JP4489564B2 - Photosensitive resin composition and color filter using the same - Google Patents

Description

  The present invention relates to a photocurable resin composition and a color filter using the same, and more particularly to a photosensitive resin composition suitable for a resist for a color filter.

  A color liquid crystal display device includes a liquid crystal unit for controlling the amount of light transmitted or reflected and a color filter as components, and the method for producing the color filter is usually black on the surface of a transparent substrate such as glass or plastic sheet. Next, a method is used in which different colors of red, green, and blue are sequentially formed in a color pattern such as a stripe shape or a mosaic shape. In recent years, color liquid crystal display devices have been used in various fields such as liquid crystal televisions, liquid crystal monitors, and color liquid crystal mobile phones, and color filters are one of the important components that influence the visibility of these color liquid crystal display devices. is there. The pattern size varies depending on the use of the color filter and each color, but red, green and blue pixels are thinned from 200 to 300 μm to 100 μm, and the black matrix is thinned from 20 μm to 10 μm. High dimensional accuracy is required.

  As a photosensitive resin composition used for these color filter applications, a radiation sensitive resin having a fluorene skeleton has been proposed. For example, JP-A-4-345673, JP-A-4-345608, JP-A-4-355450, and JP-A-4-363311 disclose an epoxy (meth) acrylate having a bisphenolfluorene structure and a polybasic property. A heat-resistant liquid resin using a reaction product with carboxylic acid or its anhydride is disclosed. Although the cured product is excellent in transparency and heat resistance, it cannot be said that this resin can sufficiently satisfy the required performance. For example, when a film is formed using these resins and prebaked, sticking occurs, which may cause mask contamination. Therefore, there is a problem that a contact exposure method advantageous for improving the contrast of the pattern shape cannot be applied. In addition, there is also a problem that significant improvement cannot be achieved in terms of heat resistance and solvent resistance.

  Improvement research of the resin which has the said bisphenol fluorene structure is performed. For example, Patent Documents 1 to 3 below describe a synthesis method in which a bifunctional aromatic epoxy acrylate compound, an acid anhydride, and an acid dianhydride are simultaneously reacted to increase the molecular weight. A synthesis method is described in which a functional aromatic epoxy acrylate compound and an acid dianhydride are reacted, and then an acid anhydride is further reacted to cause a two-step reaction. Although these resins are excellent in transparency, developability, and heat resistance, it cannot be said that these resins can sufficiently satisfy the required performance. In addition, there is a problem that significant improvement cannot be achieved in terms of heat discoloration, and it is difficult to solve by only the synthesis method.

JP-A-5-339356, JP-A-6-1938 Japanese Patent Laid-Open No. 7-3122 Japanese Patent Laid-Open No. 2003-89716

  The compound having the bisphenolfluorene structure is a photosensitive resin composition obtained by reacting with an unsaturated acid anhydride or unsaturated acid dianhydride having an aromatic ring or an aliphatic double bond. It cannot be said that the performance required for the heat resistance and the heat resistance can be sufficiently satisfied. As a result, it was difficult to obtain a color filter having high transparency, good heat yellowing resistance and high reliability.

  Accordingly, an object of the present invention is to provide an alkali development type photosensitive resin composition that solves the above problems and obtains high reliability with high transparency and good heat yellowing resistance. Another object of the present invention is to provide a coating film and a color filter formed using this alkali development type photosensitive resin composition.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a reaction product of an aromatic epoxy compound derived from bisphenols and (meth) acrylic acid, and a) a saturated dicarboxylic acid or an acid thereof. It has been found that the above-mentioned problems can be solved by using a photosensitive resin composition containing an unsaturated group-containing compound obtained by reacting an anhydride and b) a saturated tetracarboxylic acid or an acid dianhydride thereof. The present invention has been completed.

  The present invention relates to a reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and (meth) acrylic acid, a) a saturated dicarboxylic acid or an acid anhydride thereof, and b) a saturated tetracarboxylic acid or A photosensitive resin composition comprising an alkali-soluble resin (A) obtained by reacting with the acid dianhydride as a main component of a resin component. Here, the molar ratio a / b of a) saturated dicarboxylic acid or its acid anhydride and b) saturated tetracarboxylic acid or its acid dianhydride is in the range of 0.1-10.

Moreover, this invention is said photosensitive resin composition containing the component of following (B)-(D) in addition to alkali-soluble resin (A).
(B) a photopolymerizable monomer having at least one ethylenically unsaturated bond,
(C) a photopolymerization initiator or sensitizer,
(D) Compound having at least one epoxy group

（一般式（I）において、Ｒ₁、Ｒ2、Ｒ3、Ｒ₄は独立に、水素原子、炭素数１〜５のアルキル基、ハロゲン原子又はフェニル基を示し、Ｒ₅は水素原子又はメチル基を示す。また、Aは-CO-、-SO₂-、-C(CF₃)₂-、-Si(CH₃)₂-、-CH₂-、-C(CH₃)₂-、-O-、9,9-フルオレニル基又は直結合を示し、Xは4価の飽和カルボン酸残基を示し、Y₁及びY₂は独立に水素原子、-OC-Z-(COOH)_mで示される飽和カルボン酸残基（mは1〜3の数を示す）を示し、nは1〜20の数を示す。） Furthermore, this invention is the said photosensitive resin composition by which alkali-soluble resin (A) is represented with the following general formula (I).

(In the general formula (I), R ₁ , R 2, R 3 and R ₄ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₅ represents a hydrogen atom or a methyl group. A is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O- , 9,9-fluorenyl group or a direct bond, X represents a tetravalent saturated carboxylic acid residue, Y ₁ and Y ₂ independently represent a hydrogen atom, saturated represented by -OC-Z- (COOH) _m A carboxylic acid residue (m represents a number from 1 to 3), and n represents a number from 1 to 20)

  Moreover, this invention is the coating film formed by hardening | curing the said photosensitive resin composition. Furthermore, this invention is a color filter which has a coating film obtained by apply | coating and hardening the said photosensitive resin composition.

Hereinafter, the photosensitive resin composition of the present invention will be described in detail.
The photosensitive resin composition of the present invention is a resin composition having properties as an alkali-developable photosensitive resin composition containing an alkali-soluble resin (hereinafter sometimes abbreviated as component (A)) as a resin main component. It is. The alkali-soluble resin has an unsaturated group derived from (meth) acrylic acid and thus has polymerizability, and a) a saturated dicarboxylic acid or an acid anhydride thereof (hereinafter sometimes abbreviated as saturated dicarboxylic acids) and b. ) Since it has an acidic group derived from saturated tetracarboxylic acid or its acid dianhydride (hereinafter sometimes abbreviated as saturated tetracarboxylic acid), it has alkali solubility.
In the present specification, the acid component means the saturated dicarboxylic acid, the saturated tetracarboxylic acid or both, and the saturation of the saturated dicarboxylic acid and the saturated tetracarboxylic acid constitutes a carboxyl group or an acid anhydride group. It means that there is no unsaturated bond (bond other than a single bond) other than a carbonyl group (> C═O), and (meth) acrylic acid means acrylic acid, methacrylic acid or both.

  The alkali-soluble resin of component (A) is obtained by reacting an epoxy compound having two glycidyl ether groups derived from bisphenols with (meth) acrylic acid, and the resulting compound having a hydroxy group into saturated dicarboxylic acids. And an epoxy (meth) acrylate acid adduct obtained by reacting with at least one of each of saturated tetracarboxylic acids. Since the component (A) has both an ethylenically unsaturated double bond and a carboxyl group, the protective film and the light-shielding film are imparted with excellent photocurability, good developability and patterning characteristics to the alkali-developable photosensitive resin composition. The physical properties of each pixel of red, green and blue are improved.

The component (A) is preferably derived from an epoxy compound represented by the general formula (II). This epoxy compound is derived from bisphenols.

In the general formula (I) and (II), R1, R2, R3, R 4 are independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, but a halogen atom or a phenyl group, preferably a hydrogen atom , R ₅ represents a hydrogen atom or a methyl group. Also, A is _{-CO -, - SO 2 -,} - C (CF 3) 2 -, - Si (CH 3) 2 -, - CH 2 -, - C (CH 3) 2 -, - O-, 9 , 9-fluorenyl group or absence, preferably 9,9-fluorenyl group. l is an integer of 0 to 10, preferably 0 or in the range of 0 to 2 as an average value. Further, Y1, Y ₂ represents, independently, a hydrogen atom, -OC-Z- (COOH) saturated carboxylic acid residues represented by _m (m is a number of 1 to 3), the number of n is from 1 to 20 N is preferably in the range of 1 to 10 as an average value. The 9,9-fluorenyl group refers to a group represented by the following formula (III).

  Examples of the bisphenols that give the alkali-soluble resin as the preferred component (A) include the following. Bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4 -Hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) Hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4- Hydroxy-3,5-dichlorophenyl) dimethylsilane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) Methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2 , 2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, Bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4-hydroxy-3,5-dichlorophenyl) ether and the like. In addition, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4- Hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9,9-bis (4- Hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, etc. are also preferred Can be mentioned. Furthermore, 4,4′-biphenol, 3,3′-biphenol and the like are also preferred.

  The component (A) can be obtained from an epoxy compound derived from bisphenols as described above. In addition to such an epoxy compound, a phenol novolac type epoxy compound, a cresol novolac type epoxy compound, etc. are also two glycidyl ethers. Any compound containing a group-containing compound can be used. In addition, when bisphenols are glycidyl etherified, oligomer units are mixed. If the average value of l in formula (II) is in the range of 0 to 10, preferably 0 to 2, this resin composition There is no problem in the performance of things.

  The reaction between such an epoxy compound and (meth) acrylic acid is carried out using about 2 moles of (meth) acrylic acid with respect to 1 mole of the epoxy compound. It is known. The reaction product obtained by this reaction is an epoxy (meth) acrylate compound represented by the following formula (V) as well as described in the above-mentioned patent documents.

  The reaction product obtained by the reaction of the epoxy compound and (meth) acrylic acid is reacted with the acid component to obtain the alkali-soluble resin (A). As the acid component, a) a saturated dicarboxylic acid and b) a saturated tetracarboxylic acid that can react with a hydroxy group in the epoxy (meth) acrylate compound molecule are used.

Here, as the a) saturated dicarboxylic acid, a saturated linear hydrocarbon dicarboxylic acid or an acid anhydride thereof or an alicyclic dicarboxylic acid or an acid anhydride thereof is used.
Examples of the saturated linear hydrocarbon dicarboxylic acid or its acid anhydride include, for example, succinic acid, acetyl succinic acid, adipic acid, azelaic acid, citrate malic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutaric acid, pimelic acid, There are compounds such as sebacic acid, suberic acid, and diglycolic acid, and further, straight-chain hydrocarbon dicarboxylic acids substituted with saturated hydrocarbons or acid anhydrides thereof may be used.
Examples of the alicyclic dicarboxylic acid or acid anhydride thereof include compounds such as hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, and alicyclic substituted with saturated hydrocarbons. Dicarboxylic acids or acid anhydrides thereof may be used.

Further, as the b) saturated tetracarboxylic acid, saturated linear hydrocarbon tetracarboxylic acid or its acid dianhydride or alicyclic tetracarboxylic acid or its acid dianhydride is used.
Here, examples of the saturated chain tetracarboxylic acid or an acid anhydride thereof include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and the like, and further saturated chain tetracarboxylic acid substituted with saturated hydrocarbon. Carboxylic acids or acid anhydrides thereof may be used.
Examples of alicyclic tetracarboxylic acids or acid anhydrides thereof include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid norbornanetetracarboxylic acid, and saturated carbonization. It may be an alicyclic tetracarboxylic acid substituted with hydrogen or an acid anhydride thereof.

  One or more of a) saturated dicarboxylic acids and b) saturated tetracarboxylic acids can be used, respectively, and the use ratio of a) saturated dicarboxylic acids and b) saturated tetracarboxylic acids is 0.1 as a molar ratio of a / b. A range of ˜10, preferably a range of 0.2˜1. The proportion used can be selected as the optimum molecular weight, alkali developability, light transmittance, heat resistance, solvent resistance, and pattern shape, but the higher the proportion of saturated tetracarboxylic acids used, the more alkaline The solubility tends to increase and the molecular weight tends to increase.

The method for producing the component (A) by reacting the reaction product obtained by the reaction between the epoxy compound and (meth) acrylic acid and the acid component is not particularly limited, and the above-mentioned Patent Documents 1 to 4 are not limited. A publicly known method as described in the above can be adopted.
Advantageously, it is desirable to react quantitatively so that the acid component is 1/2 mole per mole of hydroxy group in the epoxy (meth) acrylate compound molecule. The reaction temperature is 90 to 130 ° C, preferably 95 to 125 ° C.

An example of a method for producing the component (A) is as follows when a bisphenol such as 9,9-bis (4-hydroxyphenyl) fluorene is used as a starting material.
First, a bisphenol type epoxy compound represented by the following general formula (IV) is synthesized by reacting bisphenols with epichlorohydrin, and this bisphenol type epoxy compound and CH ₂ ═CR ₅ —COOH are represented ( A bisphenol type epoxy acrylate resin represented by the following general formula (V) is synthesized by reacting with (meth) acrylic acid, and then the bisphenol type epoxy acrylate resin and the above acid component are reacted with heating in a propylene glycol monomethyl solvent. To obtain an alkali-soluble resin represented by the formula (I) as the component (A).

式(IV)及び(V)において、Ｒ1、Ｒ2、Ｒ3、Ｒ4、Ｒ₅及びAは、式(I)及び(II)で説明したと同様な意味を有する。

In formula (IV) and (V), R1, R2, R3, R4, R 5 and A have the meanings same as those described in formula (I) and (II).

By the way, the alkali-soluble resin of the component (A) is also a novel resin.
In the preferred novel alkali-soluble resin, in formula (V), A is a group represented by formula (III), R _{1 to} R ₄ are all hydrogen atoms, and R ₅ is a hydrogen atom or a methyl group. An alkali-soluble resin (a) obtained by reacting a compound with a) a saturated dicarboxylic acid or acid anhydride thereof and b) a saturated tetracarboxylic acid or acid dianhydride within the above-mentioned molar ratio of a / b. A) There is. And a) saturated dicarboxylic acids are preferably one or more saturated dicarboxylic acids selected from hexahydrophthalic anhydride and succinic anhydride, and b) saturated tetracarboxylic acids are cyclohexanetetracarboxylic dianhydride, One or more saturated tetracarboxylic acids selected from butanetetracarboxylic dianhydride and cyclobutanetetracarboxylic dianhydride are preferred. Such an alkali-soluble resin (A) is represented by the formula (I), wherein X is a residue of a saturated tetracarboxylic acid, Y ₁ and Y ₂ are a) a saturated dicarboxylic acid and b) a saturated tetracarboxylic acid. However, at least a portion, preferably 50% or more, is a residue of a saturated dicarboxylic acid, and the other is a residue of a saturated tetracarboxylic acid, hydrogen, or both. In addition, the above is understood as description of preferable alkali-soluble resin from a viewpoint as invention of a novel resin.

  The photosensitive resin composition of the present invention contains the component (A) as a main component of the resin component. Here, a resin component means the component which becomes resin by superposing | polymerizing or hardening, and an oligomer and a monomer other than resin are included. Moreover, containing as a main component means containing 20 wt% or more, Preferably it is 50 wt% or more, More preferably, it contains 60 wt% or more. When calculated in a state excluding the solvent, it is preferable to contain 50 wt% or more, preferably 70 wt% or more. The photosensitive resin composition of the present invention may include the component (A) as an essential component, and components other than the component (A) may be non-resin components such as solvents, fillers, and colorants, even if they are resin components. There may be. According to the above resin component definition, components (B) and (D) described later correspond to resin components, and components (C) and (E) correspond to non-resin components.

In order to take advantage of the characteristics of the photosensitive resin composition, it is preferable to contain the following components (B) to (D).
(B) a photopolymerizable monomer having at least one ethylenically unsaturated bond,
(C) a photopolymerization initiator or sensitizer,
(D) Compound having at least one epoxy group

  Examples of the photopolymerizable monomer (B) having at least one ethylenically unsaturated bond include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-ethylhexyl (meth). Monomers having a hydroxyl group such as acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tetramethylene glycol di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol (Meth) acrylic acid esters such as tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, and the like. 1 type (s) or 2 or more types can be used.

  The blending ratio of these component (A) and component (B) is 20/80 to 90/10 in weight ratio (A) / (B), preferably 40/60 to 80/20, more preferably 60 / 40-80 / 20. When the blending ratio of the component (A) is small, the cured product after photocuring becomes brittle, and the acid value of the coating film is low in the unexposed area, so that the solubility in an alkaline developer is lowered and the pattern edge is jagged. If the amount is too large, the proportion of photoreactive functional groups in the resin is small and the cross-linked structure is not sufficiently formed. Further, the acid value in the resin component is too high, and the exposed portion Therefore, there is a possibility that the formed pattern is thinner than the target line width or the pattern is easily lost.

  Examples of the photopolymerization initiator or sensitizer of component (C) include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p- Acetophenones such as tert-butylacetophenone, benzophenones, 2-chlorobenzophenone, benzophenones such as p, p'-bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, and benzoin isobutyl ether 2- (o-chlorophenyl) -4,5-phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4 , 5-Diphenylbiimidazole, 2- (o -Methoxyphenyl) -4,5-diphenylbiimidazole, biimidazole compounds such as 2,4,5-triarylbiimidazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, Halo such as 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole Methylthiazole compounds, 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-phenyl -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4- Methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloroRmethyl) -1,3,5-triazine, 2- (4-M Xistyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine and other halomethyl-S-triazine compounds, 1,2-octanedione, 1- [ 4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), 1- (4-phenylsulfanylphenyl) butane-1,2-dione-2-oxime-O-benzoate, 1- (4-methyl O-acyloxime compounds such as sulfanylphenyl) butane-1,2-dione-2-oxime-O-acetate, 1- (4-methylsulfanylphenyl) butan-1-oneoxime-O-acetate, benzyldimethyl ketal , Thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2- Sulfur compounds such as sopropylthioxanthone, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutylnitrile, benzoyl peroxide, cumene peroxide, etc. Organic peroxides, thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine.

  These photopolymerization initiators and sensitizers can be used alone or in combination of two or more thereof.

  The amount of photopolymerization initiator or sensitizer used as component (C) is 2 to 30 parts by weight, preferably 5 to 20 parts by weight, based on a total of 100 parts by weight of the components (A) and (B). Part. When the blending ratio of the component (C) is small, the photopolymerization rate is slowed and the sensitivity is lowered.On the other hand, when the amount is too large, the sensitivity is too strong and the pattern line width becomes thicker than the pattern mask. On the other hand, there may be a problem that a faithful line width cannot be reproduced or a pattern edge is not jagged and sharp.

  The epoxy compound (D) can be mixed with an epoxy resin for the purpose of further improving adhesion and alkali resistance. Examples of the compound having an epoxy group include a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a biphenyl type epoxy resin, and an alicyclic epoxy resin. And compounds having at least one epoxy group such as phenyl glycidyl ether, p-butylphenol glycidyl ether, triglycidyl isocyanurate, diglycidyl isocyanurate, allyl glycidyl ether, and glycidyl methacrylate.

The amount of the epoxy compound is preferably in the range of 10 to 30 parts by weight with respect to 100 parts by weight as the total of the above components (A) and (B).
The photosensitive resin composition containing the component (A), preferably the components (A) to (D) as essential components, is useful for color filter materials such as color filter inks and protective films, and if necessary, a solvent. Or is mixed with various additives.

  When used as a color filter ink, a colorant can also be blended as the component (E). The colorant is not particularly limited in color tone, and is appropriately selected depending on the use of the obtained color filter, and may be any of a pigment, a dye, or a natural colorant. Since color filters require high-definition color development and heat resistance, pigments, particularly preferably organic pigments and carbon black are usually used.

  As the organic pigment, a single red pigment system may be used as the red pigment, or the yellow pigment system may be mixed with the red pigment system to perform color matching. Examples of red pigments include, for example, anthraquinone pigments, quinacridone pigments, diketopyrrolol pigments, perylene pigments, and particularly preferably diketopyrrolopyrrole red (CI pigment red 254) and dianthraquinolyl red (CI pigment red 177). Etc.

  Examples of yellow pigments include isoindoline yellow (C.I. Pigment Yellow 139), nickel azo yellow (C.I. Pigment Yellow 150), and diarylide yellow (C.I. Pigment Yellow 83). Two or more of these red pigment systems and yellow pigment systems can be used in combination. Further, when a mixture of a red pigment system and a yellow pigment system is used, it is preferable to use the yellow pigment system at 90 parts by weight or less with respect to 100 parts by weight of the total amount of the red pigment system and the yellow pigment system.

  As the green pigment, a single green pigment system may be used, or a yellow pigment system may be mixed with a green pigment system to perform toning. Examples of green pigments include chlorinated phthalocyanine green (C.I. Pigment Green 7) and odor chlorinated phthalocyanine green (C.I. Pigment Green 36). Examples of the yellow pigment system include isoindoline yellow (C.I. Pigment Yellow 139) and diarylide yellow (C.I. Pigment Yellow 83). Two or more of these green pigment systems and yellow pigment systems can be used in combination. When a green pigment system and a yellow pigment system are mixed and used, it is preferable to use the yellow pigment system at 90 parts by weight or less with respect to 100 parts by weight of the total amount of the green pigment system and the yellow pigment system.

  For the blue pigment, a single blue pigment system may be used, or the purple pigment system may be mixed with the blue pigment system to perform toning. Examples of blue pigments include phthalocyanine pigments and selenium pigments, particularly preferably ε-phthalocyanine blue (C.I. Pigment Blue 15: 6). Moreover, as a purple pigment type | system | group, dioxazine violet (C.I. pigment violet 23) etc. are mentioned, for example. Two or more of these blue pigments and purple pigments can be used in combination. When a blue pigment system and a violet pigment system are used in combination, it is preferable to use the violet pigment system in an amount of 90 parts by weight or less with respect to 100 parts by weight of the total amount of the blue pigment system and the violet pigment system.

  Examples of the light-shielding pigment include black organic pigments, mixed-color organic pigments, or light-shielding materials, and examples of the black organic pigment include perylene black and cyanine black. Examples of mixed color organic pigments include those obtained by mixing at least two pigments selected from red, blue, green, purple, yellow, cyanine, magenta and the like into a pseudo black color. Examples of the light shielding material include carbon black, chromium oxide, iron oxide, titanium black, aniline black, and cyanine black. Two or more types can be appropriately selected and used. The surface smoothness, dispersion stability, and compatibility with the resin are preferable.

  Moreover, a coloring agent can be used with a dispersing agent if desired. Examples of such a dispersant include cationic, anionic, nonionic, amphoteric, silicone and fluorine surfactants. Specific examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether.

  The amount of the colorant used as the component (E) is 30 to 280 parts by weight, preferably 50 to 230 parts by weight, based on 100 parts by weight of the total amount of the components (A) and (B). If the amount is small, the color purity or light shielding property is not sufficient, and in order to obtain a desired contrast, the film thickness must be increased, and the surface smoothness of the color filter is difficult to obtain. On the other hand, if the amount is too large, the dispersion stability of the photosensitive resin composition for color filters containing the component (A) is lowered, and the content of the photosensitive resin that is the original binder is also reduced. This may cause an undesirable problem that the film forming ability is impaired.

  When the photosensitive resin composition of the present invention is used for a color filter or the like, it is preferable to use a solvent in addition to the components (A) to (E). Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, propylene glycol, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2- Ketones such as pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene Glycol ethers such as glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl Examples include acetates such as ether acetate, and the like, and these can be dissolved and mixed to form a uniform solution-like composition.

  Moreover, the photosensitive resin composition of the present invention may contain additives such as a curing accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a solvent, a leveling agent, and an antifoaming agent as necessary. . Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenothiazine and the like, and examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, tricresyl and the like. Can include glass fiber, silica, mica, alumina, and the like, and examples of the antifoaming agent and leveling agent include silicon-based, fluorine-based, and acrylic compounds.

  The photosensitive resin composition of the present invention contains the above component (A), preferably the components (A) to (D) or (A) to (E), or these and a solvent as main components. In the solid content excluding the solvent (the solid content includes monomers that become solid content after curing), the total of components (A) to (D) is 70 wt% or more, preferably 80 wt%, more preferably 90 wt% or more It is desirable to include. The amount of the solvent varies depending on the target viscosity, but is preferably in the range of 20 to 80 wt%. When the photosensitive resin composition of the present invention is used for a color filter, it is suitable for use as a protective film.

  The coating film of the present invention can be obtained, for example, by applying a solution of the photosensitive resin composition to a substrate or the like, drying, irradiating light (including ultraviolet rays, radiation, etc.) and curing it. A coating film having a desired pattern can be obtained by providing a portion that is exposed to light and a portion not exposed to light, curing only the portion that is exposed to light, and dissolving the other portion with an alkaline solution.

  Next, the manufacturing method of the color filter using the photosensitive resin composition is demonstrated. First, on the surface of the substrate, if necessary, a light shielding layer is formed so as to partition a portion for forming pixels, and a liquid composition of a photosensitive resin composition in which, for example, a red pigment is dispersed on the substrate. After applying the material, pre-baking is performed to evaporate the solvent and form a coating film. Next, after exposing the coating film through a photomask, development using an alkaline developer is performed to dissolve and remove the unexposed portion of the coating film, and then post-baking to form a predetermined red pixel pattern. A pixel array arranged in an array is formed. Thereafter, using the liquid composition of the photosensitive resin composition in which the green or blue pigment is dispersed, the liquid composition is applied, pre-baked, exposed, developed, and post-baked in the same manner as described above. By sequentially forming a pixel array and a blue pixel array on the same substrate, a pixel array of the three primary colors of red, green and blue is arranged on the substrate, and further, a photosensitive film containing no colorant is used as a protective film thereon. In the same manner as described above, the liquid composition of the conductive resin composition is coated, pre-baked, exposed, developed and post-baked to obtain a color filter on which a protective film is formed. Here, in the color filter of the present invention, at least one of the photosensitive resin composition containing the colorant and the photosensitive resin composition not containing the colorant needs to be the photosensitive resin composition of the present invention. .

  When applying the liquid composition of the photosensitive resin composition to the substrate, any method such as a method using a roller coater machine, a land coater machine or a spinner machine as well as a known solution dipping method and spray method is adopted. can do. After applying to a desired thickness by these methods, the film is formed by removing the solvent (pre-baking). Pre-baking is performed by heating with an oven, a hot plate or the like, vacuum drying, or a combination thereof. The heating temperature and the heating time in the pre-baking are appropriately selected according to the solvent used, and for example, the heating is performed at a temperature of 80 to 120 ° C. for 1 to 10 minutes.

  As the radiation used when producing the color filter, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like can be used, and radiation having a wavelength in the range of 250 to 450 nm is preferable. . Examples of the developer suitable for the alkali development include, for example, an aqueous solution of an alkali metal or alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, and the like. It is better to develop at a temperature of 20-30 ° C. using a weakly alkaline aqueous solution containing 0.05-10% by weight of carbonate such as lithium carbonate, and a fine image using a commercially available developing machine or ultrasonic cleaner. Can be formed precisely. In addition, it is usually washed with water after alkali development. As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 10 to 120 seconds at room temperature.

  After the development as described above, a heat treatment (post-bake) is performed at a temperature of 180 to 250 ° C. and a condition of 20 to 100 minutes. This post-baking is performed for the purpose of improving the adhesion between the patterned coating film and the substrate. This is performed by heating with an oven, a hot plate or the like, as in the pre-baking. The patterned coating film of this invention is formed through each process by the above photolithography method.

  As a substrate used when forming a color filter having pixels and / or a black matrix, for example, glass, transparent film (for example, polycarbonate, polyethylene terephthalate, polyethersulfone, etc.), transparent such as ITO, gold, etc. A material in which an electrode is deposited or patterned is used. In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  The photosensitive resin composition for color filters of the present invention has high transparency, good heat yellowing resistance and high reliability, and therefore, the photosensitive resin composition for color filters of the present invention is a color liquid crystal. Various multicolor displays such as display devices, color facsimiles, image sensors, etc., colored inks for color filters used in optical equipment, etc., and color filters having a black matrix formed by these, televisions, videos It can be suitably used for a monitor or a computer display. In particular, it is suitable as a color filter protective film material. The color filter thus obtained is extremely useful for, for example, a transmissive or reflective color liquid crystal display device, a color imaging tube element, a color sensor, and the like.

Hereinafter, the present invention will be described in more detail with reference to synthesis examples, examples, and comparative examples. Evaluation of the resin in the following synthesis examples is as follows unless otherwise noted.
Solid content concentration: Obtained by heating the resin solution at 160 ° C. for 2 hours.
Acid value: Determined by titration with 1/10 N-KOH ethanol (50%) aqueous solution.
Molecular weight: determined by GPC. This molecular weight is the weight average molecular weight (Mw) in terms of polystyrene of the component (A) excluding unreacted raw materials.

The abbreviations used in the synthesis examples are as follows.
FHPA: Equivalent reaction product of a fluorene bisphenol type epoxy resin and acrylic acid (in the formula (V), A is a 9,9-fluorenyl group, and R _{1 to} R ₅ are all hydrogen atoms). In this synthesis example, ASF-400 (acid value 1.28 mg KOH / g, epoxy equivalent 21300) manufactured by Nippon Steel Chemical Co., Ltd. was used.
BPTA: Benzophenone tetracarboxylic dianhydride
CHDA: Cyclohexanetetracarboxylic dianhydride
BTA: Butanetetracarboxylic dianhydride
CBDA: Cyclobutanetetracarboxylic dianhydride
HHPA: Hexahydrophthalic anhydride
SA: Succinic anhydride
THPA: Tetrahydrophthalic anhydride
TPP: Triphenylphosphine
PGMEA: Propylene glycol monomethyl ether acetate

Synthesis example 1
In a 500 ml four-necked flask with a reflux condenser, 238.0 g of 50% PGMEA solution of FHPA, 33.0 g of CHDA, SA9.81 g, 46 g of PGMEA and 0.46 g of TPP are charged, and stirred for 1 hour while heating to 120 to 125 ° C. The alkali-soluble resin solution was synthesized by heating and stirring at 75 to 80 ° C. for 6 hours. The solid content of the obtained resin solution was 53.5 wt%, the acid value (in terms of solid content) was 150 mgKOH / g, the area% of the alkali-soluble resin (A) -1 in the resin solution by GPC analysis was 91%, and Mw was 10000 Met. Further, FIG. 1 shows an infrared absorption spectrum of the obtained alkali-soluble resin (A) -1.

Synthesis Examples 2-6
Alkali-soluble resins (A) -2 to (A) -6 were synthesized in the same manner as in Synthesis Example 1 except that the saturated acid anhydrides and saturated acid dianhydrides listed in Table 1 were used. The total molar ratio of the saturated acid anhydride and saturated acid dianhydride to FHPA used is the same as in Synthesis Example 1.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example and a comparative example, this invention is not limited to these. Here, the raw materials and abbreviations used in Examples and Comparative Examples are as follows.

(A) -1 to (A) -4: alkali-soluble resins obtained in Synthesis Examples 1 to 4 above
(B): A mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (manufactured by Nippon Kayaku Co., Ltd., trade name DPHA)

(C): Oxime ester photopolymerization initiator (CGI124, manufactured by Ciba Specialty)

(D): Fluorene type epoxy resin (manufactured by Nippon Steel Chemical Co., Ltd., trade name ESF-300)

Solvent-1: Propylene glycol monomethyl ether acetate solvent-2: Ethyl lactate additive-1: Silane coupling agent additive-2: Surfactant

  The said compounding component was mix | blended in the ratio of Table 2, and the resin composition of Examples 1-4 was prepared. In addition, the numerical value of a compounding quantity is a weight part.

The film thickness after post-baking of the photosensitive resin composition obtained by uniformly mixing the photosensitive resin compositions of Examples 1 to 4 above on a 125 mm × 125 mm glass substrate using a spin coater was 3.0 μm. Apply and pre-bake at 90 ° C for 2 minutes. Thereafter, an ultraviolet ray of 200 mJ / cm ² was irradiated with an ultrahigh pressure mercury lamp with an I-line illuminance of 30 mW / cm ² to carry out a photocuring reaction of the photosensitive part. Next, this exposed coated plate is subjected to 0.1MPa pressure shower development for 60 seconds at 23 ° C in 0.04% potassium hydroxide aqueous solution and spray water washing at 0.5MPa pressure to remove the unexposed area of the coating film and dry with hot air A protective film for color filters was prepared by post-baking at 230 ° C. for 30 minutes using a machine.

Furthermore, the heat-resistant discoloration evaluation was performed on the protective film-formed substrate that had been post-baked by heat treatment at 250 ° C. for 60 minutes using a hot air dryer.
Table 3 shows the evaluation results of light transmittance and the like in Examples and Comparative Examples. These evaluation methods are as follows.

Film thickness: measured using a stylus type step shape measuring device (trade name P-10, manufactured by KLA-Tencor Corporation).
Transmittance: Using a spectrophotometer, light transmittance was evaluated in the 400 nm wavelength region.
Thermal discoloration: Using a spectrophotometer, a transmittance of 96% or more was judged as ◎ <good>, a transmittance of 93-95% was judged as ◯, and a transmittance of 92% or less was judged as × <poor>.
Line shape: Using a measuring microscope, the pixel pattern after development was observed, and the case where peeling to the substrate or the pattern edge portion was not recognized was judged as ○ <good>, and the case where it was found was judged as x <bad>.
Residual film ratio: The ratio between the film thickness after pre-baking and the film thickness after development was evaluated.

Comparative Example 1
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the component (A) was changed to (A) -7, and a protective film for a color filter was prepared. About this, the transmittance | permeability was evaluated on the conditions similar to Example 1, However, The transmittance | permeability was 92% or less. Furthermore, heat resistance discoloration evaluation was performed, but the transmittance was 87% or less, which was poor (x). (A) -7 is an alkali-soluble resin synthesized using THPA instead of SA and BPTA instead of CHDA when producing the alkali-soluble resin (A) -1 of Synthesis Example 1. .

Comparative Example 2
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the component (A) was changed to (A) -8, and a protective film for a color filter was prepared. About this, the transmittance | permeability was evaluated on the conditions similar to Example 1, However, The transmittance | permeability was 95% or less. Furthermore, heat resistance discoloration evaluation was performed, but the transmittance was 91% or less, which was poor (x).
Note that (A) -8 is an alkali-soluble resin synthesized using THPA instead of SA in the production of the alkali-soluble resin (A) -1 of Synthesis Example 1.

Comparative Example 3
A photosensitive resin composition was prepared in the same manner as in Example 1 except that the component (A) was changed to (A) -9, and a protective film for a color filter was prepared. About this, the transmittance | permeability was evaluated on the conditions similar to Example 1, However, The transmittance | permeability was 95% or less. Furthermore, heat resistance discoloration evaluation was performed, but the transmittance was 91% or less, which was poor (x).
(A) -9 is an alkali-soluble resin synthesized using BPTA instead of CHDA when the alkali-soluble resin (A) -1 of Synthesis Example 1 was produced.

  With respect to the protective films for color filters of Comparative Examples 1 to 3, the remaining film ratio was measured and all were 97%.

Examples 5 and 6 and Comparative Examples 4 and 5
Each component was mix | blended in the ratio of Table 4, and the photosensitive resin composition was prepared. Here, a green pigment (salt brominated phthalocyanine: Pigment Green 36) which requires a larger amount of pigment than other colors was used as a colorant component.

  The photosensitive resin composition shown in Table 4 is used immediately after its production (immediately after), after storage for 24 hours at 25 ° C. (after 24 hours), and after storage for 72 hours at 25 ° C. (after 72 hours). The film was baked to a thickness of 2.0 μm, pre-baked at 90 ° C. for 2 minutes, and then photocured under the same conditions as in Example 1 using a predetermined mask. Thereafter, development was performed with an alkaline solution of 0.04% aqueous potassium hydroxide, and the development time (seconds from line confirmation to completion of development) and the line width of the cured part of the mask 100 μm line were measured. Table 5 shows the average measured values of the three samples. In the table, X in the development test indicates that development is not possible, and X having a line width of 100 μ indicates that line formation is not possible.

  In general, the smaller the amount of resin, the less the resin is cured and the lower the alkali solubility, making it difficult to form a line during photocuring. This tendency can also be confirmed from the above results. That is, in the system using (A) -1 as the component (A) in Examples 5 and 6, a line width could be formed in a stable alkali development time, and good results were obtained. In addition, the results after 24 hours and 72 hours of storage at room temperature were also stable with the development end time. On the other hand, Comparative Examples 4 and 5 are systems in which (A) -7 is used as the component (A). However, in these cases, the exposed part is peeled off at the time of alkali development, and no line can be formed at all. Even if it could be confirmed, it resulted in a defect that peeled off immediately. From the above results, it can be determined that even in the photosensitive resin composition having a high pigment concentration, those using (A) -1 maintain high alkali development characteristics and sensitivity.

Examples 7-9, Comparative Examples 6-8
Next, for each of red, green, and blue colors, photosensitive resin compositions were prepared at the blending ratios shown in Table 6, and the line widths when using a 100 μm mask were compared. As the colorant, red (Pigment Red254), green (Pigment Green36), and blue (Pigment Blue15: 6) were used, but Pigment Yellow 150 was used as a complementary color for green and red.

  The above-mentioned photosensitive resin composition was applied on a glass substrate, and the actual measurement value of the photocured portion after alkali development was measured with respect to a line of a mask 100 μm used for exposure according to each exposure amount (50 mJ, 100 mJ, 150 mJ). The results are shown in Table 7.

  From the results of Table 7, in the composition where only (A) -1 and (A) -7 of each color are different, after applying on the glass substrate, exposure, and alkali development, the photocuring part of each sample of the mask 100 μm When line widths are compared, in Examples 7 to 9 using (A) -1 for each color, a wide line width is maintained despite the same exposure amount as in Comparative Examples 6 to 8, respectively. It was possible to confirm high photocurability as a photocurable resin regardless of the pigment in each color.

IR spectrum of alkali-soluble resin (A) -1 obtained in Synthesis Example 1

Claims (5)

  A reaction product of an epoxy compound having two glycidyl ether groups derived from bisphenols and (meth) acrylic acid, a) a saturated dicarboxylic acid or an acid anhydride thereof, and b) a saturated tetracarboxylic acid or an acid dianhydride thereof. A photosensitive resin composition comprising, as a main component of a resin component, an alkali-soluble resin (A) obtained by reacting a product in a molar ratio of a / b of 0.1 to 10. The photosensitive resin composition of Claim 1 containing the component of following (B)-(D) in addition to alkali-soluble resin (A).
(B) a photopolymerizable monomer having at least one ethylenically unsaturated bond,
(C) a photopolymerization initiator or sensitizer,
(D) Compound having at least one epoxy group The photosensitive resin composition of Claim 1 or 2 with which alkali-soluble resin (A) is represented by the following general formula (I).

(In the general formula (I), R ₁ , R 2, R ₃ and R ₄ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₅ represents a hydrogen atom or a methyl group. A represents -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O -Represents a 9,9-fluorenyl group or a direct bond, X represents a tetravalent saturated carboxylic acid residue, Y ₁ and Y ₂ are independently represented by a hydrogen atom, -OC-Z- (COOH) _m A saturated carboxylic acid residue (m represents a number of 1 to 3), and n represents a number of 1 to 20)   The coating film formed by hardening the photosensitive resin composition in any one of Claims 1-3.   The color filter currently formed with the coating film obtained by apply | coating and hardening the photosensitive resin composition in any one of Claims 1-3.

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