TW201700627A - Coloring composition, cured coloring film, color filter, display element, and solid-state imaging element which can form a cured coloring film capable of well-balancing and realizing in high standard heat tolerance, solvent resistance, and image-developing - Google Patents

Abstract

The topic of the present invention is to provide a coloring composition, which can form a cured coloring film capable of well-balancing and realizing in high standard heat tolerance, solvent resistance, and the image-developing. The coloring composition of the present invention comprises (A) coloring agent, (B) adhesive resin, and (C) polymeric compound. The abovementioned (A) coloring agent comprises at least one selected from a dye and a dye polymer, wherein the dye polymer has a monomer as the structural unit, which contains dye residues and ethylenically unsaturated groups; (B) the adhesive resin comprises a copolymer of ethylenically unsaturated monomers represented by the below-mentioned formula (1) with the copolymerization ratio above 11 mole% (in which the abovementioned dye polymer is not included). In the formula (1), R1 represents a hydrogen atom or a methyl group, R2 represents an alkanediyl group having2~4 carbon atoms, R3 represents a substituted or unsubstituted phenyl group, or a substituted or unsubstituted polycyclic aromatic hydrocarbon, a substituted or unsubstituted nitrogen-containing cycloaliphatic heterocyclic group, and n represents an integer of 0~100, wherein when n is 2 or more, there are multiple R2 which can be the same or different.

Description

Coloring composition, color hardening film, color filter, display element, and solid-state imaging element

The present invention relates to a coloring composition, a colored cured film, a color filter, a display element, and a solid-state imaging element, and more particularly, to a color liquid crystal display element, a solid-state imaging element, or an organic EL formed in a transmissive or reflective type. A colored composition of a colored cured film used for a display element, an electronic paper, or the like, a colored cured film formed using the colored composition, a color filter including the colored cured film, a display element, and a solid-state imaging element.

When a color filter is produced using a colored radiation-sensitive composition, a method is known in which a pigment-dispersed colored radiation-sensitive composition is applied onto a substrate and dried, and the dried coating film has a desired pattern. The shape is irradiated with radiation (hereinafter referred to as "exposure"), and development is performed to dispose the pixels of the three primary colors of red, green, and blue on the substrate (so-called photolithography. For example, refer to Patent Documents 1 and 2). Further, a method of forming a black matrix by using a photopolymerizable composition in which carbon black is dispersed is also known (for example, refer to Patent Document 3). In addition, a method of obtaining a color-developing resin composition using a pigment dispersion type and obtaining each color pixel by an inkjet method is known (for example, refer to Patent Document 4).

In recent years, high contrast of liquid crystal display elements and high definition of solid-state imaging elements have been strongly demanded, and in order to achieve these objectives, studies using dyes as colorants have been conducted. However, in the case of using a dye as a coloring agent, the heat resistance of the colored pattern becomes insufficient in most cases as compared with the case of using a pigment. In such a background, as a coloring composition which can form a coloring pattern which is excellent in heat resistance and the like, for example, Patent Document 5 proposes a dye multimer having a polymerizable group, a pigment, a polymerizable compound, and photopolymerization. The coloring composition of the initiator acts as a colorant.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open No. 2-144502

Patent Document 2 Japanese Patent Laid-Open No. 3-53201

Patent Document 3 Japanese Patent Laid-Open No. Hei 6-35188

Patent Document 4 Japanese Patent Laid-Open Publication No. 2000-310706

Patent Document 5 Japanese Patent Laid-Open Publication No. 2013-28764

However, the coloring pattern formed by the coloring composition described in the above Patent Document 5 can be found by the inventors of the present invention, and the developing property is low, and the heat resistance and the solvent resistance are also insufficient.

Therefore, an object of the present invention is to provide a colored composition capable of forming a colored cured film which is excellent in balance and can achieve heat resistance, solvent resistance, and developability at a high level. Further, an object of the present invention is to provide a colored cured film formed using the colored composition, a color filter including the colored cured film, a display element, and a solid-state imaging element.

As a result of intensive studies, the present inventors have found that a monomer having a specific structure is contained in a specific copolymerization ratio by containing at least one selected from the group consisting of dyes and dye polymers, a polymerizable compound, and an adhesive resin. The copolymer can solve the above problems.

That is, the present invention is a coloring composition comprising: (A) a colorant comprising at least one selected from the group consisting of a dye and a dye multimer, the dye multimer having a dye residue and an ethyl group The unsaturated monomer dye monomer as a structural unit, (B) an adhesive resin, and (C) a polymerizable compound, as the (B) adhesive resin, contains an ethylenic unsaturated monomer represented by the following formula (1) The copolymerization ratio of the body is 11 mol% or more of the copolymer (wherein the above dye multimer is not included).

[In the formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkanediyl group having 2 to 4 carbon atoms, and R ³ represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted polycyclic aromatic group. a hydrocarbon group, or a substituted or unsubstituted nitrogen-containing alicyclic heterocyclic group, and n represents an integer of from 0 to 100. However, when n is 2 or more, a plurality of R ² may be the same or different].

Moreover, the present invention provides a colored cured film formed using the above colored composition, and a display element including the colored cured film. Here, the "coloring cured film" means a respective color pixel, a protective film, a black matrix, a spacer, an insulating film, or the like for a display element or a solid-state imaging element.

According to the present invention, it is possible to provide a colored cured film which can achieve heat resistance, solvent resistance and developability in a well-balanced manner and at a high level even if at least one selected from the group consisting of a dye and a dye multimer is used as a colorant. The coloring composition. Therefore, the coloring composition of the present invention is extremely suitable for a color liquid crystal display element, a color separation color filter for a solid-state imaging element, a color filter for an organic EL display element, and a color filter for an electronic paper. Production of various color filters.

Hereinafter, the present invention will be described in detail.

Coloring composition

Hereinafter, the constituent components of the colored composition of the present invention will be described in detail.

- (A) colorant -

The coloring composition of the present invention contains at least one selected from the group consisting of a dye and a dye multimer as (A) a colorant containing a dye monomer having a dye residue and an ethylenically unsaturated group as Structural units.

First, the dye will be described.

The coloring material and the material are appropriately selected depending on the use of the color filter or the like, and one type or two or more types may be used in combination. As the dye used in the present invention, for example, a known dye can be used in addition to a compound classified as a dye (Dye) in a color index (C.I.; The Society of Dyers and Colourists).

As such a dye, from the structural surface of a chromophore, for example, it can mention Dyes, triarylmethane dyes, cyanine dyes, anthraquinone dyes, azo dyes, dimethylene pyrrole dyes, quinophthalone dyes, coumarin dyes, pyrazole dyes, quinoxanes A phthalic dye, a nitro dye, a quinone imine dye, an indigo dye, or the like.

As For the dyes, for example, the compound described in the paragraph [0010] of JP-A-2013-053292, and the formula (A1) described in the examples of JP-A-2013-100463 can be used. a compound represented by the above-mentioned (A6), paragraphs [0038] to [0043] of the Japanese Patent Publication No. 2012-181505, paragraphs [0048] to [0050], and [0036] of JP-A-2013-007032 ~[0038] The compound described in the paragraph or the like.

For the triarylmethane-based dye, for example, JP-A-2001-011336, JP-A-2003-246935, JP-A-2008-304766, International Publication No. 2010/123071, and JP-A-2010 Japanese Laid-Open Patent Publication No. 2011-059847, Japanese Laid-Open Patent Publication No. 2011-070172, Japanese Laid-Open Patent Publication No. 2011-070172, Japanese Laid-Open Patent Publication No. 2011-116803, No. 2011-117995, and Japanese Laid-Open Patent Publication No. 2011-133844 Japan Special Open 2011-227408 Publication No. 2011/152379, International Publication No. 2011/162217, Japanese Laid-Open Patent Publication No. 2012-017425, Japanese Laid-Open Patent Publication No. 2012-037740, International Publication No. 2012/036085, Japanese Special Japanese Laid-Open Patent Publication No. 2012-073291, Japanese Laid-Open Patent Publication No. 2012-053201, Japanese Laid-Open Patent Publication No. 2012-083652, Japanese Laid-Open Patent Publication No. 2012-088615, Japanese Laid-Open Patent Publication No. 2012-098522, and No. 2013-057053 The compound described in the publication, the specification of the U.S. Patent Application Publication No. 2013/0141810, and the International Publication No. 2013/147099.

For the cyanine dye, for example, (A-2) to (A-6) components described in the examples of JP-A-2009-235392, and JP-A-2012-212089, JP-A-2012-212089 [0108] The compound described in the paragraphs [0054] to [0063] of JP-A-2012-214718, and paragraphs [0050] to [0054] of JP-A-2012-214719 The compounds and the like described therein.

For example, the compound described in the paragraph [0049] of JP-A-2013-053292 can be used as the oxime-based dye, and JP-A-2000-129150 and JP-A-2008-015530 can be used. The compound described in the paragraph [0071] of the Japanese Patent Publication No. 2013-210621, and the like.

For the azo dyes, for example, JP-A-2003-510398, JP-A-2005-226022, JP-A-2007-212639, JP-A-2010-152160, and JP-A-2010- Japanese Patent Publication No. 170073, Japanese Patent Laid-Open No. 2011-148993, and Japanese Patent Laid-Open No. 2011-148994 The pyridone couple described in JP-A-2011-148995, JP-A-2012-041461, JP-A-2012-062461, International Publication No. 2012/039361, and JP-A-2012-194200 For example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The diazo dyes described in, for example, Japanese Laid-Open Patent Publication No. 2004-325533, and the like. Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A pyrazole azo dye described in, for example, JP-A-2010-170117, for example, JP-A-2007-293127, paragraphs [0058] to [0061], and Japanese specialties Japanese Patent Publication No. 2011-219655 [0014] Japanese Unexamined Patent Publication No. 2010-150416, JP-A-2010-152159, and JP-A-2010-- Compounds and the like described in the specification of Japanese Patent Application Laid-Open No. 2011-145540, and Japanese Patent Application Laid-Open No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. No. Nos.

As the dimethylene pyrrole dye, for example, JP-A-2008-292970 and Japanese Patent No. 5085256 can be used. In addition to the above-mentioned compound, a dimethylene pyrrole compound containing a polymerizable group described in JP-A-2011-180306 can be used.

For the quinone ketone-based dye, for example, the formula described in JP-A-H05-039269, JP-A-H06-220339, JP-A No. 8-171201, and JP-A-2006-126649 can be used. 2) The compound represented by the formula (1) described in JP-A-2010-250291, and the compound represented by the formula (1) described in JP-A-2013-209614.

For the coumarin dye, for example, a compound described in Example 4 of JP-A-4-179955, and a compound represented by Formula (1) described in JP-A-2013-151668, JP-A-2013 The compound represented by the formula (1) described in the above-mentioned publication, and the compound represented by the formula (1) described in JP-A-2014-044419.

For the pyrazolone-based dye, for example, a compound represented by the formula (1) described in JP-A-2006-016564, and a compound represented by the formula (1) described in JP-A-2006-063171 can be used.

For the indigo-based dyes, for example, the compounds described in JP-A-2004-233504 and JP-A-2006-047497 can be used, and the other [0147] of JP-A-2007-094181 can be used. a compound or the like described in the paragraph [0155].

Further, as the dye, any of an acid dye, a basic dye, and a nonionic dye can be suitably used. Here, the "acid dye" in the present specification is an ionic dye in which an anion portion becomes a chromophore. In the meantime, an ionic dye which forms a salt with the anion portion also serves as an acid dye. In the present specification, the "basic dye" means an ionic dye in which a cationic portion is a chromophore, and an ionic dye which forms a salt with the cation portion also serves as a basic dye. The "nonionic dye" means a dye other than an acid dye and a basic dye.

Examples of the acid dye include an azo acid dye, a triarylmethane acid dye, and an anthraquinone acid dye. It is an acid dye, a quinoline acid dye, a nitro acid dye, a cyanine acid dye, or the like. The acid dyes may be used alone or in combination of two or more. When two or more kinds are used, they may be used arbitrarily.

Specific examples of the azo-based acid dye include CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI. Direct yellow 12, CI direct orange 26, CI direct green 59, CI active yellow 2, CI active red 17, CI active red 120, CI active black 5, CI medium red 7, CI medium yellow 5, CI medium black 7, CI Direct green 28 and so on.

Specific examples of the triarylmethane-based acid dye include C.I. Acid Blue 9 and the like.

Specific examples of the oxime-based acid dye include C.I. Acid Blue 40, C.I. Acid Green 25, C.I. Reactive Blue 19, C.I. Reactive Blue 49, and the like.

As Specific examples of the acid dyes include, for example, CI Acid Red 52, CI Acid Red 87, CI Acid Red 92, CI Acid Red 289, and CI Acid Red 388, and other examples include JP-A-2010-32999. The dyes disclosed in the synthesis examples 1 to 3 and JP-A-2011-138094.

Specific examples of the quinoline-based acid dye include C.I. Acid Yellow 3 and the like.

Specific examples of the nitro acid dye include C.I. Acid Yellow 1, C.I. Acid Orange 3, and the like.

Specific examples of the cyanine acid dye include C.I. Reactive Yellow 1 and the like.

Examples of the basic dye include an azo basic dye and a triarylmethane basic dye. It is a basic dye, a quinone imine basic dye, a cyanine-based basic dye, or the like. The basic dyes may be used alone or in combination of two or more. When two or more kinds are used, any combination may be employed.

Specific examples of the azo-based basic dye include, for example, C.I. Basic Blue 41 and C.I. Basic Red 18, and dyes described in JP-A-2011-145540.

Specific examples of the triarylmethane-based basic dye include CI basic blue 7 and CI basic green 1, and examples thereof include International Publication No. 2010/123071, and JP-A-2011- A dye or the like described in JP-A-2011-133844, and JP-A-2011-133844.

As Specific examples of the basic dye include CI basic violet 11 and the like.

Specific examples of the quinone imine basic dye include C.I. Basic Blue 3, C.I. Basic Blue 9, and the like.

Specific examples of the cyanine-based basic dye include CI basic red 12, CI basic red 13, CI basic red 14, CI basic violet 7, CI basic violet 16, and CI basic yellow 1. , CI alkaline yellow 11, CI alkaline yellow 13, CI alkaline yellow 21, CI alkaline yellow 28, CI alkaline yellow 51 and so on.

Further, various basic dyes described in JP-A-2007-503477 can be cited.

Examples of the nonionic dye include an azo-based nonionic dye, a quinone-based nonionic dye, a indigo-based nonionic dye, a nitro-based nonionic dye, and a methine-based nonionic dye. Wait. The nonionic dyes may be used alone or in combination of two or more. When two or more kinds are used, they may be used arbitrarily.

Specific examples of the azo-based nonionic dye include CI-dispersed orange 5, CI-dispersed red 58, and CI-dispersed blue 165, and other examples include JP-A-2010-170073 and JP-A The dyes and the like described in JP-A-2010-275533, JP-A-2010-275533, and JP-A-2010-275533.

Specific examples of the quinone-based nonionic dye include C.I. reduced blue 4, C.I. dispersed red 60, C.I. dispersed blue 56, C.I. dispersed blue 60, and the like.

Specific examples of the indigo-based nonionic dye include C.I. reduced blue 5 and the like.

Specific examples of the quinoline-based nonionic dye include C.I. Solvent Yellow 33, C.I. Disperse Yellow 64, and the like.

Specific examples of the nitro-based nonionic dye include C.I. Disperse Yellow 42 and the like.

Specific examples of the methine-based nonionic dye include C.I. Solvent Yellow 179, Disperse Yellow 201, and the like.

Further, various nonionic dyes described in claim 3 or claim 4 of JP-A-2010-168531 can be cited.

In the present invention, the dye is preferably an acid dye or a basic dye, and further preferably a triarylmethane dye, from the viewpoint of the structural surface of the chromophore. a dye, an azo dye, a methine dye, a dimethylene pyrrole dye, a cyanine dye, more preferably a triarylmethane dye, a dye in a dye, a dimethylene pyrrole dye, and a cyanine dye, and more preferably a dye selected from the group consisting of a triarylmethane dye, a dimethylene pyrrole dye, and a cyanine dye, and still more preferably Triarylmethane dyes.

Next, the dye multimer will be described.

The dye multimer is a polymer having a dye monomer having a dye residue and an ethylenically unsaturated group as a structural unit. The dye multimer may be used alone or in combination of two or more.

The dye residue is, for example, selected from the structural plane of the chromophore, and is selected, for example. a dye, a triarylmethane dye, a cyanine dye, an anthraquinone dye, an azo dye, a dimethylene pyrrole dye, a quinophthalone dye, a coumarin dye, a pyrazolone dye, Residues of dyes in quinoline dyes, nitro dyes, quinone imine dyes, and indigo dyes. Here, the "dye residue" in the present specification means a residue from which one hydrogen atom is removed from the dye compound. Wherein, as the dye residue, it is preferably selected from the group consisting of triarylmethane dyes, a dye, an azo dye, a dimethylene pyrrole dye, a methine dye, and a residue of a dye in a cyanine dye, more preferably selected from a triarylmethane dye, The residue of the dye in the dye, the dimethylene pyrrole dye, and the cyanine dye is more preferably a residue of the triarylmethane dye. Further, the dye residue may be derived from any one of an acid dye, a basic dye, and a nonionic dye, but is preferably derived from an acid dye or a basic dye.

Examples of the ethylenically unsaturated group include a vinyl group, an allyl group, and a (meth)acryl fluorenyl group.

As the dye monomer, for example, a monomer represented by the following formula (2) can be given.

[In the formula (2), R ¹¹ represents a hydrogen atom or a methyl group, X ¹ represents a single bond, a substituted or unsubstituted divalent hydrocarbon group, or the divalent hydrocarbon group and an atom containing an atom other than a carbon atom and a hydrogen atom; A divalent group in which one or more linking groups are combined, and D ¹ represents a dye residue].

As R ¹¹ , a hydrogen atom or a methyl group can be appropriately selected.

Examples of the divalent hydrocarbon group of X ¹ include a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, and a divalent aromatic hydrocarbon group. In addition, the "alicyclic hydrocarbon group" in the present specification means a concept excluding an aliphatic hydrocarbon group having no cyclic structure. The divalent aliphatic hydrocarbon group may be in any form of a straight chain and a branched chain, and the divalent aliphatic hydrocarbon group and the divalent alicyclic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. In the present specification, the "alicyclic hydrocarbon group" or "aromatic hydrocarbon group" means a group including not only a ring structure but also a group further substituted with a divalent aliphatic hydrocarbon group in the ring structure. The concept is that at least an alicyclic hydrocarbon or an aromatic hydrocarbon is contained in the structure.

The divalent aliphatic hydrocarbon group is, for example, an alkanediyl group or an alkenediyl group, and the number of carbon atoms is preferably from 1 to 20, more preferably from 2 to 12, still more preferably from 2 to 6. Specific examples thereof include a methylene group, an ethane-1,1-diyl group, an ethane-1,2-diyl group, a propane-1,1-diyl group, and a propane-1,2-diyl group. Propane-1,3-diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane -1,4-diyl, pentane-1,5-diyl, hexane-1,5-diyl, hexane-1,6-diyl, 2-methylpropane-1,2-diyl , 2,2-dimethylpropane-1,3-diyl, ethylene-1,1-diyl, ethylene-1,2-diyl, propylene-1,2-diyl, propylene-1,3- Diyl, propylene-2,3-diyl, 1-butene-1,2-diyl, 1-butene-1,3-diyl, 1-butene-1,4-diyl, 2- Pentene-1,5-diyl, 3-hexene-1,6-diyl and the like.

The divalent alicyclic hydrocarbon group may, for example, be a cycloalkyl group or a cycloalkenyl group, and the number of carbon atoms thereof is preferably from 3 to 20, and more preferably from 3 to 12. Specific examples thereof include a monocyclic hydrocarbon ring group such as a cyclopropyl group, a cyclopentene group, a cyclopentylene group, a cyclohexylene group, a cyclobutenyl group, a cyclopentenyl group, or a cyclohexenyl group; , 4-norbornyl, 2,5-norbornyl and the like norbornene; 1,5-adamantylene, 2,6-adamantyl, etc. .

The divalent aromatic hydrocarbon group may, for example, be an extended aryl group, and preferably a monocyclic to 3-ring extended aryl group having 6 to 14 carbon atoms. As a specific example, For example, a phenyl group, a biphenyl group, an anthranyl group, a phenanthrenyl group, a fluorenyl group, and the like can be given.

In the divalent group in which a divalent hydrocarbon group and one or more linking groups containing an atom other than a carbon atom and a hydrogen atom are combined, examples of the linking group include -O-, - S-, -SO ₂ -, -CO-, -COO-, -OCO-, -CONR ^a - (R ^a represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), -NR ^a - (R ^a and The above meanings are the same) and may be one type or two or more types. The bonding position of the linking group is arbitrary, and for example, it may be between the terminal of the divalent hydrocarbon group or the CC bond, and preferably it is between the one-side terminal or the CC bond. Further, the divalent hydrocarbon group may be bonded to the above-mentioned linking group to form a ring structure. Further, the number of carbon atoms mentioned in the paragraph [0030] means the total number of carbon atoms of the portion of the carbon atom constituting the linking group.

Specific examples of the divalent hydrocarbon group having the above-mentioned linking group between the CC bonds include, for example, -CH ₂ -CH ₂ -CH ₂ -COO-CH ₂ -CH ₂ -, -CH ₂ -CH (- CH ₃ )-CH ₂ -COO-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -OCO-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -CH ₂ -COO- CH ₂ -CH(CH ₂ -CH ₃ )-CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH(CH ₂ -CH ₃ )-CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -(CH ₂ ) ₅ -COO-(CH ₂ ) ₁₁ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -C-(COO-CH ₂ -CH ₃ ) ₂ -, -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -, -(CH ₂ -CH ₂ -O) _p -CH ₂ - (p is an integer from 1 to 8), -(CH ₂ -CH ₂ -CH ₂ -O) _q -CH ₂ - (q is an integer from 1 to 5), -CH ₂ -CH(CH) ₃ )-O-CH ₂ -CH ₂ -, -CH ₂ -CH-(OCH ₃ )-, -CH ₂ -CH ₂ -COO-CH ₂ -CH ₂ -O-CH ₂ -CH(CH ₂ -CH ₃ )-CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -O-CO-CH ₂ -CH(CH ₂ -CH ₃ )-CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -COO-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH(CH ₂ -CH ₃ )-CH ₂ -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -NH-COO-CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -OCO-CH ₂ -, etc., but are not limited thereto.

In addition, specific examples of the group having a ring structure formed by bonding a divalent hydrocarbon group to the above-mentioned linking group include, for example, the following groups, but are not limited thereto.

Examples of the substituent of the divalent hydrocarbon group include a halogen atom, a nitro group, a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The alkoxy group may be in any form of a straight chain or a branched chain, and preferably has 1 to 6 carbon atoms. Specific examples thereof include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. The aryloxy group is preferably an aryloxy group having 6 to 14 carbon atoms, and examples thereof include a phenoxy group and a benzyloxy group. Further, examples of the substituent of the alkoxy group and the aryloxy group include a halogen Atom atom, nitro group, hydroxyl group, amine group, carboxyl group, sulfanyl group and the like. Further, when the divalent hydrocarbon group is a divalent alicyclic hydrocarbon group and a divalent aromatic hydrocarbon group, the substituent may have a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group. The alkyl group and the alkenyl group preferably have 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a hexyl group, and the like, and an alkenyl group. Specific examples thereof include a vinyl group, a 1-propenyl group, a 1-butenyl group, a 1-pentenyl group, a 1-hexenyl group, and a 2-ethyl-2-butenyl group. In addition, examples of the substituent of the alkyl group and the alkenyl group include the same groups as the substituent of the above divalent hydrocarbon group.

D ¹ represents a dye residue, and for example, may be selected from a dye, a triarylmethane dye, a cyanine dye, an anthraquinone dye, an azo dye, a dimethylene pyrrole dye, a quinophthalone dye, a coumarin dye, a pyrazolone dye, Residues of dyes in quinoline dyes, nitro dyes, quinone imine dyes, and indigo dyes. Wherein, as the dye residue, it is preferably selected from the group consisting of triarylmethane dyes, a dye, an azo dye, a dimethylene pyrrole dye, a methine dye, and a residue of a dye in a cyanine dye, more preferably selected from a triarylmethane dye, The residue of the dye in the dye, the dimethylene pyrrole dye, and the cyanine dye is more preferably a residue of the triarylmethane dye. Further, the dye residue may be derived from any one of an acid dye, a basic dye, and a nonionic dye, preferably from an acid dye or a basic dye.

The method for synthesizing the dye monomer is not particularly limited, and a conventionally known method can be used. For example, the compound represented by the above formula (2) can be used by Synthetic dyes are introduced by introducing a group having an ethylenically unsaturated group into a basic skeleton of the above dye having a functional group by a usual organic synthesis method, or introducing a group having an ethylenically unsaturated group into a synthetic raw material of the dye. And got it. More specifically, the descriptions of Japanese Patent Laid-Open Publication No. 2013-178478, JP-A-2013-173850, JP-A-2013-210621, and JP-A-2013-028764.

Moreover, dye multimers can be produced by polymerizing dye monomers. A conventionally known method can be used for the polymerization reaction, and for example, the same method as the (B) adhesive resin described later can be employed.

The weight average molecular weight (Mw) of the dye multimer of the present invention measured by gel permeation chromatography (hereinafter referred to as GPC) (eluent solvent: tetrahydrofuran) in terms of polystyrene is usually 1,000 to 100,000. Good for 3000~50000, further better for 3000~30000. By forming such an aspect, heat resistance, solvent resistance, and developability can be achieved in a well-balanced manner and at a higher level.

Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the adhesive resin in the present invention is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. In addition, the term "Mn" as used herein means the number average molecular weight converted into polystyrene measured by GPC (solution solvent: tetrahydrofuran).

The dye multimer may be composed only of a dye monomer, but is preferably a copolymerizable ethylene other than the dye monomer from the viewpoint of good balance and high heat resistance, solvent resistance, and developability. Unsaturated monomer (hereinafter, also referred to as "unsaturated monomer (a)") A copolymer as a structural unit. Examples of such an unsaturated monomer (a) include a monomer represented by the following formula (3), an ethylenically unsaturated monomer having one or more carboxyl groups, and an N-substituted maleimide. An aromatic vinyl compound, a vinyl ether, an ethylenically unsaturated monomer having an epoxyethyl group or an oxypropylene group, a macromonomer having a mono(meth)acryloyl group at the terminal of a polymer molecular chain, and the like . The unsaturated monomer (a) may be used alone or in combination of two or more.

In the formula (3), R ¹² represents a hydrogen atom or a methyl group, R ¹³ represents an alkanediyl group having 2 to 4 carbon atoms, R ¹⁴ represents a substituted or unsubstituted hydrocarbon group, and M represents an integer of 0 to 100. However, when m is 2 or more, a plurality of R ¹³ may be the same or different].

First, the definition of each symbol in the formula (3) will be described.

As R ¹² , a hydrogen atom or a methyl group can be appropriately selected.

Examples of the alkanediyl group having 2 to 4 carbon atoms in R ¹³ include an ethyl group, an ethane-1,1-diyl group, a propane-1,1-diyl group, and a propane-1,2-di group. Base, propane-1,3-diyl, propane-2,2-diyl, butane-1,2-diyl, butane-1,3-diyl, butane-1,4-diyl, etc. Among them, an alkanediyl group having 2 to 3 carbon atoms is preferred, and an ethyl group and a propane-1,2-diyl group are more preferred.

^Examples of the hydrocarbon group in R ¹⁴ include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

The aliphatic hydrocarbon group may be in any of a straight chain and a branched chain, and may be a saturated hydrocarbon group or an unsaturated hydrocarbon group. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Butyl, isobutyl, secondary butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, decyl, dodecyl and the like. Further, the alkenyl group is preferably an alkenyl group having 2 to 20 carbon atoms, more preferably an alkenyl group having 2 to 12 carbon atoms, and specific examples thereof include a vinyl group, a 1-propenyl group, and a 1-butyl group. Alkenyl, 1,3-butadienyl, 1-pentenyl, 2-pentenyl, 1-hexenyl, 2-ethyl-2-butenyl, 2-octenyl, (4- Vinyl)-5-hexenyl, 2-decenyl and the like. The alkynyl group is preferably an alkynyl group having 2 to 20 carbon atoms, more preferably an alkynyl group having 2 to 12 carbon atoms, and specific examples thereof include an ethynyl group, a 1-propynyl group, and a 1-butyne group. Base, 1-pentyne, 3-pentyne, 1-hexyne, 2-ethyl-2-butynyl, 2-octyne, (4-ethynyl)-5-hexyne, 2-decynyl Wait. In particular, the aliphatic hydrocarbon group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably a linear or branched alkyl group having 1 to 12 carbon atoms.

The alicyclic hydrocarbon group contains a cycloalkyl group, a cycloalkenyl group, a condensed polycyclic hydrocarbon group, a bridged cyclic hydrocarbon group, a spirohydrocarbyl group, a cyclic terpene group, and the like. The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 4 to 30 carbon atoms, more preferably an alicyclic hydrocarbon group having 4 to 18 carbon atoms, and still more preferably an alicyclic ring having 4 to 12 carbon atoms. Hydrocarbyl group. Specific examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a tertiary butylcyclohexyl group, a cycloheptyl group, a cyclooctyl group, a tricyclodecyl group, and a decahydro-2-naphthyl group. Tricyclo[5.2.1.0 ^2,6 ]decane-8-yl, pentacyclopentadecyl, isobornyl, adamantyl, dicyclopentanyl, dicyclopentenyl, tricyclopentanyl, Tricyclopentenyl and the like.

The aromatic hydrocarbon group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. Here, the "aryl group" in the present specification means a monocyclic to 3-ring aromatic hydrocarbon group, and specific examples thereof include a phenyl group, a benzyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, and a xylene group. Base, naphthyl, anthracenyl, phenanthryl, anthracenyl, 9-fluorenyl and the like.

Examples of the substituent of the hydrocarbon group include a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amine group, a substituted or unsubstituted alkoxy group, and the like. When R ¹⁴ is an alicyclic hydrocarbon group or an aromatic hydrocarbon group, the substituent may have a substituted or unsubstituted alkyl group. The alkyl group may be in any of a straight chain and a branched chain, and the number of carbon atoms is preferably from 1 to 10, more preferably from 1 to 6, still more preferably from 1 to 4. The alkoxy group may be in any of a straight chain and a branched chain, and the number of carbon atoms is preferably from 1 to 10, more preferably from 1 to 6, still more preferably from 1 to 4. In addition, specific examples of the halogen atom, the alkyl group, and the alkoxy group include the same groups as the above-mentioned divalent hydrocarbon group. Further, examples of the substituent of the alkyl group and the alkoxy group include a halogen atom, a hydroxyl group, a nitro group, an amine group, and a cyano group. Further, the position and number of the substituent are arbitrary, and in the case of having two or more substituents, the substituents may be the same or different.

In particular, the hydrocarbon group in R ¹⁴ is preferably an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and more preferably an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 10 carbon atoms.

m represents an integer of 0 to 100, but m may be 0 or may have no R ¹³ O group. In the case of having an R ¹³ O group, m is preferably an integer of from 1 to 30, more preferably an integer of from 1 to 15, still more preferably an integer of from 1 to 10, still more preferably an integer of from 1 to 5. When m is 2 or more, a plurality of R ¹³ may be the same or different, and a plurality of R ¹³ O groups may be bonded in any order. Examples of the difference in the plurality of R ¹³ include a combination of an alkanediyl group having 2 carbon atoms and an alkanediyl group having 3 carbon atoms; an alkanediyl group having 2 carbon atoms and a carbon atom; A combination of an alkanediyl group of 3 and an alkanediyl group of 4 carbon atoms. Among them, a combination of an ethyl group and a propane-1,2-diyl group, a combination of an ethyl group and a propane-1,3-diyl group, an ethyl group and a propane-1,2-diyl group, and a butane group are preferred. a combination of a -1,4-diyl group, a combination of an ethyl group and a propane-1,3-diyl group and a butane-1,4-diyl group.

Specific examples of the monomer represented by the following formula (3) include methyl (meth)acrylate, n-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. (meth)acrylic acid alkyl ester such as 2-hydroxyethyl acrylate; vinyl (meth) acrylate, allyl (meth) acrylate such as allyl (meth) acrylate; benzene (meth) acrylate Ethyl (meth) acrylate such as ester, benzyl (meth) acrylate; polyethylene glycol (degree of polymerization 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) methyl ether (Meth) acrylate, polyethylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2 to 10) mono (meth) acrylate, glycerol mono (meth) acrylate acrylate, isobutyl (meth) acrylate, (meth) isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decane -; polyhydric alcohol esters of such (meth) acrylates (E) acrylate having an alicyclic hydrocarbon group such as 8-based ester or dicyclopentenyl (meth)acrylate.

Examples of the ethylenically unsaturated monomer having one or more carboxyl groups include (meth)acrylic acid, maleic acid, maleic anhydride, and mono[2-(methyl)acryloxyethyl ester of succinic acid. Ω-carboxypolycaprolactone mono(meth)acrylate, p-benzoic acid vinyl ester, and the like.

Examples of the N-substituted maleimide include N-phenylmaleimide, N-cyclohexylmaleimide, and the like.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, and decene.

Examples of the vinyl ether include cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ]decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether. Wait.

Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, and β-B (meth)acrylate. Glycidyl ester, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, An ethylenically unsaturated monomer having a glycidyl ether group such as 2,3,4-glycol (glycidyloxymethyl)styrene; 1,2-epoxy-4-vinylcyclohexane; 3,4-epoxycyclohexylmethyl (meth) acrylate, and the like.

Examples of the ethylenically unsaturated monomer having an oxypropylene group include 3-(vinyloxymethyl)-2-methyl propylene oxide and 2-(vinyloxyethyl)-2- (Vinyloxyalkyl)alkyl propylene oxide such as methyl propylene oxide; 3-[(meth) propylene methoxymethyl] propylene oxide, 2-[2-(methyl) propylene oxime (Meth) propylene decyloxyalkyl propylene oxide such as oxyethyl] propylene oxide; 3-[(methyl) propylene methoxymethyl]-2-methyl propylene oxide, 2- [(Meth)propenyloxyalkyl]alkyl epoxide such as [2-(methyl) propylene methoxyethyl]-2-ethyl propylene oxide; 2-[(methyl) [(Meth) propylene oxyalkyl] phenyl propylene oxide such as propylene methoxymethyl]-2-phenyl propylene oxide; 4-[3-(3-ethyl propylene oxide- 3-methylmethoxy)propoxy]styrene, 4-[7-(3-ethylepoxypropan-3-ylmethoxy)heptyloxy]styrene, etc. having an oxypropylene group An aromatic vinyl compound or the like.

Examples of the macromonomer include polystyrene, poly(methyl) methacrylate, poly(methyl) methacrylate, polysiloxane, and the like at the end of the polymer molecular chain ( Methyl) acrylonitrile-based macromonomer.

Among them, the unsaturated monomer (a) preferably contains a monomer represented by the above formula (3).

When the dye multimer is a copolymer of a dye monomer and an unsaturated monomer (a), the copolymerization ratio of the dye monomer in the dye multimer It is preferably 5 to 30 mol%, more preferably 10 to 25 mol%, still more preferably 10 to 20 mol%.

The copolymerization ratio of the monomer represented by the above formula (3) in the dye multimer is preferably from 30 to 85 mol%, more preferably from 40 to 80 mol%, still more preferably from 50 to 75 mol%. In this case, when the aryl (meth)acrylate is used as the monomer represented by the above formula (3), the copolymerization ratio of the aryl (meth)acrylate in the dye multimer is preferably 5 mol% or more and less than 20 mol%, more preferably 7 to 18 mol%, still more preferably 10 to 16 mol%.

The colored composition of the present invention may contain a color former other than a dye and a dye multimer. As such a coloring agent, a pigment may be used, and these other coloring agents may be used alone or in combination of two or more.

As the pigment, for example, a compound classified as a pigment in a color index (C.I.; issued by The Society of Dyers and Colourists), that is, a compound having the following color index (C.I.) number can be cited.

Red pigments such as CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 264, etc.; CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Green pigment such as green 59; blue pigment such as CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 80; Yellow pigments such as CI Pigment Yellow 83, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 179, CI Pigment Yellow 180, CI Pigment Yellow 185, CI Pigment Yellow 211, CI Pigment Yellow 215, etc.; ; CI pigment purple 23 and other purple pigments.

In addition, the brominated diketopyrrolopyrrole pigment represented by the formula (Ic) of JP-A-2011-523433 may be used as the red pigment. In addition, JP-A-2001-081348, JP-A-2010-026334, JP-A-2010-191304, JP-A-2010-237384, JP-A-2010-237569, The lake pigment described in Japanese Laid-Open Patent Publication No. 2011-145346, and the like.

In the present invention, when a pigment is contained as the (A) coloring agent, the pigment may be purified by a recrystallization method, a reprecipitation method, a solvent cleaning method, a sublimation method, a vacuum heating method, or a combination thereof. Further, the pigment may be used by modifying the surface of the particles with a resin as needed. The resin which modifies the surface of the particle of the pigment, for example, the carrier resin described in JP-A-2001-108817 or a commercially available resin for dispersing various pigments. For the resin coating method of the surface of the carbon black, for example, the method described in JP-A-H09-71733, JP-A-9-95625, JP-A-9-124969, and the like can be used. Further, the organic pigment can be used by making the primary particles fine by a so-called salt milling. As a method of salt milling, for example, the method disclosed in Japanese Laid-Open Patent Publication No. Hei 08-179111 can be employed.

Further, in the present invention, when the pigment is contained as the coloring agent (A), at least one selected from the group consisting of a known dispersing agent and a dispersing aid may be further contained.

Examples of the known dispersant include a urethane dispersant, a polyethyleneimine dispersant, a polyoxyethylene alkyl ether dispersant, and a polyoxyethylene alkyl phenyl ether dispersant. A polyethylene glycol diester dispersant, a sorbitan fatty acid ester dispersant, a polyester dispersant, a (meth)acrylic dispersant, etc., as a commercial product, for example, Disperbyk-2000, Disperbyk can be used. (meth)acrylic dispersant such as -2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (above, BYK-Chemie (BYK)), Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk -167, Disperbyk-170, Disperbyk-182 (above, BYK-Chemie (BYK)), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), urethane-based dispersant, Solsperse 24000 (Lubrizol Co., Ltd.) A polyethylene-based dispersant such as AJISPER PB821, AJISPER PB822, AJISPER PB880, or AJISPER PB881 (above, Ajinomoto Fine-Techno Co., Ltd.), or a polyester-based dispersant, and BYK- LPN21324 (manufactured by BYK-Chemie (BYK)).

In the present invention, the dispersing agent may be used alone or in combination of two or more.

In the present invention, the content of the dispersant is preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, still more preferably 20 to 100 parts by mass, still more preferably 20 to 20 parts by mass based on 100 parts by mass of the pigment. 50 parts by mass.

Further, examples of the dispersing aid include a pigment derivative and the like. Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and a sulfonic acid derivative of quinacridone.

The content of the colorant (A) is usually from 5 to 70% by mass, preferably from 5 to 70% by weight in terms of solid content of the coloring composition, from the viewpoint of achieving good heat resistance, solvent resistance, and developability at a high level. 60% by mass, more preferably 10 to 50% by mass, still more preferably 15 to 40% by mass. Here, the solid component is a component other than the solvent described later.

The colored composition of the present invention may contain a dye and a dye multimer alone as the (A) colorant, but in the case of containing both a dye and a pigment as the coloring agent (A), from the viewpoint of being able to more enjoy the effects of the present invention The total content of the dye and the dye multimer is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more based on the total coloring agent. Further, in the coloring composition of the present invention, even when the content ratio of the dye and the dye multimer to the solid content of the coloring composition is high, the coloring composition can be well balanced and achieve high heat resistance and solvent resistance at a high level. It is capable of forming a colored cured film which suppresses the generation of precipitates and foreign matter of a coating film. In addition, when the dye contains a triarylmethane dye, it can be more enjoyable as long as it contains a combination of a triarylmethane dye and another blue colorant, or a triarylmethane dye of 55 mass% or more based on the total content of the dye. The effect of the present invention.

- (B) Adhesive Resin -

The colored composition of the present invention contains a specific copolymer as (B) an adhesive resin, that is, an ethylenically unsaturated monomer represented by the following formula (1). A copolymer having a copolymerization ratio of 11 mol% or more (hereinafter, also referred to as "specific copolymer". Among them, the above dye multimer is not included).

[In the formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkanediyl group having 2 to 4 carbon atoms, and R ³ represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted polycyclic aromatic group. a hydrocarbon group, or a substituted or unsubstituted nitrogen-containing alicyclic heterocyclic group, and n represents an integer of from 0 to 100. However, when n is 2 or more, a plurality of R ¹² may be the same or different].

As R ¹ , a hydrogen atom or a methyl group can be appropriately selected.

Examples of the alkanediyl group having 2 to 4 carbon atoms in R ² include the same groups as those exemplified in R ¹³ . Among them, an alkanediyl group having 2 to 3 carbon atoms is preferred, and an ethyl group and a propane-1,2-diyl group are more preferred.

Examples of the polycyclic aromatic hydrocarbon group in R ³ include a polynuclear aromatic hydrocarbon group and a condensed aromatic hydrocarbon group. Here, the "polynuclear aromatic hydrocarbon group" in the present specification means a hydrocarbon group in which two or more aromatic rings composed of carbon and hydrogen are bonded and the aromatic rings are bonded to each other by a carbon-carbon bond, not only the aromatic rings but also each other. The hydrocarbon group in which the single-bonded hydrocarbon group is bonded by an alkanediyl group or the like is also contained in the "polynuclear aromatic hydrocarbon group". In addition, the "condensed aromatic hydrocarbon group" means a hydrocarbon group in which two or more aromatic rings composed of carbon and hydrogen are present, and these aromatic rings share one or more carbon atoms bonded to each other.

The number of aromatic rings constituting the polycyclic aromatic hydrocarbon group is preferably from 2 to 10, more preferably from 2 to 7, still more preferably from 2 to 5.

Specific examples of the polynuclear aromatic hydrocarbon group include a biphenyl group, a terphenyl group, a tetraphenylene group, a bipentaphenyl group, a hexaphenyl group, a hexaphenyl group, a bis phenyl group, and a hexabenzene group. Base, hexaphenyl, benzylphenyl, phenethylphenyl, and the like. Among them, a biphenyl group and a benzylphenyl group are preferred.

Specific examples of the condensed aromatic hydrocarbon group include a naphthyl group, an anthracenyl group, an anthracenyl group, a phenanthryl group, an anthracenyl group, and an anthracenyl group. Among them, a naphthyl group, an anthracenyl group, a fluorenyl group is preferred, and a naphthyl group is more preferred.

The nitrogen-containing alicyclic heterocyclic group in R ³ may be a monocyclic ring or a polycyclic ring, and among them, a monocyclic ring is preferred, and a 5 to 7 membered ring is further more preferred.

Specific examples of the nitrogen-containing alicyclic heterocyclic group include a pyrrolidinyl group, an imidazolidinyl group, and a pyrazolidinyl group. Olinyl, thio Lolinyl, piperidinyl, N-hexahydropyridyl, piperazine Base Base. Among them, a piperidinyl group is preferred.

Examples of the substituent of the phenyl group, the polycyclic aromatic hydrocarbon group, and the nitrogen-containing alicyclic heterocyclic group include a halogen atom, a hydroxyl group, a nitro group, an amine group, a cyano group, a substituted or unsubstituted alkyl group, a substitution or Unsubstituted alkoxy groups and the like. The alkyl group may be in any of a straight chain and a branched chain, and the number of carbon atoms is preferably from 1 to 20, more preferably from 1 to 15, still more preferably from 1 to 10. Further, the alkoxy group may be in any of a straight chain and a branched chain, and the number of carbon atoms is preferably from 1 to 10, more preferably from 1 to 6, still more preferably from 1 to 4. As Specific examples of the halogen atom, the alkyl group, and the alkoxy group include the same groups as those exemplified above. Further, examples of the substituent of the alkyl group and the alkoxy group include a halogen atom, a hydroxyl group, a nitro group, an amine group, and a cyano group. Further, the position and the number of the substituent are arbitrary, and when there are two or more substituents, the substituents may be the same or different.

Further, in the case where the substituent of the phenyl group and the polycyclic aromatic hydrocarbon group is a hydroxyl group, the hydroxyl group can be protected. The protective group of the hydroxyl group may, for example, be an ether protecting group, an acetal protecting group, a thiol protecting group, an alkoxycarbonyl group or a decyl ether protecting group, and may be appropriately selected. Examples of the ether protecting group include a methyl group, a benzyl group, a methoxybenzyl group, and a tertiary butyl group. Examples of the thio group protecting group include an ethyl hydrazino group, a trimethyl acetyl group, a benzoinyl group, and the like. Examples of the alkoxycarbonyl group include an ethoxycarbonyl group, a phenoxycarbonyl group, and a tertiary butyloxycarbonyl group. Examples of the mercapto alkyl ether protecting group include a trimethyldecyl group and a tertiary tributyl group. Dimethyl decyl and the like. Further, examples of the acetal protecting group include a methoxymethyl group, an ethoxyethyl group, a tetrahydropyranyl group, and tetrahydrofuran. Among them, from the viewpoint of heat resistance, solvent resistance, and developability, a protecting group for a hydroxyl group is preferably an acetal protecting group. Further, a known method can be employed as a method of introducing a protective group into a hydroxyl group.

Wherein, as R ³ , a substituted or unsubstituted phenyl group, a substituted or unsubstituted polynuclear aromatic hydrocarbon group, a substituted or unsubstituted nitrogen-containing alicyclic heterocyclic group, more preferably substituted or unsubstituted a phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted piperidinyl group, still more preferably a phenyl group which may be substituted by a hydroxy group, a biphenyl group which may be substituted by a hydroxy group, may be substituted by a hydroxy group and an alkyl group. Benzylphenyl, substituted piperidinyl. Furthermore, the hydroxyl group can be protected by a protecting group.

n represents an integer of 1 to 100, but n may be 0 or may have no R ² O group. In the case of having an R ² O group, n is preferably an integer of from 1 to 30, more preferably an integer of from 1 to 15, still more preferably an integer of from 1 to 10, still more preferably an integer of from 1 to 5. When n is 2 or more, a plurality of R ^{2 's} may be the same or different, and a plurality of R ² O groups may be bonded in any order. Among them, n is preferably 0 from the viewpoint of good balance and high heat resistance, solvent resistance and developability.

(B) The adhesive resin may be composed only of the ethylenically unsaturated monomer represented by the formula (1), but from the viewpoint of developability, it is preferred to form the ethylenically unsaturated monomer represented by the formula (1). The other copolymerizable ethylenically unsaturated monomer (hereinafter, also referred to as "unsaturated monomer (b)") is a copolymer of structural units. Examples of such an unsaturated monomer (b) include an alkyl (meth)acrylate, an alkenyl (meth)acrylate, a (meth)acrylate of a polyhydric alcohol, and an alicyclic hydrocarbon group ( Methyl) acrylate, ethylenically unsaturated monomer having one or more carboxyl groups, N-substituted maleimide, aromatic vinyl compound, vinyl ether, ethylene having an epoxy group or propylene oxide group A monounsaturated monomer, a macromonomer having a mono(meth)acrylinyl group at the end of a polymer molecular chain, and the like. Specific examples of such monomers include the same monomers as those exemplified in the unsaturated monomer (a). The unsaturated monomer (b) may be used alone or in combination of two or more.

Among them, the unsaturated monomer (b) preferably contains an ethylenically unsaturated monomer having one or more carboxyl groups from the viewpoint of developability.

The other monomer is preferably one or more selected from the group consisting of alkyl (meth)acrylate, N-substituted maleimide, and an aromatic vinyl compound.

(B) The copolymerization ratio of the ethylenically unsaturated monomer represented by the formula (1) in the adhesive resin is 11 mol% or more in the entire structural unit, but from the viewpoint of further improving heat resistance and solvent resistance, The amount is preferably 14 mol% or more, more preferably 18 mol% or more, still more preferably 22 mol% or more, and from the viewpoint of further improving the developability and the ease of synthesis, it is preferably 60 m. % or less, more preferably 50% by mole or less, still more preferably 40% by mole or less. The range of the copolymerization ratio is preferably from 11 to 60 mol%, more preferably from 14 to 60 mol%, still more preferably from 18 to 50 mol%, still more preferably from 22 to 50 mol%, more preferably Further preferably, it is 22 to 40% by mole. Further, in the case where R ³ of the ethylenically unsaturated monomer represented by the formula (1) is a hydroxy-substituted phenyl group or a hydroxy-substituted polycyclic aromatic hydrocarbon group and the hydroxy group is protected by an acetal protecting group, (B) an adhesive The copolymerization ratio of the ethylenically unsaturated monomer represented by the formula (1) in the resin is not necessarily 11 mol% or more in the entire structural unit, and the effect of the present invention can be exhibited, and in particular, the heat resistance can be improved.

(B) The copolymerization ratio of the ethylenically unsaturated monomer having one or more carboxyl groups in the adhesive resin is preferably from 10 to 50 mol%, more preferably from 15 to 35 mol%, based on the entire structural unit.

The adhesive resin in the present invention can be produced by a known method, but the method disclosed in, for example, JP-A-2003-222717, JP-A-2006-259680, and International Publication No. 2007/029871 can be used. , control its structure, Mw, Mw / Mn.

The weight average molecular weight (Mw) of the adhesive resin in the present invention measured by GPC (dissolving solvent: tetrahydrofuran) in terms of polystyrene is usually 1,000 to 100,000, preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. . By setting it as such an aspect, it is possible to achieve good heat resistance, solvent resistance, and developability at a high level, and it is possible to suppress the generation of dry foreign matter at the time of coating at a high level.

Further, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the adhesive resin in the present invention is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. In addition, the term "Mn" as used herein means the number average molecular weight converted into polystyrene measured by GPC (solution solvent: tetrahydrofuran).

The coloring composition of the present invention may contain an adhesive resin other than the above specific copolymer as (B) an adhesive resin. As such other adhesive resin, a (co)polymer of the unsaturated monomer (b) is preferred, and an unsaturated monomer containing an ethylenically unsaturated monomer having one or more carboxyl groups is more preferred (b). Copolymer.

In the present invention, (B) the adhesive resin may be used alone or in combination of two or more.

(B) The content of the adhesive resin is usually 10 to 1000 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. By setting it as such an aspect, it is possible to achieve good balance and achieve heat resistance, solvent resistance, and developability at a higher level.

- (C) Polymeric Compound -

In the present invention, the polymerizable compound means a compound having two or more polymerizable groups. As a polymerizable group, for example, An ethylenically unsaturated group, an epoxy group, an propylene oxide group, an N-alkoxymethylamino group or the like. In the present invention, the polymerizable compound is preferably a compound having two or more (meth)acryl fluorenyl groups or a compound having two or more N-alkoxymethylamino groups.

Specific examples of the compound having two or more (meth) acrylonitrile groups include polyfunctional (meth) acrylates and caprolactone obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid. Multifunctional amino acid formic acid obtained by reacting modified polyfunctional (meth) acrylate, alkylene oxide modified polyfunctional (meth) acrylate, hydroxyl group-containing (meth) acrylate with polyfunctional isocyanate A polyfunctional (meth) acrylate having a carboxyl group obtained by reacting an ester (meth) acrylate, a (meth) acrylate having a hydroxyl group, and an acid anhydride.

Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol; A trivalent or higher aliphatic polyhydroxy compound. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and dipentaerythritol. Penta(meth) acrylate, glycerin dimethacrylate, and the like. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of the acid anhydride include acid anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride, and pyrogallite anhydride. A tetrabasic dianhydride such as phenyltetracarboxylic dianhydride or benzophenone tetracarboxylic dianhydride.

In addition, the compound described in paragraphs [0015] to [0018] of JP-A-11-44955 is exemplified as the polyfunctional (meth) acrylate which is modified by the caprolactone. The polyfunctional (meth) acrylate modified with an alkylene oxide may, for example, be bisphenol A di(meth)acrylate modified with at least one selected from the group consisting of ethylene oxide and propylene oxide. A tri(meth)acrylate isocyanate modified with at least one selected from the group consisting of ethylene oxide and propylene oxide, and at least one selected from the group consisting of ethylene oxide and propylene oxide Modified trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate modified with at least one selected from the group consisting of ethylene oxide and propylene oxide, using a ring selected from the group consisting of Pentaerythritol tetra(meth)acrylate modified with at least one of oxyethane and propylene oxide, dipentaerythritol 5 modified with at least one selected from the group consisting of ethylene oxide and propylene oxide The acrylate is dipentaerythritol hexa(meth)acrylate modified by at least one selected from the group consisting of ethylene oxide and propylene oxide.

In addition, examples of the compound having two or more N-alkoxymethylamino groups include a compound having a melamine structure, a benzoguanamine structure, and a urea structure. Furthermore, the melamine structure and the benzoguanamine structure mean that there are one or more three Ring or phenyl substituted three The ring serves as the chemical structure of the basic skeleton and also contains the concept of 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)glycolil and the like.

Among these polymerizable compounds, a polyfunctional (meth) acrylate obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid, and a caprolactone-modified polyfunctional (methyl group) are preferred. Acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate having carboxyl group, N, N, N', N', N", N"-hexa (alkoxy) Methyl) melamine, N, N, N', N'-tetrakis(alkoxymethyl)benzoguanamine. A polyfunctional (meth) group obtained by reacting a trivalent or higher aliphatic polyhydroxy compound with (meth)acrylic acid from the viewpoint of achieving good heat resistance, solvent resistance, and developability at a high level Among the acrylates, particularly preferred are trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and among polyfunctional (meth) acrylates having a carboxyl group, particularly preferred A compound obtained by reacting pentaerythritol triacrylate with succinic anhydride, and a compound obtained by reacting dipentaerythritol pentaacrylate with succinic anhydride.

In the present invention, the (C) polymerizable compound may be used alone or in combination of two or more.

The content of the (C) polymerizable compound is preferably 10 to 1000 parts by mass, more preferably 15 to 500 parts by mass, still more preferably 20 to 150 parts by mass, per 100 parts by mass of the (A) coloring agent. By adopting such an aspect, it is possible to achieve good balance and achieve heat resistance, solvent resistance, and developability at a higher level.

-(D) Photopolymerization Initiator -

A photopolymerization initiator may be contained in the coloring composition of the present invention. Thereby, it is possible to impart radiation sensitivity to the colored composition. The photopolymerization initiator used in the present invention utilizes visible light, ultraviolet light, and far ultraviolet light. Exposure of radiation such as a line, an electron beam, or an X-ray produces a compound capable of initiating polymerization of a polymerizable compound.

Examples of such a photopolymerization initiator include a thioxanthone compound, an acetophenone compound, a biimidazole compound, and the like. A compound, an O-indenyl hydrazine compound, an onium salt compound, a benzoin compound, a benzophenone compound, an α-diketone compound, a polynuclear hydrazine compound, a diazo compound, a quinone sulfinate compound, or the like.

In the present invention, the photopolymerization initiator may be used alone or in combination of two or more. As the photopolymerization initiator, it is preferably selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, and three At least one of a compound and an O-mercaptopurine compound.

In a preferred photopolymerization initiator of the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxene. Ketone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropyl Ketyl ketone and the like.

Further, specific examples of the acetophenone compound include 2-methyl-1-[4-(methylthio)phenyl]-2- Olinone propan-1-one, 2-benzyl-2-dimethylamino-1-(4- Oleinophenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Olostinophenyl)butan-1-one and the like.

Further, specific examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2 , 2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6 -Trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole and the like.

Further, when a biimidazole compound is used as the photopolymerization initiator, it is preferred to use a hydrogen donor in combination from the viewpoint of improving sensitivity. The term "hydrogen donor" as used herein refers to a compound which can supply a hydrogen atom to a radical generated by a biimidazole compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzoene. A mercaptan hydrogen donor such as azole, an amine hydrogen donor such as 4,4'-bis(dimethylamino)benzophenone or 4,4'-bis(diethylamino)benzophenone. In the present invention, the hydrogen donor may be used alone or in combination of two or more. However, in view of further improving the sensitivity, it is preferred to combine one or more kinds of thiol hydrogen donors and one or more amine hydrogen donors. use.

In addition, as three Specific examples of the compound include 2,4,6-paran (trichloromethyl)-all three 2-methyl-4,6-bis(trichloromethyl)-all three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-all three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-all three 2-[2-(4-Diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-all three , 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-all three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-all three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-all three , 2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-all three Three with a halomethyl group Compound.

Further, specific examples of the O-indenyl ruthenium compound include 1-[4-(phenylthio)phenyl]-1,2-octanedione-2-(O-benzofluorenyl), 1-[9-ethyl-6-(2-methylphenylhydrazino)-9H-indazol-3-yl]-ethanone-1-(O-ethylindenyl), 1-[9-B 5-(2-methyl-4-tetrahydrofuranmethoxyphenyl)-9H-indazol-3-yl]-ethanone-1-(O-ethylindenyl), 1-[9- Ethyl -6-{2-methyl-4-(2,2-dimethyl-1,3-dioxolanyl)methoxybenzoin}}-9H-indazol-3-yl]-B Keto-1-(O-ethylindenyl) and the like. As a commercial item of the O-indenyl ruthenium compound, NCI-831, NCI-930 (above, ADEKA CORPORATION), OXE-03, OXE-04 (above, manufactured by BASF Corporation), or the like can be used.

In the case of using a photopolymerization initiator other than the biimidazole compound such as an acetophenone compound, a sensitizer may be used in combination. Examples of such a sensitizer include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 4-di. Ethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5- Bis(4-diethylaminobenzyl)cyclohexanone, 7-diethylamino-3-(4-diethylaminophenylphenyl)coumarin, 4-(diethylamino) ) Check the ketone and so on.

In the present invention, the content of the (D) photopolymerization initiator is preferably 0.01 to 120 parts by mass, more preferably 1 to 100 parts by mass, still more preferably 5 to 50 parts by mass based on 100 parts by mass of the (C) polymerizable compound. Parts by mass. By setting it as such an aspect, it is possible to balance well and achieve heat resistance at a higher level. Since the solvent resistance and the developability are improved, the curability and film properties can be further improved.

- (E) Solvent -

The colored composition of the present invention is a colored composition containing the above components (A) to (C) and optionally added other components, and is usually prepared by mixing an organic solvent to prepare a liquid composition.

The (E) solvent can be appropriately selected and used as long as the components (A) to (C) constituting the colored composition and other components are dispersed or dissolved, and do not react with these components and have moderate volatility.

Examples of such an organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, and Ethylene 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 single 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 (poly) alkane Glycol monoalkyl ether; alkyl lactate such as methyl lactate or ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isobutanol, tertiary butanol, octanol, 2-ethyl (cyclo)alkyl alcohol such as hexanol or cyclohexanol; keto alcohol such as diacetone alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate , diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate (poly)alkylene glycol monoalkyl ether acetate such as 3-methyl-3-methoxybutyl acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol II a glycol ether such as diethyl ether; a cyclic ether such as tetrahydrofuran; a ketone such as methyl ethyl ketone, cyclohexanone, 2-heptanone or 3-heptanone; propylene glycol diacetate and 1,3-butanediol diacetic acid; Diacetate such as ester or 1,6-hexanediol diacetate; Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl Alkoxycarboxylates such as -3-methoxybutylpropionate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, acetic acid Isoamyl ester, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, B Fatty acid alkyl esters such as methyl acetate, ethyl acetate, ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N,N-dimethylformamide, N,N-di A decylamine such as methyl acetamide or N-methylpyrrolidone or an indoleamine.

Among these organic solvents, one or two selected from the group consisting of (poly)alkylene glycol monoalkyl ether acetate, keto alcohol, and ketone are preferred from the viewpoints of solubility, pigment dispersibility, and coatability. the above.

In the present invention, the solvent may be used alone or in combination of two or more.

The content of the solvent (E) is not particularly limited, and the total concentration of each component other than the solvent of the coloring composition is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass. By adopting such an aspect, dispersibility and stability can be improved, and therefore, heat resistance, solvent resistance, and developability can be achieved with a good balance and at a higher level.

-additive-

The colored composition of the present invention may contain various additives as needed.

Examples of the additive include a filler such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); a surfactant such as a fluorine-based surfactant or an anthrone-based surfactant; ; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, N-(2-aminoethyl)-3-aminopropylmethyl Dimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethyl Oxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethyl An adhesion promoter such as oxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane; 2,2-thio Bis(4-methyl-6-tertiary butylphenol), 2,6-ditributylphenol, pentaerythritol 肆[3-(3,5-ditributyl-4-hydroxyphenyl)propane Acid ester], 3,9-bis[2-[3-(3-tris-butyl-4-hydroxy-5-methylphenyl)-propenyloxy]-1,1-di Ethylethyl]-2,4,8,10-tetraoxa-spiro[5.5]undecane, thiodiethylidene bis[3-(3,5-ditributyl-4-hydroxyphenyl) An anti-oxidant such as propionate; ultraviolet absorption such as 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole or alkoxybenzophenone Anti-aggregating agent such as sodium polyacrylate; malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol a residue improving agent such as 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; Succinic acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid mono [2-(methyl) propylene oxiranyl ethyl] ester, ω-carboxy polycaprolactone single (A A developer improving agent such as acrylate or the like.

Method for producing colored composition

The coloring composition of the present invention can be prepared, for example, by adding a dye solution obtained by dissolving at least one selected from the group consisting of a dye and a dye polymer as (A) a colorant in (E) a solvent, (B) The adhesive resin, (C) a polymerizable compound, and an additional (E) solvent and other components are prepared and mixed. Further, in the case where the coloring composition of the present invention further contains a pigment as the coloring agent (A), it can be produced by: in the solvent (E), in the presence of a dispersing agent, the pigment according to the case and (B) the adhesive resin. A part of the mixture is mixed and dispersed by, for example, a bead mill, a roll mill, or the like to form a pigment dispersion liquid, and then, the pigment dispersion liquid is dissolved in (E) solvent to be dissolved (A) selected from the dye. a dye solution obtained by at least one of the dye multimers, (C) a polymerizable compound, (B) an adhesive resin, (D) a photopolymerization initiator, and an additional (E) solvent, and others The ingredients are prepared by mixing. Further, it may be prepared by mixing a pigment with (A) at least one selected from the group consisting of a dye and a dye multimer in an (E) solvent in the presence of a dispersing agent, and dispersing to form a dispersion, followed by dispersion. To the colorant dispersion, (C) a polymerizable compound, (B) an adhesive resin, (D) a photopolymerization initiator, and an additional (E) solvent and other components are added and mixed to prepare a mixture. .

Colored hardening film and method of forming same

The colored cured film of the present invention is formed using the colored composition of the present invention, and contains (A) a coloring agent containing at least one selected from the group consisting of a dye and a dye multimer, and (B) a compound represented by the above formula (1). a copolymer having a copolymerization ratio of an ethylenically unsaturated monomer of 11 mol% or more (excluding the above dye multimer), the dye multimer having a dye residue and an ethylene property A saturated group of dye monomers is used as a structural unit. Specifically, it can be used for various color pixels, black matrices, black spacers, and the like of a color filter.

Hereinafter, a colored cured film which can be used for a color filter and a method of forming the same will be described.

As a method of forming the colored cured film constituting the color filter, the first method is as follows. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide the portion where the pixels are formed as needed. Next, a liquid composition of, for example, a red radiation-sensitive coloring composition of the present invention is applied onto the substrate, and then pre-baked to evaporate the solvent to form a coating film. Next, the coating film was exposed through a photomask, and then developed using an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Then, a pixel array in which a red pixel pattern is arranged in a predetermined arrangement is formed by post-baking.

Next, using each of the radiation-sensitive coloring compositions of green or blue, coating, prebaking, exposing, developing, and post-baking each of the radiation-sensitive coloring compositions are performed in the same manner as described above, and green is sequentially formed on the same substrate. The pixel array and the blue pixel array. Thereby, a color filter in which three primary color pixel arrays of red, green, and blue are arranged on the substrate is obtained. However, in the present invention, the order in which the respective color pixels are formed is not limited to the above order.

Further, the black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern by photolithography, or a radiation-sensitive coloring composition in which a black pigment is dispersed can be used. The above-described case of forming a pixel is similarly formed.

Examples of the substrate used for forming the colored cured film include glass, ruthenium, polycarbonate, polyester, aromatic polyamide, polyamidimide, and polyimine.

Further, as appropriate, these substrates may be subjected to appropriate pretreatment such as reagent treatment using a decane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, or vacuum vapor deposition.

When the radiation-sensitive coloring composition is applied to the substrate, a spray method, a roll coating method, a spin coating method, a slit die coating method (slit coating method), a bar coating method, or the like can be used. The coating method is particularly preferably a spin coating method or a slit die coating method.

The conditions for heating and drying in the prebaking are usually about 1 to 10 minutes at 70 to 110 °C.

The coating thickness at the time of forming the cured film of the color filter used for the display element is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, in terms of the film thickness after drying. Further, the coating thickness at the time of forming the cured film of the color filter used for the solid-state image sensor is usually 0.3 to 5 μm, preferably 0.5 to 2 μm, in terms of the film thickness after drying.

Examples of the light source for forming radiation to be used in at least one selected from the group consisting of a pixel and a black matrix include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, and a medium voltage. Light source such as mercury lamp, low-pressure mercury lamp or argon ion laser, YAG laser, XeCl excimer laser, nitrogen laser and other laser light sources. As the light source for exposure, an ultraviolet LED can also be used. Radiation having a wavelength in the range of 190 to 450 nm is preferred.

The exposure amount of the radiation is generally preferably from 10 to 10000 J/m ² .

Further, as the above alkaline developing solution, for example, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline or 1,8-diazabicyclo-[5.4 is preferred. .0] an aqueous solution of 7-undecene, 1,5-diazabicyclo-[4.3.0]-5-decene.

In the alkaline developing solution, a water-soluble organic solvent such as methanol or ethanol or a surfactant may be added in an appropriate amount. Further, after alkaline development, water washing is usually carried out.

As the development treatment method, a shower development method, a spray development method, a dip development method, a dipping (liquid pool) development method, or the like can be used. The development conditions are preferably 5 to 300 seconds at normal temperature.

The post-baking conditions are usually about 10 to 60 minutes at 180 to 280 °C.

When the colored cured film of the color filter used in the display element is formed, the film thickness thus formed is 0.5 to 8 μm, preferably 1 to 4 μm. Further, in the case of forming a colored cured film of a color filter used for a solid-state image sensor, it is usually 0.3 to 4 μm, preferably 0.5 to 2 μm.

In addition, as a second method of forming the color-developing film constituting the color filter, it is possible to obtain each color pixel by the ink-jet method disclosed in Japanese Laid-Open Patent Publication No. Hei. 7-318723, No. 2000-310706, and the like. Methods. In this method, first, a partition wall having a light blocking function is formed on the surface of the substrate. Next, a liquid composition of, for example, a red thermosetting coloring composition of the present invention is ejected into the formed partition walls by an inkjet device, and then prebaked to evaporate the solvent. Next, the coating film is exposed as needed, and then hardened by post-baking to form a red pixel pattern.

Next, using a green or blue thermosetting coloring composition, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate in the same manner as described above. Thereby, a color filter in which pixel elements of three primary colors of red, green, and blue are arranged on the substrate is obtained. However, in the present invention, the order in which the respective color pixels are formed is not limited to the above order.

Further, the partition walls not only exhibit a light-shielding function but also have a function of preventing color mixing of the respective thermosetting coloring compositions discharged into the cells, so that the film thickness is thicker than the black matrix used in the first method. Therefore, the partition walls are usually formed using a black radiation sensitive composition.

The substrate used for forming the colored cured film, the light source of the radiation, and the methods and conditions for prebaking and postbaking are the same as those of the first method described above. Thus, the film thickness of the pixel formed by the inkjet method is equivalent to the height of the partition wall.

On the pixel pattern thus obtained, a protective film is formed as needed, and then a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer may be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, and may also be formed as a spacer having a light-shielding property (black spacer). At this time, a colored radiation-sensitive composition in which a black colorant is dispersed is used.

The color filter containing the colored cured film of the present invention thus formed can be well-balanced and achieves heat resistance, solvent resistance, and developability at a high level, and thus, for a color liquid crystal display element, a color photographic tube element, and a color sensor Organic EL display elements, electronic paper, and solid-state imaging elements are extremely useful.

Color filter

The color filter of the present invention comprises the colored cured film of the present invention. Specifically, the colored cured film of the present invention may be used as a member of each color pixel, black matrix, or black spacer used for the color filter.

Display component

The display element of the present invention comprises the colored cured film of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.

The color liquid crystal display element having the colored cured film of the present invention may be of a transmissive type or a reflective type, and an appropriate structure may be employed. For example, a configuration may be adopted in which a color filter is formed on a substrate different from a driving substrate on which a thin film transistor (TFT) is disposed, and the substrate for driving and the substrate on which the color filter is formed are opposed to each other via a liquid crystal layer; Further, a structure in which a substrate on which a color filter is formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed and a substrate on which an ITO (tin-doped indium oxide) electrode is formed may be employed. The liquid crystal layer is opposite. The structure of the latter can significantly increase the aperture ratio, and has the advantage of obtaining a bright and high-definition liquid crystal display element. Further, in the case of the latter structure, the black matrix and the black spacer may be formed on either the substrate side on which the color filter is formed and the substrate side on which the ITO electrode is formed.

The color liquid crystal display element including the colored cured film of the present invention may further include a backlight unit having a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As a white LED, for example, a combination of a red LED, a green LED, and a blue LED can be used to obtain white light by color mixing. White LED, combined with blue LED, red LED and green phosphor to obtain white light white LED by color mixing, combined blue LED, red illuminating phosphor and green illuminating phosphor to obtain white light by color mixing White LED, white LED with white light by blue LED and YAG-based phosphor, combined with blue LED, orange illuminating phosphor and green illuminating phosphor to obtain white light white LED by color mixing A white LED or the like which combines an ultraviolet LED, a red luminescent phosphor, a green luminescent phosphor, and a blue luminescent phosphor to obtain white light by color mixing.

A color liquid crystal display device having the colored cured film of the present invention can be applied to a TN (Twisted Nematic) type, an STN (Super Twisted Nematic) type, or an IPS (In-Planes Switching) type. A suitable liquid crystal mode such as VA (Vertical Alignment) or OCB (Optically Compensated Birefringence).

In addition, the organic EL display element having the colored cured film of the present invention may have a suitable structure, and for example, a structure disclosed in Japanese Laid-Open Patent Publication No. Hei 11-307242.

In addition, the electronic paper provided with the colored cured film of the present invention may have a suitable structure, and for example, a structure disclosed in Japanese Laid-Open Patent Publication No. 2007-41169 can be cited.

Solid state imaging element

The solid-state imaging element of the present invention comprises the colored cured film of the present invention. Further, the solid-state imaging element of the present invention can adopt a suitable structure. For example, as one embodiment, the coloring composition of the present invention is formed on a semiconductor substrate such as a CMOS substrate by the same operation as described above. By coloring a picture (coloring cured film), it is possible to produce a solid-state imaging element which is particularly excellent in color separation property.

[Example 1]

Hereinafter, embodiments of the present invention will be further specifically described by way of examples. However, the invention is not limited to the following embodiments.

<Synthesis of Colorants> Colorant Synthesis Example 1 Synthesis of dye monomers

Into a 1 L three-necked flask equipped with a stirrer and preliminarily replaced with nitrogen, ginseng (dibenzylbenzylacetate)-dipalladium (0) 3.36 g (3.67 mmol), (±)-2,2'-bis (two) Phenylphosphino)-1,1'-binaphthyl 4.58g (7.36mmol), and 450mL of 1,2-dimethoxyethane previously bubbled and degassed by nitrogen, stirred at 80 ° C under a nitrogen stream 1 hour. Thereafter, the mixture was cooled to 40 ° C or less, and 25.0 g (0.260 mol) of sodium butoxide and 23.0 g (0.200 mol) of 4-aminocyclohexanol were sequentially added without introducing air into the system. 38.0 g (0.184 mol) of bromonaphthalene was stirred under reflux for 3 hours. Thereafter, after cooling the reaction mixture to room temperature, it was filtered through celite. Further, the filtered diatomaceous earth was washed with ethyl acetate. The filtrate after filtration of diatomaceous earth and the washing liquid of celite were washed with ethyl acetate, and concentrated under reduced pressure on a rotary evaporator. The obtained residue was purified by a silica gel column chromatography to give 33.0 g (0.137 mol, yield 74%) of viscous solid. This compound was designated as (A1).

15.0 g (0.0497 mol) of the above-mentioned compound (A1), 7.55 g (0.0746 mol) of triethylamine, and 6.07 g of 4-dimethylaminopyridine were added to a 500 mL three-neck flask in which a stirrer was placed and nitrogen substitution was carried out in advance. (0.0497 mol), ethyl acetate 250 mL, and the internal temperature was cooled to 5 °C. After 6.24 g (0.0259 mol) of methacrylium fluorene chloride was added dropwise to the mixture so that the internal temperature did not exceed 10 ° C, the internal temperature was raised to room temperature, and the mixture was stirred at the same temperature for 4 hours under a nitrogen stream. Then, the reaction mixture was washed successively with 300 mL of water and 300 mL of saturated brine, and the organic layer was dried over anhydrous sodium sulfate. Thereafter, 200 g of toluene was added and concentrated under reduced pressure to 40 g with a rotary evaporator, and 85 g of toluene was again added. 40.5 g (0.0633 mol) of 4,4'-bis(diethylamino)benzophenone, 0.100 g of 4-methoxyphenol, and 8.05 g of phosphonium chloride were sequentially added to the obtained solution at room temperature. (0.0518 mol), stirred at 100 ° C for 2 hours under a nitrogen stream. Thereafter, the reaction mixture was cooled to room temperature, and most of the toluene was distilled off under reduced pressure using a rotary evaporator. The obtained residue was dissolved in 500 mL of chloroform, and washed with water (500 mL). The organic layer was concentrated under reduced pressure using a rotary evaporator, and acetone was added to the residue to give a total mass of 400 g. Again, the resulting solution was added dropwise to 3200 g of diisopropyl ether, and the obtained solid was filtered. The solid was dried under reduced pressure at 50 ° C for 12 hours to obtain 18.0 g (0.0276 mol, yield 56%) of color solid. This compound was designated as (A2).

Into a 100 mL Erlenmeyer flask to which a stir bar was placed, 9.00 g (13.8 mmol) of the above compound (A2) and 5.94 g (20.7 mmol) of lithium bis(trifluoromethanesulfonate) imide were added, and ethyl acetate 90 mL and ions were added thereto. Exchange 90 mL of water and stir at room temperature for about 2 hours. Thereafter, the aqueous layer was separated and removed, and the organic layer was washed three times with 100 mL of 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 11.4 g (12.7 mmol, yield: 92%) of the compound of the formula (A3). This was designated as the compound (A3).

Synthesis of dye multimers

A 100 mL three-necked flask equipped with a stirrer and a reflux condenser and a thermometer was placed in a nitrogen purge, and then 15.0 g of cyclohexanone was placed, and the mixture was heated to an internal temperature of 70 ± 2 ° C under a nitrogen stream. On the other hand, while maintaining the internal temperature of 70±2° C., 9.0 g (10.0 mmol) of the mixed compound (A3), 1.0 g (11.6 mmol) of methacrylic acid, and methyl methacrylate 5.0 were added dropwise using a pump for 2 hours. g (50.0 mmol), 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, trade name V-65) 2.02 g (8.13 mmol), a ring as a polymerization initiator A solution prepared from 45.0 g of hexanone. After the completion of the dropwise addition, stirring was continued for 1 hour at the same temperature. Thereafter, a solution obtained by dissolving 0.728 g (2.71 mmol) of 2,2'-azobis(2,4-dimethylvaleronitrile) in 1.16 g of cyclohexanone was added to the reaction mixture at once. Stir at temperature for 3 hours. The reaction solution was cooled to room temperature, and it was added dropwise to a large amount of hexane. The obtained colored solid was dried under reduced pressure at 50 ° C to obtain 14.4 g (yield: 96%) of a copolymer. The obtained copolymer had a Mw of 5,300. This polymer was used as a coloring agent (A-1).

Colorant Synthesis Example 2~3

In the "synthesis of the dye multimer" of the colorant synthesis example 1, the polymer (A- was synthesized in the same manner as in the colorant synthesis example 1 except that the type and amount of the monomer to be used were changed as shown in Table 1. 2)~(A-3). The obtained copolymer was used as a coloring agent (A-2) to (A-3), respectively.

<Synthesis of Adhesive Resin> Adhesive resin synthesis example 1

In a flask equipped with a condenser and a stirring device, 29 parts by mass of propylene glycol monomethyl ether acetate was placed and replaced with nitrogen. After heating to 80 ° C, 30.85 parts by mass of propylene glycol monomethyl ether acetate, 6.06 parts by mass of methacrylic acid (70.4 mmol), and 16.67 parts by mass of methyl methacrylate (166.5 mmol) were added dropwise at the same temperature for 1 hour. A mixed solution of 15.15 parts by mass of phenyl methacrylate (93.4 mmol) and 2.27 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was maintained at this temperature for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C, and polymerization was further carried out for 1 hour to obtain a solution containing a binder resin (B1) (solid content concentration: 40% by mass). This was referred to as "adhesive resin (B1) solution". The obtained adhesive resin (B1) had Mw of 9,700 and Mn of 4,800.

Adhesive resin synthesis example 2~21

The adhesive resin solution (solid content concentration: 40% by mass) was obtained in the same manner as in Adhesive Resin Synthesis Example 1 except that the materials used were changed in Table 2. These resin solutions are referred to as "adhesive resin (B2) solution" to "adhesive resin (B21) solution". Adhesive resin (B1)~(B10), adhesive resin (B12)~(B16) and adhesive resin (B18)~(B20) belong to specific copolymer, adhesive resin (B11), adhesive resin (B17) And the adhesive resin (B21) does not belong to a specific copolymer. In addition, in Table 2, "acetal protective agent of 4-hydroxyphenyl methacrylate" used the compound synthesized by the method mentioned later. Further, Table 2 indicates the use of raw materials in units of mmol.

<Synthesis of acetal protecting body of 4-hydroxyphenyl methacrylate> Synthesis Example 1

150 mL of dichloromethane, 10 g (56.1 mmol) of 4-hydroxyphenyl methacrylate, and 1.41 g (5.61 mmol) of pyridinium p-toluenesulfonate were placed in a 2-neck flask placed in a stir bar, and then stirred at room temperature. 6.07 g (84.2 mmol) of ethyl vinyl ether was added dropwise over 15 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 3 hours to carry out a sufficient reaction. After completion of the reaction, it was extracted with diethyl ether and washed with aq. After removal of the solvent, the obtained white solid was purified by a silica gel column to obtain 11.2 g (44.9 mmol, yield: 80%) of an acetal protecting agent of 4-hydroxyphenyl methacrylate.

<Preparation of colorant solution> Preparation Example 1

10 parts by mass of the coloring agent (A-1) obtained above was dissolved in 90 parts by mass of propylene glycol monomethyl ether to obtain a colorant solution (A-1).

Preparation Examples 2~9

In Preparation Example 1, the types and amounts of the coloring agent and the solvent to be used were changed as shown in Table 3 to obtain colorant solutions (A-2) to (A-9). In addition, in Table 3, "dimethylene pyrrole dye 1" is an exemplary compound III-1 described in the formula 54 of Japanese Patent No. 5085256, and "PGME" means propylene glycol monomethyl ether.

Preparation Example 10

15 parts by mass of BYK-LPN21116 (manufactured by BYK-Chemie (BYK) Co., Ltd.) as a dispersing agent, 15 parts by mass of CI Pigment Blue 15:6, 12.5 parts by mass (solid content concentration: 40% by mass), 0.5 parts by mass CI solvent blue 70 as an additive, 12.5 parts by mass (solid content concentration: 40% by mass), an adhesive resin (B2) solution, and 59.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent, which were processed by a bead mill to prepare Pigment dispersion (A-10).

Preparation 11~17

In Preparation Example 10, the types of the pigment and the adhesive resin solution to be used were changed as shown in Table 4 to obtain pigment dispersion liquids (A-11) to (A-17).

<Preparation and evaluation of coloring composition> Example 1

33.0 parts by mass of the coloring agent solution (A-1) as the coloring agent (A), and 11.9 parts by mass (solid content concentration: 40% by mass) of the adhesive resin (B1) solution as the (B) adhesive resin, as (C) 7.2 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA), NCI-930 as a photopolymerization initiator (limited by ADEKA) Company product) 0.6 parts by mass, 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole 0.3 parts by mass, 2,4- 0.2 parts by mass of diethylthioxanthone and 0.2 parts by mass of 2-mercaptobenzothiazole, 0.03 parts by mass of Megafac F-554 (manufactured by DIC Corporation) as a fluorine-based surfactant, and propylene glycol monomethyl ether as a solvent 29.9 parts by mass of acetate and 16.7 parts by mass of diacetone alcohol were mixed to prepare a blue colored composition (BS-1).

Evaluation of heat resistance

The coloring composition (BS-1) was applied onto a soda lime glass substrate having a SiO ₂ film on which a sodium ion eluted on the surface was formed by a spin coater, and then prebaked by a hot plate at 90 ° C for 2 minutes to form a film thickness of 2.5. Μm coating film.

Next, after cooling the substrate to room temperature, the coating film was exposed to radiation having wavelengths of 365 nm, 405 nm, and 436 nm at a exposure amount of 400 J/m ² through a photomask using a high pressure mercury lamp. Then, a developing solution composed of a 0.04% by mass aqueous sodium hydroxide solution at 23 ° C was sprayed onto the substrates at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm), thereby performing shower development for 60 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and then baked in a clean oven at 230 ° C for 20 minutes to form a colored cured film on the substrate.

With respect to the obtained colored cured film, a color coordinate analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) was used to measure the chromaticity coordinate value (x, y) and the stimulus value (Y) in the CIE color system using a C light source and a 2 degree field of view.

Next, the substrate was additionally baked at 230 ° C for 20 minutes for 20 minutes. The chromaticity coordinate value (x, y) and the stimulating value (Y) of the substrate after the additional baking were measured twice, and the color change before and after the double baking was evaluated, that is, ΔE ^* _ab . As a result, when the value of ΔE ^* _ab is 1.0 or less, it is evaluated as "?", when it is more than 1.0 and 2.0 or less, it is evaluated as "○", when it is more than 2.0 and 3.0 or less, it is evaluated as "△", and when it is more than 3.0, it is evaluated as "?""." Furthermore, it can be said that the smaller the ΔE ^* _ab value, the better the heat resistance.

Solvent resistance evaluation

The coloring composition (BS-1) was applied onto a soda lime glass substrate having a SiO ₂ film on which a sodium ion eluted on the surface was formed by a spin coater, and then prebaked by a hot plate at 90 ° C for 2 minutes to form a film thickness of 2.5. Μm coating film.

Next, after the substrate was cooled to room temperature, radiation of respective wavelengths of 365 nm, 405 nm, and 436 nm was exposed to each of the coating films with a high pressure mercury lamp at an exposure amount of 400 J/m ² through a photomask. Then, a developing solution composed of a 0.04% by mass aqueous sodium hydroxide solution at 23 ° C was sprayed onto the substrates at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm), thereby performing shower development for 60 seconds. Thereafter, the substrate was washed with ultrapure water, air-dried, and then baked in a clean oven at 230 ° C for 20 minutes to form a rectangular pattern on the substrate. Thereafter, the substrate was immersed in a mixed solution of 80 ° C mixed with N-methylpyrrolidone: butyl cellosolve = 50:50 (volume ratio) for 5 minutes.

The chromaticity coordinate value (x, y) and the stimulation value (Y) before and after immersion were measured, and the color change before and after immersion, that is, ΔE ^* _ab was evaluated. When the value of ΔE ^* _ab was 1.0 or less, it was evaluated as "?", when it was more than 1.0 and 2.0 or less, it was evaluated as "○", when it was more than 2.0 and 3.0 or less, it was evaluated as "△", and when it was more than 3.0, it was evaluated as "x". Further, it can be said that the smaller the ΔE ^* _ab value is, the better the solvent resistance is.

Evaluation of developability

The coloring composition (BS-1) was applied onto a soda lime glass substrate having a SiO ₂ film on which a sodium ion eluted on the surface was formed by a spin coater, and then prebaked by a hot plate at 90 ° C for 2 minutes to form a film thickness of 2.5. Μm coating film.

Next, after the substrate was cooled to room temperature, radiation of respective wavelengths of 365 nm, 405 nm, and 436 nm was exposed to each of the coating films with a high pressure mercury lamp at an exposure amount of 400 J/m ² through a photomask. Then, a developing solution composed of a 0.04% by mass aqueous sodium hydroxide solution at 23 ° C was sprayed onto the substrates at a developing pressure of 1 kgf/cm ² (nozzle diameter: 1 mm) to carry out shower development. At this time, the time (BP) at which the film surface of the unexposed portion disappeared and the substrate surface was exposed was evaluated. When BP is within 30 seconds, it is evaluated as "◎", and when it is more than 30 seconds and within 40 seconds, it is evaluated as "○", and when it is more than 40 seconds and within 50 seconds, it is evaluated as "△", and when it is more than 50 seconds, it is evaluated as "X".

Examples 2 to 21 and Comparative Examples 1 to 3

In the same manner as in Example 1, except that the type of the coloring agent solution and the adhesive resin solution to be used were changed as shown in Tables 5 and 6, a blue coloring composition (BS-2) was prepared. ) (BS-24) was evaluated in the same manner as in Example 1. The evaluation results of Examples 2 to 10 are shown in Table 5, and the evaluation results of Examples 11 to 21 and Comparative Examples 1 to 3 are shown in Table 6.

In Tables 5 and 6, the respective components are as follows.

C-1: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA)

D-1: NCI-930 (made by ADEKA Co., Ltd.)

D-2: 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole

D-3: 2,4-diethylthioxanthone

D-4: 2-mercaptobenzothiazole

F-1: Megafac F-554 (made by DIC Corporation)

E-1: propylene glycol monomethyl ether acetate

E-2: diacetone alcohol

E-3: cyclohexanone

Example 22

17.2 parts by mass of the coloring agent solution (A-2) as the coloring agent (A), 6.1 parts by mass of the pigment dispersion liquid (A-13), and 10.6 parts by mass of the adhesive resin (B2) solution (solid content concentration: 40% by mass) 6.8 parts by mass of a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as a (C) polymerizable compound, and NCI-930 as a photopolymerization initiator ( 0.6 parts by mass of ADEKA Co., Ltd., 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole 0.3 parts by mass, 2 0.2 parts by mass of 4-diethylthioxanthone and 0.2 parts by mass of 2-mercaptobenzothiazole, 0.03 parts by mass of Megafac F-554 (manufactured by DIC Corporation) as a fluorine-based surfactant, and propylene glycol as a solvent Monomethyl ether acetate 31.4 parts by mass and 16.7 parts by mass of diacetone alcohol were mixed to prepare a blue colored composition (BS-25).

The evaluation was carried out in the same manner as in Example 1 using the prepared coloring composition (BS-25). The results are shown in Table 7.

Examples 23 to 25 and Comparative Examples 4 to 6

In the same manner as in Example 22 except that the coloring agent solution, the pigment dispersion liquid, and the adhesive resin solution used were changed as shown in Table 7, a blue coloring composition (BS) was prepared. -26)~(BS-31) was evaluated in the same manner as in Example 1. The evaluation results are shown in Table 7.

In Table 7, each component is as follows.

C-1: dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylic acid A mixture of esters (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA)

D-1: NCI-930 (made by ADEKA Co., Ltd.)

D-2: 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole

D-3: 2,4-diethylthioxanthone

D-4: 2-mercaptobenzothiazole

F-1: Megafac F-554 (made by DIC Corporation)

E-1: propylene glycol monomethyl ether acetate

E-2: diacetone alcohol

E-3: cyclohexanone

Example 26

18.7 parts by mass of the pigment dispersion liquid (A-10) as the coloring agent (A) and 9.9 parts by mass of the coloring agent solution (A-5), 14.1 parts by mass of the adhesive resin (B2) solution as (B) adhesive resin (solid content: 40% by mass), a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA) as (C) a polymerizable compound, 7.0 parts by mass, as light 0.5 parts by mass of NCI-930 (made by ADEKA CORPORATION), 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2' - 0.04 parts by mass of biimidazole, 0.02 parts by mass of 2,4-diethylthioxanthone, and 0.02 parts by mass of 2-mercaptobenzothiazole, and Megafac F-554 (manufactured by DIC Corporation) as a fluorine-based surfactant 0.03 A blue coloring composition (BS-32) was prepared by mixing 35.8 parts by mass of propylene glycol monomethyl ether acetate as a solvent and 16.7 parts by mass of diacetone alcohol.

The evaluation was carried out in the same manner as in Example 1 using the prepared coloring composition (BS-32). The results are shown in Table 8.

Examples 27 to 31 and Comparative Examples 7 to 11

In Example 26, the type and amount of each component used were changed as shown in Table 8, and a colored composition was prepared. Next, the evaluation was carried out in the same manner as in Example 1 using the prepared coloring composition. The evaluation results are shown in Table 8. Further, the colored composition (BS-32) to (BS-36) is a blue composition, and the colored composition (RS-1) to (RS-4) is a red composition, and the colored composition (GS-) 1) ~(GS-2) is a green composition.

In Table 8, each component is as follows.

C-1: a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name KAYARAD DPHA)

D-1: NCI-930 (made by ADEKA Co., Ltd.)

D-2: 2,2'-bis(2-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole

D-3: 2,4-diethylthioxanthone

D-4: 2-mercaptobenzothiazole

F-1: Megafac F-554 (made by DIC Corporation)

E-1: propylene glycol monomethyl ether acetate

E-2: diacetone alcohol

E-3: cyclohexanone

Claims (10)

A coloring composition comprising: (A) a colorant comprising at least one selected from the group consisting of a dye and a dye multimer, the dye multimer having a dye having a dye residue and an ethylenically unsaturated group The monomer is a structural unit, (B) an adhesive resin, and (C) a polymerizable compound, and the copolymerization ratio of the ethylenically unsaturated monomer represented by the following formula (1) is (B) an adhesive resin: a copolymer of more than % by mole, wherein the copolymer does not include the dye multimer, In the formula (1), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkanediyl group having 2 to 4 carbon atoms, and R ³ represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted polycyclic aromatic group. The hydrocarbon group or the substituted or unsubstituted nitrogen-containing alicyclic heterocyclic group, and n represents an integer of 0 to 100. When n is 2 or more, a plurality of R ² may be the same or different. The coloring composition of claim 1, wherein the copolymerization ratio of the ethylenically unsaturated monomer represented by the formula (1) in the copolymer is 22 mol% or more. A colored composition according to claim 1, which comprises a dye or a dye multimer selected from the group consisting of a triarylmethane dye as a dye, a dye, a dimethylene pyrrole dye, and a cyanine dye, the dye multimer having a dye selected from the group consisting of triarylmethane dyes, A dye monomer, a dimethylene pyrrole dye, and a dye monomer of a cyanine dye and a dye monomer of an ethylenically unsaturated group are used as structural units. The colored composition of claim 1, wherein n = 0 in the formula (1). The coloring composition of claim 1, wherein the copolymerization ratio of the ethylenically unsaturated monomer represented by the formula (1) is 60 mol% or less. The coloring composition of claim 1, wherein the dye monomer is a monomer represented by the following formula (2), In the formula (2), R ¹¹ represents a hydrogen atom or a methyl group, and X ¹ represents a single bond, a substituted or unsubstituted divalent hydrocarbon group, or one or more of the divalent hydrocarbon group and an atom other than a carbon atom and a hydrogen atom. A divalent group in which a linking group is combined, and D ¹ represents a dye residue. A colored cured film formed using the colored composition according to any one of claims 1 to 6. A color filter comprising the colored cured film of claim 7. A display element comprising the colored cured film of claim 7. A solid-state photographic element comprising the colored cured film of claim 7.