KR20080037583A - Colored curable composition for color filter, color filter and process for producing the same - Google Patents

Abstract

A colored curable composition for a color filter is provided to be cured in high sensitivity, to ensure good pattern forming property, to suppress developed residues, and to exhibit excellent adhesiveness with a supporter. A colored curable composition for a color filter includes (a) a compound having at least one ethylenically unsaturated double bond, (b) a photopolymerization initiator, and (c) a coloring agent. The photopolymerization initiator(b) contains (A) a biimidazole-based compound, (B) a sensitizing dye, and (C) a mercapto compound. The content of the components (A)+(B)+(C) is in the range of 5-15% by mass relative to the total solids of the colored curable composition.

Description

Color curable composition for color filters, color filter and manufacturing method thereof {COLORED CURABLE COMPOSITION FOR COLOR FILTER, COLOR FILTER AND PROCESS FOR PRODUCING THE SAME}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to color curable compositions for color filters, color filters, and manufacturing methods thereof used in liquid crystal display devices (LCDs), solid state imaging devices (CCDs, CMOS, etc.).

Color filters are an essential component of liquid crystal displays.

Liquid crystal displays are being replaced by CRTs as television screens, PC screens, and other display devices in that they are more compact than the CRTs as display devices and are equal or more in performance. In recent years, the trend of the development of liquid crystal displays shows a trend of TV applications in which a large screen and high image quality are required from conventional monitor applications in which the screen is relatively small.

In liquid crystal displays for TV applications, higher image quality is demanded than in conventional monitor applications. On the other hand, in the color filter for a solid state image pickup device, a higher definition is required.

In recent years, sufficient pattern formability is not obtained due to the high concentration of the resist pigment due to the improvement of color reproducibility and the low exposure dose (throughput improvement) due to the enlargement of the substrate size, resulting in problems of panel defects due to pattern defects and developing residues.

Although the combination of chain transfer agents, such as polyfunctional thiol, and photosensitive resin is recommended for the improvement of exposure polymerization degree (refer patent document 1), since these materials have low alkali solubility, it is difficult to make both high sensitivity and proper pattern formation property. In addition, polyfunctional thiols have high reactivity, making it difficult to secure stability over time with resist.

Moreover, although the pigment | dye curable composition which is excellent in pattern formation property is proposed by defining the suitability of a chain transfer agent (refer patent document 2), even if a pigment is high concentration, in order to achieve high sensitivity, the optimal composition and ratio in a curable composition are proposed. It is not said that we do it.

(Patent Document 1) Japanese Patent No. 3120547

(Patent Document 2) Japanese Unexamined Patent Publication No. 2002-167404

This invention is made | formed in view of the problem in the prior art, and makes it a subject to achieve the following objectives.

That is, an object of the present invention is to provide a curable composition capable of forming a good colored pattern for a color filter and having excellent process aptitude.

Another object of the present invention is to provide a good coloring pattern, a color filter having the coloring pattern, and a manufacturing method capable of producing the color filter with high productivity, which are made of the curable composition of the present invention.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching, this inventor discovered that the said subject can be solved by the colored curable composition for color filters of this invention. That is, the means for solving the said subject is as follows.

<1> (a) A compound having at least one ethylenically unsaturated double bond, (b) a photoinitiator and (c) a coloring agent, and (b) a photoinitiator (A) a biimidazole compound, (B) It contains a sensitizing dye and (C) mercapto compound, and the content of (A) + (B) + (C) is 5% or more and 15% or less in mass% with respect to the total solid of the colored curable composition for color filters. Colored curable composition for color filters to be used.

The coloring curable composition for color filters as described in <1> characterized by further containing <2> (d) alkali-soluble resin.

<3> Content of (A) + (B) in said (b) photoinitiator is 2% or more and 10% or less by mass% with respect to the total solid of the colored curable composition for color filters, The said <1> characterized by the above-mentioned. Colored curable composition for color filters of description.

<4> Content of (C) with respect to the sum total of (A) + (B) in said (b) photoinitiator is 10% or more and 30% or less by mass%, The color filter as described in said <1> characterized by the above-mentioned. Coloring curable composition.

<5> The mass ratio (b) / (a) of the compound (a) having at least one ethylenically unsaturated double bond and the photopolymerization initiator (b) is 0.1 or more and 2.0 or less, wherein the <1> to < The colored curable composition for color filters in any one of 4>.

<6> The color according to any one of <1> to <5>, wherein the content of the (c) coloring agent is 35% or more and 70% or less by mass% with respect to the total solid of the colored curable composition for color filters. Colored curable composition for filters.

<7> The said (C) mercapto compound is a compound represented by the following general formula (I), The colored curable composition for color filters in any one of said <1> to <6> characterized by the above-mentioned.

Formula (I)

(In general formula (I), R represents an alkyl group or an aryl group, and A represents the atomic group which forms a heterocyclic ring with N = C-N.)

It has a coloring pattern formed on the <8> board | substrate using the colored curable composition in any one of said <1>-<7>. The color filter characterized by the above-mentioned.

Applying the colored curable composition in any one of said <1>-<7> on a <9> board | substrate, and forming a colored curable composition layer, the process of exposing the said colored curable composition through a mask, and exposure And developing the said colored curable composition layer and forming a coloring pattern, The manufacturing method of the color filter characterized by the above-mentioned.

(Effects 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 suitability can be provided.

Further, another object of the present invention can provide a good coloring pattern, a color filter having the coloring pattern, and a manufacturing method capable of producing the color filter with high productivity, which are made of the curable composition of the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, the color filter which uses the colored curable composition for color filters of this invention, the colored curable composition for color filters, and its manufacturing method are demonstrated in detail.

Colored curable composition for color filters-

The colored curable composition for color filters of this invention (a) The compound which has at least one ethylenically unsaturated double bond (Hereinafter, it may be called a specific polymeric compound suitably.), (B) Photoinitiator, (c) A coloring agent, and (d) an alkali-soluble resin, (b) a photoinitiator contains (A) a biimidazole type compound, (B) a sensitizing dye, and (C) a mercapto compound, and (A) + ( The content of B) + (C) is 5% or more and 15% or less by mass% with respect to the total solid of the colored curable composition for color filters.

Hereinafter, each component contained in the colored curable composition for color filters of this invention (Hereinafter, it may only be called a "curable composition.") Is demonstrated one by one.

<(a) specific polymerizable compound>

The specific polymerizable compound (a) usable in the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and at least one terminal ethylenically unsaturated bond, preferably 2 to 6, more preferably Preferably it is selected from the compound which has 4-6. Such compound groups are widely known in the industrial field, and in the present invention, these can be used without particular limitation. Moreover, a specific polymeric compound may be used independently or may use 2 or more types together.

These have, for example, chemical forms such as monomers, prepolymers, ie dimers, trimers and oligomers or mixtures thereof and copolymers thereof. As an example of a monomer and its copolymer, unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), its esters, and amides are preferable, Preferably it is Esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds and amides of unsaturated carboxylic acids and aliphatic polyamine compounds.

In addition, the unsaturated carboxylic ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group, with an addition reaction product of a monofunctional or polyfunctional isocyanate or an epoxy and a monofunctional or polyfunctional carboxylic acid Dehydration condensation reactants are also preferably used.

Furthermore, addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and a leaving group such as a halogen group or a tosyloxy group Substitution reaction products of unsaturated carboxylic acid esters or amides having monofunctional or polyfunctional alcohols, amines and thiols are also preferable.

As another example, it is also possible to use a compound group substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

Specific examples of ester monomers of aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, and propylene glycol as acrylic acid esters. Diacrylate, neopentylglycol diacrylate, trimetholpropane triacrylate, trimetholpropane tri (acryloyloxypropyl) ether, trimethol ethane triacrylate, hexanediol diacrylate, 1,4 -Cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylic Latex, sorbitol Tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid EO modified triacrylate and the like.

As methacrylic acid ester, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimetholpropane trimethacrylate, trimethol ethane trimethacrylate, ethylene glycol di Methacrylate, 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-hydroxypropoxy) phenyl] dimethylmethane, bis- [p- (meta Krilloxyethoxy) phenyl] dimethylmethane and the like.

As the itaconic acid ester, ethylene glycol dietaconate, propylene glycol dietaconate, 1,3-butanediol dietaconate, 1,4-butanediol dietaconate, tetramethylene glycol dietaconate, pentaerythritol dietaconate, sorbitol tetratacoate Nate and the like. Examples of the crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and the like. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of the maleic acid ester include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, sorbitol tetramalate, and the like.

Examples of other esters include, for example, the aliphatic alcohol esters described in Japanese Patent Publication No. 51-47334, Japanese Patent Publication No. 57-196231, Japanese Patent Publication No. 59-5240, Japanese Patent Publication No. 59-5241, and Japanese Patent The thing which has an aromatic skeleton of Unexamined-Japanese-Patent 2-226149, the thing containing the amino group of Unexamined-Japanese-Patent No. 1-165613, etc. are also used preferably. In addition, the above-mentioned ester monomer can be used also as a mixture.

Moreover, as an example of the amide monomer of an aliphatic polyhydric amine compound and unsaturated carboxylic acid, methylenebis- acrylamide, methylenebis-methacrylamide, 1, 6- hexamethylene bis- acrylamide, 1, 6- hexamethylene bis- meta Krillamide, diethylenetriamine trisacrylamide, xylylenebisacrylamide, xylylenebismethacrylamide and the like. As an example of another preferable amide monomer, what has a cyclohexylene structure of Unexamined-Japanese-Patent No. 54-21726 is mentioned.

Moreover, the urethane type addition polymeric compound manufactured using addition reaction of an isocyanate and a hydroxyl group is also preferable, As such an example, it has two or more isocyanate groups in 1 molecule described in Unexamined-Japanese-Patent No. 48-41708, for example. The vinylurethane compound etc. which contain two or more polymerizable vinyl groups in 1 molecule which added the vinyl monomer containing the hydroxyl group represented by following General formula (A) to a polyisocyanate compound are mentioned.

CH ₂ = C (R ⁴ ) COOCH ₂ CH (R ⁵ ) OH. (A)

(However, in general formula (A), R ⁴ and R ⁵ represent H or CH _3. )

Furthermore, urethane acrylates described in Japanese Patent Application Laid-Open No. 51-37193, Japanese Patent Application Laid-Open No. 2-32293, Japanese Patent Application Laid-Open No. 2-16765, and Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56 Also preferred are urethane compounds having an ethylene oxide-based skeleton described in -17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418. In addition, the use of addition polymerizable compounds having an amino structure or sulfide structure in a molecule described in Japanese Patent Application Laid-Open No. 63-277653, Japanese Patent Application Laid-Open No. 63-260909, and Japanese Patent Application Laid-open No. Hei 1-105238 The photopolymerizable composition which is very excellent in the photosensitive speed can be obtained.

As other examples, the polyester acrylates, epoxy resins, and (meth) acrylic acids described in Japanese Patent Application Laid-Open No. 48-64183, Japanese Patent Publication No. 49-43191, and Japanese Patent Publication No. 52-30490 Polyfunctional acrylates and methacrylates, such as the epoxy acrylate which made the reaction react, are mentioned. Moreover, the specific unsaturated compound of Unexamined-Japanese-Patent No. 46-43946, Unexamined-Japanese-Patent No. 1-40337, and Unexamined-Japanese-Patent No. 1-40336, and the vinyl phosphonic acid system of Unexamined-Japanese-Patent No. 2-25493 are mentioned. Compounds and the like. In any case, the structure containing the perfluoroalkyl group of Unexamined-Japanese-Patent No. 61-22048 is used preferably. Moreover, the thing introduce | transduced as a photocurable monomer and oligomer can also be used by Japanese adhesion association vol.20, No. 7, page 300-308 (1984).

About these addition polymeric compounds, the detail of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design of a curable composition. For example, it selects from the following viewpoints.

In terms of sensitivity, a structure having a high content of unsaturated groups per molecule is preferable, and in most cases, bifunctional or more is preferable. Moreover, in order to raise the intensity | strength of a cured film, what is more than trifunctional is good, and also it uses sensitivity and other polymerizable groups (for example, acrylic ester, methacrylic ester, styrene type compound, and vinyl ether type compound) together. The method of adjusting both strengths is also effective.

In addition, the selection and use of the addition polymerization compound are also important factors in terms of compatibility and dispersibility with other components (eg, photopolymerization initiator, colorant (pigment, dye), binder polymer, etc.) contained in the curable composition. The compatibility can be improved by using a low-purity compound and using 2 or more types together. Moreover, a specific structure can also be selected for the purpose of improving adhesiveness with a board | substrate.

(a) The mass ratio (b) / (a) of a specific polymeric compound and (b) photoinitiator mentioned later is 0.1 or more and 2.0 or less, Preferably it is 0.1 or more and 1.0 or less, Especially preferably, it is 0.1 or more and 0.5 or less. . By setting it as the said range, pattern formation property is favorable and it is excellent in adhesiveness with a board | substrate. Moreover, the mask increase amount after exposure and image development is enough, and pattern peeling is suppressed.

It is preferable that content of a specific polymeric compound is 5-30 mass% in the total solid of a curable composition, It is more preferable that it is 15-30 mass%, It is especially preferable that it is 20-30 mass%.

<(b) Photoinitiator>

The photoinitiator of this invention points out the photoinitiator containing the (A) biimidazole type compound, (B) sensitizing dye, and (C) mercapto compound.

The content of (A) + (B) + (C) in the photopolymerization initiator is 5% or more and 15% or less, more preferably 5% or more and 12% or less, based on the total solids of the colored curable composition for color filters. Especially preferably, it is 5% or more and 10% or less.

By setting it in the said range, the curable composition of this invention is hardened with high sensitivity, and has favorable pattern formation property. In addition, the alkali dissolution rate of the unexposed portion is high, and the development residue is suppressed.

Moreover, in a photoinitiator, content of (A) + (B) is 2% or more and 10% or less by mass% with respect to the total solid of the colored curable composition for color filters, More preferably, they are 2% or more and 8% or less, Especially preferably, it is 4% or more and 8% or less.

By setting it in the said range, the curable composition of this invention is hardened with high sensitivity, and has favorable pattern formation property. In addition, the alkali dissolution rate of the unexposed portion is high, and the development residue is suppressed.

Moreover, in photoinitiator, content of (C) with respect to the sum total of (A) + (B) is 10% or more and 30% or less by mass%, Preferably it is 10% or more and 25% or less, Especially preferably, it is 15 It is more than 25%.

By setting it in the said range, the curable composition of this invention is hardened with high sensitivity, and has favorable pattern formation property. In addition, the alkali dissolution rate of the unexposed portion is high, and the development residue is suppressed.

(A) Biimidazole type compound (photoinitiator)

The photoinitiator in the photoinitiator of the present invention is a compound which is decomposed by light to initiate and promote the polymerization of the above-mentioned polymerizable compound, and preferably has absorption in a region having a wavelength of 300 to 500 nm.

As a biimidazole type compound, a hexaaryl biimidazole compound etc. are preferable, for example.

As a hexaaryl biimidazole compound, for example, Unexamined-Japanese-Patent No. 6-29285, US Patent 3,479,185, 4,311,783, 4,622,286, Japan Patent Publication 45-37377, Japan Patent Publication Ropindimers described in 44-86516, specifically 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (o-bromophenyl) 4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4', 5,5'-tetraphenyl Biimidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (m-methoxyphenyl) biimidazole, 2,2'-bis (o, o' -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-nitrophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-trifluorophenyl) -4,4', 5, 5'- tetraphenylbiimidazole etc. are mentioned. Especially, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole is especially preferable.

As a photoinitiator, in addition to the said biimidazole type compound, it is an organic halogenated compound, an oxydiazole compound, a carbonyl compound, a ketal compound, a benzoin compound, an acridine compound, an organic peroxide compound, an azo compound, a coumarin compound, for example. And an azide compound, a metallocene compound, an organic boric acid compound, a disulfonic acid compound, an oxime ester compound, an onium salt compound, and an acylphosphine (oxide) compound.

Specifically as an organic halogenated compound, Wakabayashi etc., "Bull Chem. Soc Japan '' 42, 2924 (1969), US Patent No. 3,905,815, Japanese Patent Publication No. 46-4605, Japanese Patent Publication No. 48-36281, Japanese Patent Publication No. 55-32070, Japanese Patent Publication No. 60- 239736, Japanese Patent Publication No. 61-169835, Japanese Patent Publication No. 61-169837, Japanese Patent Publication No. 62-58241, Japanese Patent Publication No. 62-212401, Japanese Patent Publication No. 63-70243, Japanese Patent The compound of Unexamined-Japanese-Patent No. 63-298339 and "MPHutt" Jurnal of Heterocyclic Chemistry "1 (No3), (1970)" is mentioned, In particular, the oxazole compound substituted with the trihalomethyl group, s-triazine The compound can be mentioned.

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 2,4,6-tris (mono Chloromethyl) -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 (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6- Bis (trichloromethyl) -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 (tree Roromethyl) -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-nathoxynaphthyl) -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, etc. are mentioned.

As the oxydiazole compound, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (naphtho-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4- Oxodiazole, etc. may be mentioned.

As the carbonyl compound, benzos such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone Phenone derivatives, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, α-hydroxy-2-methylphenylpropane, 1-hydroxy- 1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 '-(methylthio) phenyl) -2-morpholino Acetophenone derivatives such as -1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone, 2-benzyl-2-dimethylamino-4-morpholinobutyllophenone, thioxanthone, 2-ethyl thioxanthone, 2-isopropyl thioxanthone, 2-chlorothioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxane Thioxanthone derivatives such as tones, ethyl p-dimethylamino benzoate, p-diethylamino Benzoate ester derivatives, such as ethyl benzoate, etc. are mentioned.

As a ketal compound, benzyl methyl ketal, benzyl- (beta)-methoxy ethyl ethyl acetal, etc. are mentioned.

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-butyl Peroxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butylhydroperoxide, cumene hydroperoxide, diisopropylbenzenehydroperoxide, 2,5-dimethylhexane-2,5 -Dihydroperoxide, 1,1,3,3-tetramethylbutylhydroperoxide, tert-butylcumylperoxide, dicumylperoxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) Hexane, 2,5-oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl Peroxydicarbonate, dimethoxyisopropylperoxycarbonate, di (3-methyl-3-methoxybutyl) peroxydi Carbonate, tert-butylperoxyacetate, tert-butylperoxypivalate, tert-butylperoxy neodecanoate, tert-butylperoxyoctanoate, tert-butylperoxy laurate, tertylcarbonate, 3, 3 ', 4,4'-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3 ' , 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxy2hydrogen2phthalate), carbonyldi (t-hexylperoxy2hydrogen2phthalate) ), And the like.

As an azo compound, the azo compound etc. which were described in Unexamined-Japanese-Patent No. 8-108621 are mentioned, for example.

Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazine- 2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, etc. are mentioned.

Examples of the azide compound include the organic azide compounds described in US Patent No. 2848328, US Patent No. 2852379, and US Patent No. 2940853, and 2,6-bis (4-azidebenzylidene) -4-ethylcyclohexa Rice (BAC-E) etc. are mentioned.

As the metallocene compound, Japanese Patent Laid-Open No. 59-152396, Japanese Patent Laid-Open No. 61-151197, Japanese Patent Laid-Open No. 63-41484, Japanese Patent Laid-Open No. 2-249, and Japanese Patent Laid-Open No. 2 Various titanocene compounds disclosed in JP-A-4705 and JP-A-5-83588, for example, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2, 6-difluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4-di-fluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4 , 6-trifluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis -2,3,4,5,6-pentafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophenyl-1-yl, di-methylcyclopenta Dienyl-Ti-bis-2,4,6-trifluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-te Lafluorophenyl-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl, Japanese Patent Laid-Open No. 1-304453, The iron-alein complex described in Unexamined-Japanese-Patent No. 1-52109 is mentioned.

As the organic borate compound, for example, Japanese Patent Laid-Open No. 62-143044, Japanese Patent Laid-Open No. 62-150242, Japanese Patent Laid-Open No. 9-188685, Japanese Patent Laid-Open No. 9-188686, Japanese Patent Laid-Open No. 9-188710 Japanese Patent Laid-Open No. 2000-131837, Japanese Patent 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, Organoborate salts described in "1998, Chicago" and the like, the organoboron sulfonium complexes or organoboron oxos described in JP-A-6-157623, JP-A-6-175564, and JP-A-6-175561 Sulfonium complex, the organoboron iodonium complex described in JP-A-6-175554, JP-A-6-175553, the organoboron phosphonium complex described in JP-A-9-188710, and Japanese patent Japanese Patent Laid-Open No. 6-348011, Japanese Patent Laid-Open No. 7-128 Organic boron transition metal coordination complexes, such as 785, Unexamined-Japanese-Patent No. 7-140589, Unexamined-Japanese-Patent No. 7-306527, and Unexamined-Japanese-Patent No. 7-292014, etc. are mentioned as a specific example. .

As a disulfone compound, the compound etc. which are described in Unexamined-Japanese-Patent No. 61-166544, Unexamined-Japanese-Patent No. 2001-132318, etc. are mentioned.

As an oxime ester compound, it is J.C.S. Perkin II (1979) 1653-1660), J.C.S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, Compounds described in JP 2000-66385, JP 2000-80068, JP 2004-534797 The compound as described in the publication is mentioned.

As the onium salt compound, for example, S.I. Schlesinger, Photogr. Sci. Diazonium salts described in Eng., 18,387 (1974), T. S. Bal et al, Polymer, 21,423 (1980), ammonium salts described in US Pat. No. 4,069,055, Japanese Patent Application Laid-open No. Hei 4-365049, and US Pat. 4,069,055, 4,069,056, phosphonium salts described in each specification, European Patent No. 104,143, US Patent No. 339,049, Japanese Patent No. Hei 2-150848, Japanese Patent Application Laid-Open No. 2-296514 The iodonium salt etc. which were described in each publication are mentioned.

The iodonium salt which can be preferably used in the present invention is a diaryl iodonium salt, and from the viewpoint of stability, it is preferable that two or more of iodonium salts are substituted with an electron donating group such as an alkyl group, an alkoxy group or an aryloxy group.

The sulfonium salts that can be preferably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, US Patent 4,933,377, 161,811, 410,201, 339,049 , Sulfonium salts described in each specification of 4,760,013, 4,734,444, 2,833,827, German Patent Nos. 2,904,626, 3,604,580, 3,604,581, and are preferably electron-withdrawing groups from the sensitivity point of stability. It is preferable that it is substituted. The electron-withdrawing group is preferably one having a Hammett value greater than zero. Preferred electron withdrawing groups include halogen atoms, carboxylic acids and the like.

Moreover, as another preferable sulfonium salt, the sulfonium salt in which one substituent of a triaryl sulfonium salt has a coumarin and an aquinone structure, and has absorption in 300 nm or more is mentioned. As another preferable sulfonium salt, the sulfonium salt which has absorption in 300 nm or more in which a triaryl sulfonium salt has an aryloxy group and an arylthio group as a substituent is mentioned.

In addition, as an onium salt compound, Crivello et al, Macromolecules, 10 (6), 1307 (1977), V. V. Crivello et al, J. Polymer Sci., Polymer Chem. Selenium salts described in Ed., 17, 1047 (1979), C. S. Wen et al, Teh, Proc. Conf. Rad. Onium salts, such as the arsonium salt as described in Curing ASIA, p478 Tokyo, Oct (1988), etc. are mentioned.

Examples of the acyl phosphine (oxide) compound include Ilgacua 819, Darocua 4265, and Darocua TPO manufactured by Chiba Specialty Chemicals.

As a photoinitiator used for this invention, at least 1 sort (s) of compound chosen from the group which consists of a biimidazole type compound, a trihalomethyl triazine type compound, and an oxime type compound from a viewpoint of high sensitivity is more preferable, and a biimidazole type Compounds are most preferred. In addition, a photoinitiator can also be used individually or in combination of 2 or more types.

It is preferable that content of (A) photoinitiator is 1-15 mass% in the total solid of a curable composition, It is more preferable that it is 2-10 mass%, It is especially preferable that it is 2-6 mass%.

(B) dark dye

As a sensitizing dye which can be used for this invention, it is preferable to sensitize with a radical initiator with an electron transfer mechanism or an energy transfer mechanism.

Examples of the sensitizing dyes that can be used in the present invention include those belonging to the compounds listed below, and those having an absorption wavelength in the wavelength range of 300 nm to 450 nm.

Examples of preferred sensitizing dyes include those belonging to the following compounds, and those having an absorption wavelength in the 330 nm to 450 nm region.

For example, polynuclear aromatics (e.g. phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10- dialkoxy anthracene), xanthenes (e.g. fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (isopropyl thioxanthone, diethyl thioxanthone, chlorothioxanthone), cyanines (e.g., thiacarbocyanine, oxacarbocyanine), merocyanines ( For example, merocyanine, carbomerocyanine), phthalocyanines, thiazines (e.g. thionine, methylene blue, toluidine blue), acridines (e.g. acridine orange, chloroflavin, arc Riflavin), anthraquinones (e.g. anthraquinones), squariases (e.g. squalanes), acridine orange, coumarins (e.g. 7-diethylamino-4-methylcoumarins) Tocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenyl Tan, distyrylbenzenes, carbazoles, porphyrins, spiro compounds, quinacridones, indigo, styryl, pyryllium compounds, pyrromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thio Aromatic ketone compounds such as barbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone, heterocyclic compounds such as N-aryloxazolidinone, and the like. A sensitizing dye may be used individually by 1 type, and may use 2 or more types together.

As an example of a more preferable sensitizing dye, the compound represented by the following general formula (B-1)-(B-4) is mentioned.

(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 forms a basic nucleus of a dye in combination with an adjacent A ¹ and an adjacent carbon atom. Represents a nonmetallic atom group, R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a monovalent nonmetallic atom group, and R ⁵¹ and R ⁵² may combine with each other to form an acidic nucleus of a dye. Indicates.)

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

(Formula (B-3) of the, A ² denotes a sulfur atom or NR ^59, L ³ represents a non-metallic atomic group forming a basic nucleus of A ² and common to pigments and carbon atom which are adjacent, R ^53, R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represent a group of a monovalent nonmetallic atom 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, A substituted or unsubstituted aryl group, L ⁴ , L ⁵ each independently represent a non-metallic atom group that forms a basic nucleus of a dye in association with adjacent A ³ , A ⁴ and adjacent carbon atoms, and R ⁶⁰ , R ⁶¹ each represent Independently represent a monovalent nonmetallic atom group or combine with 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 sort (s) chosen from the compound represented by the following general formula (IV)-(VI) besides the said sensitizing dye is mentioned. These may be used individually by 1 type and may use 2 or more types together.

In formula (IV) or 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 a monovalent substituent. Indicates. n represents an integer of 0 to 5, n 'represents an integer of 0 to 5, and n and n' do not both become 0. When n is two or more, two or more R <^1> may be same or different, respectively. When n 'is two or more, two or more R <^2> may be same or different, respectively.

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

In General Formula (IV-1), R ¹ and R ² each independently represent a monovalent substituent. n represents the integer of 0-5, n 'represents the integer of 1-5. When n is two or more, two or more R <^1> may be same or different, and when n 'is two or more, two or more R <^2> may be same or different, respectively.

In the formula ^(IV-1), R 1 and represented by a monovalent substituent in R ² is represented by motion and the monovalent substituent in R ¹ and R ² in the general formula (IV), as a preferred range.

As a compound represented by general formula (IV) or general formula (V), it is preferable that molar extinction coefficient ((epsilon)) in wavelength 365nm is 500mol <^-1> L * cm <^-1> or more, Preferably it is in wavelength 365nm. it is most preferred that ε is not less than ε in the preferred, more preferably not less than the wavelength 365㎚ ^{3000mol -1 · L · cm -1 20000mol} -1 · L · cm -1. If the value of the molar extinction coefficient (epsilon) in each wavelength is the said range, since a sensitivity improvement effect is high from a viewpoint of light absorption efficiency, it is preferable.

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.

In addition, in this specification, a chemical formula may be described by a simple structural formula, and the solid line etc. which do not specify an element and a substituent especially represent a hydrocarbon group. In the specific examples below, 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 the general formula (VI), A represents a great import FIG aromatic ring or heterocyclic ring substituents, X is an oxygen atom, a sulfur atom or -N (R ³⁾ - represents the, Y is 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 atom group, and A, R ¹ , R ² , and R ³ may be bonded to each other to form an aliphatic or aromatic ring.

In general formula (VI), R <^1> , R <^2> and R <^3> represent a hydrogen atom or monovalent nonmetallic atom group each independently. When R ¹ , R ² and R ³ represent a monovalent non-metal atom, substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkenyl group, substituted or unsubstituted aromatic heterocyclic moiety, substituted or unsubstituted It is preferable that they are an alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, and a halogen atom.

Compound of formula (VI) is Y is an oxygen atom or -N (R ³⁾ from the viewpoint of decomposition efficiency of the photopolymerization initiator is preferred. R ³ 's each independently represent a hydrogen atom or a monovalent nonmetallic atom group. Also, Y is most preferably -N (R ³ )-.

(B) It is preferable that it is 0.1-10.0 mass% in the total solid of curable composition, as for content of (B) dark dye, it is more preferable that it is 0.1-5.0 mass%, and it is especially preferable that it is 0.5-5.0 mass%.

(C) mercapto compound

The mercapto compound in this invention is a co-sensitizer which has an effect | action which further improves the sensitivity to active radiation of a sensitizing dye and a polymerization initiator, or suppresses the polymerization inhibition of a polymeric compound by oxygen.

Specific examples of the mercapto compound include ethylene glycol bisthiopropionate (EGTP), butanediol bisthiopropionate (BDTP), trimetholpropane tristyoplioionate (TMTP), and pentaerythritol tetrakistiopionopionate. (PETP) and mercaptopropionic acid derivatives such as THEIC-BMPA represented by the following formula; Mercapto ethers such as di (mercaptoethyl) ether; Aliphatic, such as hexanediol, decandithiol, 1, 4- dimethyl mercaptobenzene, butanediol bisthioglycol, trimetholol propane tristhioglycolate, pentaerythritol tetrakisthioglycolate, and tris hydroxyethyl tristyopiopioneate Aromatic mercapto compounds, such as a polyfunctional mercapto compound, mercapto benzthiazole, 2-mercapto benzoxazole, and 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazolin, (beta) -mer Captonaphthalene can be illustrated. These can be used individually or in combination of 2 or more types.

It is preferable that the mercapto compound used by this invention is substituted by the -SH group to a heterocyclic ring, As a hetero atom contained in a heterocyclic ring, nitrogen and sulfur are preferable, and it is more preferable to have two nitrogen atoms.

It is preferable that the mercapto compound of this invention is a compound represented with the following general formula (I).

(In general formula (I), R represents an alkyl group or an aryl group, and A represents the atomic group which forms a heterocyclic ring with N = C-N.)

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, straight chains having 1 to 12 carbon atoms, branched phases having 3 to 12 carbon atoms, and 5 carbon atoms. To 10 cyclic alkyl group is more preferable.

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 those in which one to three benzene rings form a condensed ring in addition to those having a monocyclic structure, those in which a benzene ring and a five-membered unsaturated ring form a condensed ring, and the like, and specific examples thereof include a phenyl group and a naphthyl group. , Anthryl group, phenanthryl group, indenyl group, acenaphthenyl group, fluorenyl group, etc. are mentioned, Among these, a phenyl group and a naphthyl group are more preferable.

These alkyl groups and aryl groups may further have a substituent, and examples of the substituents that can be introduced include linear, branched or cyclic alkyl groups having 1 to 20 carbon atoms, linear, branched or cyclic alkenyl groups 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, an alkoxycarbonyloxy group having 2 to 20 carbon atoms, and an aryloxycarbon having 7 to 20 carbon atoms A carbonyloxy group, a carbamoyloxy group having 1 to 20 carbon atoms, a carbonamide group having 1 to 20 carbon atoms, a sulfonamide group having 1 to 20 carbon atoms, a carbamoyl group having 1 to 20 carbon atoms, a sulfamoyl group, A substituted sulfamoyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, 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, and a carbon source N-acyl sulfamom of embroidery 1-20 N-sulfamoylcarbamoyl group having 1 to 20 carbon atoms, alkylsulfonyl group having 1 to 20 carbon atoms, arylsulfonyl group having 6 to 20 carbon atoms, alkoxycarbonylamino group having 2 to 20 carbon atoms, and 7 to 20 carbon atoms 20 aryloxycarbonylamino group, amino group, substituted amino group having 1 to 20 carbon atoms, imino group having 1 to 20 carbon atoms, ammonium group having 3 to 20 carbon atoms, carboxyl group, sulfo group, oxy group, mercapto group and carbon number 1-20 alkylsulfinyl groups, 6-20 carbon atoms, arylsulfinyl groups, 1-20 carbon atoms, arylthio groups 6-6 carbon atoms, 1-20 carbon atoms, 2 carbon atoms A heterocyclic group of -20, an acyl group of 1 to 20 carbon atoms, a sulfamoylamino group, a substituted sulfamoylamino group of 1 to 2 carbon atoms, a silyl group of 2 to 20 carbon atoms, an isocyanate group, an isocyanide group, a halogen atom ( For example, fluorine atom, chlorine source , A bromine atom, etc.), a cyano group, and the like can be mentioned a nitro group, o nyumgi.

In general formula (I), A represents the atomic group which forms a heterocyclic ring with N = C-N.

Examples of the atoms constituting the atomic group include carbon atoms, nitrogen atoms, hydrogen atoms, sulfur atoms, selenium atoms, and the like.

Moreover, the heterocyclic ring formed from A and N = C-N may have a substituent further, and the substituents which can be introduce | transduced include the thing similar to the substituent which can be introduced into the said alkyl group and an aryl group.

As another example of the sensitizer, thiols and sulfides, for example, the thiol compounds described in Japanese Patent Application Laid-Open No. 53-702, Japanese Patent Application Laid-Open No. 55-500806, Japanese Patent Application Laid-Open No. 5-142772, and Japanese Patent The disulfide compound of Unexamined-Japanese-Patent No. 56-75643, etc. are mentioned, Specifically, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto- 4 (3H) -quinazolin, (beta) -mercaptonaphthalene, etc. are mentioned.

Especially, mercapto compounds, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-4 (3H)-quinazoline, (beta) -mercaptonaphthalene, This is preferred.

As examples of other sensitizers, amines such as MR Sander et al., `` Ounal of Polymer Society, '' Volume 10, page 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Laid-Open No. 52-134692, Japanese Patent Laid-Open No. 59-138205, Japanese Patent Laid-Open No. 60-84305, Japanese Patent Laid-Open No. 62-18537, Japanese Patent Laid-Open No. 64-33104, The compound described in Research Disclosure 33825, etc. are mentioned, Specifically, triethanolamine, p-dimethylamino benzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline, etc. are mentioned.

Other examples of the sensitizer include amino acid compounds (e.g., N-phenylglycine), organometallic compounds (e.g., tributyltin acetate, etc.) described in JP-A-48-42965, JP-A-55-34414 The hydrogen donor described in Unexamined-Japanese-Patent No. 6, the sulfur compound (for example, trithiane etc.) of Unexamined-Japanese-Patent No. 6-308727, etc. are mentioned.

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, 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 bro atom, and an iodine atom are preferable.

Examples of the alkoxy group in the general formulas (II) and (III) include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butyloxy group, a pentyloxy group, a hexyloxy group, a dodecyloxy group, a benzyloxy group, Allyloxy group, phenethyloxy group, carboxyethyloxy group, methoxycarbonylethyloxy group, ethoxycarbonylethyloxy group, methoxyethoxy group, phenoxyoxy group, methoxyethoxyethoxy group, Methoxyethoxyethoxy group, morpholinoethoxy group, morpholinopropyloxy group, aryloxyethoxyethoxy group, phenoxy group, tolyloxy group, xylyloxy group, mesityloxy group, cumenyloxy group, meth Oxyphenyloxy group, ethoxyphenyloxy group, chlorophenyloxy group, bromophenyloxy group, acetyloxy group, benzoyloxy group, naphthyloxy group, etc. are mentioned.

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), and its preferable range is also the same.

Each group in general formula (II) and (III) may further have a substituent, and as this substituent is the same as what was enumerated as a substituent which can be introduce | transduced into the alkyl group and aryl group represented by R of general formula (I).

These mercapto compounds are Ｊ．Appl. Chem. 34, 2203-2207 (1961) can be synthesized by the method described.

(C) It is preferable that content of a mercapto compound is 0.1-10.0 mass% in the total solid of a curable composition, It is more preferable that it is 0.1-5.0 mass%, It is especially preferable that it is 0.5-5.0 mass%.

In the curable composition of this invention, the compound represented by general formula (I) may be used individually by 1 type, may use 2 or more types together, and is a compound selected from the compound represented by general formula (II), and general You may use together the compound chosen from the compound chosen from the compound represented by Formula (III).

Moreover, the preferable combination in the polymerization initiator of this invention is 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, a sensitizing dye, and mer as a photoinitiator. It is a combination of a capto compound, As a mercapto compound, the following compound C1 or C2 is preferable, Especially preferably, it is C2.

<(c) Colorant>

The curable composition of this invention contains a coloring agent.

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. As said coloring agent, it is preferable that it is a pigment from a light resistant viewpoint.

As a pigment which can be used for the curable composition of this invention, various conventionally well-known inorganic pigments or organic pigments can be used. In addition, considering that it is preferable to have a high transmittance, whether inorganic pigments or organic pigments, the use of thin ones is preferable, and in consideration of handling properties, the average particle diameter of the pigment is preferably 0.01 μm to 0.1 μm, and 0.01 μm to 0.05 μm. Is more preferable. Examples of the inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like, and specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony. And complex oxides of the above metals.

As an organic pigment, for example

Pigment Yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199 ,;

C.I. pigment orange 36,38,43,71;

Pigment Red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;

C.I. Pigment Violet 19,23,32,39;

Pigment Blue 1,2,15,15: 1,15: 3,15: 6,16,22,60,66;

C.I. pigment green 7,36,37;

C.I. Pigment Brown 25,28;

C.I. Pigment Black 1,7;

Carbon black etc. are mentioned.

Especially in this invention, what has basic N atom in the structural formula of a pigment can be used preferably. Pigments having these basic N atoms exhibit good dispersibility in the compositions of the present invention. Although the cause is not fully elucidated, it is presumed that the excellence of the affinity between the curable polymerization component and the pigment has influenced.

The following can be mentioned as a pigment which can be used preferably in this invention. However, this invention is not limited to these.

Pigment Yellow 11,24,108,109,110,138,139,150,151,154,167,180,185,

Pigment orange 36,71,

Pigment Red 122,150,171,175,177,209,224,242,254,255,264,

C.I. Pigment Violet 19,23,32,

Pigment Blue 15: 1,15: 3,15: 6,16,22,60,66,

Pigment Green 7,36,37,

C.I. pigment black

These organic pigments can be used individually or in combination in order to raise color purity. The specific example of the said combination is shown below. For example, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them as a red pigment, a disazo yellow pigment, an isoindolin yellow pigment, a quinophthalone yellow pigment or Mixtures of perylene-based red pigments and the like can be used. For example, CI pigment red 177 is mentioned as an anthraquinone pigment, CI pigment red 155 and CI pigment red 224 are mentioned as a perylene pigment, CI pigment red 254 as a diketopyrrolopyrrole pigment. The mixing with CI pigment yellow 139 is preferable at the point of color reproducibility. In addition, the mass ratio of the red pigment and the yellow pigment is preferably 100: 5 to 100: 50. By setting it as said range, the light transmittance of 400 nm-500 nm can be suppressed, and color purity can be improved. Moreover, color reproducibility becomes favorable. Especially as said mass ratio, the range of 100: 10-100: 30 is optimal. Moreover, in the case of the combination of red pigments, it can adjust to chromaticity.

As the green pigment, a halogenated phthalocyanine pigment alone or a mixture of this and a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindolin yellow pigment can be used. For example, CI Pigment Green 7, 36, 37 and CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180 or CI Pigment Yellow Mixing of 185 is preferred. The mass ratio of green pigment and 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 said range, it is easy to suppress the light transmittance of wavelength 400nm-450nm, it is easy to raise color purity, and it is easy to make the deviation from NTSC target color small.

As the blue pigment, a phthalocyanine pigment alone or a mixture of this and a dioxadine violet pigment can be used. For example, a mixture of C.I. Pigment Blue 15: 6 and C.I.Pigment Violet 23 is preferable. As for mass ratio of a blue pigment and a purple pigment, 100: 0-100: 30 are preferable, More preferably, it is 100: 10 or less.

As the pigment for the black matrix, carbon, titanium black, iron oxide, titanium oxide alone or mixed is used.

In the present invention, when the colorant is a dye, it is uniformly dissolved in the composition to obtain a curable composition.

There is no restriction | limiting in particular as dye which can be used as a coloring agent contained in the curable composition of this invention, A well-known dye can be used as a conventional color filter use. For example, Japanese Patent Laid-Open No. 64-90403, Japanese Patent Laid-Open No. 64-91102, Japanese Patent Laid-Open No. Hei 1-94301, Japanese Patent Laid-Open No. Hei 6-11614, Japanese Patent Registration 2592207, United States Patent 4,808,501, US 5,667,920, US 5,059,500, Japanese Patent Laid-Open No. 5-333207, Japanese Patent Laid-Open No. 6-35183, Japanese Patent Laid-Open No. 6-51115, Japanese Patent Laid-Open No. Hei 6-194828, Japanese Patent Laid-Open No. Hei 8-211599, Japanese Patent Laid-Open No. Hei 4-249549, Japanese Patent Laid-Open No. Hei 10-123316, Japanese Patent Laid-Open No. Hei 11-302283, Japanese Patent Laid-Open No. 7-286107, Japanese Patent Laid-Open No. 2001-4823, Japanese Patent Laid-Open No. 8-15522, Japanese Patent Laid-Open No. 8-29771, Japanese Patent Laid-Open No. 8-146215, Japan Japanese Patent Laid-Open No. 11-343437, Japanese Patent Laid-Open No. 8-62416, Japanese Patent Laid-Open 20 02-14220, Japanese Patent Publication 2002-14221, Japanese Patent Publication 2002-14222, Japanese Patent Publication 2002-14223, Japanese Patent Publication No. 8-302224, Japanese Patent Publication No. 8-73758 The pigment | dye disclosed in Unexamined-Japanese-Patent No. 8-179120, Unexamined-Japanese-Patent No. 8-151531, etc. can be used.

Examples of the chemical structure include pyrazole azo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, Dyestuffs, such as a pyrrolopyrazole azomethine series, a xanthene series, a phthalocyanine series, a benzopyran series, an indigo series, can be used.

Moreover, in the case of the resist system which performs water or alkali image development, an acidic dye and / or its derivative can be used preferably from a viewpoint of completely removing the binder and / or dye of a non-irradiated part by image development.

In addition, direct dyes, alkaline dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, useful dyes, food dyes and / or derivatives thereof, and the like can also be usefully used.

The acid dye is not particularly limited as long as it has an acid group such as sulfonic acid or carboxylic acid, but it is not particularly limited, solubility in organic solvents and developer, salt formation with basic compounds, absorbance, interaction with other components in the composition, light resistance and heat resistance. The overall performance is selected in consideration of the required performance.

Although the specific example of an acid dye is given to the following, it is not limited to these. 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 chrome 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 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88 , 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 1,3,7,9,11,17,23,25,42,54 , 73,76,79,98,99,111,112,114,116,184,243; Food Yellow 3; and derivatives of these dyes.

Among these, acid dyes include 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; Dyes such as acid green 25 and derivatives of these dyes are preferred.

Azo-based, xanthene-based, and phthalocyanine-based acid dyes other than those described above are also preferable, and C.I. Solvent Blue 44,38; C.I. Solvent orange 45; Acid dyes such as Rhodamin B and Rhodamin 110 and derivatives of these dyes are also preferably used.

Especially, as a coloring agent, triallyl methane type, anthraquinone type, azomethine type, benzylidene type, oxonol type, cyanine type, phenothiazine type, pyrrolopyrazole azomethine type, xanthene type, phthalocyanine type, benzopyran type, It is preferable that it is a coloring agent chosen from an indigo system, a pyrazole azo system, an anilino azo system, a pyrazolotriazole azo system, a pyridone azo system, and an anthrapyridone system.

The colorant that can be used in the present invention is a dye, or the average particle diameter (r) (unit nm) is 20≤r≤300, preferably 25≤r≤250, particularly preferably 30≤r≤200 Pigments are preferred. By using the pigment of such average particle diameter r, the coloring pixel of high contrast ratio and high light transmittance can be obtained. The "average particle diameter" here means the average particle diameter with respect to the secondary particle which the primary particle (single microcrystal) of a pigment aggregated.

The particle size distribution of the secondary particles of the pigment which can be used in the present invention (hereinafter, simply referred to as "particle size distribution") is 70% by mass or more of the total secondary particles having an average particle diameter of ± 100 nm. It is preferable that it is 80 mass% or more.

The pigment having the above average particle diameter and particle size distribution is preferably a pigment mixture mixed with commercially available pigments, with other pigments used in some cases (average particle diameters usually exceed 300 nm), preferably with a dispersant and a solvent. For example, it can prepare by mixing and disperse | distributing, grind | pulverizing using grinders, such as a bead mill and a roll mill. The pigment obtained in this way usually takes the form of a pigment dispersion liquid.

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 as the said range, moderate chromaticity is easy to be obtained, photocuring advances, and film intensity | strength and alkali image development latitude tend to become wide.

<(d) alkali-soluble resin>

The curable composition in this invention contains at least 1 sort (s) of alkali-soluble resin (henceforth a "binder concerning this invention"). Although it will not specifically limit, if it is alkali-soluble as a binder which concerns on this invention, What is chosen from a viewpoint of heat resistance, developability, water availability, etc. is preferable.

The alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and capable of being developed with a weak alkaline aqueous solution.

As such a "linear organic polymer", a well-known thing can be used arbitrarily. Preferably, a linear organic polymer is selected that is soluble or swellable in water or weakly alkaline water in order to enable water development or weakly alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also as a water, weak alkaline water or an organic solvent developer.

For example, the use of water-soluble organic polymers makes water development possible. As such linear organic polymers, radical polymers having a carboxylic acid group in the side chain, for example, Japanese Patent Application Laid-Open No. 59-44615, Japanese Patent Publication No. 54-34327, Japanese Patent Publication No. 58-12577, and Japanese Patent Publication No. 54 -25957, Japanese Patent Laid-Open No. 54-92723, Japanese Patent Laid-Open No. 59-53836, Japanese Patent Laid-Open No. 59-71048, that is, a resin or acid copolymerized with a monomer having a carboxyl group alone or in an acid; And resins obtained by hydrolyzing, half esterifying or half amidating an acid anhydride unit by singly or copolymerizing monomers having anhydrides, and epoxy acrylates modified with epoxy resins with unsaturated monocarboxylic acids and acid anhydrides. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxystyrene. Examples of the monomer having an acid anhydride include maleic anhydride and the like.

Similarly, there are acidic cellulose derivatives having a carboxylic acid group in the side chain. In addition, what added the cyclic acid anhydride to the polymer which has a hydroxyl group is useful.

When using alkali-soluble resin as a copolymer, you may use other monomers other than the monomer mentioned above as a compound to copolymerize. As an example of another monomer, the compound of following (1)-(12) is mentioned.

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl meth Acrylic esters and methacrylic acid esters which have aliphatic hydroxyl groups, such as a acrylate, 3-hydroxypropyl methacrylate, and 4-hydroxybutyl methacrylate.

(2) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate, Alkyl acryls, such as 3, 4- epoxycyclohexyl methyl acrylate, a vinyl acrylate, 2-phenyl vinyl acrylate, 1-propenyl acrylate, an aryl acrylate, 2-aryloxy ethyl acrylate, and propargyl acrylate Rate.

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, methacrylic acid Cyclohexyl, benzyl methacrylate, 2-chloroethyl methacrylate, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1 Alkyl methacrylates such as propenyl methacrylate, allyl methacrylate, 2-aryloxyethyl methacrylate and propargyl methacrylate.

(4) acrylamide, methacrylamide, N-metholacrylamide, N-ethylacrylamide, N-hexyl methacrylamide, N-cyclohexyl acrylamide, N-hydroxyethyl acrylamide, N-phenyl acryl Amide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, vinyl acrylamide, vinyl methacrylamide, N, N- diallyl acrylamide, N, N- diallyl methacrylamide, allyl acrylamide Acrylamide or methacrylamide, such as allyl methacrylamide.

(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 chloro acetate, vinyl butyrate, and vinyl benzoate.

(7) Styrene, such as styrene, (alpha) -methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxy styrene.

(8) Vinyl ketones, such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl petone.

(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-acryloyl acrylamide, N-acetyl methacrylamide, N-propionyl methacrylamide, and N- (p-chlorobenzoyl) methacrylamide.

(12) A methacrylic acid monomer having a hetero atom bonded to an α position. For example, the compound described in JP 2001-115595 specification, JP 2001-115598 specification, etc. are mentioned.

Among these, alkali-soluble resins having double bonds in the side chains described in (meth) acrylic resins having allyl groups, vinyl ester groups and carboxyl groups in the side chains and Japanese Patent Application Laid-Open Nos. 2000-187322 and 2002-62698; Alkali-soluble resin which has an amide group in the side chain described in Unexamined-Japanese-Patent No. 2001-242612 is preferable because it is excellent in the balance of film strength, a sensitivity, and developability.

Japanese Patent Publication No. 7-12004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Publication No. 63-287944, Japanese Patent Publication Urethane-based binder polymers containing acid groups described in 63-287947, Japanese Patent Application Laid-Open No. Hei 1-271741, Japanese Patent Application Laid-open No. Hei 10-116232, and the acid groups and double bonds described in Japanese Patent Application Laid-Open No. 2002-107918. Since the urethane type binder polymer which has is very excellent in strength, it is advantageous at the point of chain resistance and low exposure aptitude.

In addition, an acetal modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent 993966, European Patent 1204000, Japanese Patent Laid-Open No. 2001-318463, etc. is preferable because of excellent balance between film strength and developability.

Moreover, polyvinylpyrrolidone, polyethylene oxide, etc. are useful as water-soluble linear organic polymer. Moreover, in order to raise the intensity | strength of a hardened film, alcohol-soluble nylon, the polyether of 2, 2-bis- (4-hydroxyphenyl) -propane, and epichlorohydrin is also useful.

Alkali-soluble resin which can be used by this invention can be synthesize | combined by a conventionally well-known method. As a solvent used at the time of synthesis, for example, tetrahydrofuran, ethylene dichromide, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl Acetate, diethylene glycol dimethyl ether, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate And ethyl lactate, dimethyl sulfoxide, water and the like. These solvent are used individually or in mixture of 2 or more types.

As a radical polymerization initiator used when synthesize | combining alkali-soluble resin which can be used in this invention, well-known compounds, such as an azo initiator and a peroxide initiator, are mentioned.

Among the various alkali-soluble resins, an acrylic resin is preferable, and the acrylic resin is composed of a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like. Copolymer, KS resist-106 (manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.), cyclochrom P series (manufactured by Daicel Kagaku Kogyo Co., Ltd.), and the like are preferable.

The alkali-soluble resin preferably has a polymer having a weight average molecular weight (polystyrene equivalent value measured by the GPC method) of 1000 to 2 × 10 ⁵ , more preferably 2000 to 1 × 10 ⁵ , more preferably 5000 to 5 × 10 ⁴ Polymers of are particularly preferred.

These alkali-soluble resins may be any of random polymers, block polymers and graft polymers.

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

The curable composition of this invention may further contain the optional component demonstrated in detail below as needed with the above-mentioned (a)-(d) component. Hereinafter, the arbitrary components which the curable composition of this invention can contain are demonstrated.

<Solvent>

The curable composition of this invention can contain at least 1 type of solvent.

Specifically, the solvent is preferably selected from a glycol ether solvent, an alcohol solvent, an ester solvent, a ketone solvent, an amide solvent, and a chlorine-containing solvent.

Examples of the glycol ether solvents include ethyl cellosolve (ethylene glycol monoethyl ether), methyl cellosolve (ethylene glycol monomethyl ether), butyl cellosolve (ethylene glycol monobutyl ether), and methyl methoxybutanol (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, etc. are preferable.

As said alcohol solvent, methanol, ethanol, isopropanol, normal propyl alcohol, isobutyl alcohol, normal butyl alcohol, etc. are preferable.

Examples of the ester solvents include ethyl acetate, normal butyl acetate, isobutyl acetate, cellosolve acetate (ethylene glycol monomethyl ether acetate), methoxybutyl acetate (3-methoxybutyl acetate), and 3-methyl-3-methoxybutyl Preference is given to acetates, 3-ethoxypropionate (EEP), lactic acid esters (e.g. methyl lactate, ethyl lactate, propyl lactate, butyl lactate, and the like).

As said ketone solvent, 2-butanone (MEK), methyl isobutyl ketone (MIBK), cyclohexanone, cyclopentanone, acetone, diacetone alcohol (4-hydroxy-4-methyl-2-pentanone), Isophorone (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 the said curable composition, 20-50 mass% is more preferable, 30-40 mass% is especially preferable. When the said content is in the said range, the solubility of the coloring agent in a composition, and stability with time at the time of storage after melt | dissolution can be improved effectively.

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, 3-e Ethyl oxypropionate (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-cyclohexen-1-one), diisobutyl ketone (2,6-dimethyl-4-heptanone),

N-methylpyrrolidone (4-methylaminolactam or NMP),

Preferred are methanol, ethanol, isopropanol, normal propyl alcohol, isobutyl alcohol, normal butyl alcohol and the like.

Moreover, in the curable composition of this invention, the said solvent can be used individually or in combination of 2 or more types.

In addition, when preparing the curable composition of this invention, you may use together solvents other than the solvent enumerated above. Although the said other solvent will not be specifically limited if it satisfies the solubility of each component and the applicability | paintability of curable composition, It is preferable to select especially in consideration of the solubility, coating property, and safety of a coloring agent and a binder.

Examples of the other solvents include esters other than those exemplified above, for example amyl formic acid, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl oxy acetate, ethyl oxy acetate, oxy acetate Butyl, methoxy methyl acetate, methoxy ethyl acetate, methoxy butyl acetate, ethoxy methyl acetate, ethoxy ethyl acetate, and the like;

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, etc.); 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, and 2-methoxypropionic acid propyl) , Methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy Ethyl-2--2-propionate, etc.); Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetacetate, ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like;

Ethers other than those exemplified above, for example, 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, such as methyl ethyl ketone, 2-heptanone, 3-heptanone, and the like; Aromatic hydrocarbons such as 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 a (c) coloring agent, it is preferable to add a dispersing agent from a viewpoint of improving the dispersibility of the said pigment.

As a dispersant (pigment dispersant) which can be used in the present invention, a polymer dispersant [for example, polyamideamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) ) Acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine, pigment derivative, etc. are mentioned.

Polymeric dispersants can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers from the structure thereof.

The polymeric dispersant adsorbs on the surface of the pigment and acts to prevent reagglomeration. For this reason, the terminal modified | denatured type | mold polymer | macromolecule, graft-type polymer, and block polymer which have anchor site | part to a pigment surface are mentioned as a preferable structure. On the other hand, the pigment derivative has the effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

As a specific example of the pigment dispersant which can be used for this invention, the product made by BYK Chemie "Disperbyk-101 (polyamideamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide), 161 , 162, 163, 164, 165, 166, 170 (polymer copolymer), `` BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), `` EKA4047, 4050, 4010, 4165 (polyurethane), made by EFKA, EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylic acid salt), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (Azo pigment derivative), "Aji Spa PB821, PB822" made by Ajinomoto Fine Techno Co., Ltd. "Florene TG-710 (urethane oligomer)" by Kyoeisha Chemical Co., Ltd., "Polyflow No.50E, No.300 (acrylic system) Copolymer) '', `` disparon KS-860, 873SN, 874, # 2150 (aliphatic tagaka) manufactured by Kusumoto Kasei Co., Ltd. Carboxylic acid), # 7004 (polyether ester), DA-703-50, DA-705, DA-725, `` demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (Aromatic sulfonic acid formalin polycondensate) "," homogenol L-18 (polymeric polycarboxylic acid) "," emalgen 920, 930, 935, 985 (polyoxyethylene nonyl phenyl ether) "," acetamine 86 (ste Arylamine acetate) "," Solpers 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the terminal), 24000, 28000 32000, 38500 (graft type polymer), Nikko T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate), and the like.

These dispersing agents may be used independently and may be used in combination of 2 or more type. In this invention, it is especially preferable to use combining a pigment derivative and a polymer dispersing agent.

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, 10-60 mass% is further more preferable.

Specifically, in the case of using a polymer dispersant, the amount thereof is preferably in the range of 5 to 100% by mass, and more preferably in the range of 10 to 80% by mass with respect to the pigment. Moreover, when using a pigment derivative, it is preferable to exist in the range of 1-30 mass% with respect to a pigment as the usage-amount, It is more preferable to exist in the range of 3-20 mass%, and to the range of 5-15 mass% It is particularly desirable to have.

In this invention, when using the pigment and dispersing agent as a coloring agent, it is preferable that the sum total of content of a coloring agent and a dispersing agent is 25 mass% or more and 95 mass% or less with respect to the total solid which comprises a curable composition from a viewpoint of hardening sensitivity and a color density. It is more preferable that it is 25 mass% or more and 80 mass% or less, and it is still more preferable that they are 30 mass% or more and 70 mass% or less.

<Polymerization inhibitor>

In this invention, it is preferable to add a small amount of thermal polymerization inhibitor in order to prevent unnecessary thermal polymerization of the compound which has a polymerizable ethylenically unsaturated double bond during manufacture or storage of a curable composition.

Examples of the thermal polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogarol, t-butylcatechol, benzoquinone, 4,4'-thiobis ( 3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), N- (nitorophenyl hydroxyamine cerium salt, etc. are mentioned. Can be.

As for the addition amount of a thermal polymerization inhibitor, about 0.01 to about 5 mass% is preferable with respect to the total solid of a curable composition. Moreover, in order to prevent the inhibition of polymerization by oxygen, you may add higher fatty acid derivatives, such as behenic acid and behenic acid amide, and may make it localize on the surface of the photosensitive layer in the drying process after application | coating. The amount of the higher fatty acid derivative added is preferably about 0.5 to about 10 mass% of the precursor composition.

<Adhesion enhancer>

In this invention, in order to improve adhesiveness with the hard surface (substrate) which is a base material, an adhesion promoter can also be added. As an adhesion promoter, a silane coupling agent, a titanium coupling agent, etc. are mentioned.

Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, and β- (3,4-epoxycyclohexyl) ethyl. Trimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyl Trimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyl Trimethoxysilane hydrochloride, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxy Silane, methyltrimethoxysilane, methyltriethoxysilane, Vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxy Ethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, Trimethylchlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryl Oxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane, etc. are mentioned. Can be.

Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane and γ-mercaptopropyltri Methoxysilane, (gamma) -aminopropyl triethoxysilane, and phenyl trimethoxysilane are preferable, and (gamma) -methacryloxypropyl trimethoxysilane is the most preferable.

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

Color filter and its manufacturing method

Next, the color filter of this invention and its manufacturing method are demonstrated.

The color filter of this invention has a coloring pattern which uses the curable composition for color filters of this invention on a support body, It is characterized by the above-mentioned.

Hereinafter, the color filter of this invention is demonstrated in detail through the manufacturing method (manufacturing method of the color filter of this invention).

The manufacturing method of the color filter of this invention is the process of apply | coating the curable composition for color filters of this invention on a support body, and forming a colored curable composition layer (henceforth abbreviating suitably "color curable composition layer formation process"), The process of exposing the said colored curable composition layer through a mask (henceforth abbreviated "exposure process" suitably), and the process of developing the said colored curable composition layer after exposure, and forming a colored pattern (henceforth "development suitably" Abbreviated as &quot; step &quot;).

Specifically, the curable composition of the present invention is applied onto the support (substrate) directly or through another layer, to form a photopolymerizable composition layer (color curable composition layer forming step), and exposed through a predetermined mask pattern, By curing only the coated film portion irradiated with light (exposure step) and developing with a developer (development step), a patterned film composed of pixels of each color (three or four colors) is formed to produce the color filter of the present invention. Can be.

Hereinafter, each process in the manufacturing method of this invention is demonstrated.

<Coloring curable composition layer forming process>

In the colored curable composition layer forming step, the curable composition of the present invention is applied onto a support to form a colored curable composition layer.

Examples of the support that can be used in this step include soda glass, alkali free glass, pyrex (registered trademark) glass, quartz glass, plastic substrates, and transparent conductive films attached thereto, for use in liquid crystal display devices and the like, and imaging devices. Photoelectric conversion element substrates used for, for example, silicon substrates and the like, complementary metal oxide semiconductor (CMOS) and the like. These board | substrates may be provided with the black stripe which isolate | separates each pixel.

Furthermore, a primer layer may be formed on these supports to improve the adhesion to the upper layer, to prevent the diffusion of materials, or to planarize the substrate surface.

As a coating method of the curable composition of this invention on a support body, various coating methods, such as a slit coating, an inkjet method, a spin coating, a roll coating, and a screen printing method, can be applied.

As 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 more preferable.

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

Exposure process

In an exposure process, the coloring curable composition layer formed in the said colored curable composition layer formation process is exposed through a mask, and only the coating film part irradiated with light was hardened.

It is preferable to perform exposure by irradiation of radiation, and as radiation which can be used at the time of exposure, especially ultraviolet rays, such as g line | wire and i line | wire, are used preferably, 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 to elute the tail light irradiated portion in the exposure step into the aqueous alkali solution. This leaves only the photocured portion.

As image development temperature, it is 20 degreeC-30 degreeC normally, and developing time is 20 to 90 second.

Moreover, in the manufacturing method of this invention, after performing the curable composition layer forming process, exposure process, and image development process mentioned above, you may include the hardening process which hardens the coloring pattern formed by heating and / or exposure as needed. .

The color filter which consists of a desired color is produced by repeating the coloring curable composition layer forming process, exposure process, and image development process (and the hardening process as needed) as many times as desired color demonstrated above.

According to the present invention, the lack of exposure sensitivity due to the high concentration of the resist pigment due to the improvement of color reproducibility and the low exposure dose (throughput improvement) due to the enlargement of the substrate size is eliminated, and it is cured with high sensitivity, and has good pattern formation properties. Developing residue can be suppressed and the curable composition excellent in adhesiveness with a support body can be provided.

The said curable composition is especially effective when green is used as a coloring agent with high pigment concentration and low I-ray transmittance | permeability.

Moreover, the color filter which has the high color reproducibility and which has a good shape of a color pattern formed using the curable composition of this invention, and the manufacturing method which can manufacture the said color filter with high productivity can be provided.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. In addition, "part" shows a "mass part" unless there is particular notice.

Example 1

1-1.Preparation of pigment dispersion

40 mass parts of 30/70 (mass ratio) mixture of CI pigment green 36 and CI pigment yellow 150 as a pigment, 10 mass parts (by solid content conversion) of BYK2001 (Disperbyk: BYK Corporation make, solid content concentration 45.1 mass%) as a dispersing agent About 4.51 mass part) and the mixed liquid which consists of 150 mass parts of ethyl 3-ethoxy propionate as a solvent were mixed and disperse | distributed with the bead mill for 15 hours, and the pigment dispersion liquid P1 was prepared.

About the pigment dispersion (P1), the average particle diameter of the pigment was measured by the dynamic light scattering method and found to be 200 nm.

1-2.Preparation of curable composition (coating solution)

Pigment Dispersion P1 (c)... 66.6 parts by mass

Alkali-soluble resin (benzyl methacrylate / methacrylic acid copolymer, mol 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'-tetraphenyl-1,2'-biimidazole ((A) biimidazole compound)... 1.0 parts by mass

4,4-bisdiethylaminobenzophenone ((B) sensitizing dye)... 0.3 parts by mass

Compound C2 (formula) ((C) mercapto compound)... 0.3 parts by mass

Propylene glycol monomethyl ether acetate... 10.5 parts by mass

Ethyl ethoxy propionate 15.4 parts by mass

Compound C2

About Examples 2-8 and Comparative Examples 1-3, the coating liquid of the curable composition was obtained like Example 1 except having changed the composition of each component as described in Table 1 and Table 2.

[2.Production of color filter]

2-1.Formation of Curable Composition Layer

The curable composition containing the pigment was slit-coated to a glass substrate of 550 mm x 650 mm as a resist solution under the following conditions, waited for 10 minutes as it was, applied to a new glass substrate, vacuum dried and prebaked. (100 degreeC 80 second) was performed, and the curable composition coating film (curable composition layer) was formed.

(Slit application condition)

Gap between the openings at the tip of the coating head: 50 μm

Dispense Speed: 100mm / sec

Clearance of substrate and coating head: 150 μm

Coating thickness (dry thickness): 2 μm

Coating temperature: 23 ℃

Prebaking: 100 degrees Celsius * 80 second

2-2 Exposure, phenomenon

Thereafter, the photocurable coating film was exposed in a pattern form under conditions of 50mj / cm 2 and 20mW using an ultra-high pressure mercury lamp of 2.5kw, and after the exposure, the entire surface of the coating film was developed by a developer (brand name: CDK-1 FUJIFILM Materials) A 1% aqueous solution of the agent) was sprayed onto the shower, and developed for 60 seconds.

2-3.Heating

After stopping, the pure water was sprayed in the shower phase, the developer was wash | cleaned, and the coating film which performed this photocuring process and image development process was heated in 230 degreeC oven for 0.5 hour (postbaking). This formed the colored resin film (color filter) on the glass substrate.

[3. Performance evaluation]

The pattern formation property, board | substrate adhesiveness, mask increase amount, and image development residue of the curable composition coating film (color layer) formed on the glass substrate using the colored curable composition adjusted above were evaluated as follows. The results are shown in Table 1.

3-1.Pattern Formability

The cross-sectional shape of the formed pattern was observed with a scanning electron microscope (SEM). As for the pattern cross-sectional shape, pure taper is most preferable, and rectangle is next. Undercuts are undesirable.

<Pattern formability>

○ taper: the plane of the substrate and the angle to form less than 75 degrees

△ Rectangular: the plane of the substrate and the angle to form less than 90 degrees

X reverse taper: Plane of board and angle to form exceed 90 degrees

3-2.Board Adhesion

It was observed whether or not a pattern defect occurred as the evaluation of the substrate adhesion. This evaluation item was evaluated based on the following criteria.

<Substrate adhesiveness>

○: No pattern defect was observed.

(Triangle | delta): A pattern defect was hardly observed but a partial defect was observed.

X: Pattern defect was remarkably observed.

3-3.Mask increase

The dimension of the formed pattern was measured by the size measuring instrument (made by ICRON Olympus Co., Ltd.). This evaluation item was evaluated based on the following criteria.

<Mask increase>

(Circle): +5 micrometers or more increase with respect to a mask.

(Triangle | delta): +2 micrometer or more and less than 5 micrometers with respect to a mask.

X: The incremental width less than +2 micrometer with respect to a mask.

3-4.Residual residue

In the exposure process, the presence or absence of the residue of the area | region (unexposed part) which was not irradiated with light was observed, and developability was evaluated.

<Residual residue>

(Circle): The residue was not confirmed at all in an unexposed part.

(Triangle | delta): Although the residue was confirmed in the unexposed part a little, it was a degree which is satisfactory practically.

X: The residue was remarkably confirmed by the unexposed part.

Table 1

Table 2

Table 3

From the results of Tables 1-2, it is understood 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 the residue in the unexposed part is suppressed.

On the other hand, the curable composition of a comparative example was inferior in any of exposure sensitivity, board | substrate adhesiveness, and pattern cross-sectional shape.

Content of (b) component of the curable composition of the comparative example 3 was out of the preferable range, and it turns out that it is inferior in all the evaluation items compared with the curable composition of Examples 5-8.

Moreover, it turns out that the curable compositions of Examples 7 and 8 are the optimal ranges in the numerical value of (b) component, and are superior to the curable compositions of Examples 5 and 6.

Claims (9)

(a) a compound having one or more ethylenically unsaturated double bonds, (b) a photoinitiator, and (c) a coloring agent, and (b) a photoinitiator (A) a biimidazole compound, (B) a sensitizing dye , And (C) a mercapto compound, wherein the content of (A) + (B) + (C) is 5% or more and 15% or less by mass% with respect to the total solid of the colored curable composition for color filters. Colored curable composition for color filters. (D) Alkali-soluble resin is further contained, The colored curable composition for color filters of Claim 1 characterized by the above-mentioned. The content of (A) + (B) in the (b) photoinitiator is 2% or more and 10% or less in mass% with respect to the total solid of the colored curable composition for color filters. Colored curable composition for filters. The content of (C) with respect to the total of (A) + (B) in the photopolymerization initiator (b) is 10% or more and 30% or less by mass%, wherein the color curable color filter for color filters is used. Composition. The color filter according to claim 1, wherein the mass ratio (b) / (a) of the compound (a) having at least one ethylenically unsaturated double bond and (b) the photopolymerization initiator is 0.1 or more and 2.0 or less. Coloring curable composition. The colored curable composition for color filters according to claim 1, wherein the content of the (c) coloring agent is 35% or more and 70% or less by mass% with respect to the total solid of the colored curable composition for color filters. The said (C) mercapto compound is a compound represented by following General formula (I), The coloring curable composition for color filters of Claim 1 characterized by the above-mentioned. Formula (I)

(In general formula (I), R represents an alkyl group or an aryl group, and A represents the atomic group which forms a heterocyclic ring with N = C-N.) It has a coloring pattern which uses the colored curable composition of Claim 1 on a board | substrate, The color filter characterized by the above-mentioned. The process of forming the colored curable composition layer by apply | coating the colored curable composition of Claim 1 on a board | substrate, exposing the said colored curable composition through a mask, and developing the said colored curable composition layer after exposure, and coloring pattern. Method for producing a color filter comprising the step of forming a.