JP2018180531A - Photosensitive resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition which is alkali-developable with a superior development rate, which shows good adhesiveness to a metal part of a metal film such as an MAM film, and which has high acid resistance and transparency of a cured product.SOLUTION: The photosensitive resin composition comprises: a hydrophilic resin (A) having a vinyl monomer (a1) having an aromatic ring as an essential structural monomer; a polyfunctional (meth)acrylate (B) having an isocyanuric skeleton; a silane compound (C) having an amino group; and a photopolymerization initiator (D). The structural percentage of the vinyl monomer (a1) having an aromatic ring in the hydrophilic resin (A) is preferably 15 to 80 wt.% based on the whole monomers constituting (A).SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition which is cured by light irradiation and is alkali developable. Specifically, the present invention relates to an alkali-developable photosensitive resin composition suitable for a protective film for a color filter, a protective film for a touch panel, an insulating film for a touch panel, and an interlayer insulating film for a buildup substrate.

  The touch panel is classified into a resistive film method, a capacitance method, an optical method, an ultrasonic method, an electromagnetic induction method, and the like according to its operation principle. Recently, a capacitive touch panel that can be mounted on a liquid crystal display device or the like with few malfunctions and at low cost is often used. In the case of the electrostatic capacitance type, a metal film such as MAM (Molybdenum / Alminium / Molybdenum three-layer structure) is formed on a substrate to construct a wiring or an electrode portion, and a protective film for protecting these metal portions It is formed. Such a protective film is required to have adhesion to a metal film such as MAM or the like, and acid resistance to an etching solution (strong acid) of the metal film.

  In order to increase the acid resistance of the photosensitive resin composition, it is conceivable to use a polyfunctional (meth) acrylate compound to make the crosslinked structure dense. However, since the polyfunctional (meth) acrylate has a large shrinkage at the time of curing, the internal stress of the cured product is increased and the adhesion to the metal film is reduced.

  As a method for achieving both acid resistance and metal adhesion, a method using a specific silane coupling agent is disclosed (for example, Patent Document 1). However, although the adhesion is improved by the addition of the silane coupling agent, it is easily insolubilized in the developer, and the problem is that the development rate of the resin is reduced by the addition.

JP, 2013-174643, A

  The present invention is a photosensitive resin composition capable of alkali development excellent in developing speed, having good adhesion to metal parts of metal films such as MAM, and further excellent in high acid resistance and transparency of cured product. It aims to provide goods.

  The present inventors arrived at the present invention as a result of studying to achieve the above object. That is, according to the present invention, a hydrophilic resin (A) containing a vinyl monomer (a1) having an aromatic ring as an essential constituent monomer, a polyfunctional (meth) acrylate (B) having an isocyanuric skeleton, and a silane having an amino group A photosensitive resin composition containing a compound (C) and a photopolymerization initiator (D); a protective film for a touch panel or a protective film for a color filter formed by curing the photosensitive resin composition; the photosensitive resin composition It is an insulating film for a touch panel or an interlayer insulating film for a buildup substrate which is formed by curing an object.

  The photosensitive resin composition of the present invention is capable of alkali development excellent in developing speed, has good adhesion to metal parts of metal films such as MAM, and is further for high acid resistance and transparency. Alternatively, it is possible to form a protective film for a color filter or an insulating film for a touch panel or a buildup substrate.

  The photosensitive resin composition of the present invention comprises a hydrophilic resin (A) containing a vinyl monomer (a1) having an aromatic ring as an essential constituent monomer, and a polyfunctional (meth) acrylate (B) having an isocyanuric skeleton. It contains a silane compound (C) having an amino group and a photopolymerization initiator (D).

  In the present specification, "(meth) acrylate" means "acrylate and / or methacrylate", "(meth) acrylic acid" means "acrylic acid and / or methacrylic acid", and "(meth) acrylic resin" “Acrylic resin and / or methacryl resin”, “(meth) acryloyl group” means “acryloyl group and / or methacryloyl group”, “(meth) acryloyloxy group” means “acryloyloxy group and / or methacryl group” The term "leuoxy group" is meant.

  Further, “alkali developable” means that in the step of removing the uncured portion using a developer, the uncured portion can be removed cleanly with an alkaline aqueous solution of the developer.

The index of hydrophilicity in the hydrophilic resin (A) comprising a vinyl monomer (a1) having an aromatic ring which is the first essential component of the photosensitive resin composition of the present invention as an essential component monomer is defined by HLB, Generally, the larger the value, the higher the hydrophilicity.
The HLB of the hydrophilic resin (A) in the present invention is preferably 4 to 19, more preferably 5 to 19, and particularly preferably 6 to 19. If it is 4 or more, developability is further good when developing, and if it is 19 or less, the water resistance of the cured product is further good.

The “HLB” in the present invention is an index showing the balance between hydrophilicity and lipophilicity, and is described, for example, on “Introduction to surfactants” (2007 published by Sanyo Chemical Industries, Ltd., Takehiko Fujimoto) on page 212. It is known as the calculated value by the Oda method, and not the calculated value by the Griffin method.
HLB can be calculated by the following equation from the ratio between the organic value and the inorganic value of the organic compound.
HLB = 10 × Inorganicity / Organicity As the organicity value and the inorganicity value for deriving HLB, the values in the table described on page 213 of “Introduction to Surfactants” can be used.

Moreover, the solubility parameter of the hydrophilic resin (A) [unit: (cal / cm ³ ) ^1/2 : hereinafter, referred to as SP value. ] Is preferably 7 to 14, more preferably 8 to 13, and particularly preferably 9 to 13. When it is 7 or more, the developability is further good, and when it is 14 or less, the water resistance of the cured product is further good.

The SP value in the present invention is calculated by the method described in the following document proposed by Fedors et al.
"POLYMER ENGINEERING AND SCIENCE, February, 1974, Vol. 14, No. 2, Robert F. Fedors (147-154)"

  From the viewpoint of acid resistance, the hydrophilic resin (A) having an aromatic ring in the present invention preferably has a radically polymerizable group in the molecule. The radically polymerizable organic group is preferably a (meth) acryloyl group, a vinyl group and an allyl group from the viewpoint of photocurability, and more preferably a (meth) acryloyl group.

  The functional group contributed to the hydrophilicity contained in the molecule by the hydrophilic resin (A) having an aromatic ring of the present invention is a carboxyl group, an epoxy group, a sulfonic acid group and a phosphoric acid group from the viewpoint of alkali developability. Is more preferred, and more preferred is a carboxyl group.

  From the viewpoint of developability and transparency, the hydrophilic resin (A) of the present invention needs to use a vinyl monomer (a1) having an aromatic ring as an essential constituent monomer.

  As the vinyl monomer (a1) having an aromatic ring, styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, vinylnaphthalene, 4-vinylbenzoic acid, cinnamic acid, hydroxystyrene, (meth) allylsulfonic acid, styrenesulfonic acid, α-methylstyrenesulfonic acid, cinnamic acid amide and the like can be mentioned. The vinyl monomer (a1) having an aromatic ring may be used alone or in combination of two or more.

  The proportion of the aromatic monomer-containing vinyl monomer (a1) in the hydrophilic resin (A) is preferably 15 to 80% by weight, more preferably 20 to 70% by weight, based on all the monomers constituting the (A). %.

  As monomers used for producing the hydrophilic resin (A), (meth) acrylic acid (a2) and (meth) acrylic acid ester (a3) in addition to the vinyl monomer (a1) having an aromatic ring which is an essential component Etc. can be used. Each of (a2) and (a3) may be used alone or in combination of two or more.

  The (meth) acrylic acid ester (a3) includes a linear or branched alkyl group having 1 to 30 carbon atoms (meth) acrylic acid ester (a31), and a hydroxyalkyl group having 2 to 6 carbon atoms ( The (meth) acrylate ester (a32) and the (meth) acrylic acid ester (a33) which has a C3-C20 alicyclic hydrocarbon group are mentioned.

  As the (meth) acrylic acid ester (a31) having a linear or branched alkyl group having 1 to 30 carbon atoms, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylate And the like) butyl acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, heptadecyl (meth) acrylate and eicosyl (meth) acrylate etc. Meta) methyl acrylate.

  Examples of the (meth) acrylate ester (a32) having a hydroxyalkyl group having 2 to 6 carbon atoms include hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate.

  Examples of the (meth) acrylic acid ester (a33) having an alicyclic hydrocarbon group of 3 to 20 carbon atoms include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, (Meth) acrylic acid 4-t-butylcyclohexyl, bornyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, dimethyladamantyl (meth) acrylate, (meth) Norbornyl methyl acrylate, menthyl (meth) acrylate, fentyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyl oxy (meth) acrylate And (meth) acrylic acid cyclode Le, and the like.

From the viewpoint of the acid resistance of the cured product of the photosensitive resin composition, it is preferable to use methyl (meth) acrylate and / or ethyl (meth) acrylate as a constituent monomer of the hydrophilic resin (A).
Further, from the viewpoint of imparting hydrophilicity to the hydrophilic resin (A), it is preferable to use (meth) acrylic acid (a2) as a constituent monomer of the hydrophilic resin (A).
The hydrophilic resin (A) may be used alone or in combination of two or more.

  From the viewpoint of developability, the content of the hydrophilic resin (A) in the photosensitive resin composition of the present invention is preferably 10 to 70% by weight, further preferably, based on the total weight of (A) to (D). Preferably it is 20-40 weight%.

  The number average molecular weight of the hydrophilic resin (A) in the present invention is preferably 3,000 to 100,000, and more preferably 3,000 to 50,000.

  The polyfunctional (meth) acrylate (B) having an isocyanuric skeleton, which is the second essential component of the photosensitive resin composition of the present invention, has an isocyanuric skeleton and the number of (meth) acryloyl groups is 2 or more There is no particular limitation if it is. When the photosensitive resin composition contains a polyfunctional (meth) acrylate (B) having an isocyanuric skeleton, the acid resistance is improved. From the viewpoint of further improving the acid resistance, (B) preferably further contains a hydroxyl group.

Specific examples of the polyfunctional (meth) acrylate (B) having an isocyanuric skeleton include: isocyanuric acid alkylene oxide modified di (meth) acrylate, isocyanuric acid alkylene oxide modified tri (meth) acrylate, tris [2- (meth) acryloyloxy Ethyl] isocyanurate and ε-caprolactone modified tris [2- (meth) acryloyloxyethyl] isocyanurate, etc. may be mentioned, and those having a hydroxyl group are preferable.
As an alkylene oxide in the case of alkylene oxide modification | denaturation, ethylene oxide is preferable and it is preferable that the polymerization degrees of the alkylene oxide to be used are 1-10.
The polyfunctional (meth) acrylates (B) may be used alone or in combination of two or more.

  The content of the polyfunctional (meth) acrylate (B) having an isocyanuric skeleton in the photosensitive resin composition of the present invention is preferably 20 based on the total weight of (A) to (D) from the viewpoint of acid resistance. It is preferably 80 to 80% by weight, more preferably 40 to 65% by weight.

  The silane compound (C) having an amino group, which is the third essential component of the photosensitive resin composition of the present invention, is preferably a compound represented by the following general formula (1) from the viewpoint of adhesion.

R ¹ in the general formula (1), R ² and R ³ are each independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group or a hydroxyl group having 1 to 6 carbon atoms, from the viewpoint of adhesiveness, R ^1, R It is necessary that at least one of ² and R ^{3 be} an alkoxy group having 1 to 6 carbon atoms or a hydroxyl group. Moreover, when it is an alkoxy group, it is preferable that the carbon number is 1-2 from an adhesive viewpoint.
R ⁴ in the general formula (1) represents a divalent hydrocarbon group having 1 to 6 carbon atoms.

Specific examples of the compound represented by the general formula (1) include 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane.
The silane compound (C) having an amino group may be used alone or in combination of two or more.

  The content of the silane compound (C) having an amino group in the photosensitive resin composition of the present invention is preferably 0.01 to 15 based on the total weight of (A) to (D) from the viewpoint of adhesion. % By weight, more preferably 0.1 to 10% by weight.

  As the photopolymerization initiator (D) which is the fourth essential component of the photosensitive resin composition of the present invention, phosphine oxide compounds, benzoyl formate compounds, thioxanthone compounds, oxime ester compounds, hydroxybenzoyl compounds, benzophenone compounds, A ketal compound, an alpha-amino alkyl phenone compound, etc. are mentioned.

Examples of phosphine oxide compounds include bis (2,4,6-trimethyl benzoyl) -phenyl phosphine oxide and 2,4,6-trimethyl benzoyl diphenyl phosphine oxide.
Examples of benzoyl formate compounds include methyl benzoyl formate and the like.
As a thioxanthone compound, isopropyl thioxanthone etc. are mentioned.
As oxime ester compounds, 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] and ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

Examples of the hydroxybenzoyl compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone and benzoin alkyl ether.
As a benzophenone compound, benzophenone etc. are mentioned.
Examples of the ketal compound include benzyl dimethyl ketal and the like.
As the α-aminoalkylphenone compound, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopro-butanone-1 and 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- 1- [4- (4-morpholinyl) phenyl] -1-butanone etc. are mentioned.

Among these, phosphine oxide compounds, hydroxybenzoyl compounds and α-aminoalkylphenone compounds are preferable from the viewpoint of curing and coloring of the cured product.
The photopolymerization initiator (D) may be used alone or in combination of two or more.

  The amount of the photopolymerization initiator (D) used is preferably 2 to 15% by weight, more preferably 5 to 10% by weight from the viewpoints of curability and coloring of the cured product based on the total of (A) to (D). %.

  If necessary, the photosensitive resin composition of the present invention may be blended with a polyfunctional (meth) acrylate (E) having no isocyanuric skeleton, a leveling agent (F), an antioxidant (G) and a solvent. Good.

As polyfunctional (meth) acrylate (E) having no isocyanuric skeleton, any monomer having no isocyanuric skeleton and having two or more (meth) acryloyl groups can be used without particular limitation. The number average molecular weight of (E) is preferably 3,000 or less.
As such polyfunctional (meth) acrylate (E), bifunctional (meth) acrylate (E1), trifunctional (meth) acrylate (E2), 4 to 6 functional (meth) acrylate (E3) and 7 to 10 Functional (meth) acrylates (E4) can be mentioned.

Examples of the difunctional (meth) acrylate (E1) include esterified compounds of polyhydric alcohol and (meth) acrylic acid [for example, di (meth) acrylate of glycol, di (meth) acrylate of glycerin, dimeth of trimethylolpropane (Meth) acrylate, di (meth) acrylate of 3-hydroxy-1,5-pentanediol, di (meth) acrylate of 2-hydroxy-2-ethyl-1,3-propanediol]; alkylene oxide of polyhydric alcohol Esters of adducts and (meth) acrylic acid [eg, di (meth) acrylate of ethylene oxide adduct of trimethylolpropane and di (meth) acrylate of ethylene oxide adduct of glycerin]; hydroxyl group-containing both terminal epoxy acrylate; multiple Alcohol and (meta) ac Ester [example hydroxypivalic acid neopentyl glycol di (meth) acrylate] Le acid and hydroxycarboxylic acid, and the like.
In addition, it is not necessary to react all the hydroxyl groups of polyhydric alcohol with (meth) acrylic acid or an alkylene oxide adduct etc., and the unreacted hydroxyl group may remain.

  Examples of the trifunctional (meth) acrylate (E2) include tri (meth) acrylate of glycerin, tri (meth) acrylate of trimethylolpropane, tri (meth) acrylate of pentaerythritol, and tri (ethylene oxide adduct of trimethylolpropane). Meta) acrylate etc. are mentioned.

  As 4- to 6-functional (meth) acrylate (E3), tetra (meth) acrylate of pentaerythritol, penta (meth) acrylate of dipentaerythritol and hexa (meth) acrylate of dipentaerythritol, ethylene oxide addition of dipentaerythritol And penta (meth) acrylates of ethylene oxide adducts of dipentaerythritol and penta (meth) acrylates of propylene oxide adducts of dipentaerythritol.

As a 7-10 functional (meth) acrylate compound, for example, a reaction of a diisocyanate compound such as a compound obtained by the reaction of dipentaerythritol penta (meth) acrylate with hexamethylene diisocyanate and a hydroxyl group-containing polyfunctional (meth) acrylate compound And the like.
The polyfunctional (meth) acrylates (E) not having an isocyanuric skeleton may be used alone or in combination of two or more.

Examples of the leveling agent (F) include anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, fluorine surfactants, silicon surfactants and the like. Among these, from the viewpoint of coatability, fluorosurfactants and silicone surfactants are preferable, and from the viewpoint of compatibility, surfactants having an oxyalkyl chain are preferable.
The leveling agent (F) may be used alone or in combination of two or more.

Examples of the antioxidant (G) include phenol-based antioxidants, sulfur-based antioxidants, amine-based antioxidants, and the like. Among them, preferred are phenol-based antioxidants from the viewpoint of photocurability and antioxidant ability, and particularly preferred is 2,6-di-t-butyl-4-methylphenol (BHT), 2- t-Butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) Ethyl] -4,6-di-tert-pentylphenyl acrylate, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate (Irganox 1076), thiodiethylene bis [3 -(3,5-di-t-butyl-4-hydroxyphenyl) propionate (IRGANOX 1035), ethylenebis (oxyethylene) bis [3- (5-ter) -Butyl-4-hydroxy-m-tolyl) propionate] (irganox 245), hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (irganox 259) and pentaerythritol Tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (Irganox 1010).
The antioxidant (G) may be used alone or in combination of two or more.

As the solvent, ketone solvents (acetone, methyl ethyl ketone and cyclohexanone etc.), ether solvents (ether ether solvents and ether alcohol solvents including: propylene glycol monomethyl ether acetate and methoxy butyl acetate etc), ester solvents (butyl acetate and ethyl lactate etc) And alcohol solvents (such as 1,3-butylene glycol and diacetone alcohol).
The solvents may be used alone or in combination of two or more.

  The photosensitive resin composition of the present invention can be obtained, for example, by mixing each of the above components with a known mixing device such as a planetary mixer. The photosensitive resin composition is liquid at room temperature, and its viscosity is preferably 1 to 200 mPa · s at 25 ° C., more preferably 2 to 150 mPa · s.

A preferable formation process of obtaining a cured product from the photosensitive resin composition of the present invention is a process of applying a photosensitive resin composition onto a substrate, irradiating light, alkali developing to form a pattern, and post-baking. .
The formation of the cured product is generally performed in the following steps (1) to (5), but is not limited thereto.

(1) Step of applying the photosensitive resin composition of the present invention on a substrate:
The coating method may, for example, be roll coating, spin coating, spray coating or slit coating, and as the coating apparatus, a spin coater, an air knife coater, a roll coater, a bar coater, a bar coater, a die coater, a curtain coater, a gravure coater or a comma coater Etc.
The film thickness is preferably 0.5 to 100 μm.

(2) A step of applying heat and drying the applied photosensitive resin composition layer as required (prebake):
The drying temperature is preferably 20 to 120 ° C, more preferably 30 to 110 ° C. The drying time is preferably 0.5 to 10 minutes, more preferably 1 to 8 minutes, and particularly preferably 1 to 5 minutes. Drying may be either reduced pressure or normal pressure.

(3) A step of exposing the photosensitive resin composition layer by actinic light through a predetermined photomask:
Actinic radiation includes, for example, visible light, ultraviolet light and laser light. Examples of light sources include sunlight, high pressure mercury lamps, low pressure mercury lamps, metal halide lamps, and semiconductor lasers. The exposure amount is not particularly limited, preferably 20~300mJ / cm ^2, further preferably 20~100mJ / cm ² from the viewpoint of production cost. In the step of performing exposure, a component having a (meth) acryloyl group in the photosensitive resin composition reacts to cause a photocuring reaction.

(4) After light irradiation, the step of removing the unexposed area with a developer and performing development:
Generally, an alkaline aqueous solution is used as the developer. Examples of the aqueous alkali solution include aqueous solutions of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; aqueous solutions of carbonates such as sodium carbonate, potassium carbonate and sodium hydrogencarbonate; hydroxytetramethylammonium and hydroxytetraethylammonium etc. An aqueous solution of organic alkali is mentioned.
These may be used alone or in combination of two or more, and may be used by adding a surfactant such as an anionic surfactant, a cationic surfactant, an amphoteric surfactant or a nonionic surfactant.
As a developing method, there are a dip method and a shower method, but the shower method is preferable. The temperature of the developer is preferably 20 to 45 ° C. The development time is appropriately determined according to the film thickness and the solubility of the photosensitive resin composition.

(5) Post-heating (post-baking) process:
The post-baking temperature is preferably 50 to 280 ° C., more preferably 100 to 250 ° C., particularly preferably 120 to 240 ° C. The post-baking time is preferably 5 minutes to 2 hours, more preferably 10 minutes to 1 hour, and particularly preferably 15 minutes to 45 minutes.

  EXAMPLES The present invention will be further described by the following Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, parts indicate parts by weight.

Production Example 1 [Production of 50% by Weight Solution of Hydrophilic Acrylic Resin (A-1)]
In a glass reaction vessel equipped with a heating / cooling / stirring device, a reflux condenser, a dropping funnel, and a nitrogen introducing pipe, 172 parts of propylene glycol monomethyl ether acetate was charged and heated to 90 ° C. A solution prepared by uniformly mixing 127 parts of methacrylic acid, 13 parts of methyl methacrylate, 145 parts of styrene, 300 parts of isobornyl methacrylate and 207 parts of propylene glycol monomethyl ether acetate with dimethyl-2,2'-azobis (2-methyl) A solution prepared by uniformly mixing 5 parts of propionate) and 12 parts of propylene glycol monomethyl ether acetate was dropped, respectively, and radical polymerization was performed in a glass reaction vessel to obtain an acrylic resin.
Thereafter, the resultant was diluted with propylene glycol monomethyl ether acetate so as to have a resin concentration of 50% by weight to obtain a 50% by weight propylene glycol monomethyl ether acetate solution of the acrylic resin (A-1) of the present invention. This (A-1) is a hydrophilic acrylic resin having an aromatic ring, and has an SP value of 10.7 and an HLB of 6.4.

Production Example 2 [Production of 50% by Weight Solution of Hydrophilic Acrylic Resin (A-2)]
In a glass reaction vessel equipped with a heating / cooling / stirring device, a reflux condenser, a dropping funnel, and a nitrogen introducing pipe, 172 parts of propylene glycol monomethyl ether acetate was charged and heated to 90 ° C. A solution prepared by uniformly mixing 177 parts of methacrylic acid, 13 parts of methyl methacrylate, 395 parts of styrene and 207 parts of propylene glycol monomethyl ether acetate, and 5 parts of dimethyl-2,2'-azobis (2-methylpropionate) A solution prepared by uniformly mixing 12 parts of propylene glycol monomethyl ether acetate was dropped, and radical polymerization was performed in a glass reaction container to obtain an acrylic resin.
Subsequently, 19 parts of glycidyl methacrylate is charged, reacted at 90 ° C. for 5 hours, and then diluted with propylene glycol monomethyl ether acetate so that the resin concentration becomes 50% by weight, and methacroyl group as a radically polymerizable group of the present invention. The 50 weight% propylene glycol monomethyl ether acetate solution of the acrylic resin (A-2) which has is obtained. The (A-2) is a hydrophilic acrylic resin having a methacryloyl group and an aromatic ring, and has an SP value of 10.5 and an HLB of 5.8.

Comparative Production Example 1 [Production of 50% by Weight Solution of Hydrophilic Acrylic Resin (A′-1)]
In a glass reaction vessel equipped with a heating / cooling / stirring device, a reflux condenser, a dropping funnel, and a nitrogen introducing pipe, 172 parts of propylene glycol monomethyl ether acetate was charged and heated to 90 ° C. A solution prepared by uniformly mixing 177 parts of methacrylic acid, 13 parts of methyl methacrylate, 395 parts of isobornyl methacrylate and 207 parts of propylene glycol monomethyl ether acetate with dimethyl-2,2'-azobis (2-methylpropionate) A solution prepared by uniformly mixing 5 parts and 12 parts of propylene glycol monomethyl ether acetate was dropped, respectively, and radical polymerization was performed in a glass reaction vessel to obtain an acrylic resin.
Subsequently, 19 parts of glycidyl methacrylate is charged, reacted at 90 ° C. for 5 hours, and then diluted with propylene glycol monomethyl ether acetate so that the resin concentration becomes 50% by weight, and acrylic having a methacroyl group as a radically polymerizable group The 50 weight% propylene glycol monomethyl ether acetate solution of resin (A'-1) was obtained. The (A'-1) is a hydrophilic acrylic resin having a methacryloyl group and an alicyclic structure, and has an SP value of 10.9 and an HLB of 7.5.

Example 1
According to the formulation described in Table 1, (A-2), (B-1), (B-2), (C-2), (D-2), (D-3) and (G-1) The mixture was stirred until uniform, and an additional solvent (propylene glycol monomethyl ether acetate) was further added to obtain a photosensitive resin composition of Example 1.

The composition of the raw material represented by the trade name in Table 1 is as follows.
(B-1): "NK ester A-9300" (isocyanuric acid EO modified triacrylate: Shin-Nakamura Chemical Co., Ltd. product)
(B-2): "ALONIX M-215" [isocyanuric acid EO modified diacrylate: manufactured by Toagosei Co., Ltd .; having one hydroxyl group]
(C-1): "KBM-903" [aminopropyl trimethylsilane: Shin-Etsu Chemical Co., Ltd. product]
(C-2): "KBE-903" [aminopropyl triethylsilane: Shin-Etsu Chemical Co., Ltd. product]
(C'-1): "KBM-5103" [3-acryloxypropyl trimethoxysilane: Shin-Etsu Chemical Co., Ltd. product]
(D-1): “IRGACURE 819” [bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide: manufactured by BASF Ltd.]
(D-2): “IRGACURE 907” [2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one: manufactured by BASF Ltd.]
(D-3): "Lucillin TPO" [(2,4,6-trimethylbenzoyl) -diphenylphosphine oxide: manufactured by BASF Ltd.]]
(E-1): “ALONIX M-403” [a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (penta isomer ratio = 55 mol%): Toagosei Co., Ltd. product]
(E-2): "ETERMER 235" [pentaerythritol triacrylate: manufactured by Changko Chemical Co., Ltd .; 3 functional groups]
(F-1): "KF-352A" [polydimethylsiloxane having an oxyalkylene chain: leveling agent manufactured by Shin-Etsu Chemical Co., Ltd.]
(F-2): "Surflon S-386" [a fluorine compound having an oxyalkylene chain: AGC Seimi Chemical Co., Ltd. manufactured leveling agent]
(G-1): “Irganox 1010” [pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate: antioxidant manufactured by BASF Japan Ltd.]

Examples 2 to 8 and Comparative Examples 1 to 4
In the same manner as in Example 1, photosensitive resin compositions of Examples 2 to 8 and Comparative Examples 1 to 4 were obtained according to the formulation described in Table 1.

  Table 1 shows the results of performance evaluation of the adhesion, acid resistance, transparency and developability of the cured products of the photosensitive resin compositions of Examples 1 to 8 and Comparative Examples 1 to 4 by the following evaluation methods.

[Preparation of a substrate for evaluation of adhesion]
A photosensitive resin composition was applied on a 10 cm × 10 cm square MAM substrate by a spin coater to form a coating film so that the dry film thickness was 4.5 μm. The coating was dried completely under reduced pressure and then heated at 85 ° C. for 2 minutes on a hot plate. The coating film obtained was irradiated with 100 mJ / cm ² of light from an ultra-high pressure mercury lamp (illuminance 22 mW / cm ² in i-line conversion), and further heated at 220 ° C. for 50 minutes to prepare a substrate for adhesion evaluation. did.
<Evaluation of adhesion>
According to JIS K5600-5-6, a cut knife was put into a 1 mm width with a cutter knife so that 100 squares (10 x 10) could be formed on the cured film of the above substrate, and resin adhesion was measured.
The measurement result was represented by "the squares / 100 remaining on the substrate film after the test".

[Preparation of substrate for acid resistance and transparency evaluation]
The photosensitive resin composition was applied by a spin coater on a 10 cm × 10 cm glass substrate to form a coating film so that the dry film thickness was 4.5 μm. The coating was dried completely under reduced pressure and then heated at 85 ° C. for 2 minutes on a hot plate. The coating film obtained was irradiated with 100 mJ / cm ² of light from an ultra-high pressure mercury lamp (illumination 22 mW / cm ² in i-line conversion), and further heated at 220 ° C. for 50 minutes to obtain a substrate for acid resistance evaluation A substrate for transparency evaluation was produced.

<Evaluation of acid resistance>
The substrate having the cured film obtained by the above method was immersed in aqua regia at a liquid temperature of 20 ° C. and 50 ° C. for 5 minutes. After immersion, the presence or absence of the cured film peeling from the substrate was observed and judged based on the following criteria.
:: no change at 20 ° C. and 50 ° C. ○: no change at 20 ° C., slight peeling at 50 ° C. Δ: slight peeling even at 20 ° C. ×: large peeling at 20 ° C.

<Evaluation of transparency of cured product>
About the board | substrate which has a cured film obtained by said method, based on JISK7105, the haze was measured using the haze meter [brand name: "haze-gard dual" BYK gardner KK-made]. In the present evaluation method, when the haze is 1% or less, the transparency is good.

[Evaluation of developability]
The photosensitive resin composition was applied onto a 10 cm × 10 cm glass substrate by a spin coater and then dried to form a coating film having a dry film thickness of 5 μm. This coated film is heated on a hot plate at 80 ° C. for 3 minutes, then developed using a 0.05% by weight aqueous KOH solution, and the time (seconds) taken until the residue can not be visually confirmed on the substrate Development time.

As shown in Table 1, the photosensitive resin compositions of Examples 1 to 8 of the present invention are excellent in all of adhesion, acid resistance, transparency of a cured product and developability.
On the other hand, in Comparative Example 1 in which a hydrophilic acrylic resin (A'-1) having no aromatic ring is used, the transparency and developability of the cured product is insufficient, and a polyfunctional (meth) acrylate (B) having an isocyanuric skeleton The acid resistance is insufficient in Comparative Example 2 which does not use.
Further, Comparative Example 3 in which the silane compound (C) having an amino group is not used and Comparative Example 4 in which an alkylsilane (C′-1) not having an amino group is used instead of (C) have poor adhesion.

  The resin of the present invention is cured by a process including light irradiation and has excellent alkali development speed, high adhesion, chemical resistance and transparency, so the protective film for color filter, protective film for touch panel, insulation for touch panel It can be suitably used as a film, an interlayer insulating film for a buildup substrate, and the like.

Claims (7)

  A hydrophilic resin (A) containing a vinyl monomer (a1) having an aromatic ring as an essential constituent monomer, a polyfunctional (meth) acrylate (B) having an isocyanuric skeleton, and a silane compound (C) having an amino group And a photosensitive resin composition containing a photopolymerization initiator (D). The photosensitive resin composition according to claim 1, wherein the silane compound (C) is a compound represented by the following general formula (1).

[In formula (1), R ¹ , R ² and R ³ each independently represent an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a hydroxyl group, and R ¹ , R ² and R ³ At least one of them is an alkoxy group having 1 to 6 carbon atoms or a hydroxyl group, and R ⁴ represents a divalent hydrocarbon group having 1 to 6 carbon atoms. ]   The compositional ratio of the aromatic monomer-containing vinyl monomer (a1) in the hydrophilic resin (A) is 15 to 80% by weight based on the weight of all the monomers constituting the (A). Or 2 photosensitive resin compositions.   The photosensitive resin composition in any one of the Claims 1-3 in which the said hydrophilic resin (A) has a radically polymerizable group.   The photosensitive resin composition according to any one of claims 1 to 4, which contains 0.01 to 15% by weight of (C) based on the total weight of (A) to (D).   The protective film for touchscreens or the protective film for color filters which hardens the photosensitive resin composition in any one of Claims 1-5.   An insulating film for a touch panel or an interlayer insulating film for a buildup substrate, which is obtained by curing the photosensitive resin composition according to any one of claims 1 to 5.