JP2008268884A - Colored curable resin composition, colored pattern forming method, colored pattern, method for manufacturing color filter, color filter and liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored curable resin composition having good coating properties. <P>SOLUTION: The colored curable resin composition includes (a) a color material, (b) a solvent, (c) at least two kinds of binder resins, (c) a photopolymerization initiator and (e) a surfactant, wherein at least two kinds of the binder resins are resins having 0.0005-0.0050 eq/g of a (meth)acryloyl group and having an acid number of 15-150 mgKOH/g. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a colored curable resin composition, a colored pattern forming method, a colored pattern, a color filter manufacturing method, a color filter, and a liquid crystal display element.

  A color filter is a colored photosensitive composition containing a binder resin and / or monomer, a photopolymerization initiator, and other components in a solvent dispersion composition of a coloring material such as an organic pigment and an inorganic pigment. It is manufactured by the photolithographic method.

  In recent years, the use of color filters in liquid crystal display (LCD) applications has tended to expand not only to monitors but also to televisions (TVs). With this trend of expanding applications, advanced color characteristics such as chromaticity and contrast. Has come to be required. In addition, in the image sensor (solid-state imaging device) application, a device having high color characteristics is also demanded.

In addition, with the increase in size of the substrate, the method of applying the colored photosensitive composition has been shifted from the spin coating method to the slit coating method (also referred to as die coating or casting coating) for the purpose of improving productivity. Among them, a composition suitable for the coating method is required, and as such a composition, a composition in which specific physical properties are controlled is disclosed (for example, see Patent Document 1).
In recent years, with the widespread use of large-sized liquid crystal displays and the like, further increase in the size of substrates has progressed, and there has been a demand for unprecedented high-speed coating in the slit coating method. However, these techniques have a problem that there are still many coating defects when the slit coating speed is set to 200 mm / sec on a glass substrate for producing a color filter.
On the other hand, a technique of controlling coating film thickness unevenness using a specific binder is also disclosed, but there is still a problem that it cannot cope with high-speed coating slit coating (for example, see Patent Document 2).
WO2005 / 075524A1 JP 2002-20442 A

The present invention relates to a colored curable resin composition having good coating characteristics, a colored pattern forming method having a slit coating process using the colored curable resin composition, and a colored pattern formed by the colored pattern forming method. The purpose is to provide.
Another object of the present invention is to provide a method for producing a color filter having the color pattern with a good film surface shape, a color filter produced by the production method, and a liquid crystal display device using the color filter. To do.

In view of the above circumstances, the present inventors have conducted extensive research and found that the above problems can be solved, thereby completing the present invention.
That is, the present invention is achieved by the following means.

<1> A colored curable resin composition comprising (a) a color material, (b) a solvent, (c) at least two binder resins, (d) a photopolymerization initiator, and (e) a surfactant, A colored curable resin, wherein at least two of the binder resins are resins having a (meth) acryloyl group of 0.0005 to 0.0050 eq / g and an acid value of 15 to 150 mgKOH / g Composition.
<2> The colored curable resin according to <1>, wherein at least one of the binder resins includes a (meth) acrylic copolymer having an alicyclic (meth) acryloyl group in a side chain. Composition.

<3> At least one of the binder resins is any one selected from the following general formula (1-1), formula (1-2), and formula (1-3): The colored curable resin composition according to <1> or <2>.

(In the above formula, R represents a hydrogen atom or a methyl group. R ₁ represents an alkyl group having 1 to 18 carbon atoms, a phenyl group containing 1 to 4 carbon atoms or an alkoxy group, and 6 carbon atoms. Represents an -12 aryl group or an aralkyl group having 7 to 12 carbon atoms, R ₂ represents a phenylcarbamic acid ester containing an alkylene group having 1 to 18 carbon atoms and an alkyl group having 1 to 4 carbon atoms; Alternatively, it represents a carbamic acid ester containing an alicyclic group having _{3 to} 18 carbon atoms, and R ₃ represents a linear or branched alkylene group having 2 to 16 carbon atoms.
A to d in formula (1-1), a to e in formula (1-2), and a to e in formula (1-3) represent the content molar ratio (mol%) of the repeating unit: Formula (1) A to d: b in -1) represents 3 to 50, c represents 3 to 40, d represents 2 to 60, and a + b + c + d = 100. A to e: b in the formulas (1-2) and (1-3) represent 0 to 85, c represents 3 to 50, d represents 3 to 40, e represents 2 to 60, and a + b + c + d + e = 100. n is 2-16. )

<4> A colored pattern forming method comprising a step of applying the colored curable resin composition according to any one of the above items <1> to <3> by a slit coating method.
<5> A colored pattern formed by the method for forming a colored pattern according to <4> above.
<6> A method for producing a color filter having the colored pattern according to <5>.

<7> A color filter produced by the production method according to the above <6> and having a contrast of 5000 or more.
<8> A liquid crystal display device using the color filter according to <7>.

According to the present invention, a colored curable resin composition having good coating properties, a colored pattern forming method having a slit coating process using the colored curable resin composition, and a colored pattern formed by the colored pattern forming method Can be provided.
Moreover, according to this invention, the manufacturing method of the color filter which has the said coloring pattern with favorable film | membrane surface shape, and the color filter manufactured by the said manufacturing method can be provided.
Furthermore, a liquid crystal display element using the color filter can be provided.

Hereinafter, the present invention will be described in detail.
<Colored curable resin composition>
The colored curable resin composition of the present invention comprises (a) a color material, (b) a solvent, (c) at least two binder resins, (d) a photopolymerization initiator, and (e) a surfactant that contains a surfactant. And at least two of the binder resins have a (meth) acryloyl group of 0.0005 to 0.0050 eq / g and an acid value of 15 to 150 mgKOH / g It is characterized by.
Here, having a (meth) acryloyl group means having at least one of an acryloyl group and a methacryloyl group.
The colored curable resin composition may contain other optional components in addition to the essential components.

In the colored curable resin composition, the concentration of the total solid content in the entire colored curable resin composition is preferably 2 to 50% by mass, more preferably 10 to 30% by mass, particularly 15 to 25%. A range of mass% is preferred.
Hereinafter, the components and the like of the colored curable resin composition will be described in detail.

<(C) Binder resin>
The colored curable resin composition contains (c) at least two binder resins (hereinafter referred to as “resin in the present invention”) as a binder resin, and the binder resin has 0 (meth) acryloyl group. .0005-0.0050 eq / g and an acid value of 15-150 mg KOH / g.
In addition, the binder resin in the present invention is a polymer that satisfies the above-described characteristics and is soluble in an organic solvent and a weak alkaline aqueous solution. In these polymers, the (meth) acryloyl group is 0.0005 to 0.0050 eq / g, preferably 0.0007 to 0.0020 eq / g, more preferably 0.0010 to 0.0020 eq / g.
It is preferable that the (meth) acryloyl group is 0.0005 eq / g or more and 0.0050 eq / g or less in the polymer, since the curability is good and an appropriate development region can be obtained.

The acid value of the resin in the present invention is 15 to 150 mgKOH / g, preferably 35 to 150 mgKOH / g, more preferably 50 to 120 mgKOH / g.
By setting it as these ranges, it becomes easy to ensure appropriate coating property and an appropriate development area, which is preferable. In order to bring the acid value of this polymer into the above range, for example, a method of bonding an acid group (carboxyl group, sulfonic acid group, phosphoric acid group, etc.) to the side chain can be mentioned. The acid group is preferably a carboxyl group.
Moreover, it is preferable to have a hydroxyl group from the viewpoint of substrate adhesion regardless of the acid value. Examples of the hydroxyl group include a repeating unit derived from hydroxymethyl methacrylate. In this case, the content is preferably 3 to 40 and more preferably 10 to 30 in terms of mole percentage of the unit.

  At least one binder resin in the present invention preferably contains a (meth) acrylic copolymer having an alicyclic (meth) acryloyl group in the side chain. Furthermore, it is preferable that at least one of the binder resins includes any one selected from the following general formulas (1-1) to (1-3).

<(Meth) acrylic copolymer having alicyclic (meth) acryloyl group in side chain>
The binder resin in the present invention preferably contains a (meth) acrylic copolymer (hereinafter also referred to as “binder resin c1”) having an alicyclic (meth) acryloyl group as a polymerization group in the side chain.

As synthesis means for introducing such a polymer group into a resin, methods described in JP-B-50-34443, JP-B-50-34444 and the like are known.
Specifically, a carboxyl group or a hydroxyl group in the resin is polymerized to the side chain by reacting, for example, a compound having both an alicyclic epoxy group such as an epoxycyclohexyl group and an epoxycyclopentyl group and a (meth) acryloyl group. A resin having a group can be obtained.
Preferable examples of the above compounds include epoxycyclohexylmethyl (meth) acrylate and epoxycyclopentylmethyl (meth) acrylate, and among these, (3,4-epoxycyclohexyl) methyl (meth) acrylate is most preferable.

  In the present invention, by introducing an alicyclic group into the side chain of the binder resin, it is particularly excellent in adhesion with the substrate, and can be a photocurable resin composition having high chemical resistance, Particularly, it is suitable for a color filter.

  The resin skeleton into which the (meth) acryloyl group as a polymerization group is introduced is a (meth) acrylic copolymer, and the monomer to be copolymerized with (meth) acrylic acid is α such as styrene and α-methylstyrene. Styrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, vinyl acetate, which may be substituted with an alkyl group at the position , Acrylonitrile, (meth) acrylamide, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, crotonyl glycidyl ether, glycidyl ether crotonic acid, (meth) acrylic acid chloride, benzyl (meth) acrylate, hydroxyethyl (meth) ) Acrylate, N- Examples include copolymers obtained by copolymerizing monomers such as methylolacrylamide, N, N-dimethylacrylamide, N-methacryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, and N, N-dimethylaminoethylacrylamide. In particular, a copolymer containing (meth) acrylic acid and styrene optionally substituted with an alkyl group at the α-position as a copolymerization component is preferable.

  The proportion of the (meth) acrylic acid in the (meth) acrylic copolymer having the (meth) acryloyl group introduced as the polymerizing group is preferably 0.2 to 0.8, more preferably 0, in terms of molar ratio. .3 to 0.7. Moreover, 0.8-0.2 are preferable, and, as for the content rate in the copolymer of copolymerization components, such as said styrene, 0.7-0.3 are more preferable.

  The weight average molecular weight measured by GPC of the binder resin c1 used in the present invention, that is, the (meth) acrylic copolymer is preferably 5,000 to 100,000, more preferably 10,000 from the viewpoint of coatability. 000-70,000. From the viewpoint of liquid storage stability, it is preferably 1,000 to 70,000, more preferably 1,000 to 50,000.

<Resin selected from general formulas (1-1) to (1-3)>
The binder resin constituting the composition of the present invention is a resin having a (meth) acryloyl group of 0.0005 to 0.0050 eq / g and an acid value of 15 to 150 mgKOH / g. Hereinafter, “binder resin c2”) preferably includes any one selected from the following general formulas (1-1) to (1-3).

In General Formula (1-1) to General Formula (1-3), R represents a hydrogen atom or a methyl group. R ₁ is an alkyl group having 1 to 18 carbon atoms (C _{1 to} C ₁₈ ), a phenyl group containing an alkyl group having 1 to 4 carbon atoms (C _{1 to} C ₄ ) or an alkoxy group, and 6 to 12 carbon atoms. (C ₆ -C ₁₂ ) aryl groups, or C 7-12 (C ₇ -C ₁₂ ) aralkyl groups.
The C ₁ -C ₁₈ alkyl group for R ₁ may be linear, branched, or cyclic. For example, methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, decyl Group, dodecyl group, hexadecyl group, octadecyl group, 2-chloroethyl group, 2-bromoethyl group, 2-cyanoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 3-bromopropyl group and the like.

The alkyl group of C ₁ -C ₄ contained in the phenyl group, in the specific examples of the alkyl group of the C ₁ -C _18, include those of 1 to 4 carbon atoms, C contained in the phenyl group Examples of the _{1 to} C ₄ alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
Examples of the C ₆ -C ₁₂ aryl group for R ₁ include a phenyl group, a tolyl group, and a naphthyl group.
Examples of the C _{7 to} C ₁₂ aralkyl group include a benzyl group, a phenethyl group, a 3-phenylpropyl group, a naphthylmethyl group, a 2-naphthylethyl group, a chlorobenzyl group, a bromobenzyl group, a methylbenzyl group, and an ethylbenzyl group. Methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group and the like.

In the general formula (1-1) to formula (1-3), _{R 2 is} phenyl carbamic acid ester containing alkylene _group, an alkyl group of C 1 -C ₄ a _C 1 ~C _18, C 3 ~ It is a carbamic acid ester containing a _C18 alicyclic group.
Alkylene group of C ₁ -C ₁₈ include those alkyl groups of _C 1 _{-C 18} represented by _{R 1} has become divalent and the like, alkyl groups of _C 1 -C ₄ included in the phenyl carbamate Examples of the alkyl group include those having 1 to 4 carbon atoms among the specific examples of the C _{1 to} C ₁₈ alkyl group represented by R ₁ .
The phenylcarbamic acid ester has a structure represented by (—OCO—NH—C ₆ H ₄ —), and the alkyl group is a substituent of the phenylene group.
Examples of the C _{3 to} C ₁₈ alicyclic group contained in the carbamate include a cyclopentyl group, a cyclobutyl group, a cyclohexyl group, an isophorone group, and a dicyclohexyl group. The carbamic acid ester has a structure represented by (—NH—COO—), and the alicyclic group forms a divalent group together with this structure.
R ₃ represents a linear or branched alkylene group having 2 to 16 carbon atoms, and specifically, 2 to 16 carbon atoms in the C _{1 to} C ₁₈ alkyl group of the above R ₁ are 2 The one that has become worthy.

  A to d in formula (1-1), a to e in formula (1-2), and a to e in formula (1-3) represent the content molar ratio (mol%) of the repeating unit: -1) a to d: b represents 3 to 50, preferably 5 to 40, c represents 3 to 40, preferably 10 to 30, d represents 2 to 60, preferably 5 to 50, a + b + c + d = 100. n is 2 to 16, preferably 4 to 12.

  A to e: b in the formulas (1-2) and (1-3) represent 0 to 85, preferably 0 to 80, c represents 3 to 50, preferably 5 to 40, and d represents 3 to 40 , Preferably 8-30, e 2-60, preferably 2-50, a + b + c + d + e = 100. n is 2 to 16, preferably 4 to 12.

In the general formulas (1-1) to (1-3), R ₁ preferably represents an aralkyl group, more preferably a benzyl group, and R ₂ preferably has 2 to 2 carbon atoms. The residue except 16 alkylene groups and (NCO) of the following diisocyanate can be mentioned. Preferably, diphenylmethane diisocyanate, tolylene diisocyanate, xylylene diisocyanate, 2,4-toluylene diisocyanate, o-toluylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, more preferably hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate. Can be mentioned.

The R _3, n is an integer of 2 to 10 - _{(CH 2) n} - are preferred, n is a integer from 2 to 6 - _{(CH 2) n} - is preferred.

In the colored curable resin composition of the present invention, each of the c1 and c2 may be used alone, or two or more of the c1 and c2 may be used in combination. May be.
The content of the binder resin in the colored curable resin composition of the present invention is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 30 depending on the ratio (concentration) of the total solid content. -75 mass%.
By making content of binder resin in the said colored curable resin composition into 10-90 mass%, it is preferable at the point which becomes easy to form a coating film with a favorable coating surface shape.

In the present invention, in addition to the resin component described above, other resins may be added to the composition as long as the effects of the present invention are not impaired in order to improve developability and physical properties (mechanical properties, adhesion, etc.). Can be added.
Along with the above resins, benzyl (meth) acrylate / (meth) acrylic acid copolymer and benzyl (meth) acrylate / (meth) acrylic acid / and other monomers and other monomers (benzyl (meth) acrylate and acid component) Can be used in combination with a thermoplastic resin such as 5 / 5-9 / 1.

<(C3) Compound having an ethylenically unsaturated group>
The colored curable resin composition of the present invention can contain (c3) a compound having an ethylenically unsaturated group (hereinafter, appropriately referred to as a polymerizable compound).
The polymerizable compound that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and is a compound having at least one terminal ethylenically unsaturated bond, preferably two or more. To be elected. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. These have chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or mixtures thereof and copolymers thereof.

  Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate Sorbitol tetritaconate, etc. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetracrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

_{CH 2 = C (R) COOCH} 2 CH (R ') OH (A)
(However, R and R ′ represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Further, by using addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238, It is possible to obtain a photopolymerizable composition excellent in the photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these photopolymerizable compounds (addition polymerizable compounds), the details of usage, such as the structure, single use or combined use, and addition amount, can be arbitrarily set according to the performance design of the final coloring pattern. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the colored pattern, that is, the cured film, those having three or more functionalities are preferable, and furthermore, different functional numbers / different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, vinyl ether). It is also effective to adjust both sensitivity and strength by using a compound of the type). From the viewpoint of curing sensitivity, it is preferable to use a compound containing two or more (meth) acrylic acid ester structures, more preferably a compound containing three or more, and most preferably a compound containing four or more. preferable. Moreover, it is preferable to contain an EO modified body from a viewpoint of hardening sensitivity and developability of an unexposed part. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.
In addition, other components in the colored curable resin composition of the present invention (for example, (a) a color material, (d) a photopolymerization initiator and (c) a binder resin (alkali-soluble resin)) used in combination as desired. The selection and use method of the addition polymerization compound is also an important factor for the compatibility and dispersibility of the resin. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. . In addition, when the colored curable resin composition is applied to a substrate or the like, a specific structure may be selected for the purpose of improving the adhesion to the substrate or the like.

  From the above viewpoints, bisphenol A diacrylate, modified bisphenol A diacrylate EO, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D (I) Isocyanurate, pentaerythritol tetraacrylate EO modified product, dipentaerythritol hexaacrylate EO modified product, etc. are mentioned as preferable ones. Also, as commercially available products, urethane oligomer UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.) Made), DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (made by Kyoeisha).

  Among them, bisphenol A diacrylate EO modified, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified, di Examples of commercially available modified products such as pentaerythritol hexaacrylate EO include DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 ( Kyoeisha) is more preferable.

  In the present invention, (c3) polymerizable compounds can be used in combination of two or more, in addition to being used alone.

The content of the polymerizable compound (c3) in the colored curable resin composition of the present invention is preferably 1 to 90% by mass, and 5 to 80% by mass with respect to the total solid content of the composition. It is more preferable that it is 10-70 mass%. When the content of the polymerizable compound is within the above range, the curing reaction can be sufficiently performed.
In particular, when the colored curable resin composition of the present invention is used for forming a colored pattern of a color filter, the content is preferably 5 to 50% by mass, and 7 to 40% by mass. More preferably, it is more preferably 10 to 35% by mass.

<(A) Color material>
(A) A coloring material means what colors the coloring curable resin composition of this invention. As the coloring material, dyes and pigments can be used, but pigments are preferable from the viewpoint of heat resistance, light resistance and the like.
As the pigment, various color pigments such as a blue pigment, a green pigment, a red pigment, a yellow pigment, a purple pigment, an orange pigment, a brown pigment, and a black pigment can be used. The structure is organic such as azo, anthraquinone, phthalocyanine, quinacridone, benzimidazolone, isoindoline, dioxazine, indanthrene, perylene, diketopyrrolopyrrole, quinophthalone, etc. In addition to pigments, various inorganic pigments can also be used.
Specific examples of pigments that can be used are shown below by pigment numbers. In addition, “CI” described below means a color index (CI).

Examples of red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267 268, 269, 270, 271, 272, 273, 274, 275, 276.
Of these, C.I. I. Pigment Red 48: 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment red 177, 209, 224, 254.

Examples of blue pigments include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79.
Of these, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 3, 15: 6.

Examples of green pigments include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55.
Of these, C.I. I. And CI Pigment Green 7 and 36.

Examples of yellow pigments include C.I. I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208, FAST Yellow Y-5688, Yellow Pigment E4GN, and Yellow 5GN-01.
Of these, C.I. I. Pigment Yellow, 117, 129, 138, 139, 150, 154, 155, 180, 185, FAST Yellow Y-5688, Yellow Pigment E4GN, Yellow 5GN-01, more preferably C.I. I. And CI Pigment Yellow 138, 139, 150, 180, 185, FAST Yellow Y-5688, Yellow Pigment E4GN, and Yellow 5GN-01.

Examples of orange pigments include C.I. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79.
Of these, C.I. I. And CI pigment oranges 38 and 71.

Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50.
Of these, C.I. I. Pigment violet 19, 23, more preferably C.I. I. And CI Pigment Violet 23.

  Further, when the colored curable resin composition of the present invention is a colored curable resin composition for a black matrix of a color filter, a black color material can be used as the color material. The black color material may be a single black color material or a mixture of red, green, blue, and the like. These color materials can be appropriately selected from inorganic or organic pigments and dyes. In the case of inorganic and organic pigments, it is preferable to use the pigment dispersed in an average particle size of 1 μm or less, preferably 0.5 μm or less.

  Color materials that can be mixed for preparing a black color material include Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170). Safranin OK70: 100 (50240), Erioglaucine X (42080), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimla First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Dionogen Red GD (Pigment Red 1) 8), Lionol Green 2YS (such as C.I. Pigment Green 36) and the like (Note that the number in parentheses means a color index (C.I.)).

  Further, other pigments that can be used in combination are C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigments 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

Examples of black color materials that can be used alone include carbon particles such as carbon black, acetylene black, lamp black, bone blutter, graphite, iron black, aniline black, cyanine black, titanium black, and silver, or particles having metal. Can be mentioned.
Examples of preferred metals constituting these metal-based fine particles include copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium, iridium, iron, calcium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium. , Tantel, bismuth, antimony, and alloys thereof. Further preferred metals are at least one selected from copper, silver, gold, platinum, palladium, tin, calcium, and alloys thereof, and particularly preferred metals are copper, silver, gold, platinum, tin, and alloys thereof. A compound with other elements other than metals is also preferable.
Examples of the compound of metal and other elements include metal oxides, sulfides, sulfates, carbonates, and the like, and these particles are preferable as the metal compound particles. Of these, sulfide particles are preferred because of their color tone and ease of fine particle formation.
Moreover, a metal, its alloy, and a metal compound may be used together, and 2 or more types may be sufficient as it. Among these, silver or an alloy thereof and a sulfide thereof are particularly preferable because of their high shielding effect. As an example of an alloy, a silver tin alloy is mentioned as a preferable example.

  Among these black color materials, alloys such as carbon black, titanium black, silver, and silver tin, and sulfides thereof are preferable because of their high shielding effect. Examples of carbon black include the following carbon black.

  Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA100R, MA220, MA230, MA600, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 40, # 44, # 45 # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 950, # 960, # 970, # 980, # 990, # 1000, # 2200, # 2300, # 2350, # 2400, # 2600, # 3050, # 3150, # 3250, # 3600, # 3750, # 3950, # 4000, # 4010, OIL7B, OIL9B, OIL11B, OIL30B, OIL31

  Degussa: PrintexS, Printex3OP, PrintexSO, Pril: itex30OP, Printex40, Printex45, Printex55, PrintexGO, Printex75, PrintexSO, Printex85, Printex9O, PrintexA, PrintexL, PrintexG, PrintexP, PrintexU, Printexv, PrintexG, SpecialBlack550, Specia1B1ack350, Specia1B1ack250, Special Black100, Special Black6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Col r Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

  Manufactured by Cabot: Monarch120, Monarch280, Monarch4, 60, Monarch800, Monarch880, Monarch900, MonarchGA, GAR6LRE, REGAL250, REGAL250, REGAL250, REGAL250, REGAL250 PEARlS480, PEARLS130, VULCAN XC72R, ELFTEX-8

  Made by Colombian Carbon: Raven11, Raven14, Raven15, Raven16, Raven22, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven850, Raven890, Raven1000, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10, Raven10 RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVENS750, RAVEN7000

Examples of titanium black include the following.
As a method for producing titanium black, a mixture of titanium dioxide and titanium metal is heated and reduced in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium dioxide in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, No. 61-201610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610), etc. It is not a thing.

Examples of commercially available titanium black include Mitsubishi Materials Titanium Black 10S, 12S, 13R, 13M, 13M-C, and the like.
As an example of another black pigment, aniline black, an iron oxide black pigment, and organic pigments of three colors of red, green, and blue can be mixed and used as a black pigment.
In addition, barium sulfate, lead sulfate, titanium oxide, yellow lead, bengara, chromium oxide, and the like can also be used as the pigment.

  The above-mentioned various pigments can be used in combination. For example, in order to adjust the chromaticity, a green pigment and a yellow pigment can be used in combination, or a blue pigment and a violet pigment can be used in combination.

The average primary particle size of these pigments is preferably 10 nm to 100 nm, more preferably 10 nm to 50 nm.
The content of the pigment is preferably 30% by mass or more and 70% by mass or less, more preferably 38% by mass or more and 60% by mass or less, based on the total solid content of the colored curable resin composition. More preferably, it is at least 60% by mass.
In the present invention, the “total solid amount” means all components excluding the solvent component, that is, (a) a coloring material, (c) at least two binder resins, (d) a photopolymerization initiator, (e ) A surfactant, and (f) a component other than the solvent among other components.

As described above, a pigment is preferable as a color material from the viewpoint of heat resistance, light resistance, and the like, but a dye can also be used.
Examples of the dye that can be used as the colorant include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes.

  Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include Moldant Black 7.

  Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disper thread 60, C.I. I. Disperse Blue 56, C.I. I. Examples include Day Sparse Blue 60.

  Other examples of the phthalocyanine dye include C.I. I. Pad Blue 5 and the like are quinone imine dyes such as C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are quinoline dyes such as C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I, Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

<(B) Solvent>
In the colored curable resin composition, (a) a coloring material, (c) at least two binder resins, (d) a photopolymerization initiator, and (e) a component such as a surfactant are dissolved or dispersed. (B) A solvent is used.
Examples of the solvent include glycol ethers and / or alkoxyesters.

  Specific examples of glycol ethers include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether acetate, ethylene glycol mono-n-butyl ether, Ethylene glycol acetate, ethylene glycol diacetate, ethylene glycol diethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol diethyl coether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n- Butylue Ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether acetate, tripropylene glycol methyl ether.

  Specific examples of alkoxyesters include ethyl acetate, methyl isobutyrate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropionic acid. Examples include propyl, butyl 3-methoxypropionate, butyl acetate, butyl acetate (n, sec, t-), butyl stearate, ethyl propionate, ethyl benzoate, ethyl orthoformate, ethyl caprylate, propyl acetate and the like. .

  In addition, for example, diisopropyl ether, mineral spirit, n-pentane, amyl ether, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, n-octane, Barsol # 2, Apco # 18 solvent, diisobutylene, amyl acetate, Apco Thinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl noninoreketone, propyl ether, dodecane, soak solvent no. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, amyl chloride, butylene glycol diacetate, methoxymethyl pentanone, methyl butyl ketone, methyl hexyl Ketone, benzonitrile, methyl cellosolve acetate, methylenoisoamyl ketone, methyl isobutyl ketone, amyl acetate, amyl formate, bicyclohexyl, dipentene, methoxymethyl pentanol, methyl amyl ketone, methyl isopropyl ketone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve , Ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl lactate, propylene glycol, 3-methyl Kishipuropion acid, 3-ethoxy propionate, diglyme, ethyl carbitol, butyl carbitol, 3-methyl-3-methoxybutanol, 3-methyl-3-methoxybutyl acetate and the like.

A solvent may be used individually by 1 type and may use 2 or more types together.
The content of the solvent in the entire colored curable resin composition of the present invention is appropriately set in the range of usually 50 to 95% by mass, depending on the ratio (concentration) of the total solid content. More preferred is 70 to 90% by mass, and particularly preferred is 75 to 90% by mass.
By setting it as this range, applicability | paintability and a coating film formation property improve.

<(D) Photopolymerization initiator>
The colored curable resin composition of the present invention contains a photopolymerization initiator that directly absorbs light or is photosensitized to cause a decomposition reaction or a hydrogen abstraction reaction to generate a polymerization active radical. The photopolymerization initiator preferably has absorption in a wavelength region of 300 to 500 nm.

A photoinitiator may be used individually by 1 type and may use 2 or more types together.
The content of the photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and particularly preferably 1 to the total solid content of the colored curable resin composition. ˜20 mass%. Within this range, good sensitivity and pattern formability can be obtained.

When forming a black photopolymerizable layer with a colored curable resin composition, the photopolymerization initiator is sensitive to ultraviolet light to visible light because the image is exposed from the photopolymerizable layer through a pattern mask. In the image exposure, it is preferable to use an exposure light source corresponding to the compound.
Also in the red, green, and blue photopolymerizable layers, red, green, and blue allo-image patterns are formed between the four black matrix patterns by exposure through a pattern mask for each color and other methods. Therefore, as in the case of the black matrix pattern, the photopolymerization initiator is preferably a compound that exhibits sensitivity to ultraviolet light to visible light, particularly a compound that exhibits spectral sensitivity at a wavelength of 450 nm or less, particularly 400 nm or less.

  Examples of the photopolymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaaryes. Examples include rubiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.

  More preferably, they are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and trihalo. Most preferred is at least one compound selected from the group consisting of methyltriazine compounds, α-aminoketone compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds.

  Examples of the photopolymerization initiator include metallocene compounds including titanocene compounds described in JP-A-59-152396 and JP-A-61-151197, and hexaarylbiimidazoles described in JP-A-10-39503. Derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino-acids such as N-phenyl-glycine, N-aryl-α-amino-acid salts, N-aryl-α-amino-acid esters, etc. Examples include radical activators, α-amino-alkylphenone compounds, and oxime ester initiators described in JP-A No. 2000-80068.

  Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Patent Publication No. 46-4605, JP 48-36281, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP 62 -212401, JP-A-63-70243, JP-A-63-298339, M.S. P. Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and the oxazole compound and s-triazine compound substituted with a trihalomethyl group.

Specific examples of the photopolymerization initiator that can be used in the present invention are listed below.
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 -Halomethylated triazine derivatives such as ethoxynaphthyl) -4,6-bis (todichloromethyl) mono-s-triazine and 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine.

  As the s-triazine compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6- Tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 4- (o-bromo-pN) , N- (diethoxycarbonylamino) -phenyl) -2,6-di (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) -s-triazine, 2,4,6-tris (Tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6-bis (tribromomethyl) -s-triazine, etc. It is done.

  2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2-benzofuryl) vinyl] -1,3,4-oxadi Azole, 2-trichloromethyl-5- [β- (2 ′-(6 ″ -benzofuryl) vinyl)]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3 Halomethylated oxadiazole derivatives such as 4-oxadiazole.

  Examples of the oxydiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2- Examples include trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, and the like. .

  2- (2′-chlorophenyl) -4,5-diphenyl-imidazolol dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- (2 '-Fluorophenyl) -4,5-diphenyl-imidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenyl-imidazole dimer, (4'-methoxyphenyl) -4,5 -Imidazole derivatives such as diphenyl-imidazole dimer.

  Benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl edel.

  Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone.

  Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone.

  2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl (p-isopropylphenyl) ) Ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p -Acetophenone derivatives such as butylphenyl) ketone.

  Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone.

Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.
Acridine derivatives such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine.
Phenazine derivatives such as 9,10-dimethylbenzphenazine.
Anthrone derivatives such as benzanthrone.

  Dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-bisphenyl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, di Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, di Cyclopentadienyl-Ti-2,6-difluorophenyl-1-yl, dicyclopentadienyl-Ti-2,4-difluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis2,3 4,5,6-pentafluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, dicyclopen Dienyl -Ti-2,6-difluoro-3- (pyrr-1-yl) - titanocene derivatives such as phenyl-1-yl.

  2-Methyl-1 [4- (methyl-thio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 , 2-Benzyl-2-dimethyl-amino-1- (4-morpholinophenyl-) butanone-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopro Piophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. [Alpha] -aminoalkylphenone compounds.

  1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- Oxime ester compounds such as 3-yl]-, 1- (O-acetyloxime).

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl-1- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-mol Forinophenyl) -butanone-1,2,4,6 trimethylbenzoyl-diphenyl-phosphine oxide, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, 2-benzyl-2-dimethylamino-4 -Acetophenone derivatives such as morpholinobyrophenone, thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, Examples thereof include benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  Examples of the ketal compound include benzyl dimethyl ketal and benzyl-β-methoxyethyl ethyl acetal.

  Examples of the benzoin compound include m-benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoylbenzoate and the like.

  Examples of the acridine compound include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxide). Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2 , -Oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- ( t-he Sylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate), carbonyldi (t-hexylper) Oxydihydrogen diphthalate) and the like.

  Examples of the azo compound include azo compounds described in JP-A-8-108621.

  Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl). ) Amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the azide compound include organic azide compounds described in U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,553, 2,6-bis (4-azidobenzylidene) -4-ethyl. And cyclohexanone (BAC-E).

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as dicyclopentadienyl-Ti-bis-phenyl, dicyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, dicyclopenta Dienyl-Ti-bis-2,4-di-fluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, dicyclopentadienyl- Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluoro Enyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, dimethylcyclopentadienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl Dimethylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-penta Examples thereof include fluorophenyl-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, and the like.

  As the hexaarylbiimidazole compound, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, 4,622,286, etc. And, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl) )) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 ′ -Bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biidazole, 2,2'-bis (o, o'-dichlorophenyl) -4,4', 5,5 '-Tetraphenylbi Dazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5 Examples include 5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like.

  Examples of the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188585, JP-A-9-188686, JP-A-9-188710, JP-A-2000. -131837, JP-A-2002-107916, Japanese Patent No. 2764769, JP-A-2002-116539, etc., and Kunz, Martin “Rad Tech '98. Proceeding April 19-22, 1998, Chicago” etc. Organoborates described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, and organic boron oxosulfonium complexes, JP-A-6-175554 No. 6, JP-A-6-175553 Organoboron iodonium complexes described in JP-A-9-188710, organoboron phosphonium complexes described in JP-A-9-348710, JP-A-7-128785, JP-A-7-140589, JP-A-7- Specific examples include organoboron transition metal coordination complexes such as those described in Japanese Patent No. 306527 and Japanese Patent Laid-Open No. 7-292014.

  Examples of the disulfone compound include compounds described in JP-A Nos. 61-166544 and 2002-328465.

  Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797 Compounds and the like. Specific examples include Irgacure OXE-01 and OXE-02 manufactured by Ciba Specialty Chemicals.

  Examples of onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. , 18, 387 (1974), T.A. S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in U.S. Pat. No. 4,069,055, ammonium salts described in JP-A-4-365049, U.S. Pat. No. 4,069, No. 055, No. 4,069,056, phosphonium salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, JP Examples include iodonium salts described in JP-A No. -150848 and JP-A-2-296514.

  The iodonium salt that can be suitably used in the present invention is a diaryl iodonium salt, and is preferably substituted with two or more electron donating groups such as an alkyl group, an alkoxy group, and an aryloxy group from the viewpoint of stability. . In addition, as another preferable iodonium salt form, an iodonium salt in which one substituent of the triaryl iodonium salt has a coumarin and an anthraquinone structure and absorption at 300 nm or more is preferable.

Examples of the sulfonium salt that can be suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, and U.S. Pat. 933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, Germany Examples thereof include sulfonium salts described in the specifications of Patent Nos. 2,904,626, 3,604,580, and 3,604,581, and are preferably electron withdrawing groups from the viewpoint of stability. It is preferably substituted. The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorbs at 300 nm or more. As another preferable sulfonium salt, a sulfonium salt in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more can be mentioned.

  Moreover, as an onium salt compound, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Examples of the acylphosphine (oxide) compound include Irgacure 819, Darocur 4265, Darocur TPO and the like manufactured by Ciba Specialty Chemicals.

  As the photopolymerization initiator (D) used in the present invention, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, phosphine Oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyl oxa Compounds selected from the group consisting of diazole compounds and 3-aryl substituted coumarin compounds are preferred.

<(E) Surfactant>
As the surfactant, various substances such as anion, cation, nonionic (nonionic), amphoteric surfactant and the like can be used, but the nonionic surfactant is used because it has a low influence on various properties. preferable.

Examples of the anionic surfactant include alkyl sulfate ester surfactants such as EMAL 10 manufactured by Kao Corporation, alkyl naphthalene sulfonate salts such as Perex NB-L, and homogenol L-18. And special polymer surfactants such as L-100.
Of these, special polymer surfactants are preferred, and special polycarboxylic acid type polymer surfactants are more preferred.

Examples of the cationic surfactant include alkylamine salt surfactants such as Acetamine 24 manufactured by Kao Corporation, and quaternary ammonium salt surfactants such as Cotamine 24P and 86W.
Of these, quaternary ammonium salt surfactants are preferred, and stearyltrimethylammonium salt surfactants are more preferred.

  As the nonionic surfactant, it is preferable to use at least one selected from the group of compounds represented by the following general formulas (A) to (D).

In the above general formulas (A) to (D), PO represents propylene oxide, and EO represents ethylene oxide. In the propylene oxide, propylene includes both — (CH ₂ ) ₃ — and —CH ₂ CH (CH ₃ ) —.

In general formula (A) and general formula (B), (Style) represents ph-CH = CH-, and (benzyl) represents ph-CH _2- . Here, ph is a phenyl group.
N is an integer of 1 to 3, preferably 1. m is an integer of 7 to 30, preferably an integer of 8 to 20. l is an integer of 0 to 10, preferably an integer of 0 to 5. a is 0-20, b is 0-20, c is an integer of 6-30, Preferably, a is 0-10, b is 0-10, c is 10-20, respectively.

In general formula (C) and general formula (D), x is an integer of 5-100, Preferably it is an integer of 5-50. Moreover, y is an integer of 20-100. Note that x and y satisfy 0.1 ≦ x / y ≦ 2.0, preferably 0.2 ≦ x / y ≦ 1.0.
Here, four x and y which exist in general formula (C) and general formula (D) are respectively the same or different integers. That is, in the general formula (C) and the general formula (D), four ethylene oxide blocks exist, but the number of ethylene oxide units constituting each of the four blocks may be the same or different. . Moreover, although four propylene oxide blocks exist in General Formula (C) and General Formula (D), the number of propylene oxide units constituting each of the four blocks may be the same or different. .

In the present invention, among the compound groups represented by the general formulas (A) to (D), the compound represented by the general formula (A) and the compound represented by the general formula (B) are preferable. .
More specifically, in the general formula (A), n is 1, l is an integer of 0 to 5, and m is an integer of 8 to 20, and specific examples include addition of ethylene oxide 8 of styrylphenol. , 10 adducts, 12 adducts, 16 adducts, 20 adducts and the like.
In the general formula (B), a compound in which n is 1 to 3, a is 0 to 10, b is 0 to 10, and c is an integer of 10 to 20 is preferable. As a specific example, monostyrylbenzylphenyl is used. Is an addition compound in which a is 4, b is 2, and c is 10, an adduct in which a is 0, b is 0, and c is 16 in tristyrylbenzylphenyl, a is 6, b is 2, c Is an adduct of 10 and an adduct of tristyrylbenzylphenyl wherein a is 8, b is 6, and c is 18.

Moreover, in this invention, well-known surfactant other than the compound group represented by the said general formula (A)-general formula (D) may be used, and these may be used together.
As the surfactant to be used, surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600 are preferable.

  Nonionic surfactants include, for example, polyoxyethylene glycols, polyoxypropylene glycols, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, polyoxypropylene alkyl ethers, Polyoxypropylene alkyl aryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters and the like are preferable.

  Specifically, polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxypropylene glycol; polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether and polyoxyethylene oleyl ether; polyoxy Polyoxyethylene aryl ethers such as ethylene octyl phenyl ether, polyoxyethylene polystyryl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene-propylene polystyryl ether, polyoxyethylene nonylphenyl ether; polyoxyethylene dilaurate , Polyoxyalkylene dialkyl esters such as polyoxyethylene distearate, sorbitan fatty acids Ester, there is nonionic surfactants such as polyoxyalkylene sorbitan fatty acid esters.

Specific examples of nonionic surfactants include, for example, Adeka Pluronic series, Adecanol series i, Tetronic series (above ADEKA), Emulgen series, Rheodor series (above Kao), Eleminol series, Noni Pole series, Octapole series, Dodecapol series, New Pole series (above Sanyo Kasei Co., Ltd.), Pionein series (above Takemoto Yushi Co., Ltd.), Nissan Nonion series (above Nihon Yushi Co., Ltd.), etc. It is. These commercially available products can be used as appropriate.
A preferable HLB value is 8 to 20, more preferably 10 to 17.

  Examples of the silicone surfactant include SH8400 manufactured by Toray Silicone Co., Ltd., KP341 manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

Fluorosurfactants include Megafac F172, F173, F176, F177, F177, F183, 470, F475, F780, F780, Daifuku Ink Co., Ltd., Florad FC430, Novec FC -4430, FC-4432 (manufactured by Sumitomo 3M), Surflon S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (Manufactured by Seimi Chemical Co., Ltd.), F-Top EF351, 352, 801, 802 (manufactured by JEMCO).
When a fluorosurfactant is used as the surfactant, the blending amount of the surfactant is 0.01% by mass or more and 1.00% by mass or less with respect to the total solid content of the colored curable resin composition. It is preferable that it is 0.1 mass% or more and 3.0 mass% or less. When the blending amount of the surfactant is within the above range, wettability and leveling properties are improved.

  When a surfactant other than the fluorosurfactant is used, the blending amount thereof may be 0.001% by mass or more and 1.0% by mass or less with respect to the total solid content of the colored curable resin composition. Preferably, it is 0.01 mass% or more and 0.5 mass% or less.

<(F) Other ingredients>
-(F-1) Dispersant (dispersion resin)-
Examples of the dispersant include polymer dispersants such as acrylic acid and styrene, acrylic acid ester and methacrylic acid, acrylic acid and methacrylic acid ester, styrene and maleic acid, copolymers, amide compounds, urethane compounds, and lactams. Resin-type dispersants such as polyamide-based compounds, barbituric acid-based compounds, polyamide-based compounds and polyurethane-based compounds (commercially available products such as Dischavic 130, Dispersic 161, Dispersic 182 and Dispersic 170, manufactured by BYK Chemie) Efka 46, Efka 47, etc. manufactured by Efka Corporation) can be used.
Among these, a dispersant having a nitrogen-containing functional group is preferable, and an acrylic dispersant, a urethane dispersant, and a graft copolymer dispersant are more preferable.

As an acrylic dispersing agent, an AB block copolymer and / or a BAB block comprising an A block having a quaternary ammonium base in the side chain and a B block having no quaternary ammonium base. A copolymer is preferred.
The A block constituting the block copolymer of the acrylic dispersant is a quaternary ammonium base, preferably -N ⁺ R _1a R _2a R _3a · Y ⁻ (where R _1a , R _2a , and R _3a are each Independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group, or two or more of R _1a , R _2a , and R _3a are bonded to each other to form a cyclic structure; Y ⁻ represents a counter anion.) And has a quaternary ammonium base. The quaternary ammonium base may be directly bonded to the main chain, but may be bonded to the main chain via a divalent linking group.

In -N ⁺ R _1a R _2a R _3a , as a cyclic structure formed by combining two or more of R _1a , R _2a , and R _3a with each other, for example, a 5- to 7-membered nitrogen-containing heterocyclic monocycle or A condensed ring formed by condensing two of these may be mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specifically, the following are mentioned, for example.

In said formula, R represents either group among R < _1a > -R < _3a >.
These cyclic structures may further have a substituent. As _R 1a _{to R 3a} in the ^{_{-N + R 1a R 2a R 3a}} , and more preferably may have an alkyl group, or a substituent having carbon atoms of 1 to 3 may have a substituent It is a phenyl group or a benzyl group which may have a substituent.

  As the A block, those containing a partial structure represented by the following general formula (9) are particularly preferable.

In the general formula (9), R _1a , R _2a and R _3a each independently represents a hydrogen atom or an optionally substituted cyclic or chain hydrocarbon group. Alternatively, two or more of R _1a , R _2a , and R _3a may be bonded to each other to form a cyclic structure. R _4a represents a hydrogen atom or a methyl group. X represents a divalent linking group, and Y ⁻ represents a counter anion.

In the general formula (9), examples of the divalent linking group X include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, —CONH—R _5a —, —COO—R _6a — (provided that R _5a and R _6a is a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R _7a —O—R _8a —: R _7a and R _8a are each independently an alkylene group). And the like, and preferably —COO—R _6a —.

Examples of Y ⁻ of the counter anion include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ^{− and the} like.

Two or more kinds of partial structures containing a specific quaternary ammonium base such as the general formula (9) may be contained in one A block. In that case, two or more quaternary ammonium base-containing partial structures may be contained in the A block in any form of random copolymerization or block copolymerization. Moreover, the partial structure which does not contain this quaternary ammonium base may be contained in the A block, and examples of the partial structure include a partial structure derived from a (meth) acrylic acid ester monomer described later. It is done.
The content of the partial structure containing no quaternary ammonium base in the A block is preferably 0 to 50% by mass, more preferably 0 to 20% by mass. Most preferably, it is not included in the A block.

  On the other hand, as the B block constituting the block copolymer of the dispersant, for example, styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) methacrylate , Isopropyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate (Meth) acrylate monomers such as glycidyl ethyl acrylate and N, N-dimethylaminoethyl (meth) acrylate; (meth) acrylate monomers such as (meth) acrylic chloride; (meth) acrylamide, N-methylolacrylamide, , N-dimethyl-acrylamide, (meth) acrylamide monomers such as N, N-dimethylaminoethyl acrylamide; vinyl acetate; acrylonitrile; azyl glycidyl ether, crotonic acid glycidyl ether; N-methacryloylmorpholine Polymer structures.

  The B block is preferably a partial structure derived from a (meth) acrylic acid ester monomer represented by the following general formula (10).

In the general formula (10), R _9a represents a hydrogen atom or a methyl group. R _10a represents a cyclic or chain alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent.

Two or more kinds of the partial structure derived from the (meth) acrylic acid ester monomer may be contained in one B block. Of course, the B block may further contain a partial structure other than these. When a partial structure derived from two or more monomers is present in a B block that does not contain a quaternary ammonium base, each partial structure is contained in the B block in any form of random copolymerization or block copolymerization. May be.
When the B block contains a partial structure other than the partial structure derived from the (meth) acrylate monomer, the content in the B block of the partial structure other than the (meth) acrylate monomer is preferably Is 0 to 50% by mass, more preferably 0 to 20% by mass, but it is most preferable that a partial structure other than the (meth) acrylic acid ester monomer is not included in the B block.

The acrylic dispersant used in the present invention is an AB block or a B-A-B block copolymer type polymer compound composed of such an A block and a B block, and such a block copolymer. Is prepared, for example, by the living polymerization method shown below.
The diving polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical diving polymerization method. In the anion living polymerization method, the polymerization active species is an anion, for example, shown in the following scheme.

  In the radical living polymerization method, the polymerization active species is a radical, and is represented by the following scheme, for example.

  In synthesizing such an acrylic dispersant, JP-A-9-62002 and P.I. Lutz. P. Massoneta]. , Polym. Bull. 12, 79 (1984), B.I. C. Ande: rson, G.M. D. Andrewseta 1, Macromolecules, 14, 1601 (1981), K. et al. Hatada, K .; Ute, etal, Polym. J. et al. 17, 977 (1985), 18, 1037 (1986), Koichi right hand, Koichi Hatada, polymer processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawaki, Polymer Journal, 46, 189 (1989), M.M. Kuroki, T .; Aida, J .; Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D.C. Y. Sogoh, W .; R. Known methods described in, for example, Hertierta 1, Macromolecules, 20, 1473 (1987) can be employed.

  Whether the dispersant used in the present invention is an AB block copolymer or a B-A-B block copolymer, the A block / B block ratio (mass ratio) constituting the copolymer. Is usually in the range of 1/99 or more, especially 5/95 or more, and usually 80/20 or less, especially 60/40 or less. Outside this range, it may not be possible to combine good heat resistance and dispersibility.

Further, the amount of the quaternary ammonium base in 1 g of the AB block copolymer and the B-A-B block copolymer according to the present invention is usually preferably 0.1 to 10 mmol, and outside this range. In some cases, good heat resistance and dispersibility cannot be combined.
Such a block copolymer usually contains an amino group produced in the production process, but its amine value is about 1 to 100 mg-KOH / g. The amine value is a value expressed by mg acid of KOH corresponding to the acid value after neutralizing titration of a basic amino group with an acid.

  Moreover, although the acid value of this block copolymer depends on the presence and type of the acid group that is the basis of the acid value, it is generally preferable that the acid value is low, and is usually 100 mg-KOH / g or less, and its molecular weight is The weight average molecular weight (Mw) in terms of polystyrene measured by GPC is usually in the range of 1000 or more and 100,000 or less. When the molecular weight of the block copolymer is too small, the dispersion stability is lowered, and when it is too large, the developability and the resolution tend to be lowered.

In the present invention, as the dispersant, a commercially available urethane-based and / or acrylic-based dispersant having a structure similar to that described above can also be applied.
Examples of urethane dispersants include (1) polyisocyanate compounds, (2) compounds having one or two hydroxyl groups in the same molecule, and (3) compounds having active hydrogen and tertiary amino groups in the same molecule. A dispersion resin obtained by reacting is preferable.

(1) Polyisocyanate compound Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-didiphenylmethane diisocyanate, naphthalene-1,5-diisocyanate. , Aromatic diisocyanates such as tolidine diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate) ), Alicyclic diisocyanates such as ω, ω′-diisocyne trimethylcyclohexane, xylylene diisocyanate, α, an aliphatic diisocyanate having an aromatic ring such as α, α ′, α′-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, Todiisocyanates such as 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, and trimers thereof, water adducts, and polyols thereof Examples include adducts.

  Preferred as the polydiisocyanate is a trimer of an organic diisocyanate, and most preferred is a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate. These may be used individually by 1 type, and may mix and use 2 or more types.

  As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. For example, a method of obtaining a desired isocyanurate group-containing polyisocyanate by performing trimerization and stopping the trimerization by adding a catalyst poison, and then removing the polyisocyanate at the end reaction by solvent extraction and thin-film distillation.

(2) Compounds having one or two hydroxyl groups in the same molecule Examples of compounds having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like, and these compounds. And a mixture of two or more of these having one end hydroxyl group alkoxylated with an alkyl group having 1 to 25 carbon atoms.

Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these.
Examples of the polyether diol include those obtained by homopolymerizing or copolymerizing alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. The mixture of 2 or more types of these is mentioned.
Polyether ester diols include those obtained by reacting a mixture of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides or reacting polyester glycols with alkylene oxides, such as poly (poly And oxydetramethylene) adipate.

  Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Polyester glycol includes dicarboxylic acid (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof and glycol (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol 2-methyl-1,3-propane-diol, 2-methyl-2-propyl-1,3-propane-diol, 2-butyl-2-ethyl-1,3-propane-diol, 1,5-pentane Diol, 1,6-hexanediol, 2-methyl-2 4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene Glycol, aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromas such as xylylene glycol and bishydroxyethoxybenzene Group glycol, N-alkyl dialkanolamine such as N-methyl-diethanolamine), for example, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc. Diols or carbon number 1-2 Monovalent polylactone diols obtained alcohol used as initiator or polylactone monool, for example polycaprolactone glycol, polymethyl valerolactone glycol and mixtures of two or more thereof.

  Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone glycol starting with an alcohol having 1 to 25 carbon atoms, more specifically, a compound obtained by ring-opening addition polymerization of ε-caprolactone to a monool. is there.

Examples of polycarbonate glycol include poly (1,6-hexylene) carbonate and poly (3-methyl-1,5-pentylene) carbonate. Examples of polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, and hydrogenated polyisoprene glycol. Is mentioned.
Of the compounds having one or two hydroxyl groups in the same molecule, polyether glycol and polyester glycol are particularly preferred.

  The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

(3) Compound having active hydrogen and tertiary amino group in the same molecule The compound having active hydrogen and tertiary amino group in the same molecule used in the present invention will be described. Examples of the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom include a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Of these, the hydrogen atom of the amino group is preferred.
The tertiary amino group is not particularly limited. Moreover, as a tertiary amino group, the amino group which has a C1-C4 alkyl group, or a heterocyclic structure, More specifically, an imidazole ring or a triazole ring is mentioned.

  Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl 1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1, 4-butanediamine and the like can be mentioned.

  As the tertiary amino group is a nitrogen-containing heterocycle, a pyrazole ring, an imidazole ring, a todiazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, a benzimidazole ring, a benzotriazole ring, a benzoxazonole ring, Examples thereof include N-containing hetero 5-membered rings such as benzothiazole ring and benzothiadiazole ring, nitrogen-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinazine ring, acridine ring and isoquinoline ring. Preferred as these nitrogen-containing heterocycles are an imidazole ring or a triazole ring.

Specific examples of these compounds having an imidazole ring and a primary amino group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like. .
Further, specific examples of the compound having a todiazole ring and an amino group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1 2,4-todiazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-diphenyl-1,2,3 triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole preferable.

  A preferable blending ratio of the urethane-based dispersant raw material is 10 to 200 parts by mass of a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by mass of the polyisocyanate compound. Is 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and the compound having an active hydrogen and a tertiary amino group in the same molecule is 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass. .

  The polystyrene-converted weight average molecular weight (Mw) measured by GPC of such a urethane-based dispersant is usually 1,000 to 200,000, preferably 2,000 to 100,000, more preferably 3,000 to 50,000. Range. Within this molecular weight range, the dispersibility and dispersion stability are excellent, the solubility and dispersibility are excellent, and at the same time, the reaction is easily controlled.

The production of such a urethane-based dispersant is performed according to a known method for producing a polyurethane resin. As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl One or more of aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used.
In the production, a usual urethanization reaction catalyst is used. Examples of the catalyst include tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctate, and stannous octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, triethylamine, and triethylenediamine. Secondary amine type and the like can be mentioned.

The amount of the compound having an active hydrogen and a tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mg-KOH / g in terms of the amine value after the reaction. More preferably, it is the range of 5-95 mg-KOH / g. The amine value is a value expressed in mg of KOH corresponding to the acid value by neutralizing and titrating a basic group with an acid. By setting it within this range, the dispersion ability and developability are improved.
In addition, when an isocyanate group remains in the dispersion resin obtained by the above reaction, it is preferable to crush the isocyanate group with an alcohol or an amino compound because the stability with time of the product becomes high.

  As the graft copolymer dispersant, those having a repeating unit containing a nitrogen atom in the main chain are preferable. Especially, it is preferable to have a repeating unit represented by the following general formula (11) or / and a repeating unit represented by Formula (12).

In General Formula (11), R ¹ represents an alkylene group having 1 to 5 carbon atoms, and A represents a hydrogen atom or any of the following General Formulas (13) to (15).

In the general formula (11), R ¹ represents a linear or branched alkylene group having 1 to 5 carbon atoms such as methylene, ethylene or propylene, preferably 2 to 3 carbon atoms, more preferably. Ethylene group. A represents a hydrogen atom or any one of the following general formulas (13) to (15), and is preferably general formula (13).

In the general formula ^{(12), R} 1, A has the same meaning as ^R 1, A of formula (11).

In the above formula (13), W ₁ represents a linear or branched alkylene group having 2 to 10 carbon atoms, and among them, an alkylene group having 4 to 7 carbon atoms such as butylene, pentylene, and hexylene is preferable. p represents an integer of 1 to 20, preferably an integer of 5 to 10.

In the above formula (14), Y ₁ represents a divalent linking group. Among them, an alkylene group having 1 to 4 carbon atoms such as ethylene and propylene and an alkyleneoxy group having 1 to 4 carbon atoms such as ethyleneoxy and propyleneoxy are included. preferable.
W ₂ represents a linear or branched alkylene group having 2 to 10 carbon atoms such as ethylene, propylene, or butylene, and among them, an alkylene group having 2 to 3 carbon atoms such as ethylene or propylene is preferable.
Y ₂ represents a hydrogen atom or —CO—R ₂ (R ₂ represents an alkyl group having 1 to 10 carbon atoms such as ethyl-, propyl, butyl, pentyl, hexyl, etc., among which carbon number such as ethyl, propyl, butyl, pentyl, etc. 2-5 alkyl groups are preferred).
q represents the integer of 1-20, Preferably it is an integer of 5-10.

In the above formula (15), W ₃ represents an alkyl group having 1 to 50 carbon atoms or a hydroxyalkyl group having 1 to 5 carbon atoms having 1 to 5 hydroxyl groups, and among them, an alkyl group having 10 to 20 carbon atoms such as stearyl, A C10-20 hydroxyalkyl group having 1-2 hydroxyl groups such as monohydroxystearyl is preferred.

The content of the repeating unit represented by the formula (11) or (12) in the graft copolymer is preferably higher and is usually 50 mol% or more, preferably 70 mol% or more. The repeating unit represented by the formula (11) and the repeating unit represented by the formula (12) may both be present, and the content ratio is not particularly limited, but preferably the formula (11) It is preferable to contain a larger number of repeating units.
The total number of repeating units represented by formula (11) or formula (12) is usually 1 to 100, preferably 10 to 70, and more preferably 20 to 50.

Moreover, repeating units other than Formula (11) and Formula (12) may be included, and examples of other repeating units include an alkylene group and an alkyleneoxy group. The graft copolymer of the present invention preferably has a terminal having —NH ₂ and —R ₁ —NH ₂ (R ₁ is as defined above for R ₁ ).
In the case of the graft copolymer, the main chain may be linear or branched.

  The amine value of the graft copolymer is usually 5 to 100 mgKOH / g, preferably 10 to 70 mgKOH / g, and more preferably 15 to 40 mgKOH / g or less. When the amine value is within this range, the dispersion stability is good, the viscosity is stable, the residual liquid is reduced, and the electrical characteristics after the liquid crystal panel is formed are also improved.

  The weight average molecular weight measured by GPC of the dispersant is preferably from 3,000 to 100,000, particularly preferably from 5,000 to 50,000, from the viewpoints of dispersibility and developability. When the weight average molecular weight is within this range, the solubility in an organic solvent is good.

  As a method for synthesizing the dispersing agent, a known method can be employed. For example, a method described in JP-B-63-30057 can be used.

The said dispersing agent may be used individually by 1 type, and 2 or more types may be mixed and used for it.
The blending amount of the dispersant is preferably selected in the range of 0 to 30% by mass with respect to the total solid content in the colored curable resin composition.
In the colored curable resin composition of the present invention, the content of the dispersant is usually 10 to 300% by mass, preferably 20 to 100% by mass, and particularly preferably 30 to 30% by mass with respect to the color material. 80% by mass. When the content of the dispersing agent is within this range, aggregation can be prevented, the film thickness becomes an appropriate thickness, and when used in a color filter, cell gap control failure in the liquid crystal cell forming process is suppressed. It is possible.

  The colored curable resin composition of the present invention may be used in combination with conventionally known dispersants (pigment dispersants) shown below in addition to the polymer dispersant.

Known dispersants (pigment dispersants) include polymer dispersants [for example, polyamidoamines and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates, (meth) acrylic types. Copolymers], polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, pigment derivatives, and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

  The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  Specific examples of known dispersants (pigment dispersants) that can be used in the present invention include "Disperbyk-107 (carboxylic acid ester), 130 (polyamide), 161, 162, 163, 164, 165, 166" manufactured by BYK Chemie. , 170 (polymer copolymer) ”,“ EFKA 4047, 4050, 4010, 4165 (polyurethane type), EFKA 4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide) manufactured by EFKA ), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) "," Ajisper PB821, PB822 "manufactured by Ajinomoto Fine Techno Co., Ltd.," Floren TG-710 (urethane oligomer) "manufactured by Kyoeisha Chemical Co., Ltd., Poly Low No. 50E, No. 300 (acrylic copolymer) ”,“ Dispalon # 7004 (polyetherester), DA-703-50, DA-705, DA-725 ”manufactured by Enomoto Kasei Co., Ltd.,“ “Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)”, “acetamine 86 (stearylamine acetate)”, “Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyester) manufactured by Lubrizol Corporation Amine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) "," Nikkor T106 (polyoxyethylene sorbitan monooleate) "manufactured by Nikko Chemical Co., Ltd. , M YS-IEX (polyoxyethylene monostearate) ”and the like.

  In the present invention, when a known dispersant as described above is used, the compound having the acid value of 20 to 300 mg / gmg-KOH / g and a weight average molecular weight in the range of 3,000 to 100,000. Can be used in the range of 10 to 100% by mass, that is, 1/10 to 1/1 (equal amount).

(F-2) Dispersion aid As a dispersion aid, a pigment derivative is mentioned, for example.
As pigment derivatives, azo, phthalocyanine, quinacridone, benzimidazolone, quinophthalone, isoindolinone, dioxazine, anthraquinone, indanthrene, perylene, perinone, diketopyrrolopyrrole, dioxazine And derivatives such as pigments.

  Substituents of pigment derivatives include sulfonic acid groups, sulponamide groups and quaternary salts thereof, phthalimidomethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. directly on the pigment skeleton or alkyl groups, aryl groups, and heterocyclic rings. Examples thereof include those bonded via a group and the like, preferably a sulfonamide group and a quaternary salt thereof, and a sulfonic acid group, and more preferably a sulfonic acid group. In addition, a plurality of these substituents may be substituted on one pigment skeleton, or a mixture of compounds having different substituents may be used.

  Specific examples of pigment derivatives include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of anthraquinone pigments, sulphonic acid derivatives of quinacridone pigments, and sulfonic acids of diketopyrrolopyrrole pigments. And sulfonic acid derivatives of dioxazine pigments.

Examples of commercially available pigment derivatives include azo-based Solvase 22000 manufactured by Avicia, phthalocyanine-based Solsperse 5000, and Fuka 475 manufactured by Fuka. These pigment derivatives may be used individually by 1 type, and 2 or more types may be mixed and used for them.
The blending amount of the dispersion aid is preferably selected in the range of 0 to 20% by mass with respect to the total solid content in the colored curable resin composition.

(Preparation of colored curable resin composition)
In the colored curable resin composition of the present invention, as shown below, a pigment dispersion is prepared in advance, and (c) a binder resin and (d) a photopolymerization initiator are used in (b) a solvent. It can be prepared by mixing it and adding additives such as a polymerizable compound and a surfactant as necessary.

Here, the preparation method of the pigment dispersion used for the colored curable resin composition of this invention is demonstrated.
The pigment dispersion in the present invention includes, for example, a mixture of the above-mentioned (a) color material, (f-1) dispersion resin, and (b) organic solvent, a vertical or horizontal sand grinder, pin mill, slit mill, It can be obtained by performing fine dispersion treatment with beads made of glass, zirconia or the like having a particle diameter of 0.01 to 1 mm using a sonic disperser or the like.
In addition, before carrying out bead dispersion, while applying a strong shearing force using a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single or twin screw extruder, etc. It is also possible to perform a kneading and dispersing process.
For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.

  The colored curable resin composition of the present invention thus obtained contains the above-described components, so that (a) the coloring material is kept in a well dispersed state in the composition, and good color characteristics are obtained. In addition, when this composition is used, for example, when a color filter is constructed, a high contrast can be obtained.

<Coloring Pattern Forming Method, Color Filter Manufacturing Method, and Color Filter>
Next, the colored pattern forming method, the color filter manufacturing method, and the color filter of the present invention will be described.
The colored pattern forming method of the present invention includes a step of coating the colored curable resin composition of the present invention by a slit coating method at a coating speed of 200 mm / sec to 400 mm / sec, thereby forming a desired colored pattern. Can do.
Since the colored curable resin composition of the present invention has predetermined physical properties, even when slit coating is performed at a coating speed of 200 mm / sec to 400 mm / sec, there is little coating unevenness and occurrence of coating defects. It is possible to form a photosensitive film with no defects and high efficiency.
This colored pattern forming method is preferably applied to a method for producing a color filter.
Hereinafter, a color filter manufacturing method (a color filter manufacturing method of the present invention) to which the colored pattern forming method of the present invention is applied will be described.

The method for producing a color filter of the present invention comprises a step of forming a photosensitive film by applying the colored curable resin composition of the present invention directly or via another layer (hereinafter referred to as “photosensitive film” as appropriate). Abbreviated as “formation step”), a step of pattern exposure (exposed through a mask) of the formed photosensitive film (hereinafter abbreviated as “exposure step” as appropriate), and photosensitivity after exposure. A step of developing the film to form a colored pattern (hereinafter abbreviated as “development step” as appropriate).
Hereafter, each process in the manufacturing method of this invention is demonstrated.

(Photosensitive film forming process)
In the photosensitive film forming step, the colored curable resin composition of the present invention is applied (applied) directly or on a substrate having another layer to form a photosensitive film.

Examples of the substrate that can be used in this step include soda glass, Pyrex (registered trademark) glass, quartz glass, and those in which a transparent conductive film is attached to these substrates, photoelectric sensors used for imaging devices, and the like. Examples of the conversion element substrate include a silicone substrate and a complementary metal oxide semiconductor (CMOS). These substrates may have black stripes that separate pixels.
Further, if necessary, an undercoat layer (other layers) may be provided on these substrates for improving adhesion to the upper layer, preventing diffusion of substances, or flattening the substrate surface.

In the method for producing a color filter of the present invention, the method for coating the colored curable resin composition of the present invention on a substrate includes a step of coating at a coating speed of 200 mm / sec to 400 mm / sec using a slit coating method. Is preferable from the viewpoint of efficiency. According to the colored curable resin composition of the present invention, a uniform photosensitive film free from coating defects can be formed with high productivity by such high-speed slit coating, and therefore, when used in the method for producing a color filter of the present invention. Although the effect is remarkable, it goes without saying that the photosensitive film can be formed by applying various coating methods such as an inkjet method, spin coating, cast coating, roll coating, and screen printing.
As a coating film thickness of a colored curable resin composition, 0.1-10 micrometers is preferable, 0.2-5 micrometers is more preferable, 0.2-3 micrometers is still more preferable.

  The photosensitive film coated on the substrate can be dried (prebaked) at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, an oven, or the like.

(Exposure process)
In the exposure step, the photosensitive film formed in the photosensitive film forming step is exposed through a mask having a predetermined mask pattern, that is, pattern exposure is performed.
In this step, only the coating film portion irradiated with light can be cured by exposing the photosensitive film as the coating film through a predetermined mask pattern.

As radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are particularly preferably used. Irradiation dose is more preferably preferably ^{10~1000mJ / cm 2 5~1500mJ / cm 2} , and most preferably 10 to 500 mJ / cm ^2.
If the color filter to be manufactured is a liquid crystal display device, it is more preferably preferably 10~150mJ / cm ² 5~200mJ / cm ² within the above range, and most preferably 10 to 100 mJ / cm ^2. Further, when the color filter to be manufactured is a solid-state imaging device, it is more preferably preferably 50~1000mJ / cm ² 30~1500mJ / cm ² within the above range, and most preferably 80~500mJ / cm ^2.

(Development process)
Next, by performing development processing, the unexposed portion in the exposure step is eluted in the developer, and only the photocured portion remains. Any developer can be used as long as it dissolves the film of the photocurable composition in the uncured part while not dissolving the cured part. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.
The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

As said organic solvent, the above-mentioned solvent which can be used when preparing the colored curable resin composition of this invention is mentioned.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentration of an alkaline compound such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution diluted with pure water so as to be 1% by mass is preferably used as the developer.
In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

After the development step, excess developer is washed away and dried, followed by heat treatment (post-bake).
The post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 100 ° C. to 240 ° C. is performed. When the substrate is a glass substrate or a silicone substrate, 200 ° C. to 240 ° C. is preferable in the above temperature range.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater or the like so that the coating film after development is in the above-mentioned condition. be able to.

  By repeating the photosensitive film formation step, the exposure step, and the development step (and heat treatment if necessary) as described above for the desired number of hues, a color filter having the desired hue (the color filter of the present invention) is produced. Is done.

The color filter obtained by the method for producing a color filter of the present invention as described above has a colored pattern formed on the substrate using the colored curable resin composition of the present invention. The contrast was as high as 5000 or more.
Here, the contrast means a contrast that is individually evaluated for each color of R (red), G (green), and B (blue) constituting the color filter.
The contrast measurement method is as follows. In the state where the polarizing plates are overlapped on both sides of the object to be measured and the polarizing directions of the polarizing plates are parallel to each other, the backlight Y is applied from the side of one polarizing plate, and the luminance Y1 of the light passing through the other polarizing plate is obtained. taking measurement. Next, in a state where the polarizing plates are orthogonal to each other, a backlight is applied from the side of one polarizing plate, and the luminance Y2 of the light passing through the other polarizing plate is measured. The contrast is calculated by Y1 / Y2 using the obtained measurement value. Here, Nitto Denko G1220DUN was used as the polarizing plate, and a color luminance meter BM-5 (manufactured by Topcon Corporation) was used as the measuring instrument.

  When a film is formed by applying the colored curable resin composition of the present invention on a substrate, the dry thickness of the film is generally 0.3 to 5.0 μm, preferably 0.5 to 3.5 μm. Most preferably, the thickness is 1.0 to 2.5 μm.

As the substrate, for example, non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to these, solid-state imaging elements, etc. Examples of the photoelectric conversion element substrate include a silicone substrate and a plastic substrate. On these substrates, usually, black stripes for isolating each pixel are formed.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

  As the application of the colored curable resin composition of the present invention, the application mainly to the pixel of the color filter has been mainly described, but it goes without saying that the application can also be applied to the black matrix provided between the pixels of the color filter. As for the black matrix, the pattern exposure, similar to the above-described pixel manufacturing method, except that the colored curable resin composition of the present invention is added with a black colorant such as carbon black or titanium black as a colorant. It can be formed by alkali development and then post-baking to accelerate the curing of the film.

<Liquid crystal display element>
The liquid crystal display element of the present invention comprises the color filter of the present invention.
More specifically, an alignment film is formed on the inner surface side of the color filter, is opposed to the electrode substrate, and the gap is filled with liquid crystal and sealed to obtain a panel which is the liquid crystal display element of the present invention.
According to an aspect of the present invention, a colored curable resin composition having coating characteristics that can be made into a good film surface shape even at high-speed coating, and a colored pattern formation having a slit coating process using the colored curable resin composition A colored pattern formed by the method and the colored pattern forming method can be provided.
Moreover, according to this invention, the color filter manufactured by the manufacturing method of the color filter which has the said coloring pattern with favorable film | membrane surface shape at the time of high-speed application | coating, and the said manufacturing method can be provided. In particular, a color filter with little film thickness unevenness and film defects and high contrast can be provided.
Furthermore, a liquid crystal display element using the color filter can be provided.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. Unless otherwise specified, “%” and “part” are based on mass.

Example 1
Components of the following composition were mixed to prepare a pigment dispersion.

(Pigment dispersion)
・ Pigment (a)
C. I. Pigment Red 254 5 parts C.I. I. Pigment Red 177 ... 5 parts-Dispersing resin Big-BYK-161 (30% by mass of active ingredient) manufactured by Chemie Corp. ... 13.3 parts-(b) Solvent propylene glycol monomethyl ether acetate ... 32.7 parts

Separately, the following components were mixed to prepare a transparent resist solution.
[Transparent resist solution composition]
(C) Binder resin Acrylic resin (c1) represented by the following formula (6) 2.0 parts Acrylic resin (c2) (A) shown in Table 2 2.0 parts Dipentaerythritol hexaacrylate 4.0 parts (d) Photopolymerization initiator 2- (2-chlorophenyl) -4,5-diphenylimidazole dimer 0.4 parts 4,4′-bis (diethylamino) Benzophenone: 0.2 part 2-methylbenzothiazole: 0.4 part (e) Surfactant manufactured by Sumitomo 3M FC430: 0.04 part (b) Solvent propylene glycol monomethyl ether acetate: 50 parts

  The pigment dispersion and the transparent resist solution were mixed and stirred and homogenized, 300 g of zirconia beads having a particle size of 0.5 mm were added, and the mixture was dispersed by shaking for 5 hours with a paint conditioner. Then, it filtered and the uniform colored pattern formation composition (colored curable resin composition) was obtained.

The following evaluation was performed about the obtained composition for colored pattern formation.
(Evaluation 1)
The obtained colored pattern forming composition was applied onto a 550 mm × 650 mm glass substrate (1737, manufactured by Corning) at a coating speed of 200 mm / sec using a slit coater (head coater, head mounted by Faster). did. Thereafter, it was dried in an oven at 90 ° C. for 60 seconds (pre-baking). The film thickness of the dry film was 1.2 μm.

(Applied surface)
Application of 200 sheets was performed under the above conditions (application interval 20 seconds for each sheet: dummy discharge 2 seconds), and the surface of the 200th application surface was observed with an optical microscope.
The evaluation criteria are as follows, and Δ is the lower limit of the practical allowable range.
○: The number of defects is less than 1 per 0.25 square meters Δ: The number of defects is 1 or more per 0.25 square meters and less than 5 ×: The number of defects is 5 or more per 0.25 square meters thing

(Thickness unevenness)
The colored pattern forming composition 16 obtained above is discharged from a discharge port of a slit die 12 having a width of 550 mm in which a protruding shim 10 as shown in FIG. 1 is incorporated as shown in FIG. s, a coating gap of 100 μm, and applied to a glass substrate 14 (Corning 1737, 0.7 mm thick) so that the film thickness becomes 2.0 μm after the post-baking treatment. In addition, the dimensional unit in FIG. 1 is mm.

At this time, the fluctuation of the streaky film thickness unevenness 18 caused by the protrusions of the shim 10 was measured with a stylus type film thickness meter DECTAC-3 manufactured by ULVAC after post-baking. The results are shown in Table 2.
The evaluation criteria are as follows, and Δ is the lower limit of the practical allowable range.
○: Thickness unevenness within ± 1% Δ: Thickness unevenness exceeds ± 1% and within ± 2% ×: Thickness unevenness exceeds ± 2%

(contrast)
Using a slit coater (head coater, equipped with a head manufactured by Faster), a colored pattern forming composition obtained above on a 550 mm × 650 mm glass substrate (1737, manufactured by Corning) at a coating speed of 200 mm / sec. Was applied. Thereafter, it was dried in an oven at 90 ° C. for 60 seconds (pre-baking). The film thickness of the dry film was 1.2 μm.
The entire surface of the coating film is exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film is exposed to a 1% aqueous solution of an alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). Covered and rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. The film exposed and developed as described above is heat-treated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored resin film (colored pattern) for the color filter on the glass substrate. A filter substrate (color filter) was produced.
A polarizing plate is placed on the colored resin film (colored pattern) of the colored filter substrate, the colored resin film is sandwiched, and the luminance when the polarizing plate is parallel and the luminance when orthogonal is measured using BM-5 manufactured by Topcon Corporation. The value obtained by dividing the parallel brightness by the orthogonal brightness (= the parallel brightness / the orthogonal brightness) was used as an index for contrast evaluation.
The contrast indicates that the higher the value, the better.

(Examples 2 to 4)
A colored pattern forming composition was prepared and evaluated in the same manner as in Example 1 except that the binder resin (c2) was changed to the compounds shown in Table 2 in Example 1.

(Comparative Examples 100 to 103)
In Example 1, a colored pattern forming composition was prepared in the same manner as in Example 1 except that the binder resin (c2) was changed to the compounds shown in Table 2, and the same evaluation as in Example 1 was performed. I did it.

The acrylic resins (c2) A to G used above were synthesized as follows.
A synthesis scheme of the acrylic resin (c2) A is shown below. Moreover, it calculated | required as follows about the weight average molecular weight, (meth) acryloyl group content, and an acid value.

(Weight average molecular weight)
The measurement was performed in terms of polystyrene by GPC (gel permeation chromatography) measurement under the following conditions.
Column used:
TSKgel Multipore HXL-M (Porous polydisperse type linear column) Tosoh eluent: THF
Flow rate: 1.0 ml / min
Temperature: 40 ° C
Detection condition: RI
System: High-speed GPC equipment set (Toso-HLC-8220)
As a result, the weight average molecular weight was 45,000.

((Meth) acryloyl group content)
As monomers, benzyl methacrylate (BzMA) 40 g, acrylic acid (AA) 20 g, hydroxyethyl methacrylate (HEMA) 40 g, hexamethylene diisocyanate hydroxyethyl acrylate monoadduct (HMDI) 50 g are used, The molecular weight, number of moles before reaction, and number of moles after reaction are summarized in the table below.

  The unit having an allyloyl group is (HEMA + HMDI), and paying attention to the number of moles after the reaction, the total weight of the resin when this unit is 0.176 mol is 40 + 20 + 40 + 50 = 150 (g), and the resin is 1 g. The number of moles of the unit at that time is 0.176 / 150 = 0.00117 mol / g. 1 equivalent = 1 mol, which is 0.00117 eq / g.

(Acid value)
In the said table | surface, KOH which neutralizes 0.278 mol of AA origin units will be 56.11 * 0.278 = 15.55988g = 15598.58mg. Using a resin weight of 150 g, 15598.58 / 150 = 103.99, that is, an acid value of 104 mgKOH / g.

(Synthesis of acrylic resin (c2) A)
Benzyl methacrylate 40 g, acrylic acid 20 g, hydroxyethyl methacrylate 40 g, ethyl ethoxypropionate 155 g, and cyclohexanone 80 g were placed in a five-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas inlet tube, and a stirrer. 0.5 g of azoisobutyronitrile was added as a polymerization initiator, and the mixture was heated and stirred at 80 ° C. for 8 hours to complete the polymerization. Further, 50 g of hexamethylene diisocyanate monoethyl adduct of hydroxyethyl acrylate was added, and the mixture was heated and stirred at 60 ° C. for 8 hours to obtain an acrylic resin.

(Synthesis of acrylic resin (c2) B)
Benzyl methacrylate 40 g, acrylic acid 20 g, hydroxyethyl methacrylate 40 g, ethyl ethoxypropionate 155 g, and cyclohexanone 80 g were placed in a five-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas inlet tube, and a stirrer. 0.5 g of azoisobutyronitrile was added as a polymerization initiator, and the mixture was heated and stirred at 80 ° C. for 8 hours to complete the polymerization. Further, 60 g of a monoadduct of isophorone diisocyanate hydroxyethyl acrylate was added and stirred with heating at 60 ° C. for 8 hours to obtain an acrylic resin.

(Synthesis of acrylic resin (c2) C)
Benzyl methacrylate 40 g, acrylic acid 20 g, hydroxyethyl methacrylate 40 g, ethyl ethoxypropionate 155 g, and cyclohexanone 80 g were placed in a five-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas inlet tube, and a stirrer. 0.5 g of azoisobutyronitrile was added as a polymerization initiator, and the mixture was heated and stirred at 80 ° C. for 8 hours to complete the polymerization. Further, 30 g of methacryloyloxyethyl isocyanate was added, and the mixture was heated and stirred at 60 ° C. for 8 hours to obtain an acrylic resin.

(Synthesis of acrylic resin (c2) D)
A five-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas inlet tube and a stirrer was charged with 78 g of styrene, 2 g of benzyl methacrylate, 5 g of acrylic acid, 15 g of hydroxyethyl methacrylate, 155 g of ethyl ethoxypropionate, and 80 g of cyclohexanone. . 0.5 g of azoisobutyronitrile was added as a polymerization initiator, and the mixture was heated and stirred at 80 ° C. for 8 hours to complete the polymerization. Further, 5 g of a monoadduct of isophorone diisocyanate hydroxyethyl acrylate was added, and the mixture was heated and stirred at 60 ° C. for 8 hours to obtain an acrylic resin.

(Synthesis of acrylic resin (c2) E)
A five-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas inlet tube and a stirrer was charged with 25 g of styrene, 30 g of benzyl methacrylate, 5 g of acrylic acid, 40 g of hydroxyethyl methacrylate, 155 g of ethyl ethoxypropionate, and 80 g of cyclohexanone. . 0.5 g of azoisobutyronitrile was added as a polymerization initiator, and the mixture was heated and stirred at 80 ° C. for 8 hours to complete the polymerization. Further, 100 g of a monoadduct of isophorone diisocyanate hydroxyethyl acrylate was added, and the mixture was heated and stirred at 60 ° C. for 8 hours to obtain an acrylic resin.

(Synthesis of acrylic resin (c2) F)
20 g of styrene, 5 g of benzyl methacrylate, 50 g of acrylic acid, 25 g of hydroxyethyl methacrylate, 155 g of ethyl ethoxypropionate, and 80 g of cyclohexanone were placed in a five-necked flask equipped with a reflux condenser, a thermometer, a nitrogen gas inlet tube and a stirrer. . 0.5 g of azoisobutyronitrile was added as a polymerization initiator, and the mixture was heated and stirred at 80 ° C. for 8 hours to complete the polymerization. Further, 67 g of a monoadduct of isophorone diisocyanate hydroxyethyl acrylate was added and stirred with heating at 60 ° C. for 8 hours to obtain an acrylic resin.

(Synthesis of acrylic resin (c2) G)
Into a five-necked flask equipped with a reflux condenser, thermometer, nitrogen gas inlet tube and stirring device, 40 g of benzyl methacrylate, 3 g of acrylic acid, 2 g of methacrylic acid, 5 g of hydroxyethyl acrylate, 155 g of ethyl ethoxypropionate, and 80 g of cyclohexanone It was. 0.5 g of azoisobutyronitrile was added as a polymerization initiator, and the mixture was heated and stirred at 80 ° C. for 8 hours to complete the polymerization to obtain an acrylic resin.

As is apparent from the results in Table 2, the colored pattern forming compositions of Examples 1 to 4 are not uneven on the film surface when slit coater coating is performed using the colored pattern forming composition, and the coated surface shape Was good. On the other hand, it was found that the colored pattern forming compositions of Comparative Examples 100 to 103 were extremely inferior in film surface unevenness and coated surface shape as compared with Examples.
Therefore, it turned out that the color filter of this invention which has a coloring pattern formed using the composition for coloring pattern formation of Examples 1-4 is excellent in contrast compared with a comparative example.

It is a top view which shows the shim used for application | coating of a color resist in an Example. It is a perspective view which shows the application state by the slit die which attached the shim of FIG.

Explanation of symbols

10 Shim 12 Slit die 14 Glass substrate 16 Color resist 18 Streaks

Claims (8)

A colored curable resin composition comprising (a) a coloring material, (b) a solvent, (c) at least two binder resins, (d) a photopolymerization initiator, and (e) a surfactant, the binder resin A colored curable resin composition characterized in that at least two of these are resins having a (meth) acryloyl group of 0.0005 to 0.0050 eq / g and an acid value of 15 to 150 mgKOH / g. The colored curable resin composition according to claim 1, wherein at least one of the binder resins contains a (meth) acrylic copolymer having an alicyclic (meth) acryloyl group in a side chain. The at least one binder resin is any one selected from the following general formula (1-1), formula (1-2), and formula (1-3). The colored curable resin composition according to 2.

(In the above formula, R represents a hydrogen atom or a methyl group. R ₁ represents an alkyl group having 1 to 18 carbon atoms, a phenyl group containing 1 to 4 carbon atoms or an alkoxy group, and 6 carbon atoms. Represents an -12 aryl group or an aralkyl group having 7 to 12 carbon atoms, R ₂ represents a phenylcarbamic acid ester containing an alkylene group having 1 to 18 carbon atoms and an alkyl group having 1 to 4 carbon atoms; Alternatively, it represents a carbamic acid ester containing an alicyclic group having _{3 to} 18 carbon atoms, and R ₃ represents a linear or branched alkylene group having 2 to 16 carbon atoms.
A to d in formula (1-1), a to e in formula (1-2), and a to e in formula (1-3) represent the content molar ratio (mol%) of the repeating unit: Formula (1) A to d: b in -1) represents 3 to 50, c represents 3 to 40, d represents 2 to 60, and a + b + c + d = 100. A to e: b in the formulas (1-2) and (1-3) represent 0 to 85, c represents 3 to 50, d represents 3 to 40, e represents 2 to 60, and a + b + c + d + e = 100. n is 2-16. ) The coloring pattern formation method characterized by including the process of apply | coating the colored curable resin composition of any one of Claims 1-3 by the slit coat method. A colored pattern formed by the colored pattern forming method according to claim 4. The manufacturing method of the color filter which has a coloring pattern of Claim 5. A color filter manufactured by the manufacturing method according to claim 6 and having a contrast of 5000 or more. A liquid crystal display element using the color filter according to claim 7.

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