JP5191201B2 - Colored curable composition for color filter, color filter, and production method thereof - Google Patents

Abstract

The present invention relates to a color filter coloring solidifying composition, a color filter and the making method thereof. The solidifying composition has the advantages of solidifying with high sensitivity, excellent pattern forming property, restrained developing residua and excellent adhesivenss to the supporting body. The color filter has the coloring pattern which is formed by the solidifying composition of the invention and has high color reproducibility and has excellent shape. The making method can make the color filter with a high production efficiency. The color filter coloringsolidifying composition of the invention is characterized in that the composition includes the following components: (a) a compound with at least one ethylenically unsaturated double bond, (b) a photopolymerization initiating agent and (c) a colorant, wherein (b) the photopolymeriztion initiating agent includes the following component: (A) a biimidazole compound, (B) a sensibilization color element and (C) a mercapto-compound, the content of (A)+(B)+(C) is 5% to 15% calculated with wt% relative to the total solid component of the color filter coloring solidifying composition.

Description

  The present invention relates to a colored curable composition for a color filter used for a liquid crystal display element (LCD), a solid-state imaging element (CCD, CMOS, etc.), a color filter, and a method for producing the same.

A color filter is an indispensable component for a liquid crystal display.
A liquid crystal display is more compact than a CRT as a display device and is equivalent or better in terms of performance, and is thus being replaced by a CRT as a television screen, a personal computer screen, or other display device. In recent years, the development trend of liquid crystal displays is moving from conventional monitor applications where the screen has a relatively small area to TV applications where a large screen and high image quality are required.

  Liquid crystal displays for TV use are required to have higher image quality than those for conventional monitor applications. On the other hand, in the color filter for a solid-state image sensor, further higher definition is desired.

  Panels due to pattern defects and development residues, etc., due to increased resist pigment concentration due to recent improvements in color reproducibility and reduced exposure (throughput improvement) due to increased substrate size. Defects are a problem.

In order to improve the degree of exposure polymerization, a combination of a chain transfer agent such as a polyfunctional thiol and a photosensitive resin is recommended (see Patent Document 1). However, since these materials have low alkali solubility, they have high sensitivity. It is difficult to achieve both a good pattern formation and proper pattern formation. Furthermore, polyfunctional thiols are highly reactive and it is difficult to ensure resist aging stability.
Further, a coloring curable composition having a good pattern forming property even at a high concentration of pigment has been proposed by defining an appropriate amount of the chain transfer agent (see Patent Document 2). It cannot be said that the optimal composition and ratio in the composition are proposed.
Japanese Patent No. 3120547 JP 2002-167404 A

The present invention has been made in consideration of the above-mentioned problems in the prior art, and an object thereof is to achieve the following object.
That is, the objective of this invention is providing the curable composition which can form the favorable coloring pattern for color filters, and has the outstanding process aptitude.
Furthermore, another object of the present invention is to provide a good color pattern, a color filter provided with the color pattern, and a production method capable of producing the color filter with high productivity using the curable composition of the present invention. It is to provide.

  As a result of intensive studies, the present inventor has found that the above problems can be solved by the colored curable composition for a color filter of the present invention. That is, the means for solving the above problems are as follows.

<1> includes (a) a compound having at least one ethylenically unsaturated double bond, (b) a photopolymerization initiator, and (c) a colorant, and (b) the photopolymerization initiator is (A) biimidazole. System compound, (B) sensitizing dye, and (C) mercapto compound represented by the following general formula (I), wherein the content of (A) + (B) + (C) is colored and cured for color filters mass% with 5% to 15% less der Luke color filter for the colored curable composition of the total solid content of the sex composition.
<2> further (d) an alkali-soluble resin including pre Symbol colored curable composition for a color filter according to <1>.
<3> Ru Der than 10% 2% or more by mass% based on the total solids content is colored curable composition for a color filter of the (b) in the photoinitiator (A) + (B) before SL <1> or colored curable composition for a color filter according to <2>.
<4> The (b) photopolymerization in initiator (A) + (B) total for (C) the content of mass% with 10% to 30% less der Ru before Symbol of <1> or <2> The colored curable composition for color filters described in 1.

<5> The mass ratio (b) / (a) of the compound (a) having at least one ethylenically unsaturated double bond and the (b) photopolymerization initiator is 0.1 or more and 2.0 or less. der Ru before SL <1> to colored curable composition for a color filter according to any one of <4>.
<6> The content of the (c) colorant, 35% to 70% der Ru before Symbol in% by mass relative to the total solid content of the color filter colored curable composition <1> to <5> The colored curable composition for color filters according to any one of the above.
<7> The (C) a mercapto compound represented by the following general formula (II) or compound der Ru before Symbol represented by (III) <1> or colored curable composition for a color filter according to any one of <6> object.

(In the general formula (I), R represents an alkyl group or an aryl group, A represents an atomic group that forms a heterocycle with N = CN,
  In general formula (II), R ¹ Represents an aryl group, X represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, or an aryl group,
  In general formula (III), R ² Represents an alkyl group or an aryl group, and X represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, or an aryl group. )

<8> onto a substrate, Luca color filter having a colored pattern formed by using the colored curable composition according to any one of <1> to <7>.
<9> A step of applying the colored curable composition according to any one of <1> to <7> on the substrate to form a colored curable composition layer, and the colored curable composition as a mask process and method of manufacturing including color filters and forming a colored pattern by developing the colored curable composition layer after exposure to exposure through.

ADVANTAGE OF THE INVENTION According to this invention, the favorable coloring pattern for color filters can be formed, and the curable composition which has the outstanding process aptitude can be provided.
Furthermore, according to this invention, the manufacturing method which can manufacture the favorable color pattern which uses the curable composition of this invention, a color filter provided with this coloring pattern, and this color filter with high productivity is provided. be able to.

  Hereinafter, the colored curable composition for a color filter of the present invention, the color filter using the colored curable composition for a color filter, and a production method thereof will be described in detail.

-Colored curable composition for color filter-
The colored curable composition for a color filter of the present invention includes (a) a compound having at least one ethylenically unsaturated double bond (hereinafter sometimes referred to as a specific polymerizable compound as appropriate), and (b) photopolymerization. An initiator, and (c) a colorant, and (b) a photopolymerization initiator contains (A) a biimidazole compound, (B) a sensitizing dye, and (C) a mercapto compound, and (A) + ( The content of B) + (C) is from 5% to 15% by mass with respect to the total solid content of the colored curable composition for color filters.
Hereinafter, each component contained in the colored curable composition for a color filter of the present invention (hereinafter sometimes simply referred to as “curable composition”) will be described in order.

<(A) Specific polymerizable compound>
The specific polymerizable compound (a) that can be used in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one terminal ethylenically unsaturated bond, preferably 2 to 2. It is selected from 6 compounds, more preferably 4 to 6 compounds. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention. The specific polymerizable compound may be used alone or in combination of two or more.

  These have chemical forms such as monomers, prepolymers, i.e. 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 And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. 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 4)}} COOCH 2 CH (R 5) OH (A)
(In the general formula (A), R ⁴ and R ⁵ 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 addition polymerizable compounds, the details of usage, such as the structure, single use or combination, addition amount, etc. can be arbitrarily set according to the final performance design of the curable composition. 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 cured film, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). A method of adjusting both sensitivity and intensity by using a combination of these materials is also effective.
In addition, the compatibility of the addition polymerization compound with other components (for example, photopolymerization initiators, colorants (pigments, dyes, etc.), binder polymers, etc.) contained in the curable composition is also improved. The selection / use method is an important factor. For example, the compatibility may be improved by using a low-purity compound or using two or more kinds in combination. In addition, a specific structure may be selected for the purpose of improving adhesion with a substrate or the like.

  The mass ratio (b) / (a) of (a) the specific polymerizable compound and (b) the photopolymerization initiator described later is 0.1 or more and 2.0 or less, preferably 0.1 or more and 1. 0 or less, particularly preferably 0.1 or more and 0.5 or less. By setting it within the above range, the pattern formability is good and the adhesion to the substrate is excellent. Further, the amount of mask thickening after exposure and development is sufficient, and pattern peeling is suppressed.

  The content of the specific polymerizable compound is preferably 5 to 30% by mass, more preferably 15 to 30% by mass, and preferably 20 to 30% by mass in the total solid content of the curable composition. Is particularly preferred.

<(B) Photopolymerization initiator>
The photopolymerization initiator of the present invention refers to a photopolymerization initiation system containing (A) a biimidazole compound, (B) a sensitizing dye, and (C) a mercapto compound.
In the photopolymerization initiator, the content of (A) + (B) + (C) is 5% or more and 15% or less by mass% with respect to the total solid content of the colored curable composition for color filters, and more preferably. Is 5% or more and 12% or less, and particularly preferably 5% or more and 10% or less.
By being in the said range, the curable composition of this invention hardens | cures with high sensitivity, and has favorable pattern formation property. Further, the alkali dissolution rate in the unexposed area is high, and development residues are suppressed.

In the photopolymerization initiator, the content of (A) + (B) is 2% or more and 10% or less, more preferably 2% by mass based on the total solid content of the colored curable composition for color filters. It is 8% or less and particularly preferably 4% or more and 8% or less.
By being in the said range, the curable composition of this invention hardens | cures with high sensitivity, and has favorable pattern formation property. Further, the alkali dissolution rate in the unexposed area is high, and development residues are suppressed.

In the photopolymerization initiator, the content of (C) with respect to the sum of (A) + (B) is 10% to 30% by mass, preferably 10% to 25%, particularly preferably. It is 15% or more and 25% or less.
By being in the said range, the curable composition of this invention hardens | cures with high sensitivity, and has favorable pattern formation property. Further, the alkali dissolution rate in the unexposed area is high, and development residues are suppressed.

(A) Biimidazole compound (photopolymerization initiator)
The photopolymerization initiator in the photopolymerization initiation system of the present invention is a compound that is decomposed by light and initiates and accelerates the polymerization of the aforementioned polymerizable compound, and has an absorption in the wavelength region of 300 to 500 nm. preferable.

As the biimidazole compound, for example, a hexaarylbiimidazole compound is preferable.
Examples of the hexaarylbiimidazole compound include JP-B-6-29285, U.S. Pat. Nos. 3,479,185, 4,311,783, 4,622,286, and JP-B-45- No. 37377 and JP-B-44-86516, 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'-tetra Phenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) biidazole, 2,2′-bis (o, o′-dichlorophenyl)- 4,4 ', 5 '-Tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4, Examples thereof include 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, and the like. Of these, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole is particularly preferable.

  As the photopolymerization initiator, in addition to the above biimidazole compounds, for example, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds , Azide compounds, metallocene compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.

  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.

  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, 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 and the like can be mentioned.

  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. .

  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 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-butylphenyl) , Acetophenone derivatives such as 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone Thioxanthone derivatives such as 2,4-diisopropylthioxanthone, and benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

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

  Examples of the benzoin compound include mbenzoin 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, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4 '-Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate) , Carbonyldi (t-hexylperoxydihydrogen 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 di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di -Cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di- Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentaful Lophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluoropheny -1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4 , 5,6-pentafluorophen-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, 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, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin “Rad Tech '98. Proceeding April 19-22, 1998, Chicago”. Organoboron salts described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554 In Japanese Patent Laid-Open No. 6-175553 Organoboron iodonium complexes, organoboron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, 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 No. 61-166544 and Japanese Patent Application No. 2001-132318.

  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.

  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 form of the sulfonium salt, an iodonium salt in which one substituent of the triarylsulfonium salt has a coumarin or 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.

  The photopolymerization initiator used in the present invention is more preferably at least one compound selected from the group consisting of a biimidazole compound, a trihalomethyltriazine compound, and an oxime compound from the viewpoint of increasing sensitivity, and a biimidazole compound. Compounds are most preferred. Moreover, a photoinitiator can also be used individually or in combination of 2 or more types.

  (A) The content of the photopolymerization initiator in the total solid content of the curable composition is preferably 1 to 15% by mass, more preferably 2 to 10% by mass, and 2 to 6% by mass. It is particularly preferred that

(B) Sensitizing dye The sensitizing dye that can be used in the present invention is preferably a sensitizing dye that sensitizes a radical initiator by an electron transfer mechanism or an energy transfer mechanism.
Examples of the sensitizing dye that can be used in the present invention include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
Examples of preferred sensitizing dyes include those belonging to the following compounds and having an absorption wavelength in the range of 330 nm to 450 nm.

For example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (Isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, toluidine blue) , Acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg Squalium), acridine orange, coumarins (eg 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazole , Porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone and other aromatics Examples include ketone compounds and heterocyclic compounds such as N-aryloxazolidinones. A sensitizing dye may be used individually by 1 type, and may use 2 or more types together.
More preferable examples of the sensitizing dye include compounds represented by the following general formulas (B-1) to (B-4).

(In formula (B-1), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ¹ represents the basicity of the dye in combination with the adjacent A ¹ and the adjacent carbon atom. Represents a nonmetallic atomic group forming a nucleus, R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² are bonded to each other to form an acidic nucleus of the dye W may represent an oxygen atom or a sulfur atom.)

(In Formula (B-2), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond with —L ² —, where L ² represents —O— or —S—. In addition, W is synonymous with that shown in Formula (B-1).)

(In the formula (B-3), A ² represents a sulfur atom or NR ⁵⁹ , L ³ represents a nonmetallic atomic group that forms a basic nucleus of the dye in combination with adjacent A ² and a carbon atom, R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a monovalent nonmetallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.)

(In formula (B-4), A ³ and A ⁴ each independently represent —S— or —NR ⁶² — or —NR ⁶³ —, and R ⁶² and R ⁶³ each independently represent a substituted or unsubstituted alkyl group. Represents a substituted or unsubstituted aryl group, and L ⁴ and L ⁵ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in cooperation with adjacent A ³ , A ⁴ and adjacent carbon atoms. And R ⁶⁰ and R ⁶¹ each independently represent a monovalent non-metallic atomic group, or can be bonded to each other to form an aliphatic or aromatic ring.

  Moreover, as a preferable sensitizing dye which can be contained in the curable composition of this invention, at least 1 type selected from the compound represented by the following general formula (IV)-(VI) other than the said sensitizing dye is mentioned. It is done. These may be used individually by 1 type, and may use 2 or more types together.

In general formula (IV) or general formula (V), R ¹ and R ² each independently represent a monovalent substituent, and R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or Represents a monovalent substituent. n represents an integer of 0 to 5, n ′ represents an integer of 0 to 5, and n and n ′ are not both 0. When n is 2 or more, a plurality of R ¹ may be the same or different. When n ′ is 2 or more, a plurality of R ² may be the same or different.

  As a compound represented by general formula (IV), it is preferable that it is a compound represented by the following general formula (IV-1) from a viewpoint of the colorability in the case of containing a sensitivity and a coloring agent.

In general formula (IV-1), R ¹ and R ² each independently represents a monovalent substituent. n represents an integer of 0 to 5, and n ′ represents an integer of 1 to 5. When n is 2 or more, a plurality of R ¹ may be the same or different, and when n ′ is 2 or more, a plurality of R ² are the same or different. Also good.

In the general formula (IV-1), the monovalent substituent represented by ^{R 1} and ^{R 2} are synonymous with the monovalent substituent represented by ^{R 1} and ^{R 2} in the general formula (IV) The preferable range is also the same.

The general formula (IV) or general formula (V) compounds represented by is preferably a molar extinction coefficient epsilon at a wavelength of 365nm is ^{500mol -1} · L · ^cm -1 or more, epsilon at a wavelength of 365nm is 3000 mol ^- more preferably ¹ · L · ^{cm -1} or more, and most preferably ε at a wavelength of 365nm is 20000mol ^-1 · L · ^{cm -1} or more. It is preferable that the value of the molar extinction coefficient ε at each wavelength is in the above range because the sensitivity improvement effect is high from the viewpoint of light absorption efficiency.

Although the preferable specific example of a compound represented by general formula (IV) or general formula (V) is illustrated below, this invention is not limited to these.
Note that in this specification, a chemical formula may be described by a simplified structural formula, and a solid line or the like that does not clearly indicate an element or a substituent particularly represents a hydrocarbon group. In the following specific examples, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, n-Bu represents an n-butyl group, and Ph represents a phenyl group.

In general formula (VI), A represents an aromatic ring or a hetero ring which may have a substituent, X represents an oxygen atom, a sulfur atom, or —N (R ³ ) —, Y represents an oxygen atom, A sulfur atom or -N (R < ³ >)-is represented. R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and A, R ¹ , R ² , and R ³ are each bonded to each other to form an aliphatic group Or you may form an aromatic ring.

In the general formula (VI), R ¹ , R ² and R ³ each independently represents a hydrogen atom or a monovalent nonmetallic atomic group. When R ¹ , R ² and R ³ represent a monovalent nonmetal atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group It is preferably a heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, or a halogen atom.

In the compound represented by the general formula (VI), Y is preferably an oxygen atom or —N (R ³ ) — from the viewpoint of improving the decomposition efficiency of the photopolymerization initiator. R ³ each independently represents a hydrogen atom or a monovalent nonmetallic atomic group. Furthermore, Y is most preferably —N (R ³ ) —.

  (B) The content of the sensitizing dye is preferably 0.1 to 10.0% by mass and more preferably 0.1 to 5.0% by mass in the total solid content of the curable composition. Preferably, it is 0.5 to 5.0 mass%.

(C) Mercapto Compound The mercapto compound in the present invention is a co-sensitizer having functions such as further improving the sensitivity of the sensitizing dye and polymerization initiator to actinic radiation or suppressing polymerization inhibition of the polymerizable compound by oxygen. It is.

  Specific examples of the mercapto compound include ethylene glycol bisthiopropionate (EGTP), butanediol bisthiopropionate (BDTP), trimethylolpropane tristhiopropionate (TMTP), pentaerythritol tetrakisthiopropionate (TMTP) PETP), mercaptopropionic acid derivatives such as THEIC-BMPA represented by the following formula; mercapto ethers such as di (mercaptoethyl) ether; hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthioglyco Aliphatic polyfunctional mercaptolations such as rate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate Things, mercaptobenzthiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole aromatic mercapto compound such as 2-mercapto -4 (3H) - quinazoline, can be exemplified β- -mercaptonaphthalene. These can be used alone or in combination of two or more.

The mercapto compound used in the present invention is preferably one in which a -SH group is substituted on the heterocycle, and the heteroatom contained in the heterocycle is preferably nitrogen or sulfur, and more preferably has two nitrogen atoms.
The mercapto compound of the present invention is preferably a compound represented by the following general formula (I).

  (In general formula (I), R represents an alkyl group or an aryl group, and A represents an atomic group that forms a heterocycle with N = CN.)

In general formula (I), R represents an alkyl group or an aryl group.
Examples of the alkyl group include linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms, linear groups having 1 to 12 carbon atoms, and 3 to 12 carbon atoms. More preferred are branched alkyl groups and cyclic alkyl groups having 5 to 10 carbon atoms.
Specific examples thereof include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, hexadecyl group, octadecyl group. , Eicosyl group, isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group , 2-norbornyl group and the like.

  Examples of the aryl group include a monocyclic structure, one to three benzene rings forming a condensed ring, and a benzene ring and a five-membered unsaturated ring forming a condensed ring. Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, a fluorenyl group, and the like. Among these, a phenyl group and a naphthyl group are more preferable.

  These alkyl groups and aryl groups may further have a substituent. Examples of the substituent that can be introduced include linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, and the number of carbon atoms. A linear, branched or cyclic alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, and 2 carbon atoms -20 alkoxycarbonyloxy group, aryloxycarbonyloxy group having 7-20 carbon atoms, carbamoyloxy group having 1-20 carbon atoms, carbonamido group having 1-20 carbon atoms, 1-20 carbon atoms Sulfonamide group, carbamoyl group having 1 to 20 carbon atoms, sulfamoyl group, substituted sulfamoyl group having 1 to 20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, carbon atom An aryloxy group having 6 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms, an N-acylsulfamoyl group having 1 to 20 carbon atoms, and 1 carbon atom -20 N-sulfamoylcarbamoyl group, C1-C20 alkylsulfonyl group, C6-C20 arylsulfonyl group, C2-C20 alkoxycarbonylamino group, C7-20 Aryloxycarbonylamino group, amino group, substituted amino group having 1 to 20 carbon atoms, imino group having 1 to 20 carbon atoms, ammonio group having 3 to 20 carbon atoms, carboxyl group, sulfo group, oxy group, Mercapto group, alkylsulfinyl group having 1 to 20 carbon atoms, arylsulfinyl group having 6 to 20 carbon atoms, and 1-2 carbon atoms Alkylthio group, arylthio group having 6 to 20 carbon atoms, ureido group having 1 to 20 carbon atoms, heterocyclic group having 2 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms, sulfamoylamino group A substituted sulfamoylamino group having 1 to 2 carbon atoms, a silyl group having 2 to 20 carbon atoms, an isocyanate group, an isocyanide group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a cyano group, A nitro group, an onium group, etc. are mentioned.

In the general formula (I), A represents an atomic group that forms a heterocycle with N═C—N.
Examples of atoms constituting this atomic group include a carbon atom, a nitrogen atom, a hydrogen atom, a sulfur atom, and a selenium atom.
The heterocycle formed by A and N═C—N may further have a substituent. Examples of the substituent that can be introduced include substituents that can be introduced into the alkyl group and aryl group. The same thing is mentioned.

Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.
Of these, mercapto compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene and the like are preferable.

  Examples of other co-sensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- Examples include a hydrogen donor described in Japanese Patent No. 34414, a sulfur compound (eg, trithiane) described in Japanese Patent Laid-Open No. 6-308727, and the like.

  Moreover, as a mercapto compound, More preferably, it is represented by the following general formula (II) or general formula (III).

In general formula (II), R ¹ represents an aryl group, and X represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, or an aryl group.

In general formula (III), R ² represents an alkyl group or an aryl group, and X represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, or an aryl group.

  As a halogen atom in general formula (II) and (III), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are preferable.

  As the alkoxy group in the general formulas (II) and (III), methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, pentyloxy group, hexyloxy group, dodecyloxy group, benzyloxy group, allyloxy group Phenethyloxy group, carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyethoxy group, methoxyethoxyethoxy group, ethoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, ant Loxyethoxyethoxy group, phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, cumyloxy group, methoxyphenyloxy group, ethoxyphenyloxy group, chlorophenyloxy group Group, bromophenyl group, acetyloxy group, benzoyloxy group, naphthyloxy group and the like.

The alkyl group in general formula (II) and (III) is synonymous with the alkyl group represented by R of general formula (I), and its preferable range is also the same.
Moreover, the aryl group in general formula (II) and (III) is synonymous with the aryl group represented by R of general formula (I), The preferable range is also the same.

  Each group in the general formulas (II) and (III) may further have a substituent, and the substituent can be introduced into the alkyl group or aryl group represented by R in the general formula (I). These are the same as those listed as examples of the substituent.

  These mercapto compounds are described in J. Org. Appl. Chem. , 34, 2203-2207 (1961).

  (C) The content of the mercapto compound is preferably 0.1 to 10.0% by mass and more preferably 0.1 to 5.0% by mass in the total solid content of the curable composition. It is particularly preferably 0.5 to 5.0% by mass.

  In the curable composition of the present invention, the compound represented by the general formula (I) may be used alone or in combination of two or more, and is represented by the general formula (II). A compound selected from the compounds, a compound selected from the compounds represented by the general formula (III), and a compound selected from may be used in combination.

  A preferred combination in the polymerization initiation system of the present invention is 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, a sensitizing dye as a photopolymerization initiator. And a mercapto compound, and the mercapto compound is preferably the following compound C1 or C2, particularly preferably C2.

<(C) Colorant>
The curable composition of the present invention contains a colorant.
There is no restriction | limiting in particular in the coloring agent contained in the curable composition of this invention, A conventionally well-known various dye and pigment can be used 1 type or in mixture of 2 or more types. The colorant is preferably a pigment from the viewpoint of light resistance.

  As the pigment that can be used in the curable composition of the present invention, conventionally known various inorganic pigments or organic pigments can be used. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a fine one as much as possible, and considering the handling properties, the average particle diameter of the pigment is 0.01 μm to 0.1 μm is preferable, and 0.01 μm to 0.05 μm is more preferable. Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc And metal oxides such as antimony, and composite oxides of the above metals.

As an organic pigment, for example,
CI Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199,;
CI Pigment Orange 36, 38, 43, 71;
CI Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177,209, 220, 224, 242, 254, 255, 264, 270;
CI pigment violet 19, 23, 32, 39;
CI Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
CI Pigment Green 7, 36, 37;
CI Pigment Brown 25, 28;
CI pigment black 1, 7;
Examples thereof include carbon black.

  In the present invention, those having a basic N atom in the structural formula of the pigment can be preferably used. These pigments having a basic N atom exhibit good dispersibility in the composition of the present invention. Although the cause is not fully elucidated, it is presumed that the good affinity between the curable polymerization component and the pigment has an influence.

  Examples of the pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.

CI Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
CI Pigment Orange 36, 71,
CI Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
CI Pigment Violet 19, 23, 32,
CI Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
CI Pigment Green 7, 36, 37,
CI Pigment Black 1

  These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment , Etc. can be used. For example, as an anthraquinone pigment, C.I. I. Pigment red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, and C.I. I. Mixing with Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. By setting it as the above range, the light transmittance from 400 nm to 500 nm can be suppressed, and the color purity can be increased. In addition, color reproducibility is improved. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. More preferably, it is the range of 100: 30-100: 120. By setting it as the above range, it is easy to suppress the light transmittance at a wavelength of 400 nm to 450 nm, to easily increase the color purity, and to easily reduce the deviation from the NTSC target hue.

  As the blue pigment, a phthalocyanine pigment can be used alone, or a mixture thereof with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 30, more preferably 100: 10 or less.

  Further, as the pigment for the black matrix, carbon, titanium black, iron oxide, titanium oxide alone or a mixture thereof is used.

In the present invention, when the colorant is a dye, it can be uniformly dissolved in the composition to obtain a curable composition.
The dye that can be used as the colorant contained in the curable composition of the present invention is not particularly limited, and conventionally known dyes for color filters can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 The dyes disclosed in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like can be used.

  The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.

In the case of a resist system that performs water or alkali development, an acid dye and / or a derivative thereof may be suitably used from the viewpoint of completely removing the binder and / or dye in the light non-irradiated part by development.
In addition, a direct dye, a basic dye, a mordant dye, an acid mordant dye, an azoic dye, a disperse dye, an oil-soluble dye, a food dye, and / or a derivative thereof can be usefully used.

The acidic dye is not particularly limited as long as it has an acidic group such as sulfonic acid or carboxylic acid, but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, and other components in the composition. It is selected in consideration of all required performance such as interaction with components, light resistance, heat resistance and the like.
Specific examples of the acid dye are shown below, but are not limited thereto. For example,
acid alizarin violet N; acid black 1, 2, 24, 48; acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 45, 62, 70, 74, 80, 83, 86 , 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1; acid chroma violet K; acid Fuchsin; acid green 1, 3, 5 , 9, 16, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acid red 1, 4, 8, 14, 17, 18 , 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 0, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216 217,249,252,257,260,266,274; acid violet 6B, 7,9,17,19; acid yellow 1,3,7,9,11,17,23,25,29,34,36, 42, 54, 72, 73, 76, 79, 98, 99, 111, 112, 114, 116, 184, 243; Food Yellow 3; and derivatives of these dyes.

Among these, acid black 24; acid blue 23, 25, 29, 62, 80, 86, 87, 92, 138, 158, 182, 243, 324: 1; acid orange 8, 51, 56, 63 , 74; acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217; acid violet 7; acid yellow 17, 25, 29, 34 42, 72, 76, 99, 111, 112, 114, 116, 184, 243; acidgreen 25 and derivatives of these dyes are preferred.
Other than the above, azo, xanthene and phthalocyanine acid dyes are also preferred. I. Solvent Blue 44, 38; C.I. I. Acid dyes such as Solvent orange 45; Rhodamine B, Rhodamine 110, and derivatives of these dyes are also preferably used.

  Among them, as the colorant, triallylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazole azo It is preferable that the colorant is selected from a series, an anilinoazo series, a pyrazolotriazole azo series, a pyridone azo series, and an anthrapyridone series.

The colorant that can be used in the present invention is a dye or a pigment having an average particle diameter r (unit: nm) of 20 ≦ r ≦ 300, preferably 25 ≦ r ≦ 250, particularly preferably 30 ≦ r ≦ 200. desirable. By using a pigment having such an average particle diameter r, a colored pixel having a high contrast ratio and a high light transmittance can be obtained. The “average particle diameter” as used herein means the average particle diameter of secondary particles in which primary particles (single microcrystals) of the pigment are aggregated.
In addition, the particle size distribution of the secondary particles of the pigment that can be used in the present invention (hereinafter, simply referred to as “particle size distribution”) is 70% by mass of the secondary particles falling within (average particle size ± 100) nm. As mentioned above, it is desirable that it is 80 mass% or more.

  The pigment having the above average particle size and particle size distribution is preferably a commercially available pigment mixed with other pigments optionally used (average particle size is usually above 300 nm), preferably with a dispersant and a solvent. The pigment mixture can be prepared by mixing and dispersing while pulverizing using a pulverizer such as a bead mill or a roll mill. The pigment thus obtained is usually in the form of a pigment dispersion.

As content of the coloring agent contained in the curable composition of this invention, it is preferable that it is 35-70 mass% in the total solid of a curable composition. More preferably, it is 35-60 mass%, and 40-60 mass% is especially preferable.
By setting it within the above range, moderate chromaticity is easily obtained, photocuring proceeds, and film strength and alkali development latitude are likely to be widened.

<(D) Alkali-soluble resin>
The curable composition in the present invention preferably contains at least one alkali-soluble resin (hereinafter also referred to as “the binder according to the present invention”). The binder according to the present invention is not particularly limited as long as it is alkali-soluble, but is preferably selected from the viewpoints of heat resistance, developability, availability, and the like.

The alkali-soluble binder is preferably a linear organic polymer that is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.
As such a “linear organic polymer”, a known one can be arbitrarily used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer.
For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. , JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, that is, a resin obtained by homopolymerizing or copolymerizing a monomer having a carboxyl group, acid anhydride Resins in which acid anhydride units are hydrolyzed, half-esterified or half-amidated, or epoxy acrylate modified with unsaturated monocarboxylic acid and acid anhydride, etc. It is done. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. It is done.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

  When an alkali-soluble resin is used as a copolymer, a monomer other than the above-mentioned monomers can also be used as the compound to be copolymerized. Examples of other monomers include the following compounds (1) to (12).

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate.
(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, compounds described in Japanese Patent Application No. 2001-115595, Japanese Patent Application No. 2001-115598, and the like can be mentioned.

  Among these, a (meth) acrylic resin having an allyl group, a vinyl ester group, and a carboxyl group in the side chain and a side chain described in JP-A Nos. 2000-187322 and 2002-62698 are doubled. An alkali-soluble resin having a bond and an alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity, and developability.

In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. Urethane binder polymers containing acid groups described in No. 271741 and Japanese Patent Application No. 10-116232, and urethane binder polymers having acid groups and double bonds in side chains as described in JP-A No. 2002-107918 Is excellent in strength, and is advantageous in terms of printing durability and suitability for low exposure.
In addition, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent 993966, European Patent 1204000, Japanese Patent Application Laid-Open No. 2001-318463, and the like is preferable because of its excellent balance of film strength and developability.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

The alkali-soluble resin that can be used in the present invention can be synthesized by a conventionally known method. Solvents used in the synthesis include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy. Examples include 2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, and water. These solvents are used alone or in combination of two or more.
Examples of the radical polymerization initiator used when synthesizing the alkali-soluble resin that can be used in the present invention include known compounds such as an azo initiator and a peroxide initiator.

  Of the various alkali-soluble resins, an acrylic resin is preferable, and the acrylic resin is selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like. A copolymer composed of a monomer, KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.) and the like are preferable.

The alkali-soluble resin is preferably a polymer having a weight average molecular weight (polystyrene conversion value measured by GPC method) of 1000 to 2 × 10 ⁵ , more preferably 2000 to 1 × 10 ⁵ , and 5000 to ⁵ ×. 10 ⁴ polymers are particularly preferred.
In addition, these alkali-soluble resins may be random polymers, block polymers, graft polymers, or the like.

  As content in the curable composition of the said alkali-soluble resin, 1-30 mass% is preferable with respect to the total solid of this composition, 1-20 mass% is more preferable, 1-10 mass% is Particularly preferred.

The curable composition of the present invention may further contain the above-described components (a) to (c) and the optional component (d) together with optional components described in detail below as necessary. Good. Hereinafter, optional components that can be contained in the curable composition of the present invention will be described.
<Solvent>
The curable composition of the present invention can contain at least one solvent.
Specifically, the solvent is preferably selected from glycol ether solvents, alcohol solvents, ester solvents, ketone solvents, amide solvents, and chlorine-containing solvents.

  Examples of the glycol ether solvent include ethyl cellosolve (ethylene glycol monoethyl ether), methyl cellosolve (ethylene glycol monomethyl ether), butyl cellosolve (ethylene glycol monobutyl ether), methylmethoxybutanol (3-methyl-3-methoxybutanol), butyl Carbitol (diethylene glycol monobutyl ether), ethylene glycol monoethyl ether acetate, ethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1 -Ethoxy-2-propanol), propylene glycol monoethyl ether Seteto, and the like are preferable.

  As the alcohol solvent, methanol, ethanol, isopropanol, normal propyl alcohol, isobutyl alcohol, normal butyl alcohol, and the like are preferable.

  Examples of the ester solvent include ethyl acetate, normal butyl acetate, isobutyl acetate, cellosolve acetate (ethylene glycol monomethyl ether acetate), methoxybutyl acetate (3-methoxybutyl acetate), 3-methyl-3-methoxybutyl acetate, 3- Ethyl ethoxypropionate (EEP) and lactic acid esters (for example, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, etc.) are preferred.

  Examples of the ketone solvent include 2-butanone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, cyclopentanone, acetone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), and isophorone (3, 3). 5,5-trimethyl-2-cyclohexen-1-one), diisobutyl ketone (2,6-dimethyl-4-heptanone) and the like are preferable.

  As the amide solvent, dimethylformamide (DMF), N-methylpyrrolidone (4-methylaminolactam or NMP) and the like are preferable.

  As the chlorine-containing solvent, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, methylene chloride, carbon tetrachloride, chloroform, dichloroethane, dichlorobenzene and the like are preferable.

As content in the curable composition of the solvent in this invention, 15-60 mass% is preferable with respect to this curable composition, 20-50 mass% is more preferable, 30-40 mass% is especially preferable. When the content is within the above range, the solubility of the colorant in the composition and the temporal stability during storage after dissolution can be effectively improved.

  Among the above solvents, ethyl cellosolve (ethylene glycol monoethyl ether), methyl cellosolve (ethylene glycol monomethyl ether), butyl cellosolve (ethylene glycol monobutyl ether), methylmethoxybutanol (3-methyl-3-methoxybutanol), butyl carbitol ( Diethylene glycol monobutyl ether), ethylene glycol monoethyl ether acetate, ethylene glycol mono-t-butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether (1-methoxy-2-propanol), propylene glycol monoethyl ether (1-ethoxy- 2-propanol), propylene glycol monoethyl ether acetate,

  Ethyl acetate, normal butyl acetate, isobutyl acetate, cellosolve acetate (ethylene glycol monomethyl ether acetate), methoxybutyl acetate (3-methoxybutyl acetate), 3-methyl-3-methoxybutyl acetate, ethyl 3-ethoxypropionate (EEP) , Methyl lactate, ethyl lactate, propyl lactate, butyl lactate,

  2-butanone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, cyclopentanone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), isophorone (3,5,5-trimethyl-2-cyclo) Hexen-1-one), diisobutyl ketone (2,6-dimethyl-4-heptanone),

  N-methylpyrrolidone (4-methylaminolactam or NMP),

Methanol, ethanol, isopropanol, normal propyl alcohol, isobutyl alcohol, normal butyl alcohol, and the like are preferable.
Moreover, in the curable composition of this invention, the said solvent can be used individually or in combination of 2 or more types.

  Furthermore, when preparing the curable composition of this invention, you may use together other solvents other than the solvent mentioned above. The other solvent is not particularly limited as long as the solubility of each component and the applicability of the curable composition are satisfied, but it is particularly selected in consideration of the solubility, applicability, and safety of the colorant and binder. It is preferable that

  Examples of the other solvent include esters other than those exemplified above, such as amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl oxyacetate, ethyl oxyacetate, oxy Butyl acetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

  3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, etc.); 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxy Propyl propionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate 2-ethoxy-2- Chirupuropion ethyl, etc.); methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

  Ethers other than those exemplified above, such as diethylene glycol dimethyl ether, tetrahydrofuran, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol propyl ether acetate, etc .;

  Ketones other than those exemplified above, for example, methyl ethyl ketone, 2-heptanone, 3-heptanone, etc .; aromatic hydrocarbons, for example, toluene, xylene and the like.

  Of these, methyl 3-ethoxypropionate, ethyl cellosolve acetate, diethylene glycol dimethyl ether, methyl 3-methoxypropionate, 2-heptanone, ethyl carbitol acetate, butyl carbitol acetate, and the like are preferable.

<Dispersant>
When the curable composition of this invention contains a pigment as (c) a coloring agent, it is preferable to add a dispersing agent from a viewpoint of improving the dispersibility of this pigment.

Dispersants (pigment dispersants) that can be used in the present invention include polymer dispersants [for example, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified polymers. (Meth) acrylate, (meth) acrylic copolymer, naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, alkanol amine, pigment derivative 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 according to the structure.

  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 the pigment dispersant that can be used in the present invention include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide) manufactured by BYK Chemie. ), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010, manufactured by EFKA, 4165 (polyurethane series), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine) Derivatives), 6750 (azo) "Adisper PB821, PB822" manufactured by Ajinomoto Fan Techno Co., "Floren TG-710 (urethane oligomer)" manufactured by Kyoeisha Chemical Co., "Polyflow No. 50E, No. 300 (acrylic copolymer)", “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725” manufactured by Enomoto Kasei Co., Ltd., Kao “Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer polycarboxylic acid)”, “ Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ", Lubrizol" Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ”manufactured by Nikko Chemicals, and the like.

  These dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant.

As content of the dispersing agent in this invention, it is preferable that it is 1-80 mass% with respect to a pigment, 5-70 mass% is more preferable, and 10-60 mass% is still more preferable.
Specifically, if a polymer dispersant is used, the amount of use thereof is preferably in the range of 5 to 100% by mass, more preferably in the range of 10 to 80% by mass with respect to the pigment. In the case of using a pigment derivative, the amount used is preferably in the range of 1 to 30% by mass, more preferably in the range of 3 to 20% by mass, based on the pigment, A range of 15% by mass is particularly preferable.

  In the present invention, when using a pigment and a dispersant as a colorant, the total content of the colorant and the dispersant is based on the total solid content constituting the curable composition from the viewpoint of curing sensitivity and color density. It is preferably 25% by mass or more and 95% by mass or less, more preferably 25% by mass or more and 80% by mass or less, and further preferably 30% by mass or more and 70% by mass or less.

<Polymerization inhibitor>
In the present invention, a small amount of a thermal polymerization inhibitor may be added in order to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during the production or storage of the curable composition. desirable.
Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6). -T-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.

  The addition amount of the thermal polymerization inhibitor is preferably about 0.01 to about 5% by mass with respect to the total solid content of the curable composition. If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and it may be unevenly distributed on the surface of the photosensitive layer in the course of drying after coating. . The amount of the higher fatty acid derivative added is preferably from about 0.5 to about 10% by weight of the total composition.

<Adhesion improver>
In the present invention, an adhesion improver can be added in order to improve the adhesion to the hard surface (substrate) as a base material. Examples of the adhesion improver include a silane coupling agent and a titanium coupling agent.

Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyl Triethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypro Pyrtrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ- Chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl ] Ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl Chlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxy Propyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane , Etc.
Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyltri Ethoxysilane and phenyltrimethoxysilane are preferred, and γ-methacryloxypropyltrimethoxysilane is most preferred.

  0.1-30 mass% is preferable in the total solid of a curable composition, and, as for the addition amount of an adhesive improvement agent, 0.5-10 mass% is more preferable.

-Color filter and manufacturing method thereof-
Next, the color filter of the present invention and the manufacturing method thereof will be described.
The color filter of the present invention is characterized by having a colored pattern formed on the support using the curable composition for color filters of the present invention.
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

  The method for producing a color filter of the present invention comprises a step of applying a curable composition for a color filter of the present invention on a support to form a colored curable composition layer (hereinafter appropriately referred to as “colored curable composition layer”). Abbreviated as “formation step”), a step of exposing the colored curable composition layer through a mask (hereinafter abbreviated as “exposure step” as appropriate), and the colored curable composition layer after exposure. And a step of developing a colored pattern (hereinafter, abbreviated as “development step” as appropriate).

Specifically, the curable composition of the present invention is applied directly or via another layer onto a support (substrate) to form a photopolymerizable composition layer (colored curable composition layer formation) Process), exposing through a predetermined mask pattern, curing only the irradiated film portion (exposure process), and developing with a developer (development process), each color (3 colors or 4 colors) A color filter of the present invention can be produced by forming a pattern-like film composed of pixels.
Hereafter, each process in the manufacturing method of this invention is demonstrated.

<Colored curable composition layer forming step>
In the colored curable composition layer forming step, the colored curable composition layer is formed by applying the curable composition of the present invention on the support.

Examples of the support that can be used in this step include soda glass, alkali-free glass, Pyrex (registered trademark) glass, quartz glass, plastic substrate, and those obtained by attaching a transparent conductive film to these. In addition, a photoelectric conversion element substrate used for an imaging element or the like, for example, a silicon substrate, a complementary metal oxide semiconductor (CMOS), or the like can be given. These substrates may have black stripes that separate pixels.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

  As a coating method of the curable composition of the present invention on the support, various coating methods such as slit coating, ink jet method, spin coating, roll coating, screen printing method and the like can be applied.

  As a coating film thickness of a curable composition, 0.1-10 micrometers is preferable, 0.2-5 micrometers is more preferable, 0.5-3 micrometers is further more preferable.

  The curable composition applied on the support is usually dried at 70 to 110 ° C. for about 2 to 4 minutes to form a colored curable composition layer.

<Exposure process>
In the exposure step, the colored curable composition layer formed in the colored curable composition layer forming step is exposed through a mask, and only the coating film portion irradiated with light is cured.
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are preferably used, and a high-pressure mercury lamp is more preferable. The irradiation intensity is preferably 5 mJ to 1500 mJ, more preferably 10 mJ to 800 mJ, and most preferably 10 mJ to 500 mJ.

<Development process>
Subsequent to the exposure step, an alkali development treatment (development step) is performed, and the light non-irradiated part in the exposure step is eluted in an alkaline aqueous solution. Thereby, only the photocured part remains.
The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

  In the production method of the present invention, after performing the above-described curable composition layer forming step, exposure step, and development step, if necessary, the formed colored pattern is cured by heating and / or exposure. A process may be included.

  By repeating the above-described colored curable composition layer forming step, exposure step, and developing step (and, if necessary, the curing step) for the desired number of hues, a color filter having a desired hue is produced.

According to the present invention, the resist pigment deficiency due to the high concentration of the resist pigment accompanying the improvement of the color reproduction rate and the low exposure amount (throughput improvement) accompanying the enlargement of the substrate size can be solved, and the resist can be cured with a high sensitivity and a good pattern. It is possible to provide a curable composition that has formability, suppresses development residue, and has excellent adhesion to a support.
The curable composition is particularly effective when a green having a high pigment concentration and a low I-ray transmittance is used as a colorant.
Furthermore, the present invention provides a color filter having a color pattern having a high color reproducibility and a good shape, using the curable composition of the present invention, and a production method capable of producing the color filter with high productivity. be able to.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. Unless otherwise specified, “part” means “part by mass”.
<Example 1>
1-1. Preparation of pigment dispersion C.I. I. Pigment Green 36 and C.I. I. 40 parts by mass of a 30/70 (mass ratio) mixture with CI Pigment Yellow 150, and 10 parts by mass (approximately 4. 51 parts by mass) and 150 parts by mass of ethyl 3-ethoxypropionate as a solvent were mixed and dispersed by a bead mill for 15 hours to prepare a pigment dispersion (P1).
With respect to the pigment dispersion (P1), the average particle diameter of the pigment was measured by a dynamic light scattering method and found to be 200 nm.

1-2. Preparation of curable composition (coating liquid) Pigment dispersion P1 (c) 66.6 parts by mass Alkali-soluble resin (benzyl methacrylate / methacrylic acid copolymer, molar ratio: 70/30, Mw: 5000) (d 1.5 parts by mass / polyfunctional monomer dipentaerythritol hexaacrylate (a) 4.4 parts by mass / 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra Phenyl-1,2'-biimidazole ((A) biimidazole compound) 1.0 part by mass, 4,4-bisdiethylaminobenzophenone ((B) sensitizing dye) 0.3 part by mass, compound C2 (following formula ) ((C) mercapto compound) 0.3 parts by mass-propylene glycol monomethyl ether acetate 10.5 parts by mass-ethyl ethoxypropionate 15.4 parts by mass

About Example 2 , 3, 5-7 , Reference example 4, 8, and Comparative Examples 1-3, it carried out similarly to Example 1 except having changed the composition of each component as described in Table 1-2. A coating solution of the curable composition was obtained.

[2. (Production of color filter)
2-1. Formation of curable composition layer A curable composition containing the above pigment was applied as a resist solution to a 550 mm x 650 mm glass substrate by slit coating under the following conditions, then allowed to stand for 10 minutes, and then applied to a new glass substrate. Then, vacuum drying and prebaking (100 ° C., 80 seconds) were performed to form a curable composition coating film (curable composition layer).
(Slit application conditions)
Gap at the opening at the tip of the coating head: 50 μm
Coating speed: 100 mm / second Clearance between substrate and coating head: 150 μm
Application thickness (dry thickness): 2 μm
Application temperature: 23 ° C
Pre-baking 100 ° C x 80 seconds

2-2. Exposure and development Thereafter, the photocurable coating film is exposed in a pattern using a 2.5 kw ultrahigh pressure mercury lamp under the condition of 50 mj / cm ² 20 mW. After the exposure, the entire surface of the coating film is developed with a developer (trade name: A 1% aqueous solution of CDK-1 FUJIFILM Electronics Materials Co., Ltd. was sprayed in the form of a shower and developed for 60 seconds.

2-3. Heat treatment After standing still, pure water was sprayed in the form of a shower to wash away the developer, and the coating film subjected to such photocuring treatment and development treatment was heated in an oven at 230 ° C. for 0.5 hours (post-baking). Thereby, a colored resin film (color filter) was formed on the glass substrate.

[3. (Performance evaluation)
The pattern forming property of the curable composition coating film (colored layer) formed on the glass substrate using the colored curable composition adjusted as described above, the substrate adhesion, the mask thickness, and the development residue are as follows. evaluated. The results are shown in Tables 1-2.

3-1. Pattern Formability The cross-sectional shape of the formed pattern was observed with a scanning electron microscope (SEM). The pattern cross-sectional shape is most preferably a forward taper, and a rectangular shape is next preferred. Undercutting is not preferred.
<Pattern formability>
○ Forward taper: The angle formed with the plane of the substrate is less than 75 degrees ΔRectangle: The angle formed with the plane of the substrate is less than 90 degrees x Reverse taper: The angle formed with the plane of the substrate exceeds 90 degrees

3-2. Substrate adhesion As an evaluation of substrate adhesion, it was observed whether pattern defects occurred. This evaluation item was evaluated based on the following criteria.
<Board adhesion>
○: No pattern defect was observed.
(Triangle | delta): Although the pattern defect | defect was hardly observed, the defect | deletion was partially observed.
X: A pattern defect was remarkably observed.

3-3. Mask Thickness A dimension of the formed pattern was measured with a dimension measuring instrument (ICRON Olympus Co., Ltd.). This evaluation item was evaluated based on the following criteria.
<Mask weight>
◯: A width greater than +5 μm with respect to the mask.
(Triangle | delta): The thickness width of +2 micrometer or more and less than 5 micrometers with respect to a mask.
X: Thick width less than +2 μm with respect to the mask.

3-4. Development residue In the exposure process, the presence or absence of a residue in a region not irradiated with light (unexposed portion) was observed to evaluate developability.
<Development residue>
A: No residue was observed at all in the unexposed area.
Δ: A slight residue was confirmed in the unexposed area, but it was practically unproblematic.
X: Residue was remarkably confirmed in the unexposed part.

From the results of Tables 1 and 2, it can be seen that all of the curable compositions of the present invention have good exposure sensitivity and substrate adhesion, are excellent in pattern cross-sectional shape, and further, residues in unexposed portions are suppressed. On the other hand, the curable composition of the comparative example was inferior in any of exposure sensitivity, board | substrate adhesiveness, and pattern cross-sectional shape.
The curable composition of Comparative Example 3, it can be seen that the poor in content of the component (b) has deviated from the preferred ranges, compared with the curable composition of Example 5-7, all evaluation items . Moreover, the curable composition of Example 7 has the numerical value of (b) component in the optimal range, and it turns out that it is excellent compared with the curable composition of Examples 5 and 6.

Claims (9)

(A) a compound having at least one ethylenically unsaturated double bond, (b) a photopolymerization initiator, and (c) a colorant, (b) the photopolymerization initiator being (A) a biimidazole compound, (B) A sensitizing dye, and (C) a mercapto compound represented by the following general formula (I), wherein the content of (A) + (B) + (C) is a colored curable composition for color filters mass% with 5% to 15% less der Luke color filter for the colored curable composition of the total solid content of.

(In general formula (I), R represents an alkyl group or an aryl group, and A represents an atomic group that forms a heterocycle with N = CN.) Further (d) an alkali-soluble resin including請 Motomeko colored curable composition for a color filter according to 1. Wherein (b) in the photoinitiator (A) + (B) of the content of Ru der than 10% more than 2% by weight% based on the total solid content of the colored curable composition for a color filter 請 Motomeko The colored curable composition for color filters according to claim 1. Wherein (b) Color according to 請 Motomeko 1 or claim 2 content of Ru der than 30% more than 10% by mass% of the photopolymerization initiator (A) + (B) to the total of (C) Colored curable composition for filters. A compound having at least one said (a) ethylenically unsaturated double bond, wherein (b) weight ratio of the photoinitiator (b) / (a) is Ru der 0.1 to 2.0 請 Motomeko 1 to colored curable composition for a color filter according to any one of claims 4. Wherein (c) the content of the coloring agent, any one of 請 Motomeko 1 to claim 5 der Ru 70% or less than 35% by mass% based on the total solids of the color filter colored curable composition The colored curable composition for a color filter according to Item. Wherein (C) a mercapto compound colored curable composition for a color filter according to any one of the following general formula (II) or the general formula Ru compound der represented by (III) 請 Motomeko 1 to claim 6 object.

(In general formula (II), R ¹ represents an aryl group, X represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, or an aryl group;
In general formula (III), R ² represents an alkyl group or an aryl group, and X represents a hydrogen atom, a halogen atom, an alkoxy group, an alkyl group, or an aryl group. ) On a substrate, Luca color filter having a colored pattern formed by using the colored curable composition according to any one of claims 1 to 7. A step of applying a colored curable composition according to any one of claims 1 to 7 on a substrate to form a colored curable composition layer, and the colored curable composition through a mask. process and method of manufacturing including color filters and forming a colored pattern by developing the colored curable composition layer after exposure for exposing Te.