以举出N,N,N’,N’,N”,N”－六（烷氧基甲基）三聚氰胺、N,N,N’,N’－四（烷氧基甲基）苯鸟粪胺、N,N,N’,N’－四（烷氧基甲基）甘脲等。Moreover, as a compound which has the said 2 or more N-alkoxymethyl amino groups, the compound etc. which have a melamine structure, a benzoguanamine structure, a urea structure, etc. are mentioned, for example. It should be noted that the so-called melamine structure and benzoguanamine structure refer to chemical structures having more than one triazine ring or phenyl-substituted triazine ring as the basic skeleton, and also include melamine, benzoguanamine or their The concept of condensation. Specific examples of compounds having two or more N-alkoxymethylamino groups include N,N,N',N',N",N"-hexa(alkoxymethyl)melamine, N ,N,N',N'-Tetrakis(alkoxymethyl)benzoguanamine, N,N,N',N'-Tetrakis(alkoxymethyl)glycoluril, etc.

在这些交联剂中，优选使3元以上的脂肪族多羟基化合物与（甲基）丙烯酸反应而得到的多官能（甲基）丙烯酸酯、己内酯改性的多官能（甲基）丙烯酸酯、多官能聚氨酯（甲基）丙烯酸酯、具有羧基的多官能（甲基）丙烯酸酯、N,N,N’,N’,N”,N”－六（烷氧基甲基）三聚氰胺、N,N,N’,N’－四（烷氧基甲基）苯鸟粪胺。从着色层的强度高、着色层的表面平滑性优异、且在未曝光部的基板上和遮光层上难以产生浮污（地汚れ）、膜残留等的方面考虑，在使3元以上的脂肪族多羟基化合物与（甲基）丙烯酸反应而得到的多官能（甲基）丙烯酸酯中，特别优选三羟甲基丙烷三丙烯酸酯、季戊四醇三丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇六丙烯酸酯，在具有羧基的多官能（甲基）丙烯酸酯中，特别优选使季戊四醇三丙烯酸酯与琥珀酸酐反应而得到的化合物、使二季戊四醇五丙烯酸酯与琥珀酸酐反应而得到的化合物。Among these crosslinking agents, polyfunctional (meth)acrylates obtained by reacting trivalent or higher aliphatic polyols with (meth)acrylic acid, and caprolactone-modified polyfunctional (meth)acrylic acid are preferred. esters, polyfunctional urethane (meth)acrylates, polyfunctional (meth)acrylates with carboxyl groups, N,N,N',N',N",N"-hexa(alkoxymethyl)melamine, N,N,N',N'-Tetrakis(alkoxymethyl)phenylguanamine. In view of the high strength of the colored layer, the excellent surface smoothness of the colored layer, and the fact that it is difficult to generate smudges (ground stains) and film residues on the substrate of the unexposed part and the light-shielding layer, the fat of 3 yuan or more Among the polyfunctional (meth)acrylates obtained by reacting polyhydroxy compounds with (meth)acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are particularly preferred. Among polyfunctional (meth)acrylates having a carboxyl group, compounds obtained by reacting pentaerythritol triacrylate and succinic anhydride and compounds obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride are particularly preferable.

在本发明中，（C）交联剂可以单独使用或者将2种以上混合使用。In this invention, (C) crosslinking agent can be used individually or in mixture of 2 or more types.

相对于（A）着色剂100质量份，本发明中的（C）交联剂的含量优选10～1000质量份，特别优选20～500质量份。此时，如果交联剂的含有量过少，则可能得不到充分的固化性。另一方面，如果交联剂的含有量过多，则对本发明的着色组合物赋予碱显影性的情况下，具有碱显影性降低、且在未曝光部的基板上或遮光层上容易产生浮污、膜残留等的趋势。The content of the (C) crosslinking agent in the present invention is preferably 10 to 1000 parts by mass, particularly preferably 20 to 500 parts by mass, relative to 100 parts by mass of the (A) colorant. At this time, if the content of the crosslinking agent is too small, sufficient curability may not be obtained. On the other hand, if the content of the crosslinking agent is too large, when alkali developability is imparted to the coloring composition of the present invention, alkali developability will decrease, and floating will easily occur on the substrate of the unexposed portion or on the light-shielding layer. fouling, film residue, etc.

－光聚合引发剂－－Photopolymerization Initiator－

本发明的着色组合物中可以含有光聚合引发剂。由此，能够对着色组合物赋予放射线敏感性。本发明中使用的光聚合引发剂是可以通过可见光线、紫外线、远紫外线、电子束、X射线等放射线的曝光而产生能够引发上述（C）交联剂聚合的活性种的化合物。A photopolymerization initiator may be contained in the coloring composition of this invention. Thereby, radiation sensitivity can be provided to a coloring composition. The photopolymerization initiator used in the present invention is a compound capable of generating an active species capable of initiating polymerization of the above-mentioned (C) crosslinking agent by exposure to radiation such as visible rays, ultraviolet rays, extreme ultraviolet rays, electron beams, and X-rays.

作为这样的光聚合引发剂，可以列举例如噻吨酮系化合物、苯乙酮系化合物、联咪唑系化合物、三嗪系化合物、O－酰基肟系化合物、盐系化合物、苯偶姻系化合物、二苯甲酮系化合物、α－二酮系化合物、多环醌系化合物、重氮系化合物、酰亚胺磺酸酯系化合物、盐系化合物等。Examples of such photopolymerization initiators include thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, O-acyl oxime-based compounds, Salt-based compounds, benzoin-based compounds, benzophenone-based compounds, α-diketone-based compounds, polycyclic quinone-based compounds, diazo-based compounds, imidesulfonate-based compounds, Salt compounds, etc.

本发明中，光聚合引发剂可以单独使用或者将2种以上混合使用。作为光聚合引发剂，优选选自噻吨酮系化合物、苯乙酮系化合物、联咪唑系化合物、三嗪系化合物、O－酰基肟系化合物中的至少1种。另外，也可以将选自这些化合物中的2种以上混合使用。In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is preferably at least one selected from the group consisting of thioxanthone-based compounds, acetophenone-based compounds, biimidazole-based compounds, triazine-based compounds, and O-acyloxime-based compounds. In addition, two or more types selected from these compounds may be used in combination.

本发明中优选的光聚合引发剂中，作为噻吨酮系化合物的具体例，可以列举噻吨酮、2－氯噻吨酮、2－甲基噻吨酮、2－异丙基噻吨酮、4－异丙基噻吨酮、2,4－二氯噻吨酮、2,4－二甲基噻吨酮、2,4－二乙基噻吨酮、2,4－二异丙基噻吨酮等。Among preferable photopolymerization initiators in the present invention, specific examples of thioxanthone-based compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone. , 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyl Thioxanthone, etc.

另外，作为上述苯乙酮系化合物的具体例，可以列举2－甲基－1－［4－（甲硫基）苯基］－2－吗啉代丙烷－1－酮、2－苄基－2－二甲基氨基－1－（4－吗啉代苯基）丁烷－1－酮、2－（4－甲基苄基）－2－（二甲基氨基）－1－（4－吗啉代苯基）丁烷－1－酮等。In addition, specific examples of the aforementioned acetophenone-based compounds include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl- 2-Dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Morpholinophenyl) butane-1-one, etc.

另外，作为上述联咪唑系化合物的具体例，可以列举2,2’－双（2－氯苯基）－4,4’,5,5’－四苯基－1,2’－联咪唑、2,2’－双（2,4－二氯苯基）－4,4’,5,5’－四苯基－1,2’－联咪唑、2,2’－双（2,4,6－三氯苯基）－4,4’,5,5’－四苯基－1,2’－联咪唑等。In addition, specific examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4, 6-trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, etc.

再有，使用联咪唑系化合物作为其他光聚合引发剂时，在能够改进灵敏度方面，优选并用供氢体。这里所说的“供氢体”，意味着能够对通过曝光由联咪唑系化合物产生的自由基供给氢原子的化合物。作为供氢体，可以列举例如2－巯基苯并噻唑、2－巯基苯并唑等硫醇系供氢体，4,4’－双（二甲基氨基）二苯甲酮、4,4’－双（二乙基氨基）二苯甲酮等胺系供氢体。本发明中，供氢体可以单独使用或者将2种以上混合使用，从能够进一步改善灵敏度方面出发，优选将1种以上的硫醇系供氢体和1种以上的胺系供氢体组合使用。In addition, when using a biimidazole compound as another photoinitiator, it is preferable to use a hydrogen donor together at the point which can improve sensitivity. The "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a biimidazole-based compound by exposure. As the hydrogen donor, for example, 2-mercaptobenzothiazole, 2-mercaptobenzothiazole, Thiol-based hydrogen donors such as azoles, and amine-based hydrogen donors such as 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone. In the present invention, the hydrogen donor may be used alone or in combination of two or more. From the viewpoint of further improving the sensitivity, it is preferable to use a combination of one or more thiol-based hydrogen donors and one or more amine-based hydrogen donors. .

另外，作为上述三嗪系化合物的具体例，可以列举2,4,6－三（三氯甲基）均三嗪、2－甲基－4,6－双（三氯甲基）均三嗪、2－［2－（5－甲基呋喃－2－基）乙烯基］－4,6－双（三氯甲基）均三嗪、2－［2－（呋喃－2－基）乙烯基］－4,6－双（三氯甲基）均三嗪、2－［2－（4－二乙基氨基－2－甲基苯基）乙烯基］－4,6－双（三氯甲基）均三嗪、2－［2－（3,4－二甲氧基苯基）乙烯基］－4,6－双（三氯甲基）均三嗪、2－（4－甲氧基苯基）－4,6－双（三氯甲基）均三嗪、2－（4－乙氧基苯乙烯基）－4,6－双（三氯甲基）均三嗪、2－（4－正丁氧基苯基）－4,6－双（三氯甲基）均三嗪等具有卤代甲基的三嗪系化合物。In addition, specific examples of the aforementioned triazine-based compounds include 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, , 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(furan-2-yl)vinyl] ]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl) base)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy Phenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-( Triazine compounds having a halomethyl group, such as 4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine.

另外，作为O－酰基肟系化合物的具体例，可以列举1,2－辛二酮,1－［4－（苯硫基）苯基］－,2－（O－苯甲酰基肟）、乙酮,1－［9－乙基－6－（2－甲基苯甲酰基）－9H－咔唑－3－基］－,1－（O－乙酰基肟）、乙酮,1－［9－乙基－6－（2－甲基－4－四氢呋喃基甲氧基苯甲酰基）－9H－咔唑－3－基］－,1－（O－乙酰基肟）、乙酮,1－［9－乙基－6－{2－甲基－4－（2,2－二甲基－1,3－二氧戊环基）甲氧基苯甲酰基}－9H－咔唑－3－基］－,1－（O－乙酰基肟）等。作为O－酰基肟系化合物的市售品，可以使用NCI－831、NCI－930（以上由ADEKA公司制）等。In addition, specific examples of O-acyl oxime compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyl oxime), ethyl Ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), ethyl ketone, 1-[9 -Ethyl-6-(2-methyl-4-tetrahydrofurylmethoxybenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyl oxime), ethyl ketone,1- [9-Ethyl-6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoyl}-9H-carbazole-3- Base] -, 1 - (O-acetyl oxime) and so on. As a commercial item of an O-acyl oxime compound, NCI-831, NCI-930 (the above are manufactured by ADEKA Corporation), etc. can be used.

本发明中，使用苯乙酮系化合物等联咪唑系化合物以外的光聚合引发剂时，也可以并用增感剂。作为这样的增感剂，可以列举例如4,4’－双（二甲基氨基）二苯甲酮、4,4’－双（二乙基氨基）二苯甲酮、4－二乙基氨基苯乙酮、4－二甲基氨基苯丙酮、4－二甲基氨基苯甲酸乙酯、4－二甲基氨基苯甲酸2－乙基己酯、2,5－双（4－二乙基氨基亚苄基）环己酮、7－二乙基氨基－3－（4－二乙基氨基苯甲酰基）香豆素、4－（二乙基氨基）查耳酮等。In the present invention, when photopolymerization initiators other than biimidazole-based compounds such as acetophenone-based compounds are used, a sensitizer may be used in combination. Examples of such sensitizers include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-diethylamino Acetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis(4-diethyl Aminobenzylidene)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, 4-(diethylamino)chalcone, etc.

本发明中，相对于（C）交联剂100质量份，光聚合引发剂的含量优选0.01～120质量份，特别优选1～100质量份。在这种情况下，如果光聚合引发剂的含量过少，曝光产生的固化有可能变得不充分，另一方面，如果过多，存在形成的着色层在显影时容易从基板脱落的趋势。In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass, relative to 100 parts by mass of the (C) crosslinking agent. In this case, if the content of the photopolymerization initiator is too small, curing by exposure may become insufficient, while if it is too large, the formed colored layer tends to be easily peeled off from the substrate during development.

－溶剂－－Solvent－

本发明的着色组合物是含有上述（A）～（C）成分、以及任意加入的其他成分的着色组合物，通常配合溶剂而制备成液状组合物。作为上述溶剂，只要是分散或溶解构成着色组合物的（A）～（C）成分、其他成分，并与这些成分不反应，且具有适度的挥发性的溶剂，便可以适当选择使用。The coloring composition of the present invention is a coloring composition containing the above-mentioned components (A) to (C) and other components arbitrarily added, and is usually prepared as a liquid composition by mixing a solvent. As said solvent, if it disperses or dissolves (A)-(C) component which comprises a coloring composition, and other components, does not react with these components, and has moderate volatility, it can select and use suitably.

在这样的溶剂中，可举出例如：Among such solvents there may be mentioned, for example:

乙二醇单甲醚、乙二醇单乙醚、乙二醇单正丙醚、乙二醇单正丁醚、二甘醇单甲醚、二甘醇单乙醚、二甘醇单正丙醚、二甘醇单正丁醚、三甘醇单甲醚、三甘醇单乙醚、丙二醇单甲醚、丙二醇单乙醚、丙二醇单正丙醚、丙二醇单正丁醚、二丙二醇单甲醚、二丙二醇单乙醚、二丙二醇单正丙醚、二丙二醇单正丁醚、三丙二醇单甲醚、三丙二醇单乙醚等（聚）亚烷基二醇单烷基醚类；Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, Diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol (poly)alkylene glycol monoalkyl ethers such as monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether;

乳酸甲基、乳酸乙酯等乳酸烷基酯类；Alkyl lactate esters such as methyl lactate and ethyl lactate;

甲醇、乙醇、丙醇、丁醇、异丙醇、异丁醇、叔丁醇、辛醇、2－乙基己醇、环己醇等（环）烷基醇类；Methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tert-butanol, octanol, 2-ethylhexanol, cyclohexanol and other (cyclo)alkyl alcohols;

二丙酮醇等酮醇类等；Ketone alcohols such as diacetone alcohol, etc.;

乙二醇单甲醚乙酸酯、乙二醇单乙醚乙酸酯、二甘醇单甲醚乙酸酯、二甘醇单乙醚乙酸酯、丙二醇单甲醚乙酸酯、丙二醇单乙醚乙酸酯、二丙二醇单甲醚乙酸酯、乙酸3－甲氧基丁酯、乙酸3－甲基－3－甲氧基丁酯等（聚）亚烷基二醇单烷基醚乙酸酯类；Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Acetate esters, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, etc. (poly)alkylene glycol monoalkyl ether acetates ;

二甘醇二甲醚、二甘醇甲基乙基醚、二甘醇二乙醚、四氢呋喃等其他醚类；Diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran and other ethers;

甲基乙基酮、环己酮、2－庚酮、3－庚酮等酮类；Methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and other ketones;

二乙酸丙二醇酯、二乙酸1,3－丁二醇酯、二乙酸1,6－己二醇酯等二乙酸酯类；Diacetate esters such as propylene glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;

3－甲氧基丙酸甲酯、3－甲氧基丙酸乙酯、3－乙氧基丙酸甲酯、3－乙氧基丙酸乙酯、乙氧基乙酸乙酯、3－甲基－3－甲氧基丁基丙酸酯等烷氧基羧酸酯类；Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methoxypropionate Alkoxy carboxylates such as -3-methoxybutyl propionate;

醋酸乙酯、醋酸正丙酯、醋酸异丙酯、醋酸正丁酯、醋酸异丁酯、甲酸正戊酯、醋酸异戊酯、丙酸正丁酯、丁酸乙酯、丁酸正丙酯、丁酸异丙酯、丁酸正丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙酰乙酸甲酯、乙酰乙酸乙酯、2－氧代丁酸乙酯等其他酯类；Ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate , isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutyrate and other esters kind;

甲苯、二甲苯等芳香族烃类；Aromatic hydrocarbons such as toluene and xylene;

N,N－二甲基甲酰胺、N,N－二甲基乙酰胺、N－甲基吡咯烷酮等酰胺或内酰胺类等。Amides or lactams such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc.

这些溶剂中，从溶解性、颜料分散性、涂布性等观点出发，优选（聚）亚烷基二醇单烷基醚类、乳酸烷基酯类、（聚）亚烷基二醇单烷基醚乙酸酯类、其他醚类、酮类、二乙酸酯类、烷氧基羧酸酯类、其他酯类，特别优选丙二醇单甲醚、丙二醇单乙醚、乙二醇单甲醚乙酸酯、丙二醇单甲醚乙酸酯、丙二醇单乙醚乙酸酯、3－甲氧基丁基乙酸酯、二甘醇二甲醚、二甘醇甲基乙基醚、环己酮、2－庚酮、3－庚酮、1,3－丁二醇二乙酸酯、1,6－己二醇二乙酸酯、乳酸乙酯、3－甲氧基丙酸乙酯、3－乙氧基丙酸甲酯、3－乙氧基丙酸乙酯、3－甲基－3－甲氧基丁基丙酸酯、醋酸正丁酯、醋酸异丁酯、甲酸正戊酯、醋酸异戊酯、丙酸正丁酯、丁酸乙酯、丁酸异丙酯、丁酸正丁酯、丙酮酸乙酯等。Among these solvents, (poly)alkylene glycol monoalkyl ethers, lactate alkyl esters, (poly)alkylene glycol monoalkylenes, etc. Ether acetates, other ethers, ketones, diacetates, alkoxy carboxylates, other esters, especially propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate , propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diglyme, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptyl Ketone, 3-heptanone, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxy ethyl propionate, 3-ethoxy Methyl propionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isoamyl acetate , n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, etc.

在本发明中，溶剂可以单独使用或者将2种以上混合使用。将溶剂混合使用时，优选至少将（聚）亚烷基二醇单烷基醚类与（聚）亚烷基二醇单烷基醚乙酸酯类、（聚）亚烷基二醇单烷基醚乙酸酯类与烷氧基羧酸酯类、乳酸烷基酯类与（聚）亚烷基二醇单烷基醚乙酸酯类混合使用。In this invention, a solvent can be used individually or in mixture of 2 or more types. When using a solvent in combination, it is preferable to mix at least (poly)alkylene glycol monoalkyl ethers, (poly)alkylene glycol monoalkyl ether acetates, (poly)alkylene glycol monoalkyl Ether acetates are used in combination with alkoxy carboxylates, alkyl lactates and (poly)alkylene glycol monoalkyl ether acetates.

溶剂的含有量没有特别限定，不包括该组合物的溶剂的各成分的合计浓度优选为5～50质量%的量，更优选为10～40质量%的量。通过处于这种状态，可以得到分散性、稳定性良好的着色分散液，以及涂布性、稳定性良好的着色组合物。The content of the solvent is not particularly limited, but the total concentration of the components excluding the solvent of the composition is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. In such a state, a colored dispersion liquid with good dispersibility and stability, and a colored composition with good applicability and stability can be obtained.

－添加剂－-additive-

本发明的着色组合物也可根据需要含有各种添加剂。The coloring composition of the present invention may contain various additives as necessary.

作为添加剂，可以举出例如玻璃、氧化铝等填充剂；聚乙烯醇、聚（氟烷基丙烯酸酯）类等高分子化合物；氟系表面活性剂、硅系表面活性剂等表面活性剂；乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三（2－甲氧基乙氧基）硅烷、N－（2－氨基乙基）－3－氨基丙基甲基二甲氧基硅烷、N－（2－氨基乙基）－3－氨基丙基三甲氧基硅烷、3－氨基丙基三乙氧基硅烷、3－缩水甘油氧基丙基三甲氧基硅烷、3－缩水甘油氧基丙基甲基二甲氧基硅烷、2－（3,4－环氧环己基）乙基三甲氧基硅烷、3－氯丙基甲基二甲氧基硅烷、3－氯丙基三甲氧基硅烷、3－甲基丙烯酰氧基丙基三甲氧基硅烷、3－巯基丙基三甲氧基硅烷等密合促进剂；2,2－硫代双（4－甲基－6－叔丁基苯酚）、2,6－二叔丁基苯酚等抗氧化剂；2－（3－叔丁基－5－甲基－2－羟基苯基）－5－氯苯并三唑、烷氧基二苯甲酮类等紫外线吸收剂；聚丙烯酸钠等防凝聚剂；丙二酸、己二酸、衣康酸、柠康酸、富马酸、中康酸、2－氨基乙醇、3－氨基－1－丙醇、5－氨基－1－戊醇、3－氨基－1,2－丙二醇、2－氨基－1,3－丙二醇、4－氨基－1,2－丁二醇等残渣改善剂；琥珀酸单［2－（甲基）丙烯酰氧基乙基］酯、苯二甲酸单［2－（甲基）丙烯酰氧基乙基］酯、ω－羧基聚己内酯单（甲基）丙烯酸酯等显影性改善剂等。Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly(fluoroalkyl acrylate); surfactants such as fluorine-based surfactants and silicon-based surfactants; N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Silane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidol Oxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethyl Oxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and other adhesion promoters; 2,2-thiobis(4-methyl-6-tert butylphenol), 2,6-di-tert-butylphenol and other antioxidants; 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, alkoxy UV absorbers such as benzophenones; anti-aggregating agents such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino -1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol and other residue improvers ;Mono[2-(meth)acryloyloxyethyl]succinate, mono[2-(meth)acryloyloxyethyl]phthalate, ω-carboxypolycaprolactone mono(meth) base) acrylate and other developability improvers, etc.

本发明的着色组合物可以通过适当方法来制备，作为其制备方法，可举出例如日本特开2008－58642号公报、日本特开2010－132874号公报等中公开的方法。作为着色剂使用染料和颜料这两者时，可以如日本特开2010－132874号公报中公开的那样，采用以下方法：使染料溶液通过第1过滤器后，将通过了第1过滤器的染料溶液与另外制备的颜料分散液等进行混合，使得到的着色组合物通过第2过滤器而制备。另外，也可以采用以下方法：将染料和上述（B）～（C）成分以及根据需要使用的其他成分溶解于溶剂，使得到的溶液通过第1过滤器后，将通过了第1过滤器的溶液与另外制备的颜料分散液进行混合，将得到的着色组合物通过第2过滤器而制备。另外，还可以采用以下方法：使染料溶液通过第1过滤器后，将通过了第1过滤器的染料溶液和上述（B）～（C）成分以及根据需要使用的其他成分进行混合·溶解，使得到的溶液通过第2过滤器，进一步将通过了第2过滤器的溶液与另外制备的颜料分散液进行混合，使得到的着色组合物通过第3过滤器而制备。The coloring composition of the present invention can be prepared by an appropriate method, and examples of the preparation method include methods disclosed in JP-A No. 2008-58642, JP-A No. 2010-132874, and the like. When using both a dye and a pigment as a colorant, as disclosed in Japanese Patent Laid-Open No. 2010-132874, the following method can be adopted: after passing the dye solution through the first filter, the dye that has passed through the first filter The solution is mixed with a separately prepared pigment dispersion and the like, and the resulting coloring composition is passed through a second filter to prepare it. In addition, the method of dissolving the dye, the above-mentioned (B) to (C) components, and other components used as needed in a solvent, passing the obtained solution through the first filter, and dissolving the dye that has passed through the first filter may also be used. The solution is mixed with a separately prepared pigment dispersion liquid, and the obtained coloring composition is passed through a second filter to prepare it. In addition, it is also possible to use a method of mixing and dissolving the dye solution that has passed through the first filter, the above-mentioned components (B) to (C) and other components used as necessary, after passing the dye solution through the first filter, The obtained solution was passed through the second filter, the solution passed through the second filter was further mixed with a pigment dispersion liquid prepared separately, and the obtained coloring composition was passed through the third filter to prepare.

滤色器及其制造方法Color filter and manufacturing method thereof

本发明的滤色器具有使用本发明的着色组合物形成的着色层。The color filter of this invention has the coloring layer formed using the coloring composition of this invention.

作为制造滤色器的方法，第一可以举出以下的方法。首先，在基板的表面上根据需要形成遮光层（黑矩阵）以将形成像素的部分分区。接着，在该基板上涂布例如含有染料（a1）的红色的本发明的着色放射线敏感性组合物的液状组合物后，进行预烘烤使溶剂蒸发，形成涂膜。接着，介由光掩膜对该涂膜进行曝光后，使用碱显影液进行显影，将涂膜的未曝光部分溶解除去。然后，通过进行后烘烤，形成以规定的排列配置有红色的像素图案的像素阵列。As a method of manufacturing a color filter, the following methods are mentioned first. First, a light-shielding layer (black matrix) is formed as necessary on the surface of the substrate to partition portions where pixels are formed. Next, for example, a liquid composition of the colored radiation-sensitive composition of the present invention containing a dye (a1) is coated on the substrate, and then prebaked to evaporate the solvent to form a coating film. Next, after exposing this coating film through a photomask, it develops using an alkali developing solution, and dissolves and removes the unexposed part of a coating film. Then, post-baking is performed to form a pixel array in which red pixel patterns are arranged in a predetermined arrangement.

接着，使用绿色或蓝色的各着色放射线敏感性组合物，与上述同样地进行各着色放射线敏感性组合物的涂布、预烘烤、曝光、显影和后烘烤，在同一基板上依次形成绿色的像素阵列和蓝色的像素阵列。由此，得到在基板上配置有红色、绿色和蓝色的三原色的像素阵列的滤色器。但是，在本发明中，只要红色、绿色和蓝色的像素中的至少1个由本发明的着色组合物形成即可。另外，形成各色的像素的顺序不限于上述顺序。Next, using each colored radiation-sensitive composition of green or blue, coating, pre-baking, exposure, development, and post-baking of each colored radiation-sensitive composition were performed in the same manner as above, and sequentially formed on the same substrate. A green pixel array and a blue pixel array. In this way, a color filter in which a pixel array of three primary colors of red, green, and blue is arranged on a substrate is obtained. However, in the present invention, at least one of the red, green and blue pixels may be formed from the coloring composition of the present invention. In addition, the order in which the pixels of the respective colors are formed is not limited to the order described above.

另外，黑矩阵可通过利用光刻法使采用溅射、蒸镀成膜的铬等金属薄膜成为所希望的图案而形成，但也可使用分散有黑色的颜料的着色放射线敏感性组合物，与形成上述像素时同样地形成。In addition, the black matrix can be formed by making a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern by photolithography, but it is also possible to use a colored radiation-sensitive composition in which a black pigment is dispersed. The above-mentioned pixel is formed in the same manner.

作为形成滤色器时使用的基板，可以举出例如玻璃、硅、聚碳酸酯、聚酯、芳香族聚酰胺、聚酰胺酰亚胺、聚酰亚胺等。Examples of the substrate used when forming a color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamide-imide, and polyimide.

另外，对这些基板，根据需要也可实施采用硅烷偶联剂等的试剂处理、等离子体处理、离子镀、溅射、气相反应法、真空蒸镀等适当的前处理。In addition, these substrates may be subjected to appropriate pretreatments such as reagent treatment using a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, and vacuum deposition as necessary.

将着色放射线敏感性组合物涂布在基板时，可以采用喷雾法、辊涂法、旋转涂布法（旋涂法）、缝模涂布法、刮条涂布法等适当的涂布法，特别优选采用旋涂法、缝模涂布法。When coating the colored radiation-sensitive composition on the substrate, appropriate coating methods such as spray method, roll coating method, spin coating method (spin coating method), slot die coating method, and bar coating method can be used, In particular, spin coating and slot die coating are preferably used.

预烘烤通常将减压干燥与加热干燥组合进行。减压干燥通常进行至达到50～200Pa。另外，加热干燥的条件通常为70～110℃下干燥1～10分钟左右。Prebaking is usually carried out by combining drying under reduced pressure and drying under heat. Drying under reduced pressure is usually carried out until it reaches 50 to 200 Pa. Moreover, the conditions of heat drying are drying at 70-110 degreeC normally for about 1 to 10 minutes.

对于涂布厚度，作为干燥后的膜厚，通常为0.6～8μm，优选为1.2～5μm。The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm as a film thickness after drying.

作为形成像素和/或黑矩阵时使用的放射线的光源，可以举出例如氙灯、卤素灯、钨灯、高压汞灯、超高压汞灯、金属卤化物灯、中压汞灯、低压汞灯等灯光源，氩离子激光、YAG激光、XeCl准分子激光、氮激光等激光光源等，但是优选波长在190～450nm的范围的放射线。Examples of radiation sources used for forming pixels and/or black matrices include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, and low-pressure mercury lamps. Lamp light source, laser light source such as argon ion laser, YAG laser, XeCl excimer laser, nitrogen laser, etc., but radiation with a wavelength in the range of 190 to 450 nm is preferable.

放射线的曝光量一般优选10～10000J/m²。Generally, the exposure dose of radiation is preferably 10 to 10000 J/m² .

另外，作为上述碱显影液，优选例如碳酸钠、氢氧化钠、氢氧化钾、氢氧化四甲铵、胆碱、1,8－二氮杂双环－［5.4.0］－7－十一碳烯、1,5－二氮杂双环－［4.3.0］－5－壬烯等的水溶液。In addition, as the above-mentioned alkali developing solution, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7-undecane are preferable, for example. Aqueous solution of alkenes, 1,5-diazabicyclo-[4.3.0]-5-nonene, etc.

在上述碱显影液中,也可以添加适量的例如甲醇、乙醇等水溶性有机溶剂、表面活性剂等。再有，碱显影后，通常进行水洗。An appropriate amount of water-soluble organic solvents such as methanol and ethanol, surfactants, and the like may also be added to the above-mentioned alkaline developer. In addition, washing with water is usually performed after alkali image development.

作为显影处理法，可采用喷淋显影法、喷雾显影法、浸渍（dip）显影法、浸置式（覆液）显影法等。显影条件优选在常温进行5～300秒。As the developing treatment method, a shower developing method, a spray developing method, a dip developing method, a dip developing method, or the like can be employed. Image development conditions are preferably carried out at normal temperature for 5 to 300 seconds.

后烘烤的条件通常为180～280℃下进行10～60分钟左右。The post-baking conditions are usually about 10 to 60 minutes at 180 to 280°C.

这样形成的像素的膜厚度通常为0.5～5μm，优选为1.0～3μm。The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1.0 to 3 μm.

另外，作为制造滤色器的第二方法，还已知日本特开平7－318723号公报、日本特开2000－310706号公报等中公开的采用喷墨方式得到各色的像素的方法。在该方法中，首先，在基板的表面上形成兼具遮光功能的隔壁。接着，通过喷墨装置将例如含有染料（a1）的红色的本发明的着色热固性组合物的液状组合物喷出到形成的隔壁内后，进行预烘烤使溶剂蒸发。接着，将该涂膜根据需要进行曝光后，通过后烘烤进行固化，形成红色的像素图案。In addition, as a second method of manufacturing a color filter, a method of obtaining pixels of each color by an inkjet method disclosed in JP-A-7-318723 and JP-A-2000-310706 is also known. In this method, first, partition walls having a light-shielding function are formed on the surface of the substrate. Next, a liquid composition of, for example, a red colored thermosetting composition of the present invention containing a dye (a1) is ejected into the formed partition walls by an inkjet device, and then prebaking is performed to evaporate the solvent. Next, after exposing the coating film as necessary, it is cured by post-baking to form a red pixel pattern.

接着，使用绿色或蓝色的各着色热固性组合物，与上述同样地在同一基板上依次形成绿色的像素图案和蓝色的像素图案。由此，得到在基板上配置有红色、绿色和蓝色的三原色的像素图案的滤色器。但是，在本发明中，只要红色、绿色和蓝色的像素中的至少1个由本发明的着色组合物形成即可。另外，形成各色像素的顺序不限于上述顺序。Next, using each colored thermosetting composition of green or blue, a green pixel pattern and a blue pixel pattern were sequentially formed on the same substrate in the same manner as above. In this way, a color filter in which pixel patterns of three primary colors of red, green, and blue are arranged on a substrate is obtained. However, in the present invention, at least one of the red, green and blue pixels may be formed from the coloring composition of the present invention. In addition, the order of forming the pixels of each color is not limited to the above order.

再有，上述隔壁不仅具有遮光功能，还起到使喷出到分区内的各色的着色组合物不混色的功能，因此，相比于上述第一方法中使用的黑矩阵膜厚度厚。因此，隔壁通常使用黑色放射线敏感性组合物来形成。In addition, the barrier ribs not only have a light-shielding function, but also function to prevent color mixing of the coloring compositions discharged into the partitions, and therefore are thicker than the black matrix film used in the first method. Therefore, the partition wall is usually formed using a black radiation-sensitive composition.

在形成滤色器时使用的基板、放射线的光源，以及预烘烤、后烘烤的方法、条件，与上述的第一方法相同。这样，通过喷墨方式形成的像素的膜厚度与隔壁的高度为同程度。The substrate used for forming the color filter, the source of radiation, and the methods and conditions of pre-baking and post-baking are the same as those of the above-mentioned first method. In this way, the film thickness of the pixel formed by the inkjet method is about the same as the height of the partition wall.

在这样得到的像素图案上，根据需要形成保护膜后，利用溅射形成透明导电膜。形成透明导电膜后，还可以进一步形成间隔件而形成滤色器。间隔件通常可以使用放射线敏感性组合物来形成，但是也可以制成具有遮光性的间隔件（黑间隔件）。此时，使用分散有黑色着色剂的着色放射线敏感性组合物，本发明的着色组合物也可以很好地用于该黑间隔件的形成。On the pixel pattern obtained in this way, after forming a protective film as needed, a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer may be further formed to form a color filter. Usually, the spacer can be formed using a radiation-sensitive composition, but it can also be made into a light-shielding spacer (black spacer). At this time, the colored composition of the present invention can also be favorably used for the formation of the black spacer by using a colored radiation-sensitive composition in which a black colorant is dispersed.

这样得到的本发明的滤色器亮度和色纯度极高，因此对彩色液晶显示元件、彩色摄像管元件、彩色传感器、有机EL显示元件、电子纸张等极其有用。The color filter of the present invention thus obtained is extremely high in luminance and color purity, and therefore is extremely useful for color liquid crystal display devices, color image pickup tube devices, color sensors, organic EL display devices, electronic paper, and the like.

显示元件display element

本发明的显示元件具备本发明的滤色器。作为显示元件可以举出彩色液晶显示元件、有机EL显示元件、电子纸张等。The display element of this invention is provided with the color filter of this invention. As a display element, a color liquid crystal display element, an organic EL display element, electronic paper, etc. are mentioned.

具备本发明的滤色器的彩色液晶显示元件可以是透射型，也可以是反射型，可以采用适当构造。例如可以采用：在与配置有薄膜晶体管（TFT）的驱动用基板不同的基板上形成滤色器，驱动用基板和形成有滤色器的基板介由液晶层相对的结构；进而也可以采用：在配置有薄膜晶体管（TFT）的驱动用基板的表面上形成有滤色器的基板、与形成有ITO（掺杂了锡的氧化铟）电极的基板介由液晶层相对的结构。后者的结构具有能够显著提高开口率、获得明亮且高精细的液晶显示元件的优点。The color liquid crystal display element including the color filter of the present invention may be a transmissive type or a reflective type, and an appropriate structure may be employed. For example, a structure in which a color filter is formed on a substrate different from a driving substrate on which a thin-film transistor (TFT) is disposed, and the driving substrate and the substrate on which the color filter is formed is opposed to each other through a liquid crystal layer can be adopted; furthermore, it is also possible to adopt: A structure in which a substrate on which a color filter is formed on the surface of a driving substrate on which thin-film transistors (TFTs) are disposed, and a substrate on which an ITO (tin-doped indium oxide) electrode is formed face each other via a liquid crystal layer. The latter structure has the advantages of being able to significantly increase the aperture ratio and obtain a bright and high-definition liquid crystal display element.

具备本发明的滤色器的彩色液晶显示元件，除了冷阴极荧光管（CCFL:ColdCathode Fluorescent Lamp）之外，还可以具备以白色LED作为光源的背光源单元。作为白色LED，可以举出例如组合红色LED、绿色LED和蓝色LED通过混色而得到白色光的白色LED，组合蓝色LED、红色LED和绿色荧光体通过混色而得到白色光的白色LED，组合蓝色LED、红色荧光体和绿色荧光体通过混色而得到白色光的白色LED，通过蓝色LED与YAG系荧光体的混色而得到白色光的白色LED，组合蓝色LED、橙色荧光体和绿色荧光体通过混色而得到白色光的白色LED，组合紫外线LED、红色发光荧光体、绿色发光荧光体和蓝色发光荧光体通过混色而得到白色光的白色LED等。The color liquid crystal display device including the color filter of the present invention may include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent tube (CCFL: Cold Cathode Fluorescent Lamp). As the white LED, for example, a white LED that obtains white light by combining a red LED, a green LED, and a blue LED through color mixing, and a white LED that obtains white light by combining a blue LED, a red LED, and a green phosphor through color mixing, and a combination of White LEDs that obtain white light by mixing blue LEDs, red phosphors, and green phosphors, white LEDs that obtain white light by mixing blue LEDs and YAG-based phosphors, and combinations of blue LEDs, orange phosphors, and green White LEDs that produce white light by color mixing of phosphors, and white LEDs that produce white light by combining ultraviolet LEDs, red light-emitting phosphors, green light-emitting phosphors, and blue light-emitting phosphors by color mixing.

具备本发明的滤色器的彩色液晶显示元件可以适用TN（Twisted Nematic，扭曲向列）型、STN（Super Twisted Nematic，超扭曲向列）型、IPS（In－Planes Switching，面内切换）型、VA（Vertical Alignment，垂直取向）型、OCB（Optically CompensatedBirefringence，光学补偿弯曲排列）型等适合的液晶模式。The color liquid crystal display element equipped with the color filter of the present invention can be applied to TN (Twisted Nematic, twisted nematic) type, STN (Super Twisted Nematic, super twisted nematic) type, IPS (In-Planes Switching, in-plane switching) type , VA (Vertical Alignment, vertical alignment) type, OCB (Optically Compensated Birefringence, optically compensated bending alignment) type and other suitable liquid crystal modes.

另外，具备本发明的滤色器的有机EL显示元件可采用适宜的构造，可举出例如日本特开平11－307242号公报中公开的构造。Moreover, the organic electroluminescent display element provided with the color filter of this invention can employ|adopt a suitable structure, For example, the structure disclosed by Unexamined-Japanese-Patent No. 11-307242 is mentioned.

另外，具备本发明的滤色器的电子纸张可以采用适宜的构造，可举出例如日本特开2007－41169号公报中公开的构造。In addition, an electronic paper including the color filter of the present invention can have a suitable structure, for example, the structure disclosed in JP-A-2007-41169 can be mentioned.

实施例Example

以下举出实施例，进一步具体说明本发明的实施方式。但是，本发明不限于下述实施例。Examples are given below, and the embodiment of the present invention will be described in more detail. However, the present invention is not limited to the following examples.

＜本着色剂的合成＞＜Synthesis of this colorant＞

合成例1Synthesis Example 1

在加入了搅拌子的100mL的梨型烧瓶内加入氯仿25.2g、脱水DMF1.72g，在氮气流下冷却至10℃以下，添加亚硫酰氯2.27g（1.38mL、19.1mmol）在该温度下搅拌30分钟。然后加入3.5g（5.17mmol）的酸性红289，在氮气流下以35℃搅拌3小时后，进一步追加添加0.246g（0.149mL，2.07mmol）的亚硫酰氯，在该温度下进一步持续搅拌1.5小时。将反应混合物冷却至5℃，在该温度下添加十二烷基胺3.26g（17.6mmol）、三乙胺5.46g（54.0mmol）并搅拌10分钟后，以40℃持续搅拌共计15小时。将反应混合物用旋转蒸发仪减压浓缩后，添加12.3g的甲醇，将得到的溶液再浓缩至液量达到约一半。接着，添加甲醇17.8g以及醋酸1.23g，将得到的混合物在室温中搅拌30分钟。然后，将上述混合物滴加到大量水中析出红色固体，以抽滤进行滤取并充分水洗。将得到的固体用少量的二异丙基醚、接着用己烷充分洗涤后，以60℃减压干燥12小时，从而得到了4.13g的固体（收率97.2%）。通过MS谱确认了得到的红色固体为下述式（A1）表示的化合物。将该化合物作为着色剂（A－1）。25.2 g of chloroform and 1.72 g of dehydrated DMF were added to a 100 mL pear-shaped flask with a stirring bar, cooled to below 10°C under nitrogen flow, 2.27 g of thionyl chloride (1.38 mL, 19.1 mmol) was added and stirred at this temperature for 30 minute. Then add 3.5g (5.17mmol) of acid red 289, stir at 35°C under nitrogen flow for 3 hours, then add 0.246g (0.149mL, 2.07mmol) of thionyl chloride, and continue stirring at this temperature for 1.5 hours . The reaction mixture was cooled to 5° C., 3.26 g (17.6 mmol) of dodecylamine and 5.46 g (54.0 mmol) of triethylamine were added at this temperature and stirred for 10 minutes, and then stirring was continued at 40° C. for a total of 15 hours. After concentrating the reaction mixture under reduced pressure with a rotary evaporator, 12.3 g of methanol was added, and the obtained solution was further concentrated until the liquid volume became about half. Next, 17.8 g of methanol and 1.23 g of acetic acid were added, and the resulting mixture was stirred at room temperature for 30 minutes. Then, the above mixture was added dropwise to a large amount of water to precipitate a red solid, which was collected by suction filtration and fully washed with water. The obtained solid was washed sufficiently with a small amount of diisopropyl ether and then with hexane, and then dried under reduced pressure at 60° C. for 12 hours to obtain 4.13 g of a solid (yield: 97.2%). It was confirmed by MS spectrum that the obtained red solid was a compound represented by the following formula (A1). This compound was used as a coloring agent (A-1).

合成例2Synthesis example 2

在合成例1中代替十二烷基胺使用甲基乙基肟，除此以外，与合成例1同样进行而合成了着色剂。通过MS谱确认了得到的固体是由下述式（A2）表示的化合物。将该化合物作为着色剂（A－2）。In Synthesis Example 1, the colorant was synthesized in the same manner as in Synthesis Example 1 except that methyl ethyl oxime was used instead of dodecylamine. It was confirmed by MS spectrum that the obtained solid was a compound represented by the following formula (A2). This compound was used as a coloring agent (A-2).

合成例3Synthesis example 3

在合成例1中代替十二烷基胺使用苯甲酰肼，除此以外，与合成例1同样进行而合成了着色剂。通过MS谱确认了得到的固体是由下述式（A3）表示的化合物。将该化合物作为着色剂（A－3）。In synthesis example 1, except having used benzohydrazide instead of dodecylamine, it carried out similarly to synthesis example 1, and synthesize|combined the coloring agent. It was confirmed by MS spectrum that the obtained solid was a compound represented by the following formula (A3). This compound was used as a coloring agent (A-3).

合成例4Synthesis Example 4

在合成例1中代替十二烷基胺使用1－十二烷基硫醇，除此以外，与合成例1同样进行而合成了着色剂。通过MS谱确认了得到的固体是由下述式（A4）表示的化合物。将该化合物作为着色剂（A－4）。In synthesis example 1, except having used 1-dodecyl mercaptan instead of dodecylamine, it carried out similarly to synthesis example 1, and synthesize|combined the coloring agent. It was confirmed by MS spectrum that the obtained solid was a compound represented by the following formula (A4). This compound was used as a coloring agent (A-4).

合成例5Synthesis Example 5

在合成例1中代替十二烷基胺使用对甲苯磺酰胺，除此以外，与合成例1同样进行而合成了着色剂。通过MS谱确认了得到的固体是由下述式（A5）表示的化合物。将该化合物作为着色剂（A－5）。In Synthesis Example 1, a coloring agent was synthesized in the same manner as in Synthesis Example 1 except that p-toluenesulfonamide was used instead of dodecylamine. It was confirmed by MS spectrum that the obtained solid was a compound represented by the following formula (A5). This compound was used as a coloring agent (A-5).

合成例6Synthesis Example 6

在合成例1中代替酸性红289使用酸性红52，除此以外，与合成例1同样进行而合成着色剂。通过MS谱确认了得到的固体是由下述式（A6）表示的化合物。将该化合物作为着色剂（A－6）。In the synthesis example 1, except having used the acid red 52 instead of the acid red 289, it carried out similarly to the synthesis example 1, and synthesized the coloring agent. It was confirmed by MS spectrum that the obtained solid was a compound represented by the following formula (A6). This compound was used as a coloring agent (A-6).

比较合成例1Comparative Synthesis Example 1

按照日本特开2010－254964号公报的合成例1的记载，进行染料的合成。将得到的化合物作为着色剂（A－7）。The dye was synthesized according to the description in Synthesis Example 1 of JP-A-2010-254964. The obtained compound was used as a coloring agent (A-7).

溶解性的评价Solubility evaluation

称量在合成例1中得到的着色剂（A－1），以着色剂浓度达到0.1重量%、1重量%和5重量%的方式加入环己酮。利用搅拌转子将这些样品在25℃搅拌1小时，然后迅速以目视确认溶解状态。其结果确认了着色剂（A－1）相对于环己酮在5重量%时完全溶解。The colorant (A-1) obtained in Synthesis Example 1 was weighed, and cyclohexanone was added so that the concentration of the colorant became 0.1% by weight, 1% by weight, and 5% by weight. These samples were stirred at 25° C. for 1 hour with a stirring rotor, and then the dissolved state was quickly confirmed visually. As a result, it was confirmed that the colorant (A-1) was completely dissolved at 5% by weight of cyclohexanone.

同样进行对着色剂（A－2）～着色剂（A－7）和酸性红289的溶解性的评价。着色剂（A－2）～着色剂（A－6）相对于环己酮在5重量%时完全溶解。着色剂（A－7）在1重量%时完全溶解，但在5重量%时不溶解。另外，酸性红289在0.1重量%时不溶解。The solubility evaluation of coloring agent (A-2) - coloring agent (A-7) and acid red 289 was performed similarly. The colorants (A-2) to (A-6) were completely dissolved at 5% by weight of cyclohexanone. The colorant (A-7) was completely dissolved at 1% by weight, but not dissolved at 5% by weight. In addition, acid red 289 does not dissolve at 0.1% by weight.

＜染料溶液的制备和评价＞＜Preparation and evaluation of dye solution＞

制备例1Preparation Example 1

将着色剂（A－1）5质量份、作为溶剂的乳酸乙酯95质量份混合，制备染料溶液（A－1）。A dye solution (A-1) was prepared by mixing 5 parts by mass of the colorant (A-1) and 95 parts by mass of ethyl lactate as a solvent.

制备例2～6Preparation example 2-6

在制备例1中代替着色剂（A－1）使用着色剂（A－2）～着色剂（A－6），除此以外，与制备例1同样进行而制备了染料溶液（A－2）～染料溶液（A－6）。Dye solution (A-2) was prepared in the same manner as in Preparation Example 1 except that colorants (A-2) to (A-6) were used instead of colorant (A-1). ~ Dye solution (A-6).

制备例7Preparation Example 7

在制备例1中代替着色剂（A－1）使用着色剂（A－7），但着色剂（A－7）在乳酸乙酯中不完全溶解，看到了溶解后的残余。将得到的染料悬浮液作为染料溶液（A－7）。In Preparation Example 1, the colorant (A-7) was used instead of the colorant (A-1), but the colorant (A-7) was not completely dissolved in ethyl lactate, and residues after dissolution were observed. The obtained dye suspension was used as a dye solution (A-7).

制备例8Preparation example 8

在制备例1中代替着色剂（A－1）使用酸性红289，但酸性红289在乳酸乙酯中不溶解。将得到的染料悬浮液作为染料溶液（A－8）。In Preparation Example 1, Acid Red 289 was used instead of the colorant (A-1), but Acid Red 289 was insoluble in ethyl lactate. The obtained dye suspension was used as a dye solution (A-8).

＜颜料分散液的制备＞＜Preparation of pigment dispersion＞

制备例9Preparation Example 9

使用15质量份的C.I.颜料蓝15：6作为着色剂、12.5质量份（固体成分浓度40质量%）的BYK－LPN21116（BYK公司制）作为分散剂、72.5质量份的丙二醇单甲醚乙酸酯作为溶剂，利用珠磨机进行处理，从而制备了颜料分散液（A－1）。15 parts by mass of C.I. Pigment Blue 15:6 as a colorant, 12.5 parts by mass (solid content concentration: 40% by mass) of BYK-LPN21116 (manufactured by BYK) as a dispersant, and 72.5 parts by mass of propylene glycol monomethyl ether acetate As a solvent, it processed with the bead mill, and the pigment dispersion liquid (A-1) was prepared.

＜（B）粘结剂树脂的合成＞＜(B) Synthesis of binder resin＞

合成例7Synthesis Example 7

在具备冷却管和搅拌机的烧瓶中加入丙二醇单甲醚乙酸酯100质量份，进行氮置换。加热至80℃，在该温度下用1小时滴加丙二醇单甲醚乙酸酯100质量份、甲基丙烯酸20质量份、苯乙烯10质量份、甲基丙烯酸苄酯5质量份、甲基丙烯酸2－羟基乙酯15质量份、甲基丙烯酸2－乙基己酯23质量份、N－苯基马来酰亚胺12质量份、琥珀酸单（2－丙烯酰氧乙基）酯15质量份和2,2’－偶氮双（2,4－二甲基戊腈）6质量份的混合溶液，保持该温度而聚合2小时。然后、使反应溶液的温度升温至100℃，进一步聚合1小时，从而得到了粘结剂树脂溶液（固体成分浓度33质量%）。得到的粘结剂树脂的Mw为12200、Mn为6500。将该粘结剂树脂作为“粘结剂树脂（B1）”。100 parts by mass of propylene glycol monomethyl ether acetate was placed in a flask equipped with a cooling tube and a stirrer, and nitrogen substitution was performed. Heating to 80°C, at this temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, methacrylic acid 15 parts by mass of 2-hydroxyethyl ester, 23 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenylmaleimide, 15 parts by mass of mono(2-acryloyloxyethyl) succinate 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) and polymerized for 2 hours while maintaining the temperature. Then, the temperature of the reaction solution was raised to 100° C., and further polymerization was carried out for 1 hour to obtain a binder resin solution (solid content concentration: 33% by mass). Mw of the obtained binder resin was 12200, and Mn was 6500. This binder resin is referred to as "binder resin (B1)".

＜着色组合物的制备和评价＞<Preparation and evaluation of coloring composition>

实施例1Example 1

将颜料分散液（A－1）13.5质量份、染料溶液（A－1）7.2质量份、作为粘结剂树脂的粘结剂树脂（B1）溶液9.9质量份、作为交联剂的东亚合成株式会社制M－402（二季戊四醇六丙烯酸酯与二季戊四醇五丙烯酸酯的混合物）15.4质量份、作为光聚合引发剂的2－苄基－2－二甲基氨基－1－（4－吗啉代苯基）丁烷－1－酮（Ciba·Specialty·Chemicals公司制，商品名IRGAC ＵRE369）1.8质量份、作为表面活性剂的Megaface F－554（DIC株式会社製）0.2质量份、以及作为溶剂的乳酸乙酯进行混合，制备了固体成分浓度20质量%的着色组合物。13.5 parts by mass of pigment dispersion (A-1), 7.2 parts by mass of dye solution (A-1), 9.9 parts by mass of binder resin (B1) solution as binder resin, Toagosei Co., Ltd. as a crosslinking agent 15.4 parts by mass of M-402 (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) manufactured by the company, 2-benzyl-2-dimethylamino-1-(4-morpholino) as a photopolymerization initiator 1.8 parts by mass of phenyl)butan-1-one (manufactured by Ciba Specialty Chemicals, trade name IRGAC URE369), 0.2 parts by mass of Megaface F-554 (manufactured by DIC Corporation) as a surfactant, and Ethyl lactate was mixed to prepare a coloring composition having a solid content concentration of 20% by mass.

将得到的着色组合物利用旋转涂布机涂布于玻璃基板上后，用80℃的热板进行10分钟预烘烤，形成了膜厚不同的3张涂膜。After coating the obtained coloring composition on a glass substrate with a spin coater, it prebaked for 10 minutes with the hot plate of 80 degreeC, and formed three coating films with different film thicknesses.

接着，将该基板冷却至室温后，利用高压汞灯，不介由掩膜对涂膜将包含365nm、405nm和436nm各波长的放射线以2000J/m²的曝光量曝光。像这样，在基板上形成了蓝色的评价用固化膜。Next, after cooling the substrate to room temperature, the coating film was exposed to radiation including wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 2000 J/m² using a high-pressure mercury lamp without a mask. In this way, a blue cured film for evaluation was formed on the substrate.

对比度评价contrast evaluation

用2片偏振片夹持形成有固化膜的基板，从背面侧照射荧光灯（波长范围380～780nm）的同时使前面侧的偏振片旋转，利用亮度计LS-100（Minolta株式会社制）测定透射的光强度的最大值和最小值。然后，对各个固化膜，将用最小值除最大值而得到的值作为对比度比。通过测定结果，求出色度坐标值y＝0.080的对比度比。将评价结果示于表1。The substrate on which the cured film was formed was sandwiched between two polarizers, and the front polarizer was rotated while irradiating a fluorescent lamp (wavelength range: 380 to 780 nm) from the back side, and the transmission was measured with a luminance meter LS-100 (manufactured by Minolta Co., Ltd.). The maximum and minimum values of the light intensity. Then, for each cured film, the value obtained by dividing the maximum value by the minimum value was defined as the contrast ratio. From the measurement results, the contrast ratio of the chromaticity coordinate value y=0.080 was calculated|required. Table 1 shows the evaluation results.

耐热性的评价Evaluation of heat resistance

将形成有固化膜的基板在230℃的清洁炉内进行1小时的后烘烤。对后烘烤前后的基板测定色差（ΔEab＊）。然后，将ΔEab＊小于3.0的情况评价为“◎”，将3.0以上且小于5.0的情况评价为“○”，将5.0以上的情况评价为“×”。将评价结果示于表1。The substrate on which the cured film was formed was post-baked for 1 hour in a clean oven at 230°C. The color difference (ΔEab*) was measured for the substrates before and after post-baking. Then, the case where ΔEab* was less than 3.0 was evaluated as "⊚", the case where 3.0 or more and less than 5.0 was evaluated as "◯", and the case where 5.0 or more was evaluated as "×". Table 1 shows the evaluation results.

电压保持率（%）的评价Evaluation of voltage retention rate (%)

在表面形成有用于防止钠离子的溶出的SiO₂膜、进而以规定形状蒸镀有ITO（铟－氧化锡合金）电极的钠钙玻璃基板上将得到的着色组合物旋转涂布后，用100℃的热板进行1分钟的预烘烤，形成了膜厚2.0μm的被膜。接着，不介由掩膜，对被膜以700J/m²的曝光量进行曝光。然后，将该基板浸渍于23℃的由0.04质量%的氢氧化钾水溶液形成的显影液中1分钟，显影后，用超纯水清洗并风干，进而以230℃进行30分钟的后烘烤，使被膜固化，形成永久固化膜。接着，将形成有该像素的基板与以规定形状仅蒸镀有ITO电极的基板用混合有1.8mm的玻璃珠的密封剂贴合后，注入Merck制液晶（MLC6608），制作液晶单元。接着，将液晶单元放入60℃的恒温层，利用液晶电压保持率测定系统（VHR－1A型，TOYO Technica公司）测定液晶单元的电压保持率。此时的施加电压为5.5V的方形波，测定频率为60Hz。在这里，电压保持率是指利用（16.7微秒后的液晶单元电位差/以0微秒施加的电压）求得的值。液晶单元的电压保持率为90%以下时，意味着液晶单元不能在16.7微秒的时间将施加电压保持在规定水平，不能充分地使液晶取向，有可能引起残影等的“烧焦”。After spin-coating the obtained coloring composition on a soda-lime glass substrate on which a_SiO2 film for preventing the elution of sodium ions was formed on the surface and an ITO (indium-tin oxide alloy) electrode was deposited in a predetermined shape, it was sprayed with 100 °C hot plate was prebaked for 1 minute to form a film with a film thickness of 2.0 µm. Next, the film was exposed at an exposure dose of 700 J/m² without passing through a mask. Then, the substrate was immersed in a developing solution formed by 0.04 mass % potassium hydroxide aqueous solution at 23° C. for 1 minute, after development, it was washed with ultrapure water and air-dried, and then post-baked at 230° C. for 30 minutes, The film is cured to form a permanent cured film. Next, the substrate on which the pixel was formed and the substrate on which only ITO electrodes were vapor-deposited in a predetermined shape were bonded together with a sealant mixed with 1.8 mm glass beads, and liquid crystal (MLC6608) manufactured by Merck was injected to fabricate a liquid crystal cell. Next, the liquid crystal cell was placed in a constant temperature layer at 60° C., and the voltage holding rate of the liquid crystal cell was measured using a liquid crystal voltage holding rate measurement system (VHR-1A type, TOYO Technica Corporation). The applied voltage at this time was a square wave of 5.5 V, and the measurement frequency was 60 Hz. Here, the voltage holding ratio refers to a value obtained by (potential difference of the liquid crystal cell after 16.7 microseconds/voltage applied at 0 microseconds). When the voltage retention rate of the liquid crystal cell is 90% or less, it means that the liquid crystal cell cannot maintain the applied voltage at a specified level for 16.7 microseconds, and the liquid crystal cannot be aligned sufficiently, which may cause "burning" such as image sticking.

实施例2～6和比较例1～2Embodiment 2～6 and comparative example 1～2

在实施例1中，将颜料分散液和染料溶液的种类和量如表1所示进行变更，除此以外，与实施例1同样进行而制备了着色组合物。然后，对得到的着色组合物与实施例1同样进行评价。将评价结果示于表1。In Example 1, except having changed the kind and quantity of a pigment dispersion liquid and a dye solution as shown in Table 1, it carried out similarly to Example 1, and prepared the coloring composition. Then, the obtained coloring composition was evaluated in the same manner as in Example 1. Table 1 shows the evaluation results.

表1Table 1

Claims (6)

1. a kind of coloured composition, it is characterised in that contain following component (A), (B) and (C)：

(A) colouring agent of the dyestuff represented by following formula (1) is contained,

(B) resin glue, and

(C) crosslinking agent；

In formula (1),

X^-Represent anion,

A is the integer for making the compound be determined for electroneutral,

M represents 0~5 integer, wherein, when m is more than 2 integer, multiple R⁵Can be with identical, can also be different,

R¹~R⁴Hydrogen atom ,-R are represented independently of one another⁶Or the 1 valency aromatic hydrocarbyl that carbon number is 6~10, the aromatic hydrocarbonHydrogen atom contained by base can be by-R⁶,-SO₂NHR⁸,-SO₂- O-N=CR⁷R¹⁰,-SO₂NHNHR⁷,-SO₂SR⁷Or-SO₂NHSO₂R¹¹Substituted,

R⁵Expression-SO independently of one another₃^-Or-SO₂NHR⁸,

R⁶1 valency saturated hydrocarbyl is represented, the hydrogen atom contained by the saturated hydrocarbyl can be substituted by halogen atom, the saturated hydrocarbyl institute- the CH contained₂- can be by-O- ,-CO- or-NR⁷- substituted,

R⁷1 valency alkyl is represented, the hydrogen atom contained by the alkyl can be by halogen atom or-R¹¹Substituted, the alkyl can use-O- or-CO- links,

R⁸Represent 1 valency saturated aliphatic hydrocarbons, the hydrogen atom contained by the saturated aliphatic hydrocarbons can by-OH, halogen atom ,-Q ,-CH=CH₂Or-CH=CHR⁶Substituted ,-the CH contained by the saturated aliphatic hydrocarbons₂- can by-O- ,-S- ,-CO- ,-NH- or-NR⁶- substituted,

R¹⁰Represent hydrogen atom, 1 valency alkyl or R¹¹, the hydrogen atom contained by the alkyl can be by halogen atom or-R¹¹Substituted, shouldAlkyl can use-O- or-CO- to link,

R¹¹Represent there can be 1 valency alkyl of substituent,

Q represents the 1 valency aromatic hydrocarbyl that carbon number is 6~10 or the 1 valency heterocyclic radical that carbon number is 3~10, the aromatic seriesThe hydrogen atom of more than 1 contained by alkyl and the heterocyclic radical is by selected from-R⁶,-OR⁶With-CH=CHR⁶In at least one kind of takenRemaining hydrogen atom contained by generation, the aromatic hydrocarbyl and the heterocyclic radical can be by-OH ,-NO₂,-CH=CH₂Or halogen is formerSon is substituted；

Wherein, the compound meets the necessary condition of more than 1 in following (i)~(vi),

(i)R¹~R⁴In more than 1 be with selected from-SO₂- O-N=CR⁷R¹⁰,-SO₂NHNHR⁷,-SO₂SR⁷With-SO₂NHSO₂R¹¹In at least one kind of substituent aromatic hydrocarbyl,

(ii)R¹~R⁴In more than 1 be with-SO₂NHR⁸The aromatic hydrocarbyl of substituent, wherein, by R⁸1 valency represented is satisfiedCarbon number with aliphatic alkyl is more than 11,

(iii) there is the R of m⁵In more than 1 be-SO₂NHR⁸, wherein, by R⁸The carbon of the 1 valency saturated aliphatic hydrocarbons representedAtomicity is more than 11.

2. coloured composition according to claim 1, wherein, in the formula (1), a=0, and R¹~R⁴In anyIndividual is by-SO₃^-Substituted aromatic hydrocarbyl or with the R of m⁵In 1 be-SO₃^-。

3. coloured composition according to claim 1, wherein, the dyestuff that the formula (1) represents is the dye that formula (2) representsMaterial；

In formula (2),

R^1a~R^4aHydrogen atom ,-R are represented independently of one another⁶Or the 1 valency aromatic hydrocarbyl that carbon number is 6~10, the aromatic seriesHydrogen atom contained by alkyl can be with-R⁶,-SO₂NHR⁸,-SO₂- O-N=CR⁷R¹⁰,-SO₂NHNHR⁷,-SO₂SR⁷Or-SO₂NHSO₂R¹¹Substituted,

R^5aExpression-SO independently of one another₃H, or-SO₂NHR⁸,

R⁶1 valency saturated hydrocarbyl is represented, the hydrogen atom contained by the saturated hydrocarbyl can be substituted by halogen atom, the saturated hydrocarbyl institute- the CH contained₂- can be by-O- ,-CO- or-NR⁷- substituted,

R⁷1 valency alkyl is represented, the hydrogen atom contained by the alkyl can be by halogen atom or-R¹¹Substituted, the alkyl can use-O- or-CO- links,

R⁸Represent 1 valency saturated aliphatic hydrocarbons, the hydrogen atom contained by the saturated aliphatic hydrocarbons can by-OH, halogen atom ,-Q ,-CH=CH₂Or-CH=CHR⁶Substituted ,-the CH contained by the saturated aliphatic hydrocarbons₂- can by-O- ,-S- ,-CO- ,-NH- or-NR⁶- substituted,

R¹⁰Represent hydrogen atom, 1 valency alkyl or-R¹¹, the hydrogen atom contained by the alkyl can be by halogen atom or-R¹¹Substituted,The alkyl can use-O- or-CO- to link,

R¹¹Represent there can be 1 valency alkyl of substituent,

Q represents the 1 valency aromatic hydrocarbyl that carbon number is 6~10 or the 1 valency heterocyclic radical that carbon number is 3~10, the aromatic seriesThe hydrogen atom of more than 1 contained by alkyl and the heterocyclic radical is by selected from-R⁶,-OR⁶With-CH=CHR⁶In at least one kind of takenRemaining hydrogen atom contained by generation, the aromatic hydrocarbyl and the heterocyclic radical can be by-OH ,-NO₂,-CH=CH₂Or halogen is formerSon is substituted,

N represents 0~4 integer, wherein, when n is more than 2 integer, multiple R^5aCan be with identical, can also be different；

Wherein, the compound meets the necessary condition of more than 1 in following (i)~(vi),

(i)R^1a~R^4aIn more than 1 be with selected from-SO₂- O-N=CR⁷R¹⁰,-SO₂NHNHR⁷,-SO₂SR⁷With-SO₂NHSO₂R¹¹In at least one kind of substituent aromatic hydrocarbyl,

(ii)R^1a~R^4aIn more than 1 be with-SO₂NHR⁸The aromatic hydrocarbyl of substituent, wherein, by R⁸1 valency representedThe carbon number of saturated aliphatic hydrocarbons is more than 11,

(iii) there is the R of n^5aIn more than 1 be-SO₂NHR⁸, wherein, by R⁸The 1 valency saturated aliphatic hydrocarbons representedCarbon number is more than 11.

4. a kind of colour filter, possesses the dyed layer formed using the coloured composition any one of claims 1 to 33.

5. a kind of color liquid crystal display device, possesses the colour filter described in claim 4.

6. a kind of dyestuff, represented by following formula (1),

In formula (1),

X^-Represent anion,

A is the integer for making the compound be determined for electroneutral,

M represents 0~5 integer, wherein, when m is more than 2 integer, multiple R⁵Can be with identical, can also be different,

R¹~R⁴Hydrogen atom ,-R are represented independently of one another⁶Or the 1 valency aromatic hydrocarbyl that carbon number is 6~10, the aromatic hydrocarbonHydrogen atom contained by base can be by-R⁶,-SO₂NHR⁸,-SO₂- O-N=CR⁷R¹⁰,-SO₂NHNHR⁷,-SO₂SR⁷Or-SO₂NHSO₂R¹¹Substituted,

R⁵Expression-SO independently of one another₃^-Or-SO₂NHR⁸,

R⁶1 valency saturated hydrocarbyl is represented, the hydrogen atom contained by the saturated hydrocarbyl can be substituted by halogen atom, the saturated hydrocarbyl institute- the CH contained₂- can be by-O- ,-CO- or-NR⁷- substituted,

R⁷1 valency alkyl is represented, the hydrogen atom contained by the alkyl can be by halogen atom or-R¹¹Substituted, the alkyl can use-O- or-CO- links,

R⁸Represent 1 valency saturated aliphatic hydrocarbons, the hydrogen atom contained by the saturated aliphatic hydrocarbons can by-OH, halogen atom ,-Q ,-CH=CH₂Or-CH=CHR⁶Substituted ,-the CH contained by the saturated aliphatic hydrocarbons₂- can by-O- ,-S- ,-CO- ,-NH- or-NR⁶- substituted,

R¹⁰Represent hydrogen atom, 1 valency alkyl or-R¹¹, the hydrogen atom contained by the alkyl can be by halogen atom or-R¹¹Substituted,The alkyl can use-O- or-CO- to link,

R¹¹Represent there can be 1 valency alkyl of substituent,

Q represents the 1 valency aromatic hydrocarbyl that carbon number is 6~10 or the 1 valency heterocyclic radical that carbon number is 3~10, the aromatic seriesThe hydrogen atom of more than 1 contained by alkyl and the heterocyclic radical is by selected from-R⁶,-OR⁶With-CH=CHR⁶In at least one kind of takenRemaining hydrogen atom contained by generation, the aromatic hydrocarbyl and the heterocyclic radical can be by-OH ,-NO₂,-CH=CH₂Or halogen is formerSon is substituted；

Wherein, the compound meets the necessary condition of more than 1 in following (i)~(vi),

(i)R¹~R⁴In more than 1 be with selected from-SO₂- O-N=CR⁷R¹⁰,-SO₂NHNHR⁷,-SO₂SR⁷With-SO₂NHSO₂R¹¹In at least one kind of substituent aromatic hydrocarbyl,

(ii)R¹~R⁴In more than 1 be with-SO₂NHR⁸The aromatic hydrocarbyl of substituent, wherein, by R⁸1 valency represented is satisfiedCarbon number with aliphatic alkyl is more than 11,

(iii) there is the R of m⁵In more than 1 be-SO₂NHR⁸, wherein, by R⁸The carbon of the 1 valency saturated aliphatic hydrocarbons representedAtomicity is more than 11.