JP2003255120A - Resin composition for color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a resin composition for a color filter, which is excellent in polymerization property and produces neither scratch nor chip on a pixel pattern, by active energy ray irradiation and/or heating. <P>SOLUTION: The resin composition for the color filter contains an alicyclic compound (a) having at least an oxetanyl group in the molecule as expressed by a formula (1) and a compound (b) initiating cationic polymerization by the active energy ray irradiation and/or the heating. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a color filter resin composition, a color filter using the same, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, in producing a color filter using a colored radiation-sensitive composition, the colored radiation-sensitive composition is applied onto a substrate or a substrate on which a light-shielding layer having a desired pattern is previously formed. After drying by drying, the dried coating film is irradiated with radiation in a desired pattern shape (hereinafter referred to as “exposure”) and developed to obtain pixels of each color (JP-A-2-144502 and JP-A-2-144502). Kaihei 3
No. 53201) is known. However, in the case of the color filter obtained by such a method, a residue or background stain may occur on the substrate of the unexposed area or the light-shielding layer during development, and the conventional colored radiation-sensitive composition has such a problem. When removing residues and background stains by brush cleaning, the pixel surface is scratched or a pattern is missing, which is a major cause of pattern defects. Further, in a radiation-sensitive composition for a color filter using a halomethyloxadiazole-based compound or a halomethyl-s-triazine-based compound as a photopolymerization initiator, in order to suppress the influence of hydrogen halide produced as a by-product from these compounds. In addition, a technique of blending an organic compound having an epoxy group such as (di) glycidyl ether and an epoxy resin has been proposed (JP-A-1-254918, JP-A-8-94824 and JP-A-8-95238). (See the official gazette). With these radiation-sensitive compositions for color filters, it is said that a color filter having excellent electrical and chemical stability can be produced, or mask deposits can be suppressed, but since the epoxy resin has low polymerizability, When a color filter is formed by using an epoxy resin, a large amount of energy is required to sufficiently cure the resin, which causes a problem that production efficiency deteriorates.

On the other hand, it is known that cation curing is improved by mixing an oxetane compound with an epoxy compound. From this, JP-A 2000-214
Japanese Patent Laid-Open No. 592 discloses a curable composition for a color filter using these oxetane compounds, but in reality, it cannot be said that it has a sufficient curing rate.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has a novel resin composition for a color filter which is excellent in polymerizability and does not cause scratches or chips in a pixel pattern. It is to provide a color filter using the same and a manufacturing method thereof.

[0005]

Means for Solving the Problems As a result of intensive studies on the solution of the above problems, the present inventors have identified a specific alicyclic oxetane compound, a colorant and a compound which initiates polymerization upon irradiation with active energy rays. It was found that the resin composition is suitable for color filter applications, and that the use of the resin composition solves the above-mentioned problems, and has completed the present invention. That is, the present invention relates to a resin composition for a color filter shown in the following [1] to [16], a color filter manufactured using the same, and a manufacturing method using the same.

[1] A resin composition for a color filter comprising an alicyclic compound (a) having at least one oxetanyl group in the molecule and a colorant (b). [2] The resin composition for a color filter according to [1], wherein the alicyclic compound (a) having at least one oxetanyl group in the molecule is a compound represented by the general formula (1). .

[Chemical 4] (In the formula, R is a hydrogen atom, or an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a halogenated alkyl group, m is an integer of 0 to 2, and n is 0. Is 2, and the others are 1.) [3] The compound represented by the general formula (1) is 2-oxaspiro [3.5] non-6-ene or 5-methyl-2-.
The resin composition for a color filter according to [2], which is oxaspiro [3.5] non-6-ene.

[4] The color filter according to [1], wherein the alicyclic compound (a) having at least one oxetanyl group in the molecule is a compound represented by the general formula (2). Resin composition.

[Chemical 5] (In the formula, R is a hydrogen atom, or an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a halogenated alkyl group, m is an integer of 0 to 2, and n is 0. Is 2, and the others are 1.) [5] The compound represented by the general formula (2) is 2-oxaspiro [3.5] nonane or 5-methyl-2-oxaspiro [3.5] nonane. [4] The resin composition for color filters according to [4].

[6] The color filter according to [1], wherein the alicyclic compound (a) having at least one oxetanyl group in the molecule is a compound represented by the general formula (3). Resin composition.

[Chemical 6] (In the formula, R is a hydrogen atom, or an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a halogenated alkyl group, m is an integer of 0 to 2, and n is 0. Is 2, and the others are 1.) [7] The compound represented by the general formula (3) is 7,8-epoxy-5-methyl-2-oxaspiro [3.5] nonane, 6,7-epoxy- The resin composition for color filters according to [6], which is 2-oxaspiro [3.5] nonane.

[8] The alicyclic compound (a) having at least one oxetanyl group in the molecule is represented by the general formula (1),
The resin composition for a color filter according to [1], which is at least one selected from the compounds represented by the general formulas (2) and (3).

[9] A color filter according to any one of [1] to [8], which contains a compound (c) having one or more epoxy groups and not having an oxetanyl group. Resin composition. [10] The resin composition for a color filter according to any one of [1] to [9], which comprises a compound (d) which initiates cationic polymerization by irradiation with active energy rays and / or heating. . [11] The compound (d) which initiates cationic polymerization upon irradiation with active energy rays and / or heating is one or more selected from sulfonium salts, iodonium salts, phosphonium salts and diazonium salts. The resin composition for a color filter of. [12] The resin composition for color filters according to any one of [1] to [11], which contains a radically polymerizable compound (e). [13] The resin composition for color filters according to any one of [1] to [12], which comprises a photoradical initiator (f).

[14] The resin composition for a color filter according to any one of claims 1 to 13, which contains a soluble polymer (g). [15] A color filter comprising a transparent substrate on which a pixel is formed using the resin composition for a color filter according to any one of [1] to [14]. [16] A step of forming a photosensitive coloring composition layer using the resin composition for a color filter according to any one of [1] to [14] on a transparent substrate, and the photosensitivity of an exposed portion by exposure. A method for producing a color filter, which comprises a step of photo-curing a coloring composition layer.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below.

The alicyclic compound (a) having at least one oxetanyl group in the same molecule of the present invention (hereinafter abbreviated as compound (a)) is represented by the general formula (1), the general formula (2) or the general formula (2). The alicyclic compound represented by the formula (3) is preferable. In the general formulas (1), (2), and (3), each R is independently a hydrogen atom, a linear or branched alkyl group, aryl group, aralkyl group, or halogen having 1 to 12 carbon atoms. Each group of the alkylated alkyl group. Among these, a hydrogen atom and a linear alkyl group are preferable, and a hydrogen atom and a methyl group are particularly preferable. m is an integer from 0 to 2, and n
Is 2 when m is 0, and is 1 otherwise. m = 0 means that there is no crosslinking by methylene chains.

A straight or branched chain having 1 to 12 carbon atoms,
Examples of the alkyl group, aryl group and aralkyl group include a methyl group, an ethyl group, an isopropyl group, a phenyl group and a benzyl group.

Examples of the halogenated alkyl group include a fluoroalkyl group, a chloroalkyl group and a bromoalkyl group. Each of these alkyl groups may be linear or branched, and the number of each halogen atom may be 1 or more.

As the compound represented by the general formula (1),
2-Oxaspiro [3.5] non-6-ene, 9-methyl-2-oxaspiro [3.5] non-6-ene, 2-
Oxa-9-phenylspiro [3.5] non-6-ene, 9-trifluoromethyl-2-oxaspiro [3.
5] Nona-6-ene, spiro [bicyclo [2.2.1]]
Hepta-5-ene-2,3'-oxetane], spiro [3-methylbicyclo [2.2.1] hept-5-ene-2,3'-oxetane] and the like can be mentioned. Among these, 2-oxaspiro [3.5] non-6-ene, 9-
Methyl-2-oxaspiro [3.5] non-6-ene is preferred.

These compounds have an oxetanyl group and a carbon-carbon double bond, and are not only cationically polymerizable but also
It also has excellent radical polymerizability and contributes to the improvement of the curing speed. Further, since it has an alicyclic structure, the cured product of the composition of the present invention has excellent heat resistance. Furthermore, since most of the compounds represented by the general formula (1) are liquids at room temperature, it becomes possible to adjust the viscosity of the composition of the present invention and improve workability.

As the compound represented by the general formula (2),
2-oxaspiro [3.5] nonane, 7-methyl-2-
Oxaspiro [3.5] nonane, 5-methyl-2-oxaspiro [3.5] nonane, 2-oxa-5-phenylspiro [3.5] nonane, 5-trifluoromethyl-2
-Oxaspiro [3.5] nonane, spiro [adamantan-2,3'-oxetane], spiro [bicyclo [2.
2.1] heptane-2,3′-oxetane], spiro [bicyclo [2.2.2] octane-2,3′-oxetane], spiro [7-oxabicyclo [2.2.1] heptane-2. , 3′-oxetane], spiro [3-methylbicyclo [2.2.1] heptane-2,3′-oxetane] and the like. Among these, 2-oxaspiro [3.5] nonane and 5-methyl-2-oxaspiro [3.5] nonane are preferable.

These compounds have excellent cationic polymerizability and have the effect of improving the curing rate of the composition. Further, the alicyclic structure imparts heat resistance to the cured product of the composition of the present invention. Furthermore, since most of the compounds represented by the general formula (2) are liquid at room temperature, it is possible to adjust the viscosity of the composition of the present invention and improve workability.

As the compound represented by the general formula (3),
7,8-Epoxy-5-methyl-oxaspiro [3.
5] nonane, 7,8-epoxy-5-ethyl-2-oxaspiro [3.5] nonane, 7,8-epoxy-2-oxa-5-phenylspiro [3.5] nonane, 7,8-
Epoxy-5-trifluoromethyl-2-oxaspiro [3.5] nonane, 6,7-epoxy-2-oxaspiro [3.5] nonane, spiro [5,6-epoxynorbornane-2,3'-oxetane ], Spiro [5,6-epoxy-3-methylnorbornane-2,3′-oxetane] and the like. Among these, 7,8-epoxy-5
Methyl-2-oxaspiro [3.5] nonane, 6,7-
Epoxy-2-oxaspiro [3.5] nonane is preferred.

Since these compounds have both an oxetanyl group and an epoxy group, they have excellent cationic polymerizability and contribute to the improvement of the curing rate of the composition. In addition, it has an alicyclic structure and enhances the heat resistance of the cured product.

The compound (a) including alicyclic compounds having one or more oxetanyl groups in the molecule represented by the general formulas (1), (2) and (3) may be used alone or in combination of two kinds. It can be used as a mixture of the above. The compounding amount of these compounds (a) (when two or more kinds are used in combination, the total amount thereof) is preferably 1 in the color filter resin composition of the present invention.
˜90% by mass, more preferably 5 to 50% by mass.

The colorant (b) used in the present invention is not particularly limited in color tone and is appropriately selected according to the intended use of the obtained color filter, and may be an organic colorant or an inorganic colorant. The organic colorant specifically means a dye, an organic pigment, a natural pigment, or the like, and the inorganic colorant is
Specifically, it means an inorganic salt such as barium sulfate called an extender pigment, in addition to the inorganic pigment. Since the color filter is required to have high-definition color development and heat resistance, the colorant in the present invention is preferably a colorant having high color development and high heat resistance, particularly a colorant having high thermal decomposition resistance, ,
Organic colorants, particularly preferably organic pigments, are used.

Examples of the organic pigment include color index (CI; The Society of Dyers and Coloris).
(published by ts), compounds classified as Pigment (specifically, compounds having the following color index (CI) numbers) can be mentioned.

CI pigment yellow 1, CI pigment yellow 3, CI pigment yellow 12, CI pigment yellow 13, CI pigment yellow 14, C.I.
I. Pigment Yellow 15, CI Pigment Yellow 1
6, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61,
CI Pigment Yellow 65, CI Pigment Yellow 71, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI
Pigment Yellow 95, CI Pigment Yellow 9
7, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment Yellow 104, CI Pigment Yellow 10
6, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 11
4, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, CI Pigment Yellow 120, CI Pigment Yellow 12
6, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 13
9, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 15
4, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 17
5, CI Pigment Yellow 180, CI Pigment Yellow 185;

CI Pigment Orange 1, CI Pigment Orange 5, CI Pigment Orange 13, CI Pigment Orange 14, CI Pigment Orange 16, C.
I. Pigment Orange 17, CI Pigment Orange 2
4, CI Pigment Orange 34, CI Pigment Orange 36, CI Pigment Orange 38, CI Pigment Orange 40, CI Pigment Orange 43, CI Pigment Orange 46, CI Pigment Orange 49,
CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 63, CI Pigment Orange 64, CI Pigment Orange 71, CI Pigment Orange 73;

CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 3
6, CI Pigment Violet 38; CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 8, 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI
Pigment Red 40, CI Pigment Red 41, C.
I. Pigment Red 42, CI Pigment Red 48:
1, CI Pigment Red 48: 2, CI Pigment Red 48: 3, CI Pigment Red 48: 4, CI Pigment Red 49: 1, CI Pigment Red 49:
2, CI Pigment Red 50: 1, CI Pigment Red 52: 1, CI Pigment Red 53: 1, CI Pigment Red 57, CI Pigment Red 57: 1,
CI Pigment Red 57: 2, CI Pigment Red 58: 2, CI Pigment Red 58: 4, CI Pigment Red 60: 1, CI Pigment Red 63: 1,
CI Pigment Red 63: 2, CI Pigment Red 64: 1, CI Pigment Red 81: 1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90: 1, CI Pigment Red 97, C.
I. Pigment Red 101, CI Pigment Red 10
2, CI Pigment Red 104, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108, CI Pigment Red 112, CI Pigment Red 113, CI Pigment Red 114,
CI Pigment Red 122, CI Pigment Red 1
23, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 151, CI
Pigment Red 166, CI Pigment Red 16
8, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177,
CI Pigment Red 178, CI Pigment Red 1
79, CI Pigment Red 180, CI Pigment Red 185, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI
Pigment Red 193, CI Pigment Red 19
4, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216,
CI Pigment Red 220, CI Pigment Red 2
24, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI
Pigment Red 255, CI Pigment Red 26
4, CI Pigment Red 265;

CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, C.I.
I. Pigment Blue 15: 6, CI Pigment Blue 6
0; CI Pigment Green 7, CI Pigment Green 36; CI Pigment Brown 23, CI Pigment Brown 25; CI Pigment Black 1, Pigment Black 7.

These organic pigments can be used alone or in admixture of two or more. The organic pigment can be used after being purified by, for example, a sulfuric acid recrystallization method, a solvent washing method, or a combination thereof.

Examples of the inorganic colorant include, for example,
Titanium oxide, barium sulfate, calcium carbonate, zinc white,
Lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (II
I)), cadmium red, ultramarine blue, navy blue, chrome oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like. These inorganic colorants may be used alone or in admixture of two or more.

In the present invention, each colorant can be used by modifying the particle surface with a polymer, if desired. Examples of the polymer that modifies the particle surface of the colorant include the polymers described in JP-A-8-259876 and the like, and various commercially available polymers or oligomers for dispersing pigments.

Further, the colorant in the present invention can be used together with a dispersant, if desired. Examples of such a dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants. Specific examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxyethylene n- Polyoxyethylene alkyl phenyl ethers such as nonyl phenyl ethers; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid modified polyesters; tertiary amine modified polyurethanes; polyethylene imines In addition to the following, KP (produced by Shin-Etsu Chemical Co., Ltd.) and Polyflow (Kyoeisha Chemical Co., Ltd.)
), F-top (manufactured by Tochem Products), Megafac (manufactured by Dainippon Ink and Chemicals, Inc.), Florard (manufactured by Sumitomo 3M Limited), Asahi Guard, Surflon (above, manufactured by Asahi Glass Co., Ltd.) , Disperbyk (manufactured by Big Chemie Japan Co., Ltd.), Sols Perth (manufactured by Zeneca Co., Ltd.) and the like. These surfactants may be used alone or in admixture of two or more. The amount of the surfactant used is usually 50 parts by mass or less, preferably 30 parts by mass or less, based on 100 parts by mass of the colorant.

As the compound (c) having one or more epoxy groups in the molecule of the present invention and not having an oxetanyl group, known and commonly used epoxy compounds can be used. This epoxy compound is not particularly limited as long as it has one or more epoxy groups in one molecule and does not have an oxetanyl group.

Specifically, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether,
Bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether, novolac type epoxy resin (for example, phenol novolac type epoxy resin, cresol novolac type epoxy resin, Brominated phenol / novolak type epoxy resin), hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether,
Triglycidyl isocyanurate or the like can be used.

As the aliphatic epoxy compound,
(3,4-epoxycyclohexyl) methyl-3 ′,
4'-epoxy cyclohexyl carboxylate, 2-
(3,4-epoxycyclohexyl-5,5-spiro-
3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-)
6-methylcyclohexylmethyl) adipate, 3,4
-Epoxy-6-methylcyclohexyl-3 ', 4'-
Epoxy-6'-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, limonene diepoxide, di (3,4-epoxycyclohexylmethyl) ether of ethylene glycol, ethylenebis (3,3) 4-epoxycyclohexanecarboxylate)
Is mentioned.

Further, epoxy dioctyl hexahydrophthalate, di-2-ethylhexyl epoxy hexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether,
1 for aliphatic polyhydric alcohols such as glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol, propylene glycol and glycerin
Or polyglycidyl ethers of polyether polyols obtained by adding two or more alkylene oxides; diglycidyl ethers of aliphatic long-chain dibasic acids; monoglycidyl ethers of higher aliphatic alcohols; butylglycidyl ether, Phenyl glycidyl ether, cresol glycidyl ether, nonyl phenyl glycidyl ether, glycidyl methacrylate;
Phenol, cresol, butylphenol or monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxides to these; glycidyl esters of higher fatty acids; epoxidized soybean oil; butyl epoxystearate, octyl epoxystearate, epoxidized linseed Examples thereof include oil and epoxidized polybutadiene.

The compound (c) having one or more epoxy groups in the molecule and not having an oxetanyl group can be used alone or in combination of two or more kinds.

The compounding amount of the compound (c) (when two or more kinds are used in combination, the total amount thereof) is 1 to 10,000 per 100 parts by mass of the total amount of the compound (a) in the present invention.
A mass part is preferable and a 10-1,000 mass part is especially preferable.

The compound (d) used in the present invention to initiate cationic polymerization by irradiation with active energy rays and / or heating is changed by heating or irradiation with active energy rays such as ultraviolet rays to initiate cationic polymerization of acids. It can be a compound that produces a substance. Therefore, the compound (d) is a kind of cationic polymerization initiator and is also referred to as "acid generator" in the art. Hereinafter, in the present invention, the compound (c) is also referred to as an acid-generating cationic polymerization initiator.

The acid-generating type cationic polymerization initiator is a compound (a) of the present invention when heated or irradiated with light such as ultraviolet rays.
The cationic polymerization of the compound (c) and other cationically polymerizable substances (such as a compound containing an oxetanyl group) is promoted, and the curing of the color filter resin composition of the present invention proceeds smoothly.

The acid-generating type cationic polymerization initiator referred to in the present invention is a compound which changes by heating or irradiation with active energy rays such as ultraviolet rays to produce a substance such as acid which initiates cationic polymerization. Thus, compounds that are in the acid form from the beginning are not included.

As the acid-generating type cationic polymerization initiator, known sulfonium salts, iodonium salts, phosphonium salts,
Examples thereof include diazonium salts, ammonium salts and ferrocenes. Specific examples are shown below, but the present invention is not limited to these compounds.

Examples of the sulfonium salt-based acid-generating type cationic polymerization initiator include bis [4- (diphenylsulfonio)]
Phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, bis [4- (diphenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (diphenylsulfone) Nio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- (phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetra Fluoroborate, diphenyl-4- (phenylthio) phenylsulfonium tetrakis (pentafluorophenyl) borate, tri Phenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfo Nio) phenyl] sulfide bishexafluorophosphate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bishexafluoroantimonate, bis [4
-(Di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide tetrakis ( Pentafluorophenyl) borate, and the like.

Examples of the iodonium salt-based acid-generating cationic polymerization initiator include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate and bis (dodecylphenyl). ) Iodonium hexafluorophosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1) −
Methylethyl) phenyliodonium hexafluorophosphate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4
-Methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl)
Examples include borate.

Examples of the phosphonium salt-based acid-generating type cationic polymerization initiator include ethyltriphenylphosphonium tetrafluoroborate, ethyltriphenylphosphonium hexafluorophosphate, ethyltriphenylphosphonium hexafluoroantimonate, tetrabutylphosphonium tetrafluoroborate and tetra Examples thereof include butylphosphonium hexafluorophosphate and tetrabutylphosphonium hexafluoroantimonate.

Examples of the diazonium salt-based acid-generating cationic polymerization initiator include phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, and phenyldiazonium tetrakis (pentafluorophenyl) borate. .

Examples of the ammonium salt-based acid-generating cationic polymerization initiator include 1-benzyl-2-cyanopyridinium hexafluorophosphate and 1-benzyl-2-
Cyanopyridinium hexafluoroantimonate,
1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl-2-cyanopyridinium tetrakis (pentafluorophenyl) borate, 1-
(Naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-
Cyanopyridinium hexafluoroantimonate,
1- (naphthylmethyl) -2-cyanopyridinium tetrafluoroborate, 1- (naphthylmethyl) -2-
Examples include cyanopyridinium tetrakis (pentafluorophenyl) borate, and the like.

As the ferrocene-based acid-generating type cationic polymerization initiator, (2,4-cyclopentadiene-1-yl) [(1-methylethyl) benzene] -Fe (II) hexafluorophosphate, (2,4 -Cyclopentadiene-1-yl) [(1-methylethyl) benzene]-
Fe (II) hexafluoroantimonate, 2,4-cyclopentadiene-1-yl) [(1-methylethyl)
Benzene] -Fe (II) tetrafluoroborate, 2,
4-cyclopentadiene-1-yl) [(1-methylethyl) benzene] -Fe (II) tetrakis (pentafluorophenyl) borate, and the like.

Of these acid-generating type cationic polymerization initiators, sulfonium salt and iodonium salt type initiators are preferable from the viewpoint of curing rate, stability and economy. As commercial products, SP-150, SP-170, CP manufactured by Asahi Denka Co., Ltd.
-66, CP-77; CYRA manufactured by Union Carbide
CURE-UVI-6990, UVI-6974; Nippon Soda Co., Ltd. CI-2855, CI-2638; Sanshin Chemical Industry Co., Ltd., San-Aid SI-60; "Irgacure 261".
(Ciba Specialty Chemicals (2,4-cyclopentadien-1-yl) [(1-methylethyl)
Benzene] -Fe (II) hexafluorophosphate), “RHODORSIL 207
4 "; (4-methylphenyl-4 manufactured by Rhone-Poulin)
-(1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate), and the like.

These acid-generating type cationic polymerization initiators may be selected from the above-mentioned materials and used alone or in combination of two or more kinds.
The preferred range of the amount of the acid-generating cationic polymerization initiator used is
There is no particular limitation, but the total compounding amount of the compound (a) and the compound (c) (when the other cationically polymerizable compound described later is used together, the total amount thereof) is 100 parts by mass. 05 to 25 parts by mass, preferably 1 to 20 parts by mass. If the amount added is less than 0.05 parts by mass, the sensitivity will be poor, and remarkably large light irradiation energy and high temperature treatment for a long time are required for sufficient curing. Further, even if added in excess of 25 parts by mass, the sensitivity is not improved, which is economically unfavorable. On the contrary, the amount of uncured components remaining in the composition may increase and the physical properties of the cured product may deteriorate.

In the present invention, the following cationically polymerizable monomers can also be added to the color filter resin composition of the present invention within a range that does not affect the curability and physical properties of the cured product. This cationically polymerizable monomer is a compound that causes a polymerization initiation reaction or a crosslinking reaction by the acid generated by the acid-generating cationic polymerization initiator and is classified into compounds other than the compound (a) and the compound (c). For example, trimethylene oxide, 3,3-dimethyloxetane, 3,3-
Dichloromethyl oxetane, 3-ethyl-3-phenoxymethyl oxetane, 3-ethyl-3-hydroxymethyl oxetane (manufactured by Toagosei; trade name EOXA), bis [(3-ethyl-3-oxetanylmethoxy) methyl]
Benzene (also known as xylylene dioxetane; manufactured by Toagosei; trade name XDO), tri [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis [(3-ethyl-3-oxetanylmethoxy) methylphenyl] ether, Oxetane compounds having an oxetanyl group in addition to alicyclic compounds such as 3-ethyl-3-[(oxiranylmethoxy) methyl] oxetane and (3-ethyl-3-oxetanylmethoxy) oligodimethylsiloxane; tetrahydrofuran, 2 , 3-dimethyltetrahydrofuran and other oxolane compounds; trioxane, 1,3-dioxolane, and 1,3,6-trioxane cyclooctane and other cyclic acetal compounds; β-propiolactone, ε-
Cyclic lactone compounds such as caprolactone; thiirane compounds such as ethylene sulfide, 1,2-propylene sulfide and thioepichlorohydrin; thietane compounds such as 3,3-dimethylthietane; ethylene glycol divinyl ether, triethylene glycol divinyl ether, Vinyl ether compounds such as trimethylolpropane trivinyl ether; Spiro orthoester compounds which are reaction products of epoxy compounds and lactones; Ethylenically unsaturated compounds such as vinylcyclohexane, isobutylene, polybutadiene; Cyclic ether compounds; Cyclic thioether compounds; Vinyl compounds Etc. can be mentioned.

These cationically polymerizable monomers may be added alone or in combination of two or more. The amount of these cationically polymerizable monomers (when two or more kinds are used in combination, the total amount thereof) is 1 to 10,000 parts by mass, preferably 10 parts by mass, relative to 100 parts by mass of the compound (a) of the present invention. ~
1,000 parts by mass. Of the above-mentioned cationically polymerizable monomers, the compound having only one cationically polymerizable group in the molecule is 20 per 100 parts by mass of the compound (a).
If it is added in an amount of 0 part by mass or more, the curability is lowered and the energy required for curing is increased, which is not preferable.

The color filter resin composition of the present invention comprises
It is also possible to add the radically polymerizable compound (e) to the extent that the object of the present invention is not impaired in order to improve the light (active energy ray) curability. The compound (e) is not particularly limited, but a (meth) acrylic acid ester-based known and commonly used radically polymerizable monomer can be used.
Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth ) Acrylate, phenoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, ethylene glycol mono (meth) acrylate, etc. Functional (meth) acrylate compound; ethylene glycol di (meth) acrylate,
Polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, polyfunctional epoxy (meth) acrylate resin, polyfunctional urethane (meth) acrylate Resin etc. can be mentioned.

The amount of the compound (e) added is 5 to 100 parts by mass of the total amount of the compound (a), the compound (c), the compound (d) of the present invention and the above-mentioned other cationically polymerizable compounds. 200 parts by mass, preferably 10 to 100 parts by mass. If the amount added exceeds 200 parts by mass, the dryness to the touch will deteriorate. In addition, since the ratio of cross-linking of the (meth) acrylic group increases during curing, the heat resistance of the obtained cured product
Chemical resistance decreases.

In order to smoothly promote the radical polymerization of the radical-polymerizable compound (e), it is desirable to add a photo-radical initiator (f), and known and conventional ones which generate a radical in response to light can be used. . Here, “light” means visible rays, ultraviolet rays, far ultraviolet rays, X-rays, electron rays, and other radiation. Examples of the photo radical initiator (f) include benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, acetophenone, dimethylaminoacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2, 2-diethoxy-2-phenylacetophenone, 2-hydroxy-2-
Methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-
[4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by Ciba Specialty Chemicals; Irgacure 907), 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, Benzophenone, p-phenylbenzophenone,
4,4'-diethylaminobenzophenone, dichlorobenzophenone, 2-methylanthraquinone, 2-t-butylanthraquinone, 2-aminoanthraquinone, 2-
Methylthioxanthone, 2-ethylthioxanthone, 2
-Chlorothioxanthone, 2,4-diethylthioxanthone, benzyl dimethyl ketal, p-dimethylamine benzoate, 2,4,6-trimethylbenzoyldiphenylphosphine oxide (BASF; Lucillin TPO), bis (2,6- Dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide-containing initiator (manufactured by Ciba Specialty Chemicals; Irgacure 1700,149,1800),
Examples thereof include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by Ciba Specialty Chemicals; Irgacure 819). These can be used alone or as a mixture of two or more.

The amount of the photo radical initiator (f) used is 0.007 with respect to 1 equivalent of the radically polymerizable functional group such as the (meth) acryl group of the radically polymerizable compound (e) in the composition.
~ 0.5 mol can be used.

The soluble polymer (g) of the present invention is not particularly limited as long as it is soluble in the developing solution used in the developing step during the production of color filters, but is preferably transparent. As the developing solution, water, an organic solvent, a hydrophilic solvent, an alkaline aqueous solution or the like is used, and an alkaline aqueous solution is particularly preferably used. Therefore, the soluble polymer (g) of the present invention acts as a binder for colorants and is used in a developing solution, particularly preferably an alkaline developing solution, used in the development processing step of producing a color filter. It is not particularly limited as long as it is soluble with respect to it, but an alkali-soluble resin having a carboxyl group is preferable, and particularly an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter, simply "A carboxyl group-containing unsaturated monomer") and another ethylenically unsaturated monomer copolymerizable with this carboxyl group-containing unsaturated monomer (hereinafter, simply "copolymerizable unsaturated monomer"). ").) (Hereinafter, simply referred to as" carboxyl group-containing copolymer ").

Examples of the unsaturated monomer containing a carboxyl group include acrylic acid, methacrylic acid, crotonic acid,
Unsaturated monocarboxylic acids such as α-chloroacrylic acid and cinnamic acid; unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid or Anhydrides thereof; unsaturated polyvalent carboxylic acid having a valence of 3 or more or anhydrides thereof; mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) succinate, mono (2) phthalate. -Acryloyloxyethyl),
2 such as mono (2-methacryloyloxyethyl) phthalate
Mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids of valency or higher; mono (meth) acrylates of both terminal dicarboxy polymers such as ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate Etc. can be mentioned. These carboxyl group-containing unsaturated monomers,
They can be used alone or in combination of two or more.

Examples of the copolymerizable unsaturated monomer include, for example,
Styrene, α-methylstyrene, o-vinyltoluene,
m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether Aromatic vinyl compounds such as o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether; indenes such as indene and 1-methylindene;

Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-
Propyl acrylate, n-propyl methacrylate,
i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxyethyl acrylate, 2-
Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate,
3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2- Methoxyethyl acrylate, 2-methoxyethyl methacrylate, 2
-Phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol acrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxy Dipropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadienyl acrylate, dicyclopentadienyl methacrylate, 2
-Hydroxy-3-phenoxypropyl acrylate,
Unsaturated carboxylic acid esters such as 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate;

2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethylaminopropyl acrylate, 2- Unsaturated carboxylic acid aminoalkyl esters such as dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate; unsaturated such as glycidyl acrylate and glycidyl methacrylate Carboxylic acid glycidyl esters; vinyl carboxylate such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, etc. Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; acrylamide, methacrylamide, α-chloroacrylamide , N-2-hydroxyethylacrylamide, N-2-hydroxyethylmethacrylamide, N-vinylacetamide, N-vinylformamide and the like unsaturated amides; maleimide, N-
Unsaturated imides such as phenylmaleimide and N-cyclohexylmaleimide; 1,3-butadiene, isoprene,
Aliphatic conjugated dienes such as chloroprene; polystyrene,
Polymethyl acrylate, polymethyl methacrylate,
Examples thereof include macromonomers having a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer molecular chain such as poly-n-butyl acrylate, poly-n-butyl methacrylate, and polysiloxane. These copolymerizable unsaturated monomers may be used alone or in admixture of two or more.

The carboxyl group-containing copolymer in the present invention contains acrylic acid and / or methacrylic acid as essential components, and optionally monosuccinic acid (2-acryloyloxyethyl) and / or monosuccinic acid (2-).
A carboxyl group-containing unsaturated monomer component further containing methacryloyloxyethyl), styrene, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate,
Copolymer with at least one selected from the group consisting of glycerol monoacrylate, glycerol monomethacrylate, N-phenylmaleimide, polystyrene macromonomer and polymethylmethacrylate macromonomer (hereinafter referred to as "carboxyl group-containing copolymer (I)"). .) Is preferred.

Specific examples of the carboxyl group-containing copolymer (I) include (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl ( (Meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethylmethacrylate macromonomer copolymer, (meth) Acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethylmethacrylate macro Monomer weight Body, methacrylic acid / styrene / benzyl (meth) acrylate / N- phenylmaleimide copolymer, (meth) acrylic acid / succinic Sanmono [2-
(Meth) acryloyloxyethyl] / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / styrene / allyl ( (Meth) acrylate / N-phenylmaleimide copolymer (meth) acrylic acid / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N
-Phenylmaleimide copolymer etc. can be mentioned.

The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is usually 5
-50 mass%, preferably 10-40 mass%. In this case, if the copolymerization ratio of the carboxyl group-containing unsaturated monomer is less than 5% by mass, the solubility of the resulting radiation-sensitive composition in an alkaline developer tends to decrease, while if it exceeds 50% by mass. However, the solubility in an alkali developing solution becomes excessive, and when developing with an alkali developing solution, the pixels may easily come off from the substrate or the pixel surface may be roughened.

The polystyrene-equivalent weight average molecular weight (hereinafter referred to as “Mw”) of the soluble polymer (g) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) in the present invention is preferably 3,000. ˜300,000, more preferably 5,000 to 100,000. Further, the polystyrene-equivalent number average molecular weight of the soluble polymer (g) in the present invention measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) (hereinafter,
It is called "Mn". ) Is preferably 3,000 to 60,
000, more preferably 5,000 to 25,000. By using such an alkali-soluble resin having a specific Mw or Mn, a radiation-sensitive composition having excellent developability can be obtained, whereby a pixel having a sharp pattern edge can be formed, and Residues, background stains, and film residues are less likely to occur on the unexposed portion of the substrate and the light-shielding layer during development. Further, the ratio of Mw and Mn of the alkali-soluble resin in the present invention (Mw /
Mn) is usually 1 to 5, preferably 1 to 4. In the present invention, the alkali-soluble resin may be used alone or
A mixture of two or more species can be used.

The amount of the soluble polymer (g) used in the present invention is usually 10 with respect to 100 parts by mass of the colorant (b).
˜1,000 parts by mass, preferably 20 to 500 parts by mass. In this case, when the amount of the soluble polymer (g) used is less than 10 parts by mass, for example, the alkali developability is lowered,
There is a possibility that scumming and film residue may occur on the substrate or the light-shielding layer in the unexposed area. On the other hand, when it exceeds 1,000 parts by mass, the colorant concentration decreases relatively, so that the desired color of the thin film is obtained. Achieving concentrations can be difficult.

The resin composition for a color filter of the present invention may be solvent-free, but a solvent may be added as a viscosity modifier for adapting the method of use. Specifically, ethylene glycol monoalkyl ether or its acetates; diethylene glycol mono or dialkyl ethers; propylene glycol monoalkyl ether or its acetates; dipropylene glycol mono or dialkyl ethers; methyl carbitol, butyl carbitol, butyl Known organic solvents such as cellosolve acetate, carbitol acetate, ethyl methyl ketone, cyclohexane, toluene, xylene, tetramethylbenzene, petroleum ether, petroleum naphtha, solvent naphtha; or plasticizers well known in the art. Examples thereof include additives and solvents, and these can be used alone or in combination of two or more kinds. The addition amount of these solvents is preferably 0 to 2000 parts by mass with respect to 100 parts by mass of components other than the solvent, and can be appropriately selected according to the coating method.

The color filter resin composition of the present invention may contain an ion trap agent, if necessary. The ion trap agent reacts with impurities such as anions and cations, and can be converted into a substance that makes it harmless.

When the color filter resin composition of the present invention is polymerized and cured by ultraviolet rays, which is one of the active energy rays, a sensitizer may be used in order to improve the polymerization rate. Examples of the sensitizer used for such purpose include pyrene, perylene, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, 2,4-dichlorothioxanthone and phenothiazine.
When the sensitizer is used in combination, the amount used is preferably in the range of 0.1 to 100 parts by mass with respect to 100 parts by mass of the photoacid-generating cationic polymerization initiator.

Further, if necessary, an antifoaming agent such as a silicone type, a fluorine type or a polymer type; a leveling agent; an adhesion imparting agent such as an imidazole type, a thiazole type, a triazole type or a silane coupling agent, for example, Shin-Etsu Silicone. Silane coupling agent, KBM303, KBM403,
KBM402; Use of well-known and commonly used additives such as flame retardants such as antimony trioxide, phosphoric acid ester, red phosphorus, and nitrogen-containing compounds such as melamine resin, and stress relaxation agents such as silicone oil and silicone rubber powder. You can

The resin composition for a color filter of the present invention is provided with the constituent materials such as the compound (a), the colorant (b), the compound (c), the compound (d) and the compound (e) described above. It can be obtained by mixing with a known conventional mixing device such as a stirrer, a stirrer / kneader, a paint shaker, a kneader, or a three-roll mill. The mixing device is not particularly limited as long as it is a device capable of uniformly mixing the constituent substances, but it is necessary to select it in consideration of the viscosity of the composition and the like.

The resin composition for a color filter in the present invention can be polymerized (cured) by irradiation with active energy rays and / or heating. The active energy ray here means ultraviolet rays, X-rays, electron rays, γ rays and the like. As a light source when irradiating ultraviolet rays, a metal halide lamp, a mercury arc lamp, a xenon arc lamp,
Fluorescent lamps, carbon arc lamps, tungsten-halogen duplication lamps, sunlight and the like.

When the resin composition for a color filter of the present invention is cured by heating, the heating condition is preferably about 5.
The conditions may be 0 to 250 ° C, more preferably about 75 to 200 ° C for about 0.2 to 60 minutes, preferably about 0.5 to 20 minutes, more preferably about 1 to 10 minutes.

Next, a method of forming a color filter using the color filter resin composition of the present invention will be described. First, if necessary, a light-shielding layer is formed on the surface of a substrate so as to partition a portion for forming a pixel, and, for example, a red pigment-dispersed resin composition for a color filter of the present invention on the substrate. After applying the material, pre-baking is performed to evaporate the solvent and form a coating film. Then, this coating film is exposed through a photomask, and then developed using an alkali developing solution to dissolve and remove the unexposed portion of the coating film, and then post-baking to give a predetermined red pixel pattern. Form an array of pixels arranged in an array. Thereafter, using the resin composition for a color filter of the present invention in which a green or blue pigment is dispersed, in the same manner as described above, application of each liquid composition, pre-baking, exposure, development and post-baking are performed to obtain a green color. By sequentially forming the pixel array and the blue pixel array on the same substrate, a color filter in which the pixel arrays of the three primary colors of red, green, and blue are arranged on the substrate is obtained.

Examples of the substrate used for forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide and the like. If desired, these substrates may be subjected to appropriate pretreatments such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction method, vacuum deposition and the like.

When the resin composition for a color filter of the present invention is applied to a substrate, an appropriate coating method such as spin coating, cast coating, roll coating and the like can be adopted. The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 5.0 μm, more preferably 0.2 as the film thickness after drying.
Is about 3.0 μm.

As the radiation used for producing the color filter, for example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like can be used, but the wavelength is in the range of 190 to 450 nm. Radiation is preferred. The exposure amount of radiation is preferably 1 to 1,000 mJ / cm
It is about ² .

As the developing solution, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8
-Diazabicyclo- [5.4.0] -7-undecene,
An alkaline developer which is an aqueous solution of 1,5-diazabicyclo- [4.3.0] -5-nonene or the like is preferable. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the alkaline developer. After the alkali development, it is usually washed with water. As a developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid pour) developing method and the like can be applied, and the developing condition is preferably room temperature at 5 to 300 seconds.

The color filter thus formed is very useful for, for example, a transmissive or reflective color liquid crystal display device, a color image pickup tube element, a color sensor and the like.

[0080]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In addition, "part" in Examples and Comparative Examples
Is parts by mass unless otherwise specified.

Among the materials used in Examples and Comparative Examples, commercially available products are as follows, and without purification:
Used as is. POX: Toagosei Co., Ltd., 3-ethyl-3-phenoxymethyloxetane XDO: Toagosei Co., Ltd., 1,4-bis [(3-ethyl-
3-oxetanylmethoxy) methyl] benzene 3000: manufactured by Daicel Chemical Industries, Ltd. (trade name Celoxide 3000), limonendioxide 2110: manufactured by Asahi Denka Industry (trade name KRM-2110),
Bifunctional alicyclic epoxy resin Epicoat 828: manufactured by Yuka Shell Epoxy Co., Ltd. (trade name: Epicoat 828), bisphenol A type epoxy resin M-309: manufactured by Toagosei, trimethylolpropane triacrylate 3000A: epoxy ester manufactured by Kyoeisha Chemical Co., Ltd. 3000
A, bisphenol A diglycidyl ether acrylic acid adduct 6990: manufactured by Union Carbide (trade name UVI-6
990), a cationic photopolymerization initiator 907: manufactured by Ciba Specialty Chemicals (trade name Irgacure 907), a photopolymerization initiator

As the compounds not commercially available, those chemically synthesized by the inventor were used. That is, 7,8-epoxy-5
Methyl-2-oxaspiro [3.5] nonane and 6,
The 7-epoxy-2-oxaspiro [3.5] nonane was synthesized by the present inventor with reference to the method described in US Pat. No. 3,388,105. Specifically, 7,8-epoxy-5-
Methyl-2-oxaspiro [3.5] nonane was synthesized as follows.

(Production Example 1) <Synthesis of 6-methyl-3-cyclohexene-1,1-dimethanol> 2-methyl-4 which is a Diels-Alder reaction product of butadiene and crotonaldehyde in a three-necked flask. -Cyclohexene-1-carbaldehyde 327
g, 600 ml of methanol and 37% formalin water 7
29 g was added, and the temperature of this solution was raised to 60 ° C. with stirring. Subsequently, a solution prepared by dissolving 252 g of KOH in 600 ml of distilled water was added dropwise over 2 hours. After continuing stirring for 7 hours, the reaction solution was concentrated under reduced pressure to obtain a bilayer residue. About 1
The oil layer concentrated to 50 ml was washed with 300 ml of distilled water. After the oil layer was concentrated under reduced pressure, 50 mg of 3,5-di (t-butyl) -4-hydroxytoluene (BHT) was added and distilled under reduced pressure to give 6-methyl-3 as colorless crystals.
311 g (yield 82%) of cyclohexene-1,1-dimethanol was obtained.

<6-methyl-3-cyclohexene-1,
Synthesis of 1-dimethanol cyclic carbonic acid ester> A 3-necked flask was charged with 310 g (1.99 mol) of 6-methyl-3-cyclohexene-1,1-dimethanol, 894 g of dimethyl carbonate (DMC) and 0.93 g of potassium carbonate, The temperature was raised to 90 ° C. and the mixture was refluxed for 4 hours. The reaction solution was returned to room temperature and potassium carbonate was filtered off. BHT 120mg
After adding, the remaining DMC and methanol are adjusted to 2 kPa.
(15 mmHg) was removed under reduced pressure, followed by vacuum distillation to obtain 326 g of 6-methyl-3-cyclohexene-1,1-dimethanol cyclic carbonic acid ester, which is a room temperature colorless crystal.
(Yield 89.4%) was obtained.

(Production Example 2) <Synthesis of 9-methyl-2-oxaspiro [3.5] non-6-ene (CHEO)> 6-methyl-in a three-necked flask.
32.15 g of 3-cyclohexene-1,1-dimethanol cyclic carbonic acid ester, 642 mg (0.2 mass%) of BHT and 1.93 g of LiCl were charged, and the mixture was heated and stirred at 275 ° C. using a mantle heater. Product immediately about 8
The mixture was extracted from the system under a reduced pressure of kPa (60 mmHg), and heating was continued for 4 hours until distillation was stopped. BHT on product
600 mg was added and distilled under reduced pressure to obtain 187 g (yield 71%) of CHEO which was a colorless transparent liquid.

(Production Example 3) <Synthesis of 7,8-epoxy-5-methyl-2-oxaspiro [3.5] nonane (ECHO)> CHEO 50 g
Was dissolved in 150 ml of dichloromethane and then charged into the reactor. 400 g of 93.7 g of m-chloroperbenzoic acid
The reaction solution was suspended in 4 ml of dichloromethane.
The solution was added dropwise over 1 hour so as not to exceed 0 ° C. The precipitated m-chlorobenzoic acid was filtered off and washed well with cold dichloromethane. 15.0 g of calcium hydroxide was added to the organic layer, the mixture was stirred for 30 minutes, the precipitated crystals were filtered off, and washed with cold dichloromethane. The organic layer was washed with 5% aqueous NaHSO4 and saturated brine, concentrated, and then distilled under reduced pressure to give 38.1 g (yield 73.7) of colorless semisolid ECHO at room temperature.
%)Obtained.

(Production Example 4) <Synthesis of 7,8-epoxy-5-ethyl-2-oxaspiro [3.5] nonane (EECHO)> Diels-of butadiene and crotonaldehyde used in the synthesis of ECHO
Instead of Alder reaction product, butadiene and trans
Synthesized by the present inventor by a procedure similar to the above, using 6-ethyl-3-cyclohexene-1-carbaldehyde, which is the Diels-Alder reaction product with 2-pentenal.

Production Example 5 <Synthesis of 7,8-Epoxy-5-trifluoromethyl-2-oxaspiro [3.5] nonane (EFCHO)> E
In place of the Diels-Alder reaction product of butadiene and crotonaldehyde used in the synthesis of CHO, a Diels-Alder reaction product of butadiene and trans-4,4,4-trifluoro-2-butenal is used, It was synthesized by the present inventors by a procedure similar to the above.

Production Example 6 <5-Methyl-2-oxaspiro [3.5] nonane (C
Synthesis of HO)> 2-methyl obtained by hydrogenating the above-mentioned 6-methyl-3-cyclohexene-1,1-dimethanol in toluene to 5 L palladium / activated carbon as a catalyst in a 1 L three-necked flask with hydrogen gas. Cyclohexane-1,1
-474 g of dimethanol, 405 g of dimethyl carbonate, and 1.4 g of potassium carbonate were added, and the mixture was heated and stirred in an oil bath at a temperature of 100 ° C, and the reaction was carried out for 14 hours while distilling the produced methanol out of the system under normal pressure. Finally 1 in the reaction vessel
The pressure was reduced to 0 mmHg, and the corresponding carbonate was obtained with a yield of 95%.

The obtained cyclic carbonic acid ester was used as it was for 25
The mixture was heated and stirred at 0 ° C., and the generated carbon dioxide gas was discharged from the upper part of the cooling device to the outside of the system to carry out the reaction for 10 hours. The reaction solution was purified by distillation to obtain 230 g of CHO.

(Production Example 7) <Synthesis of 2-oxa-5-phenylspiro [3.5] nonane (PCHO)> Instead of 2-methylcyclohexane-1,1-dimethanol used in the synthesis of CHO, Diels-Al with butadiene and trans-cinnamic aldehyde
Using 2-phenylcyclohexane-1,1-dimethanol obtained by hydrogenating the der reaction product in toluene with hydrogen gas using 5% palladium / activated carbon as a catalyst, the present inventor conducted the same procedure as above. Synthesized.

Production Example 8 Alkali-soluble polymer cresol novolac type resin (manufactured by Nippon Kayaku Co., Ltd .;
Epoxy acrylate was obtained by reacting 1 mol of acrylic acid with 1 epoxy equivalent of EOCN-102S) by a conventional method using 30% by mass of butyl cellosolve acetate as a solvent. 0.5 mol of tetrahydrophthalic anhydride was reacted with one hydroxyl equivalent of this epoxy acrylate until the acid value reached the theoretical value. As a result, an alkali-soluble polymer was obtained.

<Examples 1 to 12, Comparative Examples 1 to 3> The alicyclic compound (a) having at least one or more oxetanyl groups in the molecule in the mass part shown in Table 1, a non-alicyclic oxetane compound, Colorant (b), compound (c) having one or more epoxy groups and not having oxetanyl group, photocationic polymerization initiator (d), radical polymerizable compound (e), photoradical polymerization initiator (f) , The alkali-soluble polymer (g) and the like were mixed to obtain a resin composition for each color filter.

Each color filter resin composition thus obtained was subjected to a color filter suitability test as follows. The resin composition for each color filter is coated with SiO ₂ which prevents the elution of sodium ions
After coating with a spin coater on the surface of the soda glass substrate on which the film was formed, prebaking was performed in a clean oven at 80 ° C. for 10 minutes to form a coating film having a film thickness of 1.8 μm. Then, after cooling this substrate to room temperature, the coating film was exposed to ultraviolet rays containing wavelengths of 365 nm, 405 nm and 436 nm at an exposure amount of 40 mJ / cm ² through a photomask using a high pressure mercury lamp.
Then, this substrate was immersed in a 0.04 wt% aqueous potassium hydroxide solution at 23 ° C. for 1 minute to develop it. The tack state of the cured composition layer was examined with a fingertip, and the obtained results are shown in Table 1.
Shown in. In the evaluation results of Examples 1 to 12 and Comparative Examples 1 to 3, when the cured product layer had no tack, "○", when there was some tack, "△", and when there was tack, "x" I wrote it.

After examining the tack state, the substrate was washed with ultrapure water, air-dried, and post-baked in a clean oven at 200 ° C. for 15 minutes to form a striped color filter on the substrate. The film surface of the obtained color filter was observed with an optical microscope, and the evaluation results are shown in Table 1.
It was shown to. In the evaluation results of Examples 1 to 12 and Comparative Examples 1 to 3, "No" was found when no scratches or pattern defects were observed on the pixel surface, and "○" when some scratches or pattern defects were observed. Δ ”, and when a large number of scratches or missing patterns were observed,“ X ”was given.

Although Examples 1 to 12 use the alicyclic alkane having an oxetanyl group of the present invention, it is found that the curability and the color filter suitability are excellent. Comparative Example 1
Shows the case where no oxetane compound was added, but remarkable tack was observed. Further, Comparative Examples 2 and 3 are cases where a non-alicyclic oxetane compound other than the present invention was used, but a slight tack was observed, and a pattern defect and the like were also observed after post-baking.

[0097]

[Table 1]

[0098]

The resin composition for a color filter to which the alicyclic alkane having an oxetanyl group of the present invention is added, the curability upon photopolymerization can be improved and a cured product free from tack can be obtained. It is possible to efficiently manufacture a color filter having no surface scratches or pattern defects.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) G03F 7/027 515 G03F 7/027 515 F term (reference) 2H025 AA03 AB13 AC01 AD01 BD03 BD04 CA48 CC11 FA17 2H048 BA45 BA47 BA48 BB02 BB42 4J002 BG014 BG054 BG074 BH024 CD002 CD012 CD022 CD052 CD062 CD142 CD162 CD182 CD193 CH031 CK023 DA036 DE036 DE096 DE106 DE156 DE236 DG046 AH 609 A0A4A048E0159 EL037 EL039 EN029 EN069 EN029 EN069 EN069 EN069 EN029

Claims (16)

[Claims] 1. A resin composition for a color filter comprising an alicyclic compound (a) having at least one oxetanyl group in the molecule and a colorant (b). 2. The resin for a color filter according to claim 1, wherein the alicyclic compound (a) having at least one oxetanyl group in the molecule is a compound represented by the general formula (1). Composition. [Chemical 1] (In the formula, R is a hydrogen atom, or an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a halogenated alkyl group, m is an integer of 0 to 2, and n is 0. Is 2, otherwise is 1.) 3. A compound represented by the general formula (1) is 2-oxaspiro [3.5] non-6-ene or 5-methyl-
The resin composition for a color filter according to claim 2, which is 2-oxaspiro [3.5] non-6-ene. 4. The color filter resin according to claim 1, wherein the alicyclic compound (a) having at least one oxetanyl group in the molecule is a compound represented by the general formula (2). Composition. [Chemical 2] (In the formula, R is a hydrogen atom, or an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a halogenated alkyl group, m is an integer of 0 to 2, and n is 0. Is 2, otherwise is 1.) 5. The compound according to claim 4, wherein the compound represented by the general formula (2) is 2-oxaspiro [3.5] nonane or 5-methyl-2-oxaspiro [3.5] nonane. The resin composition for a color filter of. 6. The color filter resin according to claim 1, wherein the alicyclic compound (a) having at least one oxetanyl group in the molecule is a compound represented by the general formula (3). Composition. [Chemical 3] (In the formula, R is a hydrogen atom, or an alkyl group having 1 to 12 carbon atoms, an aryl group, an aralkyl group, or a halogenated alkyl group, m is an integer of 0 to 2, and n is 0. Is 2, otherwise is 1.) 7. A compound represented by the general formula (3) is 7,8-
Epoxy-5-methyl-2-oxaspiro [3.5] nonane, 6,7-epoxy-2-oxaspiro [3.5]
It is nonane, The resin composition for color filters of Claim 6 characterized by the above-mentioned. 8. An alicyclic compound (a) having at least one oxetanyl group in the molecule is at least selected from compounds represented by general formula (1), general formula (2) and general formula (3). The color filter resin composition according to claim 1, which is one kind. 9. The resin composition for a color filter according to claim 1, further comprising a compound (c) having at least one epoxy group and not having an oxetanyl group. . 10. The resin composition for a color filter according to claim 1, further comprising a compound (d) which initiates cationic polymerization by irradiation with active energy rays and / or heating. . 11. The compound (d) which initiates cationic polymerization upon irradiation with active energy rays and / or heating is one or more selected from sulfonium salts, iodonium salts, phosphonium salts and diazonium salts. The resin composition for a color filter according to item 1. 12. The resin composition for a color filter according to claim 1, which contains a radically polymerizable compound (e). 13. The resin composition for color filters according to claim 1, further comprising a photoradical initiator (f). 14. The resin composition for a color filter according to claim 1, which contains a soluble polymer (g). 15. A color filter comprising a transparent substrate on which pixels are formed using the resin composition for a color filter according to any one of claims 1 to 14. 16. A step of forming a photosensitive coloring composition layer using the resin composition for a color filter according to claim 1 on a transparent substrate, and the photosensitivity of the exposed portion by exposure. A method for producing a color filter, which comprises a step of photo-curing a coloring composition layer.