JP2004280057A - Photosetting color resin composition and color filter using same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosetting color resin composition which produces no development residue, which is improved in development characteristics as development margin and development latitude, and with which a color filter having excellent adhesiveness and solvent resistance can be obtained by thermosetting treatment (post bake) in a short time and/or at low temperature. <P>SOLUTION: The photosetting color resin composition containing a coloring agent, an alkali-soluble resin, a photopolymerizable monomer and a photopolymerization initiator has 10 to 70 mass% content of the coloring agent in the solid content of the resin composition and contains an imidazole silane compound. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photocurable colored resin composition, and more particularly, to a photocurable colored resin composition suitable for producing a color filter including a black matrix used for an image sensor such as a liquid crystal display (LCD) or a CCD. It relates to a resin composition.

The color filter is usually formed by applying a photocurable colored resin composition mainly composed of a colorant, an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator and a solvent onto a substrate, drying (prebaking), pattern exposure, alkali exposure. A predetermined pixel pattern is formed by a series of steps of development and heat curing (post-baking), and the steps are sequentially repeated for each color such as red (R), green (G), and blue (B). . The heat curing treatment (post-baking) in the above color filter manufacturing process is performed to impart durability and strength to the pixel pattern film as a permanent film, and heat is used to accelerate the curing of the resin component in the film composition. By doing so, durability such as mechanical strength, solvent resistance, and light resistance as a film can be increased.
A color liquid crystal display device is compact and has the same or better performance in comparison with a CRT, and has recently made a remarkable progress as a display unit of a television, a personal computer screen, a mobile phone, and other display devices. A color filter is an essential component of such a color liquid crystal display device.

On the other hand, in the conventional color liquid crystal display device, since a glass substrate is usually used, the adhesion to the photocurable colored resin composition is not very good. Inspection tends to increase, and if the development time is too long, pattern peeling is likely to occur. Therefore, at present, development must be performed within a very limited development time range. For this reason, there has been a problem in that a constant pattern shape cannot be obtained unless careful control is performed with careful attention to not only the development time but also the developer concentration and temperature.
Therefore, how to widen the allowable range of the developing time greatly affects the appropriateness of the process of the color filter.

  It is known to use an imidazole silane compound in order to improve the adhesion of the film. However, in the prior art, even if the adhesion is improved, the development margin (the line width hardly changes with the development time). This is not effective because there is a trade-off between development characteristics such as length of time) and development latitude (ratio of line width change to development time) and development residue. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 10-186657) discloses that imidazole silane is contained in a photocurable composition in order to improve the adhesion of a resin film for a photoresist. Although it is described that this composition does not include a coloring component as an essential component and that a dye or a pigment may be added, it is described as a well-known technique for simply adding color to a photoresist composition. It's just As described above, since the transparent film containing no coloring component originally has good developing characteristics, the effect of adding imidazole silane on the developing characteristics was not exhibited, and no attention was paid to this effect.

  In recent years, in order to increase the production efficiency of color filters, the development of a photocurable composition that can be sufficiently heat-cured (post-baked) at a low temperature or in a short time has been desired. Such color filter materials have not been able to meet such demands. In particular, in order to obtain a color filter having excellent durability as a permanent film, it is necessary to promote the thermosetting of the resin by heating in the final step. It required processing at temperature and for at least one hour.

As described above, in the photocurable composition for a color filter, a thermosetting component is essential to obtain a permanent coating film having excellent durability, and an epoxy resin or a melamine resin is generally used as the component. It was a target. For example, JP-A-2937208, JP-B-2-42371, and JP-A-6-1938 disclose a photocurable composition for a color filter containing an epoxy resin.
On the other hand, in the field of resist materials, imidazole silane compounds and epoxy resin compositions are known as curing agents. For example, Patent Document 2 (Japanese Patent Application Laid-Open No. 9-12683), Patent Document 3 (Japanese Patent Application Laid-Open No. 2001-187836), and Patent Document 4 (Japanese Patent Application Laid-Open No. 2002-128872) disclose an epoxy containing an imidazole silane compound. A resin composition is disclosed. Among them, in Patent Document 2, it is used for adhesives, sealants, paints, laminates, and molding materials that require adhesion, in Patent Document 3, it is used for electronic materials, paints, primers, and adhesives. It is disclosed that each is useful as an encapsulant application for semiconductor chips and the like. However, none of these patent documents describes a color filter application.
Patent Document 1 discloses a photosensitive resin composition containing an imidazole silane compound, and discloses that this composition is useful as a resist material. However, the above patent relates to a plating resist for a printed circuit board, and a resist material using imidazole silane is a photocurable resin composition having improved adhesion to a copper foil substrate, and the used resist is removed after plating is completed. It does not heat set. Therefore, the composition does not include a thermosetting resin such as an epoxy resin.

  As described above, in the photocurable composition for a color filter, a low-temperature curing treatment that can be applied to a plastic substrate has been required. In order to increase the substrate area and increase mass production while giving high strength, adhesiveness and solvent resistance, the heat curing process (post-bake) at a lower temperature or shorter Heat curing (post-baking) over time has been strongly desired.

JP-A-10-186657 JP-A-9-12683 JP 2001-187836 A JP-A-2002-128872

An object of the present invention is to provide a photocurable colored resin composition having no development residue, improved development margin, and improved development latitude, and a color filter using the same.
Another object of the present invention is to provide a photocurable colored resin composition which can provide a color filter having excellent adhesiveness and solvent resistance in a short and / or low temperature heat curing treatment (post bake). is there.

As a result of intensive studies, the present inventors have found that excellent development characteristics can be obtained by adding an imidazole silane compound to a colorant-containing photocurable composition for a color filter, and furthermore, bifunctional or more. It has been found that the thermosetting property is improved by containing the epoxy compound of the present invention, and the present invention has been completed.
That is, according to the present invention, the photocurable colored resin composition and the color filter having the following constitutions are provided, and the above object is achieved.

  1. In a photocurable colored resin composition containing a colorant, an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator, the content of the colorant in the solid content of the photocurable colored resin composition is 10%. A photocurable colored resin composition, which is 70 to 70% by mass and contains an imidazole silane compound.

  2. The imidazole silane compound is a reaction product of an imidazole compound represented by the following general formula (I) and an epoxy silane compound represented by the following general formula (II) and / or a derivative thereof. 2. The photocurable colored resin composition according to the above item 1, which is a compound.

In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ² and R ³ each independently represent a hydrogen atom, a vinyl group or an alkyl group having 1 to 5 carbon atoms.

In the formula, R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 3 carbon atoms, m represents an integer of 1 to 20, and n represents an integer of 1 to 3.

  3. 3. The photocurable colored resin composition according to the above item 1 or 2, wherein the imidazole silane-based compound comprises at least one selected from compounds represented by the following general formulas (1) to (3) and / or derivative compounds thereof. object.

In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ² represents a hydrogen atom, a vinyl group or an alkyl group having 1 to 5 carbon atoms, and R ³ and R ⁴ each independently represent a carbon atom. Represents an alkyl group of Formulas 1 to 3, and n represents 1 to 3.

4. The photocurable colored resin composition according to any one of the above items 1 to 3, wherein the colorant is a black colorant.
5. 5. The photocurable colored resin composition according to the item 4, wherein the black colorant is carbon black.
6. The photocurable colored resin composition according to any one of the above items 1 to 5, which contains a bifunctional or higher epoxy compound.
7. 7. The photocurable composition according to the above item 6, which contains a thermal polymerization initiator.
8. 8. The photocurable colored resin composition according to the item 7, wherein the thermal polymerization initiator is an organic peroxide.

  9. 9. The photocurable colored resin composition according to the item 8, wherein the organic peroxide is a benzophenone-based organic peroxide represented by the following general formula (III).

In the formula, R ₁ and R ₂ each independently represent an alkyl group having 1 to 20 carbon atoms or an aralkyl group, and R ₃ and R ₄ each independently represent a hydrogen atom, a carboxyl group, an alkyl group having 1 to 10 carbon atoms. Represents an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a halogen atom, a cyano group, a nitro group or a dialkylamino group having 2 to 20 carbon atoms, and q represents 0, 1 or 2 And r is 1, 2, or 3.
10. The photocurable colored resin composition according to the item 9, wherein the benzophenone-based organic peroxide is at least one compound of the following formulas (1) to (5).

  11. A coating liquid comprising the photocurable colored resin composition according to any one of 1 to 10 above, is applied on a substrate, and after forming a film, exposure and development are performed by a photolithography method to form a monochromatic pattern. A color filter created by repeating the process for each color.

  According to the present invention, development characteristics such as development latitude and development margin are improved, so that conditions during development are greatly relaxed, and management of development time, development density, developer temperature, and the like is significantly larger than before. And the number of replacements of the developing solution can be reduced, and the cost can be reduced. In particular, in the case of a photocurable colored resin composition using a black colorant that is likely to inhibit the transmission of exposure light into the formed coating film, since the photocuring of the coating film does not easily progress, the present invention Brings great benefits. Further, according to the present invention, a photocurable composition which can be sufficiently cured at a low temperature or in a short time, a pigment dispersion color filter which can be sufficiently cured at a low temperature and is suitable for use on a plastic substrate Photo-curable composition, and especially photo-curing for pigment-dispersed color filters, which can be heat-treated in a short time when forming a color filter on the current glass substrate, and can significantly improve the color filter production efficiency Can be provided. Further, various conditions can be selected in a heat treatment step which is necessary and optimal for the production of a color filter.

  Hereinafter, each component used in the photocurable colored resin composition of the present invention (hereinafter sometimes abbreviated as “photocurable composition”) and a color filter using the composition will be described.

[1. Imidazole silane compound]
The photocurable composition of the present invention is characterized by containing an imidazole silane compound. As the imidazole silane compound, an imidazole silane compound which is a reaction product of the imidazole compound represented by the general formula (I) and the epoxy silane compound represented by the general formula (II) and / or a derivative thereof Compounds are preferably used.
The imidazole-based compound, epoxysilane-based compound and imidazolesilane-based compound will be described in detail below.

(A) Imidazole compound The imidazole compound represented by the general formula (I) in the present invention includes imidazole, 2-alkylimidazole, 2,4-dialkylimidazole, 4-vinylimidazole and the like. Particularly preferred are 2-methylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole and the like; and 2,4-dialkylimidazole, 2-ethyl-4-imidazole Methyl imidazole and the like can be mentioned.

(B) Epoxysilane-based compound The epoxysilane-based compound represented by the general formula (II) in the present invention includes 3-glycidoxypropyl trialkoxysilane, 3-glycidoxypropyl dialkoxyalkylsilane, There are glycidoxypropylalkoxydialkylsilanes, and among these, particularly preferred are 3-glycidoxypropyltrialkoxysilanes such as 3-glycidoxypropyltrimethoxysilane and 3-glycidoxypropyltriethoxysilane. Examples of 3-glycidoxypropyldialkoxyalkylsilane include 3-glycidoxypropyldimethoxymethylsilane, and examples of 3-glycidoxypropylalkoxydialkylsilane include 3-glycidoxypropylethoxydimethylsilane. Give be able to.

(C) Imidazole silane compound The imidazole silane compound which is a reaction product of the imidazole compound represented by the general formula (I) and the epoxy silane compound represented by the general formula (II) in the present invention. Specific examples thereof include compounds represented by the following formulas (1) to (3) described in JP-B-7-68256.

In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ² represents a hydrogen atom, a vinyl group or an alkyl group having 1 to 5 carbon atoms, and R ³ and R ⁴ each independently represent a carbon atom. Represents an alkyl group of Formulas 1 to 3, and n represents 1 to 3.

  Examples of the imidazole silane-based compound that can be used in the present invention include commercially available products such as imidazole silane manufactured by Japan Energy Co., Ltd., IM-1000, IS-1000, YA-100, IC-100P, and IA-100P. No. The amount of these components is preferably 0.01% by mass or more, more preferably 0.1 to 1% by mass in the solid content.

[2. Coloring agent]
As the coloring agent that can be used in the present invention, various kinds of conventionally known pigments, (insulating) carbon black, and dyes can be used alone or in combination of two or more.

  As the pigment that can be used in the present invention, various conventionally known inorganic or organic pigments can be used. Further, the pigment is preferably as fine as possible in consideration of the fact that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment.However, in consideration of handling properties, the average particle diameter is preferably 0.01 μm. A pigment having a thickness of from 0.1 to 0.1 μm, more preferably from 0.01 to 0.05 μm, is used. Inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony , And a composite oxide of the metal.

As organic pigments,
CIPigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199,;
CIPigment Orange 36, 38, 43, 71;
CIPigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177,209, 220, 224, 242, 254, 255, 264, 270;
CIPigment Violet 19, 23, 32, 39;
CIPigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
CIPigment Green 7, 36, 37;
CIPigment Brown 25, 28;
CIPigment Black 1, 7;
And the like.

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

  Among the various pigments, examples of the pigments that can be preferably used in the present invention include the following, but are not limited thereto.

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

  These organic pigments are used alone or in various combinations in order to increase color purity. Specific examples are shown below. As the red pigment, anthraquinone pigment, perylene pigment, diketopyrrolopyrrole pigment alone or at least one of them and a disazo yellow pigment, isoindoline yellow pigment, quinophthalone yellow pigment or perylene red pigment mixed with Are used. For example, as anthraquinone pigments, C.I. I. Pigment Red 177 and perylene pigments include C.I. I. Pigment Red 155, C.I. I. Pigment Red 224 and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment Yellow 83 or C.I. I. Pigment Yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably from 100: 5 to 100: 50. By setting the ratio to 100: 5 or more, the light transmittance from 400 nm to 500 nm can be suppressed, and the color purity can be increased. When the ratio is set to 100: 50 or less, the main wavelength is shifted to a short wavelength, and the deviation from the NTSC target hue can be suppressed. In particular, the range of 100: 10 to 100: 30 is optimal. In the case of a combination of red pigments, the adjustment is made according to the chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment alone or a mixture with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment is used. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment Yellow 150, C.I. I. Pigment Yellow 180 or C.I. I. Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. By setting the ratio to 100: 5 or more, the light transmittance from 400 nm to 450 nm can be suppressed, and the color purity can be increased. By setting the ratio to 100: 150 or less, the main wavelength becomes longer than the long wavelength, and the deviation from the NTSC target hue can be suppressed. A more preferred mass ratio is in the range of 100: 30 to 100: 120.

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

  Further, a pigment-containing photosensitive resin having good dispersibility and dispersion stability is obtained by using a powdery pigment obtained by finely dispersing the above pigment in an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer, an ethyl cellulose resin, or the like. Can be obtained.

  As the colorant for the black matrix, a black colorant is used. For example, carbon black, titanium carbon, iron oxide, and titanium oxide are used alone or in combination, and the case of carbon and titanium carbon is preferable. The mass ratio is preferably in the range of 100: 0 to 100: 60. Within the above range, good dispersion stability can be obtained.

  Examples of the carbon black that can be used as the colorant according to the present invention include, for example, carbon blacks # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, and # 960 manufactured by Mitsubishi Chemical Corporation. 950, # 900, # 850, MCF88, # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A , Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Black LI Diamond Black II, Diamond Black N339, Diamond Black SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LP. Carbon black THERMAX N990, N991, N907, N908, N990, N991, N908 manufactured by Cancarb. Asahi Carbon Co., Ltd. Carbon Black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal, Degussa Co., Ltd. S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, PrintexU, PrintexV, Printex140U, Printex140 And the like can be given.

  The insulating carbon black in the present invention means that an organic compound is present on the surface of the carbon black particle, for example, that an organic substance is adsorbed, coated or chemically bonded (grafted) on the surface of the carbon black particle. The carbon black shows insulating properties when its volume resistance as a powder is measured by the following method.

Insulating carbon black is dispersed in propylene glycol monomethyl ether so as to have a copolymer of benzyl methacrylate and methacrylic acid in a molar ratio of 70:30 (mass average molecular weight of 30,000) in a molar ratio of 20:80 and a coating solution. Was prepared and applied on a chromium substrate having a thickness of 1.1 mm and 10 cm × 10 cm to form a coating film having a dry film thickness of 3 μm. The coating film was heat-treated in an oven at 200 ° C. for 1 hour, followed by JIS K6911 The volume resistivity is measured under an environment of 23 ° C. and 65% relative humidity by applying a high resistivity meter manufactured by Mitsubishi Chemical Corporation and Hirester UP (MCP-HT450) conforming to the standard. Insulating carbon black having a volume resistance value of 10 ⁶ Ω · cm or more, more preferably 10 ⁸ Ω · cm or more, particularly preferably 10 ⁹ Ω · cm or more is preferable.

  Examples of the insulating carbon black include, for example, JP-A-11-60988, JP-A-11-60989, JP-A-10-330643, JP-A-11-80583, JP-A-11-80584, Resin-coated carbon blacks disclosed in Japanese Unexamined Patent Publication Nos. 9-124969 and 9-95625 can be used.

In addition, carbon black may be appropriately coated with a resin.
To coat carbon black with resin (coating resin), a coating base and a solvent are added to carbon black to prepare a mill base, which is then subjected to a flushing treatment, a kneader, a ball mill, a sand mill, a bead mill, a two or three roll mill, an extruder. Dispersion is performed by a method such as a paint shaker, ultrasonic wave, or a homogenizer. Two or more of these processing methods can be combined. If necessary, a dispersant can be used to uniformly disperse the carbon black.

Examples of the coating resin include the following.
1) Polyolefin-based polymer Polyethylene, polypropylene, polyisobutylene, etc. 2) Diene-based polymer Polybutadiene, polyisoprene, etc. 3) Polymer having conjugated polyene structure Polyacetylene-based polymer, polyphenylene-based polymer, etc. 4) Vinyl polymer polyvinyl chloride, polystyrene, vinyl acetate , Polyvinyl alcohol, poly (meth) acrylic acid, poly (meth) acrylate, polyacrylamide, polyacrylonitrile, polyvinyl phenol, etc. 5) polyether polyphenylene ether, polyoxirane, polyoxetane, polytetrahydrofuran, polyether ketone, polyether 6) Phenol resin, novolak resin, resol resin, etc. 7) Polyester Polyethylene terephthalate Rate, polyphenolphthalein terephthalate, polycarbonate, alkyd resin, unsaturated polyester resin, etc. 8) Polyamide nylon-6, nylon 66, water-soluble nylon, polyphenyleneamide, etc. 9) Polypeptide gelatin, casein, etc. 10) Epoxy resin and its modified products Novolak epoxy resin, bisphenol epoxy resin, novolak epoxy acrylate and modified resin with acid anhydride, etc. 11) Others polyurethane, polyimide, melamine resin, urea resin, polyimidazole, polyoxazole, polypyrrole, polyaniline, polysulfide, polysulfone, celluloses, etc.

  More specifically, the acrylic resin containing a carboxyl group includes, for example, a monomer having a carboxyl group such as (meth) acrylic acid, (anhydride) maleic acid, crotonic acid, itaconic acid, fumaric acid, and styrene, α-methyl. Styrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, vinyl acetate, acrylonitrile, (meth) acrylamide, glycidyl (meth) A) acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, glycidyl crotonate, (meth) acrylic chloride, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-methylol acrylamide, N, N-dimethyl acrylia De, N- methacryloyl morpholine, N, N- dimethylaminoethyl (meth) acrylate, N, N- dimethylaminoethyl acrylamide, polymers obtained by copolymerizing copolymerizable component such as. Among them, preferred is an acrylic resin containing at least (meth) acrylic acid or an alkyl ether of (meth) acrylic acid as a constituent monomer, and more preferred is an acrylic resin containing (meth) acrylic acid and styrene.

These resins can also add an ethylenic double bond to the resin side chain. By imparting a double bond to the resin side chain, photocurability is enhanced, and therefore, resolution and adhesion can be further improved, which is preferable.
As a synthetic means for introducing an ethylenic double bond, for example, a method described in Japanese Patent Publication No. 50-34443, Japanese Patent Publication No. 50-34444 and the like can be mentioned.
Specifically, a method of reacting a compound having a glycidyl group, an epoxycyclohexyl group, and a (meth) acryloyl group with a carboxyl group or a hydroxyl group, an acrylic acid chloride, or the like is used. For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, glycidyl ether (iso) crotonate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (meth) By using a compound such as acrylic acid chloride or (meth) allyl chloride and reacting it with a resin having a carboxyl group or a hydroxyl group, a resin having a polymer group in the side chain can be obtained.
Particularly, a resin obtained by reacting (3,4-epoxycyclohexyl) methyl (meth) acrylate is preferable.

  Further, a polymer obtained by a copolymerization reaction of at least a monomer represented by the following general formula (X) and a monomer having at least an acidic group (the above-described copolymerization component can be exemplified) can also be used.

(In the formula, R represents a hydrogen atom or a methyl group, and R _{1 to} R ₅ are each independently a group selected from a hydrogen atom, a halogen atom, a cyano group, an alkyl group, and an aryl group.)

Here, specific examples of the halogen atom include Cl, Br, and I.
The alkyl group may be linear, branched, or cyclic, and includes a methyl group, an n-propyl group, an isopropyl group, a tert-butyl group, and the like, and preferably has 1 to 7 carbon atoms. Examples of the aryl group include a phenyl group, a furyl group, and a naphthyl group.

The following resins can also be used as the coating resin.
A linear organic high molecular polymer that is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution is preferable. As such a linear organic high molecular polymer, those having an acidic group such as a carboxy group or a phenolic hydroxyl group in a resin side chain or main chain can be alkali-developed, and are therefore preferable from the viewpoint of preventing pollution. In particular, a resin having a carboxyl group, for example, an acrylic acid (co) polymer, a styrene / maleic anhydride resin, an acid anhydride-modified resin of novolak epoxy acrylate, and the like are preferable because of high alkali developability. Examples of the polymer having a carboxylic acid in the side chain include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, and JP-A-59-45957. No. 53836, JP-A-59-71048, methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, There are esterified maleic acid copolymers and the like, and similarly, there are acidic cellulose derivatives having a carboxylic acid in the side chain. In addition, those obtained by adding an acid anhydride to a polymer having a hydroxyl group are also useful. Among these, a benzyl (meth) acrylate / (meth) acrylic acid copolymer and a multi-component copolymer with benzyl (meth) acrylate / (meth) acrylic acid / and other monomers are also suitable.
In addition, 2-hydroxyethyl methacrylate, polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful as water-soluble polymers. In order to increase the strength of the cured film, alcohol-soluble nylon and polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful. These polymers can be mixed in any amount.

Furthermore, the epoxy resins listed as 1 to 8 below can also be used.
1. 1. Glycidylamine type epoxy resin 2. Triphenyl glycidyl methane type epoxy resin 3. tetraphenylglycidylmethane-type epoxy resin 4. Aminophenol type epoxy resin 5. Diamide diphenylmethane type epoxy resin 6. Phenol novolak type epoxy resin Orthocresol type epoxy resin8. Bisphenol A novolak type epoxy resin

  Among them, a copolymer of (meth) acrylic acid and (meth) acrylic acid ester is preferable as the coating resin because various monomers can be selected and the solubility and the acid value can be controlled.

  The preferable range of the mass average molecular weight (weight average molecular weight) Mw of these coated resins measured by gel permeation chromatography (GPC) is 1,000 to 300,000, more preferably 3,000 to 150,000. . When the content is 300,000 or less, good developability is obtained.

  For dispersing the organic pigment and carbon black, a dispersant is usually used. As the dispersant, the above-mentioned coating resin can be used as it is, or a dispersant as described later can be used in combination. These dispersants can be used alone or in combination of two or more. By the dispersion treatment, the resin is adsorbed on the carbon black surface, and at the same time, the aggregation of the carbon black particles is destroyed and the particle size is reduced.

In the present invention, examples of the form of the carbon black coated with the resin include powder, paste, pellet, paste, and sheet.
The preferred average particle size of the carbon black coated with the resin is in the range of 0.003 to 0.5 μm, more preferably in the range of 0.005 to 0.3 μm, thereby providing various effects of the present invention, particularly, Developability and image reproducibility are further improved.

  As dispersing agents, BY-K's Anti-Terra-U, Disperbyk-160, 161, 162, 163, ZENECA's Solspers 20000, 24000GR, 26000, 28000, Kusumoto Chemical's DA-703-50, NDC- 8194 L, NDC-8203L, NDC-8257L, KS-860, Kao's homogenal L-18, L-1820, L-95, L-100, Nippon Paint's VP5000, Goodrich's E5703P, Known dispersing resins such as VAGH manufactured by Union Carbide, UR8200 manufactured by Toyobo, and MR113 manufactured by Zeon Corporation can be used.

  Further, a phthalocyanine derivative (commercially available EFKA-745 (manufactured by Morishita Sangyo)); an organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); a (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, No. Cationic surfactants such as 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo) and W001 (manufactured by Yusho); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxy Nonionic surfactants such as ethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, and sorbitan fatty acid ester; F-top EF301, EF303, EF352 (manufactured by Shin-Akita Kasei), Megafac F171, 172, F173 (manufactured by Dainippon Ink), Florado FC430, FC431 (manufactured by Sumitomo 3M), Asahigard AG710, Surflon S382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-1068 Anionic surfactants such as W004, W005 and W017 (manufactured by Yusho); EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400; Polymer dispersants such as EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by San Nopco); Solsperse 3000, 5000, 9000 , 12000 Various sparse dispersants such as 13240, 13940, 17000, 24000, 26000 and 28000 (manufactured by Zeneca Corporation); Adecapluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka), and Isonet S-20 (manufactured by Sanyo Chemical) are also included.

In the present invention, when the coloring agent is a dye, it is uniformly dissolved in the composition to obtain a photocurable composition.
The dye that can be used as the colorant constituting the composition of the present invention is not particularly limited, and a dye that has been conventionally used for a color filter can be used. For example, JP-A-64-90403, JP-A-64-91102, JP-A-1-94301, JP-A-6-11614, JP-T-2592207, and U.S. Pat. No. 4,808,501 Specification, U.S. Pat. No. 5,667,920, U.S. Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, and JP-A-6-51115. JP-A-6-194828, JP-A-8-212599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP-A-2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, and JP-A-8-302224. Dyes disclosed in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like can be used.
The chemical structure includes pyrazole azo, anilinoazo, triphenylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xathene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.

  The content of the colorant in the photocurable composition in the present invention is 10 to 70% by mass in the solid content excluding the solvent component, and the content of the colorant varies depending on the use of the color filter. For example, a type called a reflection type such as a mobile phone may have a colorant content of about 20%, whereas a type called a transmission type for a TV or a monitor has a high chromaticity year by year, and the colorant content is high. Is as high as 25-40%. In particular, black as a black matrix has a larger amount of a coloring agent, so that it becomes difficult to satisfy development characteristics and various physical characteristics.

[3. Alkali-soluble resin]
As the alkali-soluble resin in the present invention, an acrylic copolymer having an acid value in the range of 30 to 150 mgKOH / g is preferable. When used for a color filter or a CCD, it is preferable that the alkali-soluble resin has no discoloration and has light resistance.
In the composition of the present invention, as a preferable alkali-soluble resin, an acrylic copolymer having an acid value in the range of 30 to 150, preferably 35 to 120 (mg KOH / g polymer) (hereinafter referred to as “acrylic binder resin”) Also called. "

  The acrylic binder resin satisfies the above acid value, is dissolved in a solvent described below, and is not particularly limited as long as it is an acrylic copolymer that functions as a binder resin by forming a film. it can.

  As a preferable constitutional unit of the acrylic binder resin, a copolymer of (meth) acrylic acid and another copolymerizable monomer is exemplified.

Other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, Pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate, cyclohexyl acrylate, and the like can be given.
Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like. it can.
Other particularly preferred copolymerizable monomers are phenyl (meth) acrylate, benzyl (meth) acrylate and styrene.
These other copolymerizable monomers can be used alone or in combination of two or more.

  A particularly preferred acrylic binder resin is a copolymer of (meth) acrylic acid and at least one monomer selected from phenyl (meth) acrylate, benzyl (meth) acrylate, and styrene.

The acrylic binder resin preferably has an acid value in the range of 30 to 150 mgKOH / g. By setting the acid value to 150 or less, a good development appropriate range (development latitude) can be obtained. On the other hand, by setting it to 30 or more, the development time can be set within an allowable range.
The mass average molecular weight Mw of the acrylic binder resin (in terms of polystyrene measured by the GPC method) is used to realize a viscosity range that can be easily used in a process such as application of a color resist, and also to secure film strength. Therefore, it is preferably from 5,000 to 100,000, and more preferably from 8,000 to 50,000.

In order to make the acid value of the acrylic binder resin fall within the range specified above, it is easy to appropriately adjust the copolymerization ratio of each monomer.
The range of the mass average molecular weight can be easily adjusted by using an appropriate amount of a chain transfer agent according to a polymerization method at the time of copolymerizing a monomer.
The acrylic binder resin can be produced, for example, by a radical polymerization method known per se. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, and the like when producing an acrylic binder resin by a radical polymerization method can be easily set by those skilled in the art, It is also possible to know the conditions experimentally.

  Further, in order to improve the crosslinking efficiency, a polymerizable group may be provided in the side chain, and a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group, or the like in the side chain may be an alkali in the present invention. Useful as a soluble resin. Examples of the polymer containing these polymerizable groups are shown below, but are not limited to the following, provided that they contain a base alkali-soluble group such as a COOH group, an OH group, and an ammonium group and a carbon-carbon unsaturated bond. A copolymer of, for example, 2-hydroxyethyl acrylate having an OH group, methacrylic acid having a COOH group, and a monomer such as an acrylic or vinyl compound copolymerizable therewith, has a reactivity with an OH group. A compound having an epoxy ring and a compound having a carbon-carbon unsaturated bond group, for example, a compound obtained by reacting a compound such as glycidyl acrylate can be used. In the reaction with OH, a compound having an acid anhydride and an isocyanate group in addition to the epoxy ring and having an acryloyl group can also be used. Further, a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring disclosed in JP-A-6-102669 or JP-A-6-1988 may be added to a saturated or unsaturated compound. A reaction product obtained by reacting a basic acid anhydride can also be used. Examples of a compound having both an alkali solubilizing group and a carbon-carbon unsaturated group such as COOH include, for example, Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd., acid value: 25 KOH mg / g, polyacryl (meth) acrylate), Photomer 6173 (COOH Polyurethane acrylic oligomer, Diamond Sharmrock Co., Ltd.), VISCOAT R-264, KS Resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Praxel CF200 series (all are stocks of Taicel Chemical Industry Co., Ltd.) And Ebecry 13800 (manufactured by Daicel UCP, Inc., acid value: 25 KOHmg / g, acid-functional epoxy acrylate) and the like.

Among these various resins, the alkali-soluble resins used in the present invention include polyhydroxystyrene-based resins, polysiloxane-based resins, acrylic resins, acrylamide-based resins, and acrylic / acrylamide copolymer resins from the viewpoint of heat resistance. Are preferable, and acrylic resins, polyhydroxystyrene resins, and polysiloxane resins are more preferable. Further, from the viewpoint of developing property control, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferred.
Examples of the acrylic resin include a copolymer composed of a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, as well as Cyclomer P series and Praxel CF200 series ( All are manufactured by Taicel Chemical Industries, Ltd.), Ebecry 13800 (manufactured by Daicel UCP), Dianar NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Viscoat R-264, KS Resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd. Is preferred.
In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) propane and epichlorohydrin, and the like are also useful.

  The amount of the alkali-soluble resin in the composition of the present invention is preferably from 5 to 90% by mass, more preferably from 10 to 60% by mass of the total solids of the composition. Within the above range, sufficient film strength and image density can be obtained.

[4. Photopolymerizable monomer, photopolymerization initiator and thermal polymerization initiator]
As the photopolymerizable monomer used in the photocurable composition of the present invention, a compound having an ethylenically unsaturated group having at least one addition-polymerizable ethylene group and having a boiling point of 100 ° C. or more under normal pressure is used. preferable.

  Compounds having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) Monofunctional acrylates and methacrylates such as acrylates; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (Acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, to which ethylene oxide or propylene oxide has been added and then (meth) acrylated, or pentaerythritol or dipentaerythritol poly (meth) acrylate Urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, etc .; JP-A-48-64183; Polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-A-49-43191 and JP-B-52-30490, and epoxy acrylates which are reaction products of an epoxy resin and (meth) acrylic acid. To mention Come. Further, the Journal of the Adhesion Society of Japan Vol. 20, No. 7, pages 300 to 308 as photocurable monomers and oligomers can also be used.

  Further, compounds obtained by adding ethylene oxide or propylene oxide to the above-mentioned polyfunctional alcohol and then (meth) acrylated are described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. And these can also be used as photopolymerizable monomers.

  These photopolymerizable monomers or oligomers may be used in any proportion as long as the photocurable composition can form a coating film having adhesiveness by light irradiation, as long as the object and effects of the present invention are not impaired. it can. The amount used is 5 to 90% by mass, preferably 10 to 50% by mass of the total solids of the photocurable composition. Here, the total solid content refers to the remaining components excluding the solvent from all components constituting the composition.

Next, the photopolymerization initiator contained in the photocurable composition of the present invention will be described.
As the photopolymerization initiator used in the present invention, conventionally known photopolymerization initiators can be used. For example, active halogen compounds such as halomethyl oxadiazole compounds described in JP-B-57-6096 and halomethyl-s-triazines described in JP-B-59-1281 and JP-A-53-133428. And aromatic carbonyl compounds such as ketals, acetals and benzoin alkyl ethers described in U.S. Pat. No. 4,318,791 and European Patent No. 88050A, and aromatic compounds such as benzophenones described in U.S. Pat. No. 4,199,420. Aromatic ketone compounds, (thio) xanthones and acridine compounds described in French Patent No. 2456741, coumarins and lophine dimer compounds described in JP-A-10-62986, and JP-A-8-15521. And the like sulfonium organic boron complexes described above.

  Specifically, acetophenone-based initiators (for example, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, etc.), ketal-based initiators (eg, benzyldimethylketal, benzyl-β-methoxyethylacetal, etc.), benzophenone-based initiators (eg, benzophenone, 4 , 4 '-(bisdimethylamino) benzophenone, 4,4'-(bisdiethylamino) benzophenone, 4,4'-dichlorobenzophenone, 1-hydroxy-cyclohexylphenylketone, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl)- Tanone-1,2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 ), Benzoin-based and benzoyl-based initiators (eg, benzoin propyl ether, benzoin butyl ether, benzoin methyl ether, methyl-o-benzoyl benzoate, etc.), xanthone-based initiators (diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, etc.) ), Triazine-based initiators (eg, 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine , 2,4-bis (Trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2,4-bis (trichloromethyl) -6-biphenyl-s-triazine, 2,4-bis (Trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di (trichloromethyl) -s-triazine, methoxystyryl-2,6-di (trichloromethyl) -S-triazine, 3,4-dimethoxystyryl-2,6-di (trichloromethyl) -s-triazine, 4-benzoxolan-2,6-di (trichloromethyl) -s-triazine, 4- (o -Bromo-p-N, N- (diethoxycarbonylamino) phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (p-N N- (diethoxycarbonylamino) phenyl) -2,6-di (chloromethyl) -s-triazine and the like, and a halomethyloxadiazole-based initiator (for example, 2-trichloromethyl-5-styryl-1,3) , 4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (naphth-1-yl) -1,3,4- Oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, etc.), acridine initiators (for example, 9-phenylacridine, 1,7-bis (9- Acridinyl) heptane etc.), coumarin initiators (e.g., 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro) 5-diethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin and the like , Lophine dimer initiators (eg, 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- ( o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, etc., 1-phenyl-1,2-propanedione- 2- (o-ethoxycarbonyl) oxime, o-benzoyl-4 '-(benzamercapto) benzoyl-hexyl-ketoxime, 2,4,6-trime Examples include tylphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophospho-trialkylphenylsulfonium salt, 2-mercaptobenzimidazole, 2,2'-benzothiazolyl disulfide, and the like.

  In the present invention, the blending amount of the photopolymerization initiator is preferably from 0.5% by mass to 60% by mass, more preferably from 1% by mass to 50% by mass, based on the photopolymerizable monomer in the composition. When the amount of the initiator is 0.5% by mass or more, polymerization proceeds appropriately, and when the amount is 60% by mass or less, good film strength is obtained.

It is preferable that the photocurable composition of the present invention further contains a thermal polymerization initiator. The photopolymerization initiator mainly has an effect of initiating photocuring, whereas the thermal polymerization initiator has an effect of heat-curing (post-baking) a color filter film or a pixel protective film after development. And a polymerization initiator for thermal polymerization.
As the thermal polymerization initiator, an organic peroxide is preferable. Among the organic peroxides, a benzophenone-based organic peroxide represented by the following general formula (III) is particularly preferred.

In the formula, R ₁ and R ₂ each independently represent an alkyl group or an aralkyl group having 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, more preferably 4 to 10 carbon atoms, and particularly as a peroxide. A tertiary alkyl group having 4 to 10 stable carbon atoms is most preferable, and examples thereof include a t-butyl group, a 1,1-dimethylpropyl group, a 1,1-dimethylbutyl group, and a 1,1-dimethylpentyl group. Can be

R ₃ and R ₄ are each independently a hydrogen atom, a carboxyl group, an alkyl group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 5 carbon atoms, Represents an alkyl group, a halogen atom, a cyano group, a nitro group or a dialkylamino group having 2 to 20 carbon atoms.
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group.
Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group and a butoxy group.
Examples of the halogenated alkyl group include a chloromethyl group, a dichloromethyl group, a chloromethyl group, a bromomethyl group, and a dibromomethyl group.
Examples of the halogen atom include a fluorine, chlorine, bromine, iodine atom and the like.
Examples of the dialkylamino group include an N, N-dimethylamino group and an N, N-diethylamino group.
q is 0, 1 or 2, and preferably 2.
r is 1, 2 or 3, and preferably 2.

  Specific examples of the benzophenone-based compound of the general formula (III) that can be used in the present invention are not limited, but the following compounds (1) to (5), 3,3 ′, 4,4′- Tetra (isopropylcumylperoxycarbonyl) benzophenone, 3,3 ′, 4,4′-tetra (p-menthylperoxycarbonyl) benzophenone, 3,4,4′-tri (t-butylperoxycarbonyl) benzophenone, 3,5 , 4′-tri (t-butylperoxycarbonyl) benzophenone, 3,4,5-tri (t-butylperoxycarbonyl) benzophenone, 2,3,4-tri (t-butylperoxycarbonyl) benzophenone, 3,4 4'-tri (t-amylperoxycarbonyl) benzophenone, 3,4,4'-tri (t-hexylperoxycarbonyl) Nzophenone, 3,4,4'-tri (t-octylperoxycarbonyl) benzophenone, 3,4,4'-tri (cumylperoxycarbonyl) benzophenone, 4-methoxy-3 ', 4', 5'-tri ( t-butylperoxycarbonyl) benzophenone, 4-ethoxy-3 ', 4', 5'-tri (t-butylperoxycarbonyl) benzophenone, 4-dimethylamino-3 ', 4', 5'-tri (t-butyl Peroxycarbonyl) benzophenone, 4-diethylamino-3 ′, 4 ′, 5′-tri (t-butylperoxycarbonyl) benzophenone, 4-cyano-3 ′, 4 ′, 5′-tri (t-butylperoxycarbonyl) benzophenone 4-methyl-3 ', 4', 5'-tri (t-butylperoxycarbonyl) benzophenone, 4-ethyl-3 ', 4', 5'-tri (T-butylperoxycarbonyl) benzophenone, 4-cyclohexyl-3 ′, 4 ′, 5′-tri (t-butylperoxycarbonyl) benzophenone, 4-nitro-3 ′, 4 ′, 5′-tri (t-butyl Peroxycarbonyl) benzophenone, 4-dimethylamino-3 ′, 4′-di (t-butylperoxycarbonyl) benzophenone, 4-diethylamino-3 ′, 4′-di (t-butylperoxycarbonyl) benzophenone, 4-cyano- 3 ′, 4′-di (t-butylperoxycarbonyl) benzophenone, 4-methyl-3 ′, 4′-di (t-butylperoxycarbonyl) benzophenone, 4-ethyl-3 ′, 4′-di (t- Butylperoxycarbonyl) benzophenone, 4-cyclohexyl-3 ', 4'-di (t-butylperoxycarbonyl) benzopheno , 4-nitro-3 ', 4'-di (t-butylperoxy carbonyl) benzophenone, and the like.

Among the above, the compounds (1) to (5) are particularly preferable.
These compounds can be used alone or in combination of two or more.

  In the present invention, the blending amount of the thermal polymerization initiator is preferably from 0.5% by mass to 20% by mass, more preferably from 1% by mass to 15% by mass, based on the photopolymerizable monomer in the composition.

In the present invention, in addition to the above-mentioned benzophenone-based peroxide, other organic peroxides can be used as a thermal polymerization initiator. Here, the organic peroxide is a derivative of hydrogen peroxide (HOOH), and refers to an organic compound having a -OO- bond in a molecule other than the general formula (III). .
When classified by chemical structure, ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxyester, peroxydicarbonate and the like can be mentioned. Among these organic peroxides, organic peroxides which preferably have a relatively high decomposition temperature and are stable at room temperature, decompose when heated to generate radicals, and serve as a polymerization initiator.

Such organic peroxides include benzoyl peroxide, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-hexylperoxy) -3, 3,5-trimethylcyclohexane, t-butyl peroxybenzoate, di-t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, t-butyl peroxyacetate, t-hexyl peroxybenzoate, t-butyl peroxy- 3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis (M-toluylperoxy) hexane, 2,5-di Tyl-2,5-bis (benzoylperoxy) hexane, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxyisobutyrate, 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate , T-hexyl peroxyisopropyl monocarbonate, 2,5-dimethyl-2,5-bis (2-ethylhexinoyl peroxy) hexane, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy maleic acid, cyclohexanone Peroxide, methyl acetoacetate peroxide, methylhexanone peroxide, acetylacetone peroxide, 1,1-bis (t-hexyl proxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t- Xylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1- Bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) butane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, diisopropylbenzene hydroperoxide , 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-butyl hydroperoxide, and the like, and one or more of these can be used in combination.
As the organic peroxide, a compound represented by the following general formula (A) is preferable.

In the formula (A), R ₁ and R ₂ each independently represent an alkyl group having 1 to 10 carbon atoms.
In the formula (A), examples of the alkyl group having 1 to 10 carbon atoms of R ₁ and R ₂ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, and an n-hexyl group. , N-heptyl group, n-octyl group, n-nonyl group, n-decanyl group, i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group, i-hexyl group , T-hexyl group, i-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group, t-decanyl group and the like.

In the present invention, two or more organic peroxides can be contained as a thermal polymerization initiator.
The content of the organic peroxide in the composition is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass, based on the amount of the photopolymerizable monomer in the photocurable composition. %. Within the above range, good storage stability is obtained.

[5.2 functional or higher epoxy compound]
The photocurable composition of the present invention preferably contains a bifunctional or higher functional epoxy compound in addition to the above components. By using the imidazole silane compound and a bifunctional or more epoxy compound in combination, it is possible to cure at a low temperature and in a short time, and further, it is excellent in adhesion to a substrate and solvent resistance. In particular, it has a remarkable effect on the solvent resistance of a polar solvent such as NMP (N-methylpyrrolidone).

  The bifunctional or more functional epoxy compound used in the composition of the present invention is desirably blended with an epoxy compound having an epoxy group number corresponding to the base number of the alkali-soluble resin having a carboxyl group contained in the composition.

  The ratio of the base equivalent of the alkali-soluble resin to the epoxy equivalent of the bifunctional or higher epoxy compound in the photocurable composition of the present invention is preferably from 0.2 to 6.0, more preferably from 0.5 to 3.5. In addition, since the NMP resistance can be further improved by increasing the crosslink density, an epoxy compound having a multifunctional group and a large number of functional groups is more preferable. In the color filter materials for red (R), green (G), and blue (B), from the viewpoint of heat discoloration, an alicyclic or aliphatic polyfunctional epoxy is preferable, but for a black matrix (BM). In black, heat-resistant discoloration does not pose a problem, so a polyfunctional epoxy such as a novolak type may be used.

  As such an epoxy compound, an alicyclic epoxy compound is preferable, and a polyfunctional alicyclic epoxy compound represented by the following formula is more preferable.

In the formula, R ′ represents a residue obtained by removing n hydrogen atoms substituted with [—O— (A) _m —H] _n from hydrocarbon R. A represents an alicyclic group having at least one epoxy group and having the following structure. m represents 1 to 100. n represents 1 to 100. However, m × n is 2 to 100, and a plurality of A may be the same or different.

m × n is 2 to 100. When mxn is large, problems may occur in productivity and storage stability of the photocurable composition. Preferably, m is 2 to 10, n is 3 to 6, m × n is 6 to 60, m is 3 to 6, n is 3 to 6, and m × n is more preferably 8 to 36. n is particularly preferably from 8 to 20.
A and m in n [-O- (A) m -H] may be the same or different. m × n is the total of n (m ₁ , m ₂ , m ₃ , ,,, + _mn ) of m which may be different, and the total of A of the polyfunctional alicyclic epoxy compound. Represents a number.

  Examples of the hydrocarbon of R include aliphatic hydrocarbons and aromatic hydrocarbons, and are preferably alkanes. The hydrocarbon as R may have a substituent other than [-O- (A) m-H] n. Examples of such a substituent include a hydroxyl group, a carboxyl group, halogen, and -CN.

The above-mentioned compound is, for example, an active hydrogen in alcohols, phenols, carboxylic acids (R "-(OH) n, where n is a natural number, and R" is a monovalent hydrocarbon group) is-(A) m-H Is replaced by
As described in JP-B-7-119292, a compound in which two adjacent carbon atoms constituting an alicyclic ring are bonded to the same oxygen atom to form an epoxy group as a precursor of A is represented by R " The compound can be synthesized according to the method of forming R [-O- (A) m-H] n by ring-opening polymerization of epoxy with the reaction with-(OH) n.

R in the above is preferably an alkane having 1 to 10 carbon atoms.
Examples of the alkane having 1 to 10 carbon atoms include methane, ethane, n-propane, n-butane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, i -Propane, i-butane, t-butane, i-pentane, t-pentane, i-hexane, t-hexane, i-heptane, t-heptane, i-octane, t-octane, i-nonane, t-decane And the like.
R is particularly preferably methane, ethane, n-butane, or n-pentane.

  The compound represented by the above general formula R '[-O- (A) m-H] n is specifically commercially available as EHPE3150 (2,2-bis (hydroxymethyl) -1 manufactured by Daicel Chemical Industries, Ltd.). 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of -butanol, m = 5 (average), n = 3, mxn = 15, epoxy equivalent 178 g / eq). The composition of the present invention may contain two or more polyfunctional alicyclic epoxy compounds.

  The number of functional groups of the polyfunctional alicyclic epoxy compound used in the present invention is preferably 4 or more, more preferably 6 or more, and particularly preferably 10 or more.

  The content of the bifunctional or higher epoxy compound in the composition of the present invention is preferably 1 to 30% by mass, more preferably 2 to 25% by mass, and most preferably 5 to 15% by mass of the solid content of the composition. %.

[6. solvent]
In preparing the photocurable composition of the present invention, a solvent is usually used.
Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, and methyl lactate. , Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. 3-methoxypropionate alkyl esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxyprop Ethyl pionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy- Methyl 2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, pyruvate Propyl, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol mono Tyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone and the like; aromatic hydrocarbons such as toluene, xylesi and the like.

  Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimeter ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate Butyl carbitol acetate, propylene glycol monomethyl ether acetate (PGMEA) and the like are preferably used.

  These solvents may be used alone or in combination of two or more.

[7. Other ingredients]
In the photocurable composition of the present invention, in addition to the components described above, various additives as necessary, for example, a filler, a polymer compound other than the alkali-soluble resin, a surfactant other than the above, an adhesion promoter , An antioxidant, an ultraviolet absorber, an anti-agglomeration agent and the like.

Specific examples of these additives include fillers such as glass and alumina;
Itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, polymer with hydroxyl group added with acid anhydride, alcohol-soluble nylon, bisphenol Alkali-soluble resins such as phenoxy resins formed from A and epichlorohydrin; surfactants such as nonionic, katin, and anionic surfactants, specifically, phthalocyanine derivatives (commercial product EFKA-745 (manufactured by Morishita Sangyo)); Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, No. 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo), W001 (manufactured by Yusho) Cationic surfactants: polyoxyethylene lauryl ether, polyoxyethylene stearyl ether , Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5, 17R2 manufactured by BASF) , 25R2, nonionic surfactants such as tetronic 304, 701, 704, 901, 904, 150R1; anionic surfactants such as W004, W005, W017 (manufactured by Yusho); EFKA-46, EFKA-47; EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (all manufactured by Morishita Sangyo), Disperse Aid 6, Disperse Polymer dispersants such as C. 8, Disperse Aid 15, and Disperse Aid 9100 (manufactured by San Nopco); various dispersants such as Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, and 28000 ( Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (manufactured by Asahi Denka) And isonet S-20 (manufactured by Sanyo Chemical Industries); vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- ( 2-A Noethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Adhesion promoters such as trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4- Antioxidants such as methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxy UV absorbers such as benzophenone; And an anti-agglomeration agent such as sodium polyacrylate.

  Further, in order to promote the alkali solubility of the non-irradiated portion and to further improve the developability of the composition of the present invention, the composition of the present invention may contain an organic carboxylic acid, preferably a low molecular weight of 1,000 or less. An organic carboxylic acid can be added. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, glutaric acid Aliphatic dicarboxylic acids such as acids, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as carballylic acid, aconitic acid, and camphoronic acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acid, melophanic acid and pyromellitic acid; phenylacetic acid, Doroatoropa acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

  In addition to the above components in the photocurable composition of the present invention, it is preferable to further add a polymerization inhibitor to suppress the change over time in viscosity of the resin composition at room temperature or during refrigerated storage, for example, Hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole and the like are useful. By adding a thermal polymerization inhibitor to the photocurable composition of the present invention, its storage stability can be improved. The compounding amount of the polymerization inhibitor is usually preferably from 100 ppm to 1% by mass, more preferably about 500 ppm, based on the photopolymerizable monomer.

[8. Method for producing and using composition of the present invention]
The photo-curable composition of the present invention is prepared by mixing a colorant, an alkali-soluble resin, a photo-polymerizable monomer, a photo-polymerization initiator, and other additives used as necessary with a solvent, and mixing the various types of mixers and dispersers. Can be prepared by mixing and dispersing.
The mixing and dispersing step is preferably composed of kneading and dispersing and a fine dispersing process performed subsequently thereto, but it is also possible to omit the kneading and dispersing and to perform only the fine dispersing process.

In the kneading and dispersing step, the surface of the colorant particles of the raw material is promoted to wet with a component mainly composed of the resin component of the vehicle, and the colorant particles and the solid of the vehicle solution are separated from the solid / gas interface between the colorant particles and air. / Convert to solution interface.
In the fine dispersion step, the colorant particles are dispersed into a minute state close to the primary particles by mixing and stirring with a dispersion medium of fine particles of glass or ceramic. Therefore, in the kneading and dispersing step, since it is necessary to convert the interface formed by the colorant particle surface from air to a solution, a strong shearing compressive force is required, and a suitable kneading machine and kneaded material preferably have high viscosity. On the other hand, in the fine dispersion step, it is necessary to uniformly and stably distribute the particles to a fine state, and a dispersing machine that does not require an impact force and a shear force on the aggregated colorant particles is relatively low. It is desirable that the dispersion has a relatively low viscosity.

Using the photocurable composition of the present invention, for example, a kneading and dispersing step for preparing a color filter is first performed with a colorant such as an organic pigment or carbon black and a dispersant or a surface treatment agent, an alkali-soluble resin and a solvent. Knead. The machine used for kneading is a two-roll, three-roll, ball mill, tron mill, disper, kneader, co-kneader, homogenizer, blender, single-screw and twin-screw extruder, etc., and disperses while giving a strong shearing force. Next, a solvent and an alkali-soluble resin (the remainder used in the kneading step) are added, and a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, a high-pressure disperser, or the like is used. Disperse with beads made of glass, zirconia or the like having a particle size of 1 mm. Incidentally, the kneading step can be omitted. In that case, beads are dispersed with a pigment and a dispersant or a surface treatment agent, an alkali-soluble resin and a solvent. In this case, the remaining alkali-soluble resin in the kneading step is preferably added during the dispersion. After preliminary dispersion by another dispersing means, the colorant particles can be further dispersed by a high-pressure disperser, whereby further fineness can be achieved. Particularly, in a high-pressure dispersing machine having a mechanism for back-pressure of a pressurized dispersion, even if the dispersion of the colorant proceeds, the viscosity of the dispersion does not increase, and the resulting product has excellent fluidity and is applied as a coating solution. Properly excellent.
The details of kneading and dispersion are described in "Paint Flow and Pigment Dispersion" by TC Patton (published by John Wiley and Sons, 1964).

  The photocurable composition of the present invention is applied and dried (prebaked) on a substrate by a coating method such as spin coating (spin coating), slit coating, casting coating, roll coating, or the like directly or via another layer. Forming a curable composition layer, exposing this through a predetermined mask pattern by photolithography, curing only the light-irradiated coating film portion, and developing with an alkali developer to form a one-color coloring pattern. A color filter can be manufactured by forming a film and repeating this process for each color (3 or 4 colors).

Drying (prebaking) can be performed on a hot plate, an oven, or the like at a temperature of 50C to 140C for 10 to 300 seconds.
As radiation that can be used for exposure, ultraviolet rays such as g-rays and i-rays are particularly preferably used.
By performing the alkali developing treatment, the unexposed portion is eluted into the aqueous alkali solution by the above exposure, and only the photocured portion remains. Any developer can be used as long as it dissolves the photosensitive layer in the non-light-irradiated part and does not dissolve the light-irradiated part.
Next, after the excess developer is removed by washing and drying, a heat treatment (post-bake) is performed at a temperature of 50 ° C to 240 ° C. In this manner, a cured film can be manufactured by sequentially repeating the above steps for each color. Thereby, a color filter is obtained.

  As disclosed in JP-A-6-339656 and JP-A-11-90295, a slit coating method is a method for coating a rectangular substrate having a slit (gap) having a width of several tens of microns at its tip. A coating head having a length corresponding to the width is maintained at a clearance (gap) of several tens to several hundreds of microns between the substrate and the substrate and the coating head at a constant relative speed and supplied from the slit at a predetermined discharge amount. This is a method of applying a coating solution to be applied onto a substrate. The slit coating method has less liquid loss than spin coating, there is no scattering of the coating liquid, the cleaning process is reduced, there is no re-mixing of the scattered liquid components into the coating film, and there is no rotation start stop time. Therefore, it has many advantages such as shortening of the tact time and easy application to a large-sized substrate, and it is expected to be applied as a coating method in a color filter for a large-screen liquid crystal display device in the future. The high-pressure dispersion liquid having the back pressure mechanism described above has a low viscosity as a coating liquid and excellent liquid flow properties, despite the fact that the dispersion units of the colorant particles are ultrafine, A photocurable colored resin composition optimal for slit coating can be obtained.

  As the substrate, for example, alkali-free glass used for a liquid crystal display device or the like, soda glass, Pyrex glass, quartz glass and those obtained by attaching a transparent conductive film thereto, or a photoelectric conversion element substrate used for a solid-state imaging device, for example, A silicon substrate is exemplified. Furthermore, plastic substrates are also possible. On these substrates, black stripes for isolating each pixel are usually formed.

Raw materials for the plastic substrate include (1) amorphous polyolefin, (2) polyether sulfone, (3) polyglutarimide, (4) polycarbonate, and (5) polyethylene terephthalate in terms of optical properties, heat resistance, mechanical strength, and the like. And (6) polyethylene naphthalate, (7) norbornene polymer, (8) polyimide containing bisaniline fluorene as a diamine component, and (9) polyester comprising bisphenol fluorene and a dibasic acid. Among them, (2) polyether sulfone, (4) polycarbonate, (5) polyethylene terephthalate, and (7) norbornene polymer are preferable. The above raw materials are particularly preferred for LCD applications.
The characteristics required of the plastic substrate include low thermal expansion (prevention of deterioration of display accuracy due to the curing process when creating color filters), gas barrier properties (ensure stability of liquid crystal), optical transmittance and optical isotropy. Properties, surface smoothness, etc. Regarding thermal expansion, the thermal expansion coefficient is preferably 10 ^-4 or less.
Further, the plastic substrate preferably has a gas barrier layer and / or a solvent-resistant layer on its surface.

  The coating thickness (after drying) of the photocurable composition of the present invention is generally 0.3 to 5.0 μm, preferably 0.5 to 3.5 μm, more preferably 1.0 to 2.5 μm. It is.

Any developer can be used as long as it dissolves the photocurable composition of the present invention and does not dissolve the irradiated part. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.
Examples of the organic solvent include the above-mentioned solvents used when preparing the composition of the present invention.
The development temperature is usually 20 ° C. to 30 ° C., and the development time is usually 20 to 90 seconds.

  Examples of the alkali include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, and tetraethylammonium hydroxy. , Choline, pyrrole, piperidine, an alkaline compound such as 1,8-diazabicyclo- [5,4,0] -7-undecene at a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution dissolved so as to be used is used. When a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with water after development.

Post-baking is a heat treatment after development for complete curing, and is usually performed at 200 ° C. to 220 ° C.
This post-bake treatment is performed by heating the coated film after development using a heating means such as a hot plate, a convection oven (hot air circulation type dryer), a far-infrared heater, or a high-frequency heater so as to satisfy the above conditions. Alternatively, it can be performed in a batch system.
In the usual color filter manufacturing process, the pre-bake is made continuous by a process of 2 to 3 minutes / sheet on a hot plate, but the heat curing (post-bake) process part is about 10 minutes / sheet on a hot plate. Since it takes a long time, continuity requires a number of hot plates and is inefficient. Performing heat curing (post-baking) using a batch type multi-stage convection oven to achieve in-line operation are doing. However, in this method, the loss at the time of starting operation of the line and at the time of stopping the operation are large (when the operation is stopped halfway, the degree of curing of the coating substrate in the multistage oven during curing is low). And the multistage oven itself consumes a great deal of heat energy and space. By using the photocurable composition of the present invention, post-paking can be continued at the same speed as pre-baking using a hot plate (see FIG. 1 (b)), immediate operation and pause can be performed, and Space and energy can be saved.

  In the present invention, heat curing is carried out for a short time or at a relatively low temperature, and as a reaction system that satisfies required properties such as physical properties and chemical properties, attention is paid to an alkali-soluble resin in a color filter, and Various thermosetting reactions are combined by selecting a highly reactive epoxy resin that can be cross-linked by heating and optimizing the number of functional groups, and further by adding imidazole silane, which has a curing promoting action even with the epoxy resin alone. That is, curing can be performed at a lower temperature than in the past, and a color filter can be directly formed on a plastic substrate that requires a heat treatment at 150 ° C. or less, which has been impossible so far. If the photocurable colored resin composition of the present invention is used, which has been conventionally performed when a plastic substrate is employed, once a color filter is formed on a glass substrate, and then transferred to the plastic substrate, and so on. It is not necessary to employ complicated steps, and a color filter can be directly formed on a plastic substrate. In addition, ordinary glass substrate color filters can be cured at high temperatures for a short time, and if post-baking using a conventional multi-stage convection oven, the number of ovens can be reduced to about half, saving space and energy. Using a far-infrared heating furnace or hot plate with good thermal efficiency, continuation at the same speed as pre-bake (see Fig. 1 (b)), immediate operation and stoppage are possible, improving productivity and improving yield. Improvement can be expected.

  Various components for a color filter can be applied to a spacer, a protective layer, a contact hole forming layer, and the like in addition to the color filter body (colored layer) and the black matrix. Further, the photocurable composition of the present invention can be used as a potting sealant for COB (chip-on-board) and a sealant for LCD, in addition to the above various components for color filters.

  An overcoat layer (flattening layer) is usually provided on the color filter layer obtained by using the photocurable composition of the present invention. Examples of the resin (OC agent) forming the overcoat layer include an acrylic resin composition, an epoxy resin composition, and a polyimide resin composition. Among them, the acrylic resin composition is excellent in transparency in the visible light region, and the resin component of the photocurable composition for a color filter usually contains an acrylic resin as a main component and has excellent adhesion. Things are desirable. In particular, a photo-curable (meth) acrylic resin for a photoresist used in a color filter is preferable because it matches well with the color filter manufacturing process.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention should not be construed as being limited in any way by the following examples.

[Examples 1 to 10 and Comparative Examples 1 to 4]
Test specimen preparation:
a) The composition shown in the composition table of Table 1 below was applied to an alkali-free glass for a liquid crystal panel (Corning 1737) by a spin coater so as to have a dry film thickness of 1.2 μm. Seconds went.
b) Then, ultraviolet rays of 200 mJ / cm ² were irradiated through a mask using an ultra-high pressure mercury lamp of 2.5 kW.
c) Next, the film was developed at 26 ° C. for 30 seconds with a 10% diluted aqueous solution of an organic alkali developer CD-2000 manufactured by Fuji Film Arch Co., Ltd., rinsed with pure water for 20 seconds, and dried.
d) Next, post-baking was performed using a hot-air circulation dryer at 110 ° C. to 150 ° C. for 60 minutes (low-temperature curing) and a hot plate at 220 ° C. for 5 seconds to 30 seconds (rapid curing). These were used as test specimens.

Determination of curability and adhesion to substrate:
a) The determination of the curability was performed by immersing in N-methylpyrrolidone (hereinafter abbreviated as NMP) for 10 minutes at 50 ° C., measuring the chromaticity change before and after, expressing the color difference ΔE * ab, and ΔE * ab ≦ 3. There was no problem.
b) In the NMP immersion test, the degree of adhesion of the film to the substrate was visually judged in the NMP immersion test, and the following evaluation was performed.
A: The film is not peeled at all.
B: The film is not peeled off but is partially raised.
C: About 50% of the film is peeled off, but the change in chromaticity can be measured.
NG: The film was completely peeled, and chromaticity measurement was impossible.
The low-temperature curability and adhesion evaluation were performed on Examples 1 to 9 and Comparative Examples 1 to 4, and the rapid curability and adhesion evaluation were performed only on Examples 1, 4, 8 to 9 and Comparative Examples 1 to 4. Was.
The results are shown in Tables 2 and 3 below and FIGS. 2 and 3.

From Table 2 and FIG. 2, the effect of the addition of the imidazole silane-based compound is apparent, and the curing of the coating film is greatly promoted. Even if the addition amount is reduced, the effect hardly decreases.
Although the effect of adding BTTB was observed, it was smaller than that of imidazole silane. For example, as apparent from FIG. 3, ΔE * ab ≦ 3 under the curing condition of 135 ° C. × 60 minutes in Example 1. In addition, comparison between Example 3 and Example 9 showed that the higher the number of functional groups of the selected alicyclic epoxy, the better. Furthermore, as is clear from Table 3 and FIG. 3, in Comparative Examples 3 and 4, almost no effect was obtained by adding each of imidazole and epoxysilane alone.

Also, from Table 3 and FIG. 3, it can be seen that the same result as that of the low-temperature curability was obtained for the rapid curability, and that the effect on the curing of imidazole silane was very large.
From FIG. 2 and FIG. 3, regarding the curability, 15-functional alicyclic epoxy + imidazole silane + BTTB> 15-functional alicyclic epoxy + imidazole silane> 4-functional alicyclic epoxy + imidazole silane> 15-functional alicyclic epoxy + The effect was recognized in the order of imidazole + BTTB> 15-functional alicyclic epoxy + epoxysilane + BTTB.

Development characteristics evaluation:
The composition shown in the composition table of Table 1 was applied to a non-alkali glass for a liquid crystal panel (Corning 1737) by a spin coater to a dry film thickness of 1.2 μm, and the solvent was dried on a hot plate at 120 ° C. for 120 seconds. Was. Then, using an exposure machine LE4000A manufactured by HITACHI, red, green, and blue were exposed with a mask having a line width of 20 μm and a black mask having a line width of 15 μm with a Proximity Gap of 300 μm and 100 mJ / cm ² (illuminance: 20 mW / cm ^2). ) And developed at 26 ° C. with a 1.0% diluted developing solution of alkali developing solution CDK-1 manufactured by Fuji Film Arch Co., Ltd. At this time, the development margin and the development latitude were represented by a graph of the line width change with respect to the development time. The results are shown in Table 4 and FIG. Here, the development margin is a change in the line width with respect to the development time, and the development latitude is a time from the appearance of the pattern to the peeling of the pattern. FIG. 4 is a graph of the main components from Table 4.

  As is clear from Table 4 and FIG. 4, the line width of the comparative example does not become constant with respect to the development time, so that it is difficult to obtain a constant image. In the example, good development characteristics can be obtained.

[Example 11]
A solution having the following composition was prepared and stirred for 8 hours to obtain a photosensitive resin solution.
<Alkali-soluble resin>
・ 6.4 g of benzyl methacrylate / methacrylic acid copolymer
(Molar ratio 70/30, mass average molecular weight Mw about 30,000)
<Polymerizable monomer>
・ Dipentaerythritol hexaacrylate 4g
<Photopolymerization initiator A>
-2,4-bis (trichloromethyl) -6- [3-bromo-4-
[N, N-bis (ethoxycarbonylmethyl) amino] phenyl]
-1,3,5-triazine 1g
<Photopolymerization initiator B>
-7- [L-4-chloro-6- (diethylamino) -s-triazinyl (2), 1-amino] -3-phenylcoumarin 0.3 g
<Colorant>
-Carbon black dispersion (solid content) (* 1) 9.7 g
・ 78.5 g of propylene glycol monomethyl ether acetate
・ Fluorine nonionic surfactant (* 2) 0.02g
・ Imidazole silane manufactured by Japan Energy, IM-1000 0.1g
* 1) Cabot Corporation legal (particle size: 31 nm, pH: 9, DBP lubrication amount: dispersion liquid in which carbon is dispersed at 42 ml / 100 g (compounding amount of carbon is 45% based on the solid content in the above solution))
* 2) Copolymer of 60% N-butyl perfluorooctanesulfonamidoethyl acrylate and 40% poly (oxyalkylene) acrylate

  The photosensitive resin solution was developed in the same manner as in Examples 1 to 10, and the developing characteristics were evaluated. The evaluation results are shown in Table 6 and FIG.

[Comparative Example 5]
A black matrix was prepared in the same manner as in Example 12 except that the imidazole silane compound (IM-1000) was not used, and evaluated under the same conditions as in Example 11.
[Comparative Example 6]
Performed except that 0.1 g of a silane coupling agent, KBM-403 (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. was used instead of the imidazole silane compound (IM-1000) and 0.1 g. A black matrix was prepared in the same manner as in Example 11, and evaluated under the same conditions as in Example 11.
[Comparative Example 7]
Except for using 0.1 g of the imidazole silane compound (IM-1000) and 0.1 g of a silane coupling agent, KBM-402 (3-glycidoxypropylmethyldiethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. A black matrix was prepared in the same manner as in Example 12, and evaluated under the same conditions as in Example 11.

[Comparative Example 8]
A black matrix was prepared in the same manner as in Example 12, except that 0.1 g of the imidazole silane compound (IM-1000) and 0.1 g of 3- (methacryloxypropyl) trimethoxysilane were used. The evaluation was performed under the same conditions.
[Comparative Example 9]
In the same manner as in Example 11, except that 0.1 g of the imidazole silane compound (IM-1000) and 0.1 g of a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd., KBE-04 (tetraethoxysilane), were used. A black matrix was prepared and evaluated under the same conditions as in Example 11.
[Comparative Example 10]
In the same manner as in Example 11 except that 0.1 g of the imidazole silane compound (IM-1000) and 0.1 g of a silane coupling agent KBM-1003 (vinyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. were used. Then, a black matrix was prepared and evaluated under the same conditions as in Example 11.
The composition table of Example 11 and Comparative Examples 5 to 10 is shown in Table 5 below, and the results are shown in Table 6 below and FIG.

[Example 12]
(Production of color filter)
Each color photocurable composition was prepared as follows.
Photocurable red (R) composition: Red composition of Example 10.
Photocurable green (G) composition: C.I. used as a colorant in Example 10. I. Pigment Red 254 (PR254) /C.I. I. Pigment Yellow 139 (mass ratio 100 / 17.6) 4.28 parts by C.I. I. Pigment Green 36 (PG36) /C.I. I. Pigment Yellow 150 (PY150) (mass ratio 100/58) A green light curable composition was prepared in the same manner as in Example 10, except that the composition was changed to 5.79 parts.
Photocurable blue (B) composition: C.I. used as a coloring agent in Example 10. I. Pigment Red 254 (PR254) /C.I. I. Pigment Yellow 139 (mass ratio 100 / 17.6) 4.28 parts by C.I. I. Pigment Blue 15: 6 (PB15: 6) A blue light-curable composition was prepared in the same manner as in Example 10, except that 4.28 parts were changed.
Photocurable black composition (photocurable composition for black matrix): Black composition of Example 11.

The photocurable black composition was applied to a substrate obtained by washing a non-alkali glass substrate for a liquid crystal panel (Corning 1737) with a 1% by mass aqueous solution of sodium hydroxide, and a dry film thickness of 1.1 μm using a spin coater. After the solvent was dried at 120 ° C. for 120 seconds, exposure was performed at 100 mJ / cm ² through a mask having a line width of 15 μm using an exposure machine LE4000A manufactured by HITACHI to obtain an alkaline developer CDK-1 manufactured by Fuji Film Arch Co., Ltd. %, A clear black pattern image (black matrix) was obtained. Subsequently, the substrate was rinsed with running water for 20 seconds, dried with an air knife, and heat-treated at 220 ° C. for 60 minutes with a hot air circulation type drier to obtain a black matrix substrate.
Next, using a mask having a pixel size of 100 μm corresponding to the above-mentioned black matrix, each color was sequentially applied in the order of red → green → blue to form a pattern image, thereby obtaining a color filter.
That is, the same photocurable red composition was applied to a dry film thickness of 1.2 μm using the same apparatus and developing solution as in the formation of the black matrix except for the mask, and after drying the solvent, 100 mJ was passed through a 100 μm pixel size mask. / Cm ² and developed for 100 seconds. Next, heat treatment was performed at 220 ° C. for 60 minutes to form a red pattern image (red pixel). Similarly, the positions of the green pattern image (green pixel) and the blue pattern image (blue pixel) are shifted by the same mask, and exposure is performed alternately with red, green, and blue. A stable and clear pixel was formed in 120 seconds. Observation with an optical microscope revealed no defective pixels, or no color overlap, color mixing, or bleaching.

FIG. 2 is a schematic diagram showing in-line of a multistage convection oven in a color filter manufacturing process. It is a figure which shows the graph which showed the influence on the low temperature curability of Example and the comparative example composition. It is a figure which shows the graph which showed the influence on the rapid curability of Example and the comparative example composition. 4 is a graph showing the evaluation results of the developability of the compositions of Examples and Comparative Examples. 4 is a graph showing the evaluation results of the developability of the compositions of Examples and Comparative Examples.

Claims (11)

  In a photocurable colored resin composition containing a colorant, an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator, the content of the colorant in the solid content of the photocurable colored resin composition is 10%. A photocurable colored resin composition, which is 70 to 70% by mass and contains an imidazole silane compound. The imidazole silane compound is a reaction product of an imidazole compound represented by the following general formula (I) and an epoxy silane compound represented by the following general formula (II) and / or a derivative thereof. The photocurable colored resin composition according to claim 1, which is a compound.

In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and R ² and R ³ each independently represent a hydrogen atom, a vinyl group or an alkyl group having 1 to 5 carbon atoms.

In the formula, R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 3 carbon atoms, m represents an integer of 1 to 20, and n represents an integer of 1 to 3. The photocurable colored resin according to claim 1 or 2, wherein the imidazole silane-based compound is at least one selected from compounds represented by the following general formulas (1) to (3) and / or derivative compounds thereof. Composition.

In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ² represents a hydrogen atom, a vinyl group or an alkyl group having 1 to 5 carbon atoms, and R ³ and R ⁴ each independently represent a carbon atom. Represents an alkyl group of Formulas 1 to 3, and n represents 1 to 3.   The photocurable colored resin composition according to any one of claims 1 to 3, wherein the colorant is a black colorant.   The photocurable colored resin composition according to claim 4, wherein the black colorant is carbon black.   The photocurable colored resin composition according to any one of claims 1 to 5, further comprising a bifunctional or higher epoxy compound.   The photocurable colored resin composition according to claim 6, further comprising a thermal polymerization initiator.   The photocurable colored resin composition according to claim 7, wherein the thermal polymerization initiator is an organic peroxide. The photocurable colored resin composition according to claim 8, wherein the organic peroxide is a benzophenone-based organic peroxide represented by the following general formula (III).

In the formula, R ₁ and R ₂ each independently represent an alkyl group having 1 to 20 carbon atoms or an aralkyl group, and R ₃ and R ₄ each independently represent a hydrogen atom, a carboxyl group, an alkyl group having 1 to 10 carbon atoms. Represents an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a halogen atom, a cyano group, a nitro group or a dialkylamino group having 2 to 20 carbon atoms, and q represents 0, 1 or 2 And r is 1, 2, or 3. The photocurable colored resin composition according to claim 9, wherein the benzophenone-based organic peroxide is at least one of compounds represented by the following formulas (1) to (5).

  A coating liquid comprising the photocurable colored resin composition according to any one of claims 1 to 10, applied on a substrate, formed into a film, and then exposed and developed by photolithography to form a monochromatic pattern. A color filter created by repeating the process of performing for each color.

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