JPWO2014192671A1 - Photosensitive resin composition, photo spacer, protective film for color filter, and protective film or insulating film for touch panel - Google Patents

Abstract

An object of the present invention is to provide a photosensitive resin composition that is highly developable, has a cured product with excellent elastic recovery characteristics and adhesion, and can form a high-definition spacer. The photosensitive resin composition of the present invention comprises a hydrophilic resin (A), a polyfunctional (meth) acrylate (B), a photopolymerization initiator (C), a solvent having an HLB of 8.0 to 30.0 (D ) And a compound (E) which is a condensate containing a compound represented by the following general formula (1) as an essential constituent monomer. [In the formula (1), R1 is one selected from the group consisting of (meth) acryloyloxyalkyl groups, glycidoxyalkyl groups, mercaptoalkyl groups and aminoalkyl groups having 1 to 6 carbon atoms in the alkyl group. The above organic groups, R2 is an aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, R3 is an alkyl group having 1 to 4 carbon atoms, M is a silicon atom, a titanium atom And one or more atoms selected from the group consisting of zirconium atoms, and m is 0 or 1. ] [Chemical 1]

Description

  The present invention relates to a photosensitive resin composition. Specifically, the present invention relates to a photosensitive resin composition suitable for a photo spacer, a protective film for a color filter, a protective film for a touch panel, or an insulating film for a touch panel.

  In recent years, liquid crystal display devices have attracted attention, and photosensitive resins are frequently used in the manufacturing process. For example, a photosensitive resin in which a color pigment is dispersed is used for a portion corresponding to a pixel on a color filter, and a photosensitive resin is also used for a black matrix.

  Conventionally, in a liquid crystal display panel, beads having a predetermined particle diameter are used as a photo spacer to provide a gap between two substrates. However, since these beads are dispersed randomly, there is a problem that light leakage, scattering of incident light, etc. occur due to distribution on the color display pixels, and the contrast of the liquid crystal panel is lowered.

  In order to solve these problems, a method has been proposed in which a columnar resinous spacer is formed on a black matrix located between pixels by a photolithographic method of partial pattern exposure and development using a photosensitive resin. . Since the photo spacer can be arranged at a position avoiding the pixels, it does not adversely affect the display quality as described above, and the display quality can be improved.

In order to further improve display quality, higher definition of the photo spacer is desired. However, with higher definition, higher sensitivity is required, but the sensitivity of ordinary photopolymerization initiators is low, and the elastic recovery characteristics of the formed high-definition photospacer are further reduced. There was a phenomenon that the adhesiveness was lowered and the photo spacer was peeled off.
As a high definition method, a method of adding a sulfur atom-containing compound (for example, Patent Document 1) is disclosed. However, when a fine photospacer is formed, the adhesion is remarkably lowered.

On the other hand, in recent years, a drop method (ODF: One Drop Fill) has been proposed in place of the conventional liquid crystal inflow method (vacuum suction method) as the mother glass for manufacturing a liquid crystal display (LCD) becomes larger. ing. In this ODF method, since a predetermined amount of liquid crystal is dropped and then liquid crystal is injected by being sandwiched between two substrates, the number of steps and the process time can be reduced as compared with the conventional vacuum suction method.
However, in the ODF system, a predetermined amount of liquid crystal calculated from the cell gap is dropped and held, so that a pressure change is applied to the photo spacer arranged on the glass substrate. It is desired for the photo spacer to have a high elastic recovery characteristic so that the shape does not plastically deform with respect to this pressure change.

In order to obtain such high elastic recovery characteristics, a method of nano-dispersing inorganic fine particles such as organosilica sol (for example, Patent Document 2), or a content ratio of a polyfunctional monomer such as dipentaerythritol hexaacrylate is 50% or more. A method (for example, Patent Document 3) is known in which high elasticity is obtained by increasing the thickness.
However, in any method, since the resin composition becomes hydrophobic, there is a problem that the development time becomes long and the productivity is lowered, and a photosensitive resin composition capable of achieving both high elasticity and high developability is obtained. It is not done.

Japanese Patent Laid-Open No. 10-274853 Japanese Patent Laid-Open No. 2007-10885 JP 2002-174812 A

  An object of the present invention is to provide a photosensitive resin composition that is highly developable, has a cured product having excellent elastic recovery characteristics and adhesion, and can form a high-definition spacer.

The inventors of the present invention have reached the present invention as a result of studies to achieve the above object.
That is, the present invention includes a hydrophilic resin (A), a polyfunctional (meth) acrylate (B), a photopolymerization initiator (C), a solvent (D) having an HLB of 8.0 to 30.0, and the following: A photosensitive resin composition containing a compound (E) which is a condensate containing the compound represented by the general formula (1) as an essential constituent monomer; and the photosensitive resin composition is irradiated with light and then alkali-developed. Thus, a photo spacer, a color filter protective film, and a touch panel protective film or insulating film formed by patterning and post-baking.

In the formula (1), R ¹ is one selected from the group consisting of a (meth) acryloyloxyalkyl group having 1 to 6 carbon atoms in the alkyl group, a glycidoxyalkyl group, a mercaptoalkyl group, and an aminoalkyl group. The above organic group, R ² is an aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, R ³ is an alkyl group having 1 to 4 carbon atoms, M is a silicon atom, It is one or more atoms selected from the group consisting of titanium atoms and zirconium atoms, and m is 0 or 1.

  The photosensitive resin composition of the present invention has high developability, the cured product has excellent elastic recovery properties, excellent adhesion to a glass substrate, and can form a high-definition photospacer. There is an effect.

  The photosensitive resin composition of the present invention comprises a hydrophilic resin (A), a polyfunctional (meth) acrylate (B), a photopolymerization initiator (C), a solvent having an HLB of 8.0 to 30.0 (D ) And a compound (E), which is a condensate containing the compound represented by the following general formula (1) as an essential constituent monomer, as an essential component.

In the formula (1), R ¹ is one selected from the group consisting of a (meth) acryloyloxyalkyl group having 1 to 6 carbon atoms in the alkyl group, a glycidoxyalkyl group, a mercaptoalkyl group, and an aminoalkyl group. The above organic group, R ² is an aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, R ³ is an alkyl group having 1 to 4 carbon atoms, M is a silicon atom, It is one or more atoms selected from the group consisting of titanium atoms and zirconium atoms, and m is 0 or 1.

  In this 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 methacrylic resin)", "(meth) acryloyl group" means "acryloyl group and / or methacryloyl group", "(meth) acryloyloxy group" means "acryloyloxy group and / or methacrylic group". Means a leuoxy group.

  In the following, (A), (B), (C), (D) and (E) [hereinafter referred to as (A) to (E), which are essential components of the photosensitive resin composition of the present invention. ] Will be described in order.

Examples of the hydrophilic resin (A) used in the present invention include a hydrophilic vinyl resin (A1), a hydrophilic epoxy resin (A2), a hydrophilic polyester resin, a hydrophilic polyamide resin, a hydrophilic polycarbonate resin, and a hydrophilic polyurethane resin. Can be mentioned.
(A) may use 1 type and may use 2 or more types together. Among these, the hydrophilic vinyl resin (A1) and the hydrophilic epoxy resin (A2) are preferable from the viewpoint of the sensitivity of the photosensitive resin composition and the viewpoint of ease of production. From the viewpoint of elastic recovery characteristics, a hydrophilic epoxy resin (A2) is more preferable.

The hydrophilicity index in the hydrophilic resin (A) is defined by HLB. Generally, the larger this value, the higher the hydrophilicity.
The HLB value of (A) is preferably 4 to 19, more preferably 5 to 18, and particularly preferably 6 to 17. When it is 4 or more, the developing property is further improved when developing the photospacer, and when it is 19 or less, the water resistance of the cured product is further improved.

Here, “HLB” is an index indicating a balance between hydrophilicity and lipophilicity, and is described in, for example, “Introduction to Surfactants” (published by Sanyo Chemical Industries, Ltd., 2007, Takehiko Fujimoto), page 212. It is known as the calculated value by the Oda method, not the calculated value by the Griffin method.
The HLB value can be calculated from the ratio between the organic value and the inorganic value of the organic compound.
HLB = 10 × inorganic / organic The organic value and the inorganic value for deriving HLB can be calculated using the values in the table described in the above “Introduction to Surfactant” page 213. However, the oxyethylene group (—CH ₂ CH ₂ O—) is treated specially and calculated using an inorganic value 75 and an organic value 40.

Further, the solubility parameter (hereinafter referred to as SP value) [(unit is (cal / cm ³ ) ^1/2 ]) of the hydrophilic resin (A) is preferably 7 to 14, more preferably 8 to 13, particularly preferably. Is from 9 to 13. If it is 7 or more, the developability can be further improved, and if it is 14 or less, the water resistance of the cured product is further improved.

The SP value in the present invention is calculated by the method described in the following document proposed by Fedors et al.
“POLYMER ENFINEERING AND SCIENCE, February, 1974, Vol. 14, No. 2, Robert F. Fedors (pp. 147-154)”
Those with close SP values are likely to mix with each other (highly dispersible), and those with a distant numerical value are difficult to mix.

Examples of the hydrophilic group that the hydrophilic resin (A) has include a carboxyl group, a hydroxyl group, an amino group, an amide group, a polyether group, a sulfonic acid group, a sulfate ester group, and a phosphate ester group. Of these hydrophilic groups, a carboxyl group is preferred from the viewpoint of alkali developability.
The carboxyl group content is indicated by an acid value. The acid value of (A) is preferably 10 to 500 mgKOH / g, more preferably 20 to 300 mgKOH / g. If it is 10 mgKOH / g or more, the developability is more likely to be exhibited, and if it is 500 mgKOH / g or less, the water resistance of the cured product can be further improved.

The acid value in the present invention can be measured by an indicator titration method using an alkaline titration solution. The method is as follows.
(I) About 0.1 to 10 g of a sample is precisely weighed and placed in an Erlenmeyer flask, and then a neutral methanol / acetone solution [a mixture of acetone and methanol at 1: 1 (volume ratio)] is added and dissolved.
(Ii) Add several drops of phenolphthalein indicator and titrate with 0.1 mol / L potassium hydroxide titration solution. The end point of neutralization is defined as the time when the indicator is slightly red for 30 seconds.
(Iii) Determine using the following equation.
Acid value (mgKOH / g) = (A × f × 5.61) / S
However, A: mL number of 0.1 mol / L potassium hydroxide titration solution
f: Potency of 0.1 mol / L potassium hydroxide titration solution
S: Sampling amount (g)

  Among the hydrophilic resins (A), examples of the hydrophilic vinyl resin (A1) include those having the above-mentioned hydrophilic group in the side chain and / or terminal of the vinyl polymer molecule.

  A preferred production method of (A1) is a method of vinyl polymerization of a vinyl monomer (a) having a hydrophilic group and, if necessary, a hydrophobic group-containing vinyl monomer (b).

  Examples of the vinyl monomer (a) having a hydrophilic group include the following vinyl monomers (a1) to (a7). (A) may use 1 type and may use 2 or more types together.

(A1) Hydroxyl-containing vinyl monomer:
Hydroxyalkyl (meth) acrylate having 1 to 30 carbon atoms in the hydroxyalkyl group [2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, etc.], polyalkylene ( Alkylene group having 1 to 8 carbon atoms) glycol (degree of polymerization 2 to 40) mono (meth) acrylate [polyethylene glycol mono (meth) acrylate and the like], alkylol (meth) acrylamide [N-methylol (meth) acrylamide and the like], Examples thereof include hydroxystyrene and 2-hydroxyethylpropenyl ether.

(A2) Carboxyl group-containing vinyl monomer:
C3-C30 unsaturated monocarboxylic acid [(meth) acrylic acid, crotonic acid, cinnamic acid, etc.], C4-C30 unsaturated polyvalent (2-4 valent) carboxylic acid [(anhydrous) maleic acid , Itaconic acid, fumaric acid, citraconic acid and the like], alkyl (alkyl group having 1 to 10 carbon atoms) ester of unsaturated polycarboxylic acid having 4 to 30 carbon atoms [monoalkyl maleate, monoalkyl ester of fumaric acid and Citraconic acid monoalkyl esters and the like] and salts thereof [alkali metal salts (sodium salt and potassium salt etc.), alkaline earth metal salts (calcium salt and magnesium salt etc.), amine salts and ammonium salts etc.].

(A3) Sulphonic acid group-containing vinyl monomer:
Examples include vinylsulfonic acid, (meth) allylsulfonic acid, styrenesulfonic acid, α-methylstyrenesulfonic acid, 2- (meth) acryloylamido-2-methylpropanesulfonic acid, and salts thereof. Examples of the salt include alkali metal (such as sodium and potassium) salts, alkaline earth metal (such as calcium and magnesium) salts, primary to tertiary amine salts, ammonium salts, and quaternary ammonium salts.

(A4) Amino group-containing vinyl monomer:
And tertiary amino group-containing (meth) acrylates [dialkylaminoalkyl (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate)] and the like.

(A5) Amide group-containing vinyl monomer:
(Meth) acrylamide, N-alkyl (1 to 6 carbon atoms) (meth) acrylamide, diacetone acrylamide, N, N′-methylene-bis (meth) acrylamide, N, N-dialkyl (1 to 6 carbon atoms) or N, N-diaralkyl (carbon number 7 to 15) (meth) acrylamide (for example, N, N-dimethylacrylamide and N, N-dibenzylacrylamide), methacrylformamide, N-methyl-N-vinylacetamide, cinnamic acid Examples include amides and cyclic amides (N-vinylpyrrolidone, N-allylpyrrolidone, etc.).

(A6) Quaternary ammonium base-containing vinyl monomer:
A quaternized product of a tertiary amino group-containing vinyl monomer having 6 to 50 carbon atoms (preferably 8 to 20 carbon atoms (for example, methyl chloride, dimethyl sulfate, benzyl chloride, and dimethyl carbonate). A quaternized product of aminoethyl (meth) acrylate, a quaternized product of diethylaminoethyl (meth) acrylate, a quaternized product of dimethylaminoethyl (meth) acrylamide, a quaternized product of diethylaminoethyl (meth) acrylamide, and the like.

(A7) (Poly) ether group-containing vinyl monomer:
Alkoxy (C1-C8 of alkoxy group) alkylene (C1-C8 of alkylene group) glycol mono (meth) acrylate [methoxyethylene glycol mono (meth) acrylate, methoxypropylene glycol mono (meth) acrylate, etc.], alkoxy (Alkoxy group having 1 to 8 carbon atoms) polyalkylene (alkylene group having 2 to 4 carbon atoms) glycol mono (meth) acrylate [methoxypolyethylene glycol (degree of polymerization 2 to 40) mono (meth) acrylate and methoxypolypropylene glycol (polymerization) Degree 2-30) mono (meth) acrylate etc.] etc. are mentioned.

  Examples of the hydrophobic group-containing vinyl monomer (b) used together with the hydrophilic group-containing vinyl monomer (a) in the hydrophilic vinyl polymer (A1) as necessary include the following monomers (b1) to (b5). (B) may use 1 type and may use 2 or more types together.

(B1) (Meth) acrylic acid ester:
Examples of the alkyl (meth) acrylate having 1 to 20 carbon atoms in the alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , N-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like. Examples of the alicyclic group-containing (meth) acrylate include dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate.

(B2) Aromatic hydrocarbon monomer:
Examples of the hydrocarbon monomer having a styrene skeleton include styrene, α-methyl styrene, vinyl toluene, 2,4-dimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, phenyl styrene, cyclohexyl styrene, benzyl styrene, and vinyl naphthalene. It is done.

(B3) Carboxylic acid vinyl ester:
Examples of those having 4 to 50 carbon atoms include vinyl acetate, vinyl propionate and vinyl butyrate.

(B4) Vinyl ether monomer:
Examples of those having 3 to 50 carbon atoms (preferably 6 to 20) include vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, and vinyl butyl ether.

(B5) Vinyl ketone monomer:
Examples of those having 4 to 50 carbon atoms include vinyl methyl ketone, vinyl ethyl ketone, and vinyl phenyl ketone.

  The hydrophilic vinyl resin (A1) is a polymer having (a) and (b) as a constituent monomer as described above, and a (meth) acryloyl group as a side chain or a terminal as necessary for the purpose of further improving sensitivity. You may make it contain.

  Examples of the method for incorporating a (meth) acryloyl group in the side chain include the following methods (1) and (2).

(1): A polymer is produced using a monomer having a group capable of reacting with an isocyanate group (such as a hydroxyl group or a primary or secondary amino group) in at least a part of (a), and then (meth) A method of reacting a compound having an acryloyl group and an isocyanate group (such as acryloylethyl isocyanate).

(2): A polymer is produced using a monomer having a group capable of reacting with an epoxy group (hydroxyl group, carboxyl group, primary or secondary amino group, etc.) in at least a part of (a), and then A method of reacting a compound having a (meth) acryloyl group and an epoxy group (such as glycidyl (meth) acrylate).

  The number average molecular weight of the hydrophilic vinyl resin (A1) by gel permeation chromatography (GPC) (hereinafter sometimes abbreviated as “Mn”) is preferably 1,000 to 30,000, more preferably. Is 1,500 to 10,000.

  In addition, Mn of the hydrophilic resin (A) in this invention uses GPC measuring apparatus (HLC-8120GPC, the Tosoh Corporation make), column (TSKgel GMHXL 2 book + TSKgel Multipore HXL-M, Tosoh Corporation make). , Measured in a THF solvent at a measurement temperature of 40 ° C. using TSK standard polystyrene [manufactured by Tosoh Corporation] as a reference substance.

  Of the hydrophilic resins (A), the hydrophilic epoxy resin (A2) is an epoxy resin containing a hydrophilic functional group such as a hydroxyl group, a carboxyl group, or an oxyethylene group in the molecule. (A2) preferably has a (meth) acryloyl group in the molecule from the viewpoint of photocuring reactivity.

A preferred method for producing the hydrophilic epoxy resin (A2) is that the epoxy group in the raw material epoxy resin (A2 ₀ ) (hereinafter sometimes simply referred to as (A2 ₀ )) contains a (meth) acryloyl group-containing monomer. Carboxylic acid (a21) is reacted to open an epoxy group to form a hydroxyl group to form a (meth) acryloyl group-containing monocarboxylic acid (a21) adduct of (A2 ₀ ). In this method, the polyvalent carboxylic acid or polyvalent carboxylic acid anhydride (c) is reacted.
In addition, (meth) acryloyl group containing monocarboxylic acid (a21) is unsaturated monocarboxylic acid containing a (meth) acryloyl group among carboxyl group-containing vinyl monomers (a2).

Examples of the raw material epoxy resin (A2 ₀ ) include aliphatic epoxy resins [eg, Etototo YH-300, PG-202, PG-207 (all manufactured by Toto Kasei Co., Ltd.)] and alicyclic epoxy resins [eg, CY-179. , CY-177, CY-175 (all manufactured by Asahi Kasei Epoxy Co., Ltd.)] and aromatic epoxy resins [for example, phenol novolac epoxy resin, cresol novolac epoxy resin [for example, EOCN-102S (manufactured by Nippon Kayaku Co., Ltd.)] Bisphenol A epoxy resin, biphenyl type epoxy resin, glycidyl-modified polyvinylphenol, etc.].
Among (A2 ₀ ), an aromatic epoxy resin is preferable from the viewpoint of hardness.

  As polyvalent carboxylic acid or polyvalent carboxylic acid anhydride (c) used for the production of (A2), unsaturated polyvalent carboxylic acids and their anhydrides, and saturated polyvalent (2-6 valent) carboxylic acids (For example, aliphatic saturated polyvalent carboxylic acids such as oxalic acid, succinic acid, phthalic acid, adipic acid, dodecanedioic acid, dodecenyl succinic acid, pentadecenyl succinic acid and octadecenyl succinic acid; tetrahydrophthalic acid, hexahydro Aromatic or cycloaliphatic polycarboxylic acids such as phthalic acid, methyltetrahydrophthalic acid, trimellitic acid, pyromellitic acid, biphenyltetracarboxylic acid and naphthalenetetracarboxylic acid) and their anhydrides (for example, succinic anhydride, Aliphatic saturated polyvalent carbohydrates such as dodecenyl succinic anhydride, pentadecenyl succinic anhydride and octadecenyl succinic anhydride Acid anhydrides; Fragrances such as phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic anhydride, biphenyltetracarboxylic anhydride and naphthalenetetracarboxylic anhydride Aliphatic or alicyclic polycarboxylic acid anhydrides). (C) may use 1 type and may use 2 or more types together. Of these, saturated polyvalent carboxylic acid anhydrides are preferable from the viewpoints of sensitivity and developability.

In the production of (A2), the charged weight ratio of (meth) acryloyl group-containing monocarboxylic acid (a21) / (A2 ₀ ) is preferably such that the concentration of (meth) acryloyl groups in (A2) is 1.0 mmol / g or more. The weight ratio is such that

The reaction temperature in the reaction of (A2 ₀ ) and (a21) is not particularly limited, but is preferably 70 to 110 ° C. The reaction time is not particularly limited, but is preferably 5 to 30 hours. Further, if necessary, a catalyst (for example, triphenylphosphine) and a radical polymerization inhibitor (hydroquinone, p-methoxyphenol, etc.) may be used.

The charge equivalent of the polyvalent carboxylic acid or polyvalent carboxylic acid anhydride (c) relative to the weight of the (meth) acryloyl group-containing monocarboxylic acid (a21) adduct of (A2 ₀ ) is such that the acid value of (A2) is Equivalent / g so as to be 10 to 500 mgKOH / g. For example, when (c) is a divalent carboxylic acid or an anhydride thereof, the charge equivalent of (c) / (A2 ₀ ) (meth) acrylic acid adduct is preferably 0 from the above viewpoint. .18 to 8.9 meq / g, more preferably 0.53 to 7.1 meq / g.

The reaction temperature in the reaction of the (meth) acryloyl group-containing monocarboxylic acid (a21) adduct of (A2 ₀ ) with the polyvalent carboxylic acid or polyvalent carboxylic acid anhydride (c) is not particularly limited, but preferably 70 ~ 110 ° C. The reaction time is not particularly limited, but is preferably 3 to 10 hours.

  The number average molecular weight of (A2) is preferably 500 to 3,000, more preferably 1,000 to 2,800, from the viewpoints of sensitivity and developability as the photosensitive resin composition.

  Photosensitive resin composition hydrophilic resin (A), polyfunctional (meth) acrylate (B), photopolymerization initiator (C) and compound (E) [hereinafter (A) to (C), (E) and Describe. ] The content of (A) based on the total weight is preferably 10 to 80% by weight, more preferably 15 to 78% by weight, and particularly preferably 20 to 75% by weight. If it is 10% by weight or more, the alkali developability can be exhibited satisfactorily, and if it is 80% by weight or less, the elastic recovery property can be exhibited more satisfactorily.

As the polyfunctional (meth) acrylate (B) contained as an essential component in the photosensitive resin composition of the present invention, any known polyfunctional (meth) acrylate can be used without particular limitation. A meth) acrylate (B1), a trifunctional (meth) acrylate (B2), a 4-6 functional (meth) acrylate (B3), etc. are mentioned. (B) may use 1 type and may use 2 or more types together.
For example, bifunctional (meth) acrylate means that the number of (meth) acryloyl groups is two, and the same description method is used hereinafter.

  The bifunctional (meth) acrylate (B1) is an esterified product of a polyhydric (preferably 2 to 8 valent) alcohol having 2 to 30 carbon atoms and (meth) acrylic acid [for example, di (meth) acrylate of ethylene glycol, Of di (meth) acrylate of glycerin, di (meth) acrylate of trimethylolpropane, di (meth) acrylate of 3-hydroxy-1,5-pentanediol, 2-hydroxy-2-ethyl-1,3-propanediol Di (meth) acrylate]; an alkylene oxide (2 to 4 carbon atoms of an alkylene group) of a polyhydric (preferably 2 to 8 carbon) alcohol having 2 to 30 carbon atoms and an adduct of (meth) acrylic acid Esterified products [for example, di (meth) acrylate of trimethylolpropane ethylene oxide adduct, glycerol ester Di (meth) acrylate of a lenoxide adduct]; OH group-containing both-end epoxy acrylate; and esterified product of a polyhydric alcohol having 2 to 30 carbon atoms, (meth) acrylic acid, and a hydroxycarboxylic acid having 3 to 30 carbon atoms [ For example, hydroxypivalate neopentyl glycol di (meth) acrylate] and the like.

  The trifunctional (meth) acrylate (B2) may be an ester of an alcohol and (meth) acrylic acid having 3 to 30 carbon atoms (preferably 3 to 8) having 3 to 30 carbon atoms [for example, tri (meth) acrylate of glycerin, tri A tri (meth) acrylate of methylolpropane, a tri (meth) acrylate of pentaerythritol]; and an alkylene oxide of a trivalent or higher (preferably 3-8) valent alcohol having 3 to 30 carbon atoms (the number of carbon atoms of the alkylene group is 2 to 2). 4) 1-30 mol adduct and esterified product of (meth) acrylic acid [for example, tri (meth) acrylate of ethylene oxide adduct of trimethylolpropane] and the like.

  As the tetra- to hexa-functional (meth) acrylate (B3), an esterified product of an alcohol and (meth) acrylic acid having 4 to 30 carbon atoms (preferably 4 to 8) having 5 to 30 carbon atoms [for example, tetra (meth) of pentaerythritol Acrylate, penta (meth) acrylate of dipentaerythritol, and hexa (meth) acrylate of dipentaerythritol]; and alkylene oxides of alkylene having 5 to 30 carbon atoms (preferably 4 to 8 valences) Carbonate 2-4) 1-30 mol adduct and esterified product of (meth) acrylic acid [for example, tetra (meth) acrylate of ethylene oxide adduct of dipentaerythritol, penta (meth) acrylate of ethylene oxide adduct of dipentaerythritol ) Propylene acrylate and dipentaerythritol Penta (meth) acrylate], etc. emissions oxide adducts.

  Of the polyfunctional (meth) acrylate (B), from the viewpoint of elastic recovery properties, (B2) and (B3) are preferable, and (B3) is more preferable.

  Examples of (B) that can be easily obtained from the market include light acrylate PE-3A (manufactured by Kyoeisha Chemical Co., Ltd .: pentaerythritol triacrylate), neomer DA-600 (manufactured by Sanyo Chemical Industries, Ltd .: dipentaerythritol pentaacrylate) and neomer. And EA-300 (manufactured by Sanyo Chemical Industries, Ltd .: pentaerythritol tetraacrylate).

Moreover, the polyfunctional (meth) acrylate (B) used by this invention may contain the photosensitive acrylic oligomer (B4) in the one part.
Examples of such (B4) include urethane acrylate, polyester acrylate, and polyether acrylate that have Mn of 1,000 or less, do not contain a carboxyl group, and have two or more acryloyl groups in one molecule. It is.

  The content of the polyfunctional (meth) acrylate (B) in the photosensitive resin composition of the present invention is preferably based on the total weight of (A) to (C) and (E) from the viewpoint of the elastic recovery rate. Is 10 to 80% by weight, more preferably 15 to 75% by weight.

  The photopolymerization initiator (C) used in the photosensitive resin composition of the present invention starts polymerization of a polymerizable unsaturated compound by exposure to radiation such as visible light, ultraviolet light, far infrared light, charged particle beam, and X-ray. Any component may be used as long as it can generate radicals that can be generated.

  Examples of such a photopolymerization initiator (C) include acetophenone derivative (C1), acylphosphine oxide derivative (C2), titanocene derivative (C3), triazine derivative (C4), bisimidazole derivative (C5), O -Acyl oxime (oxime ester) derivative (C6), benzophenone derivative (C7), thioxanthone derivative (C8), α-diketone derivative (C9), anthraquinone derivative (C10), acridine derivative (C11), and two or more of these The mixture which contains is mentioned.

  Examples of the acetophenone derivative (C1) include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, benzyldimethyl ketal, 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 2 -Methyl-1- (4- (methylthio) phenyl) -2-morpholino-1-propanone, dimethylbenzyl ketal, methylbenzoylformate, 2-benzyl-2-dimethylamino-1- (4-morpholino Eniru) - butan-1-one] and the like.

  Examples of the acylphosphine oxide derivative (C2) include trimethylbenzoyldiphenylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide.

Examples of the titanocene derivative (C3) include bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium. Is mentioned.

  Examples of the triazine derivative (C4) include trichloromethyltriazine and benzyl-2,4,6- (trihalomethyl) triazine.

  Examples of the bisimidazole derivative (C5) include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer.

  Examples of the O-acyl oxime (oxime ester) derivative (C6) include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9. -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime).

  Examples of the benzophenone derivative (C7) include benzophenone, 4,4-bis (dimethylamino) benzophenone, 3,3-dimethyl-4-methoxy-benzophenone, and Michler's ketone.

  Examples of the thioxanthone derivative (C8) include isopropylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, and diisopropylthioxanthone.

  Examples of the α-diketone derivative (C9) include camphorquinone.

  Examples of the anthraquinone derivative (C10) include anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, and tert-butylanthraquinone.

  Examples of the acridine derivative (C11) include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, 1,5-bis (9-acridinyl) pentane, and 1,3-bis (9-acridinyl) propane. Is mentioned.

  Of these (C1) to (C11), (C1), (C2), and (C8) are preferable from the viewpoint of ease of synthesis, and 2-methyl-1- [4- (methylthio) phenyl] -2- Morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and 2, 4-Diethylthioxanthone is more preferable, and from the viewpoint of reactivity, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone and bis (2,4,6-trimethylbenzoyl) -phenyl Phosphine oxide is particularly preferred.

  As the photopolymerization initiator (C), a commercially available product can be easily obtained. For example, as 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone, Irgacure 907 ( BASF), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one include Irgacure 369 (BASF), bis (2,4,6-trimethylbenzoyl) ) -Phenylphosphine oxide includes Irgacure 819 (manufactured by BASF), and 2,4-diethylthioxanthone includes Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.).

  The content of the photopolymerization initiator (C) based on the total weight of (A) to (C) and (E) in the photosensitive resin composition of the present invention is preferably 2 to 15% by weight, more preferably 3 -12% by weight, particularly preferably 4-11% by weight. If it is 2% by weight or more, curing reactivity and elastic recovery characteristics can be exhibited more satisfactorily, and if it is 15% by weight or less, reduction of mask contamination at the time of light exposure can be further exhibited.

  The photosensitive resin composition of this invention contains the solvent (D) whose HLB is 8.0 or more and 30.0 or less as a 4th essential component. If the solvent (D) is not included, developability becomes insufficient.

  The HLB of the solvent (D) is from 8.0 to 30.0, preferably from 9.0 to 25.0, and more preferably from 10.0 to 20.0. If the HLB is less than 8.0, the developability deteriorates, and if it exceeds 30.0, the development adhesion deteriorates.

As the solvent (D), ether solvents (including ether ester solvents and ether alcohol solvents) (ethylene glycol dimethyl ether (HLB: 11.9), ethylene glycol monomethyl ether (HLB: 29.2), ethylene glycol monoethyl ether ( HLB: 21.9), ethylene glycol monomethyl ether acetate (HLB: 13.5), ethylene glycol monobutyl ether (HLB: 14.6), diethylene glycol dimethyl ether (HLB: 14.2), diethylene glycol diethyl ether (HLB: 10. 6), diethylene glycol ethyl methyl ether (HLB: 12.1), diethylene glycol monomethyl ether (HLB: 25.0), diethylene glycol monoethyl ether (H B: 20.8), diethylene glycol isopropyl methyl ether (HLB: 11.3), diethylene glycol monobutyl ether (HLB: 15.6), diethylene glycol monoethyl ether acetate (HLB: 13.1), triethylene glycol dimethyl ether (HLB: 14.1), tetraethylene glycol dimethyl ether (HLB: 15.0), propylene glycol monomethyl ether (HLB: 17.1), propylene glycol monoethyl ether (HLB: 13.3), propylene glycol propyl ether (HLB: 10) .9), dipropylene glycol monomethyl ether (HLB: 10.0), tripropylene glycol monomethyl ether (HLB: 9.4), 3-methoxybutanol (H B: 17.1) and 3-methoxy-3-methyl-1-butanol (HLB: 15.0) and the like), alcohol solvents (including ketone alcohol solvents) (1.3-butylene glycol (HLB: 28.6), And diacetone alcohol (HLB: 16.5), etc., ester solvents (ethyl lactate (HLB: 17.8), etc.), ketone solvents (acetone (HLB: 10.8), methyl ethyl ketone (HLB: 8.1), etc.) ) And the like.
Among these, ether solvents and ester solvents are preferable from the viewpoint of coatability. Among these, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, 3-methoxybutanol, and ethyl lactate.
(D) may use 1 type and may use 2 or more types together.

  The solvent (D) is a “water-soluble solvent”, and the term “water-soluble solvent” here refers to a glass flask containing pure water and solvent in a volume ratio of 1: 1, and then stirred at 25 ° C. for 5 minutes. Then, after standing for 10 minutes after stopping the stirring, when visually confirmed, the pure water and the solvent are not separated into two layers, and the mixed solution of water and the solvent is uniformly transparent.

  The solvent can dissolve or disperse each component, and is selected according to the method of using the photosensitive resin composition of the present invention, but a solvent having a boiling point in the range of 100 to 280 ° C is selected. Is preferred.

As the solvent, a solvent (F) other than the solvent (D) may be contained. Such solvents (F) include ketone solvents (such as cyclohexanone), ether solvents (including ether ester solvents and ether alcohol solvents) (such as propylene glycol monomethyl ether acetate and methoxybutyl acetate), and ester solvents (such as butyl acetate). Etc.
Among these, ether solvents and ester solvents are preferable from the viewpoint of coatability.
(F) may use 1 type and may use 2 or more types together.

  The content of the solvent (D) is preferably 5% by weight or more based on the total weight of (A) to (E), more preferably 8 to 90% by weight, particularly preferably 10 to 89% by weight, and most preferably 15%. ~ 88 wt%. Further, the content of the solvent (F) is preferably 0 to 95% by weight, more preferably 3 to 95% by weight, and particularly preferably 5 to 95% by weight with respect to the weight of the solvent (D).

  Moreover, the photosensitive resin composition of this invention contains the compound (E) which is a condensate which uses the compound shown by following General formula (1) as an essential structural monomer as a 5th essential component.

In the formula (1), R ¹ is one selected from the group consisting of a (meth) acryloyloxyalkyl group having 1 to 6 carbon atoms in the alkyl group, a glycidoxyalkyl group, a mercaptoalkyl group, and an aminoalkyl group. The above organic group, R ² is an aliphatic saturated hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 12 carbon atoms, R ³ is an alkyl group having 1 to 4 carbon atoms, M is a silicon atom, It is one or more atoms selected from the group consisting of titanium atoms and zirconium atoms, and m is 0 or 1.

  In the general formula (1), among M, from the viewpoint of elastic recovery characteristics, a silicon atom and a titanium atom are preferable, and a silicon atom is more preferable.

Among R ² , examples of the aliphatic saturated hydrocarbon group include a linear alkyl group, a branched alkyl group, and an alicyclic saturated hydrocarbon group.
The straight chain alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-octyl and n-dodecyl groups and their deuterium substitutes; the branched alkyl groups include isopropyl, isobutyl, sec-butyl and 2 Examples of the cyclic saturated hydrocarbon group include a cyclohexyl group, a cyclooctyl group, a cyclohexylmethyl group, a cyclohexylethyl group, and a methylcyclohexyl group.

Examples of the aromatic hydrocarbon group include an aryl group, an aralkyl group, and an alkylaryl group.
Aryl groups include phenyl, biphenyl, naphthyl groups and their deuterium, fluorine or chlorine substituents; aralkyl groups include tolyl, xylyl, mesityl and their deuterium, fluorine or chloride; and alkylaryl Groups include methylphenyl and ethylphenyl groups.

R ² is preferably a linear alkyl group, branched alkyl group and aryl group from the viewpoint of curing reactivity, more preferably a linear alkyl group and an aryl group, particularly preferably a methyl group, an ethyl group, A phenyl group and a combination thereof.
Examples of R ³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a sec-butyl group, and preferred are a methyl group and an ethyl group from the viewpoint of thermosetting reactivity. is there.

In the general formula (1), examples of the compound having a (meth) acryloyloxyalkyl group as R ¹ include the following compounds.
m is 0, that is, a trifunctional compound having three alkoxy groups: 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-acrylic Leuoxypropyltriethoxysilane, 3-methacryloyloxypropyltrimethoxytitanium, 3-methacryloyloxypropyltrimethoxyaluminum, 3-methacryloyloxypropyltrimethoxyzirconium and the like.

  m is 1, that is, a trifunctional compound having two alkoxy groups ... 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-acryloyloxypropylmethyldimethoxysilane, 3- Acryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropylmethyldimethoxytitanium, 3-methacryloyloxypropylmethyldimethoxyaluminum, 3-methacryloyloxypropylmethyldimethoxyzirconium and the like.

Examples of the compound having a glycidoxyalkyl group as R ¹ include the following compounds.
m is 0, that is, a trifunctional compound having three alkoxy groups: 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltrimethoxytitanium, and the like.
m is 1, that is, trifunctional compound having two alkoxy groups: 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxytitanium, 3- Glycidoxypropylmethyldimethoxyaluminum, 3-glycidoxypropylmethyldimethoxyzirconium and the like.

Examples of the compound having a mercaptoalkyl group as R ¹ include the following compounds.
m is 0, that is, trifunctional compound having three alkoxy groups: 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropyltrimethoxytitanium, 3-mercaptopropyltrimethoxyaluminum, 3 -Mercaptopropyltrimethoxyzirconium and the like.
m is 1, that is, a trifunctional compound having two alkoxy groups: 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropylmethyldiethoxysilane, 3-mercaptopropylmethyldimethoxytitanium, 3-mercaptopropylmethyldimethoxyaluminum, 3-mercaptopropylmethyldimethoxyzirconium and the like.

Examples of the compound having an aminoalkyl group as R ¹ include the following compounds.
m is 0, that is, trifunctional compound having three alkoxy groups: N-2 aminoethyl γ-aminopropyltrimethoxysilane, N-2 aminoethyl γ-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane 3-aminopropyltriethoxysilane, N-2 aminoethyl γ-aminopropyltrimethoxytitanium, N-2 aminoethyl γ-aminopropyltrimethoxyaluminum, N-2 aminoethyl γ-aminopropyltrimethoxyzirconium and the like.
m is 1, that is, trifunctional compound having two alkoxy groups: N-2 aminoethyl γ-aminopropylmethyldimethoxysilane, N-2 aminoethyl γ-aminopropylmethyldiethoxysilane, 3-aminopropylmethyldimethoxy Silane, 3-aminopropylmethyldiethoxysilane, N-2 aminoethyl γ-aminopropylmethyldimethoxytitanium, N-2 aminoethyl γ-aminopropylmethyldimethoxyaluminum, N-2 aminoethyl γ-aminopropylmethyldimethoxyzirconium, etc. .

Of the compounds (E) which are condensates (condensation degree: 2 to 100) having the compound represented by the general formula (1) as an essential constituent monomer, (meth) acrylic having 3 alkoxy groups is preferable. A condensate comprising a leuoxyalkyl group-containing trifunctional silane compound as an essential constituent monomer, and a condensate comprising a glycidoxyalkyl group-containing trifunctional silane compound having three alkoxy groups as an essential constituent monomer, More preferred are condensates containing 3-acryloyloxypropyltrimethoxysilane as an essential constituent monomer and condensates containing 3-glycidoxypropyltrimethoxysilane as an essential constituent monomer.
As a monomer constituting the condensate of the compound (E), in addition to the compound represented by the general formula (1), dialkyl dialkoxysilane (eg, dimethyldimethoxysilane, diethyldimethoxysilane, etc.), diaryl dialkoxy Silane (for example, diphenyldimethoxysilane etc.) etc. are mentioned.

  Examples of (E) that can be easily obtained from the market include KR-513 [manufactured by Shin-Etsu Chemical Co., Ltd .: acrylic group and methyl group-containing methoxysiloxane (acrylic-modified alkoxypolysiloxane)].

  The content of the compound (E) is 0.1 to 20% by weight, preferably 0.5 based on the total weight of (A) to (C) and (E) from the viewpoints of elastic recovery and adhesion. -15% by weight, more preferably 1-12% by weight.

  The photosensitive resin composition of the present invention may further contain other components as necessary, and examples thereof include inorganic fine particles, surfactants, silane coupling agents, antioxidants, and polymerization inhibitors. The total addition amount of the other components is 0 to 10% by weight, preferably 0.1 to 8% by weight, more preferably 0.3 to 5% based on the total weight of (A) to (C) and (E). % By weight.

  As the inorganic fine particles, metal oxides and metal salts can be used. Examples of the metal oxide include titanium oxide, silicon oxide, and aluminum oxide. Examples of the metal salt include calcium carbonate and barium sulfate. Of these, metal oxides are preferable and silicon oxide is more preferable from the viewpoints of heat-resistant transparency and chemical resistance. The inorganic fine particles preferably have a volume average primary particle diameter of 1 to 200 nm.

  As the surfactant, various anionic, cationic, nonionic, amphoteric, fluorine and silicon surfactants can be used. Of these, fluorine-based and silicon-based surfactants are preferable from the viewpoint of applicability.

  Examples of the silane coupling agent include vinyl silane, acrylic silane, epoxy silane, amino silane, and the like.

  Antioxidants include 2,6-di-t-butyl-4-methylphenol, 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-t-pentylphenyl acrylate, 6- [3- (3-t-butyl- 4-hydroxy-5-methylphenyl) propoxy] -2,4,6,10-tetra-butyldibenz [d, f] [1,3,2] dioxaphosphine, 3-4′-hydroxy-3 ′ -5'-di-t-butylphenyl) propionic acid-n-octadecyl, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, 3,9-bis [2- [ 3- (3-t Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1dimethylethyl] -2,4,8,10-tetraoxaspiro [5 · 5] undecane, 2,2′-methylenebis (6-t -Butyl-4-methylphenol), 4,4′butylidenebis (6-tert-butyl-3-methylphenol), 3,6-dioxaoctamethylene = bis [3- (3-tert-butyl-4-hydroxy) -5-methylphenyl) propionate], 4,4'-thiobis (2-tert-butyl-5-methylphenol), 4,4'-thiobis (6-tert-butyl-3-methylphenol), thiodiethyl Ellenbis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxy Benzyl) isocyanuric acid, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4 -Hydroxyphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like.

  Examples of the polymerization inhibitor include p-methoxyphenol, hydroquinone, naphthylamine, tert-butylcatechol, 2,3-di-tert-butyl-p-cresol and the like.

  The photosensitive resin composition of the present invention can be obtained, for example, by mixing the above-described components with a known mixing device such as a planetary mixer. The photosensitive resin composition is usually liquid at room temperature, and its viscosity is 25 ° C., preferably 0.1 to 10,000 mPa · s, more preferably 1 to 8,000 mPa · s.

  The photosensitive resin composition of the present invention is excellent in elastic recovery characteristics and high developability, and has high resolution. Therefore, the photo spacer, the protective film for the color filter, the protective film for the touch panel, or the insulating film for the touch panel Suitable as a photosensitive resin composition for film formation.

A preferable forming step of obtaining a cured product from the photosensitive resin composition of the present invention is a step of applying a photosensitive resin composition on a substrate, irradiating with light, forming a pattern by alkali development, and performing post-baking. .
Formation of hardened | cured material is normally performed at the process of (1)-(5) below.

(1) The process of apply | coating the photosensitive resin composition of this invention on a board | substrate. Examples of the coating method include roll coating, spin coating, spray coating, and slit coating. Examples of the coating device include spin coater, air knife coater, roll coater, bar coater, die coater, curtain coater, gravure coater, and comma coater. Etc.
The film thickness is preferably 0.5 to 10 μm, more preferably 1 to 5 μm.

(2) A step of drying (prebaking) the applied photosensitive resin composition layer by applying heat as necessary. 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 performed under reduced pressure or normal pressure.

(3) A step of exposing the photosensitive resin composition layer with actinic rays through a predetermined photomask. Examples of the actinic rays include visible rays, ultraviolet rays, far infrared rays, charged particle beams, X-rays, and laser beams. Examples of the light source include sunlight, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, and a semiconductor laser. Although it does not specifically limit as an exposure amount, Preferably it is 20-300 mJ / cm < ² >, and 20-100 mJ / cm < ² > is more preferable from a viewpoint of production cost. In the step of performing exposure, a component having a (meth) acryloyl group in the photosensitive resin composition reacts to undergo photocuring reaction.

(4) A step of developing after removing the unexposed portion with a developer after light irradiation. As the developer, an alkaline aqueous solution is usually used. Examples of the alkaline aqueous 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. And an aqueous solution of an organic alkali. These can be used alone or in combination of two or more kinds, and a surfactant such as an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant can be added and used.
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) step. The post-baking temperature is preferably 50 to 280 ° C, more preferably 100 to 250 ° C. The post-bake time is preferably 5 minutes to 2 hours.

  Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Hereinafter, unless otherwise specified, “%” represents “% by weight” and “parts” represents “parts by weight”.

Production Example 1
A glass flask equipped with a heating / cooling / stirring device, a reflux condenser, and a nitrogen inlet tube was charged with 60 parts of styrene, 20 parts of methyl methacrylate, 20 parts of methacrylic acid, and 217 parts of diethylene glycol dimethyl ether. After substituting the gas phase part in the system with nitrogen, 36 parts of a solution in which 6 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 30 parts of diethylene glycol dimethyl ether were added and heated to 90 ° C. The mixture was further reacted at the same temperature for 4 hours. Furthermore, 15 parts of glycidyl methacrylate and 1 part of triethylamine were added to the obtained solution and reacted at 90 ° C. for 6 hours to obtain a 30% diethylene glycol dimethyl ether solution of the hydrophilic vinyl resin (A-1).
The acid value in terms of solid content of the hydrophilic vinyl resin was 131.5. Mn by GPC was 4,000. The hydrophilic vinyl resin had an SP value of 10.8 and an HLB value of 7.1.

Production Example 2
A glass flask equipped with a heating / cooling / stirring device, a reflux condenser, and a nitrogen introduction tube was charged with 90 parts of styrene, 10 parts of methyl methacrylate, 30 parts of methacrylic acid, and 327 parts of propylene glycol monomethyl ether acetate. After substituting the gas phase part in the system with nitrogen, 38 parts of a solution prepared by dissolving 8 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) in 30 parts of propylene glycol monomethyl ether acetate were added, and 90 ° C. And further reacted at the same temperature for 4 hours. Furthermore, 15 parts of glycidyl methacrylate and 1 part of triethylamine were added to the obtained solution and reacted at 90 ° C. for 6 hours to obtain a 30% propylene glycol monomethyl ether acetate solution of the hydrophilic vinyl resin (A-2).
The acid value in terms of solid content of the hydrophilic vinyl resin was 96.1. Mn by GPC was 4,500. The hydrophilic vinyl resin had an SP value of 11.1 and an HLB value of 6.8.

Production Example 3
In a glass flask equipped with a heating / cooling / stirring device, a reflux condenser, a dropping funnel and a nitrogen introduction tube, 200 parts of cresol novolac type epoxy resin “EOCN-102S” (epoxy equivalent 200 manufactured by Nippon Kayaku Co., Ltd.) and propylene 145 parts of glycol monomethyl ether acetate was charged and heated to 90 ° C. to dissolve uniformly. Subsequently, 76 parts of acrylic acid, 2 parts of triphenylphosphine and 0.2 part of p-methoxyphenol were charged and reacted at 90 ° C. for 10 hours.
The reaction product was further charged with 91 parts of tetrahydrophthalic anhydride, further reacted at 90 ° C. for 5 hours, and then diluted with propylene glycol monomethyl ether acetate so that the content of hydrophilic epoxy resin was 60%. A 60% propylene glycol monomethyl ether acetate solution of epoxy resin (A-3) was obtained.
The acid value in terms of solid content of the hydrophilic epoxy resin was 88.4. The Mn by GPC was 2,200. The hydrophilic epoxy resin had an SP value of 11.3 and an HLB value of 9.8.

Production Example 4
[Production of Compound (E-1)]
In a glass flask equipped with a heating / cooling / stirring device, a reflux condenser, a dropping funnel and a nitrogen introducing tube, 46 parts (0.2 mole part) of 3-acryloyloxypropyltrimethoxysilane, 160 parts of diphenyldimethoxysilane (0 .65 mol parts), 45 g (2.5 mol parts) of ion-exchanged water, and 0.1 part (0.001 mol parts) of oxalic acid, and heated and stirred at 60 ° C. for 6 hours. The methanol by-produced by hydrolysis was removed over 2 hours under reduced pressure to obtain acrylic-modified alkoxypolysiloxane (E-1) (Mn: 2,100).

Examples 1-9 and Comparative Examples 1-4
According to the number of parts in Table 1, a solution of the hydrophilic resin (A-1) produced in Production Example 1 in a glass container, the following (B-1), (C-1), (C-3), ( D-1), (D-2) surfactants (G-1) and (G-2), and the acrylic-modified alkoxypolysiloxane (E-1) produced in Production Example 4 were charged until uniform. The mixture was stirred to obtain a photosensitive resin composition of Example 1. Moreover, using the same apparatus, the photosensitive resin composition of Examples 2-9 and Comparative Examples 1-4 was similarly obtained using the raw material of the compounding part number of Table 1. FIG.

The details of the abbreviated chemicals in Table 1 are as follows.
(B-1): “Neomer DA-600” (dipentaerythritol pentaacrylate: manufactured by Sanyo Chemical Industries, Ltd.) (HLB: 9.4)
(B-2): “Neomer EA-300” (pentaerythritol tetraacrylate: manufactured by Sanyo Chemical Industries, Ltd.) (HLB: 7.8)
(C-1): “Irgacure 819” (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide: manufactured by BASF)
(C-2): “Irgacure 907” (2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-1-propanone: manufactured by BASF)
(C-3): “Kayacure-DETX-S” (2,4-diethylthioxanthone: manufactured by Nippon Kayaku Co., Ltd.)
(D-1) Diethylene glycol ethyl methyl ether (D-2) Diethylene glycol dimethyl ether (D-3) Ethyl lactate (D-4) Ethylene glycol monomethyl ether (D-5) Tripropylene glycol monomethyl ether (E-2): “KR -513 "[acrylic group and methyl group-containing methoxysiloxane (acrylic-modified alkoxypolysiloxane): manufactured by Shin-Etsu Chemical Co., Ltd.]
(F-1) Propylene glycol monomethyl ether acetate (F-2) Butyl acetate (G-1): “KF-352A” [Polyether-modified polydimethylsiloxane (surfactant): manufactured by Shin-Etsu Chemical Co., Ltd.]
(G-2): “Megafac TF-2066” [polyether-modified fluorine compound (surfactant): manufactured by DIC Corporation]

Measurement method of number average molecular weight (Mn) of compound (E) HLC-8320GPC (manufactured by Tosoh Corporation) was used, and THF solvent and TSK standard polystyrene (manufactured by Tosoh Corporation) were used as reference substances. Moreover, GPC workstation EcoSEC-WS (made by Tosoh Corporation) was used as analysis software.

The performance evaluation method will be described below.
[Evaluation of developability]
A photosensitive resin composition was applied onto a 10 cm × 10 cm square glass substrate by a spin coater and dried to form a coating film having a dry film thickness of 5 μm. This coating film was heated on a hot plate at 80 ° C. for 3 minutes, and then developed with a 0.05% aqueous KOH solution for 30 seconds to evaluate the developability. The evaluation criteria are as follows.
A: There is no residue visually.
○: There is a slight residue visually.
Δ: There are many residues by visual inspection.
X: Development is not possible.

[Evaluation of elastic recovery characteristics]
A photosensitive resin composition was applied onto a 10 cm × 10 cm square glass substrate by a spin coater and dried to form a coating film having a dry film thickness of 5 μm. This coating film was heated on a hot plate at 80 ° C. for 3 minutes.
The resulting coating film was irradiated with 60 mJ / cm ^{2 of} light from an ultrahigh pressure mercury lamp through a mask for forming a photospacer (illuminance 22 mW / cm ^{2 in} terms of i-line).
In addition, it exposed with the space | interval (exposure gap) of a mask and a board | substrate 100 micrometers.
Thereafter, alkali development was performed using a 0.05% aqueous KOH solution. After washing with water, post-baking was performed at 230 ° C. for 30 minutes to form a photo spacer on the glass substrate.

The elastic recovery characteristic of the photospacer can be evaluated by the “elastic recovery rate” when a certain pressure defined by the following formula (1) is applied. The higher the elastic recovery rate (%), the better the elastic recovery characteristic. If it is 70% or more, it can be said that the elastic recovery characteristic is good.
The elastic recovery characteristic was evaluated by measuring the elastic recovery rate under a pressure condition of 0.5 mN / μm ² .

(1) A micro hardness tester (Fischer Instruments, Inc .; “Fischer Scope H-100”) and a planar indenter having a square cross section for one photo spacer selected arbitrarily from among photo spacers formed on a glass substrate. (50 μm × 50 μm) was used to measure the amount of deformation when a load was applied and when the load was returned.
At this time, a load was applied to 0.5 mN / μm ² over 30 seconds at a load speed of 0.017 mN / μm ² · sec and held for 5 seconds.
The amount of deformation from the initial position of the photospacer in a state where a load was applied was measured. The amount of change at this time is defined as a total deformation amount T ₀ (μm).
(2) Next, the load was released to 0 over 30 seconds at an unloading speed of 0.017 mN / μm ² · sec, and the state was maintained for 5 seconds. The deformation amount from the initial position of the photo spacer at this time is defined as a plastic deformation amount T ₁ (μm).
(3) From the T ₀ and T ₁ measured as described above, the elastic recovery rate was calculated using the following formula (1).

Elastic recovery rate (%) = [(T ₀ −T ₁ ) / T ₀ ] × 100 (1)

[Resolution evaluation]
Among the photo spacers obtained in the same manner as in [Evaluation of Elastic Recovery Properties], the bottom diameter of a photo spacer having a photomask opening diameter of 10 μm was measured with a laser microscope, and this was used as an evaluation of resolution. . It can be said that the smaller the bottom shape, the higher the resolution, and the better the resolution is 10.8 μm or less.

[Evaluation of development adhesion]
A photosensitive resin composition was applied onto a 10 cm × 10 cm square glass substrate by a spin coater and dried to form a coating film having a dry film thickness of 5 μm. This coating film was heated on a hot plate at 80 ° C. for 3 minutes. The resulting coating film was irradiated with 60 mJ / cm ^{2 of} light from an ultrahigh pressure mercury lamp through a mask for forming a photospacer (illuminance 22 mW / cm ^{2 in} terms of i-line). In addition, it exposed with the space | interval (exposure gap) of a mask and a board | substrate 100 micrometers. Thereafter, development was performed for 90 seconds using a 0.05% aqueous KOH solution, and the development adhesion was evaluated. The evaluation criteria are as follows. If it is 現 像 or ◯, it can be said that the development adhesion is good.
◎: No peeling with photomask opening diameter of 10 μm ○: No peeling with photomask opening diameter of 12 μm (Peeling off at 10 μm)
Δ: No peeling with photomask opening diameter of 16 μm (Peeling with 10 μm and 12 μm)
×: Photomask opening diameter is 16 μm and there is peeling

[Evaluation of transparency]
The photosensitive resin composition was applied onto a transparent glass substrate (thickness 0.7 mm) with a spin coater and dried to form a coating film. This coating film was heated at 80 ° C. for 3 minutes.
The obtained coating film was irradiated with light from an ultrahigh pressure mercury lamp at 60 mJ / cm ² (illuminance 22 mW / cm ^{2 in} terms of i-line).
Thereafter, alkali development was performed using a 0.05% aqueous KOH solution. After washing with water, post-baking was performed at 230 ° C. for 30 minutes to form a protective film having a thickness of 2 μm.
About the protective film obtained as mentioned above, the transmittance | permeability of light with a wavelength of 400 nm was measured using ultraviolet visible spectrophotometer UV-2400 (made by Shimadzu Corp.).
The transmittance at 400 nm is shown in Table 1. When this value is 97% or more, it can be said that the transparency of the protective film is good.

[Evaluation of adhesion]
About the protective film obtained by the same operation as evaluation of transparency, the adhesiveness of the protective film was evaluated by the adhesiveness (cross-cut method) of JIS K5600-5-6.
Table 1 shows the number of grids of the cross-cut protective film remaining on the glass substrate in 100 (10 × 10) grids. If it is 95 or more, it can be said that adhesiveness is favorable.

[Evaluation of pencil hardness]
The protective film thus obtained was evaluated for the pencil hardness of the protective film by the scratch hardness (pencil method) of JIS K5600-5-4 by the same operation as the evaluation of transparency.
The pencil hardness is shown in Table 1.
When this value is 3H or more, it can be said that the hardness of the protective film is good.

The photosensitive resin compositions of the present invention of Examples 1 to 9 are excellent in all points of developability, elastic recovery characteristics, resolution, development adhesion, transparency, adhesion, and pencil hardness as shown in Table 1. Yes.
On the other hand, since Comparative Examples 1 and 2 do not contain the solvent (D), the developability is poor. Since Comparative Examples 3 and 4 do not contain the hydrophilic resin (A), development cannot be performed.

  Since the photosensitive resin composition of the present invention is excellent in developability and elastic recovery characteristics after curing and adhesion to a glass substrate, a photo spacer for a display element, a protective film for a color filter, a protective film for a touch panel, or an insulating film for a touch panel Can be suitably used. Furthermore, it is also suitable as a photosensitive resin composition for various other resist materials such as a photo solder resist, a photosensitive resist film, a photosensitive resin relief plate, a screen plate, a photoadhesive or a hard coat material.

Claims (6)

Hydrophilic resin (A), polyfunctional (meth) acrylate (B), photopolymerization initiator (C), solvent (D) having HLB of 8.0 to 30.0, and the following general formula (1) The photosensitive resin composition containing the compound (E) which is a condensate which uses the compound shown as an essential structural monomer.

[In the formula (1), R ¹ is selected from the group consisting of a (meth) acryloyloxyalkyl group having 1 to 6 carbon atoms, a glycidoxyalkyl group, a mercaptoalkyl group, and an aminoalkyl group. seed or more organic groups, R ² is an aromatic hydrocarbon group having 6 to 12 carbon aliphatic saturated hydrocarbon group or a C 1 to 12 carbon atoms, R ³ is an alkyl group having 1 to 4 carbon atoms, M is silicon atom , One or more atoms selected from the group consisting of titanium atoms and zirconium atoms, and m is 0 or 1. ]   The photosensitive resin composition according to claim 1, wherein M in the general formula (1) is a silicon atom. In the general formula (1), R ¹ is a (meth) acryloyloxyalkyl group having 1 to 6 carbon atoms in the alkyl group and / or a glycidoxyalkyl group having 1 to 6 carbon atoms in the alkyl group. The photosensitive resin composition of Claim 1 or 2.   A photo spacer formed by subjecting the photosensitive resin composition according to claim 1 to light development, followed by alkali development to form a pattern, and further post-baking.   A protective film for a color filter formed by subjecting the photosensitive resin composition according to any one of claims 1 to 3 to light development, followed by alkali development to form a pattern, and further post-baking. A protective film or insulating film for a touch panel formed by subjecting the photosensitive resin composition according to any one of claims 1 to 3 to light development, alkali development to form a pattern, and further post-baking.