JP7069081B2 - A photosensitive resin composition containing silica sol and a cured product using the same. - Google Patents

Description

In the present invention, a silica sol treated with a specific surface treatment agent (coupling agent) is used as an essential component, and a photosensitive film having excellent optical properties, hardness, adhesion, light resistance, chemical resistance, etc. can be obtained. The present invention relates to a sex resin composition.

Surface protective materials such as protective films for color filters, hard coat materials, and encapsulants for organic devices have transparency, light resistance, weather resistance, heat resistance, flatness, surface hardness, adhesion, chemical resistance, etc. Desired. In addition, as seen in the growing demand for touch panels, the demand for flat panel displays continues, and the required characteristics of surface protective materials are increasing in these fields as well. For example, the structure of a touch panel tends to be thinner and lighter, and the insulating film is required to have adhesion to a metal substrate, chemical resistance, etc. in addition to transparency, and the required items are diversified.

A cured resin product containing an inorganic compound such as silica particles or an inorganic filler is widely used as a protective material for a flexible circuit board, an interlayer insulating film, a protective film for a color filter, and the like. For example, Japanese Patent Application Laid-Open No. 2009-217037 exemplifies its application as a protective material for a circuit board, and discloses that it has a fine wire forming ability of about 30 μm and high thermal impact resistance. However, since the particle size of silica particles is relatively large at 0.5 μm, silica is assumed to be used as a coating material with high transparency and high hardness, for example, when a protective film for a color filter has a strong demand for high hardness. When the particles are contained in a high concentration, there is a concern that the resolution and transparency may decrease.

Further, Japanese Patent Application Laid-Open No. 2010-32916 exemplifies the application to a scratch-resistant layer material for an optical film containing nanosilica particles, and discloses an antiglare film having no whitening and excellent scratch resistance. Has been done. However, the curable resin used to obtain this film does not have alkali developability in particular, and cannot be applied to applications using an optical processing process utilizing alkali developability.

Further, Japanese Patent Application Laid-Open No. 2002-179993 exemplifies the application of a resin composition containing silica particles as a protective material for a thermosetting color filter, and discloses that the film thickness distribution due to foreign matter on the color filter can be reduced. Has been done. However, in this technique, the effect of correcting the non-uniformity of the film thickness is aimed at depending on the resin type used for the resin composition, and the effect directly given by the silica particles is limited.

On the other hand, Japanese Patent Application Laid-Open No. 2010-27033 discloses a photosensitive resin composition for an insulating film of a touch panel that does not contain an inorganic compound, and is excellent in transparency, adhesion to a glass substrate and a transparent conductive film, and scratch resistance. It is stated that it is. However, there is no mention of developability, chemical resistance and adhesion under high temperature and high humidity.

Japanese Unexamined Patent Publication No. 2009-217037 Japanese Unexamined Patent Publication No. 2010-32916 Japanese Patent Application Laid-Open No. 2002-179993 Japanese Unexamined Patent Publication No. 2010-27033

Therefore, as a result of diligent studies to solve the above-mentioned problems in the photosensitive resin composition containing an inorganic compound such as silica particles and an inorganic filler, the present inventors have obtained a specific surface treatment agent. By using the treated silica sol, the developability is not impaired even if the content of the silica sol in the photosensitive resin composition is increased, and the transparency, light resistance, weather resistance, heat resistance, flatness, and surface hardness are not impaired. The present invention has been completed by finding that a cured film having excellent adhesion and chemical resistance can be obtained.

Therefore, an object of the present invention is to provide a photosensitive resin composition having excellent transparency, light resistance, weather resistance, heat resistance, flatness, surface hardness, adhesion, chemical resistance, etc. while maintaining alkali developability. To do.

Another object of the present invention is to provide a cured product that is not deteriorated by light or heat, discolored with time, or the like.

（ただし、Ｒ₁、Ｒ₂、Ｒ₃、及び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、Ｘは9,9-フルオレニレン基を示し、Ｙは４価のカルボン酸残基を示す。Ｚは下記一般式（２）で表される置換基を示し、ｎは１～２０の数を表す。）

（但し、Ｌは２または３価のカルボン酸残基を示し、ｐは１または２である）

（但し、Ｒ₆は分子内にヘテロ原子を含んでもよい炭素数１～１０の炭化水素基を示し、Ｒ₇はそれぞれ独立に水素原子、炭素数１～４のアルキル基を示し、Ｒ₈はそれぞれ独立に炭素数１～４のアルキル基を示し、ｑは１～３である）
In the present specification, (i) an alkali-soluble resin having a carboxyl group and a polymerizable double bond in one molecule represented by the general formula (1), and (ii) polymerization having at least one polymerizable double bond. Essential is a sex compound, (iii) a silica sol treated with a surface treatment agent represented by the general formula (3) and having an average particle size of 10 to 300 nm, (iv) a photopolymerization initiator, and (v) a silane coupling agent. Disclosed is a photosensitive resin composition characterized by being contained as a component of the above.
That is, the present invention
(I) An epoxy-soluble resin having a carboxyl group and a polymerizable double bond in one molecule represented by the general formula (1), (ii) a polymerizable compound having at least one polymerizable double bond, (iii). ) Silica sol with an average particle size of 10 to 200 nm treated with a surface treatment agent represented by the general formula (3), (iv) a photopolymerization initiator, (v) a silane coupling agent, and (vi) two or more. Epoxy resin or epoxy compound having an epoxy group of is contained as an essential component, and the content of the essential component in the solid content is (i) 20 to 50% by mass for the alkali-soluble resin and (iii) 20 to 20 to the silica sol. 70% by mass, (v) 0.5 to 10% by mass of silane coupling agent, and (ii) polymerizable compound (i) / (ii) (mass ratio) = 40/60 to 90/10 , (Iv) The photopolymerization initiator is in the range of [(iv) / [(i) + (ii)]] (mass ratio) = 0.005 to 0.1, and (vi) the epoxy resin or epoxy compound. [(Vi) / [(i) + (ii)]] (mass ratio) = 0.05 to 0.3 with respect to the total of the alkali-soluble resin of the component (i) and the polymerizable compound of the component (ii). It is a photosensitive resin composition characterized by being in the range.

(However, R ₁ , R ₂ , R ₃ and R ₄ independently indicate a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₅ indicates a hydrogen atom or a methyl group. Further, X indicates a 9,9-fluorenylene group , Y indicates a tetravalent carboxylic acid residue, Z indicates a substituent represented by the following general formula (2), and n represents a number of 1 to 20. show.)

(However, L indicates a divalent or trivalent carboxylic acid residue, and p is 1 or 2).

(However, R ₆ indicates a hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom in the molecule, R ₇ independently indicates a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, respectively, and R ₈ indicates an alkyl group having 1 to 4 carbon atoms. Each independently represents an alkyl group having 1 to 4 carbon atoms, and q is 1 to 3).

In the present invention, (iv) the photopolymerization initiator is preferably an oxime ester-based photopolymerization initiator. (Vi) The epoxy resin or epoxy compound is a bisphenol fluorene type epoxy resin. (Iii) In a silica sol treated with a surface treatment agent represented by the general formula (3), R of the formula (3) ₆ Is a methyl group, an ethyl group or a propyl group, and R ₇ Is a methyl group or an ethyl group, and R ₈ Is a methyl group or an ethyl group.

Further, the present invention is a cured product obtained by curing the photosensitive resin composition. This cured product is particularly suitable as a protective layer for a color filter.

Since the photosensitive resin composition of the present invention contains a silica sol treated with a specific surface treatment agent, it has transparency and light resistance while maintaining developability as compared with the resin composition conventionally used in the field of electronic materials and the like. A cured product having excellent properties, weather resistance, heat resistance, flatness, surface hardness, adhesion, chemical resistance and the like can be obtained. Further, in the present invention, the developability is not impaired even if the content of the silica sol treated with the specific surface treatment agent in the photosensitive resin composition is increased. Therefore, the photosensitive resin composition of the present invention is extremely useful for forming protective films for semiconductor devices, encapsulants, insulating materials, etc., as well as color filter-related materials.

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 containing an alkali-soluble resin having a carboxyl group and a polymerizable double bond in one molecule represented by the general formula (1).

（ただし、Ｒ₁、Ｒ₂、Ｒ₃、及び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す。また、Ｘは-CO-、-SO₂-、-C(CF₃)₂-、-Si(CH₃)₂-、-CH₂-、-C(CH₃)₂-、-O-、9,9-フルオレニレン基又は直結合を示す。ここで、9,9-フルオレニレン基は、下記一般式（５）で表される基をいう。）

A method for producing an alkali-soluble resin having a carboxyl group and a polymerizable double bond in one molecule represented by the general formula (1) of the present invention will be described in detail.
First, (meth) acrylic acid is reacted with an epoxy compound having two glycidyl ether groups derived from bisphenols, particularly preferably an epoxy compound derived from bisphenols represented by the following general formula (4). Obtainable.

(However, 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 X is -CO-, -SO ₂ . -, -C (CF ₃ ) _2- , -Si (CH ₃ ) _{2-, -CH 2-, -C (CH 3) 2- , -O- ,} 9,9- shows a fluorenylene group or a direct bond. Here, the 9,9-fluorenylene group refers to a group represented by the following general formula (5).)

A known method can be used for the reaction of such an epoxy compound with (meth) acrylic acid, for example, about 2 mol of (meth) acrylic acid is used for 1 mol of the epoxy compound. The reactants obtained by this reaction are described in, for example, Japanese Patent Application Laid-Open No. 4-355450. The reactant obtained by this reaction is a diol compound (A) containing a polymerizable double bond, and is an epoxy (meth) acrylate compound as represented by the following general formula (6).

Preferred bisphenols that give epoxy (meth) acrylate from the bisphenol type epoxy compound represented by the general formula (6) include, for example, bis (4-hydroxyphenyl) ketone and bis (4-hydroxy-3,5-dimethyl). Phenyl) 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, etc. Can be mentioned. In addition, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, and 9,9-bis (4-hydroxyphenyl) fluorene in which X is a 9,9-fluorenyl group. 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 preferable. Can be mentioned. Further, 4,4'-biphenol, 3,3'-biphenol and the like are also preferably mentioned.

The alkali-soluble resin of the general formula (1) can be obtained from an epoxy compound derived from bisphenols as described above, but in addition to such epoxy compounds, phenol novolac type epoxy compounds, cresol novolac type epoxy compounds and the like are also available. Any compound having two glycidyl ether groups can be used as long as it significantly contains the compound. Further, when the bisphenols are glycidyl etherified, the oligomer unit represented by the following general formula (7) is mixed, and the average value of m in this general formula (7) is 0 to 10, preferably 0. If it is in the range of about 2, there is no problem in the performance of this resin composition.

In the production of an epoxy (meth) acrylate compound represented by the general formula (6) and an alkali-soluble resin having a carboxyl group and a polymerizable double bond in one molecule represented by the following general formula (1). The reaction conditions such as the solvent and the catalyst to be used are not particularly limited, but for example, a solvent having no hydroxyl group and having a boiling point higher than the reaction temperature is preferably used as the reaction solvent, and as such a solvent, for example, ethyl. Cellosolve-based solvents such as cellosolve acetate and butyl cellosolve acetate, high-boiling ether-based or ester-based solvents such as jiglime, ethylcarbitol acetate, butylcarbitol acetate and propylene glycol monomethyl ether acetate, and ketones such as cyclohexanone and diisobutylketone. It is preferable to use a system solvent or the like. As the catalyst to be used, for example, known catalysts such as ammonium salts such as tetraethylammonium bromide and triethylbenzylammonium chloride, and phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine may be used. can. These are described in detail in Japanese Patent Application Laid-Open No. 9-325494.

Next, the diol compound (A) containing a polymerizable double bond obtained by the reaction of the epoxy compound and (meth) acrylic acid is reacted with the acid component, and the inside of one molecule represented by the general formula (1) is formed. An alkali-soluble resin having a carboxyl group and a polymerizable double bond can be obtained. As the acid component, it is preferable to use a tetracarboxylic acid dianhydride (B), a dicarboxylic acid, a tricarboxylic acid or an acid monoanhydride (C) thereof that can react with a hydroxyl group in an epoxy (meth) acrylate compound molecule. The carboxylic acid residue of this acid component may have either a saturated hydrocarbon or an unsaturated hydrocarbon. Further, these carboxylic acid residues may contain a bond containing a hetero element such as —O—, —S—, and a carbonyl group. Among these, the tetracarboxylic acid dianhydride (B) includes an acid dianhydride of a chain hydrocarbon tetracarboxylic acid, an acid dianhydride of an alicyclic tetracarboxylic acid, and an acid dianhydride of an aromatic tetracarboxylic acid. Etc. can be used, and as the dicarboxylic acid, tricarboxylic acid or its acid monoanhydride (C), chain hydrocarbon dicarboxylic acid and tricarboxylic acid, alicyclic dicarboxylic acid and tricarboxylic acid, aromatic dicarboxylic acid and tricarboxylic acid can be used. Acids and the like can be used.

Here, examples of the acid dianhydride of the chain hydrocarbon tetracarboxylic acid include butanetetracarboxylic acid, pentanetetracarboxylic acid, acid dianhydride of hexanetetracarboxylic acid, and the like, and further, an alicyclic. It may be an acid dianhydride of a chain hydrocarbon tetracarboxylic acid having a substituent of the hydrocarbon.

As the acid dianhydride of the alicyclic tetracarboxylic acid, cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid, acid dianhydride of norbornantetracarboxylic acid and the like can be used. Further, it may be an acid dianhydride of an alicyclic tetracarboxylic acid having a substituent of a chain hydrocarbon. Examples of the acid dianhydride of the aromatic tetracarboxylic acid include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, diphenyl ether tetracarboxylic acid, and acid dianhydride of diphenylsulfone tetracarboxylic acid. .. The acid dianhydride in the present invention is preferably an acid dianhydride of biphenyltetracarboxylic acid, benzophenone tetracarboxylic acid or diphenyl ether tetracarboxylic acid, and more preferably an acid dianhydride of biphenyltetracarboxylic acid or diphenyl ether tetracarboxylic acid. be. Two or more of these acid dianhydrides can also be used in combination. For these, a simple tetracarboxylic acid may be used instead of the acid dianhydride.

Examples of the saturated chain hydrocarbon dicarboxylic acid and tricarboxylic acid include succinic acid, acetylsuccinic acid, adipic acid, azelaic acid, citralinic acid, malonic acid, glutaric acid, citric acid, tartrate acid, oxoglutaric acid, and pimelic acid. Examples thereof include sebacic acid, suberic acid, diglycolic acid and the like, and saturated chain hydrocarbon dicarboxylic acid and tricarboxylic acid having a substituent of an alicyclic hydrocarbon group may be used. Examples of the saturated alicyclic hydrocarbon dicarboxylic acid and tricarboxylic acid include hexahydrophthalic acid, cyclobutanedicarboxylic acid, cyclopentanedicarboxylic acid, norbornandicarboxylic acid, hexahydrotrimellitic acid and the like, and further. It may be an alicyclic dicarboxylic acid or a tricarboxylic acid having a substituent of a chain hydrocarbon. Examples of the unsaturated dicarboxylic acid and tricarboxylic acid include maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, chlorendic acid and trimellitic acid. Among these, succinic acid, itaconic acid, tetrahydrophthalic acid, hexahydrotrimellitic acid, phthalic acid and trimellitic acid are preferable, and succinic acid, itaconic acid and tetrahydrophthalic acid are more preferable. In addition, these acid monoanhydrides can also be used in combination of 2 or more types.

The method for reacting the diol compound (A) containing the polymerizable double bond with the acid components (B) and (C) is not particularly limited, and is described in, for example, JP-A-9-325494. As described, a known method is adopted in which the diol compound (A) containing a polymerizable double bond is reacted with the tetracarboxylic acid dianhydride (B) at a reaction temperature of 90 to 140 ° C. Can be done. Preferably, a diol compound (A), a tetracarboxylic acid dianhydride (B), a dicarboxylic acid, a tricarboxylic acid or an acid monoanhydride thereof containing a polymerizable double bond so that the terminal of the compound becomes a carboxyl group (A). It is desirable to make a quantitative reaction so that the molar ratio with C) is (A) :( B) :( C) = 1: 0.2 to 1.0: 0.2 to 1.0. In this case, the molar ratio [[(B) + (C)] / (A)] of the total amount of the acid component [(B) + (C)] to the diol compound (A) containing the polymerizable double bond is 0. It is desirable to react quantitatively so as to be .5 to 1.0. When the molar ratio is less than 0.5, the content of the diol compound containing an unreacted polymerizable double bond increases, and there is a concern that the stability of the alkali-soluble resin composition over time may decrease. On the other hand, when the molar ratio exceeds 1.0, the terminal of the alkali-soluble resin represented by the general formula (1) becomes an acid anhydride, and the content of the unreacted acid dianhydride increases to be alkaline-soluble. There is concern that the stability of the resin composition may decrease over time. The molar ratio of each component (A), (B) and (C) can be arbitrarily changed within the above range for the purpose of adjusting the acid value and molecular weight of the alkali-soluble resin represented by the above general formula (1). ..

Further, the polystyrene-equivalent weight average molecular weight (Mw) of the alkali-soluble resin of the above general formula (1) of the present invention as measured by gel permeation chromatography (GPC) is usually 1000 to 100,000 and 2000 to 20000. Is preferable. If the weight average molecular weight is less than 1000, the adhesion of the pattern during alkaline development may decrease.

The content of the alkali-soluble resin of the general formula (1), that is, the component (i) in the solid content of the photosensitive resin composition of the present invention is preferably 10 to 70% by mass, and 20 to 50% by mass. preferable. If the content of the component (i) in the solid content is small, the strength of the cured product decreases. On the contrary, if the amount is too large, the proportion of the silica sol of the component (iii) in the photosensitive resin composition of the present invention is reduced, and the effect of the silica sol on improving the surface hardness is not exhibited.

As the resin component of the photosensitive resin composition of the present invention, an alkali-soluble resin having a carboxyl group and a polymerizable double bond may be contained as an essential component in one molecule represented by the general formula (1), and one molecule may be contained. The components other than the alkali-soluble resin having a carboxyl group and a polymerizable double bond inside may be a resin component or a non-resin component such as a solvent or a filler. Here, the resin component refers to a component that becomes a resin by polymerization or curing, and examples thereof include epoxy resins and acrylic resins that are polymerized or cured by light or heat. Further, the resin component includes an oligomer and a monomer in addition to the resin.

In the present invention, in order to utilize the characteristics of the photosensitive resin composition, the following components (i), (ii), (iii), (iv) and (v) are contained as essential components. That is, (i) an alkali-soluble resin having a carboxyl group and a polymerizable double bond in one molecule represented by the general formula (1), and (ii) a polymerizable compound having at least one polymerizable double bond. (Iii) A silica sol having an average particle size of 10 to 300 nm treated with a surface treatment agent represented by the general formula (3), (iv) a photopolymerization initiator, and (v) a silane coupling agent are essential components. include.

Among these, as the polymerizable compound having at least one polymerizable double bond which is the component (ii), a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate and a monomer having a hydroxyl group and the like can be used. , Urethane (meth) acrylates such as pentaerythritol triacrylate and hexamethylene diisocyanate adduct, dipentaerythritol pentaacrylate and hexamethylene diisocyanate adduct, 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, Trimethylol propantri (meth) acrylate, Trimethylol ethanetri (meth) acrylate, Pentaerythritol di ( Meta) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, polyethylene glycol-modified bisphenol A di Examples of (meth) acrylic acid esters of polyhydric alcohols such as acrylates can be exemplified, and one or more of them can be used.

The compounding mass ratio [(i) / (ii)] of the component (i) and these components (ii) is preferably 20/80 to 95/5, preferably 40/60 to 90 /. It should be 10. If the proportion of the alkali-soluble resin having a carboxyl group and a polymerizable double bond in one molecule of (i) is small, there arises a problem that the cured product becomes brittle after curing. On the contrary, when the compounding ratio of the alkali-soluble resin having a carboxyl group and a polymerizable double bond in one molecule of (i) is larger than the above range, the ratio of the curable functional group in the resin component is small and the crosslinked structure is formed. May cause problems such as insufficient.

Further, as the silica sol treated with the specific surface treatment agent (coupling agent) represented by the general formula (3) in the component (iii), for example, methanol silica manufactured by Nissan Chemical Industry Co., Ltd., IPA-ST. , NPC-ST-30, MEK-ST, PMA-ST, MIBK-ST and other organosilica sol, Admatex Co., Ltd. SO-E1, SO-C1, Fuso Chemical Industry Co., Ltd. PL-1-IPA, Examples thereof include solvent-dispersed silica sol such as PL-1-PGME and PL-1-MEK. The average particle size of the silica sol is the average particle size obtained by the cumulant method using a measuring device of the dynamic light scattering method, and retains the transparency of the cured product obtained by curing the photosensitive resin composition of the present invention. The diameter is 10 to 300 nm, preferably 10 to 200 nm, and more preferably 20 to 100 nm. Further, the content of the silica sol in the solid content of the photosensitive resin composition of the present invention is preferably 10 to 70% by mass, preferably 15 to 70% by mass, and more preferably 20 to 70% by mass. If the content of the silica sol in the solid content is small, the effect of improving the surface hardness of the silica sol will not be exhibited. On the contrary, if it is too large, the ratio of the component (i) and the component (ii) in the photosensitive resin composition of the present invention decreases, and the strength of the cured product decreases.

Further, in the surface treatment agent represented by the general formula (3) used for the surface treatment of the silica sol of the component (iii), R ₆ represents a hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom in the molecule. Examples of these hydrocarbon groups include methyl group, ethyl group, propyl group, hexyl group, decyl group, 3-glycidoxypropyl group, vinyl group, styryl group, 3-methacryloyloxypropyl group and 3-acryloyloxy. Examples include propyl groups. Of these, when a surface treatment agent such as a hydrocarbon group having a polymerizable double bond or a reactive epoxy group is used for R ₆ , due to curing shrinkage when the photosensitive resin composition of the present invention is cured. Since there is a concern that the adhesion will be reduced, it is advantageous to have a large content of the silica sol that reduces the curing shrinkage. However, when the content of the silica _sol is high, a residue tends to remain during development, so a surface treatment agent such as a hydrocarbon group having a polymerizable double bond or a reactive epoxy group was used. In some cases, it becomes necessary to use a developer having a strong alkalinity (high pH) in alkaline development. Hydrocarbon groups in which R ₆ does not contain reactive groups such as polymerizable double bonds and epoxy groups are preferable from the viewpoint that adhesion is emphasized and it is difficult to use a developing solution having a strong alkalinity in development. .. Particularly preferably, it is a methyl group, an ethyl group or a propyl group. In the general formula (3), R ₇ independently represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, and R ₈ independently represents an alkyl group having 1 to 4 carbon atoms. Examples of these alkyl groups include a methyl group, an ethyl group, a propyl group and a butyl group, and a methyl group or an ethyl group is preferable. Q in the general formula (3) is 1 to 3.

Further, as a method for treating the silanol group on the silica sol surface with the surface treatment agent represented by the general formula (3), a known method can be used, for example, as described in Japanese Patent Publication No. 3-29823. It can be obtained by adding a surface treatment agent, an acid catalyst, and water to the silica sol and heating and stirring. The ratio of silanol groups on the surface of the silica sol with the surface treatment agent represented by the general formula (3) varies depending on the charging ratio of the silica sol and the surface treatment agent to be used, and the solvent type used for the silica sol and the photosensitive resin of the present invention. It can be arbitrarily changed according to each component in the composition.

In the silica sol treated with the surface treatment agent represented by the general formula (3), one R ₇ was eliminated from the general formula (3), R ₆ (OR ₇ ) _(q-1) R _{8 (3-q} ). ₎ A functional group in the form of Si-O- will be formed, and R ₆ , R ₇ , and R ₈ can be identified by ¹ H-NMR analysis.
Here, the amount of functional groups in the form of R ₆ (OR ₇ ) _(q-1) R _{8 (3-q)} Si-O- can be determined from the amount of weight loss in thermogravimetric analysis (TG). Specifically, the ratio of heat weight loss in the solid content of the surface-treated silica sol is defined as the degree of surface treatment. Regarding the measurement conditions of TG, in the present invention, first, the temperature was raised from room temperature to 150 ° C. at 10 ° C./min under a nitrogen atmosphere, and then the temperature was maintained at 150 ° C. for 30 minutes to remove volatile components. Then, in an air atmosphere, the temperature was raised from 150 ° C. to 550 ° C. at 10 ° C./min and then kept at 550 ° C. for 10 minutes to burn and volatilize all the organic components. The degree of surface treatment can be arbitrarily changed depending on the type of surface treatment agent and the alkali developability of the photosensitive resin composition of the present invention, but in the present invention, it is preferably in the range of 0.5 to 4% by mass. If the surface treatment degree is less than 0.5% by mass, the dispersion stability in the organic medium is lost and aggregation is caused. On the contrary, if it exceeds 4% by mass, the alkali developability is lost and a residue may be generated. There is.

Examples of the photopolymerization initiator of the component (iv) include acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone and p-tert-butyl. Acetphenones such as acetophenone, benzophenone, 2-chlorobenzophenone, benzophenones such as 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-diphenyl Biimidazole compounds such as biimidazole, 2- (o-methoxyphenyl) -4,5-diphenylbiimidazole, 2,4,5-triarylbiimidazole, 2-trichloromethyl-5-styryl-1,3 , 4-Oxaziazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4 -Halomethylthiazole compounds such as 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 (trichloro R-methyl) -1 , 3,5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4, Halomethyl-s-triazines such as 6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine Compounds, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (o-benzoyloxime), 1- (4-f) Enylsulfanylphenyl) Butane-1,2-dione-2-oxime-o-benzoate, 1- (4-methylsulfanylphenyl) butane-1,2-dione-2-oxime-o-acetate, 1- (4) -O-acyloxime compounds such as -methylsulfanylphenyl) butane-1-one oxime-o-acetate, benzyldimethylketal, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxane. Sonic, sulfur compounds such as 2-isopropylthioxanson, anthraquinones such as 2-ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutylnitrile, benzoyl peroxide, cumene Examples thereof include organic peroxides such as peroxide, thiol compounds such as 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole, and tertiary amines such as triethanolamine and triethylamine. As these photopolymerization initiators, one kind or two or more kinds thereof can be used.

Further, in the present invention, in addition to the photopolymerization initiator of the component (iv), a (vii) thermal polymerization initiator can be further used in combination. Examples of the thermal polymerization initiator of the component (vii) include benzoyl peroxide, lauroyl peroxide, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-2-ethylhexanoate, 1,1-. Organic peroxides such as t-butylperoxy-3,3,5-trimethylcyclohexane, azobisisobutyronitrile, azobis-4-methoxy-2,4-dimethylvaleronitrile, azobiscyclohexanone-1-carbonitrile , Azodibenzoyl, azo compounds such as 2,2-azobis (1-acetoxy-1-phenylethane), water-soluble catalysts such as potassium persulfate and ammonium persulfate, and peroxides or combinations of persulfates and reducing agents. Any material that can be used for ordinary radical polymerization, such as a redox catalyst, can be used. The thermal polymerization initiator of the component (vii) can be selected in consideration of the storage stability of the photosensitive resin composition of the present invention, the formation conditions of the cured product, and the transparency of the cured product.

The amount of the photopolymerization initiator used as the component (iv) is an alkali-soluble resin [(i) component] having a carboxyl group and a polymerizable double bond in one molecule, and polymerization having at least one polymerizable double bond. The mass ratio of the component (iv) to the total of the sex compounds [(ii) component] [(iv) / [(i) + (ii)]] is preferably 0.005 to 0.1, preferably 0. It should be 0.01 to 0.05. If the proportion of the polymerization initiator is small, the rate of polymerization is slowed down and the curability is lowered. On the other hand, if there are too many, the sensitivity will be too strong and the pattern line width will be thicker than the pattern mask, and the line width faithful to the mask cannot be reproduced, or the pattern edges will not be rattled and sharpened. May occur.

Examples of the silane coupling agent of the component (v) include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Etc., (meth) acrylates such as 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, p. -Vinyl compounds such as styryltrimethoxysilane, isocyanates such as 3-isosyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, ureidos such as 3-ureidopropyltrimethoxysilane and 3-ureidopropyltriethoxysilane Examples thereof include silane coupling agents.

The amount of the silane coupling agent used as the component (v) is preferably 0.1 to 20% by mass, preferably 0.5 to 10% by mass in the solid content of the photocurable resin composition of the present invention. It is good to be.

The photosensitive resin composition of the present invention can be dissolved in a solvent or mixed with various additives, if necessary. That is, 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 above essential components. Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone, cyclohexanone and 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 ethers such as glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethyl acetate, butyl acetate, ethyl lactate, Examples thereof include esters such as cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate, which are used for dissolution. , By mixing, a uniform solution-like composition can be obtained. Two or more kinds of these solvents may be used in order to obtain necessary properties such as coatability.

In addition, additives such as a curing accelerator, a plasticizer, a leveling agent, and an antifoaming agent can be added to the photosensitive resin composition of the present invention, if necessary. Among these, examples of the plasticizer include dibutyl phthalate, dioctyl phthalate, and tricresyl phosphate. Examples of the defoaming agent and leveling agent include silicon-based, fluorine-based, and acrylic-based compounds.

The photosensitive resin composition of the present invention has a carboxyl group and a polymerizable double in one molecule of the component (i) in the solid content excluding the solvent (the solid content contains a monomer that becomes a solid content after curing). An alkali-soluble resin having a bond, a polymerizable compound having at least one polymerizable double bond of the component (ii), and an average particle treated with a surface treatment agent represented by the general formula (3) of the component (iii). It is desirable that the silica sol having a diameter of 10 to 300 nm and the photopolymerization initiator of the component (iv) are contained in a total amount of 70% by mass or more, preferably 80% by mass or more, and more preferably 90% by mass or more. The amount of the solvent varies depending on the target solution viscosity suitable for film formation, but is preferably in the range of 20 to 80% by mass with respect to the total amount of the photosensitive resin composition.

The photosensitive resin composition of the present invention has an alkali-soluble resin having a carboxyl group and a polymerizable double bond in one molecule of the component (i) above, and at least one polymerizable double bond of the component (ii). In addition to the polymerizable compound, other resin components that are polymerized or cured by heat may be used in combination. As other resin components, (vi) an epoxy resin or an epoxy compound having two or more epoxy groups is preferable, and 3,3', 5,5'-tetramethyl-4,4'-biphenol type epoxy resin, bisphenol. A-type epoxy resin, bisphenol fluorene-type epoxy resin, phenol novolac-type epoxy resin, 3,4-epoxycyclohexenylmethyl-3', 4'-epoxycyclohexene carboxylate, 2,2-bis (hydroxymethyl) -1-butanol 1,2-Epoxy-4- (2-oxylanyl) cyclohexane adduct, epoxy silicone resin and the like can be mentioned.

The amount of the epoxy resin or epoxy compound having two or more epoxy groups of the component (vi) is the sum of the alkali-soluble resin of the component (i) and the polymerizable compound of the component (ii) [(vi) / [(I) + (ii)]] (mass ratio) is preferably in the range of 0.05 to 0.3, preferably 0.05 to 0.2. If the compounding ratio of the epoxy resin or the epoxy compound having two or more epoxy groups of the component (vi) is small, the effect of the component (vi) such as improvement of adhesion is not exhibited. On the contrary, if the compounding ratio of the epoxy resin or the epoxy compound having two or more epoxy groups of the component (vi) is larger than the above range, there may be a problem that the alkali developability is lowered.

The addition of these epoxy resins makes it possible to design a composition that meets the required properties of the cured product in each application, but for example, if an attempt is made to improve the surface hardness of the cured product, the adhesion to the substrate will decrease. By using the composition of the present invention, it is possible to exhibit sufficient adhesion while ensuring the required surface hardness. Further, from the viewpoint of imparting weather resistance, light resistance, and heat resistance, it is possible to design the physical properties according to the required characteristics, such that a silicone compound such as an epoxy silicone resin is preferable. When used in combination with these resin components, it is desirable that the obtained cured product (coating film) be uniformly compatible so as not to cause turbidity, and the present invention has a carboxyl group in one molecule of the above component (i). It is possible to suppress the turbidity of the cured product (coating film) by finding the optimum mixing ratio between the alkali-soluble resin having a polymerizable double bond and these resin components.

Further, in the coating film (cured product) of the present invention, for example, a solution of the above-mentioned photosensitive resin composition is applied to a substrate or the like, dried, and irradiated with light (including ultraviolet rays, radiation, etc.) to cure the coating film (cured product). It is obtained by. A coating film having a desired pattern can be obtained by providing a portion exposed to light and a portion not exposed to light, curing only the portion exposed to light, and dissolving the other portion with an alkaline solution.

Next, an example of a method for forming a coating film (cured product) using the photosensitive resin composition will be described below. First, the photosensitive resin composition is applied onto the surface of a substrate or the like, and then the first-stage baking is performed to evaporate the solvent to form a coating film. Next, when forming a pattern, the coating film is exposed to a photomask and then developed with an alkaline developer to dissolve and remove the unexposed portion of the coating film. Then, in the second stage baking, the thermal polymerization reaction is promoted to form a cured product.

When applying the photosensitive resin composition to the substrate, any method such as a roller coater machine, a land coater machine, a slit coater machine or a spinner machine is adopted in addition to the known solution dipping method and spray method. can do. By these methods, after coating to a desired thickness, the solvent is removed by baking, and the thermal polymerization reaction is further promoted to form a cured product. The first stage baking is performed by heating with an oven, a hot plate, etc., vacuum drying, or a combination thereof. The heating temperature and heating time in the first stage baking are appropriately selected depending on the solvent used, and are performed at a temperature of, for example, 80 to 120 ° C. for 1 to 20 minutes. The second stage baking is carried out at a temperature of, for example, 150 to 300 ° C. for 10 to 120 minutes.

Examples of the substrate used for forming the cured product include glass, a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, etc.) and the like. Further, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if necessary. .. Of course, the cured product may be obtained by a procedure different from that described above.

Hereinafter, the present invention will be described in more detail based on an example of synthesizing an alkali-soluble resin represented by the general formula (1). The scope of the present invention is not limited by these synthetic examples and the like. In addition, the evaluation of the resin in the following synthetic examples was performed as follows unless otherwise specified.

[Solid content concentration]
1 g of the resin solution obtained in the synthesis example was impregnated into a glass filter [weight: W ₀ (g)], weighed [W ₁ (g)], and heated at 160 ° C. for 2 hours, and then weight [W ₂ ( g)] was obtained from the following equation.
Solid content concentration (% by weight) = 100 × (W ₂ -W ₀ ) / (W ₁ -W ₀ )

[Epoxy equivalent]
After dissolving the resin solution in dioxane, add an acetic acid solution of tetraethylammonium bromide, and titrate with a 1 / 10N-perchloric acid solution using a potentiometric titrator (trade name COM-1600 manufactured by Hiranuma Seisakusho Co., Ltd.). I asked.

[Acid value]
The resin solution was dissolved in dioxane and titrated with a 1 / 10N-KOH aqueous solution using a potentiometric titrator (trade name COM-1600 manufactured by Hiranuma Seisakusho Co., Ltd.).

[Molecular weight]
Gel Permeation Chromatography (GPC) (HLC-8220GPC manufactured by Tosoh Corporation, solvent: tetrahydrofuran, column: TSKgelSuperH-2000 (2) + TSKgelSuperH-3000 (1) + TSKgelSuperH-4000 (1) + TSKgelSuper-H5000 ( 1) (manufactured by Tosoh Corporation), temperature: 40 ° C, speed: 0.6 ml / min), and weight average molecular weight (Mw) as a standard polystyrene (PS-oligoform kit manufactured by Tosoh Corporation) Is the calculated value.

The abbreviations used in the synthetic example and the comparative synthetic example are as follows.
FHPA: Equivalent reaction product of 9,9-bis (4-hydroxyphenyl) fluorene and chloromethyloxylan and acrylic acid (PGMEA solution with a solid content concentration of 50 wt%)
BPDA: 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride
BTDA: 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride
THPA: 1,2,3,6-tetrahydrophthalic anhydride
TPP: Triphenylphosphine
PGMEA: Propylene Glycol Monomethyl Ether Acetate

[Synthesis Example 1]
206.26g (0.17mol) of FHPA 50% PGMEA solution, 0.085mol of BPDA, 0.085mol of THPA, 26.0g of PGMEA and 0.45g of TPP are charged in a 500ml four-necked flask with a return condenser, 120-125. The mixture was stirred under heating at ° C. for 6 hours to obtain an alkali-soluble resin solution (i) -1. The solid content concentration of the obtained resin solution was 55.6 wt%, the acid value (in terms of solid content) was 103 mgKOH / g, and the Mw by GPC analysis was 2600.

[Synthesis Example 2]
206.26g (0.17mol) of FHPA 50% PGMEA solution, 0.085mol of BTDA, 0.085mol of THPA, 26.0g of PGMEA and 0.45g of TPP are charged in a 500ml four-necked flask with a return condenser, 120-125. The mixture was stirred under heating at ° C. for 6 hours to obtain an alkali-soluble resin solution (i) -2. The solid content concentration of the obtained resin solution was 55.8 wt%, the acid value (solid content equivalent) was 101.5 mgKOH / g, and the Mw by GPC analysis was 2850.

(Examples 1 to 8, Comparative Examples 1 to 8)
Next, the present invention will be specifically described based on Examples and Comparative Examples relating to the production of the photosensitive resin composition and the cured product thereof, but the present invention is not limited thereto. Here, the raw materials and abbreviations used in the production of the photosensitive resin compositions of the following Examples and Comparative Examples and the cured products thereof are as follows.

(i) -1 component: Alkali-soluble resin solution obtained in the above synthesis example 1.
(i) -2 component: The alkali-soluble resin solution obtained in the above synthesis example 2.
(ii) Ingredient: Dipentaerythritol hexaacrylate
(iii) -1 Component: Solvent-dispersed silica sol (PMA-ST manufactured by Nissan Chemical Co., Ltd., Dispersion medium: PGMEA, Solid content concentration = 30.3%, Measuring instrument of dynamic light scattering method (Otsuka Electronics particle size analyzer FPAR-1000) Cumulant method average particle size 41 nm, surface treatment agent (q = 1, R ₆ , R _7, R ₈ = CH ₃ (1H-NMR) in formula (3). The surface treatment degree of the silica sol is the silica sol. Is precipitated in hexane, dried, and calculated from the thermal weight loss measured using a differential heat / thermal weight measuring device (TG-DTA) (EXSTER6000 manufactured by SII Co., Ltd.). The measurement conditions are room temperature in a nitrogen atmosphere. After raising the temperature from 150 ° C to 150 ° C at 10 ° C / min, hold at 150 ° C for 30 minutes to remove volatile components. Then, in an air atmosphere, raise the temperature from 150 ° C to 550 ° C at 10 ° C / min and then at 550 ° C. Hold for 10 minutes. Surface treatment is evaluated from the weight loss rate from 150 ° C to 550 ° C. Surface treatment calculated from heat weight loss = 1.6%)
(iii) -2 component: solvent-dispersed silica sol (MEK-AC-2101 manufactured by Nissan Chemical Co., Ltd., dispersion medium: methyl ethyl ketone, solid content concentration = 33%, cumulant average particle size 66 nm (light scattering method), surface treatment agent: 3- (Trimethoxysilyl) propyl methacrylate, surface treatment degree calculated from heat weight loss in the same manner as above = 5.4%)
(iii) -3 components: solvent-dispersed silica sol (YA015C-DFD manufactured by Admatex, dispersion medium: diethylene glycol dimethyl ether, solid content concentration = 33%, cumulant average particle size 84 nm (light scattering method), surface treatment agent: 3-glyce Sidoxypropyltrimethoxysilane, surface treatment degree calculated from heat weight loss in the same manner as above = 4.2%)
(iv) Ingredients: Oxime ester-based photopolymerization initiator (BASF, Irgacure OXE01)
(v) Ingredient: Silane coupling agent (3-glycidoxypropyltrimethoxysilane)
(vi) Ingredients: Epoxy resin solvent obtained by the reaction of 9,9-bis (4-hydroxyphenyl) fluorene with chloromethyloxylane-1: propylene glycol monomethyl ether acetate solvent-2: ethyl lactate solvent-3: ethoxy Ethyl propionate solvent-4: diethylene glycol methyl ethyl ether additive: surfactant (manufactured by Toray Dow Corning, trade name FZ-2122)

The above-mentioned compounding components were blended in the proportions shown in Tables 1 and 2 to prepare photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 8. The numerical values in Tables 1 and 2 all represent parts by mass.

[Creating a cured product]
The photosensitive resin compositions shown in Tables 1 and 2 were placed on a 125 mm × 125 mm glass substrate (EAGLE XG manufactured by Corning Inc.) using a spin coater to have a film thickness of 1.3 to 1.7 μm after baking in the second stage. The coating plate was prepared by baking at 80 ° C. for 1 minute in the first stage using a hot air dryer. Next, a photocuring reaction was carried out by irradiating ultraviolet rays of 100 mJ / cm ² with a high-pressure mercury lamp having an illuminance of 500 W / cm ² at a wavelength of 365 nm. Then, the second stage baking was performed at 230 ° C. for 30 minutes using a hot air dryer to obtain a cured product (coating film) according to Examples 1 to 8 and Comparative Examples 1 to 8.

Tables 3 and 4 show the results of evaluation of the following items with respect to the cured product (coating film) composed of the photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 8 obtained above. These evaluation methods were performed as follows.

Film thickness:
The measurement was performed using a stylus type step shape measuring device (trade name P-10 manufactured by KLA Tencor Co., Ltd.).

Adhesion:
The cured product prepared on a glass substrate (EAGLE XG manufactured by Corning Inc.) was left to stand for 5 hours under the conditions of a temperature of 121 ° C., a humidity of 100%, and an atmospheric pressure of 2 atm. In addition, use the Super Cutter Guide manufactured by Taiyu Kikai Co., Ltd. to make cuts in the left-standing cured material so that 100 square cells of 1 mm × 1 mm are formed, and then use cellophane tape (manufactured by Nichiban) on the cells. ) Was attached and then peeled off. A tape peeling test was conducted. ○ if the hardened material in the squares is not peeled off at all, △ if less than 1/3 of the hardened material in the squares is peeled off, × if 1/3 or more is peeled off And said.

Coating film hardness 1:
The highest level of scratches on the coating film created on a glass substrate (EAGLE XG manufactured by Corning) when a load of 1 kg is applied using a pencil hardness tester according to the JIS-K5400 test method. Displayed with pencil hardness. The pencil used is "Mitsubishi Hi-Uni". Here, this evaluation was carried out as an index of resistance to lateral force (scratch) on the surface of the coating film.

Coating film hardness 2:
The cured product prepared on a glass substrate (EAGLE XG manufactured by Corning Inc.) was measured using a microfilm hardness tester (HM2000 manufactured by Fisher Instruments). The indenter was loaded with a load of 5 mN / μm ² at a load rate of 0.25 mN / sec using a Vickers indenter, and after holding for 1 second, the load was removed and the Martens hardness (according to ISO 14577) was measured. The Martens hardness here is the hardness calculated from the load-entry depth curve, and is ○ when the Martens hardness is 65 N / mm ² or more, and less than 65 N / mm ² to 60 N / mm ² or more. In some cases, it was evaluated as Δ, and in the case of less than 60 N / mm ² , it was evaluated as ×. Here, this evaluation was carried out as an index of resistance to a vertical force (pushing) of the coating film surface.

Transmittance:
The transmittance of the cured product created on a glass substrate (EAGLE XG manufactured by Corning) was measured using a transmittance meter (trade name SPECTRO PHOTOMETER SD5000 manufactured by Nippon Denshoku Kogyo), and the transmittance at a wavelength of 400 nm was 95%. In the above cases, it was evaluated as ◯, in the case of less than 95% to 90% or more, it was evaluated as Δ, and in the case of less than 90%, it was evaluated as ×.

Gas emission:
The cured product created on a glass substrate (EAGLE XG manufactured by Corning) is scraped with a scraper or the like, and the thermal weight loss of 4 to 6 mg of the obtained powdered cured product is shown by a differential thermogravimetric analyzer (TG / DTA) (SII). It was measured using EXSTER6000) manufactured by Co., Ltd. The measurement conditions were pretreatment at 120 ° C for 30 minutes in the atmosphere and then holding at 230 ° C for 2 hours. The gas-generating property was evaluated from the weight loss rate, and the smaller the weight loss rate, the better the low gas-generating property. The weight loss rate is calculated from the weight loss before and after heating at 230 ° C. If the weight loss rate is less than 5%, it is ◎, if it is 5 or more and less than 10%, it is ○, and if it is 10 or more and less than 15%, it is △. , If it is 15% or more, it is marked as x.

Alkaline developability:
The photosensitive resin compositions shown in Tables 1 and 2 were placed on a 125 mm × 125 mm glass substrate (EAGLE XG manufactured by Corning Inc.) using a spin coater to have a film thickness of 1.3 to 1.7 μm after baking in the second stage. The coating plate was prepared by baking at 80 ° C. for 1 minute in the first stage using a hot air dryer. Next, a high-pressure mercury lamp with an illuminance of 500 W / cm ² at a wavelength of 365 nm was irradiated with ultraviolet rays of 100 mJ / cm ² , and a photocuring reaction was performed on the photosensitive portion. Next, this exposed coated plate was developed in a 0.04 wt% potassium hydroxide aqueous solution or a 0.5 wt% sodium carbonate aqueous solution at 23 ° C. for 1 minute by dip development, and further washed with water to remove the unexposed part of the coating film. bottom. Then, the second stage baking was performed at 230 ° C. for 30 minutes using a hot air dryer to obtain the patterns of Examples 1 to 8 and Comparative Examples 1 to 8. The alkali developability is evaluated by the presence or absence of a coating film on the unexposed portion in the obtained pattern. If all the coating film on the unexposed portion is removed, the coating film is ○, and the coating film is within a range of less than 2 μm from the end face of the pattern. When it remained, it was evaluated as Δ, and when the coating film remained in the range of 2 μm or more from the end face of the pattern, it was evaluated as ×.

As is clear from the results of Tables 3 and 4, the cured products according to Examples 1 to 8 are excellent in each performance, and in particular, both adhesion and coating film hardness are compatible with those of Comparative Examples 1 to 8. Further, a cured product having a high transmittance can be formed. That is, it was found that by using the photosensitive resin composition of the present invention, it is possible to provide a color filter protective layer having transparency, light resistance, weather resistance, heat resistance, surface hardness, adhesion, and low gas generation property. ..

The photosensitive resin composition of the present invention does not impair alkali developability even if it contains a silica sol, and is excellent in transparency, light resistance, weather resistance, heat resistance, flatness, surface hardness, adhesion, chemical resistance, and the like. A hardened product can be formed. Therefore, it is suitable as various display elements such as color liquid crystal display devices, color facsimiles, and image sensors, protective film materials for color filters, protective layers for organic devices such as organic semiconductors, encapsulants, adhesives, and insulating films. Can be used.

Claims (6)

(I) An epoxy-soluble resin having a carboxyl group and a polymerizable double bond in one molecule represented by the general formula (1), (ii) a polymerizable compound having at least one polymerizable double bond, (iii). ) Silica sol having an average particle size of 10 to 300 nm with a surface treatment degree of 0.5 to 4% by mass treated with a surface treatment agent represented by the general formula (3), (iv) a photopolymerization initiator, and (v) silane. The coupling agent and (vi) an epoxy resin or epoxy compound having two or more epoxy groups are contained as essential components, and the content of the essential components in the solid content is (i) an alkali-soluble resin of 20 to 20. 50% by mass, (iii) 20 to 70% by mass of silica sol, (v) 0.1 to 20% by mass of silane coupling agent, and (ii) polymerizable compound (i) / (ii) ( Mass ratio) = 40/60 to 90/10, (iv) Photopolymerization initiator in the range of [(iv) / [(i) + (ii)]] (mass ratio) = 0.005 to 0.1 Yes, (vi) epoxy resin or epoxy compound is [(vi) / [(i) + (ii)]] (mass) with respect to the sum of the alkali-soluble resin of (i) component and the polymerizable compound of (ii) component. Ratio) = A photosensitive resin composition in the range of 0.05 to 0.3.

(However, R ₁ , R ₂ , R ₃ and R ₄ independently indicate a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₅ indicates a hydrogen atom or a methyl group. Further, X indicates a 9,9-fluorenylene group, Y indicates a tetravalent carboxylic acid residue, Z indicates a substituent represented by the following general formula (2), and n represents a number of 1 to 20. show.)

(However, L indicates a divalent or trivalent carboxylic acid residue, and p is 1 or 2).

(However, R ₆ indicates a hydrocarbon group having 1 to 10 carbon atoms which may contain a hetero atom in the molecule, R ₇ independently indicates a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, respectively, and R ₈ indicates an alkyl group having 1 to 4 carbon atoms. Each independently represents an alkyl group having 1 to 4 carbon atoms, and q is 1 to 3). (Iv) The photosensitive resin composition according to claim 1, wherein the photopolymerization initiator is an oxime ester-based photopolymerization initiator. (Vi) The photosensitive resin composition according to claim 1, wherein the epoxy resin or the epoxy compound is a bisphenol fluorene type epoxy resin. (Iii) In the silica sol treated with the surface treatment agent represented by the general formula (3), R ₆ of the formula (3) is a methyl group, an ethyl group or a propyl group, and R ₇ is a methyl group or an ethyl group. The photosensitive resin composition according to claim 1, wherein R ₈ is a methyl group or an ethyl group. A cured product obtained by curing the photosensitive resin composition according to any one of claims 1 to 4 . A color filter having the cured product according to claim 5 as a protective layer.