JP4508928B2 - Photosensitive resin composition and color filter using the same - Google Patents

Description

  The present invention relates to a photocurable photosensitive 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.Red, green and blue pixels are thinned from 100 μm to 50 μm or less, and the black matrix is thinned from 20 μm to 10 μm or less. 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. For example, Patent Document 4 discloses a bifunctional aromatic compound. A synthesis method is described in which an epoxy acrylate compound and an acid dianhydride are reacted, and 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 remarkable improvement cannot be achieved in terms of heat discoloration, and it is difficult to solve by the manufacturing 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. There has been a demand for providing an improved material that does not sufficiently meet the fine line formation required for the forming material.

  Accordingly, an object of the present invention is to provide an alkali development type photosensitive resin composition that solves the above-mentioned problems, has high transparency, good heat yellowing resistance, and has high reliability capable of forming good fine lines. There is to do. 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 modified the alkali-soluble resin that has been conventionally used, and made this a component of the photosensitive resin composition. As a result, the present invention has been completed.

（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価のカルボン酸残基を示し、Y1、Y₂は独立に水素原子、-OC-Q-(COOH)_mで示され、Qはカルボン酸残基（mは1〜3の数を示す）を示し、nは1〜200の数を示す。） That is, the present invention is obtained by reacting a monofunctional epoxy compound with an alkali-soluble resin (I) represented by general formula (I) as an alkali-soluble resin in a photosensitive resin composition containing an alkali-soluble resin, It is a photosensitive resin composition characterized by containing an alkali-soluble resin (A) having an acid value in the range of 1 to 100 mgKOH / g.

(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 methyl. A represents -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) ₂ -,- O-, 9,9-fluorenyl group, or a straight bond, X represents a tetravalent carboxylic acid residue, Y1, Y ₂ is independently a hydrogen atom, represented by -OC-Q- (COOH) _m, Q represents a carboxylic acid residue (m represents a number of 1 to 3), and n represents a number of 1 to 200.)

（Zは、-C_mH_2n+1、-C₆H₅又は-C_nH_2n-OHを示し、m及びnは、それぞれ１〜10の数を示す。） Here, as a monofunctional epoxy compound, what is represented by the following general formula (II) is illustrated preferably.

(Z represents a _{-C m H 2n + 1, -C} 6 H 5 or -C _n H _2n -OH, m and n are each the number of 1 to 10.)

  The photosensitive resin composition of the present invention contains at least one photopolymerizable monomer (B) having an ethylenically unsaturated bond in addition to the alkali-soluble resin (A), and is photopolymerized with the alkali-soluble resin (A). It is preferable that the mixing ratio of the functional monomer (B) is 20/80 to 80/20 by weight. Also, 1 to 150 weights of one or more initiators (C) selected from a photopolymerization initiator and a sensitizer for 100 parts by weight of the total of the alkali-soluble resin (A) and the photopolymerizable monomer (B). A photosensitive resin composition comprising 50 parts by weight and 2 parts by weight of a colorant (E) is suitable for coloring applications. Furthermore, it is also possible to add 10 to 30 parts by weight of an epoxy compound (D) having one or more epoxy groups to a total of 100 parts by weight of the alkali-soluble resin (A) and the photopolymerizable monomer (B). Suitable for applications.

  Moreover, this invention is the coating film formed by hardening the said photosensitive resin composition. Furthermore, this invention is a color filter formed with the said coating film.

Hereinafter, the photosensitive resin composition of the present invention will be described in detail.
The photosensitive resin composition of the present invention is a photosensitive resin composition containing an alkali-soluble resin (A) as an essential component, and has properties as an alkali-developable photosensitive resin composition. This alkali-soluble resin (A) is also referred to as component (A). Other preferable optional components include the following components (B) to (E).
(B) a photopolymerizable monomer having at least one ethylenically unsaturated bond,
(C) a photopolymerization initiator, a sensitizer, or both (referred to as initiators),
(D) Compound having at least one epoxy group
(E) Colorant

  The alkali-soluble resin (A) is an alkali-soluble resin having an acid value in the range of 1 to 100 mgKOH / g obtained by reacting the alkali-soluble resin (I) represented by the general formula (I) with a monofunctional epoxy compound. Resin (A). When the acid value of the alkali-soluble resin (A) exceeds 100 mgKOH / g, the alkali solubility is too high, and the pattern of the exposed part penetrates into the alkaline aqueous solution, and it is easy to form a chipped or fringe shape in the pattern part. Absent.

  Here, the alkali-soluble resin (I) to be reacted with the monofunctional epoxy compound is obtained by reacting (meth) acrylic acid with an epoxy compound having two glycidyl ether groups derived from bisphenols. It is an epoxy (meth) acrylate acid adduct obtained by further reacting a compound having a polyvalent carboxylic acid. This alkali-soluble resin has an unsaturated group derived from (meth) acrylic acid having a photopolymerizable unsaturated bond, and is polymerizable, and has an acidic group derived from a polyvalent carboxylic acid. Show. In the present specification, the acid component means polyvalent carboxylic acids, and (meth) acrylic acid means acrylic acid, methacrylic acid or both.

The alkali-soluble resin (I) is preferably derived from an epoxy compound represented by the general formula (III). This epoxy compound is derived from bisphenols.

In the general formula (III), R ₁ , R ₂ , R ₃ and R ₄ are the same as described above, preferably a hydrogen atom, and 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 absent, preferably 9,9- A fluorenyl group; l is an integer of 0 to 10, preferably 0 or in the range of 0 to 2 as an average value. Here, the 9,9-fluorenyl group refers to a group represented by the following formula (IV).

  Examples of bisphenols that give preferred alkali-soluble resins 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 alkali-soluble resin can be obtained via 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. Any compound that significantly contains a compound having a glycidyl ether group can be used. Further, when the bisphenols are glycidyl etherified, oligomer units are mixed. If the average value of l in the formula (III) is in the range of 0 to 10, preferably 0 to 2, the present 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 (I). As the acid component, a polyvalent carboxylic acid capable of reacting with a hydroxy group in the molecule of the epoxy (meth) acrylate compound or an acid anhydride thereof (referred to as carboxylic acids) is used, and preferably a) dicarboxylic acids and b) Tetracarboxylic acids are used in combination.

Here, as a) dicarboxylic acids, chain hydrocarbon dicarboxylic acid or its acid anhydride, alicyclic dicarboxylic acid or its acid anhydride, aromatic dicarboxylic acid or its acid anhydride is used.
Examples of the chain hydrocarbon dicarboxylic acid or its acid anhydride include succinic acid, acetyl succinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citralmalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, oxoglutar There are compounds such as acid, pimelic acid, sebacic acid, suberic acid, diglycolic acid and the like, and further dicarboxylic acids having an arbitrary substituent introduced therein or acid anhydrides thereof may be used.
Examples of the alicyclic dicarboxylic acid or its acid anhydride include compounds such as hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, and any substituents introduced. Dicarboxylic acids or acid anhydrides thereof may be used.
Furthermore, examples of the aromatic dicarboxylic acid and its acid anhydride include compounds such as phthalic acid and isophthalic acid, and further dicarboxylic acids into which an arbitrary substituent is introduced or acid anhydrides thereof may be used.

In addition, as b) tetracarboxylic acids, chain hydrocarbon tetracarboxylic acid or its acid dianhydride, alicyclic tetracarboxylic acid or its acid dianhydride, or aromatic polyvalent carboxylic acid or its acid dianhydride Things are used.
Here, examples of the chain tetracarboxylic acid or its acid anhydride include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and the like, and further, tetracarboxylic acids having a substituent introduced therein or acids thereof. An anhydride may be used. Examples of the alicyclic tetracarboxylic acid or its acid anhydride include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid norbornanetetracarboxylic acid, and the like. It may be a tetracarboxylic acid having a substituent introduced therein or an acid anhydride thereof.
Furthermore, examples of the aromatic tetracarboxylic acid and acid anhydride thereof include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid, and acid anhydrides thereof, and further, substituents thereof. The introduced tetracarboxylic acids or acid anhydrides thereof may be used.

  One or more of a) dicarboxylic acids and b) tetracarboxylic acids can be used, respectively. The use ratio of a) dicarboxylic acids and b) tetracarboxylic acids is 0.1 to 10 as a molar ratio of a / b. The range is preferably 0.2 to 1.0. The use ratio can be selected as the optimum molecular weight, alkali developability, light transmittance, heat resistance, solvent resistance, and the pattern shape effect, but the higher the use ratio of tetracarboxylic acids, the higher the alkali solubility. Tend to be large and have a high molecular weight.

  The method for producing an alkali-soluble resin by reacting a reaction product obtained by reacting an epoxy compound with (meth) acrylic acid and a carboxylic acid is not particularly limited. Known methods as described can be employed. 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 the method for producing the alkali-soluble resin (I) is as follows when 9,9-bis (4-hydroxyphenyl) fluorene is used as a starting material.
First, 9,9-bis (4-hydroxyphenyl) fluorene and epichlorohydrin are reacted to synthesize a bisphenolfluorene type epoxy compound represented by the following general formula (III). A bisphenolfluorene type epoxy acrylate resin represented by the following general formula (V) was synthesized by reacting with (meth) acrylic acid represented by CH ₂ = CR ₅ -COOH, and then bisphenolfluorene in a propylene glycol monomethyl solvent. The epoxy acrylate resin and the acid component are reacted with heating to obtain a fluorene type alkali-soluble resin represented by the formula (I).

The alkali-soluble resin (I) represented by the general formula (I) obtained as described above is reacted with a monofunctional epoxy compound and has an acid value in the range of 1 to 100 mgKOH / g (A ) The reaction between the alkali-soluble resin and the monofunctional epoxy compound may be performed at a temperature of 60 to 80 ° C. for 6 hours or more.
Here, the monofunctional epoxy resin used in the reaction is not particularly limited as long as it is a monofunctional epoxy resin. For example, it is a powder compound at room temperature such as epoxypropylphthalimide and epoxynorbornene, or phenylglycidyl. Examples thereof include high boiling point compounds such as ether and p-butylphenol glycidyl ether, which are liquid at room temperature. Among the monofunctional epoxy resins, those represented by the general formula (II) are preferable, and styrene oxide, glycidol and the like are exemplified as preferable ones. In the general formula (II), Z represents —C _m H _{2n + 1} , —C ₆ H ₅ or —C _n H _2n —OH, and m and n each represent a number of 1 to 10.

  In the reaction between the alkali-soluble resin (I) and the monofunctional epoxy compound represented by the general formula (II), the acid value of the alkali-soluble resin (A) obtained by the reaction is the acid value of the alkali-soluble resin (I). The monofunctional epoxy compound is preferably reacted so as to be 1/10 to 9/10, preferably 2/10 to 8/10.

  The photosensitive resin composition of the present invention contains an effective amount of the alkali-soluble resin (A). The desirable blending amount of the alkali-soluble resin (A) varies depending on other blending components in the photosensitive resin composition, but the effect is obtained by containing it in a proportion of 1% by weight or more in the resin component. Here, the resin component includes a component that becomes a resin by polymerization or curing, and includes an oligomer and a monomer in addition to the resin.

  In the present invention, it is preferable to contain the above components (B) to (D) in addition to the above component (A) in order to take advantage of the characteristics of the photosensitive resin composition. Moreover, you may contain alkali-soluble resin (I) with the said (A) component. When the alkali-soluble resin (I) is contained together with the alkali-soluble resin (A), the alkali-soluble resin (I) is calculated as one of the components (A) in calculating the blending amount or blending ratio with other components. It is good.

  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, preferably 20/80 to 80/20, more preferably 40/60 to weight ratio (A) / (B). 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 the solubility in an alkali developer is lowered, and the pattern edge is scratched. If the amount of the photoreactive functional group in the resin is small, the cross-linked structure is not sufficiently formed, and the acid value in the resin component is too high. Since the solubility with respect to the alkaline developer in the portion is increased, there is a possibility that the formed pattern is thinner than the target line width or the pattern is easily lost.

  Examples of the (C) component initiators include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone. Benzophenones such as benzophenone, 2-chlorobenzophenone, p, p'-bisdimethylaminobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2- ( o-chlorophenyl) -4,5-phenylbiimidazole, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) biimidazole, 2- (o-fluorophenyl) -4,5-diphenylbiimidazole Imidazole, 2- (o-methoxyphenyl)- Biimidazole compounds such as 4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl- Halomethylthiazole compounds such as 5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole, 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- Methoxystyryl) -4,6- (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-methylsulfanylphenyl) butane-1, O-acyloxime compounds such as 2-dione-2-oxime-O-acetate and 1- (4-methylsulfanylphenyl) butan-1-oneoxime-O-acetate, benzyldimethyl ketal, thioxanthone, 2-chlorothio Xanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxone Organic compounds such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, anthraquinones such as 2,3-diphenylanthraquinone, organic peroxidation such as azobisisobutylnitrile, benzoyl peroxide, cumene peroxide Products, thiol compounds such as 2-mercaptobenzimidazole, 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.

  (C) The amount of the initiator used as the component is preferably 1 to 150 parts by weight, more preferably 2 to 30 parts by weight, based on a total of 100 parts by weight of the components (A) and (B). Particularly preferred is 5 to 20 parts by weight. 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 the pattern edge is not rattling and sharp.

  An epoxy resin can be mixed with the epoxy compound of component (D) 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 compounding amount of this epoxy compound is preferably in the range of 1 to 30 parts by weight, more preferably in the range of 10 to 30 parts by weight, with respect to 100 parts by weight of the total of the components (A) and (B). preferable.
The photosensitive resin composition containing the above components (A) to (E) as essential components is useful for color filter materials such as color filter inks and protective films, and can be dissolved in a solvent or various additives as necessary. Is blended.

  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 according to the use of the obtained color filter, and may be any of a pigment, a dye, or a natural pigment. 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 in the range of 50 to 2500 parts by weight, preferably 100 to 2000 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 (D) is lowered, and the content of the photosensitive resin as the original binder is also reduced. This may cause an undesirable problem that the film forming ability is impaired. The amount of colorant used varies depending on the color used, and may be used at a high concentration. Especially when a green pigment is used, it ranges from 5 to 25 times the total amount of the resin. It is preferable to make it. In the case of other colors, the range is preferably 0.5 to 5 times the total resin amount.

  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, additives, such as a hardening accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a leveling agent, an antifoamer, can be mix | blended with the photosensitive resin composition of this invention as needed. 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 advantageously comprises the above components (A) to (C) as essential components, and contains at least one of (D) and (E) components, or these and a solvent as main components. contains. 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%.

  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 three primary colors of red, green and blue is arranged on the substrate, and further, a protective film is formed on the photosensitive resin composition as a protective film thereon. In the same manner as described above, the liquid composition is coated, pre-baked, exposed, developed and post-baked to obtain a color filter on which a protective film is formed.

  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.

  According to the present invention, it is possible to provide an alkali-developable photosensitive resin composition that has high transparency, good heat yellowing resistance, and high reliability that enables good fine line formation. For this reason, the photosensitive resin composition of the present invention is particularly suitable for photosensitive resin compositions for color filters, and various multicolor display bodies such as color liquid crystal display devices, displays, color facsimiles, and image sensors, optical devices, and the like. It can be suitably used for colored inks used in the above.

Hereinafter, the present invention will be described in more detail with reference to synthesis examples, examples, and comparative examples. In addition, evaluation of resin in the following synthesis examples is as follows unless otherwise noted.
Solid content concentration: Determined by heating the resin solution at 160 ° C. for 2 hours.
Acid value: Determined by titration with 1 / 10N-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 fluorene bisphenol type epoxy resin and acrylic acid (manufactured by NS )
BPTA: Benzophenone tetracarboxylic dianhydride
CHDA: cyclohexanecarboxylic dianhydride
SA: Succinic anhydride
TPP: Triphenylphosphine
PGMEA: Propylene glycol monomethyl ether acetate
STO: Styrene oxide

Synthesis example 1
In a 500 ml four-necked flask equipped with a reflux condenser, were charged 198.53 g of 50% PGMEA solution of FHPA, 18.36 g of CHDA, 8.13 g of SA and 0.45 g of TPP, and stirred for 1 hour while heating at 120 to 125 ° C. The mixture was heated and stirred at -80 ° C for 6 hours. Thereafter, 8.6 g of STO was added, and the mixture was further stirred at 80 ° C. for 6 hours to synthesize an alkali-soluble resin solution (A) -1. The obtained resin solution had a solid content of 55 wt%, an acid value (in terms of solid content) of 50 mg KOH / g, an area% of alkali-soluble resin (A) -1 by GPC analysis of 91%, and Mw of 5500.

  In Synthesis Example 1, except that the amount of the monofunctional epoxy compound was changed, (A) -2 to (A) -4 were synthesized in the same manner, and (A) -5 to (A) -8 were synthesized. Were carried out in the same manner as (A) -1 to (A) -4 except that BPTA was used instead of CHDA, and eight types of resins described in Table 1 were synthesized.

  Hereinafter, the present invention will be described in detail based on examples of color filter production and comparative examples, but the present invention is not limited thereto. Here, the raw materials and abbreviations used in the production of the color filters of Examples and Comparative Examples are as follows.

(A) -1 to (A) -8: Alkali-soluble resins obtained in Synthesis Examples 1 to 8 above
(B) Ingredient: Trimethylolpropane triacrylate (trade name: TMPTA, manufactured by Nippon Shokubai Co., Ltd.)
(C) Component: Oxime ester photopolymerization initiator (CGI-242, manufactured by Ciba Specialty)
(D) Component: Biphenyl type epoxy resin (Japan Epoxy Resin, trade name YX-4000HK)
(E) -1 Component: Carbon black
(E) -2 Ingredients: Diketopyrrolopyrrole Red (CI Pigment Red 254)
(E) -3 Ingredients: Odor chlorinated phthalocyanine green (CI Pigment Green 36)
(E) -4 component: ε-phthalocyanine blue (CI pigment blue 15: 6)
Solvent-1: Propylene glycol monomethyl ether acetate solvent-2: Ethyl lactate additive-1: Silane coupling agent additive-2: Surfactant additive-3: Dispersant and dispersion aid

Examples 1 to 6 and Comparative Examples 1 and 2
The said compounding component was mix | blended in the ratio of Table 2, and the resin composition for BK resists of Examples 1-6 and Comparative Examples 1-2 was prepared.

Examples 7 to 12 and Comparative Examples 3 and 4
In the same manner as described above, resin compositions for red resist of Examples 7 to 12 and Comparative Examples 3 to 4 were prepared.

Examples 13 to 18 and Comparative Example 5
Resin compositions for green resists of Examples 13 to 18 and Comparative Example 5 were prepared in the same manner as described above.

Examples 19-24 and Comparative Examples 7-8
In the same manner as described above, resin compositions for blue resists of Examples 19 to 24 and Comparative Examples 7 to 8 were prepared.

The photosensitive resin composition obtained by uniformly mixing the BK resist and the RGB resist photosensitive resin compositions of Examples 1 to 24 and Comparative Examples 1 to 8, respectively, was obtained by using a spin coater to obtain a glass of 125 mm × 125 mm. It is applied on the substrate so that the film thickness after post-baking is 1.0 μm to 2.0 μm, pre-baked at 90 ° C. for 1 minute, and then 100 mj / cm ² ultraviolet rays with an ultra-high pressure mercury lamp with I-line illuminance of 30 mW / cm ² The photocuring reaction of the photosensitive part was performed. Next, this exposed coated plate is subjected to 0.1 MPa pressure shower development at 25 ° C. in 0.1% potassium hydroxide aqueous solution and 0.5 MPa pressure spray water washing to remove the unexposed portion of the coating film and evaluate the developability. I did it. Thereafter, the film was subjected to hot post-baking at 230 ° C. for 30 minutes using a hot air dryer to prepare a black matrix and an RGB application film, and development property evaluation and pattern shape evaluation were performed.

  Table 6 shows the evaluation results of development characteristics 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).
Development: Judgment was made when the pattern could be formed by an automatic alkali developing device, and when it was impossible, it was judged as x.
Development state: When patterning by development, the unexposed portion has a high dissolution mode in which a high solubility is maintained.
Development margin: When the exposed portion was developed with a 10 μm pattern mask, the time during which the pattern portion maintained 10 ± 1 μm was recorded. The line width was measured using a measuring microscope (trade name XD-20, manufactured by Nikon Corporation).
Taper margin: In the time obtained by the development margin, when observing the SEM shape, the pattern cross section maintained a forward taper, and a reverse taper or peeling occurred.
Adhesion: A post-baked patterned substrate is subjected to a PCT (pressure cooker) test under conditions of 121 ° C, 100% RH, 2atm, 24 hours, and then a cellophane tape is applied to the 20μm pattern area for a peeling test. The pattern adhesion was evaluated.
Line shape: The 10 μm line after development was evaluated with a microscope for the linearity of the pattern portion and the presence or absence of fringe. Therefore, those with very good linearity and no fringes were evaluated as “Good”, and those with fringe and poor linearity were evaluated as “No”.

  The evaluation results for the black resists listed in Table 2 are shown in Table 6. The evaluation results for the red resists listed in Table 3 are shown in Table 7. The evaluation results for the green resists listed in Table 4 are shown in Table 8. The experimental results for the blue resists listed in Table 5 are shown in Table 9.

  For the comparative example in which the component (A) is only (A) -1 or (A) -5, the pattern property evaluation was poor for any resist, and the overall evaluation as a resist was x. The evaluation of other resists to which the alkali-soluble resin (A) with reduced acid value was added was good.

Claims (7)

A photosensitive resin composition containing an alkali-soluble resin, obtained by reacting an alkali-soluble resin (I) represented by the general formula (I) with a monofunctional epoxy compound as an alkali-soluble resin, and having an acid value of 1 to 100 mgKOH A photosensitive resin composition comprising an alkali-soluble resin (A) in the range of / g.

(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 methyl. A represents -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) ₂ -,- O-, 9,9-fluorenyl group, or a straight bond, X represents a tetravalent carboxylic acid residue, Y1, Y ₂ is independently a hydrogen atom, represented by -OC-Q- (COOH) _m, Q represents a carboxylic acid residue (m represents a number of 1 to 3), and n represents a number of 1 to 200.) The photosensitive resin composition according to claim 1, wherein the monofunctional epoxy compound is represented by the following general formula (II).

(In the general formula (II), Z represents —C _m H _{2n + 1} , —C ₆ H ₅ or —C _n H _2n —OH, and m and n each represent a number of 1 to 10.)   It contains at least one photopolymerizable monomer (B) having an ethylenically unsaturated bond, and the blending ratio of the alkali-soluble resin (A) and the photopolymerizable monomer (B) is 20/80 to 80/20 by weight. The photosensitive resin composition according to claim 1 or 2.   1 to 150 parts by weight of one or more initiators (C) selected from a photopolymerization initiator and a sensitizer for a total of 100 parts by weight of the alkali-soluble resin (A) and the photopolymerizable monomer (B) The photosensitive resin composition of Claim 3 formed by mix | blending 50-2500 weight part of coloring agents (E).   4 or 3 parts by weight of 1 to 30 parts by weight of an epoxy compound (D) having one or more epoxy groups based on a total of 100 parts by weight of the alkali-soluble resin (A) and the photopolymerizable monomer (B). 4. The photosensitive resin composition according to 4.   The coating film formed by hardening the photosensitive resin composition in any one of Claims 1-5.   A color filter formed with a coating film obtained by applying and curing the photosensitive resin composition according to claim 1.