JP4276923B2 - Photocurable colored resin composition and color filter using the same - Google Patents

Description

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

A 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 (pre-baking), pattern exposure, and alkali. It is obtained by forming a predetermined pixel pattern through a series of steps of development and thermosetting (post-baking), and repeating this step for each color such as red (R), green (G), and blue (B). . The thermosetting treatment (post-bake) in the color filter manufacturing process is performed to impart durability and strength using the pixel pattern film as a permanent film, and accelerates the curing of the resin component in the film composition by heat. By doing so, durability, such as mechanical strength as a film | membrane, solvent resistance, and light resistance, can be improved.
Color liquid crystal display devices are compact and have the same or better performance than CRTs, and have recently made great strides as televisions, personal computer screens, mobile phone display units, and other display devices. The color filter is an essential component for such a color liquid crystal display device.

On the other hand, in conventional color liquid crystal display devices, since a glass substrate is usually used, the adhesion with the photocurable coloring resin composition is not so good, and development with an alkaline developer leaves the remaining if the development time is too short. However, if the development time is too long, pattern peeling tends to occur. Therefore, it has been necessary to perform development within a very limited development time range at present. For this reason, there has been a problem that a constant pattern shape cannot be obtained unless the development time and the control of the developer concentration and temperature are carefully controlled and finely controlled.
Therefore, how wide the allowable range of development time greatly affects the appropriateness of the color filter process.

  In addition, it is known to use an imidazolesilane compound in order to improve the adhesion of the film, but in the prior art, even if the adhesion is improved, the development margin (the line width hardly changes with the development time). The problem of development characteristics such as time length) and development latitude (ratio of change in line width with respect to development time) and development residue has a trade-off relationship, and thus is not effective. For example, Patent Document 1 (Japanese Patent Application Laid-Open No. 10-186657) discloses that imidazolesilane is contained in a photocurable composition in order to improve the adhesion of a resin film for photoresist applications. 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 to be added for mere coloring of a photoresist composition. Only. Thus, since the transparent film containing no coloring component originally has good development characteristics, the effect of adding imidazole silane to the development characteristics was not exhibited, and this effect was not noted.

  In recent years, in order to increase the production efficiency of color filters, it has been desired to develop a photocurable composition that can be sufficiently heat-cured (post-baked) at a low temperature or in a short time. The color filter material that has been used cannot meet such a demand. In particular, in order to obtain a color filter having excellent durability as a permanent film, it is necessary to promote the thermal curing of the resin by heating in the final step. However, in a conventional curable composition for a color filter, It required processing at temperature and for at least nearly 1 hour.

As mentioned above, in the photocurable composition for color filters, a thermosetting component is essential to obtain a permanent coating film with excellent durability, and epoxy resin and melamine resin are generally used as the component. It was the target. For example, Japanese Patent No. 2937208, Japanese Patent Publication No. 2-42371, and Japanese Patent Application Laid-Open No. 6-1938 disclose photocurable compositions for color filters containing an epoxy resin.
On the other hand, in the resist material field, imidazole silane compounds and epoxy resin compositions are known as curing agents. For example, Patent Document 2 (Japanese Patent Laid-Open No. 9-12683), Patent Document 3 (Japanese Patent Laid-Open No. 2001-187836), and Patent Document 4 (Japanese Patent Laid-Open No. 2002-128872) disclose an epoxy containing an imidazolesilane compound. A resin composition is disclosed. Of these, Patent Document 2 uses adhesives, sealants, paints, laminates, and molding materials that require adhesion, Patent Document 3 uses electronic materials, paints, primers, and adhesives, and Patent Document 4 uses them. It is disclosed that each is useful as a sealing agent for semiconductor chips and the like. However, none of these patent documents describes a color filter application.
Moreover, the said patent document 1 is disclosing that the photosensitive resin composition containing an imidazole silane compound is useful as a resist material use. However, the above-mentioned patent relates to a plating resist for printed circuit boards. The resist material using imidazole silane is a photo-curable resin composition with improved adhesion to a copper foil substrate, and the used resist is removed when plating is finished. It will not be cured. Therefore, the composition does not contain a thermosetting resin such as an epoxy resin.

  As described above, a photocurable composition for a color filter is required to be cured at a low temperature that can be applied to a plastic substrate. In order to increase the production efficiency in response to the increase in substrate area and mass production while providing high strength, adhesion and high solvent resistance, low temperature thermosetting (post bake) or short Time-hardening treatment (post-baking) has been strongly desired.

JP-A-10-186657 Japanese Patent Laid-Open No. 9-12683 JP 2001-187836 A Japanese Patent Laid-Open No. 2002-128772

An object of the present invention is to provide a photocurable coloring resin composition having no development residue and improved development margin and development characteristics of development latitude, and a color filter using the same.
Another object of the present invention is to provide a photo-curable colored resin composition from which a color filter having excellent adhesion and solvent resistance can be obtained by heat curing (post-baking) at a short time and / or at a low temperature. is there.

As a result of intensive studies, the present inventors have found that excellent development characteristics can be obtained by adding an imidazolesilane compound to a colorant-containing photocurable composition for a color filter. It was found that the thermosetting property was improved by containing the epoxy compound, and the present invention was completed.
That is, according to the present invention, a photocurable colored resin composition and a color filter having the following constitution are provided to achieve the above object.

1. In the 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 for a color filter , which is ˜70% by mass and contains an imidazolesilane 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 coloring resin composition for color filters as described in 1 above, 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 represents 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 photocuring property for a color filter as described in 1 or 2 above, wherein the imidazole silane compound comprises at least one compound selected from compounds represented by the following general formulas (1) to (3) and / or derivative compounds thereof. Colored resin 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 are each independently carbon. The alkyl group of number 1-3 is represented, n represents 1-3.

4). 4. The photocurable color resin composition for a color filter according to any one of 1 to 3, wherein the colorant is a black colorant.
5. 5. The photocurable colored resin composition for color filters as described in 4 above, wherein the black colorant is carbon black.
6). 6. The photocurable colored resin composition for color filters according to any one of 1 to 5 above, which contains a bifunctional or higher functional epoxy compound.
7). 7. The photocurable composition for a color filter as described in 6 above, which contains a thermal polymerization initiator.
8). 8. The photocurable colored resin composition for a color filter as described in 7 above, wherein the thermal polymerization initiator is an organic peroxide.

9. 9. The photocurable colored resin composition for a color filter according to 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 or aralkyl group having 1 to 20 carbon atoms, and R ₃ and R ₄ each independently represent a hydrogen atom, a carboxyl group, or an alkyl having 1 to 10 carbon atoms. Group, 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, q is 0, 1 or 2 And r is 1, 2 or 3.
10. 10. The photocurable colored resin composition for a color filter as described in 9 above, wherein the benzophenone-based organic peroxide is at least one compound of the following formulas (1) to (5).

11. A coating solution comprising the photocurable coloring resin composition for a color filter according to any one of 1 to 10 above is applied onto a substrate, formed into a film, and then exposed and developed by a photolithography method to obtain a single color. A color filter created by repeating the pattern formation process for each color.

  According to the present invention, development characteristics such as development latitude and development margin are improved, so that the condition restrictions during development are greatly relaxed, and in terms of management of developable time, development density, developer temperature, etc., it is significantly greater than before. In addition, the restriction can be relaxed, the quality improvement rate in development can be increased, the number of times of changing the developer 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 impede transmission of exposure light into a coated film, the present invention is difficult to proceed with photocuring of the film. Bring great benefits. In addition, according to the present invention, a photocurable composition that can be sufficiently cured at a low temperature or in a short time, and a pigment-dispersed color filter that can be sufficiently cured at a low temperature and is suitable for use in a plastic substrate. Photocurable composition for pigment dispersions, especially when forming color filters on current glass substrates, which can be heat-treated in a short time and can significantly improve color filter production efficiency Sex compositions can be provided. Furthermore, various conditions can be selected in the heat treatment step necessary and optimum for manufacturing the color filter.

  Hereinafter, each component used for 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 contains an imidazolesilane compound. As the imidazole silane compound, an imidazole silane compound and / or a derivative thereof, 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). A compound is preferably used.
The imidazole compound, epoxy silane compound and imidazole silane compound will be described in detail below.

(A) Imidazole compound As the imidazole compound represented by the general formula (I) in the present invention, there are imidazole, 2-alkylimidazole, 2,4-dialkylimidazole, 4-vinylimidazole, and the like. Particularly preferable for 2-alkylimidazole is 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, etc .; and for 2,4-dialkylimidazole, 2-ethyl-4- And methyl imidazole.

(B) Epoxysilane compound As the epoxysilane compound represented by the general formula (II) in the present invention, 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyl dialkoxyalkylsilane, 3- Examples of glycidoxypropylalkoxydialkylsilane include 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like. Further, as 3-glycidoxypropyl dialkoxyalkylsilane, 3-glycidoxypropyldimethoxymethylsilane and the like, and as 3-glycidoxypropylalkoxydialkylsilane, 3-glycidoxypropylethoxydimethylsilane and the like. Give be able to.

(C) Imidazolesilane compound As an imidazolesilane compound that is a reaction product of the imidazole compound represented by the general formula (I) and the epoxysilane compound represented by the general formula (II) in the present invention. Specific examples 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 are each independently carbon. The alkyl group of number 1-3 is represented, n represents 1-3.

  Examples of commercially available imidazole silane compounds that can be used in the present invention include imidazole silane, IM-1000, IS-1000, YA-100, IC-100P, and IA-100P manufactured by Japan Energy Co., Ltd. Can be mentioned. These blending amounts are preferably 0.01% by mass or more, more preferably 0.1 to 1% by mass in the solid content.

[2. Colorant]
As the colorant that can be used in the present invention, various conventionally known pigments, (insulating) carbon black, and dyes can be used singly or in combination.

  As the pigment that can be used in the present invention, conventionally known various inorganic pigments or organic pigments can be used. Also, considering that it is preferable that the pigment has a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment that is as fine as possible. However, in consideration of handling properties, the average particle size is preferably 0.01 μm. A pigment having a thickness of ˜0.1 μm, more preferably 0.01 μm to 0.05 μm is used. Examples of inorganic pigments are metal compounds such as metal oxides and metal complex salts. Specifically, metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony And composite oxides of the above metals.

As an organic pigment,
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;
Etc.

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

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

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. Red pigments include anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or at least one of them and disazo yellow pigments, isoindoline yellow pigments, quinophthalone yellow pigments or perylene red pigments Etc. are used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177 and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224 and diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, and C.I. I. Pigment yellow 83 or C.I. I. Mixing with 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 it to 100: 5 or more, the light transmittance from 400 nm to 500 nm can be suppressed, and the color purity can be increased. Further, by setting the ratio to 100: 50 or less, the dominant wavelength becomes closer to the short wavelength, and deviation from the NTSC target hue can be suppressed. In particular, the range of 100: 30 to 100: 30 is optimal. In the case of a combination of red pigments, it is adjusted 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. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. By setting it to 100: 5 or more, the light transmittance from 400 nm to 450 nm can be suppressed, and the color purity can be increased. Further, by setting it to 100: 150 or less, the dominant wavelength becomes longer 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. Mixing with Pigment Violet 23 is preferred. The mass ratio of the blue pigment to the purple pigment is preferably 100: 30 to 100: 0, more preferably 100: 10 or less.

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

  As the black matrix colorant, a black colorant is used. For example, carbon black, titanium carbon, iron oxide, titanium oxide alone or a mixture thereof is used, 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 carbon black # 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 made by Cancarb. 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's carbon black ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw2, ColorBlack Fw1, ColorBlack 170, BlackBlack, BlackBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, PrintexU, PrintexV, Printex140U, Printex140 And the like can be given.

  Insulating carbon black in the present invention means having an organic compound on the surface of carbon black particles, for example, organic substances are adsorbed, coated or chemically bonded (grafted) on the surface of carbon black particles. And it is carbon black which shows insulation, when the volume resistance as a powder is measured by the following methods.

Insulating carbon black is dispersed in propylene glycol monomethyl ether so that benzyl methacrylate and methacrylic acid have a molar ratio of 70:30 copolymer (mass average molecular weight 30,000) and 20:80 mass ratio. Was applied to a chrome substrate having a thickness of 1.1 mm and 10 cm × 10 cm to prepare a coating film having a dry film thickness of 3 μm. The coating film was further heat-treated in an oven at 200 ° C. for 1 hour, and then JISK6911. Is applied with a high resistivity meter manufactured by Mitsubishi Chemical Co., Ltd., Hirestor UP (MCP-HT450), and the volume resistance value is measured in an environment of 23 ° C. and 65% relative humidity. An insulating carbon black having a volume resistance value of 10 ⁶ Ω · cm or more, more preferably 10 ⁸ Ω · cm or more, and particularly preferably 10 ⁹ Ω · cm or more is preferable.

  As the insulating carbon black, for example, JP-A-11-60988, JP-A-11-60989, JP-A-10-330634, JP-A-11-80583, JP-A-11-80584, Resin-coated carbon black disclosed in Kaihei 9-124969 and JP-A-9-95625 can be used.

In addition, carbon black may be appropriately coated with a resin.
In order to coat carbon black with resin (coating resin), a coating base and a solvent are added to carbon black to form a mill base, which is then subjected to a flashing treatment, kneader, ball mill, sand mill, bead mill, two or three roll mill, and extruder. Dispersion treatment is performed by a method such as paint shaker, ultrasonic wave, 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 polymers Polyethylene, polypropylene, polyisobutylene, etc. 2) Diene polymers, polybutadiene, polyisoprene, etc. 3) Polymers having a conjugated polyene structure Polyacetylene polymers, polyphenylene polymers, etc. 4) Vinyl polymers Polyvinyl chloride, polystyrene, vinyl acetate , Polyvinyl alcohol, poly (meth) acrylic acid, poly (meth) acrylic acid ester, polyacrylamide, polyacrylonitrile, polyvinylphenol, etc. 5) polyether polyphenylene ether, polyoxirane, polyoxetane, polytetrahydrofuran, polyether ketone, polyether Ether ketone, polyacetal, etc. 6) Phenol resin, novolac resin, resole 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 Novolac epoxy resin, bisphenol epoxy resin, modified resin with novolac epoxy acrylate and 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 is, for example, a monomer having a carboxyl group such as (meth) acrylic acid, (anhydrous) maleic acid, crotonic acid, itaconic acid, fumaric acid, styrene, α-methyl, etc. Styrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, vinyl acetate, acrylonitrile, (meth) acrylamide, glycidyl (meth) ) Acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, glycidyl crotonic acid ether, (meth) acrylic acid chloride, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-methylol acrylamide, N, N-dimethyl acryl 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 (meth) acrylic acid alkyl ether as a constituent monomer, and more preferred is an acrylic resin containing (meth) acrylic acid and styrene.

Moreover, these resins can also add an ethylenic double bond to the resin side chain. Since the photocurability is increased by imparting a double bond to the resin side chain, it is preferable because the resolution and adhesion can be further improved.
Examples of the synthesis means for introducing an ethylenic double bond include the methods described in JP-B-50-34443 and JP-B-50-34444.
Specific examples include a method of reacting a compound having both a glycidyl group, an epoxycyclohexyl group and a (meth) acryloyl group with a carboxyl group or a hydroxyl group, or acrylic acid chloride. For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (meth) By using a compound such as acrylic acid chloride or (meth) allyl chloride and reacting with a resin having a carboxyl group or a hydroxyl group, a resin having a polymer group in the side chain can be obtained.
In particular, a resin obtained by reacting (3,4-epoxycyclohexyl) methyl (meth) acrylate is preferable.

  In addition, 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 (including the above-described copolymerization component) 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 iso-propyl group, a tert-butyl group, and the like, preferably having 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 which is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution is preferred. As such a linear organic polymer, those having an acid group such as a carboxy group or a phenolic hydroxyl group in the resin side chain or main chain are preferable from the viewpoint of pollution prevention because they can be alkali-developed. 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, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59- A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partial, as described in Japanese Patent No. 53836 and JP-A-59-71048 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, a polymer in which an acid anhydride is added to a polymer having a hydroxyl group is also useful. Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers with benzyl (meth) acrylate / (meth) acrylic acid / and other monomers are also suitable.
In addition, 2-hydroxyethyl methacrylate, polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful as the water-soluble polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, 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 mentioned as 1 to 8 below can also be used.
1. 1. Glycidylamine type epoxy resin 2. Triphenylglycidylmethane type epoxy resin 3. Tetraphenylglycidylmethane type epoxy resin 4. Aminophenol type epoxy resin 5. Diamide diphenylmethane type epoxy resin 6. Phenol novolac type epoxy resin Ortho-cresol type epoxy resin8. Bisphenol A novolac epoxy resin

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

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

  A dispersant is usually used for dispersing the organic pigment and carbon black. As the dispersant, the above-described 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. The resin is adsorbed on the surface of the carbon black by the dispersion treatment, and at the same time, the aggregation of the carbon black particles is broken and the particle size is reduced.

In the present invention, examples of the form of 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, whereby various effects of the present invention, in particular, Developability and image reproducibility are further improved.

  As the dispersant, Anti-Terra-U, Disperbyk-160, 161, 162, 163 manufactured by BYK, Solspers 20000, 24000GR, 26000, 28000 manufactured by ZENECA, DA-703-50, NDC- manufactured by Enomoto Kasei 8194 L, NDC-8203L, NDC-8257L, KS-860, Kaogen's homogenal L-18, L-1820, L-95, L-100, Nippon Paint VP5000, Goodrich E5703P, Known dispersion resins such as VAGH manufactured by Union Carbide, UR8200 manufactured by Toyobo, and MR113 manufactured by Nippon Zeon can be used.

  Moreover, a phthalocyanine derivative (commercial product 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 Chemical Co., Ltd.) and W001 (manufactured by Yusho); polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxy Nonionic surfactants such as ethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester; F-top EF301, EF303, EF352 (manufactured by Shin-Akita Kasei), MegaFuck F171, 172, F173 (Dainippon Ink), Florard FC430, FC431 (Sumitomo 3M), Asahi Guard AG710, Surflon S382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-1068 Fluorosurfactants such as Asahi Glass; 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 (San Nopco); Solsperse 3000, 5000, 9000 12000 13240, 13940, 17000, 24000, 26000, 28000, etc., various Solsperse dispersants (manufactured by Geneca Corporation); 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) are also included.

In the present invention, when the colorant 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 conventionally known dyes for color filters can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 The dyes disclosed in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like can be used.
The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Dyes such as xanthene, phthalocyanine, benzopyran, and indigo 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%, but a type called a transmission type for TVs and monitors, etc., has a high chromaticity year by year, and the colorant content. Is as high as 25-40%. In particular, black as a black matrix further increases the amount of colorant, so that it is difficult to satisfy development characteristics and various physical characteristics.

[3. Alkali-soluble resin]
The alkali-soluble resin in the present invention is preferably an acrylic copolymer having an acid value in the range of 30 to 150 mgKOH / g. In addition, when used in a color filter or CCD, an alkali-soluble resin is preferably one that has no discoloration and is light-resistant.
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”). Is also used.

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

  A preferred structural unit of the acrylic binder resin is a copolymer of (meth) acrylic acid and another monomer that can be copolymerized.

Examples of 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, Examples include pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate, cyclohexyl acrylate, and the like.
Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like. it can.
Particularly preferred other copolymerizable monomers are phenyl (meth) acrylate, benzyl (meth) acrylate and styrene.
These other copolymerizable monomers can be used singly 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 within an allowable range.
Further, the mass average molecular weight Mw (polystyrene conversion value measured by GPC method) of the acrylic binder resin is used to realize a viscosity range that is easy to use in a process such as applying a color resist, and to secure film strength. Therefore, it is preferably 5,000 to 100,000, more preferably 8,000 to 50,000.

In order to set the acid value of the acrylic binder resin within the range specified above, it can be easily performed by appropriately adjusting the copolymerization ratio of each monomer.
Further, the range of the mass average molecular weight can be easily set by using an appropriate amount of a chain transfer agent according to the polymerization method when the monomers are copolymerized.
The acrylic binder resin can be produced, for example, by a known radical polymerization method. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an acrylic binder resin by radical polymerization can be easily set by those skilled in the art, You can also know the conditions experimentally.

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

Among these various resins, the alkali-soluble resin used in the present invention includes polyhydroxystyrene resin, polysiloxane resin, acrylic resin, acrylamide resin, and acrylic / acrylamide copolymer resin from the viewpoint of heat resistance. Acrylic resins, polyhydroxystyrene resins, and polysiloxane resins are more preferable. From the viewpoint of control of developability, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable.
Examples of the acrylic resin include copolymers consisting of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and cyclomer P series, Plaxel CF200 series ( All are manufactured by Taicel Chemical Industry Co., Ltd.), Ebecry 13800 (manufactured by Daicel UCP Co., Ltd.), Dynal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Biscote R-264, KS resist 106 (all of which are Osaka Organic Chemical Industries, Ltd.) And the like are preferable.
In addition, 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 5 to 90% by mass, more preferably 10 to 60% by mass, based on the total solid content of the composition. A sufficient film strength and image density can be obtained within the above range.

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

  Compounds having at least one addition-polymerizable ethylenically unsaturated group and 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, after addition of ethylene oxide or propylene oxide and (meth) acrylate, pentaerythritol or dipentaerythritol poly (meth) acrylate Urethane acrylates such as those described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, Polyfunctional acrylates and methacrylates such as polyester acrylates and epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid, as described in JP-A-49-43191 and JP-B-52-30490 To mention Come. Furthermore, the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308, those introduced as photocurable monomers and oligomers can also be used.

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

  These photopolymerizable monomers or oligomers may be used in any proportion within a range that does not impair the object and effect of the present invention, provided that the photocurable composition can form a coating film having adhesiveness upon irradiation with light. it can. The usage-amount is 5-90 mass% of the total solid of the said photocurable composition, Preferably it is 10-50 mass%. Here, the total solid content refers to the remaining components obtained by removing the solvent from all the components constituting the composition.

Next, the photoinitiator contained in the photocurable composition in this invention is demonstrated.
A conventionally well-known thing can be used as a photoinitiator used in this invention. For example, active halogen compounds such as halomethyloxadiazole compounds described in JP-B-57-6096, halomethyl-s-triazines described in JP-B-59-1281 and JP-A-53-133428, etc. Aromatic carbonyl compounds such as ketals, acetals and benzoin alkyl ethers described in US Pat. No. 4,318,791 and European Patent No. 88050A, and fragrances such as benzophenones described in US Pat. No. 4,199,420. Group ketone compounds, (thio) xanthones, acridine compounds described in French Patent No. 2456741, coumarins, lophine dimer compounds described in JP-A-10-62986, JP-A-8-15521 And the described sulfonium organoboron complexes.

  Specifically, an acetophenone initiator (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 initiators (eg, benzyldimethyl ketal, benzyl-β-methoxyethyl acetal, etc.), benzophenone initiators (eg, benzophenone, 4 , 4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, 1-hydroxy-cyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl)- Thanone-1, 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, etc. ), Benzoin-based and benzoyl-based initiators (eg, benzoinpropyl ether, benzoin butyl ether, benzoin methyl ether, methyl-o-benzoylbenzoate, etc.), xanthone-based initiators (diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, etc. ), Triazine initiators (for example, 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-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o -Bromo-pN, N- (diethoxycarbonylamino) phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (p-N N- (diethoxycarbonylamino) phenyl) -2,6-di (chloromethyl) -s-triazine, etc.), halomethyloxadiazole-based initiators (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 (eg 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, etc.) , 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 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trime Examples include tilphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophospho-trialkylphenylsulfonium salt, 2-mercaptobenzimidazole, 2,2'-benzothiazolyl disulfide and the like.

  In this invention, 0.5 mass%-60 mass% are preferable with respect to the photopolymerizable monomer in a composition, and, as for the compounding quantity of a photoinitiator, More preferably, it is 1 mass%-50 mass%. When the amount of the initiator used is 0.5% by mass or more, polymerization proceeds moderately, and when it is 60% by mass or less, good film strength can be obtained.

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

In the formula, each of R ₁ and R ₂ independently represents 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, particularly as a peroxide. Most preferred are tertiary alkyl groups having 4 to 10 stable carbon atoms, such as t-butyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1-dimethylpentyl and the like. It is done.

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 an alkoxy group having 1 to 5 carbon atoms, or halogenated. An alkyl group, a halogen atom, a cyano group, a nitro group, or a dialkylamino group having 2 to 20 carbon atoms is represented.
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 collected chloromethyl group, a bromomethyl group, a dibromomethyl group, and the like.
Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.
Examples of the dialkylamino group include an N, N-dimethylamino group and an N, N-diethylamino group.
q is 0, 1 or 2, preferably 2.
r is 1, 2 or 3, preferably 2.

  Specific examples of the benzophenone compound of the general formula (III) that can be used in the present invention are not limited, but include 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.
In addition, these compounds can be used individually or in combination of 2 or more types.

  In this invention, 0.5 mass%-20 mass% are preferable with respect to the photopolymerizable monomer in a composition, and, as for the compounding quantity of a thermal-polymerization initiator, More preferably, it is 1 mass%-15 mass%.

In the present invention, in addition to the benzophenone-based peroxide, other organic peroxides can be used as a thermal polymerization initiator. Here, the organic peroxide is a derivative of hydrogen peroxide (H—O—O—H) and refers to an organic compound other than the above general formula (III) having —O—O— bond in the molecule. .
When classified by chemical structure, ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates and the like can be mentioned. Among these organic peroxides, the organic peroxide is preferably an organic peroxide which has a high decomposition temperature and is stable at room temperature, decomposes when heated and generates radicals, and serves as a polymerization initiator.

Examples of 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 Cyl-2,5-bis (benzoylperoxy) hexane, t-hexyl peroxy isopropyl 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 these can be used alone or in combination.
As the organic peroxide, a compound represented by the following general formula (A) is preferable.

In formula (A), R ₁ and R ₂ each independently represents an alkyl group having 1 to 10 carbon atoms.
Examples of the alkyl group having 1 to 10 carbon atoms of R ₁ and R ₂ in the formula (A) 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 with respect to the amount of the photopolymerizable monomer in the photocurable composition. %. Within the above range, good storage stability can be obtained.

[Epoxy compound having two or more functions]
The photocurable composition of the present invention preferably contains a bifunctional or higher functional epoxy compound in addition to the components described above. By using a combination of the imidazole silane compound and the bifunctional or higher functional epoxy compound, it is possible to cure at a low temperature and in a short time, and further excellent in adhesion to the 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 higher functional epoxy compound used in the composition of the present invention is desirably blended with an epoxy compound having an epoxy group number that matches 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 and the epoxy equivalent of the bifunctional or higher epoxy compound in the photocurable composition of the present invention is preferably 0.2 to 6.0, and more preferably 0.5 to 3.5. Moreover, since the NMP resistance can be further improved by increasing the crosslinking density, a polyfunctional epoxy compound having a large number of functional groups is more preferable. In the color filter material for red (R), green (G), and blue (B), alicyclic or aliphatic polyfunctional epoxy is desirable from the viewpoint of heat discoloration, but for 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 by [—O— (A) _m —H] _n from the hydrocarbon R. A represents an alicyclic group having the following structure having at least one epoxy group. m represents 1-100. n represents 1-100. 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 m × n is large, there may be a problem in productivity and storage stability of the photocurable composition. Preferably, m is 2 to 10, n is 3 to 6, and 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 8-20.
A and m in n [-O- (A) m-H] may be the same or different. m × n is the sum of m which may be different from n (m ₁ , m ₂ , m ₃ , ,,, + _mn ), and the sum of A possessed by the polyfunctional alicyclic epoxy compound Represents a number.

  Examples of R hydrocarbons include aliphatic hydrocarbons and aromatic hydrocarbons, with alkanes being preferred. 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.

For example, the above-mentioned compound is an active hydrogen in alcohols, phenols, carboxylic acids (R ″-(OH) n, n is a natural number, R ″ is a monovalent hydrocarbon group), and the like is represented by-(A) m-H. Is replaced with.
As in the Japanese Patent Publication No. 7-119292, as a precursor of A, a compound in which two adjacent carbon atoms constituting an alicyclic ring are bonded to the same oxygen atom to form an epoxy group is represented by R ″. Epoxy ring-opening polymerization is carried out together with the reaction with-(OH) n, and can be synthesized according to the method of forming R [-O- (A) m-H] 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 a methane group, 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 Etc.
R is particularly preferably methane, ethane, n-butane, or n-pentane.

  The compound represented by the general formula R ′ [— O— (A) m—H] n is a commercially available product, specifically, EHPE3150 (2,2-bis (hydroxymethyl) -1 manufactured by Daicel Chemical Industries, Ltd. -Butanol 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct, m = 5 (average), n = 3, m × n = 15, epoxy equivalent 178 g / eq). In the composition of this invention, you may contain 2 or more types of 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 functional 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]
When 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-methoxypropionic acid alkyl esters of; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropyl 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 Chill 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, etc .; aromatic hydrocarbons such as toluene, xyles and the like.

  Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl 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 above-described components, various additives, for example, a filler, a polymer compound other than the alkali-soluble resin, a surfactant other than the above, and an adhesion promoter Antioxidants, ultraviolet absorbers, anti-aggregation agents and the like can be blended.

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 having hydroxyl group, acid anhydride added, alcohol-soluble nylon, bisphenol Alkali-soluble resins such as phenoxy resins formed from A and epichlorohydrin; nonionic, kachin, and anionic surfactants, specifically phthalocyanine derivatives (commercially available 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 Chemical Co., Ltd.), W001 (manufactured by Yusho), etc. 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) Nonionic surfactants such as 25R2, Tetronic 304, 701, 704, 901, 904, and 150R1; Anionic surfactants such as W004, W005, and W017 (manufactured by Yusho); EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 (manufactured by Morishita Sangyo), Disperse Aid 6, Disperse Polymer Dispersants such as Dos 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by Sannopco); Solsols 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000, etc. Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (Asahi Denka) And Isonet S-20 (manufactured by Sanyo Chemical); 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, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4- Antioxidants such as methyl-6-tert-butylphenol) and 2,6-di-tert-butylphenol; 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxy UV absorbers such as benzophenone; And an aggregation inhibitor such as sodium polyacrylate.

  In addition, when promoting the alkali solubility in the unirradiated part and further improving the developability of the composition of the present invention, the composition of the present invention is an organic carboxylic acid, preferably a low molecular weight having a molecular weight of 1000 or less. An organic carboxylic acid can be added. Specifically, 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, glutar Aliphatic dicarboxylic acids such as acid, 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 carbaryl 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, merophanic acid, 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-described components, the photocurable composition of the present invention preferably further contains a polymerization inhibitor in order to suppress a change in viscosity over time at room temperature or refrigerated storage of the resin composition. 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-tert-butylphenol), 2-mercaptobenzimidazole and the like are useful. The storage stability can be improved by adding a thermal polymerization inhibitor to the photocurable composition of the present invention. As a compounding quantity of a polymerization inhibitor, 100 ppm-1 mass% is preferable normally with respect to a photopolymerizable monomer, More preferably, about 500 ppm is added.

[8. Method for producing and using composition of the present invention]
The photocurable composition of the present invention comprises a colorant, an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and other additives used as necessary by mixing them with a solvent. Can be prepared by mixing and dispersing.
The mixing and dispersing step preferably comprises kneading and dispersing followed by fine dispersion treatment, but it is also possible to omit the kneading and dispersion and perform only fine dispersion treatment.

In the kneading and dispersing step, the surface of the colorant particles of the raw material is promoted to wet with the constituent components mainly composed of the resin component of the vehicle, and the solid colorant particles and vehicle solution are solidified 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 to a fine state close to the primary particles by mixing and stirring together with a dispersion medium for fine particles of glass or ceramic. Therefore, in the kneading and dispersing step, it is necessary to convert the interface formed by the surface of the colorant particles from air to a solution. Therefore, a strong shearing force and compressive force are required. On the other hand, in the fine dispersion step, it is necessary to distribute the particles uniformly and stably to a fine state, and a disperser that does not require impact force and shear force on the agglomerated colorant particles is relatively low. It is desirable that the material to be dispersed has a relatively low viscosity.

For example, the kneading and dispersing step for producing a color filter using the photocurable composition of the present invention is first performed with a colorant such as an organic pigment or carbon black and a dispersant or surface treatment agent, an alkali-soluble resin and a solvent. Knead. The machines used for kneading are two rolls, three rolls, ball mills, tron mills, dispersers, kneaders, kneaders, homogenizers, blenders, single-screw and twin-screw extruders, etc., which disperse while giving a strong shearing force. Subsequently, a solvent and an alkali-soluble resin (the remainder used in the kneading step) are added, and mainly a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, high pressure disperser, etc. are used. Disperse with beads made of glass, zirconia or the like having a particle diameter of 1 mm. It is possible to omit this kneading step. 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. Further, after preliminarily dispersing with other dispersing means, further miniaturization is possible by dispersing the colorant particles with a high-pressure disperser. In particular, in a high-pressure disperser having a mechanism for back-pressing a pressurized dispersion, the viscosity of the dispersion does not increase even when the dispersion of the colorant progresses, and the resulting product is excellent in fluidity and applied as a coating liquid. Appropriately good.
Details of kneading and dispersing are described in TC Patton's "Paint Flow and Pigment Dispersion" (published by John Wiley and Sons, 1964) and the like.

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

Drying (pre-baking) can be performed in a hot plate, oven, or the like at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds.
As radiation that can be used in exposure, ultraviolet rays such as g-line and i-line are particularly preferably used.
By performing the alkali development treatment, the light-irradiated portion is eluted in the alkaline aqueous solution by the exposure, and only the photocured portion remains. Any developer can be used as long as it dissolves the light-irradiated portion of the photosensitive layer but does not dissolve the light-irradiated portion.
Next, after the excess developer is washed away and dried, heat treatment (post-bake) is performed at a temperature of 50 ° C. to 240 ° C. Thus, the said process can be repeated sequentially for every color, and a cured film can be manufactured. Thereby, a color filter is obtained.

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

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

Raw materials for plastic substrates include (1) amorphous polyolefin, (2) polyethersulfone, (3) polyglutarimide, (4) polycarbonate, and (5) polyethylene terephthalate in terms of optical properties, heat resistance, mechanical strength, etc. , (6) polyethylene naphthalate, (7) norbornene polymer, (8) polyimide using bisaniline fluorene as a diamine component, and (9) polyester composed of bisphenol fluorene and dibasic acid. Among these, (2) polyethersulfone, (4) polycarbonate, (5) polyethylene terephthalate, and (7) norbornene polymer are preferable. Such raw materials are particularly preferred for LCD applications.
The properties required for plastic substrates include low thermal expansion (preventing deterioration of display accuracy associated with the curing process during color filter creation), gas barrier properties (ensuring liquid crystal stability), optical transmittance and optical isotropy, etc. Characteristics, surface smoothness, etc. Regarding thermal expansion, the thermal expansion coefficient is preferably 10 ⁻⁴ or less.
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 radiation irradiated portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.
Examples of the organic solvent include the aforementioned solvents used in 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 bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxy Concentrations of alkaline compounds such as do, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene are 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. In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it wash | cleans (rinse) with water after image development.

The post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 200 ° C. to 220 ° C. is performed.
In this post-baking treatment, the coating film after development is continuously applied using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a far-infrared heater, a high-frequency heater or the like so as to satisfy the above conditions. Or it can carry out by a batch type.
In a normal color filter manufacturing process, pre-baking is continued for 2-3 minutes / sheet on a hot plate, but the thermosetting (post-baking) process is about 10 minutes / sheet for a hot plate. Since it takes a long time, many hot plates are required for continuation, and it is inefficient, so heat curing (post-baking) is performed using a batch-type multi-stage convection oven to achieve in-line operation. is doing. (See FIG. 1A.) However, in this method, there is a large loss at the start and stop of operation of the line (the degree of curing of the coated substrate in the middle of curing in the multistage oven when the operation is stopped halfway). And the multi-stage oven itself consumes a great deal of heat energy and space. By using the photocurable composition of the present invention, it is possible to continuously post-pake using a hot plate at the same speed as the pre-bake (see FIG. 1 (b)), immediate operation, and pause. Space saving and energy saving are possible.

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

  Various components for color filters can be applied to spacers, protective layers, contact hole forming layers, etc. in addition to the color filter body (colored layer) and the black matrix. Furthermore, the photocurable composition of the present invention can be used as a sealing agent for potting of COB (chip on board) or a sealing agent for LCD, in addition to the above-mentioned various components for color filters.

  An overcoat layer (planarization layer) is usually provided on the color filter layer obtained using the photocurable composition of the present invention. Examples of the resin (OC agent) that forms the overcoat layer include an acrylic resin composition, an epoxy resin composition, and a polyimide resin composition. Above all, it is excellent in transparency in the visible light region, and the resin component of the photocurable composition for color filters is usually composed mainly of an acrylic resin and has excellent adhesion, so that the acrylic resin composition Things are desirable. In particular, a photo-curable (meth) acrylic resin for a photoresist used in a color filter is preferable because matching with the manufacturing process of the color filter is improved.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

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

Determination of curability and adhesion to the substrate:
a) Determination of curability was determined by immersing in N-methylpyrrolidone (hereinafter abbreviated as NMP) at 50 ° C. for 10 minutes, measuring the chromaticity change before and after, and expressing the color difference ΔE * ab, where ΔE * ab ≦ 3 There was no problem.
b) Adhesion to the substrate was determined by visual observation to what extent the film was not peeled off the substrate in the NMP immersion test, and the following evaluation was performed.
A: The film is not peeled off at all.
B: The film is not peeled off, but is partially lifted.
C: The film is peeled off by about 50%, but the chromaticity change can be measured.
NG: The film is completely peeled and chromaticity cannot be measured.
In addition, low-temperature curability and adhesion evaluation are performed for Examples 1 to 9 and Comparative Examples 1 to 4, and rapid curability and adhesion evaluation are performed only for Examples 1, 4, 8 and 9 and Comparative Examples 1 to 4. It 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 adding the imidazole silane-based compound is clear, the curing of the coating film is greatly promoted, and even if the addition amount is reduced, the effect is hardly lowered.
Although the effect of addition of BTTB was observed, it was smaller than that of imidazole silane. For example, as is clear from FIG. 3, ΔE * ab ≦ 3 in Example 1 under the curing conditions of 135 ° C. × 60 minutes. Moreover, it turned out that the one where the functional group number of the alicyclic epoxy selected is higher is better from the comparison between Example 3 and Example 9. Furthermore, as is clear from Table 3 and FIG. 3, in Comparative Example 3 and Comparative Example 4, the effect of adding each of imidazole and epoxysilane alone was hardly observed.

Further, from Table 3 and FIG. 3, it can be seen that the same results as the low temperature curability are obtained for the rapid curability and the influence on the curing of the imidazole silane is 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 formulation table of Table 1 was applied to a non-alkali glass for liquid crystal panels (Corning 1737) with a spin coater to a dry film thickness of 1.2 μm, and solvent drying was performed on a 120 ° C. hot plate for 120 seconds. It was. Next, using a HITACHI exposure machine LE4000A, red, green, and blue are masks with a line width of 20 μm, black is a mask with a line width of 15 μm, and a proximity gap of 300 μm is exposed at 100 mJ / cm ² (illuminance: 20 mW / cm ² And developed at 26 ° C. with a 1.0% diluted developer of alkali developer CDK-1 manufactured by Fuji Film Arch. The development margin and development latitude at this time are represented by a graph of line width change with respect to development time. The results are shown in Table 4 and FIG. Here, the development margin is a change in line width with respect to the development time, and the development latitude is the time from pattern development to pattern peeling. FIG. 4 is a graph of the main ones from Table 4.

  As is apparent from Table 4 and FIG. 4, the comparative example has no constant line width with respect to the development time, and thus it is difficult to obtain a constant image. Examples can obtain good development properties.

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 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
・ Propylene glycol monomethyl ether acetate 78.5g
・ Fluorine-based nonionic surfactant (* 2) 0.02g
・ Japan Energy Imidazolesilane, IM-1000 0.1g
* 1) Legal manufactured by Cabot Corporation (particle size: 31 nm, pH: 9, DBP oil supply amount: dispersion of 42 ml / 100 g of carbon (carbon content is 45% of solid content in the above solution))
* 2) Copolymer of 60% N-butylperfluorooctanesulfonamidoethyl acrylate and 40% poly (oxyalkylene) acrylate

  This photosensitive resin solution was developed in the same manner as in Examples 1 to 10, and the development 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 imidazolesilane compound (IM-1000) was not used, and evaluated under the same conditions as in Example 11.
[Comparative Example 6]
Implemented except that 0.1 g of imidazole silane compound (IM-1000), 0.1 g of silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403 (3-glycidoxypropyltrimethoxysilane) was used. A black matrix was produced in the same manner as in Example 11, and evaluated under the same conditions as in Example 11.
[Comparative Example 7]
Instead of using 0.1 g of imidazole silane compound (IM-1000), 0.1 g of silane coupling agent, KBM-402 (3-glycidoxypropylmethyldiethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. was used. A black matrix was produced 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 3- (methacryloxypropyl) trimethoxysilane was used instead of 0.1 g of the imidazolesilane compound (IM-1000). And evaluated under the same conditions.
[Comparative Example 9]
Instead of 0.1 g of imidazole silane compound (IM-1000), 0.1 g of silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd., and 0.1 g of KBE-04 (tetraethoxysilane) were used. A black matrix was prepared and evaluated under the same conditions as in Example 11.
[Comparative Example 10]
Instead of 0.1 g of imidazole silane compound (IM-1000), 0.1 g of silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd., and 0.1 g of KBM-1003 (vinyltriethoxysilane) were used. A black matrix was prepared and evaluated under the same conditions as in Example 11.
The formulation 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, C.I. I. Pigment Green 36 (PG36) /C.I. I. A green light curable composition was prepared in the same manner as in Example 10 except that the pigment yellow 150 (PY150) (mass ratio 100/58) was changed to 5.79 parts.
Photocurable blue (B) 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, C.I. I. A blue light curable composition was prepared in the same manner as in Example 10 except that the pigment blue 15: 6 (PB15: 6) was changed to 4.28 parts.
Photocurable black composition (photocurable composition for black matrix): Black composition of Example 11.

The said photocurable black composition was apply | coated so that it might become a dry film thickness of 1.1 micrometers using the board | substrate which wash | cleaned the alkali free glass substrate (Corning 1737) for liquid crystal panels with 1 mass% sodium hydroxide aqueous solution, and a spin coater. After solvent drying at 120 ° C. for 120 seconds, exposure was performed at 100 mJ / cm ² through a 15 μm line width mask using an exposure machine LE4000A manufactured by HITACHI, and an alkali developer CDK-1 of 1.0 manufactured by Fuji Film Arch Co., Ltd. was used. When developed with a% developer at 26 ° C. for 100 seconds, a clear black pattern image (black matrix) was obtained. Subsequently, after rinsing with running water for 20 seconds, it was dried with an air knife, and heat-treated at 220 ° C. for 60 minutes with a hot-air circulating dryer to obtain a black matrix substrate.
Next, using a mask having a pixel size of 100 μm corresponding to the black matrix as a mask, each color was sequentially applied in the order of red → green → blue to form a pattern image to obtain a color filter.
That is, using the same apparatus and developer as in the black matrix formation except for the mask, the photocurable red composition was applied to a dry film thickness of 1.2 μm, and after solvent drying, passed through a 100 μm pixel size mask to 100 mJ. / Cm ² exposure and development for 100 seconds. Next, heat treatment was performed at 220 ° C. for 60 minutes to form a red pattern image (red pixel). Similarly, the green pattern image (green pixel) and the blue pattern image (blue pixel) are sequentially shifted in position with the same mask, and are exposed alternately in red, green, and blue, and the development conditions are 80 seconds to A stable and clear pixel was formed in 120 seconds. Further, when observed with an optical microscope, pixel defects, color overlap, color mixing, and color removal were not found.

The schematic diagram showing the in-line of the multistage convection oven in a color filter manufacturing process is shown. It is a figure which shows the graph which showed the influence on the low temperature curability of an Example and a comparative example composition. It is a figure which shows the graph which showed the influence on the rapid curability of an Example and a comparative example composition. It is a graph which shows the developability evaluation result of an Example and a comparative example composition. It is a graph which shows the developability evaluation result of an Example and a comparative example composition.

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 for a color filter , which is ˜70% by mass and contains an imidazolesilane 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 for a color filter 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 represents 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 photocuring for a color filter according to claim 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. Coloring resin 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 are each independently carbon. The alkyl group of number 1-3 is represented, n represents 1-3. The photocurable coloring resin composition for a color filter according to any one of claims 1 to 3, wherein the colorant is a black colorant. The photocurable colored resin composition for a color filter according to claim 4, wherein the black colorant is carbon black. The photocurable coloring resin composition for color filters of any one of Claims 1-5 containing a bifunctional or more epoxy compound. The photocurable coloring resin composition for color filters of Claim 6 containing a thermal polymerization initiator. The photocurable colored resin composition for a color filter according to claim 7, wherein the thermal polymerization initiator is an organic peroxide. The photocurable colored resin composition for a color filter 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 or aralkyl group having 1 to 20 carbon atoms, and R ₃ and R ₄ each independently represent a hydrogen atom, a carboxyl group, or an alkyl having 1 to 10 carbon atoms. Group, 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, q is 0, 1 or 2 And r is 1, 2 or 3. The photocurable colored resin composition for a color filter 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 solution comprising the photocurable coloring resin composition for a color filter according to any one of claims 1 to 10 is applied on a substrate, formed into a film, and then exposed and developed by a photolithography method to obtain a single color. A color filter created by repeating the pattern forming process for each color.

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