CN104749882B - Coloring composition, colored cured film, and display element - Google Patents
Coloring composition, colored cured film, and display elementDownload PDFInfo
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- CN104749882B CN104749882BCN201410822660.8ACN201410822660ACN104749882BCN 104749882 BCN104749882 BCN 104749882BCN 201410822660 ACN201410822660 ACN 201410822660ACN 104749882 BCN104749882 BCN 104749882B
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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Abstract
Description
Translated fromChinese技术领域technical field
本发明涉及着色组合物、着色固化膜和显示元件，更详细地，涉及用于形成透射型或反射型彩色液晶显示元件、固体摄像元件、有机EL显示元件、电子纸等中使用的着色固化膜的着色组合物、使用该着色组合物形成的着色固化膜和具有该着色固化膜的显示元件。The present invention relates to a colored composition, a colored cured film, and a display element, and more particularly, to a colored cured film used for forming a transmissive or reflective color liquid crystal display element, a solid-state imaging element, an organic EL display element, electronic paper, and the like A coloring composition, a colored cured film formed using the colored composition, and a display element having the colored cured film.
背景技术Background technique
已知有在使用着色放射线敏感性组合物制造彩色滤光片时，在基板上涂布颜料分散型着色放射线敏感性组合物、进行干燥之后，以所希望的图案形状对干燥涂膜照射放射线(下面称“曝光”)并进行显影，由此得到各色像素的方法(例如可参见专利文献1～2。)。还已知有用分散有炭黑的光聚合性组合物形成黑色矩阵的方法(例如可参见专利文献3。)。另外，还已知有使用颜料分散型着色树脂组合物、通过喷墨方式得到各色像素的方法(例如可参见专利文献4)。When producing a color filter using a colored radiation-sensitive composition, it is known to apply a pigment-dispersed colored radiation-sensitive composition to a substrate, dry it, and then irradiate the dried coating film with radiation in a desired pattern shape ( A method of obtaining a pixel of each color by calling "exposure" hereinafter) and developing it (for example, refer to Patent Documents 1 to 2). A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed is also known (for example, see Patent Document 3). In addition, a method of obtaining pixels of each color by an inkjet method using a pigment dispersion-type colored resin composition is also known (for example, see Patent Document 4).
为了实现显示元件的高亮度化和高色纯度化或固体摄像元件的高精细化，已知使用染料作为着色剂是有效的。但是，已经知道，一般而言，与颜料相比，染料的耐热性、耐溶剂性差，这就强烈期望开发一种耐热性、耐溶剂性优异的染料。为此，作为耐热性等优异的染料，已有人提出使用例如三芳基甲烷化合物(例如可参见专利文献5、6)。In order to achieve high brightness and high color purity of a display element or high definition of a solid-state imaging element, it is known that it is effective to use a dye as a colorant. However, it is known that, in general, dyes are inferior in heat resistance and solvent resistance compared with pigments, and development of a dye excellent in heat resistance and solvent resistance is strongly desired. Therefore, as a dye excellent in heat resistance and the like, it has been proposed to use, for example, a triarylmethane compound (for example, see Patent Documents 5 and 6).
专利文献：Patent Literature:
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：PCT申请第2010/123071号公开公报Patent Document 5: PCT Application Publication No. 2010/123071
专利文献6：日本特开2012－017425号公报Patent Document 6: Japanese Patent Laid-Open No. 2012-017425
发明内容SUMMARY OF THE INVENTION
然而，即使使用专利文献5～6中记载的三芳基甲烷化合物，也无法说是能够充分满足对耐热性、耐溶剂性的要求。此外，着色图案的像素中的染料会向邻接的其他颜色的像素、保护膜等的不含着色剂的固化膜进行色迁移(下面也称其为“移染性”。)，从而出现显示元件的显示特性低下的问题，就该问题而言、有上述三芳基甲烷化合物并不一定能令人充分满意的情况。因此，即使在使用三芳基甲烷化合物作为着色剂的情况下，仍然强烈期望有一种能够形成耐热性、耐溶剂性优异且移染性得到抑制的着色固化膜的着色剂组合物。However, even if the triarylmethane compounds described in Patent Documents 5 to 6 are used, it cannot be said that the requirements for heat resistance and solvent resistance can be sufficiently satisfied. In addition, the dye in the pixels of the colored pattern undergoes color migration (hereinafter also referred to as "migration") to adjacent pixels of other colors, a cured film containing no colorant such as a protective film, and a display element appears. There is a problem that the display properties of the above-mentioned triarylmethane compounds are not necessarily satisfactory. Therefore, even when a triarylmethane compound is used as a colorant, a colorant composition capable of forming a colored cured film having excellent heat resistance and solvent resistance and suppressed dye migration is strongly desired.
因此，本发明的目的在于提供一种能够形成耐热性、耐溶剂性优异且移染性得到抑制的着色固化膜的着色组合物。此外，本发明的目的还在于提供使用该着色组合物形成的着色固化膜和具有该着固化膜的显示元件。Then, the objective of this invention is to provide the coloring composition which can form the coloring cured film which is excellent in heat resistance and solvent resistance, and suppresses dye migration. Moreover, the objective of this invention is to provide the coloring cured film formed using this coloring composition, and the display element which has this attached cured film.
本发明者进行了深入研究，结果发现，通过使用特定的聚合物作为着色剂，能够解决上述问题。As a result of intensive studies, the present inventors found that the above-mentioned problems can be solved by using a specific polymer as a colorant.
即，本发明提供一种着色组合物，该着色组合物含有(A)着色剂和(B)聚合性化合物，That is, the present invention provides a coloring composition containing (A) a colorant and (B) a polymerizable compound,
其中，(A)着色剂含有不饱和单体的聚合物(下面也称作“本着色剂”(本发明着色剂))，所述不饱和单体含有具有下述式(1)表示的结构的不饱和单体(a1)，Among them, (A) the colorant contains a polymer of an unsaturated monomer (hereinafter also referred to as "the colorant" (colorant of the present invention)) having a structure represented by the following formula (1) The unsaturated monomer (a1),
〔化学式1〕[Chemical formula 1]
〔式(1)中，[In formula (1),
R1～R6相互独立地表示氢原子、碳数1～8的烷基、苯基或具有烯不饱和基团的基团，R1 to R6 independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a group having an ethylenically unsaturated group,
Ar表示芳香族烃基，Ar represents an aromatic hydrocarbon group,
R7～R8相互独立地表示碳数1～8的烷基或氯原子，R7 to R8 independently represent an alkyl group having 1 to 8 carbon atoms or a chlorine atom,
R9～R10相互独立地表示氢原子、碳数1～8的烷基或氯原子，R9 to R10 independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a chlorine atom,
l和m相互独立地表示0～4的整数。l and m represent an integer of 0 to 4 independently of each other.
其中，R1～R6中的至少1个为具有烯不饱和基团的基团，该具有烯不饱和基团的基团为CH2＝CR11－COO－X－基团(R11表示氢原子或甲基，X表示碳数5～12的2价烃基)。〕Wherein, at least one of R1 to R6 is a group having an ethylenically unsaturated group, and the group having an ethylenically unsaturated group is a CH2 =CR11 -COO-X- group (R11 represents A hydrogen atom or a methyl group, X represents a divalent hydrocarbon group having 5 to 12 carbon atoms). ]
此外，本发明提供使用上述着色组合物形成的着色固化膜和具有该着色固化膜的显示元件。这里，“着色固化膜”是指显示元件、固体摄像元件中使用的各色像素、黑色矩阵(matrix)、黑色间隔件(spacer，或称“隔垫物”)等。Moreover, this invention provides the colored cured film formed using the said coloring composition, and the display element which has this colored cured film. Here, the "colored cured film" refers to pixels of various colors used in display elements and solid-state imaging elements, black matrices, black spacers (or "spacers"), and the like.
使用本发明的着色组合物，能够形成耐热性、耐溶剂性优异且移染性得到抑制的着色固化膜。Using the coloring composition of the present invention, it is possible to form a colored cured film having excellent heat resistance and solvent resistance and suppressing dye migration.
因此，本发明的着色组合物能够非常良好地用来制作彩色液晶显示元件、有机EL显示元件、电子纸等显示元件、CMOS图像传感器等固体摄像元件。Therefore, the coloring composition of the present invention can be used very favorably for production of color liquid crystal display elements, organic EL display elements, display elements such as electronic paper, and solid-state imaging elements such as CMOS image sensors.
具体实施方式Detailed ways
下面对本发明进行详细说明。The present invention will be described in detail below.
着色组合物coloring composition
下面对本发明的着色组合物的构成成分进行详细说明。The constituent components of the coloring composition of the present invention will be described in detail below.
－(A)着色剂－-(A) Colorant-
本发明的着色组合物含有本着色剂。The coloring composition of this invention contains this coloring agent.
首先对构成本着色剂的具有下述式(1)表示的结构的不饱和单体(a1)(下面也简称“不饱和单体(a1)”)进行说明。不饱和单体(a1)有各种共振结构，但在本说明书中，将这些共振结构视作与具有下述式(1)表示的结构的不饱和单体同等的结构。First, the unsaturated monomer (a1) (henceforth abbreviated as "unsaturated monomer (a1)") which has the structure represented by following formula (1) which comprises this coloring agent is demonstrated. The unsaturated monomer (a1) has various resonance structures, but in this specification, these resonance structures are regarded as structures equivalent to the unsaturated monomer having the structure represented by the following formula (1).
〔化学式2〕[Chemical formula 2]
〔式(1)中，[In formula (1),
R1～R6相互独立地表示氢原子、碳数1～8的烷基、苯基或具有烯不饱和基团的基团，R1 to R6 independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a phenyl group, or a group having an ethylenically unsaturated group,
Ar表示芳香族烃基，Ar represents an aromatic hydrocarbon group,
R7～R8相互独立地表示碳数1～8的烷基或氯原子，R7 to R8 independently represent an alkyl group having 1 to 8 carbon atoms or a chlorine atom,
R9～R10相互独立地表示氢原子、碳数1～8的烷基或氯原子，R9 to R10 independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a chlorine atom,
l和m相互独立地表示0～4的整数。l and m represent an integer of 0 to 4 independently of each other.
其中，R1～R6中的至少1个为具有烯不饱和基团的基团，该具有烯不饱和基团的基团为CH2＝CR11－COO－X－基团(R11表示氢原子或甲基，X表示碳数5～12的2价烃基。)。〕Wherein, at least one of R1 to R6 is a group having an ethylenically unsaturated group, and the group having an ethylenically unsaturated group is a CH2 =CR11 -COO-X- group (R11 represents A hydrogen atom or a methyl group, and X represents a divalent hydrocarbon group having 5 to 12 carbon atoms). ]
上述式(1)中的R1～R10中的碳数1～8的烷基可以是直链，也可以是支链。作为具体例子，例如可以是甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、仲戊基、新戊基、正己基、正庚基、正辛基等。其中，作为R1～R6中的碳数1～8的烷基，优选为碳数1～4的烷基，尤其优选为甲基或乙基。此外，作为R7～R10中的碳数1～8的烷基，优选为碳数1～4的烷基，尤其优选为甲基。The alkyl group having 1 to 8 carbon atoms in R1 to R10 in the above formula (1) may be linear or branched. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, neopentyl, n-hexyl base, n-heptyl, n-octyl, etc. Among them, as the alkyl group having 1 to 8 carbon atoms in R1 to R6 , an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is particularly preferable. Further, as the alkyl group having 1 to 8 carbon atoms in R7 to R10 , an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group is particularly preferable.
在R1～R6中的具有烯不饱和基团的基团中，烯不饱和基团的数目可以是1个，也可以是2个以上，但优选具有1个烯不饱和基团。作为烯不饱和基团，例如可以是具有(甲基)丙烯酰基、乙烯基芳基、乙烯氧基、烯丙基等的基团。其中，从反应性的角度考虑，优选为(甲基)丙烯酰基。Among the groups having an ethylenically unsaturated group among R1 to R6 , the number of the ethylenically unsaturated group may be one or two or more, but preferably one ethylenically unsaturated group is present. As an ethylenically unsaturated group, the group which has a (meth)acryloyl group, a vinylaryl group, a vinyloxy group, an allyl group, etc. can be used, for example. Among them, a (meth)acryloyl group is preferable from the viewpoint of reactivity.
不饱和单体(a1)是R1～R6中的至少1个具有烯不饱和基团的基团，该具有烯不饱和基团的基团为CH2＝CR11－COO－X－基团。The unsaturated monomer (a1) is at least one of R1 to R6 having an ethylenically unsaturated group, and the group having an ethylenically unsaturated group is a CH2 =CR11 -COO-X- group group.
这里，R11是氢原子或甲基，可以适当选择。此外，X表示碳数5～12的2价烃基。Here, R11 is a hydrogen atom or a methyl group, which can be appropriately selected. Further, X represents a divalent hydrocarbon group having 5 to 12 carbon atoms.
作为X所表示的碳数5～12的2价烃基，可以是碳数5～12的2价脂肪族烃基、2价脂环式烃基、2价芳香族烃基。The divalent hydrocarbon group having 5 to 12 carbon atoms represented by X may be a divalent aliphatic hydrocarbon group having 5 to 12 carbon atoms, a divalent alicyclic hydrocarbon group, or a divalent aromatic hydrocarbon group.
作为碳数5～12的脂肪族烃基，可以是碳数5～12的烷二基，可以是直链，也可以是支链。作为具体例子，例如可以是戊烷－1,5－二基、己烷－1,6－二基、己烷－1,5－二基、己烷－1,2－二基、庚烷－1,7－二基、辛烷－1,8－二基、癸烷－1,10－二基、十二烷－1,12－二基等。其中，优选为碳数5～10的烷二基，更优选为碳数6～8的烷二基，尤其优选为己烷－1,6－二基、辛烷－1,8－二基。The aliphatic hydrocarbon group having 5 to 12 carbon atoms may be an alkanediyl group having 5 to 12 carbon atoms, and may be a straight chain or a branched chain. Specific examples include pentane-1,5-diyl, hexane-1,6-diyl, hexane-1,5-diyl, hexane-1,2-diyl, heptane- 1,7-diyl, octane-1,8-diyl, decane-1,10-diyl, dodecane-1,12-diyl, and the like. Among them, an alkanediyl group having 5 to 10 carbon atoms is preferable, an alkanediyl group having 6 to 8 carbon atoms is more preferable, and a hexane-1,6-diyl group and an octane-1,8-diyl group are particularly preferable.
作为碳数5～12的2价脂环式烃基，可以是碳数5～12的亚环烷基。作为具体例子，例如可以是亚环戊基、亚环己基、亚环辛基等。其中，优选为碳数5～8的亚环烷基，更优选为碳数6～8的亚环烷基，尤其优选为亚环己基。亚环己基有1,4－亚环己基、1,3－亚环己基、1,2－亚环己基，从空间位阻小的角度考虑，优选为1,4－亚环己基。As the divalent alicyclic hydrocarbon group having 5 to 12 carbon atoms, a cycloalkylene group having 5 to 12 carbon atoms may be used. Specific examples include cyclopentylene, cyclohexylene, cyclooctylene, and the like. Among them, a cycloalkylene group having 5 to 8 carbon atoms is preferable, a cycloalkylene group having 6 to 8 carbon atoms is more preferable, and a cyclohexylene group is particularly preferable. The cyclohexylene group includes 1,4-cyclohexylene, 1,3-cyclohexylene, and 1,2-cyclohexylene, and 1,4-cyclohexylene is preferable from the viewpoint of small steric hindrance.
作为碳数5～12的2价芳香族烃基，可以是碳数6～12的亚芳基。作为具体例子，例如可以是亚苯基、亚萘基、亚联苯基等。其中，优选为碳数6～10的亚芳基，更优选为亚苯基、亚萘基。另外，亚苯基有邻位体、间位体和对位体，从空间位阻小的角度考虑，优选为对位体。在亚萘基中，优选1,4－亚萘基。As the divalent aromatic hydrocarbon group having 5 to 12 carbon atoms, an arylene group having 6 to 12 carbon atoms may be used. As a specific example, a phenylene group, a naphthylene group, a biphenylene group, etc. are mentioned, for example. Among them, an arylene group having 6 to 10 carbon atoms is preferable, and a phenylene group and a naphthylene group are more preferable. In addition, the phenylene group has an ortho-, meta- and para-isomer, and the para-isomer is preferable from the viewpoint of small steric hindrance. Among the naphthylene groups, 1,4-naphthylene groups are preferred.
在上述X中，优选碳数5～12的2价脂肪族烃基、碳数5～12的2价脂环式烃基，更优选碳数5～12的2价脂环式烃基。Among the above X, a divalent aliphatic hydrocarbon group having 5 to 12 carbon atoms and a divalent alicyclic hydrocarbon group having 5 to 12 carbon atoms are preferred, and a divalent alicyclic hydrocarbon group having 5 to 12 carbon atoms is more preferred.
在R1～R6中的任一个为具有烯不饱和基团的基团的情况下，优选R1～R6中的1个或2个为CH2＝CR11－COO－X－基团，更优选R1～R6中的1个为CH2＝CR11－COO－X－基团。When any one of R1 to R6 is a group having an ethylenically unsaturated group, it is preferable that one or two of R1 to R6 be a CH2 =CR11 -COO-X- group , more preferably one of R1 to R6 is a CH2 =CR11 -COO-X- group.
此外，不饱和单体(a1)所具有的CH2＝CR11－COO－X－基团和其他具有烯不饱和基团的基团也可合计在2个以上，更优选具有1个CH2＝CR11－COO－X－基团。In addition, the CH2 =CR11 -COO-X- group and other groups having an ethylenically unsaturated group in the unsaturated monomer (a1) may be 2 or more in total, more preferably 1 CH2 =CR11 -COO-X- group.
作为Ar中的芳香族烃基，优选为碳数6～20、进而为6～10的芳香族烃基。作为具体例子，例如可以是从苯、萘、联苯或蒽中除去2～4个氢原子的基团。其中，优选为从苯或萘中除去2～4个氢原子的基团。The aromatic hydrocarbon group in Ar is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably 6 to 10 carbon atoms. As a specific example, for example, it may be a group in which 2 to 4 hydrogen atoms are removed from benzene, naphthalene, biphenyl or anthracene. Among them, a group obtained by removing 2 to 4 hydrogen atoms from benzene or naphthalene is preferable.
作为l和m，优选为0或1。As l and m, 0 or 1 is preferable.
不饱和单体(a1)可单独或混合2种以上进行使用。下面显示式(1)表示的结构的具体例子。The unsaturated monomer (a1) may be used alone or in combination of two or more. Specific examples of the structure represented by the formula (1) are shown below.
〔化学式3〕[Chemical formula 3]
本着色剂优选为含有不饱和单体(a1)以外的其他可共聚的烯不饱和单体(下面也称“不饱和单体(a2)”)的不饱和单体的共聚物。作为这种不饱和单体(a2)的例子，例如可以是具有1个以上羧基的烯不饱和单体、N－取代马来酰亚胺、芳香族乙烯基化合物、(甲基)丙烯酸酯、乙烯基醚、聚合物分子链的末端上具有单(甲基)丙烯酰基的大分子单体等。不饱和单体(a2)可以单独或混合2种以上进行使用。This colorant is preferably a copolymer of an unsaturated monomer containing another copolymerizable ethylenically unsaturated monomer (hereinafter also referred to as "unsaturated monomer (a2)") other than the unsaturated monomer (a1). Examples of such unsaturated monomers (a2) include ethylenically unsaturated monomers having one or more carboxyl groups, N-substituted maleimides, aromatic vinyl compounds, (meth)acrylates, A vinyl ether, a macromonomer having a mono(meth)acryloyl group at the end of the polymer molecular chain, and the like. An unsaturated monomer (a2) can be used individually or in mixture of 2 or more types.
作为上述具有1个以上羧基的烯不饱和单体，例如可以是(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 ethylenically unsaturated monomer having one or more carboxyl groups include (meth)acrylic acid, maleic acid, maleic anhydride, mono[2-(meth)acryloyloxyethyl] succinate, ω-carboxy polycaprolactone mono(meth)acrylate, p-vinyl benzoic acid, etc.
此外，作为上述N－取代马来酰亚胺，例如可以是N－苯基马来酰亚胺、N－环己基马来酰亚胺等。Moreover, as said N-substituted maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, etc. are mentioned, for example.
此外，作为上述芳香族乙烯基化合物，例如可以是苯乙烯、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、苊烯等。In addition, as the above-mentioned aromatic vinyl compound, for example, styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, acenaphthylene, etc. may be mentioned. .
此外，作为上述(甲基)丙烯酸酯，例如可以是(甲基)丙烯酸酯甲酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸2－乙基己酯之类的(甲基)丙烯酸烷基酯，In addition, as said (meth)acrylate, (meth)acrylate, such as methyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate, may be used, for example. Alkyl Acrylate,
(甲基)丙烯酸2－羟乙酯、(甲基)丙烯酸2－羟丙酯之类的(甲基)丙烯酸羟烷基酯，Hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate,
(甲基)丙烯酸乙烯基酯、(甲基)丙烯酸烯丙酯之类的不饱和醇的(甲基)丙烯酸酯，(meth)acrylates of unsaturated alcohols such as vinyl (meth)acrylate and allyl (meth)acrylate,
(甲基)丙烯酸苯基酯、(甲基)丙烯酸苄基酯之类的(甲基)丙烯酸芳基酯，Aryl (meth)acrylates such as phenyl (meth)acrylate and benzyl (meth)acrylate,
聚乙二醇(聚合度2～10)甲基醚(甲基)丙烯酸酯、聚丙二醇(聚合度2～10)甲基醚(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、甘油单(甲基)丙烯酸酯之类的多元醇的(甲基)丙烯酸酯，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) ) (meth)acrylates of polyhydric alcohols such as mono(meth)acrylates, polypropylene glycol (degree of polymerization 2 to 10) mono(meth)acrylic acid, and glycerol mono(meth)acrylates,
(甲基)丙烯酸环己基酯、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸三环〔5.2.1.02,6〕癸烷－8－基酯、(甲基)丙烯酸二环戊烯基酯之类的具有脂环烃基的(甲基)丙烯酸酯，Cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, tricyclo[5.2.1.02,6 ]decane-8-yl (meth)acrylate, dicyclopentene (meth)acrylate (meth)acrylates having alicyclic hydrocarbon groups such as base esters,
(甲基)丙烯酸4－羟基苯基酯、对枯基苯酚的环氧乙烷改性(甲基)丙烯酸酯之类的芳醇的(甲基)丙烯酸酯，等等。4-hydroxyphenyl (meth)acrylate, (meth)acrylates of aromatic alcohols such as ethylene oxide-modified (meth)acrylates of p-cumylphenol, and the like.
作为(甲基)丙烯酸酯，也可以使用具有含氧饱和杂环基的(甲基)丙烯酸酯。这里，“含氧饱和杂环基”是指含有氧原子作为构成杂环的杂原子的饱和杂环基，优选构成环的原子数为3～7个的环状醚基。作为环状醚基，可以是环氧乙烷基(oxiranyl)、氧杂环丁基(oxetanyl)、3,4－环氧环己基、四氢呋喃基等，其中，从反应性的角度考虑，优选为环氧乙烷基、氧杂环丁基、3,4－环氧环己基。As the (meth)acrylate, a (meth)acrylate having an oxygen-containing saturated heterocyclic group can also be used. Here, the "oxygen-containing saturated heterocyclic group" refers to a saturated heterocyclic group containing an oxygen atom as a heteroatom constituting a heterocycle, and preferably a cyclic ether group having 3 to 7 atoms constituting the ring. Examples of the cyclic ether group include oxiranyl, oxetanyl, 3,4-epoxycyclohexyl, tetrahydrofuranyl, and the like. Among them, from the viewpoint of reactivity, preferred are Ethylene oxide group, oxetanyl group, 3,4-epoxycyclohexyl group.
作为具有含氧饱和杂环基的(甲基)丙烯酸酯，例如可以是(甲基)丙烯酸缩水甘油酯、(甲基)丙烯酸2－羟乙基缩水甘油醚、(甲基)丙烯酸2－羟丙基缩水甘油醚、(甲基)丙烯酸3－羟丙基缩水甘油醚、(甲基)丙烯酸4－羟丁基缩水甘油醚、聚乙二醇-聚丙二醇(甲基)丙烯酸缩水甘油醚之类的具有环氧乙烷基的(甲基)丙烯酸酯，Examples of the (meth)acrylate having an oxygen-containing saturated heterocyclic group include glycidyl (meth)acrylate, 2-hydroxyethyl glycidyl ether (meth)acrylate, and 2-hydroxy (meth)acrylate. Propyl glycidyl ether, (meth)acrylic acid 3-hydroxypropyl glycidyl ether, (meth)acrylic acid 4-hydroxybutyl glycidyl ether, polyethylene glycol-polypropylene glycol (meth)acrylic acid glycidyl ether (meth)acrylates with oxirane groups,
(甲基)丙烯酸3,4－环氧环己基甲基酯之类的具有3,4－环氧环己基的(甲基)丙烯酸酯，(meth)acrylates having a 3,4-epoxycyclohexyl group such as 3,4-epoxycyclohexylmethyl (meth)acrylate,
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具有氧杂环丁基的(甲基)丙烯酸酯，3-[(meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]-3-ethyloxetane, etc. (meth)acrylate of cyclobutyl,
甲基丙烯酸四氢呋喃酯之类的具有四氢呋喃基的(甲基)丙烯酸酯，等等。A (meth)acrylate having a tetrahydrofuran group such as tetrahydrofuran methacrylate, and the like.
此外，作为上述乙烯基醚，例如可以是乙酸乙烯酯、环己基乙烯基醚、异冰片基乙烯基醚、三环〔5.2.1.02,6〕癸烷－8－基乙烯基醚、五环十五烷基乙烯基醚、3－(乙烯基氧基甲基)－3－乙基氧杂环丁烷等。In addition, examples of the above vinyl ether include vinyl acetate, cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.02,6 ]decane-8-yl vinyl ether, pentacyclic vinyl ether, and pentacyclic vinyl ether. Pentadecyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane, etc.
此外，作为上述在聚合物分子链的末端具有单(甲基)丙烯酰基的大分子单体，例如可以是聚苯乙烯、聚(甲基)丙烯酸甲酯、聚(甲基)丙烯酸正丁基酯、聚硅氧烷之类的在聚合物分子链的末端具有单(甲基)丙烯酰基的大分子单体。In addition, as the macromonomer having a mono(meth)acryloyl group at the end of the polymer molecular chain, for example, polystyrene, polymethyl(meth)acrylate, and n-butyl poly(meth)acrylate can be used. A macromonomer which has a mono(meth)acryloyl group at the terminal of a polymer molecular chain, such as an ester and a polysiloxane.
其中，从耐热性、耐溶剂性、移染性抑制、分散性的角度考虑，在本着色剂中，作为其他可共聚的烯不饱和单体(a2)，优选含有(甲基)丙烯酸酯，更优选含有选自具有含氧饱和杂环基的(甲基)丙烯酸酯和(甲基)丙烯酸芳基酯中的至少1种。通过这种方式能够提高本着色剂的耐热性，因而优选。在具有含氧饱和杂环基的(甲基)丙烯酸酯中，优选具有选自环氧乙烷基、氧杂环丁基和3,4－环氧环己基中的至少1种基团的(甲基)丙烯酸酯。在(甲基)丙烯酸芳基酯中，优选(甲基)丙烯酸苯酯。Among them, in this colorant, it is preferable to contain (meth)acrylate as another copolymerizable ethylenically unsaturated monomer (a2) from the viewpoints of heat resistance, solvent resistance, dye migration inhibition, and dispersibility. , more preferably at least one selected from the group consisting of (meth)acrylates and aryl (meth)acrylates having an oxygen-containing saturated heterocyclic group. In this way, the heat resistance of the present colorant can be improved, which is preferable. Among the (meth)acrylates having an oxygen-containing saturated heterocyclic group, those having at least one group selected from the group consisting of oxirane, oxetanyl, and 3,4-epoxycyclohexyl are preferred ( meth)acrylate. Among the aryl (meth)acrylates, phenyl (meth)acrylates are preferred.
在本着色剂具有不饱和单体(a2)的情况下，从耐热性、耐溶剂性、移染性抑制、分散性的角度考虑，不饱和单体(a2)的共聚比例优选为以下方式。When the present colorant has an unsaturated monomer (a2), the copolymerization ratio of the unsaturated monomer (a2) is preferably as follows from the viewpoints of heat resistance, solvent resistance, migration suppression, and dispersibility .
即，本着色剂的所有结构单元中的不饱和单体(a1)的比例p和不饱和单体(a2)的比例r以摩尔比计，优选为p/r＝1/99～30/70，更优选为p/r＝2/98～25/75，尤其优选为p/r＝3/97～20/80。That is, the ratio p of the unsaturated monomer (a1) and the ratio r of the unsaturated monomer (a2) in all the structural units of the colorant are preferably p/r=1/99 to 30/70 in terms of molar ratio , more preferably p/r=2/98 to 25/75, and particularly preferably p/r=3/97 to 20/80.
此外，在使用选自具有含氧饱和杂环基的(甲基)丙烯酸酯和(甲基)丙烯酸芳基酯中的至少1种作为不饱和单体(a2)的情况下，从耐热性、耐溶剂性的角度考虑，不饱和单体(a2)中的具有含氧饱和杂环基的(甲基)丙烯酸酯和(甲基)丙烯酸芳基酯的共聚比例(s)优选为5～45摩尔％，更优选为10～40摩尔％，尤其优选为15～30％。In addition, when at least one selected from the group consisting of (meth)acrylates and aryl (meth)acrylates having an oxygen-containing saturated heterocyclic group is used as the unsaturated monomer (a2), from the heat resistance From the viewpoint of solvent resistance, the copolymerization ratio (s) of the (meth)acrylate having an oxygen-containing saturated heterocyclic group and the aryl (meth)acrylate in the unsaturated monomer (a2) is preferably 5 to 45 mol%, more preferably 10 to 40 mol%, particularly preferably 15 to 30%.
本着色剂可根据需要而含有阴离子，以总体上呈电中性。The present colorant may contain anions as required to be generally electrically neutral.
作为这类阴离子，例如可以是卤素离子、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。As such anions, for example, halogen ions, boron anions, phosphoric acid anions, carboxylate anions, sulfate anions, organic sulfonic acid anions, nitrogen anions, methide anions and the like can be mentioned.
作为上述卤素离子，可以是氟化物离子、氯化物离子、溴化物离子、碘化物离子等。As said halogen ion, a fluoride ion, a chloride ion, a bromide ion, an iodide ion, etc. are mentioned.
此外，作为硼阴离子，例如可以是BF4－等无机硼阴离子；In addition, as the boron anion, for example, an inorganic boron anion such as BF4- may be used;
(CF3)4B－、(CF3)3BF－、(CF3)2BF2－、(CF3)BF3－、(C2F5)4B－、(C2F5)3BF－、(C2F5)BF3－、(C2F5)2BF2－、(CF3)(C2F5)2BF－、(C6F5)4B－、〔(CF3)2C6H3〕4B－、(CF3C6H4)4B－、(C6F5)2BF2－、(C6F5)BF3－、(C6H3F2)4B－、B(CN)4－、B(CN)F3－、B(CN)2F2－、B(CN)3F－、(CF3)3B(CN)－、(CF3)2B(CN)2－、(C2F5)3B(CN)－、(C2F5)2B(CN)2－、(n－C3F7)3B(CN)－、(n－C4F9)3B(CN)－、(n－C4F9)2B(CN)2－、(n－C6F13)3B(CN)－、(CHF2)3B(CN)－、(CHF2)2B(CN)2－、(CH2CF3)3B(CN)－、(CH2CF3)2B(CN)2－、(CH2C2F5)3B(CN)－、(CH2C2F5)2B(CN)2－、(CH2CH2C3F7)2B(CN)2－、(n－C3F7CH2)2B(CN)2－、(C6H5)3B(CN)－、四苯基硼酸根阴离子、四(单氟苯基)硼酸根阴离子、四(二氟苯基)硼酸根阴离子、四(三氟苯基)硼酸根阴离子、四(四氟苯基)硼酸根阴离子、四(五氟苯基)硼酸根阴离子、四(四氟甲基苯基)硼酸根阴离子、四(甲苯基)硼酸根阴离子、四(二甲苯基)硼酸根阴离子、(三苯基，五氟苯基)硼酸根阴离子、〔三(五氟苯基)，苯基〕硼酸根阴离子、十三氢－7,8－二碳十一硼酸根阴离子(tridecahydride-7,8-dicarbaundecaborate anion)等有机硼阴离子，此外，还可以是日本特开平10－195119号公报、日本特开2010－094807号公报、日本特开2006－243594号公报、日本特开2002－341533号公报、日本特开平8－015521号公报等中记载的硼阴离子。(CF3 )4 B- , (CF3 )3 BF- , (CF3 )2 BF2- , (CF3 )BF3- , (C2 F5 )4 B- , (C2 F5 )3 BF- , (C2 F5 )BF3- , (C2 F5 )2 BF2- , (CF3 )(C2 F5 )2 BF- , (C6 F5 )4 B- , [( CF3 )2 C6 H3 ]4 B- , (CF3 C6 H4 )4 B- , (C6 F5 )2 BF2- , (C6 F5 )BF3- , (C6 H )3 F2 )4 B- , B(CN)4- , B(CN)F3- , B(CN)2 F2- , B(CN)3 F- , (CF3 )3 B(CN)- , (CF3 )2 B(CN)2- , (C2 F5 )3 B(CN)- , (C2 F5 )2 B(CN)2- , (n-C3 F7 )3 B (CN)- , (n-C4 F9 )3 B(CN)- , (n-C4 F9 )2 B(CN)2- , (n-C6 F13 )3 B(CN)- , (CHF2 )3 B(CN)- , (CHF2 )2 B(CN)2- , (CH2 CF3 )3 B(CN)- , (CH2 CF3 )2 B(CN)2- , (CH2 C2 F5 )3 B(CN)- , (CH2 C2 F5 )2 B(CN)2- , (CH2 CH2 C3 F7 )2 B(CN)2- , (n-C3 F7 CH2 )2 B(CN)2- , (C6 H5 )3 B(CN)- , tetraphenylborate anion, tetrakis(monofluorophenyl)borate anion, tetrakis (difluorophenyl)borate anion, tetrakis(trifluorophenyl)borate anion, tetrakis(tetrafluorophenyl)borate anion, tetrakis(pentafluorophenyl)borate anion, tetrakis(tetrafluoromethylbenzene) base) borate anion, tetrakis (tolyl) borate anion, tetrakis (xylyl) borate anion, (triphenyl, pentafluorophenyl) borate anion, [tris (pentafluorophenyl), phenyl ] borate anion, tridecahydride-7,8-dicarbaundecaborate anion (tridecahydride-7,8-dicarbaundecaborate anion) and other organoboron anions, in addition , can also be in Japanese Patent Laid-Open No. 10-195119, Japanese Patent Laid-Open No. 2010-094807, Japanese Patent Laid-Open No. 2006-243594, Japanese Patent Laid-Open No. 2002-341533, Japanese Patent Laid-Open No. 8-015521, etc. The boron anion described.
此外，作为磷酸阴离子，例如可以是HPO42－、PO43－、PF6－等无机磷酸阴离子；In addition, as the phosphate anion, for example, inorganic phosphate anions such as HPO42− , PO43− , and PF6− may be used;
(C2F5)2PF4－、(C2F5)3PF3－、〔(CF3)2CF〕2PF4－、〔(CF3)2CF〕3PF3、(n－C3F7)2PF4－、(n－C3F7)3PF3－、(n－C4F9)3PF3－、(C2F5)(CF3)2PF3－、〔(CF3)2CFCF2〕2PF4－、〔(CF3)2CFCF2〕3PF3－、(n－C4F9)2PF4－、(n－C4F9)3PF3－、(C2F4H)(CF3)2PF3－、(C2F3H2)3PF3－、(C2F5)(CF3)2PF3－、辛基磷酸阴离子、十二烷基磷酸阴离子、十八烷基磷酸阴离子、苯基磷酸阴离子、壬基苯基磷酸阴离子等有机磷酸阴离子。(C2 F5 )2 PF4- , (C2 F5 )3 PF3- , [(CF3 )2 CF]2 PF4- , [(CF3 )2 CF]3 PF3 , (n- C3 F7 )2 PF4- , (n-C3 F7 )3 PF3- , (n-C4 F9 )3 PF3- , (C2 F5 )(CF3 )2 PF3- , [(CF3 )2 CFCF2 ]2 PF4- , [(CF3 )2 CFCF2 ]3 PF3- , (n-C4 F9 )2 PF4- , (n-C4 F9 )3 PF3- , (C2 F4 H)(CF3 )2 PF3- , (C2 F3 H2 )3 PF3- , (C2 F5 )(CF3 )2 PF3- , Xin Organophosphoric acid anions such as base phosphate anion, dodecyl phosphate anion, octadecyl phosphate anion, phenyl phosphate anion, nonylphenyl phosphate anion, etc.
此外，作为羧酸阴离子，例如可以是CH3COO－、C2H5COO－、C6H5COO－等，此外还可以是在日本特开2009－265641号公报、日本特开2008－096680号公报等中记载的羧酸阴离子。In addition, the carboxylate anion may be, for example, CH3 COO− , C2 H5 COO− , C6 H5 COO− , or the like, and may be described in JP 2009-265641 A and JP 2008-096680 . Carboxylic acid anions described in Gazette No.
此外，作为硫酸阴离子，例如可以是硫酸阴离子、亚硫酸阴离子。Further, as the sulfate anion, for example, a sulfate anion and a sulfite anion may be used.
作为有机磺酸阴离子，例如可以是甲磺酸阴离子、乙磺酸阴离子、三氟甲磺酸阴离子、九氟丁磺酸阴离子等烷基磺酸阴离子；As the organic sulfonic acid anion, for example, it can be an alkyl sulfonic acid anion such as methanesulfonic acid anion, ethanesulfonic acid anion, trifluoromethanesulfonic acid anion, nonafluorobutanesulfonic acid anion;
苯磺酸阴离子、苯二磺酸阴离子、对甲苯磺酸阴离子、对三氟甲基磺酸阴离子、五氟苯磺酸阴离子、萘磺酸阴离子、萘二磺酸阴离子等芳基磺酸阴离子；2－(甲基)丙烯酰氧基－1,1,2,2－四氟乙磺酸阴离子、2－(4－乙烯基苯基氧基)－1,1,2,2－四氟乙磺酸阴离子、以及在PCT申请第2011/037195号公开公报、日本专利第3736221号说明书、日本特开2011－070172号公报等中记载的有机磺酸阴离子。Arylsulfonic acid anions such as benzenesulfonic acid anion, benzenedisulfonic acid anion, p-toluenesulfonic acid anion, p-trifluoromethanesulfonic acid anion, pentafluorobenzenesulfonic acid anion, naphthalenesulfonic acid anion, naphthalene disulfonic acid anion; 2-(Meth)acryloyloxy-1,1,2,2-tetrafluoroethanesulfonic acid anion, 2-(4-vinylphenyloxy)-1,1,2,2-tetrafluoroethane Sulfonic acid anions, and organic sulfonic acid anions described in PCT Application Publication No. 2011/037195, the specification of Japanese Patent No. 3736221, Japanese Patent Laid-Open Publication No. 2011-070172, and the like.
此外，作为氮阴离子，例如可以是〔(CN)2N〕－、〔(FSO2)2N〕－、〔(FSO2)N(CF3SO2)〕－、〔(CF3SO2)2N〕－、〔(FSO2)N(CF3CF2SO2)〕－、〔(FSO2)N{(CF3)2CFSO2}〕－、〔(FSO2)N(CF3CF2CF2SO2)〕－、〔(FSO2)N(CF3CF2CF2CF2SO2)〕－、〔(FSO2)N{(CF3)2CFCF2SO2}〕－、〔(FSO2)N{CF3CF2(CF3)CFSO2}〕－、〔(FSO2)N{(CF3)3CSO2}〕－等，以及在日本特开2011－133844号公报、日本特开2011－116803号公报、日本特开2010－090341号公报中记载的氮阴离子。In addition, as the nitrogen anion, for example, [(CN)2 N]− , [(FSO2 )2 N]− , [(FSO2 )N(CF3 SO2 )]− , [(CF3 SO2 )2 N]- , [(FSO2 )N(CF3 CF2 SO2 )]- , [(FSO2 )N{(CF3 )2 CFSO2 }]- , [(FSO2 )N(CF3 CF2 CF2 SO2 )]- , [(FSO2 )N(CF3 CF2 CF2 CF2 SO2 )]- , [(FSO2 )N{(CF3 )2 CFCF2 SO2 }]- , [(FSO2 )N{CF3 CF2 (CF3 )CFSO2 }]- , [(FSO2 )N{(CF3 )3 CSO2 }]- , etc., and in Japanese Patent Laid-Open No. 2011-133844 , Nitrogen anions described in Japanese Patent Laid-Open No. 2011-116803 and Japanese Patent Laid-Open No. 2010-090341.
此外，作为甲基化物阴离子，例如可以是(CF3SO2)3C－、(CF3CF2SO2)3C－、〔(CF3)2CFSO2〕3C－、(CF3CF2CF2SO2)3C－、(CF3CF2CF2CF2SO2)3C－、〔(CF3)2CFCF2SO2〕3C－、〔CF3CF2(CF3)CFSO2〕3C－、〔(CF3)3CSO2〕3C－、(FSO2)3C－等、以及在日本特开2011－145540号公报、美国专利第5,554,664号说明书、日本特开2005－309408号公报、日本特开2004－085657号公报、日本特表2010－505787号公报等中记载的甲基化物阴离子。In addition, as the methide anion, for example, (CF3 SO2 )3 C− , (CF3 CF2 SO2 )3 C− , [(CF3 )2 CFSO2 ]3 C− , (CF3 CF ) may be used2 CF2 SO2 )3 C− , (CF3 CF2 CF2 CF2 SO2 )3 C− , [(CF3 )2 CFCF2 SO2 ]3 C− , [CF3 CF2 (CF3 ) CFSO2 ]3 C− , [(CF3 )3 CSO2 ]3 C− , (FSO2 )3 C− , etc., as well as in Japanese Patent Application Laid-Open No. 2011-145540, US Patent No. 5,554,664, and Japanese Patent Application Laid-Open Publication No. 2011-145540 The methide anions described in 2005-309408 A, JP 2004-085657 A, JP 2010-505787 A, and the like.
本着色剂用凝胶渗透色谱法(下面简称GPC)(溶出溶剂：四氢呋喃)测得的聚苯乙烯换算的重均分子量(Mw)通常为1,000～100,000，优选为3,000～50,000。通过这种方式，能使耐热性、耐溶剂性、移染性抑制、覆膜特性、电特性、图案形状、分辨率变得良好。The weight average molecular weight (Mw) of this colorant in terms of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran) is usually 1,000 to 100,000, preferably 3,000 to 50,000. In this way, heat resistance, solvent resistance, suppression of dye migration, film properties, electrical properties, pattern shape, and resolution can be improved.
此外，本发明中的本着色剂的重均分子量(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。这里所说的Mn是用GPC(溶出溶剂：四氢呋喃)测得的聚苯乙烯换算的数均分子量。Moreover, it is preferable that the ratio (Mw/Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of this coloring agent in this invention is 1.0-5.0, More preferably, it is 1.0-3.0. Mn referred to here is the number average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran).
本发明的着色组合物也可混合本着色剂以外的其他着色剂进行使用。作为其他着色剂，无特殊限制，可根据用途适当选择色彩、材质。作为其他着色剂，可以是本着色剂以外的颜料、染料，其他着色剂可单独或组合2种以上进行使用。其中，从得到亮度、对比度和着色力高的像素的角度考虑，作为颜料，优选有机颜料，此外，作为染料，优选有机染料。The coloring composition of this invention can also mix and use another coloring agent other than this coloring agent. There are no particular limitations on other colorants, and colors and materials can be appropriately selected according to the application. As other colorants, pigments and dyes other than this colorant may be used, and other colorants may be used alone or in combination of two or more. Among them, from the viewpoint of obtaining a pixel with high brightness, contrast, and tinting strength, organic pigments are preferable as pigments, and organic dyes are preferable as dyes.
作为有机颜料，例如可以是在染料索引(C.I.；The Society of Dyers andColourists公司发行)中分类为颜料的化合物，即，下述附染料索引(C.I.)号的化合物。Examples of the organic pigment include compounds classified as pigments in the Dye Index (C.I.; issued by The Society of Dyers and Colourists), that is, compounds with the following Dye Index (C.I.) numbers.
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、颜料红264等红色颜料；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, Pigment Red 264 and other red pigments;
C.I.颜料绿7、C.I.颜料绿36、C.I.颜料绿58等绿色颜料；C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 58 and other green pigments;
C.I.颜料蓝15:6、C.I.颜料蓝16、C.I.颜料蓝80等蓝色颜料；C.I. Pigment Blue 15:6, C.I. Pigment Blue 16, C.I. Pigment Blue 80 and other blue pigments;
C.I.颜料黄83、C.I.颜料黄129、C.I.颜料黄138、C.I.颜料黄139、C.I.颜料黄150、C.I.颜料黄179、C.I.颜料黄180、C.I.颜料黄185、C.I.颜料黄211、C.I.颜料黄215等黄色颜料；C.I. Pigment Yellow 83, C.I. Pigment Yellow 129, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 179, C.I. Pigment Yellow 180, C.I. Pigment Yellow 185, C.I. Pigment Yellow 211, C.I. yellow pigment;
C.I.颜料橙38等橙色颜料；Orange pigments such as C.I. Pigment Orange 38;
C.I.颜料紫23等紫色颜料。Violet pigments such as C.I. Pigment Violet 23.
此外，可以是在日本特开2001－081348号公报、日本特开2010－026334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号公报等中记载的色淀颜料。In addition, it may be described in Japanese Patent Laid-Open No. 2001-081348, Japanese Patent Laid-Open No. 2010-026334, Japanese Patent Laid-Open No. 2010-237384, Japanese Patent Laid-Open No. 2010-237569, Japanese Patent Laid-Open No. 2011-006602, Lake pigments described in Japanese Patent Laid-Open No. 2011-145346 and the like.
其中，优选含有选自蓝色颜料和紫色颜料中的至少1种，更优选含有选自C.I.颜料蓝15:6和C.I.颜料紫23中的至少1种。由此，能够容易地形成耐热性和耐溶剂性优异且移染性得到抑制的着色固化膜，尤其是蓝色像素。Among them, at least one selected from blue pigments and violet pigments is preferably contained, and at least one selected from C.I. Pigment Blue 15:6 and C.I. Pigment Violet 23 is more preferably contained. Thereby, it is possible to easily form a colored cured film having excellent heat resistance and solvent resistance and suppressing dye migration, especially a blue pixel.
此外，作为染料，优选三芳基甲烷染料、蒽醌染料、偶氮染料等。更具体地，可以是在PCT申请第2010/123071号公开公报、日本特开2011－116803号公报、日本特开2011－117995号公报、日本特开2011－133844号公报、日本特开2011－174987号公报等中记载的有机染料。Moreover, as a dye, a triarylmethane dye, an anthraquinone dye, an azo dye, etc. are preferable. More specifically, it may be disclosed in PCT Application Publication No. 2010/123071, Japanese Patent Laid-Open No. 2011-116803, Japanese Patent Laid-Open No. 2011-117995, Japanese Patent Laid-Open No. 2011-133844, and Japanese Patent Laid-Open No. 2011-174987 Organic dyes described in Gazette No.
在本发明中，可将任意混合的其他颜料通过重结晶法、再沉淀法、溶剂清洗法、升华法、真空加热法或这些方法的组合进行精制后使用。此外，这些颜料也可根据要求用树脂将其粒子表面进行改性后使用。作为对颜料粒子表面进行改性的树脂，例如可以是在日本特开2001－108817号公报中记载的载色基树脂或市售的各种颜料分散用树脂。作为炭黑表面的树脂包覆方法，例如可以采用在日本特开平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。此外，有机颜料可通过所谓的盐磨法将一次粒子进行微细化后使用。作为盐磨的方法，例如可以采用在日本特开平8－179111号公报中公开的方法。In the present invention, other pigments that are arbitrarily mixed can be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination of these methods. In addition, these pigments can also be used by modifying their particle surfaces with resins as required. As the resin for modifying the surface of the pigment particles, for example, the vehicle-based resin described in Japanese Patent Laid-Open No. 2001-108817 or various commercially available resins for pigment dispersion can be used. As a resin coating method of the carbon black surface, the methods described in, for example, Japanese Patent Laid-Open No. 9-71733, Japanese Patent Laid-Open No. 9-95625, and Japanese Patent Laid-Open No. 9-124969 can be employed. In addition, the organic pigment can be used by refining primary particles by a so-called salt milling method. As a method of salt milling, the method disclosed in Unexamined-Japanese-Patent No. 8-179111 can be employ|adopted, for example.
此外，在本发明中，在使用任意混合的其他着色剂的同时，还可添加公知的分散剂和分散助剂。作为公知的分散剂，例如可以是聚氨酯类分散剂、聚乙烯亚胺类分散剂、聚氧乙烯烷基醚类分散剂、聚氧乙烯烷基苯基醚类分散剂、聚乙二醇二酯类分散剂、脱水山梨醇脂肪酸酯类分散剂、聚酯类分散剂、丙烯酸类分散剂等，此外，作为分散助剂，可以是颜料衍生物等。Moreover, in this invention, a well-known dispersing agent and a dispersing auxiliary agent can also be added together with other coloring agent mixed arbitrarily. Examples of known dispersants include polyurethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene alkyl phenyl ether-based dispersants, and polyethylene glycol diesters. dispersants, sorbitan fatty acid ester-based dispersants, polyester-based dispersants, acrylic-based dispersants, and the like, and as dispersing aids, pigment derivatives and the like may be used.
上述分散剂可从商业途径获得，例如可分别列举如下：作为丙烯酸类分散剂的Disperbyk－2000、Disperbyk－2001、BYK－LPN 6919、BYK－LPN 21116、BYK－LPN 22102(以上为毕克化学(BYK)公司产品)等；作为聚氨酯类分散剂的Disperbyk－161、Disperbyk－162、Disperbyk－165、Disperbyk－167、Disperbyk－170、Disperbyk－182(以上为毕克化学(BYK)公司产品)、Solsperse 76500(路博润公司产品)等；作为聚乙烯亚胺类分散剂的Solsperse－24000(路博润公司产品)等；作为聚酯类分散剂的Ajisper－PB821、Ajisper－PB822、Ajisper－PB880、Ajisper－PB881(以上为Ajinomoto Fine-Techno公司产品)等；以及BYK－LPN21324(毕克化学(BYK)公司产品)。The above-mentioned dispersants can be obtained from commercial sources, for example, they can be listed as follows: Disperbyk-2000, Disperbyk-2001, BYK-LPN 6919, BYK-LPN 21116, BYK-LPN 22102 (the above are BYK chemical (the above) are acrylic dispersants. Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (the above are products of BYK), Solsperse as polyurethane dispersants 76500 (product of Lubrizol), etc.; Solsperse-24000 (product of Lubrizol), etc. as polyethyleneimine dispersant; Ajisper-PB821, Ajisper-PB822, Ajisper-PB880, Ajisper-PB881 (the above are products of Ajinomoto Fine-Techno), etc.; and BYK-LPN21324 (products of BYK).
此外，作为颜料衍生物，具体而言，可以是铜酞菁、二酮基吡咯并吡咯、喹酞酮的磺酸衍生物等。In addition, specific examples of the pigment derivatives include copper phthalocyanine, diketopyrrolopyrrole, sulfonic acid derivatives of quinophthalone, and the like.
在本发明中，其他着色剂可单独或混合2种以上进行使用。In the present invention, other colorants may be used alone or in combination of two or more.
相对于着色剂的合计含量，其他着色剂的含有比例优选在70质量％以下，更优选在50质量％以下。对其下限值无特殊限制，在0.01质量％以上即可。The content ratio of other colorants is preferably 70% by mass or less, more preferably 50% by mass or less, with respect to the total content of the colorants. The lower limit is not particularly limited, and it may be 0.01% by mass or more.
从形成耐热性、耐溶剂性、移染性抑制和亮度高、色纯度优异的像素或遮光性优异的黑色矩阵、黑色间隔件的角度考虑，着色组合物的固体成分中的(A)着色剂的含有比例通常占5～70质量％，优选为10～60质量％。这里，固体成分是指后述的溶剂以外的成分。(A) in the solid content of the coloring composition is colored from the viewpoint of forming a pixel with high heat resistance, solvent resistance, dye migration inhibition, high brightness, and excellent color purity, or a black matrix and black spacer excellent in light-shielding properties. The content of the agent is usually 5 to 70% by mass, preferably 10 to 60% by mass. Here, the solid content refers to components other than the solvent described later.
－(B)聚合性化合物－-(B) Polymerizable compound-
在本发明中，聚合性化合物是指具有2个以上可聚合基团的化合物。作为可聚合基团，例如可以是烯不饱和基团、环氧乙烷基、氧杂环丁基、N－烷氧基甲基氨基等。在本发明中，优选使用具有2个以上(甲基)丙烯酰基的化合物或具有2个以上N－烷氧基甲基氨基的化合物作为聚合性化合物。In the present invention, the polymerizable compound refers to a compound having two or more polymerizable groups. As a polymerizable group, an ethylenically unsaturated group, an oxirane group, an oxetanyl group, an N-alkoxymethylamino group, etc. are mentioned, for example. In the present invention, a compound having two or more (meth)acryloyl groups or a compound having two or more N-alkoxymethylamino groups is preferably used as the polymerizable compound.
作为具有2个以上(甲基)丙烯酰基的化合物的具体例子，可以是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、己内酯改性多官能(甲基)丙烯酸酯、环氧烷改性多官能(甲基)丙烯酸酯、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氨基甲酸酯(甲基)丙烯酸酯、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 an aliphatic polyhydroxy compound with (meth)acrylic acid, and caprolactone-modified polyfunctional (Meth)acrylate, alkylene oxide-modified polyfunctional (meth)acrylate, polyfunctional urethane (meth)acrylate obtained by reacting (meth)acrylate having a hydroxyl group with polyfunctional isocyanate , 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.
这里，作为脂肪族多羟基化合物，例如可以是乙二醇、丙二醇、聚乙二醇、聚丙二醇之类的2价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价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，例如可以是(甲基)丙烯酸2－羟乙酯、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、丙三醇二甲基丙烯酸酯等。作为上述多官能异氰酸酯，例如可以是甲苯二异氰酸酯、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，例如可以是琥珀酸酐、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酸酐，均苯四甲酸二酐、联苯四甲酸二酐、二苯甲酮四甲酸二酐之类的四元酸二酐。Here, the aliphatic polyhydroxy compound may be, for example, a divalent aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and the like. trivalent or higher aliphatic polyhydroxy compound. Examples of the (meth)acrylate having the above-mentioned hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol. Penta(meth)acrylate, glycerol dimethacrylate, etc. As said polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, etc. are mentioned, for example. Examples of the acid anhydride include acid anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, Tetrabasic acid dianhydrides such as biphenyltetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride.
此外，作为己内酯改性多官能(甲基)丙烯酸酯，例如可以是在日本特开平11－44955号公报的段落〔0015〕～〔0018〕中记载的化合物。作为上述环氧烷改性多官能(甲基)丙烯酸酯，例如可以是由选自环氧乙烷和环氧丙烷中的至少1种改性的双酚A二(甲基)丙烯酸酯、由选自环氧乙烷和环氧丙烷中的至少1种改性的异氰脲酸三(甲基)丙烯酸酯、由选自环氧乙烷和环氧丙烷中的至少1种改性的三羟甲基丙烷三(甲基)丙烯酸酯、由选自环氧乙烷和环氧丙烷中的至少1种改性的季戊四醇三(甲基)丙烯酸酯、由选自环氧乙烷和环氧丙烷中的至少1种改性的季戊四醇四(甲基)丙烯酸酯、由选自环氧乙烷和环氧丙烷中的至少1种改性的二季戊四醇五(甲基)丙烯酸酯、由选自环氧乙烷和环氧丙烷中的至少1种改性的二季戊四醇六(甲基)丙烯酸酯等。Moreover, as a caprolactone-modified polyfunctional (meth)acrylate, the compound described in the paragraph [0015] - [0018] of Unexamined-Japanese-Patent No. 11-44955 can be used, for example. As the above-mentioned alkylene oxide-modified polyfunctional (meth)acrylate, for example, bisphenol A di(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide, a Isocyanurate tri(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide, tris(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide Methylol propane tri(meth)acrylate, pentaerythritol tri(meth)acrylate modified by at least one selected from ethylene oxide and propylene oxide, modified from ethylene oxide and epoxy At least one modified pentaerythritol tetra(meth)acrylate in propane, dipentaerythritol penta(meth)acrylate modified with at least one selected from ethylene oxide and propylene oxide, Dipentaerythritol hexa(meth)acrylate modified by at least one of ethylene oxide and propylene oxide, and the like.
此外，作为具有2个以上N－烷氧基甲基氨基的化合物，例如可以是具有三聚氰胺结构、苯并胍胺结构或脲结构的化合物等。三聚氰胺结构、苯并胍胺结构是指是指具有1个以上三嗪环或苯基取代三嗪环作为基本骨架的化学结构，该概念包括三聚氰胺、苯并胍胺或它们的缩合物。作为具有2个以上N－烷氧基甲基氨基的化合物的具体例子，例如可以是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)苯并胍胺、N,N,N’,N’－四(烷氧基甲基)甘脲等。Moreover, as a compound which has two or more N-alkoxymethylamino groups, the compound etc. which have a melamine structure, a benzoguanamine structure, or a urea structure are mentioned, for example. The melamine structure and the benzoguanamine structure refer to chemical structures having one or more triazine rings or phenyl-substituted triazine rings as the basic skeleton, and the concept includes melamine, benzoguanamine or their condensates. Specific examples of the compound 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.
这些聚合性化合物中，优选3价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、己内酯改性多官能(甲基)丙烯酸酯、多官能氨基甲酸酯(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)苯并胍胺。从耐热性、耐溶剂性、移染性抑制良好，而且着色层的强度高、着色层的表面平滑性优异，并且未曝光部的基板上和遮光层上不易起脏、膜残留等的角度考虑，尤其优选3价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)丙烯酸酯中的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，具有羧基的多官能(甲基)丙烯酸酯中的季戊四醇三丙烯酸酯与琥珀酸酐反应而得到的化合物、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 polymerizable compounds, polyfunctional (meth)acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth)acrylic acid, caprolactone-modified polyfunctional (meth)acrylates, polyfunctional (meth)acrylates, etc. are preferred. Functional urethane (meth)acrylate, polyfunctional (meth)acrylate with carboxyl group, N,N,N',N',N",N"-hexa(alkoxymethyl)melamine, N,N,N',N'-tetrakis(alkoxymethyl)benzoguanamine. From the viewpoints of good heat resistance, solvent resistance, and dye migration suppression, high strength of the colored layer, excellent surface smoothness of the colored layer, and less smearing and film residue on the substrate and the light-shielding layer in the unexposed portion Among the polyfunctional (meth)acrylates obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol pentaacrylate are considered particularly preferable. Acrylate, dipentaerythritol hexaacrylate, the compound obtained by reacting pentaerythritol triacrylate and succinic anhydride among the polyfunctional (meth)acrylates having a carboxyl group, and the compound obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride.
在本发明中，(B)聚合性化合物可单独或混合2种以上进行使用。In the present invention, the (B) polymerizable compound can be used alone or in combination of two or more.
相对于(A)着色剂100质量份，本发明中的(B)聚合性化合物的含量优选为10～1,000质量份，更优选为20～700质量份，尤其优选为100～500质量份。通过这种方式，耐热性、耐溶剂性、移染性抑制变得良好，而且固化性、碱显影性进一步提高，能够以高水平抑制在未曝光部的基板上或遮光层上出现脏版、膜残留等。－(C)粘合树脂－The content of the (B) polymerizable compound in the present invention is preferably 10 to 1,000 parts by mass, more preferably 20 to 700 parts by mass, and particularly preferably 100 to 500 parts by mass relative to 100 parts by mass of the (A) colorant. In this way, the heat resistance, solvent resistance, and dye migration suppression are improved, and the curability and alkali developability are further improved, and it is possible to suppress the occurrence of smears on the substrate in the unexposed portion or on the light shielding layer at a high level. , film residue, etc. -(C) Binder resin-
作为本发明中的(C)粘合树脂，无特殊限制，但优选具有羧基、酚羟基等酸性官能团的树脂。其中，优选具有羧基的聚合物(下面也称作“含羧基聚合物”)，例如可以是具有1个以上羧基的烯不饱和单体(下面也称作“不饱和单体(c1)”)与其他可共聚的烯不饱和单体(下面也称作“不饱和单体(c2)”)的共聚物。Although it does not specifically limit as (C) binder resin in this invention, Resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group, is preferable. Among them, a polymer having a carboxyl group (hereinafter also referred to as "carboxyl group-containing polymer") is preferable, and, for example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter also referred to as "unsaturated monomer (c1)") is preferable. Copolymers with other copolymerizable ethylenically unsaturated monomers (hereinafter also referred to as "unsaturated monomers (c2)").
作为不饱和单体(c1)，例如可以是(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 (c1) include (meth)acrylic acid, maleic acid, maleic anhydride, mono[2-(meth)acryloyloxyethyl] succinate, ω-carboxypolyhexamethylene Lactone mono(meth)acrylate, p-vinyl benzoic acid, etc.
这些不饱和单体(c1)可单独或混合2种以上进行使用。These unsaturated monomers (c1) can be used individually or in mixture of 2 or more types.
此外，作为不饱和单体(c2)，例如可以是在上述关于不饱和单体(a2)的部分中举例示出的具有1个以上羧基的烯不饱和单体、N－取代马来酰亚胺、芳香族乙烯基化合物、(甲基)丙烯酸酯、乙烯基醚、在聚合物分子链末端具有单(甲基)丙烯酰基的大分子单体等。作为具体例子，可以是与上述相同的物质。In addition, as the unsaturated monomer (c2), for example, the ethylenically unsaturated monomer having one or more carboxyl groups, N-substituted maleimide, exemplified in the above-mentioned section about the unsaturated monomer (a2) can be used Amines, aromatic vinyl compounds, (meth)acrylates, vinyl ethers, macromonomers having a mono(meth)acryloyl group at the end of the polymer molecular chain, and the like. As a specific example, the same substances as described above may be used.
不饱和单体(c2)可以单独或混合2种以上进行使用。The unsaturated monomer (c2) may be used alone or in combination of two or more.
在不饱和单体(c1)与不饱和单体(c2)的共聚物中，该共聚物中的不饱和单体(c1)的共聚比例优选为5～50质量％，更优选为10～40质量％。通过使不饱和单体(c1)在该范围内共聚，能够得到碱显影性和保存稳定性优异的着色组合物。In the copolymer of the unsaturated monomer (c1) and the unsaturated monomer (c2), the copolymerization ratio of the unsaturated monomer (c1) in the copolymer is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass. quality%. By copolymerizing the unsaturated monomer (c1) within this range, a coloring composition excellent in alkali developability and storage stability can be obtained.
作为不饱和单体(c1)与不饱和单体(c2)的共聚物的具体例子，例如可以是在日本特开平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号公报等中公开的共聚物。As specific examples of the copolymer of the unsaturated monomer (c1) and the unsaturated monomer (c2), for example, those disclosed in Japanese Patent Laid-Open No. 7-140654, Japanese Patent Laid-Open No. 8-259876, and Japanese Patent Laid-Open No. 10- Japanese Patent Laid-Open No. 31308, Japanese Patent Laid-Open No. 10-300922, Japanese Patent Laid-Open No. 11-174224, Japanese Patent Laid-Open No. 11-258415, Japanese Patent Laid-Open No. 2000-56118, Japanese Patent Laid-Open No. 2004-101728, etc. Disclosed copolymers.
在不饱和单体(c1)与不饱和单体(c2)的共聚物中，作为优选的方式，可以是含有具有含氧饱和杂环基作为不饱和单体(c2)的(甲基)丙烯酸酯的共聚物(下面也称作“特定共聚物”)。In the copolymer of the unsaturated monomer (c1) and the unsaturated monomer (c2), as a preferred embodiment, (meth)acrylic acid containing an oxygen-containing saturated heterocyclic group as the unsaturated monomer (c2) may be used Copolymers of esters (hereinafter also referred to as "specific copolymers").
此外，在本发明中，如在例如日本特开平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9－325494号公报、日本特开平11－140144号公报、日本特开2008－181095号公报等中公开的那样，也可以使用在侧链上具有(甲基)丙烯酰基等聚合性不饱和键的含羧基聚合物作为粘合树脂。In addition, in the present invention, as described in, for example, Japanese Patent Laid-Open No. 5-19467, Japanese Patent Laid-Open No. 6-230212, Japanese Patent Laid-Open No. 7-207211, Japanese Patent Laid-Open No. 9-325494, and Japanese Patent Laid-Open No. 11 As disclosed in -140144 A, JP 2008-181095 A, etc., a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth)acryloyl group in a side chain can also be used as a binder resin.
作为在侧链上具有(甲基)丙烯酰基等聚合性不饱和键的含羧基聚合物的具体例子，例如可以是含不饱和羧酸而成的单体的共聚物与具有环氧乙烷基的聚合性不饱和化合物反应而得到的共聚物、As a specific example of a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth)acryloyl group in a side chain, for example, a copolymer of a monomer containing an unsaturated carboxylic acid and an ethylene oxide group may be used. The copolymer obtained by the reaction of the polymerizable unsaturated compound,
含不饱和羧酸和具有环氧乙烷基的聚合性不饱和化合物而成的单体的共聚物与不饱和羧酸反应而得到的共聚物、A copolymer containing an unsaturated carboxylic acid and a monomer comprising a polymerizable unsaturated compound having an oxirane group reacted with an unsaturated carboxylic acid,
含不饱和羧酸和具有羟基的聚合性不饱和化合物而成的单体的共聚物与不饱和异氰酸酯化合物而反应得到的聚合物。A polymer obtained by reacting a copolymer of a monomer comprising an unsaturated carboxylic acid and a polymerizable unsaturated compound having a hydroxyl group with an unsaturated isocyanate compound.
本发明中的粘合树脂用凝胶渗透色谱(下面简称GPC)(溶出溶剂：四氢呋喃)测得的聚苯乙烯换算的重均分子量(Mw)通常为1,000～100,000，优选为3,000～50,000,。通过这种方式，覆膜的残膜率、图案形状、耐热性、电特性、分辨率进一步提高，而且能以高水平抑制涂布时干燥异物的产生。The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran) of the binder resin in the present invention is usually 1,000 to 100,000, preferably 3,000 to 50,000. In this way, the residual film ratio, pattern shape, heat resistance, electrical properties, and resolution of the coating film are further improved, and the generation of dry foreign matter during coating can be suppressed at a high level.
此外，本发明中的粘合树脂的重均分子量(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。这里所说的Mn是指用GPC(溶出溶剂：四氢呋喃)测得的聚苯乙烯换算的数均分子量。Furthermore, 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, and more preferably 1.0 to 3.0. The Mn referred to here refers to the number average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran).
本发明中的粘合树脂可通过公知的方法进行制造，例如可通过在日本特开2003－222717号公报、日本特开2006－259680号公报、PCT申请第2007/029871号公开公报等中公开的方法来控制粘合树脂的结构、Mw、Mw/Mn。The binder resin in the present invention can be produced by a known method, for example, by the methods disclosed in Japanese Patent Laid-Open No. 2003-222717, Japanese Patent Laid-Open No. 2006-259680, PCT Application No. 2007/029871, etc. Methods to control the structure, Mw, Mw/Mn of the adhesive resin.
在本发明中，(C)粘合树脂可单独或混合2种以上进行使用。In this invention, (C) binder resin can be used individually or in mixture of 2 or more types.
在本发明中，相对于(A)着色剂100质量份，(C)粘合树脂的含量通常为10～1,000质量份，优选为20～500质量份。通过这种方式，能够进一步提高碱显影性、着色组合物的保存稳定性、色度特性。In this invention, content of (C) binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) colorants, Preferably it is 20-500 mass parts. In this way, alkali developability, storage stability of the coloring composition, and chromaticity characteristics can be further improved.
－光聚合引发剂－-Photopolymerization initiator-
本发明的着色组合物中可以添加光聚合引发剂。由此能够赋予着色组合物以放射线敏感性。本发明中使用的光聚合引发剂是产生活性种的化合物，该活性种能够通过在可见光、紫外线、远紫外线、电子射线、X射线等放射线下的曝光而使(B)聚合性化合物开始聚合。A photopolymerization initiator may be added to the coloring composition of the present invention. Thereby, radiation sensitivity can be imparted to the coloring composition. The photopolymerization initiator used in the present invention is a compound that generates an active species that can initiate polymerization of the (B) polymerizable compound by exposure to radiation such as visible light, ultraviolet rays, extreme ultraviolet rays, electron beams, and X-rays.
作为这种光聚合引发剂，例如可以是噻吨酮化合物、苯乙酮化合物、联咪唑化合物、三嗪化合物、O－酰基肟化合物、鎓盐化合物、苯偶姻化合物、二苯甲酮化合物、α－二酮化合物、多核醌化合物、重氮化合物、酰亚胺磺酸酯化合物等。Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyl oxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, and the like.
在本发明中，光聚合引发剂可单独或混合2种以上进行使用。作为光聚合引发剂，优选选自噻吨酮化合物、苯乙酮化合物、联咪唑化合物、三嗪化合物、O－酰基肟化合物中的至少1种。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 compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyl oxime compounds.
本发明的优选的光聚合引发剂中，作为噻吨酮化合物的具体例子，可以是噻吨酮、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 the preferred photopolymerization initiators of the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-Isopropylthioxanthone, 2,4-Dichlorothioxanthone, 2,4-Dimethylthioxanthone, 2,4-Diethylthioxanthone, 2,4-Diisopropylthioxanthone Tonone, etc.
此外，作为苯乙酮化合物的具体例子，可以是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 acetophenone compound include 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2- Dimethylamino-1-(4-morpholinophenyl)butane-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4-morpholine Substituted phenyl) butane-1-one, etc.
此外，作为联咪唑化合物的具体例子，可以是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, as a specific example of the biimidazole compound, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 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 and the like.
另外，在使用联咪唑作为光聚合引发剂的情况下，从能够改良灵敏度的角度考虑，优选并用氢供体。这里所说的“氢供体”是指能向通过曝光而由联咪唑化合物产生的自由基供给氢原子的化合物。作为氢供体，例如可以是2－巯基苯并噻唑、2－巯基苯并噁唑等硫醇氢供体、4,4’－双(二甲基氨基)二苯甲酮、4,4’－双(二乙基氨基)二苯甲酮等胺氢供体。在本发明中，这些氢供体可以单独或混合2种以上进行使用，但从能够进一步改良光灵敏度的角度考虑，优选将1种以上硫醇氢供体和1种以上胺氢供体组合起来使用。In addition, in the case of using biimidazole as the photopolymerization initiator, it is preferable to use a hydrogen donor in combination from the viewpoint that the sensitivity can be improved. The "hydrogen donor" referred to here refers to a compound capable of donating a hydrogen atom to a radical generated from a biimidazole compound by exposure to light. Examples of the hydrogen donor include thiol hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4'-bis(dimethylamino)benzophenone, 4,4' - Amine hydrogen donors such as bis(diethylamino)benzophenone. In the present invention, these hydrogen donors may be used alone or in combination of two or more, but it is preferable to combine one or more thiol hydrogen donors and one or more amine hydrogen donors from the viewpoint that the photosensitivity can be further improved use.
此外，作为三嗪化合物的具体例子，可以是2,4,6－三(三氯甲基)－s－三嗪、2－甲基－4,6－双(三氯甲基)－s－三嗪、2－〔2－(5－甲基呋喃－2－基)乙烯基〕－4,6－双(三氯甲基)－s－三嗪、2－〔2－(呋喃－2－基)乙烯基〕－4,6－双(三氯甲基)－s－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)－s－三嗪、2－〔2－(3,4－二甲氧基苯基)乙烯基〕－4,6－双(三氯甲基)－s－三嗪、2－(4－甲氧基苯基)－4,6－双(三氯甲基)－s－三嗪、2－(4－乙氧基苯乙烯基)－4,6－双(三氯甲基)－s－三嗪、2－(4－正丁氧基苯基)－4,6－双(三氯甲基)－s－三嗪等具有卤甲基的三嗪化合物。Further, as specific examples of the triazine compound, 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- base) vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6 -Bis(trichloromethyl)-s-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine oxazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxystyryl)-4,6-bis( Triazine compounds having a halomethyl group such as trichloromethyl)-s-triazine and 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine.
此外，作为O－酰基肟化合物的具体例子，可以是1,2－辛二酮,1－〔4－(苯硫基)苯基〕－,2－(O－苯甲酰肟)、乙酮,1－〔9－乙基－6－(2－甲基苯甲酰基)－9H－咔唑－3－基〕－,1－(O－乙酰肟)、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－乙酰肟)等。作为O－酰基肟化合物的市售品，也可以使用NCI－831、NCI－930(以上为ADEKA公司产品)、DFI－020、DFI－091(以上为Daito Chemix公司产品)等。In addition, specific examples of the O-acyl oxime compound include 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), ethyl ketone ,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyl oxime), ethyl ketone, 1-[9-ethyl Base-6-(2-methyl-4-tetrahydrofuranylmethoxybenzoyl)-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-carbazol-3-yl]- , 1-(O-acetyl oxime) and so on. As a commercial item of an O-acyl oxime compound, NCI-831, NCI-930 (the above are products of ADEKA company), DFI-020, DFI-091 (the above are products of Daito Chemix company), etc. can be used.
在本发明中，在使用苯乙酮化合物等联咪唑化合物以外的光聚合引发剂的情况下，可以并用敏化剂。作为这种敏化剂，例如可以是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 a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound is used, a sensitizer may be used in combination. Examples of such sensitizers include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 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, and the like.
在本发明中，相对于(B)聚合性化合物100质量份，光聚合引发剂的含量优选为0.01～120质量份，尤其优选为1～100质量份。通过这种方式，能够进一步提高固化性和覆膜特性。In this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (B) polymerizable compounds, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. In this way, curability and coating properties can be further improved.
－溶剂－-Solvent-
本发明的着色组合物含有上述(A)和(B)成分以及任意添加的其他成分，但通常添加溶剂而调制成液状组合物。The coloring composition of this invention contains the said (A) and (B) component and other components added arbitrarily, Usually, it adds a solvent and prepares it as a liquid composition.
作为上述溶剂，只要是能分散或溶解构成着色组合物的(A)和(B)成分、其他成分且不与这些成分反应、具有适度的挥发性的溶剂，就可适当选择使用。The above-mentioned solvent can be appropriately selected and used as long as it can disperse or dissolve the components (A) and (B) and other components constituting the coloring composition, does not react with these components, and has moderate volatility.
这种溶剂中，例如可以是：乙二醇单甲醚、乙二醇单乙醚、乙二醇单正丙基醚、乙二醇单正丁基醚、二乙二醇单甲醚、二乙二醇单乙醚、二乙二醇单正丙基醚、二乙二醇单正丁基醚、三乙二醇单甲醚、三乙二醇单乙醚、丙二醇单甲醚、丙二醇单乙醚、丙二醇单正丙基醚、丙二醇单正丁基醚、二丙二醇单甲醚、二丙二醇单乙醚、二丙二醇单正丙基醚、二丙二醇单正丁基醚、三丙二醇单甲醚、三丙二醇单乙醚等(多)亚烷基二醇单烷基醚类；In this solvent, for example, it can be: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethyl ether 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 monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether Equal (poly) alkylene glycol monoalkyl ethers;
乳酸甲酯、乳酸乙酯等乳酸烷基酯类；Lactic acid alkyl 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；(Cyclo)alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tert-butanol, octanol, 2-ethylhexanol, cyclohexanol;
二丙酮醇等酮醇类；Ketone alcohols such as diacetone alcohol;
乙二醇单甲基醚乙酸酯、乙二醇单乙醚乙酸酯、二乙二醇单甲醚乙酸酯、二乙二醇单乙醚乙酸酯、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、3－甲氧基丁基乙酸酯、3－甲基－3－甲氧基丁基乙酸酯等(多)亚烷基二醇单烷基醚乙酸酯；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 (poly)alkylene glycols such as monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate Monoalkyl ether acetate;
二乙二醇二甲醚、二乙二醇甲基乙基醚、二乙二醇二乙醚、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；Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
丙二醇二乙酸酯、1,3－丁二醇二乙酸酯、1,6－己二醇二乙酸酯等二乙酸酯类；Diacetates such as propylene glycol diacetate, 1,3-butanediol 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-methylpropionate Alkoxy carboxylic acid esters such as 3-methoxybutyl propionate;
乙酸乙酯、乙酸正丙酯、乙酸异丙酯、乙酸正丁酯、乙酸异丁酯、甲酸正戊酯、乙酸异戊酯、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-amyl formate, iso-amyl 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；等等。Amides or lactams such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone; and the like.
这些溶剂中，从溶解性、颜料分散性、涂布性等角度考虑，优选使用(多)亚烷基二醇单烷基醚类、乳酸烷基酯类、(多)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，尤其优选使用丙二醇单甲醚、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、二乙二醇二甲醚、二乙二醇甲基乙基醚、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、乙酸正丁酯、乙酸异丁酯、甲酸正戊酯、乙酸异戊酯、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, lactic acid alkyl esters, (poly) alkylene glycol mono Alkyl ether acetates, other ethers, ketones, diacetates, alkoxycarboxylates, and other esters, particularly preferably propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether ethyl acid ester, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone , 2-heptanone, 3-heptanone, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxy ethyl propionate, 3 -Methyl ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate, n-amyl formate, Isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, etc.
在本发明中，溶剂可单独或混合2种以上进行使用。In this invention, a solvent can be used individually or in mixture of 2 or more types.
对溶剂的含量无特殊限制，但优选着色组合物的除溶剂以外的各成分的合计浓度为5～50质量％，更优选为10～40质量％。通过这种方式，能够得到分散性、稳定性良好的着色剂分散液、以及涂布性、稳定性良好的着色组合物。Although content of a solvent is not specifically limited, It is preferable that the total density|concentration of each component other than a solvent of a coloring composition is 5-50 mass %, More preferably, it is 10-40 mass %. In this way, a colorant dispersion liquid having favorable dispersibility and stability, and a coloring composition having favorable 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 this invention may contain various additives as needed.
作为添加剂，例如可以是：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；氟表面活性剂、硅酮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－环氧丙氧基丙基三甲氧基硅烷、3－环氧丙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粘附促进剂；2,2－硫代双(4－甲基－6－叔丁基苯酚)、2,6－二叔丁基苯酚、季戊四醇四〔3－(3,5－二叔丁基－4－羟基苯基)丙酸酯〕、3,9－双〔2－〔3－(3－叔丁基－4－羟基－5－甲基苯基)－丙酰氧基〕－1,1－二甲基乙基〕－2,4,8,10－四氧杂螺〔5.5〕十一烷、硫代二亚乙基双〔3－(3,5－二叔丁基－4－羟基苯基)丙酸酯〕等抗氧化剂；2－(3－叔丁基－5－甲基－2－羟基苯基)－5－氯苯并三唑、烷氧基二苯甲酮等紫外线吸收剂；聚丙烯酸钠等抗凝集剂；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、邻苯二甲酸单〔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；甲基丙烯酸2－(0－〔1’－甲基亚丙基氨基〕羧基氨基)乙酯等固化促进剂，等等。另外，作为固化促进剂，可以采用在日本特开2012－088457号公报的段落〔0162〕～〔0169〕中记载的固化促进剂。Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly(fluoroalkyl acrylate); surfactants such as fluorosurfactants and silicone surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane , N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-epoxy Propoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyl Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis(4-methyl-6- tert-butylphenol), 2,6-di-tert-butylphenol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 3,9-bis[2- [3-(3-tert-Butyl-4-hydroxy-5-methylphenyl)-propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxa Antioxidants such as spiro[5.5]undecane, thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]; 2-(3-tert-butyl) UV absorbers such as -5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole and alkoxybenzophenone; 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 - Residue improvers such as amino-1,3-propanediol and 4-amino-1,2-butanediol; mono[2-(meth)acryloyloxyethyl] succinate, mono[2-phthalate] Developability improvers such as 2-(meth)acryloyloxyethyl]ester and ω-carboxypolycaprolactone mono(meth)acrylate; 2-(0-[1'-methylidene methacrylate] propylamino]carboxyamino)ethyl ester and other curing accelerators, and the like. Moreover, as a hardening accelerator, the hardening accelerator described in the paragraphs [0162] to [0169] of JP-A-2012-088457 can be used.
本发明的着色组合物可采用适宜的方法进行调制，作为其调制方法，例如可以是在日本特开2008－58642号公报、日本特开2010－132874号公报等中公开的方法。在使用染料和颜料两者作为着色剂的情况下，可以采用如在日本特开2010－132874号公报中公开的那样的方法，即，在将染料通入第1滤器之后、将通过第1滤器的染料溶液与另行调制好的颜料分散液等混合，得到着色组合物，再将该着色组合物通入第2滤器，由此进行调制。此外，也可采用如下方法，即，在将染料、上述(B)成分和根据需要使用的其他成分溶解到溶剂中、并将所得溶液通入第1滤器之后，将通过第1滤器的溶液与另行调制好的颜料分散液混合，得到着色组合物，再将该着色组合物通人第2滤器中，由此进行调制。此外，还可采用如下方法，即，在将染料溶液通入第1滤器之后，将通过第1滤器的染料溶液与上述(B)成分、以及根据需要使用的其他成分混合、进行溶解，将所得溶液通入第2滤器，再将通过第2滤器的溶液与另行调制好的颜料分散液混合，得到着色组合物，将该着色组合物通入第3滤器，由此进行调制。The coloring composition of the present invention can be prepared by an appropriate method, and as the preparation method, the methods disclosed in, for example, Japanese Patent Laid-Open No. 2008-58642, Japanese Patent Laid-Open No. 2010-132874, and the like can be used. In the case of using both dyes and pigments as colorants, a method as disclosed in Japanese Patent Laid-Open No. 2010-132874 can be adopted, that is, after passing the dye through the first filter, the dye is passed through the first filter. The dye solution prepared separately is mixed with a separately prepared pigment dispersion liquid and the like to obtain a coloring composition, and the coloring composition is passed through a second filter to prepare. In addition, a method of dissolving the dye, the above-mentioned component (B), and other components used as necessary in a solvent, and passing the obtained solution through the first filter, may be adopted, and the solution passed through the first filter is mixed with The separately prepared pigment dispersion liquid was mixed to obtain a coloring composition, and the coloring composition was passed through the second filter to prepare. In addition, the following method can also be adopted, that is, after passing the dye solution into the first filter, the dye solution passing through the first filter is mixed with the above-mentioned (B) component and other components used as needed, and dissolved, and the obtained The solution was passed through the second filter, and the solution passed through the second filter was mixed with a separately prepared pigment dispersion to obtain a coloring composition, and the coloring composition was passed through the third filter to prepare.
着色固化膜及其制造方法Colored cured film and method for producing the same
本发明的着色固化膜用本发明的着色组合物形成，具体而言，是指彩色滤光片中使用的各色像素、黑色矩阵、黑色间隔件等。The colored cured film of the present invention is formed from the colored composition of the present invention, and specifically refers to each color pixel, black matrix, black spacer, and the like used in a color filter.
下面对彩色滤光片中使用的着色固化膜及其形成方法进行说明。Next, the colored cured film used for the color filter and its formation method will be described.
作为制造彩色滤光片的方法，第一，可以举出以下方法。首先，在基板的表面上根据需要形成遮光层(黑色矩阵)，将形成像素的部分进行划分。然后，在该基板上涂布例如蓝色的本发明的放射线敏感性着色组合物的液状组成物之后，进行预烘烤，蒸发掉溶剂，形成涂膜。接着，在介由光掩模对该涂膜进行曝光之后，使用碱显影液进行显影，溶解除去涂膜的未曝光部。然后，通过后烘烤形成以规定的序列配置的蓝色像素图案(着色固化膜)的像素阵列。As a method of manufacturing a color filter, first, the following methods can be mentioned. First, a light-shielding layer (black matrix) is formed on the surface of the substrate as necessary, and the portion where the pixels are to be formed is divided. Then, after applying, for example, a blue liquid composition of the radiation-sensitive coloring composition of the present invention on the substrate, prebaking is performed to evaporate the solvent to form a coating film. Next, after exposing the coating film through a photomask, it is developed using an alkali developing solution, and the unexposed portion of the coating film is dissolved and removed. Then, a pixel array of blue pixel patterns (colored cured films) arranged in a predetermined sequence is formed by post-baking.
接着，使用绿色或红色的各放射线敏感性树脂着色组合物，与上述同样地进行各放射线敏感性着色组合物的涂布、预烘烤、曝光、显影和后烘烤，在同一基板上依次形成绿色像素阵列和红色像素阵列。由此得到在基板上配置有蓝、绿、红三原色的像素阵列的彩色滤光片。但是，在本发明中，形成各色像素的顺序不限于上述顺序。Next, using each radiation-sensitive resin coloring composition of green or red, coating, pre-baking, exposure, development, and post-baking of each radiation-sensitive coloring composition were performed in the same manner as described above, and formed sequentially on the same substrate. Green pixel array and red pixel array. In this way, a color filter in which pixel arrays of three primary colors of blue, green, and red are arranged on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above-mentioned order.
此外，黑色矩阵可通过将用溅射法、蒸镀法以膜的方式形成的铬等金属薄膜利用光刻法形成所希望的图案而形成，也可使用分散有黑色颜料的放射线敏感性着色组合物，与形成上述像素的情况同样地形成。In addition, the black matrix can be formed by forming a desired pattern of a metal thin film such as chromium formed as a film by a sputtering method or a vapor deposition method by a photolithography method, and a radiation-sensitive coloring combination in which a black pigment is dispersed can also be used. The object is formed in the same manner as in the case of forming the above-mentioned pixels.
作为形成彩色滤光片时使用的基板，例如可以是玻璃、硅酮、聚碳酸酯、聚酯、芳香族聚酰胺、聚酰胺酰亚胺、聚酰亚胺等。As the substrate used for forming the color filter, for example, glass, silicone, polycarbonate, polyester, aramid, polyamideimide, polyimide, or the like can be used.
此外，也可根据要求预先对这些基板进行适宜的前处理，所述前处理例如可以是用硅烷偶联剂等进行的化学品处理、等离子体处理、离子镀、溅射、气相反应法、真空蒸镀等。In addition, these substrates may be subjected to appropriate pretreatment in advance as required, such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum treatment, etc. Evaporation etc.
在将放射线敏感性着色组合物涂布到基板上时，可以采用喷涂法、辊涂法、旋转涂布法(旋涂法)、缝模涂布法(狭缝涂布法)、棒涂法等适宜的涂布法，尤其优选采用旋涂法或缝模涂布法。When applying the radiation-sensitive coloring composition to the substrate, a spray coating method, a roll coating method, a spin coating method (spin coating method), a slot die coating method (slot coating method), and a bar coating method can be used A suitable coating method such as the spin coating method or the slot die coating method is particularly preferably used.
预烘烤通常通过组合减压干燥和加热干燥而进行。减压干燥通常进行至压力达到50～200Pa。此外，加热干燥的条件通常为在70～110℃下进行1～10分钟。Prebaking is usually performed by combining drying under reduced pressure and drying with heat. Drying under reduced pressure is usually performed until the pressure reaches 50 to 200 Pa. In addition, the conditions of heat-drying are normally performed at 70-110 degreeC for 1-10 minutes.
涂布厚度以干燥后的膜厚计，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, in terms of the film thickness after drying.
作为在形成选自像素和黑色矩阵中的至少1种时使用的放射线光源，例如可以是氙灯、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激准分子激光、氮激光等激光光源等。作为曝光光源，也可以使用紫外线LED。优选波长在190～450nm范围的放射线。Examples of the radiation light source used for forming at least one selected from the group consisting of pixels and 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, Light sources such as low pressure mercury lamps, argon ion lasers, YAG lasers, XeCl excimer lasers, nitrogen lasers and other laser light sources. As an exposure light source, an ultraviolet LED can also be used. Radiation having a wavelength in the range of 190 to 450 nm is preferred.
放射线的曝光量一般优选为10～10,000J/m2。The exposure amount of radiation is generally preferably 10 to 10,000 J/m2 .
此外，作为上述碱显影液，优选例如碳酸钠、碳酸氢钠、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。Moreover, as said alkali developing solution, for example, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-[5.4.0]-7 are preferable, for example -Aqueous solution of undecene, 1,5-diazabicyclo-[4.3.0]-5-nonene, etc.
碱显影液中也可适量添加例如甲醇、乙醇等水溶性有机溶剂、表面活性剂等。另外，碱显影后通常进行水洗。For example, an appropriate amount of water-soluble organic solvents such as methanol and ethanol, and surfactants may be added to the alkaline developer. In addition, water washing is usually performed after alkali development.
作为显影处理法，可以使用喷淋显影法、喷雾显影法、浸渍显影法、浸置式(覆液)显影法等。显影条件优选为在常温下进行5～300秒。As the development treatment method, a shower development method, a spray development method, an immersion development method, an immersion (liquid-coated) development method, or the like can be used. The development conditions are preferably performed at normal temperature for 5 to 300 seconds.
后烘烤的条件通常为在180～280℃下进行10～60分钟左右。The conditions of the post-baking are usually about 10 to 60 minutes at 180 to 280°C.
这样形成的像素的膜厚通常为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.
此外，作为制造彩色滤光片的第二种方法，可以采用在日本特开平7－318723号公报、日本特开2000－310706号公报等中公开的用喷墨方式得到各色像素的方法。在该方法中，首先在基板表面上形成兼具遮光功能的隔壁。然后，在形成的隔壁内用喷墨装置喷射例如蓝色的本发明的热固性着色组合物的液状组合物，之后进行预烘烤，蒸发溶剂。然后，在根据需要对该涂膜曝光后，进行后烘烤使其固化，形成蓝色的像素图案。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 Japanese Patent Laid-Open No. 7-318723, Japanese Patent Laid-Open No. 2000-310706 and the like can be used. In this method, first, a partition wall having a light-shielding function is formed on the surface of the substrate. Then, the liquid composition of the thermosetting coloring composition of the present invention, for example, blue, is sprayed with an ink jet device in the formed partition wall, and then prebaking is performed to evaporate the solvent. Then, after exposing the coating film as necessary, post-baking is performed to cure it, and a blue pixel pattern is formed.
然后，使用绿色或红色的各热固性着色组合物，与上述同样地在同一基板上依次形成绿色的像素图案和红色的像素图案。由此得到在基板上配置有蓝、绿和红三原色的像素图案的彩色滤光片。但是，在本发明中，形成各色像素的顺序不限于上述顺序。Then, using each green or red thermosetting coloring composition, a green pixel pattern and a red pixel pattern were sequentially formed on the same substrate in the same manner as described above. In this way, a color filter in which pixel patterns of three primary colors of blue, green and red are arranged on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above-mentioned order.
另外，隔壁不仅具有遮光功能，还起到使喷射到区划内的各色热固性着色组合物不混色的作用，因此，与上述第一种方法中使用的黑色矩阵相比，膜厚厚。所以，隔壁通常用黑色放射线敏感性组合物形成。In addition, the partition wall not only has a light-shielding function but also functions to prevent the color mixing of the thermosetting coloring compositions sprayed into the partitions, so that the film thickness is thicker than that of the black matrix used in the above-mentioned first method. Therefore, the partition walls are usually formed with a black radiation-sensitive composition.
形成彩色滤光片时使用的基板、放射线的光源、此外还有预烘烤、后烘烤的方法和条件与上述第一种方法相同。这样，通过喷墨方式形成的像素的膜厚与隔壁的高度为相同程度。The substrate used in forming the color filter, the light source for radiation, and the methods and conditions of pre-baking and post-baking are the same as the above-mentioned first method. In this way, the film thickness of the pixel formed by the ink jet method is approximately the same as the height of the partition wall.
根据需要在这样形成的像素图案上形成保护膜之后，通过溅射法形成透明导电膜。也可在形成透明导电膜后进一步形成间隔件，由此制成彩色滤光片。间隔件通常用放射线敏感性组合物形成，但也可以制成具有遮光性的间隔件(黑色间隔件)。这种情况下，使用分散有黑色着色剂的着色放射线敏感性组合物，但本发明的着色组合物也可良好地用于该黑色间隔件的形成。After forming a protective film on the pixel pattern thus formed as necessary, a transparent conductive film is formed by a sputtering method. After forming the transparent conductive film, spacers may be further formed, thereby producing a color filter. The spacer is usually formed of a radiation-sensitive composition, but a light-shielding spacer (black spacer) may also be used. In this case, the colored radiation-sensitive composition in which the black colorant is dispersed is used, but the colored composition of the present invention can also be favorably used for the formation of the black spacer.
本发明的着色组合物在形成上述彩色滤光片中使用的各色像素、黑色矩阵、黑色间隔件等任一着色固化膜时均能够良好地使用。The coloring composition of the present invention can be favorably used when forming any colored cured films such as pixels of each color, black matrix, and black spacer used for the above-mentioned color filter.
含有通过这种方法形成的本发明的着色固化膜的彩色滤光片具有极高的亮度和着色力，因而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、电子纸等极其有用。另外，后述的显示元件只要具有至少1种以上使用本发明的着色组合物形成的着色固化膜即可。The color filter containing the colored cured film of the present invention formed by this method has extremely high brightness and tinting strength, and is therefore suitable for color liquid crystal display elements, color image pickup tube elements, color sensors, organic EL display elements, electronic paper, etc. Extremely useful. Moreover, the display element mentioned later should just have at least 1 type of colored cured film formed using the coloring composition of this invention.
显示元件display element
本发明的显示元件具有本发明的着色固化膜。作为显示元件，可以是彩色液晶显示器、有机EL显示元件、电子纸等。The display element of this invention has the colored cured film of this invention. As the display element, a color liquid crystal display, an organic EL display element, electronic paper, and the like can be used.
具有本发明的着色固化膜的彩色液晶显示元件可以是透射型也可以是反射型，可以采用适宜的结构。例如可以采用如下结构：将彩色滤光片形成在与配置有薄膜晶体管(TFT)的驱动用基板不同的基板上，驱动用基板与形成有彩色滤光片的基板夹着液晶层彼此相向。进而还可采用如下结构：在配置有薄膜晶体管(TFT)的驱动用基板的表面上形成有彩色滤光片的基板与形成有ITO(掺杂有锡的氧化铟)电极的基板夹着液晶层彼此相向。后者的结构具有能够格外地提高开口率、能够得到明亮、高精细的液晶显示元件的优点。另外，在采用后者的结构的情况下，黑色矩阵和黑色间隔件可以形成在形成有彩色滤光片的基板一侧和形成有ITO的基板一侧中的任一侧。The color liquid crystal display element having the colored cured film of the present invention may be of a transmission type or a reflection type, and an appropriate structure may be employed. For example, a structure in which the color filter is formed on a substrate different from the driving substrate on which thin film transistors (TFTs) are arranged may be adopted, and the driving substrate and the substrate on which the color filter is formed face each other with the liquid crystal layer interposed therebetween. Furthermore, a structure in which a color filter is formed on the surface of a driving substrate on which thin film transistors (TFTs) are arranged and a substrate on which ITO (indium tin-doped oxide) electrodes are formed sandwich a liquid crystal layer may be adopted. towards each other. The latter structure has the advantage that the aperture ratio can be remarkably increased, and a bright, high-definition liquid crystal display element can be obtained. In addition, in the case of adopting the latter structure, the black matrix and the black spacer may be formed on either the side of the substrate on which the color filter is formed or the side of the substrate on which the ITO is formed.
具有本发明的着色固化膜的彩色液晶显示元件除了冷阴极荧光管(CCFL：coldcathode fluorescent lamp)外，可具有以白色LED为光源的背光单元。作为白色LED，例如可以是组合红色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、红色发光荧光体和绿色发光荧光体、通过混色而得到白色光的白色LED，通过蓝色LED和YAG荧光体的混色而得到白色光的白色LED，组合蓝色LED、橙色发光荧光体和绿色发光荧光体、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 element having the colored cured film of the present invention may have a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL: coldcathode fluorescent lamp). Examples of white LEDs include white LEDs that combine red LEDs, green LEDs, and blue LEDs to obtain white light by color mixing, and white LEDs that combine blue LEDs, red LEDs, and green phosphors to obtain white light by color mixing, Combining blue LED, red light-emitting phosphor and green light-emitting phosphor, white LED that obtains white light by color mixing, white LED that obtains white light by color mixing of blue LED and YAG phosphor, blue LED, orange light emission Phosphors and green light-emitting phosphors, white LEDs that obtain white light by color mixing, ultraviolet LEDs, red light-emitting phosphors, green light-emitting phosphors, and blue light-emitting phosphors, white LEDs that obtain white light by color mixing, and the like.
具有本发明的着色固化膜的彩色液晶显示元件可以采用TN(扭曲向列)型、STN(超扭曲向列)型、IPS(共面开关)型、VA(垂直取向)型、OCB(光学补偿双折射)型等适宜的液晶模式。The color liquid crystal display element having the colored cured film of the present invention can adopt TN (twisted nematic) type, STN (super twisted nematic) type, IPS (coplanar switching) type, VA (vertical alignment) type, OCB (optical compensation) type birefringence) type and other suitable liquid crystal modes.
此外，具有本发明的着色固化膜的有机EL显示元件可以采用适宜的结构，例如可以是在日本特开平11－307242号公报中公开的结构。Moreover, the organic electroluminescent display element which has the colored cured film of this invention can employ|adopt a suitable structure, for example, the structure disclosed in Unexamined-Japanese-Patent No. 11-307242 can be used.
此外，具有本发明的着色固化膜的电子纸可以采用适宜的结构，例如可以是在日本特开2007－41169号公报中公开的结构。Moreover, the electronic paper which has the colored cured film of this invention can take a suitable structure, for example, the structure disclosed in Unexamined-Japanese-Patent No. 2007-41169 can be used.
〔实施例〕[Example]
下面通过列举实施例进一步对本发明的实施方式进行具体说明。但本发明并不限于下述实施例。The embodiments of the present invention will be further specifically described below by citing examples. 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
(式(1)表示的不饱和单体(a1)的合成)(Synthesis of unsaturated monomer (a1) represented by formula (1))
向装有搅拌子并预先进行过氮置换的1L的三颈瓶中加入三(二亚苄基丙酮)二钯(0)3.36g(3.67mmol)、(±)－2,2’－双(二苯膦基)－1,1’－联萘4.58g(7.36mmol)和预先通过氮气鼓泡进行过脱气的1,2－二甲氧基乙烷450mL，在氮气流下、在80℃搅拌1小时。然后，将混合物冷却至40℃以下，在不使空气进入体系内的情况下依次加入叔丁醇钠25.0g(0.260mol)、4－氨基环己醇23.0g(0.200mol)、1－溴萘38.0g(0.184mol)，回流下搅拌3小时。之后，将反应混合物冷却到室温，用硅藻土过滤，并用乙酸乙酯清洗不溶物，将所得溶液用旋转蒸发仪减压浓缩。将所得残渣通过硅胶柱色谱进行精制，得到33.0g(0.137mol、收率74％)的饴状固体。将该化合物作为(A1)。To a 1 L three-necked flask equipped with a stirring bar and previously substituted with nitrogen, 3.36 g (3.67 mmol) of tris(dibenzylideneacetone)dipalladium(0), (±)-2,2'-bis( Diphenylphosphino)-1,1'-binaphthyl 4.58 g (7.36 mmol) and 450 mL of 1,2-dimethoxyethane previously degassed by nitrogen bubbling were stirred at 80°C under nitrogen flow 1 hour. Then, the mixture was cooled to below 40°C, and 25.0 g (0.260 mol) of sodium tert-butoxide, 23.0 g (0.200 mol) of 4-aminocyclohexanol, and 1-bromonaphthalene were sequentially added without introducing air into the system. 38.0 g (0.184 mol), stirred under reflux for 3 hours. After that, the reaction mixture was cooled to room temperature, filtered through Celite, and insolubles were washed with ethyl acetate, and the resulting solution was concentrated under reduced pressure using a rotary evaporator. The obtained residue was purified by silica gel column chromatography to obtain 33.0 g (0.137 mol, yield 74%) of a caramel-like solid. This compound is taken as (A1).
〔化学式4〕[Chemical formula 4]
向装有搅拌子并预先进行过氮置换的500mL的三颈瓶中加入上述化合物(A1)12.0g(0.0497mol)、三乙胺7.55g(0.0746mol)、4－二甲氨基吡啶6.07g(0.0497mol)、乙酸乙酯250mL，冷却至内温5℃。在使内温不超过10℃的情况下向该混合物中滴加甲基丙烯酰氯6.24g(0.0259mol)，然后，使内温升至室温，在氮气流下、在同一温度搅拌4小时。之后，用水300mL、饱和食盐水300mL依次清洗反应混合物，用无水硫酸钠干燥有机层后，用旋转蒸发仪减压浓缩至40g。然后，加入甲苯200g，用旋转蒸发仪减压浓缩至40g，再加入甲苯85g。在室温下向所得溶液中依次加入4,4’－双(二乙基氨基)二苯甲酮20.5g(0.0633mol)、4－甲氧基苯酚0.100g、磷酰氯8.05g(0.0518mol)，在氮气流下、在100℃搅拌2小时。之后，将反应混合物冷却至室温，用旋转蒸发仪减压蒸馏除去大部分甲苯，将所得残渣溶解在氯仿500mL中，用水500mL进行水洗。用旋转蒸发仪对有机层进行减压浓缩，向所得残渣中加入丙酮，使合计重量为400g。将这里所得的溶液滴加到二异丙醚3200g中，滤取所得固体。将该固体在50℃下减压干燥12小时，得到18.0g(0.0276mol、收率56％)的着色固体。将该化合物作为(A2)。To a 500 mL three-necked flask equipped with a stirring bar and previously subjected to nitrogen replacement, 12.0 g (0.0497 mol) of the above compound (A1), 7.55 g (0.0746 mol) of triethylamine, and 6.07 g of 4-dimethylaminopyridine ( 0.0497mol), 250 mL of ethyl acetate, and cooled to an inner temperature of 5°C. To the mixture was added dropwise 6.24 g (0.0259 mol) of methacryloyl chloride so that the internal temperature did not exceed 10°C, and the internal temperature was raised to room temperature, followed by stirring at the same temperature for 4 hours under nitrogen flow. Then, the reaction mixture was washed with 300 mL of water and 300 mL of saturated brine in this order, and the organic layer was dried over anhydrous sodium sulfate, and then concentrated to 40 g under reduced pressure with a rotary evaporator. Then, 200 g of toluene was added, and the mixture was concentrated under reduced pressure to 40 g with a rotary evaporator, and then 85 g of toluene was added. To the obtained solution at room temperature, 20.5 g (0.0633 mol) of 4,4'-bis(diethylamino)benzophenone, 0.100 g (0.100 g of 4-methoxyphenol) and 8.05 g (0.0518 mol) of phosphorus oxychloride were sequentially added, It was stirred at 100°C for 2 hours under nitrogen flow. Then, the reaction mixture was cooled to room temperature, most of the toluene was distilled off under reduced pressure with a rotary evaporator, the obtained residue was dissolved in 500 mL of chloroform, and washed with 500 mL of water. The organic layer was concentrated under reduced pressure with a rotary evaporator, and acetone was added to the obtained residue to make the total weight 400 g. The solution obtained here was added dropwise to 3200 g of diisopropyl ether, and the obtained solid was collected by filtration. The solid was dried under reduced pressure at 50°C for 12 hours to obtain 18.0 g (0.0276 mol, yield 56%) of a colored solid. This compound is taken as (A2).
〔化学式5〕[Chemical formula 5]
向装有搅拌子的100mL锥形瓶中加入上述化合物(A2)9.00g(13.8mmol)、双(三氟甲磺酰)亚胺锂5.94g(20.7mmol)，再添加乙酸乙酯90mL、离子交换水90mL，室温下搅拌约2小时。然后分离除去水层，将有机层用离子交换水100mL清洗3次。将有机层在减压下浓缩后，将残渣在50℃下减压干燥12小时，由此得到下述式(A3)表示的化合物11.4g(12.7mmol、收率92％)。将该化合物作为(A3)。To a 100 mL conical flask equipped with a stirring bar, 9.00 g (13.8 mmol) of the above-mentioned compound (A2), 5.94 g (20.7 mmol) of lithium bis(trifluoromethanesulfonyl)imide were added, and 90 mL of ethyl acetate, ion 90 mL of water was exchanged, and the mixture was stirred at room temperature for about 2 hours. Then, the aqueous layer was separated and removed, and the organic layer was washed three times with 100 mL of ion-exchanged water. The organic layer was concentrated under reduced pressure, and the residue was dried under reduced pressure at 50° C. for 12 hours to obtain 11.4 g (12.7 mmol, 92% yield) of a compound represented by the following formula (A3). This compound is taken as (A3).
〔化学式6〕[Chemical formula 6]
(聚合物(1)的合成)(Synthesis of polymer (1))
将装有搅拌子且安装有回流冷却管和温度计的100mL三颈瓶充分氮置换，加入环己酮15.0g，在氮气流下加热到内温80±2℃。混合化合物(A3)4.50g(5.02mmol)、甲基丙烯酸甲酯6.00g(59.9mmol)、甲基丙烯酸4.50g(52.3mmol)、聚合引发剂V－65(和光纯药公司产品)2.18g(8.79mmol)、环己酮45.0g，调制成溶液，保持内温为80±2℃，将该溶液用泵花2小时滴加至三颈瓶中。滴加结束后，在同一温度下再继续搅拌1小时。然后，将使0.728g(2.93mmol)2,2’－偶氮双(2,4－二甲基戊腈)(和光纯药公司产品，商品名V－65)溶解在环己酮1.13g中所得的溶液一次加入反应混合物中，在同一温度下搅拌30分钟，继续在95℃下搅拌30分钟。将反应液冷却至室温，再将其滴加到大量己烷中，得到着色固体，将该着色固体在50℃下减压干燥，得到下述结构式表示的聚合物13.9g(收率93％)。所得聚合物(1)的Mw为5,100。将该聚合物作为着色剂(A－1)。A 100 mL three-necked flask equipped with a stirring bar, a reflux cooling tube and a thermometer was fully nitrogen replaced, 15.0 g of cyclohexanone was added, and heated to an internal temperature of 80±2°C under nitrogen flow. Mixed compound (A3) 4.50 g (5.02 mmol), methyl methacrylate 6.00 g (59.9 mmol), methacrylic acid 4.50 g (52.3 mmol), polymerization initiator V-65 (product of Wako Pure Chemical Industries) 2.18 g ( 8.79 mmol) and 45.0 g of cyclohexanone were prepared into a solution, the internal temperature was kept at 80±2° C., and the solution was added dropwise to a three-necked flask using a pump over 2 hours. After the dropwise addition was completed, stirring was continued at the same temperature for another 1 hour. Then, 0.728 g (2.93 mmol) of 2,2'-azobis(2,4-dimethylvaleronitrile) (product of Wako Pure Chemical Industries, trade name V-65) was dissolved in 1.13 g of cyclohexanone The resulting solution was added to the reaction mixture in one portion, stirred at the same temperature for 30 minutes and continued at 95°C for 30 minutes. The reaction solution was cooled to room temperature and added dropwise to a large amount of hexane to obtain a colored solid, which was dried under reduced pressure at 50°C to obtain 13.9 g of a polymer represented by the following structural formula (yield: 93%) . The Mw of the obtained polymer (1) was 5,100. This polymer was used as a coloring agent (A-1).
〔化学式7〕[Chemical formula 7]
合成例2Synthesis Example 2
(聚合物(2)的合成)(Synthesis of polymer (2))
将装有搅拌子且安装有回流冷却管和温度计的100mL三颈瓶充分氮置换，加入环己酮15.0g，在氮气流下加热到内温70±2℃。混合化合物(A3)4.50g(5.02mmol)、甲基丙烯酸甲酯3.00g(30.0mmol)、甲基丙烯酸缩水甘油酯3.00g(21.1mmol)、甲基丙烯酸4.50g(52.3mmol)、聚合引发剂V－65(和光纯药公司产品)2.02g(8.13mmol)、环己酮45.0g，调制成溶液，保持内温为70±2℃，将该溶液用泵花2小时滴加至三颈瓶中。滴加结束后，在同一温度下再继续搅拌1小时。然后，将使0.728g(2.71mmol)2,2’－偶氮双(2,4－二甲基戊腈)(和光纯药公司产品，商品名V－65)溶解在环己酮1.16g中所得的溶液一次加入反应混合物中，在同一温度下搅拌3小时。将反应液冷却至室温，再将其滴加到大量己烷中，得到着色固体，将该着色固体在50℃下减压干燥，得到下述结构式表示的聚合物14.1g(收率94％)。所得聚合物(2)的Mw为5,300。将该聚合物作为着色剂(A－2)。A 100 mL three-necked flask equipped with a stirring bar, a reflux cooling tube and a thermometer was fully nitrogen replaced, 15.0 g of cyclohexanone was added, and heated to an internal temperature of 70±2°C under nitrogen flow. Mixed compound (A3) 4.50 g (5.02 mmol), methyl methacrylate 3.00 g (30.0 mmol), glycidyl methacrylate 3.00 g (21.1 mmol), methacrylic acid 4.50 g (52.3 mmol), polymerization initiator 2.02 g (8.13 mmol) of V-65 (product of Wako Pure Chemical Industries, Ltd.) and 45.0 g of cyclohexanone were prepared into a solution, and the internal temperature was kept at 70±2°C, and the solution was added dropwise to a three-necked flask using a pump for 2 hours. middle. After the dropwise addition was completed, stirring was continued at the same temperature for another 1 hour. Then, 0.728 g (2.71 mmol) of 2,2'-azobis(2,4-dimethylvaleronitrile) (product of Wako Pure Chemical Industries, trade name V-65) was dissolved in 1.16 g of cyclohexanone The resulting solution was added to the reaction mixture in one portion and stirred at the same temperature for 3 hours. The reaction solution was cooled to room temperature, and then added dropwise to a large amount of hexane to obtain a colored solid, which was dried under reduced pressure at 50°C to obtain 14.1 g of a polymer represented by the following structural formula (yield: 94%) . The Mw of the obtained polymer (2) was 5,300. This polymer was used as a coloring agent (A-2).
〔化学式8〕[Chemical formula 8]
合成例3～11Synthesis Examples 3 to 11
除了在合成例2中将不饱和单体(a1)和不饱和单体(a2)的种类和量变更为表1所示以外，与合成例2同样地合成了聚合物(3)～(11)。将所得聚合物(3)～(11)分别作为着色剂(A－6)～(A－14)。此外，在表2中以物质量记载所使用的不饱和单体(a1)和不饱和单体(a2)的量，并将本着色剂中的不饱和单体(a1)的共聚比例用“p”、本着色剂中的不饱和单体(a2)的共聚比例用“r”、以及不饱和单体(a2)中的具有含氧饱和杂环基的(甲基)丙烯酸酯和(甲基)丙烯酸芳基酯的共聚比例用“s”表示。Polymers (3) to (11 were synthesized in the same manner as in Synthesis Example 2, except that the types and amounts of the unsaturated monomer (a1) and the unsaturated monomer (a2) were changed to those shown in Table 1 in Synthesis Example 2. ). The obtained polymers (3) to (11) were used as colorants (A-6) to (A-14), respectively. In addition, in Table 2, the amount of the unsaturated monomer (a1) and the unsaturated monomer (a2) used is described in terms of the material amount, and the copolymerization ratio of the unsaturated monomer (a1) in the colorant is used as " p", the copolymerization ratio of the unsaturated monomer (a2) in the colorant is "r", and the (meth)acrylate and (methyl) acrylate having an oxygen-containing saturated heterocyclic group in the unsaturated monomer (a2) The copolymerization ratio of aryl acrylate is denoted by "s".
表1Table 1
表2Table 2
在表1～2中，各成分如下所示。In Tables 1 and 2, each component is shown below.
(A3)：上述化合物(A3)(A3): the above-mentioned compound (A3)
MMA：甲基丙烯酸甲酯MMA: methyl methacrylate
GMA：甲基丙烯酸缩水甘油酯GMA: Glycidyl Methacrylate
OXMA：3－(甲基丙烯酰氧基甲基)－3－乙基氧杂环丁烷OXMA: 3-(methacryloyloxymethyl)-3-ethyloxetane
M100：甲基丙烯酸3,4－环氧环己基酯(商品名CYCLOMER M100，Daicel Chemical公司产品)M100: 3,4-epoxycyclohexyl methacrylate (trade name CYCLOMER M100, product of Daicel Chemical)
MAA：甲基丙烯酸MAA: methacrylic acid
EHMA：甲基丙烯酸2－乙基己酯EHMA: 2-ethylhexyl methacrylate
PhMA：甲基丙烯酸苯酯PhMA: phenyl methacrylate
PMI：N－苯基马来酰亚胺PMI: N-phenylmaleimide
VA：乙酸乙烯酯VA: Vinyl Acetate
比较合成例1Comparative Synthesis Example 1
向装有搅拌子的100mL锥形瓶中加入5.00g(9.72mmol)的C.I.碱性蓝7、双(三氟甲磺酰)亚胺锂4.19g(14.6mmol)，再添加氯仿50mL、离子交换水25mL，室温下搅拌约2小时。然后，分离除去水层，用离子交换水清洗有机层2次。将有机层在减压下浓缩后，将残渣在50℃下减压干燥12小时，由此得到下式表示的化合物5.88g(7.78mmol、收率80％)。将所得化合物作为着色剂(A－3)。5.00 g (9.72 mmol) of C.I. basic blue 7, 4.19 g (14.6 mmol) of lithium bis(trifluoromethanesulfonyl)imide were added to a 100 mL conical flask equipped with a stirring bar, and 50 mL of chloroform, ion exchange 25 mL of water, stirred at room temperature for about 2 hours. Then, the aqueous layer was separated and removed, and the organic layer was washed twice with ion-exchanged water. After concentrating the organic layer under reduced pressure, the residue was dried under reduced pressure at 50° C. for 12 hours to obtain 5.88 g (7.78 mmol, 80% yield) of a compound represented by the following formula. The obtained compound was used as a coloring agent (A-3).
〔化学式9〕[Chemical formula 9]
比较合成例2Comparative Synthesis Example 2
用日本专利第3736221号说明书的实施例中记载的方法合成下述式(A4)表示的化合物的ClO4－盐。然后，除了在上述聚合物(1)的合成中用下述式(A4)表示的化合物的ClO4－盐代替化合物(A3)以外，与聚合物(1)同样地进行合成，得到聚合物。将该聚合物作为着色剂(A－5)。The ClO4-salt of the compound represented by the following formula (A4) was synthesized by the method described in the Example of Japanese Patent No. 3736221. Then, in the synthesis of the above-mentioned polymer (1), the synthesis was carried out in the same manner as the polymer (1), except that the compound (A3) was replaced by ClO4-salt of the compound represented by the following formula (A4) to obtain a polymer. This polymer was used as a colorant (A-5).
〔化学式10〕[Chemical formula 10]
<粘合树脂的合成><Synthesis of binder resin>
合成例12Synthesis Example 12
向带有冷却管和搅拌器的烧瓶中加入丙二醇单甲醚乙酸酯100质量份，进行氮置换。加热到80℃，在同一温度下用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－丙烯酰氧基乙基)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，聚合2小时。然后，将反应溶液的温度升温至100℃，进一步聚合1小时，由此得到粘合树脂溶液(固体成分浓度33质量％)。所得粘合树脂的Mw为12,200，Mn为6,500。将该粘合树脂作为“粘合树脂(C1)”。<着色剂溶液的调制>100 parts by mass of propylene glycol monomethyl ether acetate was added to a flask equipped with a cooling pipe and a stirrer, and nitrogen substitution was performed. Heating to 80°C, 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, and methacrylic acid were added dropwise at the same temperature for 1 hour. 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 A mixed solution of 6 parts by mass and 2,2'-azobis(2,4-dimethylvaleronitrile) was polymerized for 2 hours while maintaining the temperature. Then, the temperature of the reaction solution was raised to 100° C., and the polymerization was further conducted for 1 hour to obtain a binder resin solution (solid content concentration: 33% by mass). The Mw of the obtained binder resin was 12,200, and the Mn was 6,500. This binder resin is called "binder resin (C1)". <Preparation of colorant solution>
调制例1Modulation Example 1
将上述所得的着色剂(A－1)10质量份溶解到丙二醇单甲醚90质量份中，调制出着色剂溶液(A－1)。10 parts by mass of the colorant (A-1) obtained above was dissolved in 90 parts by mass of propylene glycol monomethyl ether to prepare a colorant solution (A-1).
调制例2Modulation example 2
将上述所得的着色剂(A－2)10质量份溶解在丙二醇单甲醚90质量份中，调制出着色剂溶液(A－2)。10 parts by mass of the colorant (A-2) obtained above was dissolved in 90 parts by mass of propylene glycol monomethyl ether to prepare a colorant solution (A-2).
调制例3Preparation example 3
将上述所得的着色剂(A－3)5质量份溶解在丙二醇单甲醚95质量份中，调制出着色剂溶液(A－3)。5 parts by mass of the colorant (A-3) obtained above was dissolved in 95 parts by mass of propylene glycol monomethyl ether to prepare a colorant solution (A-3).
调制例4Preparation example 4
将5质量份的C.I.碱性蓝7溶解在丙二醇单甲醚95质量份中，调制出着色剂溶液(A－4)。5 parts by mass of C.I. Basic Blue 7 was dissolved in 95 parts by mass of propylene glycol monomethyl ether to prepare a colorant solution (A-4).
调制例5～14Preparation Examples 5 to 14
除了在调制例1中用着色剂(A－5)～(A－14)代替着色剂(A－1)以外，与调制例1同样地调制出着色剂溶液(A－5)～(A－14)。The colorant solutions (A-5) to (A- 14).
<颜料分散液的调制><Preparation of Pigment Dispersion>
调制例15Preparation example 15
使用作为着色剂的15质量份的C.I.颜料蓝15:6、作为分散剂的BYK－LPN21116(毕克化学(BYK)公司产品)12.5质量份(固体成分浓度40质量％)、作为溶剂的丙二醇单甲醚乙酸酯72.5质量份，用珠磨机进行处理，调制出颜料分散液(a－1)。调制例1615 parts by mass of C.I. Pigment Blue 15:6 as a colorant, 12.5 parts by mass of BYK-LPN21116 (product of BYK) as a dispersant (solid content concentration of 40% by mass), and propylene glycol monohydrate as a solvent 72.5 parts by mass of methyl ether acetate was treated with a bead mill to prepare a pigment dispersion liquid (a-1). Preparation example 16
使用作为着色剂的15质量份的C.I.颜料绿58、作为分散剂的BYK－LPN6919(毕克化学(BYK)公司产品)8.3质量份(固体成分浓度60质量％)、作为溶剂的丙二醇单甲醚乙酸酯76.7质量份，用珠磨机进行处理，调制出颜料分散液(a－2)。调制例1715 parts by mass of C.I. Pigment Green 58 as a colorant, 8.3 parts by mass of BYK-LPN6919 (product of BYK) as a dispersant (solid content concentration 60% by mass), and propylene glycol monomethyl ether as a solvent 76.7 parts by mass of acetate was treated with a bead mill to prepare a pigment dispersion liquid (a-2). Preparation Example 17
使用作为着色剂的15质量份的C.I.颜料黄138、作为分散剂的BYK－LPN21116(毕克化学(BYK)公司产品)12.5质量份(固体成分浓度40质量％)、作为溶剂的丙二醇单甲醚乙酸酯72.5质量份，用珠磨机进行处理，调制出颜料分散液(a－3)。实施例115 parts by mass of C.I. Pigment Yellow 138 as a colorant, 12.5 parts by mass (solid content concentration 40% by mass) of BYK-LPN21116 (product of BYK) as a dispersant, and propylene glycol monomethyl ether as a solvent 72.5 parts by mass of acetate was processed with a bead mill to prepare a pigment dispersion liquid (a-3). Example 1
将作为(A)着色剂的颜料分散液(a－1)30.5质量份、着色剂溶液(A－1)23.0质量份、作为(C)粘合树脂的粘合树脂(C1)溶液(固体成分浓度33质量％)26.3质量份、作为(B)聚合性化合物的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(日本化药公司产品，商品名KAYARAD DPHA)9.9质量份、作为光聚合引发剂的2－苄基－2－二甲基氨基－1－(4－吗啉基苯基)丁烷－1－酮(商品名Irgacure369，汽巴精化公司产品)1.8质量份和NCI－930(ADEKA公司产品)0.1质量份、作为氟类表面活性剂的Megafac F－554(DIC公司产品)0.05质量份和作为溶剂的丙二醇单甲醚乙酸酯混合，调制出固体成分浓度20质量％的蓝色着色组合物(B－1)。30.5 parts by mass of pigment dispersion liquid (a-1) as (A) colorant, 23.0 parts by mass of colorant solution (A-1), and binder resin (C1) solution (solid content) as (C) binder resin Concentration 33% by mass) 26.3 parts by mass, (B) a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (product of Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as (B) polymerizable compound, 9.9 parts by mass, as photopolymerization initiator 1.8 parts by mass of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one (trade name Irgacure369, product of Ciba Refinery Co., Ltd.) and NCI-930 (product of ADEKA) 0.1 part by mass, 0.05 part by mass of Megafac F-554 (product of DIC) as a fluorosurfactant, and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a solid concentration of 20% by mass. A blue coloring composition (B-1).
耐热性评价Heat resistance evaluation
在将蓝色着色组合物(B－1)用旋涂机涂布到表面形成有防止钠离子溶出的SiO2膜的钠玻璃基板上之后，用90℃的热板进行2分钟预烘烤，形成膜厚2.5μm的涂膜。After applying the blue coloring composition (B-1) to the soda glass substrate on which the SiO2 film preventing the elution of sodium ions was formed on the surface by a spin coater, prebaking was performed on a hot plate at 90° C. for 2 minutes, A coating film with a film thickness of 2.5 μm was formed.
然后，将该基板冷却到室温后，用高压汞灯介由光掩模对涂膜照射包括365nm、405nm和436nm各波长的放射线，以400J/m2的曝光量进行曝光。之后，向这些基板以1kgf/cm2(喷嘴径1mm)的显影压喷射23℃的由0.04质量％的氢氧化钾水溶液构成的显影液，进行90秒喷淋显影。然后，用超纯水清洗该基板，风干后，进一步在200℃的洁净烘箱内进行30分钟后烘烤，由此在基板上形成点图案。Then, after cooling the substrate to room temperature, the coating film was irradiated with radiation having wavelengths of 365 nm, 405 nm, and 436 nm through a photomask using a high-pressure mercury lamp at an exposure amount of 400 J/m2 . Then, the developing solution which consists of a 0.04 mass % potassium hydroxide aqueous solution at 23 degreeC was sprayed to these board|substrates with the developing pressure of 1 kgf/cm<2 > (nozzle diameter 1 mm), and the shower development was performed for 90 seconds. Then, the substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 200° C. for 30 minutes, thereby forming a dot pattern on the substrate.
对于所得点图案，使用彩色分析仪(大塚电子公司生产的MCPD2000)以C光源、2度视野测定了CIE显色体系中的色度坐标值(x,y)和刺激值(Y)。About the obtained dot pattern, the chromaticity coordinate value (x, y) and stimulus value (Y) in the CIE color development system were measured using a color analyzer (MCPD2000 by Otsuka Electronics Co., Ltd.) with a C light source and a 2-degree field of view.
然后，在将上述基板在230℃下追加烘烤90分钟后，测定色度坐标值(x，y)和刺激值(Y)，对追加烘烤前后的色变化、即⊿E*ab进行了评价。其结果，将⊿E*ab值小于3.0的情况评价为“○”，在3.0以上、小于5.0的情况评价为“△”，5.0以上的情况评价为“×”。评价结果示于表3。⊿E*ab值越小，说明耐热性越良好。Then, after the above-mentioned substrate was additionally baked at 230° C. for 90 minutes, the chromaticity coordinate values (x, y) and the stimulus value (Y) were measured, and the color change before and after additional baking, that is, ⊿E* ab, was measured. Evaluation. As a result, the case where the ⊿E* ab value was less than 3.0 was evaluated as "○", the case of 3.0 or more and less than 5.0 was evaluated as "△", and the case of 5.0 or more was evaluated as "x". The evaluation results are shown in Table 3. ⊿ The smaller the E* ab value, the better the heat resistance.
耐溶剂性评价Solvent resistance evaluation
在将蓝色着色组合物(B－1)用旋涂机涂布到表面形成有防止钠离子溶出的SiO2膜的钠玻璃基板上之后，用90℃的热板进行2分钟预烘烤，形成膜厚2.5μm的涂膜。After applying the blue coloring composition (B-1) to the soda glass substrate on which the SiO2 film preventing the elution of sodium ions was formed on the surface by a spin coater, prebaking was performed on a hot plate at 90° C. for 2 minutes, A coating film with a film thickness of 2.5 μm was formed.
然后，将该基板冷却到室温后，用高压汞灯介由光掩模对涂膜照射包括365nm、405nm和436nm各波长的放射线，以400J/m2的曝光量进行曝光。之后，向这些基板以1kgf/cm2(喷嘴径1mm)的显影压喷射23℃的由0.04质量％的氢氧化钾水溶液构成的显影液，进行90秒喷淋显影。然后，用超纯水清洗该基板，风干后，进一步在230℃的洁净烘箱内进行30分钟后烘烤，由此在基板上形成点图案。然后，将上述基板在80℃的丙二醇单甲醚乙酸酯中浸渍40分钟。Then, after cooling the substrate to room temperature, the coating film was irradiated with radiation having wavelengths of 365 nm, 405 nm, and 436 nm through a photomask using a high-pressure mercury lamp at an exposure amount of 400 J/m2 . Then, the developing solution which consists of a 0.04 mass % potassium hydroxide aqueous solution at 23 degreeC was sprayed to these board|substrates with the developing pressure of 1 kgf/cm<2 > (nozzle diameter 1 mm), and the shower development was performed for 90 seconds. Then, the substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230° C. for 30 minutes to form a dot pattern on the substrate. Then, the said board|substrate was immersed in 80 degreeC propylene glycol monomethyl ether acetate for 40 minutes.
分别测定浸渍前后的色度坐标值(x，y)和刺激值(Y)，对浸渍前后的色变化即⊿E*ab进行了评价。其结果，将⊿E*ab值小于3.0的情况评价为“○”，在3.0以上、小于5.0的情况评价为“△”，在5.0以上的情况评价为“×”。评价结果示于表3。⊿E*ab值越小，说明耐溶剂性越良好。The chromaticity coordinate values (x, y) and stimulus value (Y) before and after immersion were measured, respectively, and the color change before and after immersion, ie, ⊿E* ab, was evaluated. As a result, the case where the ⊿E* ab value was less than 3.0 was evaluated as "○", the case of 3.0 or more and less than 5.0 was evaluated as "△", and the case of 5.0 or more was evaluated as "x". The evaluation results are shown in Table 3. ⊿ The smaller the E* ab value, the better the solvent resistance.
移染性评价Migration evaluation
在将通过后述方法调制出的绿色着色组合物(G－1)用旋涂机涂布在表面上形成有防止钠离子溶出的SiO2膜的钠玻璃基板上之后，用90℃的热板进行2分钟预烘烤，形成膜厚2.4μm的涂膜。After applying the green coloring composition (G-1) prepared by the method described later on the soda glass substrate on which the SiO2 film preventing the elution of sodium ions was formed on the surface by a spin coater, the green coloring composition (G-1) was coated with a hot plate at 90° C. Prebaking was performed for 2 minutes to form a coating film with a film thickness of 2.4 μm.
然后，在将该基板冷却至室温后，使用高压汞灯在不介由光掩模的情况下对涂膜照射包括365nm、405nm和436nm各波长的放射线，以400J/m2的曝光量进行整面曝光。之后，向这些基板以1kgf/cm2(喷嘴径1mm)的显影压喷射23℃的由0.04质量％的氢氧化钾水溶液构成的显影液，进行90秒喷淋显影。然后，用超纯水清洗该基板，风干后，进一步在230℃的洁净烘箱内进行30分钟后烘烤，由此在基板上形成绿色固化膜(T－1)。Then, after cooling the substrate to room temperature, the coating film was irradiated with radiation including wavelengths of 365 nm, 405 nm, and 436 nm using a high-pressure mercury lamp without interposing a photomask, and adjusted at an exposure amount of 400 J/m2 . face exposure. Then, the developing solution which consists of a 0.04 mass % potassium hydroxide aqueous solution at 23 degreeC was sprayed to these board|substrates with the developing pressure of 1 kgf/cm<2 > (nozzle diameter 1 mm), and the shower development was performed for 90 seconds. Then, the substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230° C. for 30 minutes to form a green cured film (T-1) on the substrate.
在将蓝色着色组合物(B－1)用旋涂机涂布到绿色固化膜(T－1)上之后，用90℃热板进行2分钟预烘烤，形成膜厚2.5μm的涂膜。然后，在将该基板冷却至室温之后，向该基板以1kgf/cm2(喷嘴径1mm)的显影压喷射23℃的由0.04质量％的氢氧化钾水溶液构成的显影液，进行90秒喷淋显影。然后，用超纯水清洗该基板，进行风干。将从在绿色固化膜(T－1)上涂布蓝色着色组合物(B－1)起至风干之间的工序称为(工序－1)。After applying the blue coloring composition (B-1) on the green cured film (T-1) with a spin coater, prebaking was performed on a 90° C. hot plate for 2 minutes to form a coating film with a film thickness of 2.5 μm . Then, after cooling the substrate to room temperature, a developing solution composed of a 0.04 mass % potassium hydroxide aqueous solution at 23° C. was sprayed onto the substrate at a developing pressure of 1 kgf/cm2 (nozzle diameter 1 mm), and sprayed for 90 seconds. development. Then, the substrate was washed with ultrapure water and air-dried. The process from apply|coating blue coloring composition (B-1) to air-drying on the green cured film (T-1) is called (process-1).
在(工序－1)前后分别测定绿色固化膜(T－1)的刺激值(Y)，对(工序－1)前后的刺激值变化即⊿Y进行评价。其结果，将⊿Y值小于0.2的情况评价为“○”，将在0.2以上、小于0.7的情况评价为“△”，将在0.7以上的情况评价为“×”。评价结果示于表3。⊿Y值越小，说明移染性越受到抑制。The stimulus value (Y) of the green cured film (T-1) was measured before and after (step-1), respectively, and ⊿Y, which is a change in stimulus value before and after (step-1), was evaluated. As a result, the case where the ⊿Y value was less than 0.2 was evaluated as "○", the case of 0.2 or more and less than 0.7 was evaluated as "△", and the case of 0.7 or more was evaluated as "x". The evaluation results are shown in Table 3. The smaller the ⊿Y value, the more inhibited the dye migration.
移染性评价中使用的绿色着色组合物(G－1)的调制方法如下。The preparation method of the green coloring composition (G-1) used for migration property evaluation is as follows.
将作为(A)着色剂的颜料分散液(a－2)30.5质量份、颜料分散液(a－3)25.0质量份、作为(C)粘合树脂的粘合树脂(C1)溶液(固体成分浓度33质量％)26.3质量份、作为(B)聚合性化合物的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(日本化药公司产品，商品名KAYARAD DPHA)9.9质量份、作为光聚合引发剂的2－苄基－2二甲基氨基－1－(4－吗啉基苯基)丁烷－1－酮(商品名Irgacure369，汽巴精化公司产品)1.8质量份和NCI－930(ADEKA公司产品)0.1质量份、作为氟类表面活性剂的Megafac F－554(DIC公司产品)0.05质量份和作为溶剂的丙二醇单甲醚乙酸酯混合，调制出固体成分浓度20质量％的绿色着色组合物(G－1)。30.5 parts by mass of pigment dispersion liquid (a-2) as (A) colorant, 25.0 parts by mass of pigment dispersion liquid (a-3), and binder resin (C1) solution (solid content) as (C) binder resin Concentration 33% by mass) 26.3 parts by mass, (B) a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (product of Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as (B) polymerizable compound, 9.9 parts by mass, as photopolymerization initiator 1.8 parts by mass of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one (trade name Irgacure369, product of Ciba Refinery Co., Ltd.) and NCI-930 ( 0.1 part by mass of ADEKA Co., Ltd.), 0.05 mass part of Megafac F-554 (product of DIC Co., Ltd.) as a fluorosurfactant, and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a green with a solid content concentration of 20 mass % Coloring composition (G-1).
实施例2～6、比较例1～3Examples 2 to 6, Comparative Examples 1 to 3
除了在实施例1中用着色剂溶液(A－2)～(A－9)代替着色剂溶液(A－1)以外，与实施例1同样地调制出蓝色着色组合物(B－2)～(B－9)。并除了用蓝色着色组合物(B－2)～(B－9)代替蓝色着色组合物(B－1)之外，与实施例1同样地进行了耐热性、耐溶剂性和移染性评价。评价结果示于表3。A blue coloring composition (B-2) was prepared in the same manner as in Example 1, except that the coloring agent solutions (A-2) to (A-9) were used instead of the coloring agent solution (A-1) in Example 1. ~ (B-9). Heat resistance, solvent resistance, and migration were performed in the same manner as in Example 1, except that the blue coloring compositions (B-2) to (B-9) were used instead of the blue coloring composition (B-1). Dyeing evaluation. The evaluation results are shown in Table 3.
实施例7Example 7
将作为(A)着色剂的着色剂溶液(A－10)50.0质量份、作为(C)粘合树脂的粘合树脂(C1)溶液(固体成分浓度33质量％)14.4质量份、作为(B)聚合性化合物的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(日本化药公司产品，商品名KAYARAD DPHA)8.2质量份、作为光聚合引发剂的NCI－930(ADEKA公司产品)1.3质量份、2,2’－双(2－氯苯基)－4,4’,5,5’－四苯基－1,2’－联咪唑0.2质量份、2,4－二乙基噻吨酮0.2质量份和2－巯基苯并噻唑0.1质量份、作为氟类表面活性剂的Megafac F－554(DIC公司产品)0.04质量份和作为溶剂的丙二醇单甲醚乙酸酯，调制出固体成分浓度20质量％的蓝色着色组合物(B－10)。50.0 parts by mass of colorant solution (A-10) as (A) colorant, 14.4 parts by mass of binder resin (C1) solution (solid content concentration 33% by mass) as (C) binder resin, and (B) ) 8.2 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (product of Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as a polymerizable compound, 1.3 mass parts of NCI-930 (product of ADEKA company) as a photopolymerization initiator parts, 0.2 parts by mass of 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,4-diethylthioxanthene 0.2 part by mass of ketone, 0.1 part by mass of 2-mercaptobenzothiazole, 0.04 part by mass of Megafac F-554 (product of DIC Corporation) as a fluorosurfactant, and propylene glycol monomethyl ether acetate as a solvent to prepare a solid content A blue coloring composition (B-10) with a concentration of 20% by mass.
然后，除了在实施例1中用蓝色着色组合物(B－10)代替蓝色着色组合物(B－1)以外，与实施例1同样地进行了耐热性、耐溶剂性和移染性评价。评价结果示于表3。Then, heat resistance, solvent resistance, and color migration were performed in the same manner as in Example 1, except that the blue coloring composition (B-10) was used in place of the blue coloring composition (B-1) in Example 1. Sexual evaluation. The evaluation results are shown in Table 3.
实施例8～11Examples 8 to 11
除了在实施例7中用着色剂溶液(A－11)～(A－14)代替着色剂溶液(A－10)以外，与实施例7同样地调制出蓝色着色组合物(B－11)～(B－14)。并除了使用蓝色着色组合物(B－11)～(B－14)代替蓝色着色组合物(B－10)以外，与实施例7同样地进行了耐热性、耐溶剂性和移染性评价。评价结果示于表3。A blue coloring composition (B-11) was prepared in the same manner as in Example 7, except that the coloring agent solutions (A-11) to (A-14) were used instead of the coloring agent solution (A-10) in Example 7. ~ (B-14). Heat resistance, solvent resistance, and dye migration were performed in the same manner as in Example 7, except that the blue coloring compositions (B-11) to (B-14) were used instead of the blue coloring composition (B-10). Sexual evaluation. The evaluation results are shown in Table 3.
表3table 3
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