JP2005084111A - Color filter and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a color filter which can be easily aligned, which can be made with a high opening rate, and which has high yield and high production efficiency. <P>SOLUTION: In the color filter where pixel electrodes are formed directly or across other layers (excluding a liquid crystal layer) on the respective pixels formed directly or across other layers on a TFT substrate, each pixel is made of a photosetting composition containing at least a colorant, an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator and a polyfunctional epoxy compound having four or more functional groups. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a color filter and a method for manufacturing the same, and more particularly, a color filter that is easy to align and has a high aperture ratio, and further requires only a small number of manufacturing steps, and has a high quality improvement rate and high production efficiency. The present invention also relates to a production method for producing the color filter easily and simply.

A color liquid crystal display device of a thin film transistor (hereinafter abbreviated as “TFT”) type usually produces a color filter substrate for displaying a color image separately from a driving substrate on which TFTs are arranged. The substrate is manufactured by being bonded to the driving substrate. However, in this method, since the alignment accuracy when bonding is low, the width of the black matrix has to be increased. For this reason, there has been a problem that it is difficult to increase the aperture ratio (the ratio of the aperture that transmits light).
In recent years, as glass substrates and LCD screens for LCD (liquid crystal display) TV applications have become larger, the method of injecting liquid crystal after bonding has increased the area of the substrate with larger screens. Therefore, it took a long time for the liquid crystal composition to spread between the substrates. For this reason, as a new technology, a manufacturing method has been proposed in which the time required for this step is significantly shortened by printing a sealing material, further dropping a liquid crystal, and bonding them together. In this case, alignment is very difficult, and there is a problem that alignment accuracy is lowered.

On the other hand, a color filter on array (hereinafter abbreviated as “COA”) is a method of forming a colored layer including a black matrix on a driving substrate of a TFT color liquid crystal display device. There is no need for a color filter substrate, and a substrate on which a transparent electrode is simply attached by sputtering is attached to the facing surface, which makes it easy to align and increases the aperture ratio.
However, COA usually forms pixel electrodes on a color filter by a photolithography method using a positive resist. For this reason, it is necessary to peel and remove the resist film after electrode formation. That is, in the case of COA, a transparent electrode film is formed on a colored pixel of a color filter, a positive resist film is applied on the transparent electrode film, and pattern exposure and development are applied to the resist coating film to form a pixel electrode. Form. After the pixel electrode is formed, the resist film remaining on the pixel electrode is peeled off with a resist stripping solution. For this reason, the color filter needs to be resistant to the positive resist stripping solution (hereinafter simply referred to as “stripping solution”), but the conventional photocurable coloring composition for color filters is resistant to such stripping solution. There was no.

For this reason, conventionally, after forming an image, a transparent film (pixel protective film) having a peeling liquid resistance is further formed, and then a pixel electrode is formed (see, for example, Patent Document 1). In order to reduce the influence of the stripper on the color filter layer, the method of not providing the pixel protective film is to remove the positive resist over a long period of time at a low temperature by using a mild stripper. Had gone.
However, these conventional methods have a problem that the number of steps and time increase, resulting in a decrease in the quality improvement rate and a decrease in production efficiency.

Therefore, in order to solve these problems, Patent Document 2 (Japanese Patent Laid-Open No. 2001-318220) discloses a radiation sensitivity in which the swelling ratio of the cured film for forming the COA colored layer to the peeling solution is 5% or less. A color filter using the composition has been proposed.
Moreover, in patent document 3 (Unexamined-Japanese-Patent No. 2003-113224), by using a polyfunctional alicyclic epoxy compound for a thermal-polymerization crosslinking agent, and also using a benzophenone-type peroxide as a photothermal polymerization initiator, In particular, a color filter having an improved thermal polymerization crosslinking effect has been proposed. According to this proposal, curing at a low temperature is possible, curing in a short time is possible, and a color filter having excellent durability and good adhesion can be obtained.
However, the proposal of Patent Document 2 has not yet obtained a sufficient effect. In addition, although the proposal of Patent Document 3 can achieve a certain effect, it has recently been required to have a higher image quality and larger screen than those at the time of filing of Patent Document 3, and in response to such a request, In addition, there is a demand for the development of a high-performance color filter having a high aperture ratio.
JP 2002-357901 A JP 2001-318220 A JP 2003-113224 A

  An object of the present invention is to produce a COA color filter that can be easily aligned and has a high aperture ratio, and is intended to provide a color filter that is excellent in terms of yield and production efficiency and a method for producing the same. It is.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a specific photocurable composition is excellent in resistance to a stripping solution for a positive resist, and uses this photocurable composition. Thus, it has been found that the above object can be achieved by forming pixels, and the present invention has been completed.
That is, according to the present invention, a color filter having the following constitution and a method for producing the color filter are provided, and the above object is achieved.

1. In a color filter in which a pixel electrode is formed directly on each pixel formed on a TFT substrate or via another layer or directly via another layer (excluding a liquid crystal layer),
Each pixel is formed using a photocurable composition containing at least a colorant, an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a polyfunctional epoxy compound having four or more functions. Color filter.

2. 2. The color filter as described in 1 above, wherein the polyfunctional epoxy compound contained in the photocurable composition is a polyfunctional alicyclic epoxy compound represented by the following general formula (1).

In the formula, R ′ represents a residue obtained by removing n hydrogen atoms substituted by [—O— (A) _m —H] _n from the hydrocarbon R. A represents an alicyclic group having the following structure having at least one epoxy group. m represents 1-100. n represents 1-100. However, m × n is 4 to 100, and a plurality of A may be the same or different.

3. 3. The color filter according to 1 or 2, wherein the photocurable composition further contains an imidazole compound represented by the following general formula (I) and an epoxysilane-based compound represented by the following general formula (II).

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

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

4). The photocurable composition further includes an imidazole silane compound and / or a reaction product of the imidazole compound represented by the general formula (I) and the epoxy silane compound represented by the general formula (II). 3. The color filter according to 1 or 2 containing a derivative thereof.
5). The color filter according to any one of 1 to 4, wherein the photocurable composition further contains a thermal polymerization initiator.
6). 6. The color filter as described in 5 above, wherein the thermal polymerization initiator is an organic peroxide.

7). 7. The color filter as described in 6 above, wherein the organic peroxide is a benzophenone-based organic peroxide represented by the following general formula (III).

In the formula, R ₁ and R ₂ each independently represent an alkyl group or aralkyl group having 1 to 20 carbon atoms, and R ₃ and R ₄ each independently represent a hydrogen atom, a carboxyl group, or an alkyl having 1 to 10 carbon atoms. Group, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a halogen atom, a cyano group, a nitro group, or a dialkylamino group having 2 to 20 carbon atoms, q is 0, 1 or 2 And r is 1, 2 or 3.

8). 8. The color filter according to 7, wherein the benzophenone-based organic peroxide is at least one kind represented by the following chemical formulas (1) to (5).

9. In a color filter in which a pixel electrode is formed directly on each pixel formed on a TFT substrate or via another layer or directly via another layer (excluding a liquid crystal layer),
Each pixel is formed of a photocurable composition for pixels containing a colorant, an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator,
A pixel protective film formed from a photocurable composition containing at least an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a polyfunctional epoxy compound having four or more functionalities between each pixel and the pixel electrode The color filter characterized by being arranged.

10. 10. The color filter according to 9, wherein the polyfunctional epoxy compound contained in the photocurable composition is a polyfunctional alicyclic epoxy compound represented by the following general formula (1).

In the formula, R ′ represents a residue obtained by removing n hydrogen atoms substituted by [—O— (A) _m —H] _n from the hydrocarbon R. A represents an alicyclic group having the following structure having at least one epoxy group. m represents 1-100. n represents 1-100. However, m × n is 4 to 100, and a plurality of A may be the same or different.

11. 11. The color filter according to 9 or 10, wherein the photocurable composition further contains an imidazole compound represented by the following general formula (I) and an epoxysilane-based compound represented by the following general formula (II).

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

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

12 The photocurable composition further includes an imidazole silane compound and / or a reaction product of the imidazole compound represented by the general formula (I) and the epoxy silane compound represented by the general formula (II). 11. The color filter according to 9 or 10 containing a derivative thereof.
13. The color filter according to any one of 9 to 12, wherein the photocurable composition further contains a thermal polymerization initiator.
14 14. The color filter as described in 13, wherein the thermal polymerization initiator is an organic peroxide.

15. 15. The color filter according to 14, wherein the organic peroxide is a benzophenone organic peroxide represented by the following general formula (III).

In the formula, R ₁ and R ₂ each independently represent an alkyl group or aralkyl group having 1 to 20 carbon atoms, and R ₃ and R ₄ each independently represent a hydrogen atom, a carboxyl group, or an alkyl having 1 to 10 carbon atoms. Group, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a halogen atom, a cyano group, a nitro group, or a dialkylamino group having 2 to 20 carbon atoms, q is 0, 1 or 2 And r is 1, 2 or 3.

16. 16. The color filter according to 15, wherein the benzophenone-based organic peroxide is at least one kind represented by the following chemical formulas (1) to (5).

17. The photocurable composition according to any one of 1 to 8 above is applied onto a TFT substrate to form a coating film of the photocurable composition, and pattern exposure, alkali development, post-processing is performed on the coating film. Bake treatment is performed to form each pixel, a transparent electrode (ITO) film is formed on each pixel, and then a positive photoresist coating film is formed on the transparent electrode (ITO) film. The photoresist coating film is subjected to pattern exposure and development, and further, an unnecessary transparent electrode (ITO) film is etched to form a transparent pixel electrode pattern, and then the photoresist coating film remaining on the transparent pixel electrode pattern is formed. A method for producing a color filter that is removed with a stripping solution.

18. Each pixel of the color filter is formed on the TFT substrate, the photocurable composition according to any one of 9 to 16 is applied on the pixel to form a pixel protective film, and then The pixel protective film is subjected to pattern exposure, alkali development, and post-baking to form a pixel protective film, and then a transparent electrode (ITO) film is formed on the pixel protective film, and the transparent electrode (ITO) After forming a positive photoresist coating film on the coating, pattern exposure and development on the positive photoresist coating film, and further etching unnecessary transparent electrode (ITO) film to form a transparent pixel electrode pattern, A method for producing a color filter, wherein a photoresist coating film remaining on the transparent pixel electrode pattern is removed with a remover.
19. 19. The method for producing a color filter as described in 17 or 18 above, wherein the stripper is an organic solvent at 60 ° C. or higher.

  According to the present invention, it is possible to provide a color filter excellent in terms of yield and production efficiency, and a method for manufacturing the same, in the manufacture of a COA color filter that can be easily aligned and can have a high aperture ratio. .

Hereinafter, the color filter of the present invention will be described in detail.
The color filter of the present invention is configured in the following two forms.
(1) A pixel electrode is formed directly or via another layer (excluding the liquid crystal layer) on each pixel formed directly on the TFT substrate or via another layer. The form (color filter of Claims 1-8) currently formed from the photocurable composition.
(2) In the color filter in which the pixel electrode is formed directly or via another layer (excluding the liquid crystal layer) on each pixel formed directly on the TFT substrate or via another layer, each pixel Is formed of a photocurable composition for pixels, and a pixel protective film formed of a specific photocurable composition is disposed between each of the pixels and the pixel electrode. Item 17. A color filter according to Items 9 to 16.
Hereinafter, first, regarding the present invention of the form (1) of the present invention, [I] the photocurable composition, [II] the structure of the color filter, and [III] the method for producing and using the color filter of the present invention. The method will be described, and then [IV] the mode (2) of the present invention will be described.

[I] Photocurable composition The photocurable composition used in the color filter of the present invention contains at least a colorant, an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a polyfunctional epoxy compound.
Hereinafter, each component of the photocurable composition used in the color filter of the present invention will be described in detail.

(A) Polyfunctional epoxy compound The polyfunctional epoxy compound used in the present invention is not limited as long as it is an epoxy compound having 4 or more functional groups, but the base number of the alkali-soluble resin having a carboxyl group contained in the composition. It is desirable to blend an epoxy compound having the number of epoxy groups that meets the requirements.

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

  As such an epoxy compound, an alicyclic epoxy compound is preferable, and a polyfunctional alicyclic epoxy compound represented by the following formula (1) is more preferable.

In the formula, R ′ represents a residue obtained by removing n hydrogen atoms substituted by [—O— (A) _m —H] _n from the hydrocarbon R. A represents an alicyclic group having the following structure having at least one epoxy group. m represents 1-100. n represents 1-100. However, m × n is 4 to 100, and a plurality of A may be the same or different.

m × n is 4 to 100. When m × n is large, there may be a problem in productivity and storage stability of the photocurable composition. Preferably, m is 2 to 10, n is 3 to 6, and m × n is 6 to 60, m is 3 to 6, n is 3 to 6, and m × n is more preferably 8 to 36. n is particularly preferably 8-20.
A and m in n [-O- (A) m-H] may be the same or different. m × n is the sum of m which may be different from n (m ₁ , m ₂ , m ₃ , ,,, + _mn ), and the sum of A possessed by the polyfunctional alicyclic epoxy compound Represents a number.

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

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

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

  The compound represented by the general formula R ′ [— O— (A) m—H] n is a commercially available product, specifically, EHPE3150 (2,2-bis (hydroxymethyl) -1 manufactured by Daicel Chemical Industries, Ltd. -Butanol 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct, m = 5 (average), n = 3, m × n = 15, epoxy equivalent 178 g / eq). In the said photocurable composition, you may contain 2 or more types of polyfunctional alicyclic epoxy compounds.

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

  The content of the polyfunctional epoxy compound in the photocurable composition is desirably 1 to 30% by mass, more desirably 2 to 25% by mass, and most desirably 5 to 15% by mass of the solid content of the composition. .

In the present invention, an imidazole compound represented by the following formula (I) and an epoxysilane compound represented by the following formula (II) are used together with the polyfunctional epoxy compound, or the imidazole compound and the epoxy are used. It is preferable to use an imidazole silane compound and / or a derivative thereof, which is a reaction product with a silane compound.
Next, these compounds will be described.

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

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

(B) Imidazole compound As the imidazole compound represented by the general formula (I), there are imidazole, 2-alkylimidazole, 2,4-dialkylimidazole, 4-vinylimidazole, and the like, among these being particularly preferable. For 2-alkylimidazole, 2-methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, etc .; and for 2,4-dialkylimidazole, 2-ethyl-4-methylimidazole, etc. Can be mentioned.

(C) Epoxysilane compound As the epoxysilane compound represented by the general formula (II), 3-glycidoxypropyltrialkoxysilane, 3-glycidoxypropyl dialkoxyalkylsilane, 3-glycidoxy There are propylalkoxydialkylsilanes, and among these, particularly preferred as 3-glycidoxypropyltrialkoxysilane are 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. Examples of 3-glycidoxypropyl dialkoxyalkylsilane include 3-glycidoxypropyldimethoxymethylsilane, and examples of 3-glycidoxypropylalkoxydialkylsilane include 3-glycidoxypropylethoxydimethylsilane. Can .

(D) Imidazolesilane compound As an imidazolesilane compound that is a reaction product of the imidazole compound represented by the general formula (I) and the epoxysilane compound represented by the general formula (II) in the present invention. Specific examples include compounds represented by the following formulas (1) to (3) described in JP-B-7-68256.

In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, R ² represents a hydrogen atom, a vinyl group or an alkyl group having 1 to 5 carbon atoms, and R ³ and R ⁴ are each independently carbon. The alkyl group of number 1-3 is represented, n represents 1-3.

  Examples of imidazole silane compounds that can be used in the present invention include commercially available products such as imidazole silane, IS-1000, YA-100, IC-100P, and IA-100P manufactured by Japan Energy Co., Ltd. Examples of commercially available imidazole compounds include various imidazole compounds such as 2E4MZ manufactured by Shikoku Kasei Co., Ltd., and examples of commercially available epoxysilane compounds include TSL8350 and TSL8355 manufactured by Toshiba Silicone Co., Ltd. .

  Examples of the derivatives of imidazole silane compounds include reaction products of hydroxyl groups and organic acids of the above-mentioned compounds. Examples of organic acids include monovalent compounds such as acetic acid and palmitic acid, phthalic anhydride, tetrahydrophthalic anhydride, and the like. An acid anhydride etc. are mentioned.

  The compounding amount of the imidazole compound and the epoxysilane compound, and the compounding amount of the imidazolesilane compound and / or derivative thereof may be very small because the imidazole skeleton functions as an epoxy resin curing accelerator. Preferably it is 0.1 mass part or more with respect to 100 mass parts of polyfunctional epoxy compounds to do, More preferably, it is 0.8-10 mass parts.

(E) Photopolymerizable monomer, photopolymerization initiator, and thermal polymerization initiator The photopolymerizable monomer used in the present invention has at least one addition-polymerizable ethylene group, and has a temperature of 100 ° C. or higher under normal pressure. A compound having an ethylenically unsaturated group having a boiling point is preferred.

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

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

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

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

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

  In this invention, the compounding quantity of a photoinitiator is 0.5 mass%-60 mass% with respect to the photopolymerizable monomer in a composition, Preferably it is 1 mass%-50 mass%. When the amount of the initiator used is less than 0.5% by mass, the polymerization may not proceed easily. When the amount exceeds 60% by mass, the polymerization rate increases, but the molecular weight tends to decrease and the film strength tends to decrease.

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

In the formula, each of R ₁ and R ₂ independently represents an alkyl group or an aralkyl group having 1 to 20 carbon atoms, preferably 2 to 15 carbon atoms, more preferably 4 to 10 carbon atoms, particularly as a peroxide. Most preferred are tertiary alkyl groups having 4 to 10 stable carbon atoms, such as t-butyl, 1,1-dimethylpropyl, 1,1-dimethylbutyl, 1,1-dimethylpentyl and the like. It is done.

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

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

Among the above, the compounds (1) to (5) are particularly preferable.
In addition, these compounds can be used individually or in combination of 2 or more types.

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

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

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

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

In the present invention, two or more organic peroxides can be contained as a thermal polymerization initiator.
The content of the organic peroxide in the composition is preferably 0.5 to 20% by mass, more preferably 1 to 15% by mass with respect to the amount of the photopolymerizable monomer in the photocurable composition. %. When the amount of the organic peroxide is less than 0.5% by mass relative to the photopolymerizable monomer, the effect is not so great. When the amount exceeds 20% by mass, the viscosity of the composition changes with time, and the resolution of the photolithography characteristics There may be problems with storage stability, such as the deterioration of aging over time.

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

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

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

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

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

The acrylic binder resin preferably has an acid value in the range of 30 to 150 mgKOH / g. When the acid value exceeds 150, the acrylic binder resin may become so soluble in alkali that the appropriate development range (development latitude) may be narrowed. On the other hand, if it is too small as less than 30, the solubility in alkali is so small that it may take too long to develop.
Moreover, the weight average molecular weight Mw (polystyrene conversion value measured by GPC method) of the acrylic binder resin is used to realize a viscosity range that is easy to use in a process such as applying a color resist, and to secure film strength. Therefore, it is preferably 5,000 to 100,000, more preferably 8,000 to 50,000.

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

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

Among these various resins, the alkali-soluble resin used in the present invention includes polyhydroxystyrene resin, polysiloxane resin, acrylic resin, acrylamide resin, and acrylic / acrylamide copolymer resin from the viewpoint of heat resistance. Acrylic resins, polyhydroxystyrene resins, and polysiloxane resins are more preferable. From the viewpoint of control of developability, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable.
Examples of the acrylic resin include copolymers consisting of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and cyclomer P series, Plaxel CF200 series ( All are manufactured by Taicel Chemical Industry Co., Ltd.), Ebecry 13800 (manufactured by Daicel UCP Co., Ltd.), Dynal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Biscote R-264, KS resist 106 (all of which are Osaka Organic Chemical Industries, Ltd.) And the like are preferable.
In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) propane and epichlorohydrin, and the like are also useful.

  The amount of the alkali-soluble resin in the photocurable composition is preferably 5 to 90% by mass, more preferably 10 to 60% by mass, based on the total solid content of the composition. When the amount of the alkali-soluble resin is less than 5% by mass, the film strength tends to decrease. When the amount is more than 90% by mass, the acid content increases, so that it is difficult to control the solubility, and the pigment is relatively pigmented. In some cases, sufficient image density cannot be obtained.

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

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

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

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

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

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

  These organic pigments are used alone or in various combinations in order to increase color purity. Specific examples are shown below. Red pigments include anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or at least one of them and disazo yellow pigments, isoindoline yellow pigments, quinophthalone yellow pigments or perylene red pigments Etc. are used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177 and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224 and diketopyrrolopyrrole pigments include C.I. I. Pigment red 254, and C.I. I. Pigment yellow 83 or C.I. I. Mixing with Pigment Yellow 139 was good. The mass ratio of the red pigment to the yellow pigment was good from 100: 5 to 100: 50. Below 100: 4, the light transmittance from 400 nm to 500 nm could not be suppressed, and the color purity could not be increased. At 100: 51 or more, the dominant wavelength became shorter and the deviation from the NTSC target hue became large. In particular, the range of 100: 30 to 100: 30 was optimal. In the case of a combination of red pigments, it is adjusted according to the chromaticity.

  As the green pigment, a halogenated phthalocyanine pigment alone or a mixture with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment is used. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 was good. The mass ratio of the green pigment to the yellow pigment was 100: 5 to 100: 150. If the ratio is less than 100: 5, the light transmittance from 400 nm to 450 nm cannot be suppressed, and the color purity cannot be increased. When the ratio exceeded 100: 150, the dominant wavelength became longer and the deviation from the NTSC target hue increased. A more preferred mass ratio is in the range of 100: 30 to 100: 120.

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

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

  Further, as the black matrix colorant, carbon, titanium carbon, iron oxide, titanium oxide alone or a mixture thereof was used, and the case of carbon and titanium carbon was satisfactory. The mass ratio was in the range of 100: 0 to 100: 60. When the ratio is 100: 61 or more, the dispersion stability tends to decrease.

  Examples of the carbon black that can be used as the colorant according to the present invention include carbon black # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, and # 960 manufactured by Mitsubishi Chemical Corporation. 950, # 900, # 850, MCF88, # 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40, # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Black LI Diamond Black II, Diamond Black N339, Diamond Black SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LP. Carbon black thermax N990, N991, N907, N908, N990, N991, N908 made by Cancarb. Carbon black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal, Degussa's carbon black ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw2, ColorBlack Fw1, ColorBlack 170, BlackBlack, BlackBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, PrintexU, PrintexV, Printex140U, Printex140 And the like can be given.

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

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

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

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

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

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

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

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

(In the formula, R represents a hydrogen atom or a methyl group, and R _{1 to} R ₅ are each independently a group selected from a hydrogen atom, a halogen atom, a cyano group, an alkyl group, and an aryl group.)
Here, specific examples of the halogen atom include Cl, Br, and I.
The alkyl group may be linear, branched, or cyclic, and includes a methyl group, an n-propyl group, an iso-propyl group, a tert-butyl group, and the like, preferably having 1 to 7 carbon atoms. Examples of the aryl group include a phenyl group, a furyl group, and a naphthyl group.

The following resins can also be used as the coating resin.
A linear organic high molecular polymer which is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution is preferred. As such a linear organic polymer, those having an acid group such as a carboxy group or a phenolic hydroxyl group in the resin side chain or main chain are preferable from the viewpoint of pollution prevention because they can be alkali-developed. In particular, a resin having a carboxyl group, for example, an acrylic acid (co) polymer, a styrene / maleic anhydride resin, an acid anhydride-modified resin of novolak epoxy acrylate, and the like are preferable because of high alkali developability. Examples of the polymer having a carboxylic acid in the side chain include, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59- A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partial, as described in Japanese Patent No. 53836 and JP-A-59-71048 There are esterified maleic acid copolymers and the like, and similarly there are acidic cellulose derivatives having a carboxylic acid in the side chain. In addition, a polymer in which an acid anhydride is added to a polymer having a hydroxyl group is also useful. Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers with benzyl (meth) acrylate / (meth) acrylic acid / and other monomers are also suitable.
In addition, 2-hydroxyethyl methacrylate, polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like are also useful as the water-soluble polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful. These polymers can be mixed in any amount.

Furthermore, the following epoxy resins can also be used.
1. 1. Glycidylamine type epoxy resin 2. Triphenylglycidylmethane type epoxy resin 3. Tetraphenylglycidylmethane type epoxy resin 4. Aminophenol type epoxy resin 5. Diamide diphenylmethane type epoxy resin 6. Phenol novolac type epoxy resin Ortho-cresol type epoxy resin8. Bisphenol A novolac epoxy resin

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

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

  A dispersant is usually used for dispersing the organic pigment and carbon black. As the dispersant, the above-described coating resin can be used as it is, or a dispersant as described later can be used in combination. These dispersants can be used alone or in combination. The resin is adsorbed on the surface of the carbon black by the dispersion treatment, and at the same time, the aggregation of the carbon black particles is broken and the particle size is refined.

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

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

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

In the present invention, when the colorant is a dye, it is uniformly dissolved in the composition to obtain a photocurable composition.
The dye that can be used as the colorant constituting the photocurable composition is not particularly limited, and conventionally known dyes for color filters can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 The dyes disclosed in JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like can be used.
The chemical structure is pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.

  The content rate of the coloring agent in the said photocurable composition is 20-60 mass% except a solvent component, Preferably it is 25-65 mass%. The higher the content, the better the light-shielding properties and the high chromaticity color characteristics can be obtained, but the relative dielectric constant may be increased by reducing the resin component.

(H) Solvent In the present invention, a solvent is usually used when preparing the photocurable composition. For example, esters, specifically ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Such as ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate 3-oxypropionic acid alkyl esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropionic acid Chill, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy-2- Methyl methyl propionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, Methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether , Methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .; aromatic hydrocarbons such as toluene, xyles and the like.

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

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

(I) Additive In addition to the above-described components, the photocurable composition contains various additives as necessary, for example, a filler, a polymer compound other than the alkali-soluble resin, a surfactant other than the above, Adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, and the like can be blended.

  Specific examples of these additives include fillers such as glass and alumina; itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, acidic cellulose derivative, hydroxyl group A polymer having an acid anhydride added thereto, an alcohol-soluble nylon, an alkali-soluble resin such as a phenoxy resin formed from bisphenol A and epichlorohydrin; a nonionic, a kachin-based, an anionic surfactant, etc. Phthalocyanine derivatives (commercially available products EFKA-745 (manufactured by Morishita Sangyo)); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, No. 90, No .95 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), W001 (manufactured by Yusho), and other cationic surfactants; polyoxy Tylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, manufactured by BASF) Nonionic surfactants such as L31, L61, L62, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1; anionic surfactants such as W004, W005, W017 (manufactured by Yusho) EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 4; Polymer dispersing agents such as 50 (manufactured by Morishita Sangyo), Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (San Nopco); Solsperse 3000, 5000, 9000, 12000, 13240, 13940 17000, 24000, 26000, 28000, etc. (Seneca Co., Ltd.); Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101 , P103, F108, L121, P-123 (Asahi Denka) and Isonet S-20 (Sanyo Kasei);

  Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl Adhesion promoters such as methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol) , 2, -Antioxidants such as di-t-butylphenol; ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone; and sodium polyacrylate And the like.

  Further, in the case of promoting alkali solubility in the unirradiated part and further improving the developability of the photocurable composition, an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less. Additions can be made. Specifically, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, glutar Aliphatic dicarboxylic acids such as acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as carbaryl acid, aconitic acid and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesin Aromatic polycarboxylic acids such as acid, merophanic acid, pyromellitic acid; phenylacetic acid, Doroatoropa acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

  In addition to the above components, the photocurable composition preferably further contains a polymerization inhibitor in order to suppress the change in viscosity over time of the resin composition at room temperature or refrigerated storage, for example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2'-methylenebis (4 -Methyl-6-t-butylphenol), 2-mercaptobenzimidazole and the like are useful. The storage stability can be improved by adding a thermal polymerization inhibitor to the photocurable composition of the present invention. As a compounding quantity of a polymerization inhibitor, it is 100 ppm-1 mass% normally with respect to a photopolymerizable monomer, Preferably about 500 ppm is added.

Next, the manufacturing method of the said photocurable composition is demonstrated.
The photocurable composition is prepared by mixing a colorant, an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and other additives used as necessary with a solvent and using various mixers and dispersers. Then, it can be prepared by mixing and dispersing.
The mixing and dispersing step preferably comprises kneading and dispersing followed by fine dispersion treatment, but it is also possible to omit the kneading and dispersion and perform only fine dispersion treatment.

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

In a particularly preferable kneading and dispersing step, first, a colorant such as an organic pigment or carbon black is kneaded with 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, blenders, single-screw and twin-screw extruders, etc., which disperse while giving a strong shearing force. Next, a solvent and an alkali-soluble resin (the remainder used in the kneading step) are added, and a particle size of 0.1 to 1 mm is mainly used using a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc. Disperse with beads made of glass, zirconia or the like. It is possible to omit this kneading step. In that case, beads are dispersed with a pigment and a dispersant or a surface treatment agent, an alkali-soluble resin and a solvent. In this case, the remaining alkali-soluble resin in the kneading step is preferably added during the dispersion.
Details of kneading and dispersing are described in TC Patton "Paint Flow and Pigment Dispersion" (published by John Wiley and Sons, 1964) and the like.

[II] Structure of Color Filter The color filter of this embodiment is a so-called COA type color filter disclosed in FIG. 1 of Japanese Patent Laid-Open No. 9-31347, and has a pixel and a pixel electrode on a TFT substrate. It is formed.

As the TFT substrate, for example, non-alkali glass, soda glass, pyrex glass, quartz glass used for liquid crystal display elements and the like, and those obtained by attaching a transparent conductive film to these, photoelectric conversion element substrates used for solid-state imaging elements, For example, a silicon substrate can be used. Furthermore, a plastic substrate is also possible. On these substrates, usually, black stripes for isolating each pixel are formed.
A TFT film is formed on the substrate, each pixel pattern is formed thereon, and a color filter layer is provided. Usually, a metal film such as a chromium thin film or a black colorant such as carbon black is dispersed in a portion facing the gate electrode. A light-shielding film made of a coating film is formed. Further, a pixel electrode corresponding to the gate electrode is formed in a pattern on the color filter layer. The pixel electrode is formed on a metal oxide thin film formed by a vacuum film formation method such as sputtering or vapor deposition of metal oxides such as ITO (indium tin oxide, a mixture of indium oxide and tin oxide), tin oxide, and indium oxide. A positive photoresist is applied, and a pixel electrode pattern is formed by a photoresist method. After forming the pixel electrode, the resist film remaining on the electrode is removed with a stripping solution. The removal of the cured resist film with the stripping solution is usually performed with an organic solvent having a high dissolving power at a high temperature close to 100 ° C., and thus the color filter layer may be destroyed. Therefore, a pixel protective film may be formed between the color filter layer and the pixel electrode in order to protect the color filter layer from the peeling solution. As a protective film forming material, the photocurable composition according to claims 9 to 16 is applicable.

Raw materials for plastic substrates include (1) amorphous polyolefin, (2) polyethersulfone, (3) polyglutarimide, (4) polycarbonate, and (5) polyethylene terephthalate in terms of optical properties, heat resistance, mechanical strength, etc. , (6) polyethylene naphthalate, (7) norbornene polymer, (8) polyimide using bisaniline fluorene as a diamine component, and (9) polyester composed of bisphenol fluorene and dibasic acid. Among these, (2) polyethersulfone, (4) polycarbonate, (5) polyethylene terephthalate, and (7) norbornene polymer are preferable. Such raw materials are particularly preferred for LCD applications.
The properties required for plastic substrates include low thermal expansion (preventing deterioration of display accuracy associated with the curing process during color filter creation), gas barrier properties (ensuring liquid crystal stability), optical transmittance and optical isotropy, etc. Characteristics, surface smoothness, etc. Regarding thermal expansion, the thermal expansion coefficient is preferably 10 ⁻⁴ or less.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface.

The pixel is a layer formed by applying a photocurable composition onto the TFT substrate. The coating thickness (after drying) of the photocurable composition is generally 0.3 to 5.0 μm, preferably 0.5 to 3.5 μm. The higher the coating thickness, the higher the chromaticity can be achieved. However, the thicker the coating thickness, the lower the resolution of the contact hole.
As the pixel electrode, a conventionally known pixel electrode can be used without particular limitation.

The color filter of the present invention can be provided with a black matrix, a spacer, a protective layer, a contact hole forming layer, and the like in addition to the pixel and the pixel electrode. That is, when these layers are not provided, the configuration is TFT substrate / pixel / pixel electrode. When these layers are provided, these layers are provided between the TFT substrate and the pixel or between the pixel and the pixel electrode. Intervening layers.
When these layers are disposed, conventionally known materials and thicknesses can be adopted without particular limitation as the forming material and thickness of these layers.

[III] Color filter production method and method of use The color filter of the present invention is formed by coating the photocurable composition on a TFT substrate to form a coating film of the photocurable composition, and forming a pattern on the coating film. Exposure, alkali development, and post-bake treatment are performed to form each pixel, a transparent electrode (ITO) film is formed on each pixel by sputtering, and then a positive-type photoresist coating film is formed. It can be manufactured by performing pattern exposure and development on the film, further etching the necessary ITO to form a pixel electrode pattern, and then removing the photoresist film remaining on the pixel electrode pattern with a stripping solution it can.

  In order to form the coating film by applying the photocurable composition, it is applied to the substrate by a coating method such as spin coating, slit coating, casting coating, roll coating or the like directly or via another layer. What is necessary is just to dry (pre-bake). Drying (prebaking) of the photocurable composition layer applied on the substrate can be performed at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, an oven, or the like.

Further, the pattern exposure of the coating film is made up of pixels of each color (three colors or four colors) by exposing through a predetermined mask pattern, curing only the coating film portion irradiated with light, and developing with a developer. This can be done by forming a patterned film. As radiation that can be used in exposure, ultraviolet rays such as g-line and i-line are particularly preferably used.
Next, by performing an alkali development treatment, the light-irradiated portion is eluted in the alkaline aqueous solution by the exposure, and only the photocured portion remains. As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.
Examples of the alkali include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene. An alkaline aqueous solution obtained by diluting an organic alkaline compound such as the above with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is used. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.
Next, excess developer is washed away and dried, followed by heat treatment (post-bake). Thus, the said process can be repeated sequentially for every color, and a cured film can be manufactured. Thereby, a color filter is obtained.

The post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 200 ° C. to 240 ° C. is performed.
This post-bake treatment is performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.

Then, a transparent electrode (ITO) film is formed on the formed pixel by sputtering, a positive photoresist film is further formed thereon, pattern exposure and development are performed, and unnecessary with chemicals such as hydrofluoric acid. ITO is etched to form pixel electrodes. As the photoresist used at this time, a positive photoresist having etching resistance is required. In addition, pattern exposure, development, and etching can be performed using any known method without limitation.
Next, the positive resist remaining on the formed pixel electrode is quickly stripped and removed with a stripping solution. There is no restriction | limiting in particular as this stripping solution, A conventionally well-known stripping solution can be used. For example, various publications disclosed in JP-A-51-72503, JP-A-57-84456, JP-A-6-222573, etc., and U.S. Pat. No. 4,165,294 and European Patent No. 0119337. These organic solvents can be used. A typical stripping solution includes a mixed solvent of monoethanolamine (MEA) and dimethyl sulfoxide (DMSO). Further, by using an organic solvent heated to 60 ° C. or higher as the stripping solution, the stripping process can be shortened, and further, there can be no problem of development residue. Since the photocurable composition in the present invention is particularly excellent in stripping liquid resistance, the coating film of the color filter is not peeled off even when an organic solvent heated to 60 ° C. or higher is used. Can be removed.

The color filter of the present invention is usually used in various display devices such as a TFT liquid crystal display device having a structure as disclosed in FIG. 1 of JP-A-9-31347.
Since the color filter of the present invention is a COA type, alignment is easy and the aperture ratio can be increased. In addition, since the pixels are formed using the photocurable composition, the resistance to the stripping solution is high, so that the non-defective rate is high and the production efficiency is also high. In addition, heat discoloration, low dielectric constant, film thickness uniformity, resolution, voltage holding ratio, light resistance and the like normally required for color filters are also good.

[IV] Description of Form (2) of the Present Invention In the form (2) of the present invention, the pixel protection according to (2) does not include a colorant between the color filter layer (pixel layer) and the pixel electrode. By providing the film layer, it is possible to protect the pixel of the conventional color filter having poor resistance to the stripping solution and to flatten the transparent electrode applied thereon by sputtering.
Hereinafter, differences from the above-described form (1) of the present invention will be particularly described. In addition, the description in said [I]-[III] is applied suitably about the point which is not demonstrated in particular.

(A) Photocurable composition for pixels The photocurable composition for pixels contains the colorant, the alkali-soluble resin, the photopolymerizable monomer, and the photopolymerization initiator. That is, it does not contain the polyfunctional epoxy compound, and is the same as the photocurable composition except that it does not contain the imidazole compound, the epoxysilane compound, and the imidazolesilane compound that are preferably blended, These specific examples and blending ratios are the same as those of the above-described photocurable composition.
(B) Photocurable composition for pixel protective film The photocurable composition for pixel protective film contains the alkali-soluble resin, the photopolymerizable monomer, the photopolymerization initiator, and the polyfunctional epoxy compound. Become. That is, it is the same as the photocurable composition except that it does not contain the colorant, and preferably contains the imidazole compound, the epoxysilane compound, and the imidazolesilane compound and / or a derivative thereof. The The benzophenone-based organic peroxide is preferably used as the thermal polymerization initiator.
These specific examples and blending ratios are the same as those of the above-described photocurable composition.

(C) Color filter structure The color filter structure is composed of only one layer of pixels in the embodiment (1) of the present invention, whereas in the present embodiment, the pixel photocuring is performed. Two layers of a pixel film made of a coating film of a photosensitive composition and a pixel protective film made of the photocurable composition for a pixel protective film formed on the pixel film are provided between the substrate and the pixel electrode.
The film thickness of the pixel film is preferably 0.3 to 5.0 μm, and more preferably 0.5 to 3.5 μm. The higher the coating thickness, the higher the chromaticity can be achieved. However, the thicker the coating thickness, the lower the resolution of the contact hole. The film thickness of the pixel protective film is preferably 0.2 to 5.0 μm, and more preferably 0.2 to 3.0 μm. Further, it is desirable that the unevenness of the underlying pixel is flattened so that the surface is smooth.

(D) Color filter manufacturing method The color filter of the present embodiment is formed by coating the pixel photocurable composition on a TFT substrate to form a pixel photocurable composition coating film, followed by pattern exposure. After each pixel is formed by performing alkali development and post-baking treatment, a coating film of the photo-curable composition for the pixel protective film is further formed, and contact holes are formed by pattern exposure and alkali development, and post-baking treatment. I do. Next, a transparent electrode (ITO) film is formed, and pixel electrodes are formed by pattern exposure, development, and etching in the same manner as described above. Next, the positive resist is stripped with a stripping solution. As the stripping solution, it is preferable to use the organic solvent having a temperature of 60 ° C. or higher. That is, by using a relatively high temperature polar organic solvent, the resist stripping process is shortened, leading to a reduction in fixing cost.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not restrict | limited to these.

[Examples 1 to 9]
A color filter specimen was prepared as described below.
a) The film thickness after curing (after post-baking) the photocurable coloring composition having the composition shown in Table 1 on a glass substrate for LCD (product name 1737, 1.1t) manufactured by Corning, Inc. is 3.0 μm. The number of rotations was adjusted so that
b) Next, it was pre-baked on a hot plate at 100 ° C. for 120 seconds and dried in a solvent.
c) Then, using a 2.5 Kw ultra-high pressure mercury lamp, light was irradiated through the mask at an exposure amount of 200 mJ / cm ² .
d) Next, it was immersed in an organic alkali developer (manufactured by Fuji Film Arch Co., Ltd., organic alkaline aqueous solution CD-2000, diluted with 12.5% pure water) at 26 ° C. for 50 seconds, developed, washed with water, and dried.
e) Next, it was heat-cured (post-baked) at 220 ° C. for 40 minutes in a hot air circulating dryer.
And the following peeling solution tolerance test was done about the obtained test piece. The results are shown in Table 1 below.

<Release solution resistance>
The stripping solution was a mixture of monoethanolamine (MEA) and dimethyl sulfoxide (DMSO) (I; MEA / DMSO = 3/7, II; MEA / DMSO = 7/3 (both mass ratio)), After immersing the test piece at 80 ° C. × 2 minutes, it was washed with water, dried at 90 ° C. for 20 minutes, and then subjected to a stripping solution resistance test.
The superiority or inferiority of the stripping solution resistance is determined by measuring the swelling ratio before and after immersion in the stripping solution with a film thickness change (film thickness meter = stylus type surface shape measuring instrument; DEKTAK3 manufactured by ULVAC, Inc.) and chromaticity change ΔE * ab It was judged by measuring (spectrophotometer: MCPD-1000 manufactured by Otsuka Electronics Co., Ltd.).
The swelling ratio is determined by measuring the film thickness (A) of the test piece in advance, immersing the test piece at 80 ° C. for 2 minutes, washing with water, and further drying at 90 ° C. for 20 minutes, and then again the film thickness (B). Was calculated by the formula Sw = (BA) × 100 / A.
The results were measured for both stripping solutions I and II for chromaticity changes and for the stripping solution I only for the swelling rate. The results are shown in Table 1.

[Comparative Examples 1-5]
A test piece was prepared in the same manner as in Examples 1 to 9 except that the composition of the composition was as shown in Table 2 below, and the stripping solution resistance was evaluated. The results are shown in Table 2.

[Example 10 and Comparative Examples 6-7]
A test piece was prepared in the same manner as in Examples 1 to 9 except that the composition of the composition was as shown in Table 3 below, and the stripping solution resistance was evaluated only for the swelling rate. The results are shown in Table 3.

As is apparent from the results shown in Tables 1 to 3, Examples 1 to 9 which are the color filters of the present invention have practically all films firmly adhered to the glass substrate even after immersion in the stripping solution. Although the swelling ratio and chromaticity change were satisfactory without any problem, in Comparative Examples 1 to 5, the cured film was peeled off from the glass substrate when immersed in the stripping solution, and the change in film thickness or chromaticity could not be measured. It was.
Further, Example 10 had no problem in the swelling rate, but Comparative Examples 6 to 7 were peeled off and could not be measured.
When the film thickness was measured again after further heating the swollen test piece at 220 ° C. for 40 minutes, in Examples 1 to 9 and Example 10, both returned to the original film thickness before immersion in the stripping solution. This means that the stripping solution contained in the swollen film was evaporated by heating above the boiling point of the stripping solution. Even when the film itself was observed with an optical microscope, no change was observed. Therefore, in the stripping solution resistance test of the example, the film is not eroded at all and is swollen with the stripping solution, and it can be seen that it returns to the original state by performing the heat treatment above the boiling point of the stripping solution again. .
Other than this, there was no difference in resolution, heat discoloration, light resistance, relative permittivity, and storage stability at 25 ° C., and good performance was exhibited.

Claims (19)

In a color filter in which a pixel electrode is formed directly on each pixel formed on a TFT substrate or via another layer or directly via another layer (excluding a liquid crystal layer),
Each pixel is formed using a photocurable composition containing at least a colorant, an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a polyfunctional epoxy compound having four or more functions. Color filter. The color filter according to claim 1, wherein the polyfunctional epoxy compound contained in the photocurable composition is a polyfunctional alicyclic epoxy compound represented by the following general formula (1).

In the formula, R ′ represents a residue obtained by removing n hydrogen atoms substituted by [—O— (A) _m —H] _n from the hydrocarbon R. A represents an alicyclic group having the following structure having at least one epoxy group. m represents 1-100. n represents 1-100. However, m × n is 4 to 100, and a plurality of A may be the same or different.

The color filter according to claim 1 or 2, wherein the photocurable composition further contains an imidazole compound represented by the following general formula (I) and an epoxysilane-based compound represented by the following general formula (II).

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

In the formula, R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 3 carbon atoms, m represents an integer of 1 to 20, and n represents an integer of 1 to 3.   The photocurable composition further includes an imidazole silane compound and / or a reaction product of the imidazole compound represented by the general formula (I) and the epoxy silane compound represented by the general formula (II). The color filter according to claim 1 or 2, comprising a derivative thereof.   The color filter according to claim 1, wherein the photocurable composition further contains a thermal polymerization initiator.   The color filter according to claim 5, wherein the thermal polymerization initiator is an organic peroxide. The color filter according to claim 6, wherein the organic peroxide is a benzophenone-based organic peroxide represented by the following general formula (III).

In the formula, R ₁ and R ₂ each independently represent an alkyl group or aralkyl group having 1 to 20 carbon atoms, and R ₃ and R ₄ each independently represent a hydrogen atom, a carboxyl group, or an alkyl having 1 to 10 carbon atoms. Group, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a halogen atom, a cyano group, a nitro group, or a dialkylamino group having 2 to 20 carbon atoms, q is 0, 1 or 2 And r is 1, 2 or 3. The color filter according to claim 7, wherein the benzophenone-based organic peroxide is at least one kind represented by the following chemical formulas (1) to (5).

In a color filter in which a pixel electrode is formed directly on each pixel formed on a TFT substrate or via another layer or directly via another layer (excluding a liquid crystal layer),
Each pixel is formed of a photocurable composition for pixels containing a colorant, an alkali-soluble resin, a photopolymerizable monomer, and a photopolymerization initiator,
A pixel protective film formed from a photocurable composition containing at least an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, and a polyfunctional epoxy compound having four or more functionalities between each pixel and the pixel electrode The color filter characterized by being arranged. The color filter according to claim 9, wherein the polyfunctional epoxy compound contained in the photocurable composition is a polyfunctional alicyclic epoxy compound represented by the following general formula (1).

In the formula, R ′ represents a residue obtained by removing n hydrogen atoms substituted by [—O— (A) _m —H] _n from the hydrocarbon R. A represents an alicyclic group having the following structure having at least one epoxy group. m represents 1-100. n represents 1-100. However, m × n is 4 to 100, and a plurality of A may be the same or different.

The color filter according to claim 9 or 10, wherein the photocurable composition further contains an imidazole compound represented by the following general formula (I) and an epoxysilane-based compound represented by the following general formula (II).

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

In the formula, R ⁴ and R ⁵ each independently represent an alkyl group having 1 to 3 carbon atoms, m represents an integer of 1 to 20, and n represents an integer of 1 to 3.   The photocurable composition further includes an imidazole silane compound and / or a reaction product of the imidazole compound represented by the general formula (I) and the epoxy silane compound represented by the general formula (II). The color filter according to claim 9 or 10 containing the derivative.   The color filter according to any one of claims 9 to 12, wherein the photocurable composition further contains a thermal polymerization initiator.   The color filter according to claim 13, wherein the thermal polymerization initiator is an organic peroxide. The color filter according to claim 14, wherein the organic peroxide is a benzophenone-based organic peroxide represented by the following general formula (III).

In the formula, R ₁ and R ₂ each independently represent an alkyl group or aralkyl group having 1 to 20 carbon atoms, and R ₃ and R ₄ each independently represent a hydrogen atom, a carboxyl group, or an alkyl having 1 to 10 carbon atoms. Group, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 10 carbon atoms, a halogen atom, a cyano group, a nitro group, or a dialkylamino group having 2 to 20 carbon atoms, q is 0, 1 or 2 And r is 1, 2 or 3. The color filter according to claim 15, wherein the benzophenone-based organic peroxide is at least one kind represented by the following chemical formulas (1) to (5).

  The photocurable composition according to any one of claims 1 to 8 is applied on a TFT substrate to form a coating film of the photocurable composition, and pattern exposure, alkali development, A post-baking process is performed to form each pixel, a transparent electrode (ITO) film is formed on each pixel, and then a positive photoresist coating film is formed on the transparent electrode (ITO) film. A photoresist coating film remaining on the transparent pixel electrode pattern after pattern exposure and development are performed on the photoresist coating film and an unnecessary transparent electrode (ITO) film is etched to form a transparent pixel electrode pattern. A method for producing a color filter that removes a film with a stripping solution.   Each pixel of a color filter is formed on a TFT substrate, and the photocurable composition according to any one of claims 9 to 16 is applied to the pixel to form a pixel protective film, The pixel protective film is subjected to pattern exposure, alkali development, and post-baking to form a pixel protective film, and then a transparent electrode (ITO) film is formed on the pixel protective film. ) After forming a positive photoresist coating film on the coating, pattern exposure and development on the positive photoresist coating film, and etching an unnecessary transparent electrode (ITO) film to form a transparent pixel electrode pattern A method for producing a color filter, wherein a photoresist coating film remaining on the transparent pixel electrode pattern is removed with a stripping solution.   The method for producing a color filter according to claim 17 or 18, wherein the stripping solution is an organic solvent at 60 ° C or higher.