KR101051645B1 - Photocurable colored resin composition for color filters and color filter using the same - Google Patents

Abstract

(Problem) A sight in which a color filter having no development residue, further improving development margin and development characteristics of the development latitude, and having excellent adhesiveness and solvent resistance by heat curing treatment (post bake) at a short time and / or low temperature is obtained. It is providing a chemical conversion colored resin composition.

(Solution means) In the photocurable colored resin composition containing a coloring agent, alkali-soluble resin, a photopolymerization monomer, and a photoinitiator, content of the said coloring agent in solid content of the said photocurable colored resin composition is 10-70 mass%, Moreover, the photocurable colored resin composition characterized by containing an imidazolesilane compound.

Description

PHOTOCURABLE COLORED RESIN COMPOSITION FOR COLOR FILTER AND COLOR FILTER PREPARED USING THE SAME}

BRIEF DESCRIPTION OF THE DRAWINGS The schematic diagram which shows inlining of the multistage convection oven in a color filter manufacturing process.

2 is a graph showing the effect on the low temperature curability of the Example and Comparative Example compositions.

3 is a graph showing the effect of rapid curing properties of the Example and Comparative Example compositions.

4 is a graph showing the results of evaluation of developability of Examples and Comparative Example compositions.

5 is a graph showing the results of evaluation of developability of Examples and Comparative Example compositions.

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

The color filter is usually coated on a substrate with a photocurable colored resin composition mainly composed of a colorant, an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a solvent, drying (prebaking), pattern exposure, alkali development, and thermosetting treatment. It is obtained by forming a predetermined pixel pattern by a series of (post-baking) steps, and repeating the above steps for each color such as red (R), green (G), and blue (B). The heat curing treatment (post-baking) in the manufacturing process of the color filter is performed to impart durability and strength as the pixel pattern film as a permanent film, and by heat promoting the curing of the resin component in the film composition by heat. Durability, such as mechanical strength, solvent resistance, and light resistance, can be improved.

Compared with CRT, color liquid crystal display devices are compact and equivalent in performance, and have recently made great progress as televisions, personal computer screens, display units of mobile phones, and other display devices. The color filter is an essential component of such a color liquid crystal display device.

On the other hand, since the glass substrate is normally used for the conventional color liquid crystal display device, adhesiveness with a photocurable coloring resin composition is not very good, and when developing time is too short for image development with alkaline developing solution, there exists a tendency for many residues to become large. In addition, since the pattern peeling easily occurs when the developing time is too long, it is necessary to perform the development under a very limited developing time range in the present state. For this reason, there is a problem that a constant pattern shape cannot be obtained unless not only the development time but also the developer concentration and the temperature are not sufficiently limited and carefully restricted.

Therefore, how wide the allowable range of development time greatly affects the process titration of the color filter.

It is also known to use an imidazole silane compound in order to improve the adhesion of the film, but in the prior art, even if the adhesion is good, the development margin (the length of time with little change in line width with respect to the development time) or the development latitude (developing) The development characteristics such as the ratio of the change of the line width to time and the problem of the development residue are not effective because they are in a trade off relationship. For example, Patent Document 1 (Japanese Patent Application Laid-open No. Hei 10-186657) discloses that imidazolesilane is contained in a photocurable composition for improving the adhesion of a resin film for photoresist use. Although the case where it is not made into a component and may add dye and a pigment is described, it is only described as a well-known technique added in order to impart a simple color of a photoresist composition. As described above, since the original development characteristics are good as the transparent film containing no coloring component, the effect of adding imidazole silane to the development characteristics is not exhibited, and no attention is paid to this effect.

In addition, in order to improve the production effect of a color filter conventionally, the development of the photocurable composition which can fully heat-cure (post-bak) at low temperature or a short time is calculated | required, As a material of the color filter known so far, We could not respond to such a request. In particular, in order to obtain a color filter excellent in durability as a permanent film, it is necessary to promote thermosetting of the resin by heating in the final step. However, in a curable composition for a conventional color filter, at least one temperature is at least 200 ° C. I needed a close treatment.

As mentioned above, in the photocurable composition for color filters, in order to obtain the permanent coating film excellent in durability, a thermosetting component is essential and epoxy resin and melamine resin were common as the component. For example, Japanese Patent No. 2,937,208, Japanese Patent Laid-Open No. 2-42371 and Japanese Patent Laid-Open No. 6-1938 disclose photocurable compositions for color filters containing epoxy resins.

On the other hand, in the field of resist materials, an imidazole silane compound and an epoxy resin composition are known as a hardening | curing agent. For example, Patent Document 2 (Japanese Patent Laid-Open No. 9-12683), Patent Document 3 (Patent Publication 2001-187836), and Patent Document 4 (Japanese Patent Laid-Open No. 2002-128872) include an imidazole silane compound An epoxy resin composition containing is disclosed. Among these, Patent Document 2 is used as an adhesive, a sealant, a coating material, a laminated material, and a molding material that require adhesion, and Patent Document 3 is used as an electronic material, a paint, a primer, and an adhesive agent. As sealant applications, each useful one is disclosed. However, none of these patent documents describe the use of color filters.

Moreover, the said photosensitive resin composition containing the imidazole silane compound is disclosed by the said patent document 1, and it is disclosed that this composition is useful as a resist material use. However, the above patent relates to a coating resist of a printed circuit board, and the resist material using imidazole silane is a photocurable resin composition which improves adhesion with a copper foil substrate, and when the coating is finished, the used resist is removed and thermally cured. It is not. Therefore, the composition did not contain a thermosetting resin such as an epoxy resin.

As mentioned above, in the photocurable composition for color filters, the hardening process at the low temperature applicable also to a plastic substrate is calculated | required, and while giving a color filter the characteristic of high mechanical strength, adhesiveness, and solvent resistance as a permanent coating film, In response to the increase in the substrate area and the mass production, in order to increase the production efficiency, there has been a strong demand for a thermosetting treatment (post bake) or a short time thermosetting treatment (post bake) at a lower temperature.

An object of the present invention is to provide a photocurable colored resin composition having no development residue and improved development characteristics of the development margin and development latitude, and a color filter using the same.

Another object of the present invention is to provide a photocurable colored resin composition in which a color filter excellent in adhesiveness and solvent resistance is obtained by a thermosetting treatment (post bake) at a short time and / or at a low temperature.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors discovered that the outstanding image development characteristic was obtained by adding an imidazole silane compound to the colorant-containing photocurable composition for color filters, and also the thermosetting property is further contained by containing an epoxy compound more than bifunctional. It has been found to be improved and has reached the completion of the present invention.                     

That is, according to this invention, the photocurable colored resin composition and color filter of the following structures are provided and the said objective is achieved.

1. In the photocurable colored resin composition containing a colorant, alkali-soluble resin, a photopolymerizable monomer, and a photoinitiator, content of the said coloring agent in solid content of the said photocurable colored resin composition is 10-70 mass%, and already The photocurable colored resin composition further containing a dazolesilane compound.

2. The imidazole silane compound according to 1 above, wherein 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 derivative compounds thereof. The photocurable colored resin composition.

[In formula, R <^1> represents a hydrogen atom or a C1-C20 alkyl group, and R <^2> and R <^3> represents a hydrogen atom, a vinyl group, or a C1-C5 alkyl group each independently.)

(In formula, R <^4> and R <^5> represents a C1-C3 alkyl group each independently, m shows the integer of 1-20, n shows the integer of 1-3. "

3. Said 1 or 2 WHEREIN: The said imidazole silane type compound consists of at least 1 sort (s) chosen from the compound represented by following General formula (1)-(3), and / or its derivative compound. Chemically 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 each independently represent 1 to 3 carbon atoms. Is an alkyl group, and n represents 1 to 3.)

4. The photocurable colored resin composition according to any one of 1 to 3, wherein the colorant is a black colorant.

5. The photocurable colored resin composition according to the above 4, wherein the black colorant is carbon black.

6. Photocurable colored resin composition in any one of said 1-5 containing bifunctional or more than one epoxy compound.

7. The photocurable colored resin composition according to the above 6, which contains a thermal polymerization initiator.

8. The photocurable colored resin composition according to the above 7, wherein the thermal polymerization initiator is an organic peroxide.

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

(In formula, R <_1> and R <_2> respectively independently represents a C1-C20 alkyl group or an aralkyl group, R <_3> and R <_4> respectively independently represents a hydrogen atom, a carboxyl group, a C1-C10 alkyl group, and C1-C1 An alkoxy group of 10 to 10, a halogenated alkyl group of 1 to 10 carbon atoms, a halogen atom, a cyano group, a nitro group or a dialkylamino group of 2 to 20 carbon atoms, q is 0, 1 or 2, and r is 1, 2 or 3 to be.)

10. The photocurable colored resin composition according to the above 9, wherein the benzophenone organic peroxide is at least one of the compounds represented by the following formulas (1) to (5).

11. The process of apply | coating the coating liquid which consists of photocurable colored resin composition in any one of said 1-10 on a board | substrate, forming a film, and exposing and developing by photolithographic method, and forming a monochromatic pattern. A color filter, which is produced by repeating a for each color.                     

Hereinafter, each component used for the photocurable colored resin composition (henceforth a "photocurable composition") of this invention, and the color filter using the said composition are demonstrated.

[One. Imidazolesilane compound]

The photocurable composition of this invention contains an imidazole silane compound, It is characterized by the above-mentioned. As the imidazole silane compound, an imidazole silane compound and / or a derivative compound 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), are preferable. Is used.

The imidazole compound, the epoxy silane compound and the imidazole silane compound will be described in detail below.

(a) imidazole compound

Examples of the imidazole compound represented by the general formula (I) in the present invention include imidazole, 2-alkylimidazole, 2,4-dialkylimidazole, 4-vinylimidazole, and the like. Among these, especially preferable 2-alkylimidazole is 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, etc .; Moreover, 2-ethyl-4-methylimidazole etc. can be mentioned as 2, 4- dialkyl imidazole.

(b) epoxysilane-based compounds

As an epoxysilane type compound represented by the said General formula (II) in this invention, 3-glycidoxy propyl trialkoxysilane, 3-glycidoxy propyl dialkoxyalkylsilane, 3-glycidoxy propyl alkoxydialkyl There are silanes, and particularly preferred among these are 3-glycidoxypropyl trialkoxysilane, such as 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl triethoxysilane, and 3-glycidyl silane. Examples of the doxypropyl dialkoxyalkylsilane include 3-glycidoxypropyl dimethoxymethylsilane, and examples of the 3-glycidoxypropyl alkoxydialkylsilane include 3-glycidoxypropyl ethoxydimethylsilane.

(c) imidazole silane compounds

As an imidazole silane compound which is a reaction product of the imidazole compound represented by the said General formula (I) in this invention, and the epoxy silane compound represented by the said General formula (II), Specifically, Japanese patent publication The compound represented by following formula (1)-(3) described in Unexamined-Japanese-Patent No. 7-68256 is mentioned.

In formula, R <^1> represents a hydrogen atom or a C1-C20 alkyl group, R <^2> represents a hydrogen atom, a vinyl group, or a C1-C5 alkyl group, R <^3> and R <^4> respectively independently represents C1-C3 An alkyl group is represented and n represents 1-3.

As imidazole silane type compound which can be used by this invention, the imidazole silane, IM-1000, IS-1000, YA-100, IC-100P, IA-100P etc. by Japan Energy Corporation are mentioned as a commercial item, for example. do. It is preferable that these compounding quantities are 0.01 mass% or more in solid content, More preferably, it is 0.1-1 mass%.

[2. coloring agent]                     

As a coloring agent which can be used for this invention, a conventionally well-known various pigment, (insulating) carbon black, and dye can be used 1 type or in mixture of 2 or more types.

As a pigment which can be used for this invention, a conventionally well-known various inorganic pigment or organic pigment can be used. In addition, considering that the pigment is preferably an inorganic pigment, an organic pigment or a high transmittance, the use of the finest one is preferable, but considering the handleability, the average particle size is preferably 0.01 µm to 0.1 µm, more preferably. The pigment of 0.01 micrometer-0.05 micrometers is used. As an inorganic pigment, it is a metal compound represented by metal oxide, metal complex salt, etc., Specifically, Metal oxide, such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and the said metal complex Oxides may be enumerated.

As an organic pigment,

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

C.I. Pigment Orange 36, 38, 43, 71;

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

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

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

C.I. Pigment Green 7, 36, 37;

C. I. Pigment Brown 25, 28;                     

C.I. Pigment Black 1, 7;

And the like.

In this invention, what has basic N atom can especially be used preferably in the structural formula of a pigment. The pigment which has these basic N atom shows favorable dispersibility in the composition of this invention. Although the cause is not fully elucidated, it is presumed that the affinity between the photosensitive polymerization component and the pigment is good and influenced.

Among the various pigments described above, the pigments that can be used more preferably in the present invention may be listed below, but are not limited thereto.

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

C.I. Pigment Orange 36, 71,

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

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

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

C.I.Pigment Black 1

These organic pigments are used alone or in various combinations to increase color purity. A specific example is shown below. Examples of the red pigment include anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or one or more of these and disazo yellow pigments, isoindolin yellow pigments, quinophthalone yellow pigments or perylene red pigments. And mixing and the like are used. For example, as an anthraquinone pigment, C.I. As Pigment Red 177, a perylene pigment, C.I. Pigment Red 155, C.I. As Pigment Red 224, a diketopyrrolopyrrole pigment, C.I. Pigment Red 254 is listed, and C.I. Pigment Yellow 83, or C.I. Mixing with Pigment Yellow 139 is preferred. As for the mass ratio of a red pigment and a yellow pigment, 100: 5-100: 50 are preferable. By setting it as 100: 5 or more, the light transmittance of 400 nm-500 nm can be suppressed, and color purity can be improved. In addition, by setting it as 100: 50 or less, the dominant wavelength becomes a short wavelength set and the deviation from the NTSC target color can be suppressed. Especially the range of 100: 10-10: 30 is the most preferable. In the case of the combination of red pigments, it adjusts according to chromaticity.

As the green pigment, a halogenated phthalocyanine pigment alone or a mixture of disazo yellow pigments, quinophthalone yellow pigments, azomethine yellow pigments or isoindolin yellow pigments is used. For example, C.I. Pigment Green 7, 36, 37 and C.I. Pigment Yellow 83, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180 or C.I. Mixing with Pigment Yellow 185 is preferred. As for the mass ratio of a green pigment and a yellow pigment, 100: 5-100: 150 are preferable. By setting it as 100: 5 or more, the light transmittance of 400 nm-450 nm can be suppressed, and color purity can be improved. Moreover, by setting it as 100: 150 or less, the dominant wavelength becomes a short wavelength set, and the deviation from NTSC target color can be suppressed. More preferable mass ratio is in the range of 100: 30 to 100: 120.

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

In addition, a pigment-containing photosensitive resin having good dispersibility and dispersion stability can be obtained by using a powdery processing pigment obtained by finely dispersing the pigment with an acrylic resin, a maleic acid resin, a vinyl chloride-vinyl acetate copolymer, an ethyl cellulose resin, or the like. .

As the colorant for the black matrix, a black colorant is used, for example, carbon black, titanium carbon, iron oxide, titanium oxide alone or mixed, and carbon and titanium carbon are preferable. The mass ratio is preferably in the range of 100: 0 to 100: 60. If it is in the said range, favorable dispersion stability will be obtained.

Examples of the carbon black that can be used as the coloring agent according to the present invention include, for example, carbon black # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, and # 950 manufactured by Mitsubishi Chemical Corporation. , # 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 N 220M, Diamond Black N 234, Diamond Black I, Diamond Black LI, Diamond Black II, Diamond Black N 339, Diamond Black SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF , Diamond Black N 550M, Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N 760M, Diamond Black LP,

Carbon Black Thermomax N990, N991, N907, N908, N990, N991, N908, made by CanCurve Co., Ltd.                     

Carbon black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, made by Asahi carbon Co., Ltd. Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi thermal, Degusa Kabushikisha carbon black Color Black Fw200, Color Black Fw2V, Color Black Fw2V, Color Black Fw1, Color Black Fw18, Color Black S170, Color Black S160, Special Black 6, Special Black 5, Special Black 4, Special Black 4A, Printex U, Printex V, Printex 140U, Printex 140V, and the like.

The insulating carbon black in the present invention is one having an organic compound on the surface of the carbon black particles, such as organic matter adsorbed, coated or chemically bonded (grafted) on the surface of the carbon black particles. When the volume resistance as a powder is measured, it is carbon black which shows insulation.

The insulating carbon black was dispersed in propylene glycol monomethyl ether so as to form a benzyl methacrylate and methacrylic acid in a molar ratio of 70:30 copolymer (mass average molecular weight 30,000) and 20:80 mass ratio to prepare a coating solution, and the thickness was 1.1. After coating on a chromium substrate of 10 mm × 10 cm, producing a coating film having a dry film thickness of 3 μm, and further heat-treating the coating film at 200 ° C. in an oven for 1 hour, Mitsubishi Chemical Corporation complies with JISK 6911. A high resistivity meter, Hirester UP (MCP-HT450) was applied, and the volume resistivity value was measured under an environment of 65% relative humidity at 23 ° C. And as this volume resistance value, the insulating carbon black which shows 10 <^6> Pa * cm or more, More preferably, it is 10 <^8> Pa * cm or more, Especially preferably, 10 <^9> Pa * cm or more is preferable.

As insulating carbon black, for example, Unexamined-Japanese-Patent No. 11-60988, Unexamined-Japanese-Patent No. 11-60989, Unexamined-Japanese-Patent No. 10-330643, Unexamined-Japanese-Patent No. 11-80583, Japan Patent Publication The resin-coated carbon black disclosed in Japanese Patent Application Laid-Open Nos. 11-80584, 9-124969 and 9-95625 can be used.

Other carbon blacks may be coated with a suitable resin.

To coat the carbon black with a resin (coating resin), a coating base and a solvent are added to the carbon black to make a mill base, which is brushed or kneaded, ball mill, sand mill, bead mill, two or three roll mills, extrusion Dispersion is performed by a molding machine, a paint shaker, an ultrasonic wave, a homogenizer, or the like. These treatment methods can also be combined 2 or more. If necessary, a dispersant for uniformly dispersing the carbon black can be used.

As coating resin, the following are mentioned, for example.

1) polyolefin polymer

Polyethylene, polypropylene, polyisobutylene, etc.

2) diene polymer

Polybutadiene, polyisoprene, etc.                     

3) polymer with conjugated polyene structure

Polyacetylene polymer, polyphenylene polymer, etc.

4) vinyl polymer

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, polyetherketone, polyetheretherketone, polyacetal, etc.

6) phenolic resin

Novolac resin, resol resin, etc.

7) polyester

Polyethylene terephthalate, 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 resins and their modified substances

Novolak epoxy resin, bisphenol epoxy resin, novolak epoxy acrylate and modified resin by acid anhydride, etc.

11) Other

Polyurethane, polyimide, melamine resin, urea resin, polyimidazole, polyoxazole, polypyrrole, polyaniline, polysulfide, polysulfone, cellulose

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, fmaric acid, styrene, α-methylstyrene, or (meth) acrylic acid. Methyl, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, vinyl acetate, acrylonitrile, (meth) acrylamide, glycidyl (meth) acrylate, allyl Glycidyl ether, ethyl acrylate glycidyl, crotonic acid glycidyl ether, (meth) acrylic acid chloride, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-metholacrylamide, N, N The polymer which copolymerized copolymerization components, such as -dimethylacrylamide, N-methacryloyl morpholine, N, N- dimethylaminoethyl (meth) acrylate, and N, N-dimethylaminoethyl acrylamide, is mentioned. Among them, preferred are acrylic resins containing at least (meth) acrylic acid or (meth) acrylic acid alkyl ether as the constituent monomer, and more preferably acrylic resins containing (meth) acrylic acid and styrene.

Moreover, these resin can also add ethylenic double bond to a resin side chain. Since a photocurability becomes high by providing a double bond to a resin side chain, since resolution and adhesiveness can be improved further, it is preferable.

As a synthetic means which introduce | transduces an ethylenic double bond, the method etc. which were described in Unexamined-Japanese-Patent No. 50-34443, Unexamined-Japanese-Patent No. 50-34444, etc. are mentioned, for example.

Specifically, the method of making the carboxyl group and the hydroxyl group react with the compound, acrylic acid chloride, etc. which have glycidyl group, an epoxycyclohexyl group, and a (meth) acryloyl group, etc. are mentioned. For example, (meth) glycidyl acrylate, allyl glycidyl ether, (alpha)-ethyl acrylate glycidyl, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, (3, 4- epoxycyclohexyl) Resin which has a polymerization group in a side chain can be obtained by making it react with resin which has a carboxyl group or a hydroxyl group using compounds, such as methyl (meth) acrylate, (meth) acrylic acid chloride, and (meth) allyl chloride.

In particular, resin in which (3,4-epoxycyclohexyl) methyl (meth) acrylate is reacted is preferable.

Moreover, the polymer obtained by the copolymerization reaction of the monomer represented by the following general formula (X) and the monomer which has at least a hydroxyl group (the copolymerization component mentioned above can be enumerated) can also be used.

(Wherein R represents a hydrogen atom or a methyl group, and R ₁ to R ₅ each independently represent a group selected from a hydrogen atom, a halogen atom, a cyano group, an alkyl group and an aryl group.)

Here, examples of the halogen atom include Cl, Br, I and the like.

Examples of the alkyl group include a linear, branched or cyclic methyl group, n-propyl group, iso-propyl group, tert-butyl group, etc., and those having 1 to 7 carbon atoms are preferable. As an aryl group, a phenyl group, a furyl group, a naphthyl group, etc. are mentioned.

Moreover, the following resin can also be used as coating resin.

It is preferable that it is a linear organic high polymer, it is soluble in the organic solvent, and can develop in a weak alkali aqueous solution. As such linear organic polymer, what has an acidic group, such as a carboxyl group or a phenolic hydroxyl group, in a resin side chain or a main chain is alkali-developable, and is preferable from a viewpoint of pollution prevention. In particular, resins having a carboxyl group, such as acrylic acid (co) polymers, styrene / maleic anhydride resins, acid anhydride modified resins of novolac epoxy acrylates, and the like are preferred because they are highly alkaline developable. As a polymer which has a carboxylic acid in a side chain, For example, Unexamined-Japanese-Patent No. 59-44615, Unexamined-Japanese-Patent No. 54-34327, Unexamined-Japanese-Patent No. 58-12577, and Japan Patent No. 54-25957. The methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partial described in Unexamined-Japanese-Patent No. 59-53836 and Unexamined-Japanese-Patent No. 59-71048. Esterified maleic acid copolymers, and the like, and acidic cellulose derivatives having a carboxylic acid in the side chain in the same form. In addition, addition of an acid anhydride to a polymer having a hydroxyl group is also useful. Among these, a benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / and a multicomponent copolymer with other monomers are also preferable.

In addition, 2-hydroxyethyl methacrylate, polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. are also useful as a water-soluble polymer. Moreover, alcohol-soluble nylon, the polyether of 2, 2-bis- (4-hydroxyphenyl) propane, epichlorohydrin, etc. are also useful by raising the intensity | strength of a hardened film. These polymers may be mixed in any amount.

Moreover, the epoxy resins listed as following 1-8 can also be used.

1. Glycidylamine type epoxy resin

2. Triphenyl glycidyl methane epoxy resin

3. Tetraphenylglycidyl methane epoxy resin

4. Aminophenol Type Epoxy Resin

5. Diamide diphenylmethane type epoxy resin

6. Phenolic novolac type epoxy resin

7. Orthocresol type epoxy resin

8. Bisphenol A novolac type epoxy resin

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

The range with preferable mass average molecular weight (weight average molecular weight) Mw measured by the gel permeation chromatography (GPC) of these coating resins is 1,000-300,000, More preferably, it is 3,000-150,000. By setting it as 300,000 or less, favorable developability is obtained.

A dispersant is usually used for dispersion of the said organic pigment and carbon black. In addition to using the said coating resin as it is for a dispersing agent, the dispersing agent mentioned later can be used together. These dispersing agents can be used individually or in combination of two or more. When the resin is adsorbed on the surface of the carbon black by the dispersion treatment, the aggregation of the carbon black particles is destroyed at the same time, and the particle size is made fine.

In the present invention, examples of the carbon black coated with the resin include powder, paste, pellet, paste, sheet, and the like.

The preferred average particle diameter of the carbon black coated with the resin is in the range of 0.003 to 0.5 µm, more preferably in the range of 0.005 to 0.3 µm, thereby making the various effects of the present invention particularly excellent in developing and image reproducibility. .

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

Furthermore, phthalocyanine derivative (commercially available EFKA-745 (made by Morishita Sangyo)); Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), methacrylic acid-based (co) polymer polyflow No. 75, No. 90, no. Cationic surfactants such as 95 (manufactured by Yugyo Kagaku Kogyo Co., Ltd.) and W001 (manufactured by Yusho); Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan aliphatic Nonionic surfactants such as esters; F-Top EP301, EP303, EP352 (manufactured by Shin-Akita Kasei), Mega Pack F171, F172, F173 (manufactured by Dainippon Ink), Florid FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Supron S382, SC- Fluorine surfactants such as 101, SC-102, SC-103, SC-104, SC-105, and SC-1068 (made by 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, EFKA 401, EFKA Polymer 450 (made by Morishita Sangyo), Disperse Ade 6, Disperse Ade 8, Disperse Ade 15, Disperse Polymer dispersants such as ADE 9100 (manufactured by Sanofko); Various solvent dispersants such as Solsper's 3000, 5000, 9000, 12000, 13240, 13940, 17000, 24000, 26000, 28000 (manufactured by Geneca Co., Ltd.); Adekaplanic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 (made by Asahi Denka) and Isonet S- 20 (made by Sanyokasei) etc. are also listed.

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

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

Examples of the chemical structure include pyrazole azo, anilinoazo, triphenylmethane, anthraquinone, anthripyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridoneazo, cyanine, phenothiazine and pi Dye, such as a rolopyrazole azomethine series, a xanthene series, a phthalocyanine series, a benzopyran series, an indigo series, can be used.

Content of the coloring agent in the photocurable composition in this invention is 10-70 mass% in solid content except a solvent component, and content of a coloring agent changes with uses of a color filter. For example, a type called a reflective type such as a mobile phone has a good colorant content of about 20%, but a type called a transmissive type such as a TV or a monitor has a high chromaticity every year, and the colorant content is increased to 25 to 40%. have. In particular, since black as the black matrix has a larger amount of colorant, it becomes difficult to satisfy the development time and various physical properties.

[3. Alkali-soluble resin]

As alkali-soluble resin in this invention, the acrylic copolymer whose acid value exists in the range of 30-150 mgKOH / g is preferable. In addition, when used for a color filter or CCD, it is preferable that alkali-soluble resin does not have discoloration property and is light resistance.

As a preferable alkali-soluble resin, the acrylic copolymer (henceforth "acrylic binder resin") whose acid value is the range of 30-150, Preferably 35-120 (mg KOH / g polymer) is used for the composition of this invention. do.

The acrylic binder resin can be used without particular limitation so long as it is an acrylic copolymer that satisfies the acid value and is dissolved in a solvent to be described later and forms a film to function as a binder resin.

As a structural unit of preferable acrylic binder resin, the copolymer of the other monomer copolymerizable with (meth) acrylic acid is mentioned.

As another monomer copolymerizable with (meth) acrylic acid, an alkyl (meth) acrylate, an aryl (meth) acrylate, a vinyl compound, etc. are mentioned. Here, the hydrogen atom of an alkyl group and an aryl group may be substituted by the substituent.                     

As a specific example of the said alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) ) Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate, cyclohexyl acrylate, etc. Can be enumerated.

Moreover, as said vinyl compound, styrene, (alpha) -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, a polystyrene macromonomer, Polymethyl methacrylate macromonomer etc. can be mentioned.

Particularly preferred other copolymerizable monomers are phenyl (meth) acrylate, benzyl (meth) acrylate and styrene.

These other copolymerizable monomers can be used individually by 1 type or in combination of 2 or more types.

Especially preferable acrylic binder resin is a copolymer of (meth) acrylic acid and 1 or more types of monomers chosen 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 mg KOH / g. By setting the acid value to 150 or less, a good developing proper range (developing latitude) is obtained. On the other hand, by setting it as 30 or more, developing time can be made into the tolerance range.                     

In addition, the mass average molecular weight (Mw) (polystyrene conversion value measured by the GPC method) of the acrylic binder resin is used to secure the film strength in order to realize an easy-to-use viscosity range in a process such as applying a color resist. For this reason, it is preferable that it is 5,000-100,000, More preferably, it is 8,000-50,000.

In order to make the acid value of acrylic binder resin into the range specified above, it can carry out easily by adjusting the copolymerization ratio of each monomer suitably.

In addition, in making the range of a mass average molecular weight into the said range, when copolymerizing a monomer, it can carry out easily by using the chain transfer agent which concerns on a polymerization method in an appropriate quantity.

Acrylic-based binder resin can be manufactured by the radical polymerization method known by itself, for example. The polymerization conditions such as the temperature, pressure, the kind and amount of the radical initiator, the kind of the solvent, and the like when the acrylic binder resin is produced by the radical polymerization method can be easily set by those skilled in the art, and the conditions can also be known experimentally.

Moreover, in order to improve crosslinking efficiency, you may have a polymeric group in a side chain, and the polymer etc. which contained an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in a side chain are also useful as alkali-soluble resin in this invention. Although the example of the polymer containing these polymerizable groups is shown below, if alkali-soluble group and carbon carbon unsaturated bonds of bases, such as a COOH group, an OH group, and an ammonium group, are contained, it will not be limited to the following. Epoxy ring and carbon-carbon unsaturated bond group having reactivity with an OH group in a copolymer of, for example, 2-hydroxyethyl acrylate having a OH group and a monomer such as an acrylic or vinyl compound copolymerizable with methacrylic acid containing a COOH group A compound having, for example, a compound obtained by reacting a compound such as glycidyl acrylate can be used. In the reaction with OH, in addition to the epoxy ring, a compound having an acid anhydride and an isocyanate group and having an acryloyl group can also be used. In addition, saturated or unsaturated polybasic anhydrides are added to a compound obtained by reacting an unsaturated carboxylic acid such as acrylic acid with a compound having an epoxy ring disclosed in JP-A-6-102669 or JP-A-6-1988. The reactant obtained by making it react can also be used. Examples of the compound having both an alkali solubilizer and a carbon carbon unsaturated group, such as COOH, include, for example, Diamond NR series (manufactured by Mitsubishi Rayon Co., Ltd., acid value: 25 KOH mg / g, polyacrylic (meth) acrylate), and Photomer 6173 (COOH-containing polyurethane). acrylic oligomer, manufactured by Diamond Sharmrock Co., Ltd.), biscoat-264, KS resist 106 (all made by Osaka Organic Chemical Industries, Ltd.), cyclomer P series, Fraxel CF200 series (all, Daicel Kagaku) And Ebecry 13800 (manufactured by Daicel Corp., Inc., acid value: 25 KOH mg / g, acid functional epoxy acrylate).

Among these various resins, as the alkali-soluble resin used in the present invention, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable from the viewpoint of heat resistance. , Acrylic resins, polyhydroxystyrene resins, and polysiloxane resins are more preferable. Moreover, acrylic resin, acrylamide resin, and acryl / acrylamide copolymer resin are preferable from a viewpoint of developability control.                     

As said acrylic resin, the copolymer which consists of a monomer chosen from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, etc., and cyclomer P series, Fraxel CF200 series (All manufactured by Daicel Kagaku Kogyo Co., Ltd.), Ebecry13800 (manufactured by Daicel Yushipi Co., Ltd.), diamond NR series (made by Mitsubishi Rayon Co., Ltd.), biscot R-264, KS resist 106 (all Osaka) Organic Kagaku Kogyo Co., Ltd.) etc. are preferable.

Moreover, alcohol soluble nylon, the polyether of 2, 2-bis- (4-hydroxyphenyl) propane, epichlorohydrin, etc. are also useful in order to raise the intensity | strength of a hardened film.

In the composition of this invention, it is preferable that the quantity of alkali-soluble resin is 5-90 mass% of the total solid of a composition, More preferably, it is 10-60 mass%. Sufficient film strength and image density are obtained within this range.

[4. Photopolymerizable monomer, photopolymerization initiator, and thermal polymerization initiator]

As a photopolymerizable monomer used for the photocurable composition of this invention, the compound which has an ethylenically unsaturated group which has a boiling point of 100 degreeC or more under normal pressure which has one or more addition-polymerizable ethylene group is preferable.

Polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, etc. as a compound which has one or more addition-polymerizable ethylenically unsaturated groups and whose boiling point is 100 degreeC or more at normal pressure. Monofunctional acrylates and methacrylates; Polyethylene glycol di (meth) acrylate, trimethylol ethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, di Pentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, glycerin or trimethylol ethane (Meth) acrylated after addition of ethylene oxide or propylene oxide to polyfunctional alcohols; poly (meth) acrylated of pentaerythritol or dipentaerythritol, Japanese Patent Publication No. 48-41708 Urethane acrylates described in Japanese Patent Application Laid-Open No. 50-6034, Japanese Patent Laid-Open No. 51-37193, and Japanese Patent Publication No. 48-64183 The polyester acrylates described in Japanese Patent Application Laid-Open No. 49-43191, Japanese Patent Laid-Open No. 52-30490, and the like, and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acids. Functional acrylate and methacrylate can be mentioned. In addition, the Japan Adhesive Society Association Vol. 20, No. It is also possible to use those introduced as photocurable monomers and oligomers on 7, 300 to 308 pages.

Furthermore, after adding ethylene oxide or propylene oxide to the above-mentioned polyfunctional alcohol, the (meth) acrylated compound is represented by the general formulas (1) and (2) in JP-A-10-62986. It is described with an example, and these can also be used as the photopolymerizable monomer.

These photopolymerizable monomers or oligomers can be used in arbitrary ratio as long as the said photocurable composition can form the coating film which has adhesiveness by irradiation of light, and does not impair the objective and effect of this invention. The usage-amount is 5-90 mass% of the total solid of the said photocurable composition, Preferably it is 10-50 mass%. Here, total solid means the remaining component except the solvent from the all components which comprise a composition.

Next, the photoinitiator contained in the photocurable composition in this invention is demonstrated.

In this invention, a conventionally well-known thing can be used as a photoinitiator used. For example, halomethyloxadiazole compounds disclosed in JP-A-57-6096, halomethyl-s-triazine and the like described in JP-A-59-1281 and JP-A-53-133428. Aromatic carbonyl compounds, such as ketal, acetal, and benzoin alkyl ether, such as an active halogen compound, US Patent 4318791 specification, and European Patent 8880A specification, aromatic ketone compounds, such as the benzophenols described in US Pat. (Thio) xanthones, acridine compounds described in the specification of French Patent No. 2456741, coumarins, ropin dimer compounds described in Japanese Patent Application Laid-Open No. 10-62986, Japanese Patent Application Laid-Open No. 8-15521 The sulfonium organoboron complexes etc. which were described are mentioned.

Specifically, an acetophenone type initiator (for example, 2, 2- diethoxy acetophenone, p-dimethylamino acetophenone, 2-hydroxy-2-methyl-1- phenyl- propane- 1-one, p-dimethylamino Acetophenone, 4'-isopropyl-2-hydroxy-2-methyl-propionphenone, and the like, ketal initiators (eg, benzyldimethyl ketal, benzyl-β-methoxyethylacetal, etc.), benzophenone initiators (eg, , Benzophenone, 4,4 '-(bisdimethylamino) benzophenone, 4,4'-(bisdiethylamino) benzophenone, 4,4'-dichlorobenzophenone, 1-hydroxycyclohexylphenylketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2- Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 and the like), benzoin and benzoyl initiators (e.g., benzoinpropyl ether, benzoin butyl ether, benzoin methyl ether, methyl -o-benzoylbenzoether and the like), xanthone initiator (di Ethyl thioxanthone, diisopropyl thioxanthone, monoisopropyl thioxanthone, chlorothioxanthone, etc., a triazine initiator (e.g., 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-dimethyl Aminophenyl) -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-benoxoxolane-2,6-di (trichloromethyl ) -s-triazine, 4- (o-bromo-pN, N- (diethoxycarbonylamino) phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (pN, N -(Diethoxycarbonylamino) phenyl) -2,6-di (chloromethyl) -s- Triazine and the like), halomethyloxadiazole-based initiators (e.g., 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1 , 3,4-oxodiazole, 2-trichloromethyl-5- (naphtho-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) Styryl-1,3,4-oxodiazole, etc.), acridines initiators (e.g., 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, etc.), coumarins initiators (e.g. , 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl) amino ) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, etc.), ropindimer initiators (for example, 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-diphenyl Midazolyl dimers, etc.), 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, o-benzoyl-4 '-(benzmercapto) benzoyl-hexyl-ketoxime, 2 , 4,6-trimethylphenylcarbonyl-diphenylphosphonyl oxide, hexafluorophosphoro-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, they are 1 mass%-50 mass%. By using the amount of the initiator at 0.5% by mass or more, the polymerization proceeds appropriately, and by setting it at 60% by mass or less, good film strength is obtained.

It is preferable to contain a thermal polymerization initiator further in the photocurable composition in this invention. Whereas the photopolymerization initiator mainly has an effect of initiating photocuring, the thermal polymerization initiator is a polymerization initiator for thermal polymerization having an effect of heat curing (post-baking) the color filter film or the pixel protective film film after development. .

As the thermal polymerization initiator, organic peroxides are preferable. Among the organic peroxides, benzophenone organic peroxides represented by the following general formula (III) are particularly preferable.

In the formulas, R ₁ and R ₂ each independently represent an alkyl group or aralkyl group having 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, more preferably 4 to 10 carbon atoms, and in particular, 4 to 4 carbon atoms that are stable as peroxides. The tertiary alkyl group which has ten is the most preferable, For example, a t-butyl group, a 1, 1- dimethylpropyl group, a 1, 1- dimethylbutyl group, a 1, 1- dimethyl pentyl group, etc. are mentioned.

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 a 1 to 5 carbon atoms, a halogenated alkyl group, a halogen atom, A cyano group, a nitro group, or a C2-C20 dialkyl amino group is shown.

Examples of the alkyl group include methyl group, ethyl group, propyl group and butyl group.

As an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, butoxy group, etc. are mentioned.

Examples of the halogenated alkyl group include chloromethyl group, dichloromethyl group, adopted chloromethyl group, bromomethyl group, dibromomethyl group and the like.

Examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.

Examples of the dialkylamino group include N, N-dimethylamino group, N, N-diethylamino group and the like.

q is 0, 1 or 2, Preferably it is 2.

r is 1, 2 or 3, Preferably it is 2.

As a specific example of the benzophenone type compound of general formula (III) which can be used by this invention, although it is not specified, the compound of following (1)-(5), 3,3 ', 4,4'-tetra (isopropyl) Cumylperoxide) 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-butyl Peroxycarbonyl) benzophenone, 3,4,4'-tri (t-amylperoxycarbonyl) benzophenone, 3,4,4'-tri (t-hexylperoxycarbonyl) benzophenone, 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-butylperoxycarbonyl) benzophenone, 4-diethyla Mino-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-butylperoxy Carbonyl) benzophenone, 4-dimethylamino-3 ', 4'-di (t-butylperoxycarbonyl) benzophenone, 4-diethylamino-3', 4'-di (t-butylperoxycarbon Bonyl) benzophenone, 4-cyano-3 ', 4'-di (t-butylperoxycarbonyl) benzophenone, 4-methyl-3', 4'-di (t-butylperoxycarbonyl) benzo Phenone, 4-ethyl-3 ', 4'-di (t-butylperoxycarbonyl) benzophenone, 4-cyclohexyl-3', 4'-di (t-butylperoxycarbonyl) benzophenone, 4 -Nitro-3 ', 4'-di (t-butylperoxycarbonyl) benzophenone and the like.

Among the above-mentioned, the compound of said (1)-(5) is especially 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, they are 1 mass%-15 mass%.

In the present invention, in addition to the benzophenone peroxide, other organic peroxides can be used as the thermal polymerization initiator. Here, the organic peroxide is a derivative of hydrogen peroxide (H-O-O-H), has an -O-O- bond in the molecule, and refers to an organic compound other than the general formula (III).

Classification by chemical structure includes ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy ester, peroxydicarbonate and the like. Among these organic peroxides, preferably, the decomposition temperature is somewhat high and stable at room temperature. The organic peroxide is an organic peroxide that decomposes when heat is applied to generate radicals and becomes a polymerization initiator.

Examples of such organic peroxides include benzoyl peroxide, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, and 1,1-bis (t-hexylperoxy) -3,3,5 -Trimethylcyclohexane, t-butylperoxybenzoate, dit-butylperoxybenzoate, dit-butylperoxyisophthalate, t-butylperoxy acetate, t-hexyl peroxybenzoate, t-butylper Oxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, 2,5-dimethyl- 2,5-bis (m-toluylperoxy) hexane, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-hexyl peroxy isopropyl monocarbonate, t-butylperoxy isobutyrate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, 2,5-dimethyl-2,5-bis (2-ethylhexanoylperoxy Hexane, t-butylperoxy-2-ethylhexa Et, t-butylperoxymaleic acid, cyclohexanone peroxide, methyl acetoacetate peroxide, methyl hexanonperoxide, acetylacetone peroxide, 1,1-bis (t-hexylproxy) -3,3,5-trimethyl Cyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butyl Peroxy) -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-tetramethylbutylhydroperoxide, cumene hydroperoxide, t-butylhydroperoxide and the like. These can also be used 1 type or in combination of 2 or more types.

As an organic peroxide, the compound represented with the following general formula (A) is preferable.

In formula (A), R <_1> and R <_2> represents a C1-C10 alkyl group each independently.

As a C1-C10 alkyl group of R <_1> , R <_2> in Formula (A), for example, a methyl group, an ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptane Tyl 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-hex The actual group, i-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group, t-decanyl group, etc. are mentioned.

In this invention, 2 or more types of organic peroxide can be contained as a thermal polymerization initiator.

It is preferable that content in the composition of an organic peroxide is 0.5-20 mass% with respect to the quantity of the photopolymerizable monomer in a photocurable composition, More preferably, it is 1-15 mass%. Within this range, good storage stability is obtained.

[5. Bifunctional or higher epoxy compounds]

It is preferable to add to the above-mentioned component to the photocurable composition of this invention, and to contain an epoxy compound more than bifunctional. By using the said imidazole silane compound and the bifunctional or more epoxy compound in combination, it becomes possible to harden at low temperature and a short time, and also it is excellent also in adhesiveness and solvent resistance with a board | substrate. In particular, it has a remarkable effect on the solvent resistance of polar solvents such as NMP (N-methylpyrrolidone).

It is preferable that the bifunctional or more functional epoxy compound used for the composition of this invention mix | blends the epoxy compound of epoxy group number according to the base number of alkali-soluble resin which has a carboxyl group contained in a composition.

0.2-6.0 are preferable and, as for the base equivalent of alkali-soluble resin in the photocurable composition of this invention, and the epoxy equivalent ratio of a bifunctional or more functional epoxy compound, 0.5-3.5 are more preferable. Moreover, since NMP resistance can be made more favorable by increasing a crosslinking density, the epoxy compound with many functional groups and many functional groups is more preferable. In addition, in the color filter material for red (R), green (G), and blue (B), an alicyclic or aliphatic polyfunctional epoxy is preferable from the viewpoint of heat discoloration, but it is suitable for black for black matrix (BM). Since the heat discoloration does not become a problem, a polyfunctional epoxy such as a novolac type may be used.

As such an epoxy compound, an alicyclic epoxy compound is preferable, More preferably, it is a polyfunctional alicyclic epoxy compound represented by a following formula.

R '[-O- (A) _m -H] _n

In the formula, R 'represents a moiety excluding n hydrogen atoms in which [-O- (A) _m -H] _n is substituted from 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 2-100, and some A may be same or different.

m × n is 2 to 100. When m x n is large, problems may occur in productivity or storage stability of the photocurable composition. Preferably m is 2-10, n is 3-6, m * n is 6-60, m is 3-6, n is 3-6, and mxn has 8-36 more preferable, and mx As for n, 8-20 are especially preferable.

A and m in n (-O- (A) _m -H) may be same or different. It is m × n, n of the total of good or different m (m _1, m _2, m _3, m + _n ,,,,), and represents the total number of A with which the polyfunctional cycloaliphatic epoxy compound.

R may include aliphatic hydrocarbons and aromatic hydrocarbons as the hydrocarbon, and is preferably alkane. The hydrocarbon as R may have a substituent in addition to [O- (A) _m -H] _n . As such a substituent, a hydroxyl group, a carboxyl group, a halogen, -CN, etc. are mentioned.

The compound is obtained by substituting-(A) mH for active hydrogen in alcohols, phenols, carboxylic acids (R &quot;-( OH) _n , n is natural water, R " monovalent hydrocarbon group) and the like.

As Japanese Unexamined Patent Publication No. Hei 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, and R ″-( It can be synthesize | combined according to the method of forming an R (-O- (A) _m- H] _{n by} carrying out epoxy ring-opening polymerization with reaction with OH) _n .

R in the above is preferably alkane having 1 to 10 carbon atoms.

Examples of alkanes having 1 to 10 carbon atoms include methane, ethane, n-propane, n-butane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and i-propane , i-butane, t-butane, i-pentane, t-pentane, i-hexane, t-hexane, i-heptane, t-heptane, i-octane, t-octane, i-nonane, t-decane and the like Listed.

Especially preferred as R are methane, ethane, n-butane, or n-pentane.

The compound represented by said general formula R '[-O- (A) _m- H] _n is a commercial item specifically, EHPE3150 (2, 2-bis (hydroxymethyl) -made by Daicel Chemical Industries, Ltd. 1,2-epoxy-4- (2-oxyranyl) cyclohexane adduct of 1-butanol, m = 5 (average), n = 3, m × n = 15, epoxy equivalent 178 g / eq) have. In the composition of this invention, you may contain 2 or more types of polyfunctional alicyclic epoxy compounds.

As functional group number of the polyfunctional alicyclic epoxy compound used in this invention, Preferably it is four or more, More preferably, it is six or more, Especially preferably, it is ten or more.

As content of the said bifunctional or higher epoxy compound in the composition of this invention, Preferably it is 1-30 mass%, More preferably, it is 2-25 mass%, Most preferably, 5-15 mass% of solid content of a composition.

[6. solvent]

When preparing the photocurable composition of this invention, a solvent is used normally.

Examples of the solvent include, for example, esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoam acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, and alkyl esters. Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, methoxyacetate, methoxyacetate, ethoxyacetic acid methyl, ethoxyacetate, methyl 3-oxypropionate 3-oxypropionate alkyl esters, such as 3-oxyethyl propionate; Methyl 3-methoxy propionate, 3-methoxy ethylpropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-methoxy Methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxo-2-methylpropionate, ethyl 2-oxy-2-methylpropionate , 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxo moiety Methyl carbonate, ethyl 2-oxobutyrate and the like; Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, and the like; Aromatic hydrocarbons such as toluene, xylene and the like.

Among them, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, and 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 thereof.

[7. Other ingredients]

In the photocurable composition of the present invention, in addition to the components described above, various additives such as fillers, polymer compounds other than the alkali-soluble resins, surfactants other than those described above, adhesion promoters, antioxidants, ultraviolet absorbers, anti-agglomerating agents, etc. may be necessary. 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, addition of acid anhydride to a polymer having a hydroxyl group, formed from alcohol soluble nylon, bisphenol A and epichlorohydrin Alkali-soluble resins such as phenoxy resins; Surfactants such as nonionics, cationics and anionics, specifically phthalocyanine derivatives (commercially available EFKA-745 (manufactured by Morishita Sangyo)); Organosiloxane Polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) crylic acid-based (co) polymer polyflow Nos. 75, No.90, No.95 (manufactured by Kyoiisha Yuji Kagaku High School), W001 (Yushou) Cationic surfactants such as production); Polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid Ester (nonionic surfactants such as BASF, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1; W004, W005, W017 ( Anionic surfactants such as Yusho Yu), EFKA-46, EFKA-47, EFKA-47EA, EFKA Polymer 100, EFKA Polymer 400, EFKA Polymer 401, EFKA Polymer 450 (above, manufactured by Morishita Sangyo), and Disperse Ade 6 Polymer dispersants such as Disperse Ade 8, Disperse Ade 15, and Disperse Ade 9100 (manufactured by Sanofco); Solsper Dispersant (Geneca Kabushigaki) Manufactured by Isha); 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 Kasei); vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyl Methyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyl Dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacrylooxypropyltrimethoxysilane Adhesion promoters, such as 3-mercaptopropyltrimethoxysilane, antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; -(3-t-butyl-5-methyl-2-hydroxyphenyl) -5-cle Ultraviolet absorbers such as rorobenzotriazole and alkoxybenzophenone; And anti-agglomerating agents such as sodium polyacrylate.

In addition, when promoting alkali solubility of the non-irradiated portion and further developing 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 organic carboxylic acid having a molecular weight of 1000 or less. May be added. Specifically, For example, aliphatic monocarboxylic acids, such as formic acid, acetic acid, propionic acid, butyric acid, gil acetic acid, pivalic acid, capronic acid, diethyl acetic acid, enanthic acid, caprylic acid; Oxalic acid, maronic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, schweric acid, azelaic acid, sebacic acid, brasyl acid, methylmaronic acid, ethylmaronic acid, dimethylmaronic acid, methylsuccinic acid, tetramethylsuccinic acid, Aliphatic dicarboxylic acids such as citraconic acid; Aliphatic tricarboxylic acids such as tricarbaric acid, aconitic acid and camphoronic acid; Aromatic mono carboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelic acid and mesitylene acid; Aromatic polycarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; Other carboxylic acids such as phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamic acid, methyl cinnamic acid, cinnamic acid benzyl, cinnamylidene acetic acid, coumalic acid and umberic acid Listed.

In addition to the above components, it is preferable to further add a polymerization inhibitor to the photocurable composition of the present invention in order to suppress the change in viscosity over time during normal temperature or cold storage of the resin composition, for example, hydroquinone, p-methoxyphenol, Di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis ( 4-methyl-6-t-butylphenol), 2-mercaptobenzoimidazole and the like are useful. By adding a thermal polymerization inhibitor to the photocurable composition of this invention, the storage safety can be improved. As a compounding quantity of a polymerization inhibitor, 100 ppm-1 mass% are preferable with respect to a photopolymerizable monomer normally, More preferably, about 500 ppm is added.

[8. Method for producing and using the composition of the present invention]

The photocurable composition of this invention can be prepared by mixing and disperse | distributing a coloring agent, alkali-soluble resin, a photopolymerizable monomer, a photoinitiator, and other various additives and dispersers which mix the other additive used as needed with a solvent.

In addition, the mixing and dispersing step preferably comprises a kneading dispersion and a microdispersion treatment performed subsequently. However, the kneading dispersion may be omitted and only the microdispersion treatment may be performed.

In the kneading dispersion step, the particle surface of the raw material colorant is promoted to be wetted with the constituent mainly composed of the resin component of the vehicle, and the colorant particles and the vehicle solution are separated from the solid / gas interface between the colorant particles and the air. Convert to a solid / solution interface.

In the fine dispersion step, the colorant particles are dispersed to a minute state close to the primary particles by mixing and stirring together with the medium for dispersing fine particles of glass or ceramic. Therefore, in the kneading dispersion step, since the interface formed by the colorant particle surface needs to be converted from air to a solution, strong shear force compressive force is required, and the kneader and the kneaded material suitable for it are preferably of high viscosity. In the dispersing step, it is necessary to apply the particles uniformly and stably to a minute state, and the disperser and the relatively low dispersion to be dispersed are preferably low viscosity so that impact force and shear force are unnecessary on the aggregated colorant particles.                     

Using the photocurable composition of the present invention, for example, a kneading dispersion step for producing a color filter is first kneaded with a colorant such as an organic pigment or carbon black, a dispersant or a surface treatment agent, an alkali-soluble resin and a solvent. The machines used for kneading are two rolls, three rolls, ball mills, tron mills, dispersers, kneaders, kneaders, homogenizers, mixers, single- and twin-screw extruders, etc., and disperse with strong shearing force. Subsequently, a solvent and alkali-soluble resin (residue used in the kneading process) are added, and a glass having a particle diameter of 0.1 to 1 mm, mainly using a longitudinal or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic dispersion machine, a high pressure dispersion machine, Disperse it into beads as much as possible, such as zirconia. In addition, this kneading process can also be omitted. In that case, bead dispersion is performed with a pigment and a dispersing agent or a surface treating agent, an alkali-soluble resin and a solvent. In this case, it is preferable that the alkali-soluble resin remaining in the kneading step is added during the dispersion. In addition, by preliminarily dispersing with other dispersing means, further finer is possible by dispersing the colorant particles with a high pressure disperser. In particular, as a high-pressure disperser having a mechanism for backing the pressurized dispersion liquid, even if dispersion of the colorant proceeds, the viscosity of the dispersion liquid does not become high, so that the obtained one is excellent in fluidity and excellent in coating titration as a coating liquid.

For details on kneading and dispersion, see T.C. Patton, "Paint Flow and Pigment Dispersion" (published by John Wiley and Sons, 1964).

The photocurable composition of this invention is apply | coated and dried (prebaked) by application | coating methods, such as spin coating (spin coat), slit coating, cast coating, roll coating, on a board | substrate directly or another layer, and a cured composition layer The film was exposed by a photolithography method through a predetermined mask pattern, and only the coated film portion irradiated with light was cured and developed with an alkaline developer to form a colored patterned film of one color. By repeatedly performing each color (three or four colors), a color filter can be manufactured.

Drying (prebaking) can be carried out in a hot plate, oven, or the like at 10 to 300 seconds at a temperature of 50 ℃ to 140 ℃.

In the case of exposure, as radiation which can be used, especially ultraviolet rays, such as g line | wire and i line | wire, are used preferably.

By performing the alkali development treatment, the tailings irradiated portion is eluted with an aqueous alkali solution by the exposure, leaving only the photocured portion. As the developing solution, any one can be used as long as it dissolves the photosensitive layer of the tailings irradiation section and does not dissolve the light irradiation section.

Subsequently, the excess developer is washed off, dried, and then heated (post-baked) at a temperature of 50 ° C to 240 ° C. Thus, a cured film can be manufactured by repeating the said process for every color one by one. As a result, a color filter is obtained.

In addition, the slit coating method is, as disclosed in Japanese Patent Laid-Open No. 6-339656, Japanese Patent Laid-Open No. Hei 11-90295, and the like. A coating head having a length corresponding to the coating width is maintained at a clearance of 10 to several 100 microns with the substrate to maintain the substrate and the coating head at a constant relative speed, and is supplied from the slit at a predetermined discharge amount. It is a method of apply | coating a coating liquid on a board | substrate. The slit coating method has less liquid loss than the spin coat, less scattering of the coating liquid, less washing process, no remixing of the scattered liquid component into the coating film, and no stop time to start the rotation. It has a number of advantages, such as easy to apply to a large substrate, which can shorten the time (tact time), in particular, has been expected in the future as a coating method in a color filter for a large screen liquid crystal display device. In addition, the high-pressure dispersion-treated liquid having the above-mentioned back pressure mechanism has a low viscosity as the coating liquid and excellent flow characteristics of the liquid, regardless of whether the dispersion unit of the colorant particles is ultrafine, and therefore is optimal for the slit coating. It can be set as a phosphorus photocurable colored resin composition.

Examples of the substrate include alkali-free glass, soda glass, pyrex glass, quartz glass, and a transparent conductive film attached thereto, and photoelectric conversion element substrates, for example, silicon substrates, etc., used in solid-state imaging devices. Listed. Plastic substrates are also possible. On these board | substrates, the black stripe which isolate | separates each pixel is formed normally.

As a raw material of a plastic substrate, it is (1) amorphous polyolefin, (2) polyether sulfone, (3) poly glutarimide, (4) polycarbonate, (5) polyethylene terephthalate from an optical characteristic, heat resistance, mechanical strength, etc. And (6) polyethylene naphthalate, (7) norbornene polymer, (8) polyimide containing bisaniline fluorene as diamine component, (9) polyester comprising bisphenol fluorene and dibasic acid, and the like. Among these, (2) polyether sulfone, (4) polycarbonate, (5) polyethylene terephthalate, and (7) norbornene polymer are preferable. The raw material is particularly preferable for LCD applications.

The properties required for the plastic substrate include low thermal expansion (prevention of display deterioration due to curing treatment at the time of color filter creation), gas barrier properties (securing liquid crystals), optical properties such as light transmittance and optical isotropy, surface smoothness, and the like. There is this. Regarding thermal expansion, the thermal expansion coefficient is preferably 10 ^-4 or less.

In addition, 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 this invention is generally 0.3-5.0 micrometers, Preferably it is 0.5-3.5 micrometers, More preferably, it is 1.0-2.5 micrometers.

As the developing solution, any composition can be used as long as it dissolves the photocurable composition of the present invention and does not dissolve the radiation irradiation section. Specifically, a combination of various organic solvents and an alkaline aqueous solution can be used.

As an organic solvent, the above-mentioned solvent used when preparing the composition of this invention is mentioned.

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

As alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide The concentration of the alkaline compound such as seed, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene is 0.001-10% by mass, preferably 0.01-1% by mass An alkaline aqueous solution dissolved to be% is used. In addition, when the developing solution which consists of such alkaline aqueous solution is used, generally, after image development, it wash | cleans (rinses) with water.

Post-baking is the heat processing after image development, in order to make hardening complete, and usually performs the thermosetting process of 200 degreeC-220 degreeC.

This post-baking process is performed continuously or batchwise using heating means, such as a hotplate, a convection oven (hot air circulation dryer), a far-infrared heater, and a high frequency heater, so that the coating film after image development may be said conditions. can do.

In the normal color filter manufacturing process, the prebaking is continued in the hot plate for 2-3 minutes / one sheet, but the heat curing (post-baking) portion is about 10 minutes / 1 sheet for the hot plate. Since the sequencing requires several hot plates and is inefficient, thermal curing treatment (post bake) is performed using a batch type multi-stage convection oven to achieve inline (see Fig. 1 (a)). ). However, in this method, the loss at the start of the line and the stop of operation is large (stopping the operation in the middle prevents the degree of curing of the coated substrate during the curing in the multistage oven) or the multistage type. Another problem is that the oven itself consumes a very large amount of thermal energy and space. By using the photocurable composition of the present invention, post-baking can be carried out at the same speed as the pre-baking by using a hot plate (see Fig. 1 (b)), immediately starting and stopping, and also space-saving. And energy savings are possible.

In the present invention, the thermal curing is heat-treated at a short time or relatively low temperature, and meets the required characteristics such as physical properties, chemical properties, etc., which can be crosslinked by heating with an alkali-soluble resin in a color filter. Various thermosetting reactions are combined by the selection of highly reactive epoxy resins, the optimization of functional groups, or by the addition of imidazolesilanes having a curing promoting action even with the epoxy resins alone. That is, it becomes possible to harden | cure at low temperature conventionally, and also the direct color filter to the plastic substrate which requires the heat processing of 150 degrees C or less which was impossible until now is attained. Using the photocurable colored resin composition of the present invention, it is not necessary to employ a complicated process of performing a conventionally employed plastic substrate, once forming a color filter on the glass substrate and then transferring it to the plastic substrate, Color filters can be created directly on plastic substrates. In addition, in the color filter of a normal glass substrate, if it is post-baking by the conventional multistage convection oven by short time hardening at high temperature, oven water can be reduced by half, space-saving, energy saving, and thermal efficiency By using this far-infrared heating furnace or a hot plate, it is possible to continue at the same speed as the pre-baking (see Fig. 1 (b)), immediately start and stop, and improve productivity and yield.

As various component parts for color filters, it is applicable to a spacer, a protective layer, a contact hole forming layer, etc. other than the said color filter main body (coloring layer) and a black matrix. Moreover, the photocurable composition of this invention can be used also as a sealing agent for potting of COB (chip on board), and a sealing compound for LCDs, in addition to the said various components for color filters.

On the color filter layer obtained using the photocurable composition of this invention, an overcoat layer (planarization layer) is normally formed. As resin (product made from OC) which forms an overcoat layer, an acrylic resin composition, an epoxy resin composition, a polyimide resin composition, etc. are mentioned. Especially, since the resin component of the photocurable composition for color filters is excellent in transparency in the visible light region, and usually has acrylic resin as a main component, and is excellent in adhesiveness, acrylic resin composition is preferable. In particular, if it is a photocurable (meth) acrylic-type resin for photoresists used by a color filter, since matching with the manufacturing process of a color filter becomes favorable, it is preferable.

(Example)

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by the following example.

[Examples 1-10 and Comparative Examples 1-4]

Preparation of the test piece:

a) The composition shown in the compounding table of Table 1 was applied to anhydrous alkali glass (Corning 1737) for a liquid crystal panel so as to have a dry film thickness of 1.2 μm with a spin coater, and solvent drying was performed for 120 seconds on a 90 ° C. hot plate.

b) Subsequently, an ultra-high pressure mercury lamp of ^2.5 kw was used, and a mask was irradiated with ultraviolet light of 200 mJ / cm ² .

c) Subsequently, it developed for 30 second at 26 degreeC of the 10% dilution aqueous solution of the organic alkali developing solution CD-2000 by Fuji Film Arch Co., Ltd., and rinsed pure water for 20 seconds, and dried.

d) Then, as a post-baking, it was set as the test piece which hardened on the conditions of 110 degreeC-150 degreeC, 60 minutes (low temperature hardening), and 220 degreeC, 5 second-30 second (fast hardening) in a hotplate each time with a hot-air circulation type dryer. .

Determination of Curability, Adhesion to Substrate:

a) Hardness judgment is made by immersing in 50 degreeC N-methylpyrrolidone (henceforth NMP) for 10 minutes, and measuring the chromaticity change before and after, it is represented by the color difference (DELTA) E * ab and (DELTA) E * ab <= 3 is a problem It was set as the range which is not.

b) The adhesion to the substrate was visually determined to what extent the film was peeled off the substrate in the NMR immersion test, and the following evaluation was performed.

A: The film is not peeled at all.

B: The film is not peeled off, but part is floating.

C: Although the film peeled about 50%, chromaticity change can be measured.

NG: The film is completely peeled off and chromaticity measurement is impossible.

In addition, low temperature curability and adhesive evaluation were performed about Examples 1-9 and Comparative Examples 1-4, and rapid curing property and adhesive evaluation were performed only about Examples 1, 4, 8-9, and Comparative Examples 1-4.

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 compound was obvious, and the effect was hardly reduced even if the curing of the coating film was greatly promoted and the addition amount was small.

In addition, the addition effect of BTTB can be seen, but less than imidazole silane, for example, ΔE * ab ≦ 3 under curing conditions of 135 ° C. × 60 min in Example 1, as is apparent from FIG. 3. In addition, it was confirmed from the comparison between Example 3 and Example 9 that the higher the functional group number of the alicyclic epoxy selected was, the better. In addition, as apparent from Table 3 and Fig. 3, in Comparative Example 3 and Comparative Example 4, the effect of the addition of imidazole and epoxysilane alone was hardly seen.

In addition, from Tables 3 and 3, the same results as in the low-temperature curability are obtained also in the fast curing property, and it is found that the effect on the curing of the imidazole silane is very large.

2 and 3, in terms of curability, 15 functional alicyclic epoxy + imidazole silane + BTTB> 15 functional alicyclic epoxy + imidazole silane> 4 functional alicyclic epoxy + imidazole silane> 15 functional alicyclic epoxy + Imidazole + BTTB> 15 functional alicyclic epoxy + epoxysilane + BTTB in order of effect was confirmed.

Development characteristic evaluation:

The composition shown in the compounding table of Table 1 was applied to an alkali-free glass (Corning 1737) for a liquid crystal panel so as to have a dry film thickness of 1.2 μm with a spin coater, and solvent drying was performed for 120 seconds on a 120 ° C. hot plate. Subsequently, using HITACHI manufactured exposure machine LE4000A, red, green, and blue were masks having a 20 µm line width, and blacks were exposed at 100 mJ / cm ² with a Proximity Gap of 300 µm with a mask having a line width of 15 µm (roughness: 20 mW / cm). ² ) and developed at 26 ° C with 1.0% dilution developer of Alkali developer CDK-1 manufactured by Fuji Film Arch. At this time, the development margin and the development latitude are shown as a graph of the line width change with the development time. The results are shown in Table 4 and FIG. Here, development margin is a thing of the line width change with respect to development time, and development latitude is time from pattern expression to pattern peeling. 4 is a graph showing the main ones from Table 4.

As is apparent from Table 4 and Fig. 4, the comparative example has no place where the line width becomes constant with respect to the developing time, and therefore it is difficult to obtain a constant image, whereas the example to which imidazole silane is added has good developing characteristics. Can be obtained.

Example 11

The solution of the following composition was produced and the photosensitive resin solution was obtained by stirring for 8 hours.

<Alkali Soluble Resin>

Benzyl methacrylate / methacrylic acid copolymer 6.4 g

  (Molar ratio 70/30, mass average molecular weight (Mw) approximately 30,000)

<Polymeric Monomer>

Dipentaerythritol hexaacrylate 4g

<Photoinitiator A>

1 g of 2,4-bis (trichloromethyl) -6- [3-bromo-4- [N, N-bis (ethoxycarbonylmethyl) amino] phenyl] -1,3,5-triazine

<Photoinitiator B>

0.3 g of 7- [L-4-chloro-6- (diethylamino) -s-triazinyl (2), 1-amino] -3-phenylcoumarin

<Colorant>

Carbon black dispersion (solid) (* 1) 9.7 g

Propylene glycol monomethyl ether acetate 78.5 g                     

Fluorinated nonionic surfactant (* 2) 0.02 g

Japan energy production imidazole silane, IM-1000 0.1g

* 1) Regal manufactured by Kabot Co., Ltd. (particle size: 31 nm, pH: 9, DBP oil supply: 42 ml / 100 g of dispersion in which carbon is dispersed (the amount of carbon is 45% of the solid content in the solution))

* 2) copolymer of 60% N-butylperfluorooctanesulfonamide ethylacrylate and 40% poly (oxyalkylene) acrylate

About this photosensitive resin solution, image development was performed similarly to Examples 1-10, and image development characteristic was evaluated. The evaluation results are shown in FIGS. 6 and 5.

[Comparative Example 5]

A black matrix was prepared in the same manner as in Example 12 except that the imidazole silane compound (IM-1000) was not used, and evaluated under the same conditions as in Example 11.

[Comparative Example 6]

Example except using 0.1 g of silane coupling agent, KBM-403 (3-glycidoxypropyl trimethoxysilane) by Shin-Etsu Chemical Co., Ltd. instead of 0.1 g of imidazole silane compounds (IM-1000). It carried out similarly to 11, the black matrix was produced, and it evaluated on the conditions similar to Example 11.

Comparative Example 7

Example except using 0.1 g of the silane coupling agent made by Shin-Etsu Chemical Co., Ltd., KBM-402 (3-glycidoxypropylmethyl diethoxysilane) instead of 0.1 g of imidazole silane compounds (IM-1000). In the same manner as in 12, a black matrix was produced 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) methoxysilane was used instead of 0.1 g of the imidazolesilane compound (IM-1000), and the same conditions as in Example 11 were used. Evaluated.

[Comparative Example 9]

It carried out similarly to Example 11 except having used 0.1 g of silane coupling agents and KBE-04 (tetraethoxysilane) by Shin-Etsu Chemical Co., Ltd. instead of 0.1 g of imidazole silane compounds (IM-1000). A matrix was produced and evaluated under the same conditions as in Example 11.

[Comparative Example 10]

In the same manner as in Example 11, except that 0.1 g of the silane coupling agent, KBM-1003 (vinyltriethoxysilane) produced by Shin-Etsu Chemical Co., Ltd., was used instead of 0.1 g of the imidazole silane compound (IM-1000). A black matrix was produced and evaluated under the same conditions as in Example 11.

The compounding table of Example 11 and Comparative Examples 5-10 is shown in following Table 5, and a result is shown in following Table 6 and FIG.                     

Example 12

(Production of color filter)

A color photocurable composition was prepared as follows.

Photocurable Red (R) Composition: Red composition of Example 10.

Photocurable Green (G) Composition: The C.I. Pigment Red 254 (PR254) /C.I. Pigment Yellow 139 (mass ratio 100 / 17.6) 4.28 parts, C.I. Pigment Green 36 (PG 36) /C.I. Pigment Yellow 150 (PY150) A green photocurable composition was prepared in the same manner as in Example 10 except that 5.79 parts of a mass ratio of 100/58 was used.

Composition of photocurable blue (B): In Example 10, C.I. Pigment Red 254 (PR254) /C.I. Pigment Yellow 139 (mass ratio 100 / 17.6) 4.28 parts, C.I. Pigment Blue 15: 6 (PB 15: 6) A blue photocurable composition was prepared in the same manner as in Example 10 except that 4.28 parts were replaced.

Photocurable Black Composition (Photocurable Composition for Black Matrix): Black Composition of Example 11

The said photocurable black composition was apply | coated so that the dry film thickness might be set to 1.1 micrometers using the board | substrate which wash | cleaned the alkali free glass substrate for liquid crystal panels (Corning 1737) 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 using a 15 μm line width mask using a HITACHI manufactured exposure machine LE4000A, and 1.0% developer solution of alkaline developer CDK-1 manufactured by Fujifilm Arch Co., Ltd. When developed at 26 ° C. for 100 seconds, a clear black pattern image (black matrix) was obtained. Subsequently, the resultant was washed with running water for 20 seconds, dried with an air knife, and heat-treated at 220 ° C. for 60 minutes with a hot air circulation dryer to obtain a black matrix substrate.

Subsequently, a mask was used as a mask having a pixel size of 100 µm corresponding to the black matrix, and each color was applied in order from red to green to blue to form a pattern color to obtain a color filter.

That is, except for the mask, the same apparatus and developer as in the formation of the black matrix were used, and the photocurable red composition was applied so as to have a dry film thickness of 1.2 μm, and after solvent drying, 100 mJ / cm through a mask having a pixel size of 100 μm. ² was exposed and developed for 100 seconds. Subsequently, heat treatment was performed at 220 ° C. for 60 minutes to form a red pattern image (red pixel). In the same order, the green pattern image (green pixel) and the blue pattern image (blue pixel) are also replaced with the same mask, and are exposed so as to be exchanged with red, green, and blue, and the developing conditions are stable from 80 to 120 seconds. Clear pixels were formed. Moreover, when observed with the optical microscope, the pixel incompatibility, the color overlap, mixing, or discoloration were not seen.

According to the present invention, the development characteristics such as the development latitude and the development margin are improved, so that the constraints on the conditions at the time of development are alleviated, and the restrictions are significantly reduced in the management of the development time, development concentration, developer temperature, and the like. In addition, the increase in the quantitative rate in the development and the number of exchanges of the developing solution can also be reduced, and the cost can be reduced. In particular, in the case of the photocurable colored resin composition using a black colorant, the permeation of the exposure light into the film in which the film is formed by coating is easy to be inhibited, so that the photocuring of the film hardly proceeds, and thus the present invention brings great advantages.

Moreover, according to this invention, the photocurable composition which can fully harden at low temperature or a short time, the photocurable composition for pigment component type color filters which can be fully hardened at low temperature, and is suitable for the use of a plastic substrate, and especially presently When forming a color filter in the glass substrate of a state, it can heat-process in a short time and can provide the photocurable composition for pigment component type color filters which can remarkably improve the color filter production efficiency. In addition, various conditions can be selected in the necessary and optimal heat treatment process in manufacturing the color filter.

Claims (11)

In the photocurable colored resin composition containing a coloring agent, alkali-soluble resin, a photopolymerizable monomer, and a photoinitiator, content of the said coloring agent in solid content of the said photocurable colored resin composition is 10-70 mass%, and imidazolesilane It further contains a compound, The photocurable colored resin composition for color filters. The imidazole silane compound according to claim 1, wherein 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); Or it is a derivative compound, The photocurable colored resin composition for color filters characterized by the above-mentioned.

[In formula, R <^1> represents a hydrogen atom or a C1-C20 alkyl group, and R <^2> and R <^3> represents a hydrogen atom, a vinyl group, or a C1-C5 alkyl group each independently.)

(In formula, R <^4> and R <^5> represents a C1-C3 alkyl group each independently, m shows the integer of 1-20, n shows the integer of 1-3. " The color according to claim 1 or 2, wherein the imidazole silane compound is composed of one or more selected from compounds represented by the following general formulas (1) to (3) and / or derivative compounds thereof. Photocurable colored resin composition for filters.

In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ² represents a hydrogen atom, a vinyl group or an alkyl group having 1 to 5 carbon atoms, and R ³ and R ⁴ each independently represent 1 to 3 carbon atoms. Is an alkyl group, and n represents 1 to 3.) The photocurable colored resin composition for color filters according to claim 1 or 2, wherein the colorant is a black colorant. 5. The photocurable colored resin composition for color filters according to claim 4, wherein the black colorant is carbon black. The photocurable colored resin composition for color filters of Claim 1 or 2 containing an epoxy compound more than bifunctional. The photocurable colored resin composition for color filters of Claim 6 containing a thermal-polymerization initiator. 8. The photocurable colored resin composition for color filters according to claim 7, wherein the thermal polymerization initiator is an organic peroxide. 9. The photocurable colored resin composition for color filters according to claim 8, wherein the organic peroxide is a benzophenone organic peroxide represented by the following general formula (III).

(In formula, R <_1> and R <_2> respectively independently represents a C1-C20 alkyl group or an aralkyl group, R <_3> and R <_4> respectively independently represents a hydrogen atom, a carboxyl group, a C1-C10 alkyl group, and C1-C1 An alkoxy group of 10 to 10, a halogenated alkyl group of 1 to 10 carbon atoms, a halogen atom, a cyano group, a nitro group or a dialkylamino group of 2 to 20 carbon atoms, q is 0, 1 or 2, and r is 1, 2 or 3 to be.) 10. The photocurable colored resin composition for color filters according to claim 9, wherein the benzophenone organic peroxide is at least one of the compounds represented by the following formulas (1) to (5).

After apply | coating the coating liquid which consists of a photocurable colored resin composition for color filters of Claim 1 or 2 on a board | substrate, preparing a film | membrane, it exposes and develops by the photolithographic method, and forms a monochromatic pattern. A color filter produced by repeating the process for each color.

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