WO2022270407A1

WO2022270407A1 - Photosensitive resin composition, cured resin film, and image display device

Info

Publication number: WO2022270407A1
Application number: PCT/JP2022/024139
Authority: WO
Inventors: 正偉周; 正義柳; 健宏木下
Original assignee: 昭和電工株式会社
Priority date: 2021-06-21
Filing date: 2022-06-16
Publication date: 2022-12-29
Also published as: JPWO2022270407A1; TW202311305A

Abstract

A photosensitive resin composition comprising an alkali-soluble resin, an alkoxysilylated resin, a reactive diluent, a photo-radical polymerization initiator, and a solvent, wherein the alkali-soluble resin contains a constituent unit (a-1) derived from a compound having an ethylenically unsaturated group and containing an aromatic group, has an acid group and a (meth)acryloyloxy group, has an ethylenically-unsaturated-group equivalent of 400-2,500 g/mol, and contains the constituent unit (a-1) in an amount of 15-60 mol% with respect to all the repeating constituent units of the alkali-soluble resin and the alkoxysilylated resin includes a constituent unit derived from a compound having an ethylenically unsaturated group and containing an alkoxysilyl group.

Description

Photosensitive resin composition, cured resin film and image display device

The present invention relates to a photosensitive resin composition, a cured resin film thereof, and an image display device comprising the cured resin film.
This application claims priority based on Japanese Patent Application No. 2021-102284 filed in Japan on June 21, 2021, the content of which is incorporated herein.

In recent years, touch panels have become popular as input devices for mobile phones, tablet computers, vending machines, bank ATMs (automated teller machines), etc. As touch panels, there are resistive type, optical type, ultrasonic type, and capacitive type touch panels. A capacitive touch panel detects an input position by detecting a change in capacitance between electrodes caused by pressing.

In Patent Document 1, even if a detection electrode portion having a wide-pitch mesh pattern with small parasitic capacitance and high detection sensitivity is used, visibility is improved, and moire occurs when a touch panel and a display device are combined. A touch panel using a conductive member capable of suppressing is described.
Patent Document 2 discloses a touch panel using a glass substrate coated with a film-forming composition. Patent Document 2 describes a film-forming composition containing a polysiloxane compound, a polythiol compound containing no silicon in the molecule, a polymerization initiator and an organic solvent.

Patent Document 3 describes a touch panel protective film and a touch panel insulating film obtained by curing a photosensitive resin composition. Patent Document 3 discloses a hydrophilic resin (A) having a radically polymerizable group, a polyfunctional (meth)acrylate (B) having no phosphoric acid group, and a (meth)acrylate (C) having a phosphoric acid group. , a photosensitive resin composition containing a silane compound (D) having an amino group and a photopolymerization initiator (E).

WO2018/163603 Japanese Patent Application Laid-Open No. 2020-75992 JP 2018-116271 A

In an image display device such as a touch panel, a photosensitive resin composition used as a material for a resin cured film used as an insulating film and/or a protective film has good storage stability and is highly accurate using a photolithography method. It is required to have good developability capable of forming a cured resin film having a pattern shape of . Furthermore, in the photosensitive resin composition used for the above applications, the resin cured film obtained by curing the photosensitive resin composition has high hardness, adhesion to the substrate and / or base, water resistance, High temperature and high humidity resistance and good transparency are required.
However, conventional photosensitive resin compositions do not satisfy all of the above performances required for materials for cured resin films used in image display devices.

The present invention has been made in view of the above circumstances, has good storage stability, and has good developability that can form a resin cured film having a highly accurate pattern shape using a photolithography method, Provided is a photosensitive resin composition which, when cured, provides a cured resin film having high hardness, adhesion to substrates and/or substrates, water resistance, resistance to high temperature and high humidity, and transparency. and
Furthermore, the present invention provides a cured resin obtained by curing the photosensitive resin composition of the present invention, which has high hardness, adhesion to a substrate and / or a base, water resistance, high temperature and high humidity resistance, and good transparency. An object of the present invention is to provide a film and an image display device having the same.

The present invention provides a composition of the following first aspect.
[1] (A) an alkali-soluble resin;
(B) an alkoxysilyl group-containing resin;
(C) a reactive diluent;
(D) a radical photopolymerization initiator;
(E) a solvent, and
The (A) alkali-soluble resin contains a structural unit (a-1) derived from an ethylenically unsaturated group-containing compound (ma-1) having an aromatic group, and has an acid group and a (meth)acryloyloxy group. and having an ethylenically unsaturated group equivalent of 400 g/mol or more and 2500 g/mol or less, and containing 15 mol% or more and 60 mol% or less of the structural unit (a-1) among all the repeating structural units of the alkali-soluble resin (A). death,
A photosensitive resin composition, wherein the (B) alkoxysilyl group-containing resin comprises a structural unit (b-1) derived from an ethylenically unsaturated group-containing compound (mb-1) having an alkoxysilyl group.

Preferably, the first aspect of the present invention has the following features. Combinations of two or more of the following features are also preferred.
[2] The photosensitive resin composition according to [1], wherein the mass ratio of (A) the alkali-soluble resin and (B) the alkoxysilyl group-containing resin is 40:60 to 99:1.
[3] The photosensitive resin according to [1] or [2], wherein the content of the structural unit (b-1) in all repeating structural units of the alkoxysilyl group-containing resin (B) is 45 mol% or more. Composition.

[4] The (A) alkali-soluble resin comprises the structural unit (a-1), the structural unit (a-2) derived from an unsaturated monobasic acid (ma-2), and an alicyclic hydrocarbon group. A part of the carboxy groups of the copolymer containing the structural unit (a-3) derived from the ethylenically unsaturated group-containing compound (ma-3) having an epoxy group-containing (meth) acrylate (ma-5) derived from The photosensitive resin composition according to any one of [1] to [3], which is a resin modified with the structural unit (a-5).

[5] The photosensitive resin composition according to any one of [1] to [4], wherein the alkali-soluble resin (A) has an acid value of 20 KOHmg/g or more and 200 KOHmg/g or less.
[6] The photosensitive resin composition according to any one of [1] to [5], wherein the alkali-soluble resin (A) has a weight average molecular weight (Mw) of 1000 or more and 50000 or less.
[7] The (B) alkoxysilyl group-containing resin contains a structural unit (b-2) derived from an unsaturated monobasic acid (mb-2),
The photosensitive resin composition according to any one of [1] to [6], which has an acid value of 150 KOHmg/g or less.
[8] The photosensitive resin composition according to any one of [1] to [7], wherein the (B) alkoxysilyl group-containing resin has a weight average molecular weight (Mw) of 1,000 to 20,000.

[9] With respect to a total of 100 parts by mass of the (A) alkali-soluble resin, the (B) alkoxysilyl group-containing alkoxysilyl group-containing resin, and the (C) reactive diluent,
Containing 5 to 75 parts by mass of the (C) reactive diluent,
The photosensitive resin composition according to any one of [1] to [8], containing 0.1 to 20 parts by mass of the (D) photoradical polymerization initiator.
[10] The solvent (E) contains one or more alcohols selected from primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms,
The photosensitive resin composition according to any one of [1] to [9], wherein the total alcohol content in all solvents is 15 to 100% by mass.

[11] (F) The photosensitive resin composition according to any one of [1] to [10], further comprising a silane coupling agent.
[12] The photosensitive resin composition according to [11], wherein the (F) silane coupling agent has one or more functional groups selected from (meth)acrylic, vinyl and styryl groups.
[13] With respect to a total of 100 parts by mass of the (A) alkali-soluble resin, the (B) alkoxysilyl group-containing resin, and the (C) reactive diluent,
The photosensitive resin composition according to [11] or [12], containing 0.1 to 20 parts by mass of the (F) silane coupling agent.

The present invention provides a cured resin film of the following second aspect.
[14] A cured resin film comprising a cured product of the photosensitive resin composition according to any one of [1] to [13].
The present invention provides an image display device according to a third aspect described below.
[15] An image display device comprising the cured resin film of [14].
The device of the third aspect of the invention preferably has the following features. Combinations of two or more of the following features are also preferred.
[16] The image display device according to [15], which has a protective film made of the cured resin film.
[17] The image display device according to [15], which has an insulating film made of the cured resin film.

The photosensitive resin composition of the present invention comprises a specific (A) alkali-soluble resin, a specific (B) alkoxysilyl group-containing resin, (C) a reactive diluent, and (D) a photoradical polymerization initiator. , and (E) a solvent. Therefore, the photosensitive resin composition of the present invention has good storage stability. Moreover, since the photosensitive resin composition of the present invention has good developability, a cured resin film having a highly accurate pattern shape can be formed using a photolithographic method. Moreover, by curing the photosensitive resin composition of the present invention, a cured resin film having high hardness, good adhesion to the base material and/or base, water resistance, resistance to high temperature and high humidity, and transparency can be obtained. be done. Therefore, the photosensitive resin composition of the present invention is suitable as a material for cured resin films used as insulating films and/or protective films in image display devices such as touch panels.

Since the cured resin film of the present invention is made of the cured product of the photosensitive resin composition of the present invention, it has high hardness, adhesion to the base material and / or the base, water resistance, high temperature and high humidity resistance, transparency. Good properties.
Since the image display device of the present invention includes the cured resin film of the present invention, it is excellent in reliability and durability.

Preferred examples of the photosensitive resin composition, the cured resin film and the image display device of the present invention are described in detail below. In addition, this invention is not limited only to embodiment shown below. For example, numerical values, types, amounts, materials, types, times, temperatures, orders, etc. may be omitted, added, replaced, or otherwise changed within the scope of the present invention.
As used herein, "(meth)acrylic acid" means at least one selected from methacrylic acid and acrylic acid. The same applies to "(meth)acrylate", "(meth)acryloyloxy" and the like.

[Photosensitive resin composition]
The photosensitive resin composition of the present embodiment includes (A) an alkali-soluble resin, (B) an alkoxysilyl group-containing resin, (C) a reactive diluent, (D) a photoradical polymerization initiator, and (E ) solvent and The photosensitive resin composition of the present embodiment may further contain (F) a silane coupling agent, if necessary. In the photosensitive resin composition of the present embodiment, when irradiated with light, (A) an alkali-soluble resin, (B) an alkoxysilyl group-containing resin, and (C) a reactive diluent are polymerized and cured to form a cured product. , to form a cured resin film.

[(A) alkali-soluble resin]
(A) The alkali-soluble resin is a structural unit (a-1) derived from an ethylenically unsaturated group-containing compound (ma-1) having an aromatic group (hereinafter also simply referred to as "structural unit (a-1)"). ) and has an acid group and a (meth)acryloyloxy group. However, a resin having an alkoxysilyl group does not correspond to (A) an alkali-soluble resin.
Since the photosensitive resin composition of the present embodiment contains (A) an alkali-soluble resin, it has good storage stability. In addition, since (A) contains an alkali-soluble resin, the photosensitive resin composition has good developability and can form a resin cured film having good water resistance and high temperature and high humidity resistance.

(A) Examples of the acid group possessed by the alkali-soluble resin include a carboxy group, a phosphoric acid group (-OP(=O)(OH) ₂ ), a sulfonic acid group (-S(=O) ₂ OH), and the like. be done. As the acid group, it is preferable to have a carboxy group from the viewpoint of alkali solubility of the photosensitive resin composition. (A) As a method for introducing an acid group into an alkali-soluble resin, for example, a method of introducing by polymerizing a raw material monomer containing a monomer having an acid group, a method of introducing an epoxy group into a precursor of (A) an alkali-soluble resin , a method of introducing by adding an acid anhydride, and the like.

(A) As a method for introducing a (meth)acryloyloxy group into an alkali-soluble resin, for example, the following method can be used. A functional group-containing resin precursor is produced by polymerizing a raw material monomer containing a monomer having a functional group. After that, a group reactive with the functional group contained in the functional group-containing resin precursor and a compound having a (meth)acryloyloxy group are reacted with the functional group-containing resin precursor. As a result, (A) an alkali-soluble resin having a (meth)acryloyloxy group is obtained.

Examples of the combination of the functional group contained in the functional group-containing resin precursor and the group reactive with the functional group include a combination of a carboxy group and an epoxy group, an isocyanato group and a hydroxy group, and the like. Specific examples of the combination of a carboxy group and an epoxy group include a combination of an unsaturated monobasic acid such as (meth)acrylic acid and an epoxy group-containing (meth)acrylate such as glycidyl (meth)acrylate. Specific examples of combinations of isocyanato groups and hydroxy groups include isocyanato group-containing monomers such as 2-(meth)acryloyloxyethyl isocyanate and hydroxy group-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate. combinations, etc.

(A) The alkali-soluble resin includes, in addition to the structural unit (a-1), a structural unit (a-2) derived from an unsaturated monobasic acid (ma-2) (hereinafter simply referred to as "structural unit (a-2 )". It is preferable that an acid group is introduced by having ). (A) the alkali-soluble resin is derived from an ethylenically unsaturated group-containing compound (ma-3) having an alicyclic hydrocarbon group in addition to the structural unit (a-1) and the structural unit (a-2) (hereinafter simply referred to as “structural unit (a-3)”). (A) the alkali-soluble resin includes, in addition to the structural units (a-1) to (a-3), the structural unit (a-4) derived from another ethylenically unsaturated group-containing compound (ma-4) ( Hereinafter, it may be simply referred to as “structural unit (a-4)”).

(A) the alkali-soluble resin is such that when the acid group of (A) the alkali-soluble resin is a carboxy group, a part of the carboxy group is an epoxy group-containing (meth)acrylate (ma-5)-derived structural unit ( It is preferably a resin modified with a-5) (hereinafter also simply referred to as “structural unit (a-5)”). That is, (A) the alkali-soluble resin is preferably a resin in which a (meth)acryloyloxy group is introduced into the side chain.

(A) The alkali-soluble resin has an ethylenically unsaturated group equivalent of 400 g/mol or more, preferably 500 g/mol or more, more preferably 550 g/mol or more, and still more preferably 590 g/mol or more. When the ethylenically unsaturated group equivalent is 400 g / mol or more, it can sufficiently react with the reactive diluent (C), resulting in a photosensitive resin composition having good developability and obtaining a cured resin film with high hardness. It becomes a photosensitive resin composition. Further, when the ethylenically unsaturated group equivalent is 400 g/mol or more, curing shrinkage in a cured resin film obtained by curing the photosensitive resin composition can be suppressed. As a result, a cured resin film having good adhesion to the substrate and/or base can be obtained.

(A) The alkali-soluble resin has an ethylenically unsaturated group equivalent of 2500 g/mol or less, preferably 2000 g/mol or less, more preferably 1500 g/mol or less, and still more preferably 1400 g/mol or less. When the ethylenically unsaturated group equivalent is 2500 g/mol or less, it is possible to ensure sufficient alkali solubility, to have sufficient developability, and to obtain a resin cured film having sufficient high temperature and high humidity resistance by curing. It becomes the photosensitive resin composition obtained.
(A) The ethylenically unsaturated group equivalent of the alkali-soluble resin is, for example, (A) the ratio of the structural unit (a-2) derived from the unsaturated monobasic acid (ma-2) in the alkali-soluble resin and / or epoxy It can be adjusted by the proportion of the structural unit (a-5) derived from the group-containing (meth)acrylate (ma-5).

"Ethylenically unsaturated bond equivalent" as used herein is the mass of the polymer per 1 mol of unsaturated bond of the polymer. (A) The ethylenically unsaturated bond equivalent of the alkali-soluble resin is obtained by dividing the mass of the (A) alkali-soluble resin by the number of moles of unsaturated bonds contained in the (A) alkali-soluble resin (g /mol). In this specification, as the "ethylenically unsaturated bond equivalent", (A) a theoretical value calculated from the charged amount of the monomers (ma-1) to (ma-5) used in producing the alkali-soluble resin is used. .

<Constituent unit (a-1)>
(A) The alkali-soluble resin contains a structural unit (a-1) derived from an ethylenically unsaturated group-containing compound (ma-1) having an aromatic group and having no acid group or epoxy group. In the present embodiment, since the alkali-soluble resin (A) contains the structural unit (a-1), it has good developability and is photosensitive to form a cured resin film with good water resistance and high temperature and high humidity resistance. It becomes a resin composition.
The structural unit (a-1) may be derived from only one ethylenically unsaturated group-containing compound (ma-1) having an aromatic group, or two or more aromatic groups. It may be derived from the ethylenically unsaturated group-containing compound (ma-1) having

Examples of the ethylenically unsaturated group-containing compound (ma-1) having an aromatic group as a starting material for the structural unit (a-1) include styrene, methoxystyrene, tert-butoxystyrene, methylstyrene, chlorostyrene, p - Styrene compounds such as nitrostyrene, p-cyanostyrene, p-acetylaminostyrene; benzyl (meth)acrylate, rosin (meth)acrylate, triphenylmethyl (meth)acrylate, phenyl (meth)acrylate, cumyl (meth)acrylate , 4-phenoxyphenyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol mono (meth)acrylate, biphenyloxyethyl (meth)acrylate, naphthalene (meth)acrylate, anthracene (meth)acrylic acid esters having an aromatic ring such as (meth)acrylate; ethylenically unsaturated monomers having a phenolic hydroxyl group such as 4-hydroxyphenyl methacrylate and N-hydroxyphenylmaleimide; and vinyltoluene.

Among these aromatic group-containing ethylenically unsaturated group-containing compounds (ma-1), styrene compounds and aromatic ring-containing (meth)acrylic acid esters are preferred from the viewpoint of raw material availability and reaction easiness. Moreover, from the viewpoint of controlling alkali developability, an ethylenically unsaturated monomer having a phenolic hydroxyl group is preferred. The ethylenically unsaturated group-containing compound (ma-1) is more preferably one or more selected from benzyl (meth) acrylate, styrene, and 4-hydroxyphenyl methacrylate, and benzyl (meth) acrylate and/or styrene. It is even more preferable to have

<Constituent unit (a-2)>
The (A) alkali-soluble resin may have an acid group introduced therein by containing a structural unit (a-2) derived from an unsaturated monobasic acid (ma-2). When the alkali-soluble resin (A) contains the structural unit (a-2), a photosensitive resin composition having better alkali solubility can be obtained.

The structural unit (a-2) may be derived from only one unsaturated monobasic acid (ma-2), or derived from two or more unsaturated monobasic acids (ma-2). It may be something to do. Examples of the unsaturated monobasic acid (ma-2) as a starting material for the structural unit (a-2) include (meth)acrylic acid, itaconic acid, crotonic acid, vinyl benzoic acid, and α-position of (meth)acrylic acid. Haloalkyl, alkoxyl, halogen, nitro, cyano substituted and the like. Among these unsaturated monobasic acids (ma-2), (meth)acrylic acid is preferred because it provides a photosensitive resin composition with good developability.

<Constituent unit (a-3)>
(A) the alkali-soluble resin has an ethylenically unsaturated group-containing compound (ma-3) having no aromatic group, acid group, or epoxy group and having an alicyclic hydrocarbon group (ma-3)-derived structural unit (a- 3). (A) When the alkali-soluble resin has the structural unit (a-3), a cured resin film having higher hardness, excellent high-temperature and high-humidity resistance, excellent resistance to heat yellowing, and good transparency can be obtained. .

The structural unit (a-3) may be derived from only one ethylenically unsaturated group-containing compound (ma-3) having an alicyclic hydrocarbon group, or may be derived from two or more It may be derived from an ethylenically unsaturated group-containing compound (ma-3) having an alicyclic hydrocarbon group. The structural unit (a-3) includes a monomer unit derived from an ester compound of alicyclic alcohol and methacrylic acid.
Alicyclic alcohols preferably have 6 to 20 carbon atoms, more preferably 6 to 18 carbon atoms. The alicyclic alcohol may be a monocyclic alicyclic alcohol or a polycyclic alicyclic alcohol, preferably a polycyclic alicyclic alcohol.

Examples of the ethylenically unsaturated group-containing compound (ma-3) having an alicyclic hydrocarbon group as a starting material for the structural unit (a-3) include cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, and methylcyclohexyl. (meth)acrylate, ethylcyclohexyl (meth)acrylate, dicyclohexyl (meth)acrylate, 1,4-cyclohexanedimethanol mono (meth)acrylate, tricyclodecanyl (meth)acrylate (dicyclopentanyl (meth)acrylate), tricyclodecanyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, rosin (meth)acrylate, norbornyl (meth)acrylate ) acrylate, 5-methylnorbornyl (meth)acrylate, 5-ethylnorbornyl (meth)acrylate and the like.

Among these ethylenically unsaturated group-containing compounds (ma-3) having an alicyclic hydrocarbon group, resins with high hardness, good high-temperature and high-humidity resistance, excellent heat resistance to yellowing, and good transparency (Meth) acrylate having an alicyclic hydrocarbon group having 6 to 20 carbon atoms is preferable, and a (meth) acrylate having a polycyclic alicyclic hydrocarbon group is preferred because the photosensitive resin composition provides a cured film. is more preferred, and tricyclodecanyl (meth)acrylate is even more preferred.

(A) As a preferred combination of structural units contained in the alkali-soluble resin, from the viewpoint of the physical properties of the cured resin film obtained by curing the photosensitive resin composition and the availability of raw materials, the structural unit (a-1) A structural unit derived from one or more selected from benzyl (meth) acrylate, styrene, and hydroxyphenyl (meth) acrylate, which are ethylenically unsaturated group-containing compounds (ma-1) having a group, and The unit (a-2) is a structural unit derived from (meth)acrylic acid, which is an unsaturated monobasic acid (ma-2), and the structural unit (a-3) has an alicyclic hydrocarbon group. Structural units derived from tricyclodecanyl (meth)acrylate, which is the ethylenically unsaturated group-containing compound (ma-3), are preferred.

<Constituent unit (a-4)>
(A) the alkali-soluble resin, if necessary, in addition to the structural units (a-1) to (a-3), structural units derived from other ethylenically unsaturated group-containing compounds (ma-4) ( a-4) may be included. The structural unit (a-4) may be derived from only one other ethylenically unsaturated group-containing compound (ma-4), or two or more other ethylenically unsaturated group-containing It may be derived from the compound (ma-4).

The other ethylenically unsaturated group-containing compound (ma-4), which is a raw material for the structural unit (a-4), does not have an aromatic group, an acid group, or an alicyclic hydrocarbon group and is ethylenically unsaturated. Any compound having a group is not particularly limited, and examples include dienes such as butadiene, isoprene, and chloroprene; methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, iso-propyl (meth)acrylate , n-butyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) (Meth) acrylic acid esters having no aromatic ring such as acrylate, perfluoro-isopropyl (meth) acrylate, 3-(N,N-dimethylamino) propyl (meth) acrylate; (meth) acrylic acid amide, (meth) ) acrylic acid N,N-dimethylamide, (meth) acrylic acid N,N-diethylamide, (meth)acrylic acid N,N-dipropylamide, (meth)acrylic acid N,N-di-isopropylamide ( meth)acrylic acid amide; (meth)acrylate anilide, (meth)acrylonitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate, vinyl such as vinyltoluene compounds; unsaturated dicarboxylic acid diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate and diethyl itaconate; monomaleimides such as N-phenylmaleimide and N-laurylmaleimide;

Among the other ethylenically unsaturated group-containing compounds (ma-4) used as raw materials for these structural units (a-4), a photosensitive resin cured film having good adhesion to the substrate and/or the undercoat can be obtained. (Meth)acrylic acid esters having no aromatic ring are preferred, and tetrahydrofurfuryl (meth)acrylate is more preferred, since the resin composition is a flexible resin composition.

<Epoxy group-containing (meth)acrylate (ma-5)>
(A) When the acid group possessed by the alkali-soluble resin is a carboxy group, (A) the alkali-soluble resin has a structural unit (a -5) may be modified to introduce a (meth)acryloyloxy group. (A) The alkali-soluble resin is preferably one in which a part of the carboxy groups derived from the unsaturated monobasic acid (ma-2) is modified with the structural unit (m-5).

(A) When the alkali-soluble resin is partially modified with the structural unit (m-5), in the step of producing the (A) alkali-soluble resin, the resin during production is treated with an epoxy group-containing (meta ) A portion of the resin is modified into the structural unit (m-5) by reacting with acrylate (ma-5). Therefore, (A) an alkali-soluble resin having an ethylenically unsaturated group equivalent in a preferred range can be easily obtained. Therefore, when a part of the alkali-soluble resin (A) is modified to the structural unit (m-5), it has good developability and can form a cured resin film having good high-temperature and high-humidity resistance. A flexible resin composition can be obtained easily.

The epoxy group-containing (meth)acrylate (ma-5) is not particularly limited as long as it is a (meth)acrylate having an epoxy group and having neither an aromatic group nor an acid group.
The structural unit (a-5) may be derived from only one epoxy group-containing (meth)acrylate (ma-5), or may be derived from two or more epoxy group-containing (meth)acrylates (ma- 5) may be derived.

Examples of the epoxy group-containing (meth)acrylate (ma-5) as a starting material for the structural unit (a-5) include glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, and alicyclic epoxy groups. (meth)acrylates and their lactone adducts, 3,4-epoxycyclohexylmethyl-3′,4′-epoxycyclohexane carboxylate, epoxidized dicyclopentenyl (meth)acrylate, and dicyclopentenyloxyethyl (meth) Examples include epoxidized acrylates.
Among these epoxy group-containing (meth)acrylates (ma-5), glycidyl (meth)acrylate and 3,4-epoxycyclohexylmethyl (meth)acrylate are preferred from the standpoint of availability of raw materials.

(A) Alkali-soluble resin comprises a structural unit (a-1) derived from an ethylenically unsaturated group-containing compound (ma-1) having an aromatic group, and a structural unit derived from an unsaturated monobasic acid (ma-2) (a-2), and a configuration (a-3) derived from an ethylenically unsaturated group-containing compound (ma-3) having an alicyclic hydrocarbon group, and if necessary, other ethylenically unsaturated Part of the carboxy groups of the resin precursor comprising a copolymer containing the structural unit (a-4) derived from the saturated group-containing compound (ma-4) is converted to the epoxy group-containing (meth)acrylate (ma-5). It is preferably a resin modified with the derived functional group (a-5). That is, (A) the alkali-soluble resin contains structural units (a-1) to (a-3) which are resin precursors, and optionally further contains a structural unit (a-4). The chain is preferably a resin modified with the structural unit (a-5).

<Proportion of each structural unit contained in (A) alkali-soluble resin>
In the present specification, "(A) all repeating structural units of the alkali-soluble resin" refers to the structural units constituting the main chain of the (A) alkali-soluble resin, and the structural units introduced into the side chains by modification. does not include

(A) The content of the structural unit (a-1) in all repeating structural units of the alkali-soluble resin is 15 mol% or more, preferably 20 mol% or more, more preferably 30 mol% or more, and still more preferably. is 35 mol % or more. When the content of the structural unit (a-1) is 15 mol% or more, the photosensitive resin composition has sufficient developability and can form a resin cured film having sufficient water resistance and high temperature and high humidity resistance. Become.

In addition, the content of the structural unit (a-1) is 60 mol% or less, preferably 50 mol% or less, more preferably 45 mol% or less. When the content of the structural unit (a-1) is 60 mol % or less, a cured resin film having sufficient transparency can be obtained. Further, when the content of the structural unit (a-1) is 60 mol % or less, the function due to inclusion of other components of the structural unit (a-1) can be sufficiently obtained. Therefore, it is possible to prevent the formation of a photosensitive resin composition that easily provides a cured resin film having poor adhesion to the substrate and/or the undercoat due to an excessive content of the structural unit (a-1).

(A) When the alkali-soluble resin contains the structural unit (a-2), the content of the structural unit (a-2) in all repeating structural units of the alkali-soluble resin (A) is the alkali of the photosensitive resin composition. From the viewpoint of solubility in a developer, it is preferably 15 mol % to 60 mol %, more preferably 20 mol % to 55 mol %, even more preferably 25 mol % to 50 mol %.

(A) When the alkali-soluble resin contains the structural unit (a-3), the content of the structural unit (a-3) in all repeating structural units of the alkali-soluble resin (A) is preferably 2 mol% to 50 mol%. , more preferably 5 mol % to 40 mol %, more preferably 9 mol % to 30 mol %. When the content of the structural unit (a-3) is 2 mol% or more, a photosensitive resin film having higher hardness, excellent high-temperature and high-humidity resistance, excellent resistance to heat yellowing, and good transparency can be obtained. It becomes a flexible resin composition. When the content of the structural unit (a-3) is 50 mol% or less, the content of other structural units of the structural unit (a-3) can be sufficiently ensured, and the balance of various performances is further improved. It becomes the removed photosensitive resin composition or a resin cured film.

(A) The acid group of the alkali-soluble resin is a carboxy group, and a part of the carboxy group is modified with an epoxy group-containing (meth)acrylate (ma-5) to be converted into the structural unit (a-5). is, the modification amount of the carboxy group converted to the structural unit (a-5) is preferably 15 mol% to 90 mol%, more preferably 20 mol% to 80 mol%, and 30 mol% to More preferably, it is 70 mol %. The modified amount of the carboxy group converted to the structural unit (a-5) is the structural unit (a-5) relative to the sum of the number of structural units (a-5) and the number of carboxy groups of the alkali-soluble resin (A). means a percentage of numbers.

When the modification amount of the carboxy group converted to the structural unit (a-5) is 15 mol% or more, a sufficient amount of (meth)acryloyloxy group is introduced into (A) the alkali-soluble resin, and (C) the reaction It is possible to obtain a cured resin film which can sufficiently react with a polar diluent, has good developability, and has sufficient hardness and adhesion to a base material and/or an undercoat.
When the modified amount of carboxy groups is 90 mol % or less, a sufficient amount of carboxy groups remains in (A) the alkali-soluble resin. Therefore, the photosensitive resin composition can ensure sufficient alkali solubility, has good developability, and can provide a cured resin film having sufficient resistance to high temperature and high humidity.
When the modified amount of the carboxy group is 15 mol % to 90 mol %, the photosensitive resin composition in which the ethylenically unsaturated group equivalent of (A) the alkali-soluble resin is in the range of 400 g/mol to 2500 g/mol is likely to be obtained.

<(A) Acid value of alkali-soluble resin>
(A) The acid value of the alkali-soluble resin is preferably 20KOHmg/g to 200KOHmg/g, more preferably 25KOHmg/g to 180KOHmg/g, and further preferably 30KOHmg/g to 150KOHmg/g. preferable. When the acid value is 20 KOHmg/g or more, the photosensitive resin composition has excellent solubility in an alkaline developer and good developability. When the acid value is 200 KOH mg/g or less, the decomposition of the (B) alkoxysilyl group-containing resin due to the too high acid value of the (A) alkali-soluble resin can be suppressed, and the photosensitive resin has good storage stability. It becomes a composition. The acid value can be arbitrarily selected within the above range, and may be, for example, 40 mg KOH/g to 130 mg KOH/g or 60 mg KOH/g to 100 mg KOH/g.

(A) The acid value of the alkali-soluble resin can be adjusted, for example, by adjusting the amount of the unsaturated monobasic acid (ma-2) used as the starting material for the structural unit (a-2). ) can be adjusted by adjusting the content. (A) When a portion of the alkali-soluble resin is modified to the structural unit (m-5), (A) in the step of producing the alkali-soluble resin, a carboxy group derived from an unsaturated monobasic acid (ma-2) is modified into structural units (m-5) derived from epoxy group-containing (meth)acrylate (ma-5), and the acid value of (A) the alkali-soluble resin may be insufficient. In this case, a carboxyl group may be introduced into (A) the alkali-soluble resin partially modified with the structural unit (m-5) to compensate for the insufficient acid value. Specifically, an acid anhydride is added to a hydroxy group generated by ring-opening of the epoxy group contained in (A) the alkali-soluble resin partially modified with the structural unit (m-5). and other methods can be used.

The acid value of (A) the alkali-soluble resin in this embodiment is a value measured using a mixed indicator of bromothymol blue and phenol red according to JIS K6901 5.3. (A) The acid value of the alkali-soluble resin means the number of mg of potassium hydroxide required to neutralize the acidic component contained in 1 g of the sample comprising the (A) alkali-soluble resin.

<(A) Weight average molecular weight (Mw) of alkali-soluble resin>
(A) the alkali-soluble resin preferably has a polystyrene equivalent weight average molecular weight (Mw) of 1,000 to 50,000, more preferably 5,000 to 45,000, and 8,000 to 42 ,000 is more preferred. (A) When the weight average molecular weight (Mw) of the alkali-soluble resin is 1,000 or more, the cured resin film obtained by curing the photosensitive resin composition has sufficiently small curing shrinkage, The adhesiveness with is good. (A) When the weight average molecular weight (Mw) of the alkali-soluble resin is 50,000 or less, the photosensitive resin composition has good developability.

The weight average molecular weight (Mw) of (A) the alkali-soluble resin in the present embodiment is measured using gel permeation chromatography (GPC) under the following conditions and calculated in terms of polystyrene. .
Column: Shodex (registered trademark) LF-804 + LF-804 (manufactured by Showa Denko Co., Ltd.)
Column temperature: 40°C
Sample: (A) Tetrahydrofuran solution containing 0.2% by mass of sample made of alkali-soluble resin Developing solvent: Tetrahydrofuran Detector: Differential refractometer (trade name: Shodex (registered trademark) RI-71S, Showa Denko Co., Ltd.)
Flow rate: 1 mL/min

<(A) Method for producing alkali-soluble resin>
(A) As a method for producing the alkali-soluble resin, a conventionally known method can be used. For example, (A) an alkali-soluble resin is a structural unit (a-1) derived from an ethylenically unsaturated group-containing compound (ma-1) having an aromatic group, and an unsaturated monobasic acid (ma-2) derived from Containing a structural unit (a-2) and a structure (a-3) derived from an ethylenically unsaturated group-containing compound (ma-3) having an alicyclic hydrocarbon group, and optionally other ethylene Part of the carboxy groups of the resin precursor comprising a copolymer containing a structural unit (a-4) derived from a polyunsaturated group-containing compound (ma-4) is an epoxy group-containing (meth)acrylate (ma-5 ) derived from the structural unit (a-5), it can be produced by the following method.

An ethylenically unsaturated group-containing compound (ma-1) having an aromatic group, an unsaturated monobasic acid (ma-2), and an ethylenically unsaturated group-containing compound (ma-3) having an alicyclic hydrocarbon group ) and optionally containing other ethylenically unsaturated group-containing compound (a-4) are placed in a solvent together with a polymerization initiator, and heated to 1 to 20 at 50 to 130 ° C. Allow time to copolymerize. As a result, a reaction liquid containing a resin precursor composed of a copolymer containing the structural units (a-1) to (a-3) and optionally the structural unit (a-4) is produced.

Examples of polymerization initiators include t-butyl peroxy-2-ethylhexanoate, azobisisobutyronitrile, azobisisovaleronitrile, 2,2'-azobis(methyl isobutyrate), benzoyl peroxide, and the like. can be used. These polymerization initiators can be used alone or in combination of two or more.
The amount of the polymerization initiator used is generally 0.5 to 20 parts by mass, preferably 1.0 to 10 parts by mass, per 100 parts by mass of the raw material monomers.

The solvent is not particularly limited as long as it is inert in the polymerization reaction of the raw material monomers. Examples of solvents include alkyl alcohols such as propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, and dodecyl alcohol; benzyl alcohol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol (poly)alkylene glycol monoalkyl ethers such as monoethyl ether and 3-methoxy-1-butanol;
(poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate;
other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;
methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, Ethyl ethoxyacetate, Ethyl hydroxyacetate, Methyl 2-hydroxy-3-methylbutyrate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl Propionate, ethyl acetate, n-butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl acetate, i-amyl acetate, n-butyl propionate, ethyl butyrate , n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, esters such as ethyl 2-oxobutyrate;
aromatic hydrocarbons such as toluene and xylene;
Examples thereof include carboxylic acid amides such as N-methylpyrrolidone, N,N-dimethylformamide and N,N-dimethylacetamide.

Among these solvents, glycol ether solvents are preferable, and (poly)alkylene glycol monoalkyl ethers such as propylene glycol monomethyl ether and (poly)alkylene glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate are particularly preferred. preferable. These solvents can be used alone or in combination of two or more.

Thereafter, an epoxy group-containing (meth)acrylate (ma-5) and, if necessary, a catalyst and/or a polymerization inhibitor are added to the reaction solution and reacted. As a result, the epoxy group in the epoxy group-containing (meth)acrylate (ma-5) undergoes a ring-opening addition reaction with some of the carboxy groups in the structural unit (a-2) contained in the resin precursor. As a result, part of the side chain of the copolymer, which is the resin precursor, was modified to the structural unit (m-5) derived from the epoxy group-containing (meth)acrylate (ma-5) (A) alkali-soluble resin is obtained.
In the present embodiment, all of the epoxy group-containing (meth)acrylate (ma-5) used in the reaction reacts with the carboxy group in the structural unit (a-2) contained in the resin precursor, and the structural unit (a -5) can be regarded as denatured.

Examples of catalysts include triphenylphosphine, tri(o-tolyl)phosphine, tri(m-tolyl)phosphine, tri(p-tolyl)phosphine, tris(p-methoxyphenyl)phosphine, tris(2,6-dimethoxy phenyl)phosphine, p-styryldiphenylphosphine, and the like can be used.
Examples of polymerization inhibitors that can be used include methylhydroquinone, butylhydroxytoluene, hydroquinone, methoquinone, and methylhydroquinone.

[(B) Alkoxysilyl group-containing resin]
(B) the alkoxysilyl group-containing resin is a structural unit (b-1) derived from an ethylenically unsaturated group-containing compound (mb-1) having an alkoxysilyl group (hereinafter simply referred to as "structural unit (b-1)" Say.) including.
(B) The alkoxysilyl group-containing resin is, if necessary, a structural unit (b-2) derived from unsaturated monobasic acid (mb-2) (hereinafter simply referred to as "structural unit (b-2)"). ) and/or other ethylenically unsaturated group-containing compound (mb-3)-derived structural units (b-3) (hereinafter also simply referred to as “structural units (b-3)”). .
Since the photosensitive resin composition of the present embodiment contains (B) the alkoxysilyl group-containing resin, it becomes a photosensitive resin composition that can form a resin cured film having high hardness and good resistance to high temperature and high humidity.

<Constituent unit (b-1)>
The structural unit (b-1) may be derived from only one ethylenically unsaturated group-containing compound (mb-1) having an alkoxysilyl group, or may be derived from two or more alkoxysilyl groups. It may be derived from the ethylenically unsaturated group-containing compound (mb-1) having

The ethylenically unsaturated group-containing compound (mb-1) having an alkoxysilyl group, which is a raw material for the structural unit (b-1), may be a monomer having an alkoxysilyl group and an ethylenically unsaturated group, and is particularly limited. not. The alkoxy group of the alkoxysilyl group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, even more preferably 1 to 2 carbon atoms. The number of alkoxy groups in the alkoxysilyl group may be one or plural. When the alkoxysilyl group is a trialkoxysilyl group having three alkoxy groups, the (B) alkoxysilyl group-containing resin having many cross-linking points of the structural unit (b-1) is obtained, so that photosensitivity with better curability is obtained. It becomes a flexible resin composition, which is preferable.

The ethylenically unsaturated group-containing compound (mb-1) having an alkoxysilyl group has good reaction easiness when synthesizing the alkoxysilyl group-containing resin (B), and is easily available. (Meth)acrylate is preferable, and the structural unit (b-1) is more preferably a structural unit represented by the following formula (1).

[In formula (1), R ¹ represents a hydrogen atom or a methyl group. Each of R ² to R ⁴ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. At least one of R ² to R ⁴ is an alkoxy group having 1 to 6 carbon atoms. n is an integer of 1-10. ]

In formula (1), R ¹ represents a hydrogen atom or a methyl group, preferably a methyl group.
In formula (1), R ² to R ⁴ each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. At least one of R ² to R ⁴ is an alkoxy group having 1 to 6 carbon atoms.
When R ² to R ⁴ are alkyl groups having 1 to 6 carbon atoms, the number of carbon atoms is preferably 1 to 4, more preferably 1 to 2. When R ² to R ⁴ are alkoxy groups having 1 to 6 carbon atoms, the number of carbon atoms is preferably 1 to 4, more preferably 1 to 2.

In formula (1), each of R ² to R ⁴ is preferably an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, and two of R ² to R ⁴ Or it is more preferable that three of them are alkoxy groups having 1 to 6 carbon atoms, resulting in (B) an alkoxysilyl group-containing resin with many cross-linking points of the structural unit (b-1), and a photosensitive resin with better curability. More preferably, all three of R ² to R ⁴ are alkoxy groups having 1 to 6 carbon atoms in order to obtain a composition.
As a specific example, in formula (1), R ² to R ⁴ are each independently preferably a methyl group, an ethyl group, a methoxy group, or an ethoxy group, and at least one of R ² to R ⁴ is A methoxy group or an ethoxy group is more preferred.
In formula (1), n is an integer of 1-10, preferably 1-4.

Specific examples of the structural unit represented by the above formula (1) include, for example,
3-(meth)acryloyloxypropylmethyldimethoxysilane (in formula (1), R ¹ : hydrogen atom (or methyl group); R ² : methyl group; R ³ , R ⁴ : methoxy group; n: 3),
3-(meth)acryloyloxypropylethyldimethoxysilane (in formula (1), R ¹ : hydrogen atom (or methyl group); R ² : ethyl group; R ³ , R ⁴ : methoxy group; n: 3),
3-(meth)acryloyloxypropylmethyldiethoxysilane (in formula (1), R ¹ : hydrogen atom (or methyl group); R ² : methyl group; R ³ , R ⁴ : ethoxy group; n: 3),
3-(meth)acryloyloxypropylethyldiethoxysilane (in formula (1), R ¹ : hydrogen atom (or methyl group); R ² : ethyl group; R ³ , R ⁴ : ethoxy group; n: 3),
3-(meth)acryloyloxypropyltrimethoxysilane (in formula (1), R ¹ : hydrogen atom (or methyl group); R ² to R ⁴ : methoxy group; n: 3),
3-(meth)acryloyloxypropyltriethoxysilane (in formula (1), R ¹ : hydrogen atom (or methyl group); R ² to R ⁴ : ethoxy group; n: 3)
Structural units derived from compounds such as

Among the structural units represented by these formulas (1), 3-(meth)acryloyloxypropyl Structural units derived from methyldiethoxysilane and/or structural units derived from 3-(meth)acryloyloxypropyltriethoxysilane are preferred.

As the ethylenically unsaturated group-containing compound (mb-1) having an alkoxysilyl group, a commercially available one may be used. For example, the following compounds manufactured by Shin-Etsu Chemical Co., Ltd. (the description in parentheses is the trade name) 3-methacryloyloxypropylmethyldiethoxysilane (KBE-502), 3-methacryloyloxypropyltriethoxysilane (KBE- 503), 3-methacryloyloxypropylmethyldimethoxysilane (KBM-502), 3-methacryloyloxypropyltrimethoxysilane (KBM-503), methacryloxyoctyltrimethoxysilane (KBM-5803), 3-acryloxypropyltrimethoxy Examples include silane (KBM-5103).

<Constituent unit (b-2)>
The structural unit (b-2) may be derived from only one unsaturated monobasic acid (mb-2), or derived from two or more unsaturated monobasic acids (mb-2). It may be something to do. The unsaturated monobasic acid (mb-2), which is the starting material for the structural unit (b-2), is preferably a silicon-free compound having an acid group and an ethylenically unsaturated group. The acid group of the unsaturated monobasic acid (mb-2) is not particularly limited, but a carboxy group, a phosphoric acid group (-OP(=O)(OH) ₂ ), a sulfonic acid group (-S(= O) ₂ OH) and the like are preferred. Among these acid groups, a carboxy group is more preferable because it results in a photosensitive resin composition having good developability.

Examples of the unsaturated monobasic acid (mb-2) as a starting material for the structural unit (b-2) include (meth)acrylic acid, crotonic acid, cinnamic acid, vinylsulfonic acid, and 2-(meth)acryloyloxyethyl. succinic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl acid phosphate and the like. Among these unsaturated monobasic acids (mb-2), (meth)acrylic acid is preferred because of its favorable reaction easiness in synthesizing the (B) alkoxysilyl group-containing resin and its easy availability.

<Constituent unit (b-3)>
The structural unit (b-3) is neither an ethylenically unsaturated group-containing compound (mb-1) having an alkoxysilyl group nor an unsaturated monobasic acid (mb-2), other ethylenic It may be derived only from the unsaturated group-containing compound (mb-3), or may be derived from two or more ethylenically unsaturated group-containing compounds (mb-3).

As the other ethylenically unsaturated group-containing compound (mb-3) that is a raw material for the structural unit (b-3), an ethylenically unsaturated group-containing compound that does not have an acid group and an alkoxysilyl group can be used. , for example, dienes such as butadiene, (meth)acrylic acid esters, (meth)acrylic acid amides, vinyl compounds, styrenes, unsaturated dicarboxylic acid diesters, unsaturated polybasic acid anhydrides, and the like.

Specific examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, sec- Butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, neopentyl (meth)acrylate, benzyl (meth)acrylate, isoamyl (meth)acrylate, hexyl (meth)acrylate , 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, dodecyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, methylcyclohexyl (meth)acrylate, ethylcyclohexyl (meth)acrylate ) acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, rosin (meth) acrylate, norbornyl (meth) acrylate, 5-methylnorbornyl (meth) acrylate, 5-ethylnorbornyl (meth) acrylate, allyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro- Isopropyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3-(N,N-dimethylamino) propyl (meth) acrylate, glycerol mono (meth) acrylate, butanetriol mono (meth) acrylate , pentanetriol mono (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, naphthalene (meth) acrylate, anthracene (meth) acrylate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, glycidyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, 2 - isocyanatoethyl (meth) acrylate, 2-isocyanatopropyl (meth) acrylate, 3-iso Cyanatopropyl (meth) acrylate, 2-isocyanato-1-methylethyl (meth) acrylate, 2-isocyanato-1,1-dimethylethyl (meth) acrylate, 4-isocyanatocyclohexyl (meth) acrylate, the above isocyanato groups A compound having a blocked isocyanato group obtained by blocking the isocyanato group of the ethylenically unsaturated compound with a blocking agent, N,N-dimethylaminoethyl (meth) acrylate, N,N-diethylaminoethyl (meth) acrylate , N-tert-butylaminoethyl (meth)acrylate, tetramethylpiperidyl (meth)acrylate, hexamethylpiperidyl (meth)acrylate and the like.

Specific examples of (meth)acrylic acid amides include (meth)acrylic acid amide, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic acid N,N-diethylamide, (meth)acrylic acid N, N-dipropylamide, (meth)acrylic acid N,N-di-isopropylamide, (meth)acrylic acid anthracenylamide, N-isopropyl (meth)acrylamide, (meth)acrylic morpholine, diacetone (meth) acrylamide and the like.

Specific examples of vinyl compounds include norbornene (bicyclo[2.2.1]hept-2-ene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2 .1]hept-2-ene, tetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-methyltetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, 8-ethyltetracyclo[4.4.0.1 ^2,5 . 1 ^7,10 ]dodeca-3-ene, dicyclopentadiene, tricyclo[5.2.1.0 ^2,6 ]dec-8-ene, tricyclo[5.2.1.0 ^2,6 ]dec-3 -ene, tricyclo[4.4.0.1 ^2,5 ]undec-3-ene, tricyclo[6.2.1.0 ^1,8 ]undec-9-ene, tricyclo[6.2.1.0 ^1,8 ]undec-4-ene, tetracyclo[4.4.0.1 ^2,5 . 1 ^{7, 10} . 0 ^1,6 ]dodeca-3-ene, 8-methyltetracyclo[4.4.0.1 ^2,5 . 1 ^{7, 10} . 0 ^1,6 ]dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.1 ^2,5 . 1 ^7,12 ]dodeca-3-ene, 8-ethylidenetetracyclo[4.4.0.1 ^2,5 . 1 ^{7, 10} . 0 ^1,6 ]dodeca-3-ene, pentacyclo[6.5.1.1 ^3,6 . 0 ^{2, 7} . 0 ^9,13 ]pentadeca-4-ene, pentacyclo[7.4.0.1 ^2,5 . ^{19, 12} . 0 ^8,13 ]pentadeca-3-ene, 5-norbornene-2,3-dicarboxylic anhydride, (meth)acrylic anilide, (meth)acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, fluorine vinylidene chloride, vinylpyridine, vinyl acetate, vinyltoluene, norbornene and the like.

Specific examples of styrene derivatives include styrene, α-, o-, m-, and p-alkyl, nitro, cyano, and amide derivatives of styrene.
Specific examples of unsaturated dicarboxylic acid diesters include diethyl citraconate, diethyl maleate, diethyl fumarate, and diethyl itaconate.
Specific examples of unsaturated polybasic acid anhydrides include maleic anhydride, itaconic anhydride, and citraconic anhydride.

Among these other ethylenically unsaturated group-containing compounds (mb-3), the reaction easiness in synthesizing the (B) alkoxysilyl group-containing resin is good and is easily available, so methyl (meth) Acrylate, 2-ethylhexyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentanyl (meth)acrylate, glycidyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, N, N - diethylaminoethyl (meth)acrylate, (meth)acrylic acid N,N-dimethylamide, (meth)acrylic morpholine, styrene, vinyltoluene and norbornene are preferred, methyl (meth)acrylate, benzyl (meth)acrylate, dicyclo More preferred are pentanyl (meth)acrylate, glycidyl (meth)acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate, styrene and vinyltoluene.

In addition, as the other ethylenically unsaturated group-containing compound (mb-3), it is excellent in heat decomposition resistance and heat yellowing resistance, and it becomes a photosensitive resin composition that can obtain a cured resin film with good high temperature and high humidity resistance. , alkyl (meth)acrylates are preferred, and methyl (meth)acrylate, benzyl (meth)acrylate and dicyclopentanyl (meth)acrylate are preferred.

Further, the other ethylenically unsaturated group-containing compound (mb-3) has a functional group that reacts with an acid group from the viewpoint of forming a photosensitive resin composition capable of obtaining a cured resin film having good solvent resistance. It is preferred to use a polymerizable compound. Functional groups that react with acid groups include glycidyl groups, oxetanyl groups, isocyanato groups, or blocked isocyanato groups. Specific examples of the polymerizable compound having a functional group that reacts with an acid group include glycidyl (meta- ) acrylate, (3-ethyloxetan-3-yl)methyl (meth)acrylate and the like are preferably used.

Blocking when the other ethylenically unsaturated group-containing compound (mb-3) is a compound having a blocked isocyanato group obtained by blocking the isocyanato group of the ethylenically unsaturated compound having an isocyanato group using a blocking agent Examples of agents include lactams such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam; methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol , benzyl alcohol, phenyl cellosolve, furfuryl alcohol, alcohols such as cyclohexanol; Phenols such as nonylphenol, styrenated phenol, oxybenzoate, thymol, p-naphthol, p-nitrophenol, p-chlorophenol; dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone active methylene; mercaptans such as butyl mercaptan, thiophenol and tert-dodecylmercaptan; amines such as diphenylamine, phenylnaphthylamine, aniline and carbazole; acid amides such as acetanilide, acetanisidide, acetic amide and benzamide; Acid imides such as maleic acid imide; imidazoles such as imidazole, 2-methylimidazole and 2-ethylimidazole; urea systems such as urea, thiourea and ethylene urea; carbamides such as phenyl N-phenylcarbamate and 2-oxazolidone acid salts; imine-based compounds such as ethyleneimine and polyethyleneimine; A sulfite system etc. are mentioned.

<Ratio of Each Structural Unit Contained in (B) Alkoxysilyl Group-Containing Resin>
(B) The content of the structural unit (b-1) in all repeating structural units of the alkoxysilyl group-containing resin is preferably 45 mol% or more, more preferably 50 mol% or more, and 55 mol% or more. It is even more preferable to have When the content of the structural unit (b-1) is 45 mol % or more, the photosensitive resin composition can provide a cured resin film having even higher hardness and excellent resistance to high temperature and high humidity.
The upper limit of the content of the structural unit (b-1) is not particularly limited, but may be 99 mol% or less, 90 mol% or less, or 85 mol% or less. The content of the structural unit (b-1) can be arbitrarily selected within the above range. % or more and 75 mol % or less.

(B) When the alkoxysilyl group-containing resin contains the structural unit (b-2), the content thereof is From the viewpoint of solubility and storage stability, the content is preferably 1 mol % to 40 mol %, more preferably 10 mol % to 30 mol %, even more preferably 15 mol % to 25 mol %.

When the alkoxysilyl group-containing resin (B) contains the structural unit (b-3), the content thereof is preferably 1 mol% to 40 mol% of all repeating structural units of the alkoxysilyl group-containing resin (B). , more preferably 5 mol % to 30 mol %, even more preferably 10 mol % to 25 mol %.

<(B) Acid value of alkoxysilyl group-containing resin>
(B) The acid value of the alkoxysilyl group-containing resin is preferably 150 mg KOH/g or less, more preferably 100 mg KOH/g or less, and even more preferably 70 mg KOH/g or less. When the acid value is 150 KOHmg/g or less, the photosensitive resin composition has excellent storage stability, excellent solubility in an alkaline developer, and good developability. (B) The lower limit of the acid value of the alkoxysilyl group-containing resin is not particularly limited, but may be, for example, 1 mg KOH/g or more, 5 mg KOH/g or more, or 10 mg KOH/g or more. Also good. When the acid value of the alkoxysilyl group-containing resin (B) is 1 KOHmg/g or more, alkali developability can be imparted to the alkoxysilyl group-containing resin (B). (B) The acid value of the alkoxysilyl group-containing resin can be adjusted, for example, by adjusting the amount of the unsaturated monobasic acid (mb-2) used as the starting material for the structural unit (b-2). -2) can be adjusted by adjusting the content.
The acid value of the (B) alkoxysilyl group-containing resin is measured in the same manner as the acid value of the (A) alkali-soluble resin.

<(B) Weight Average Molecular Weight (Mw) of Alkoxysilyl Group-Containing Resin>
(B) The alkoxysilyl group-containing resin preferably has a polystyrene equivalent weight average molecular weight (Mw) of 1,000 to 20,000, more preferably 1,500 to 10,000, and 3,000. ~6,000 is more preferred. (B) When the weight average molecular weight (Mw) of the alkoxysilyl group-containing resin is 1,000 or more, the photosensitive resin composition has good developability. When the weight-average molecular weight (Mw) of (B) the alkoxysilyl group-containing resin is 20,000 or less, the photosensitive resin composition has an appropriate development time.
The weight average molecular weight (Mw) of the (B) alkoxysilyl group-containing resin is calculated in the same manner as the weight average molecular weight (Mw) of the (A) alkali-soluble resin.

<(B) Silyl Group Equivalent of Alkoxysilyl Group-Containing Resin>
The silyl group equivalent weight of (B) the alkoxysilyl group-containing resin is not particularly limited, but is preferably 100 g/mol to 700 g/mol, preferably 150 g/mol to 500 g/mol, most preferably 290 g/mol to 450 g/mol. When the silyl group equivalent of (B) the alkoxysilyl group-containing resin is 100 g/mol or more, the resulting photosensitive resin composition has high hardness and excellent developability. On the other hand, when the silyl group equivalent weight of the alkoxysilyl group-containing resin (B) is 700 g/mol or less, a photosensitized resin film having sufficient hardness and good adhesion to the base material and/or base can be obtained. It becomes a flexible resin composition.

The silyl group equivalent of (B) alkoxysilyl group-containing resin is a value obtained by dividing the molecular weight of (B) alkoxysilyl group-containing resin by the average number of silyl groups per molecule of (B) alkoxysilyl group-containing resin. (B) The average number of silyl groups per molecule of the alkoxysilyl group-containing resin contains an ethylenically unsaturated group having an alkoxysilyl group serving as a raw material for the structural unit (b-1) of the (B) alkoxysilyl group-containing resin. It is a calculated value calculated based on the charged amount of compound (mb-1).

<Contents of (A) alkali-soluble resin and (B) alkoxysilyl group-containing resin>
The mass ratio of (A) alkali-soluble resin to (B) alkoxysilyl group-containing resin ((A) alkali-soluble resin: (B) alkoxysilyl group-containing resin) contained in the photosensitive resin composition of the present embodiment is It is preferably 40:60 to 99:1, more preferably 50:50 to 99:1, even more preferably 60:40 to 90:10, and 60:40 to 80:20. is particularly preferred. The ratio can be selected as necessary within the above range, and may be, for example, 55:45 to 85:15 or 65:35 to 75:25. When the mass ratio of (A) the alkali-soluble resin and (B) the alkoxysilyl group-containing resin is within the above range, the function due to the inclusion of the (B) alkoxysilyl group-containing resin can be sufficiently obtained. It becomes a photosensitive resin composition that can form a cured resin film having high hardness and good resistance to high temperature and high humidity. In addition, when the mass ratio of (A) the alkali-soluble resin and (B) the alkoxysilyl group-containing resin is within the above range, the function due to the inclusion of (A) the alkali-soluble resin can be sufficiently obtained. The photosensitive resin composition has good storage stability, excellent developability, and can form a resin cured film having good water resistance and high temperature and high humidity resistance.

<(B) Method for producing alkoxysilyl group-containing resin>
(B) A conventionally known method can be used as a method for producing the alkoxysilyl group-containing resin. Specifically, for example, an ethylenically unsaturated group-containing compound (mb-1) having an alkoxysilyl group, and optionally added other unsaturated monobasic acid (mb-2) and ethylenically unsaturated The group-containing compound (mb-3) is put into a solvent together with a polymerization initiator and subjected to a copolymerization reaction to form a reaction liquid containing the copolymer (B) alkoxysilyl group-containing resin.

Examples of polymerization initiators include 2,2′-azobis(isobutyrate)dimethyl, t-butylperoxy-2-ethylhexanoate, azobisisobutyronitrile, azobisisovaleronitrile, benzoyl peroxide, etc. can be used.
As the solvent, those mentioned as the solvent that can be used in (A) the method for producing an alkali-soluble resin can be used in the same manner. Among them, from the viewpoint of availability and storage stability as a photosensitive resin composition, a primary alcohol or secondary alcohol solvent is preferable, and 3-methoxy-1-butanol, propylene glycol monomethyl Ethers are more preferred.

[(C) reactive diluent]
(C) As the reactive diluent, a low molecular weight compound having an ethylenically unsaturated group such as a vinyl group, an allyl group and a (meth)acryloyloxy group can be used. (C) Reactive diluents may be used singly or in combination of two or more. (C) Reactive diluents include, for example, aromatic vinyl monomers; polycarboxylic acid monomers such as vinyl acetate and vinyl adipate; (meth)acrylates; polyfunctional (meth)acrylates; nurate and the like. Among these (C) reactive diluents, polyfunctional (meth)acrylates are used because the photosensitive resin composition has good developability and provides a cured resin film having sufficient hardness. is particularly preferred.

Specific examples of aromatic vinyl monomers include styrene, α-methylstyrene, α-chloromethylstyrene, vinyltoluene, divinylbenzene, diallyl phthalate, diallylbenzene phosphonate and the like.
Specific examples of (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, β-hydroxyethyl (meth)acrylate, and hydroxypropyl (meth)acrylate. etc.

Specific examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate. ) acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tris(hydroxyethyl)isocyanurate tri(meth)acrylate, and the like.

<(C) Content of reactive diluent>
The content of the (C) reactive diluent contained in the photosensitive resin composition of the present embodiment includes (A) the alkali-soluble resin contained in the photosensitive resin composition, (B) the alkoxysilyl group-containing resin, (C) with respect to 100 parts by mass in total with the reactive diluent, preferably 5 parts by mass to 75 parts by mass, more preferably 15 parts by mass to 65 parts by mass, most preferably 20 parts by mass to 55 parts by mass part by mass. (C) When the content of the reactive diluent is within the above range, the viscosity and photocurability of the photosensitive resin composition become more appropriate.

[(D) Photoradical polymerization initiator]
(D) The radical photopolymerization initiator is not particularly limited as long as it is a compound that generates radicals upon irradiation with light. (D) Photoradical polymerization initiators may be used alone or in combination of two or more.

(D) Photoradical polymerization initiators include, for example, benzoin and alkyl ethers thereof such as benzoin, benzoin methyl ether, benzoin ethyl ether; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone , 4-(1-t-butyldioxy-1-methylethyl)acetophenone and other acetophenones; 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one and other alkylphenones; Anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone and 1-chloroanthraquinone; Thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Acetophenone Ketals such as dimethyl ketal and benzyl dimethyl ketal; benzophenone, 4-(1-t-butyldioxy-1-methylethyl)benzophenone, 3,3′,4,4′-tetrakis(t-butyldioxycarbonyl)benzophenone, etc. benzophenones; 1,2-octanedione, 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, 1-[4-(phenylthio)-2-(o-benzoyloxime )], ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(o-acetyloxime) and other oxime esters; 2-methyl-1- [4-(methylthio)phenyl]-2-morpholino-propan-1-one; 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1; 2,4,6-trimethylbenzoyldiphenylphosphine oxides, acylphosphine oxides such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide; and xanthones.

<(D) Content of radical photopolymerization initiator>
The content of the (D) photoradical polymerization initiator contained in the photosensitive resin composition of the present embodiment is the (A) alkali-soluble resin contained in the photosensitive resin composition and the (B) alkoxysilyl group-containing resin. , (C) with respect to 100 parts by mass in total with the reactive diluent, preferably 0.1 parts by mass to 20 parts by mass, more preferably 1 part by mass to 15 parts by mass, most preferably 3 parts by mass parts to 10 parts by mass. (D) When the content of the radical photopolymerization initiator is 0.1 parts by mass or more, the photosensitive resin composition has sufficient photocurability. When the content of the (D) photoradical polymerization initiator is 20 parts by mass or less, the (D) photoradical polymerization initiator provides the storage stability of the photosensitive resin composition and the performance of the cured resin film obtained by curing the composition. have no adverse effect on

[(E) solvent]
(E) The solvent is not particularly limited as long as it is inert to each component contained in the photosensitive resin composition of the present embodiment and can dissolve each component. (E) A solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

The (E) solvent may contain the same solvent as the solvent used in the preparation of (A) the alkali-soluble resin and/or (B) the alkoxysilyl group-containing resin, or may be a different solvent alone. For example, the (E ) may be used as part or all of the solvent. Further, when mixing each component of the photosensitive resin composition, the same solvent or a different solvent as the solvent used for preparing (A) the alkali-soluble resin and/or (B) the alkoxysilyl group-containing resin is newly added. may be added. (A) Alkali-soluble resin and / or (B) The solvent used in the preparation of the alkoxysilyl group-containing resin is partially or entirely removed, and when mixing the components of the photosensitive resin composition, a new (A ) the alkali-soluble resin and/or (B) the solvent used in the preparation of the alkoxysilyl group-containing resin, or a different solvent may be added.

(E) The solvent is one or more selected from primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms, so that the photosensitive resin composition has good storage stability. of alcohol. Examples of primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms include alkyl alcohols, benzyl alcohol, (poly)alkylene glycol monoalkyl ethers, and the like. (Poly)alkylene glycol monoalkyl ethers are preferably used because they are readily available and provide a photosensitive resin composition with good storage stability.

(E) The solvent is not one or more alcohols selected from primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms. may be used instead of the above alcohol. Only one type of other solvent may be used, or two or more types may be used.

Among the solvents used in the preparation of the above-mentioned (A) alkali-soluble resin and/or (B) alkoxysilyl group-containing resin, (poly)alkylene glycol monoalkyl ether acetate-based solvents such as propylene glycol monomethyl ether acetate, It is preferable because the solubility of each component contained in the photosensitive resin composition is good. In addition, the (poly)alkylene glycol monoalkyl ether acetate-based solvent is mixed with one or more alcohols selected from primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms. The compatibility when used is also good, which is preferable.

(E) The total content of one or more alcohols selected from primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms contained in the solvent is 15 to It is preferably 100% by mass. The content of the alcohol is more preferably 25% by mass or more, still more preferably 35% by mass or more, in order to obtain a photosensitive composition with better storage stability. The upper limit of the alcohol content is not particularly limited, but may be 90% by mass or 80% by mass.

<(E) Content of solvent>
The content of the (E) solvent contained in the photosensitive resin composition of the present embodiment is preferably 30 parts by mass to 100 parts by mass in total of the components excluding the (E) solvent in the photosensitive resin composition. 1000 parts by mass, more preferably 50 to 800 parts by mass, most preferably 100 to 500 parts by mass. (E) When the content of the solvent is within the above range, the viscosity of the photosensitive resin composition can be adjusted to an appropriate range.

The viscosity of the photosensitive resin composition of the present embodiment can be appropriately adjusted according to the desired thickness of the cured resin film. For example, when the thickness of the cured resin film is adjusted to 1 μm to 4 μm, the viscosity of the photosensitive resin composition is preferably 4 mP s to 25 mP s, more preferably 6 mP s to 20 mP s. More preferably, it is 8 mP·s to 15 mP·s.

In this specification, the viscosity of the photosensitive resin composition is measured using an E-type viscometer (RE-80, manufactured by Toki Sangyo, rotor type: standard cone 1°34′×R24, rotor code: 1). It means the value measured at 25°C.

[(F) Silane coupling agent]
(F) A silane coupling agent can be contained in the photosensitive resin composition of the present embodiment, if necessary. (F) The silane coupling agent improves compatibility among (A) the alkali-soluble resin, (B) the alkoxysilyl group-containing resin, and (C) the reactive diluent contained in the photosensitive resin composition.
(F) As the silane coupling agent, it is preferable to use a low molecular weight compound having one or more functional groups selected from (meth)acrylic groups, vinyl groups and styryl groups. (F) The silane coupling agent may be used alone or in combination of two or more.

(F) As the silane coupling agent, a commercially available one may be used. For example, the following silane coupling agents manufactured by Shin-Etsu Chemical Co., Ltd. (descriptions in parentheses are trade names) can be used. Vinyltrimethoxysilane (KBM-1003), Vinyltriethoxysilane (KBE-1003), Octenyltrimethoxysilane (KBM-1083), p-Styryltrimethoxysilane (KBM-1403), 3-Methacryloyloxypropylmethyldimethoxy Silane (KBM-502), 3-methacryloyloxypropyltrimethoxysilane (KBM-503), 3-methacryloyloxypropylmethyldiethoxysilane (KBE-502), 3-methacryloyloxypropyltriethoxysilane (KBE-503), methacryloyloxyoctyltrimethoxysilane (KBM-5803), 3-acryloxypropyltrimethoxysilane (KBM-5103) and the like.

<(F) Content of silane coupling agent>
When the photosensitive resin composition of the present embodiment contains (F) a silane coupling agent, the content of (F) the silane coupling agent is (A) the alkali-soluble resin contained in the photosensitive resin composition, ( It is preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass, relative to a total of 100 parts by mass of B) the alkoxysilyl group-containing resin and (C) the reactive diluent. and most preferably 3 parts by mass to 10 parts by mass. (F) When the content of the silane coupling agent is within the above range, the compatibility and photocurability of (A) the alkali-soluble resin, (B) the alkoxysilyl group-containing resin, and (C) the reactive diluent are improved. It becomes a more suitable photosensitive resin composition.

[Other ingredients]
The photosensitive resin composition of the present embodiment contains (A) an alkali-soluble resin, (B) an alkoxysilyl group-containing resin, and (C) a reactive diluent in order to impart predetermined properties as necessary. , (D) a photoradical polymerization initiator, (E) a solvent, and (F) other components different from the silane coupling agent.
Other components include, for example, known additives such as leveling agents and thermal polymerization inhibitors. The content of other components contained in the photosensitive resin composition is not particularly limited as long as it does not impair the effects of the present invention.

[Method for producing a photosensitive resin composition]
The photosensitive resin composition of the present embodiment includes, for example, (A) an alkali-soluble resin, (B) an alkoxysilyl group-containing resin, (C) a reactive diluent, and (D) a photoradical polymerization initiator, (E) a solvent and (F) a silane coupling agent and/or other components that are optionally contained can be mixed using a known mixing apparatus.

In the method for producing a photosensitive resin composition of the present embodiment, (A) an alkali-soluble resin, (B) an alkoxysilyl group-containing resin, (C) a reactive diluent, and (D) a radical photopolymerization initiator , (E) the solvent, and (F) the silane coupling agent and/or other components that are optionally contained are not particularly limited. For example, a resin composition containing (A) an alkali-soluble resin, (B) an alkoxysilyl group-containing resin, and (E) a solvent is prepared, and the resulting resin composition is added with (C) a reactive diluent. , (D) a radical photopolymerization initiator, and (F) a silane coupling agent and/or other components, which are optionally contained, may be mixed.

The photosensitive resin composition of the present embodiment includes (A) an alkali-soluble resin, (B) an alkoxysilyl group-containing resin, (C) a reactive diluent, (D) a photoradical polymerization initiator, and (E ) solvent and Therefore, due to the synergistic effects of (1) to (3) shown below, the storage stability and developability are good, and by curing, the hardness is high, the adhesion to the substrate and / or the base, and the water resistance , a cured resin film having excellent high-temperature and high-humidity resistance and transparency can be obtained. Therefore, the photosensitive resin composition of the present embodiment is suitable as a material for cured resin films used as insulating films and/or protective films in image display devices such as touch panels.

(1) The (A) alkali-soluble resin contained in the photosensitive resin composition has an acid group and a (meth)acryloyloxy group, and has an ethylenically unsaturated group equivalent of 400 g/mol or more and 2500 g/mol or less. , Curing shrinkage is sufficiently small, a cured resin film with good adhesion to the substrate and / or substrate can be obtained, and the resin cure has good storage stability and developability, and has good high temperature and high humidity resistance. A membrane is obtained.

(2) (A) the alkali-soluble resin contains a structural unit (a-1) derived from an ethylenically unsaturated group-containing compound (ma-1) having an aromatic group, and (A) the total repetition of the alkali-soluble resin Since 15 mol % or more and 60 mol % or less of the structural unit (a-1) is contained in the structural units, it has good developability, and can form a resin cured film having good water resistance, high temperature and high humidity resistance, and transparency. It becomes a photosensitive resin composition.
(3) Because the (B) alkoxysilyl group-containing resin contained in the photosensitive resin composition contains a structural unit (b-1) derived from an ethylenically unsaturated group-containing compound (mb-1) having an alkoxysilyl group , a cured resin film having high hardness and good resistance to high temperature and high humidity can be obtained.

[Resin cured film]
The cured resin film of the present embodiment is composed of a cured product of the photosensitive resin composition of the present embodiment. The cured resin film of the present embodiment can be suitably used, for example, as a protective film and/or an insulating film in an image display device such as a touch panel.
The cured resin film of this embodiment is formed on a substrate or a base. Examples of the base material or base include those made of members used in image display devices such as touch panels. Specifically, as the base material or underlayer, a base material such as a glass base material, an electrode material such as ITO, molybdenum, or a metal mesh, an organic film, or the like can be used.

The cured resin film of the present embodiment can be produced using a known method. For example, the photosensitive resin composition of the present embodiment is applied to a base material or a substrate by a known method to form a coating film, and the resulting coating film is irradiated with light by a known method to obtain a photosensitive resin. It can be produced by a method of curing the composition.
Further, when the cured resin film of this embodiment has a predetermined pattern shape, a photolithography method can be used. Specifically, it is preferable to use a method in which the following coating step, pre-baking (pre-heat treatment) step, exposure step, development step, and post-baking step are performed in this order.

(Coating process)
In the coating step, a coating film is formed by coating the photosensitive resin composition of the present embodiment on a substrate or a base.
A known method can be used as a method of applying the photosensitive resin composition to the base material or base. Specifically, for example, the coating method of the photosensitive resin composition includes a screen printing method, a roll coating method, a curtain coating method, a spray coating method, a spin coating method, a slit coating method, and the like.

(Pre-baking (pre-heat treatment) step)
In the pre-baking step, the content of the solvent (E) contained in the coating film is reduced by heating the base material or base on which the coating film is formed.
In the pre-baking step, a known method such as a method using a hot plate can be used as a method for heating the base material or base on which the coating film is formed.

The heating temperature in the prebaking step can be appropriately determined according to the composition of the photosensitive resin composition and the like. The heating temperature can be, for example, 70 to 120.degree. C., preferably 90 to 110.degree.
The heating time in the prebaking step can be appropriately determined according to the composition of the photosensitive resin composition, the thickness of the coating film, and the like. The heating time can be, for example, 10 to 600 seconds, preferably 120 to 180 seconds.

(Exposure process)
In the exposure step, a part of the coating film after the pre-baking step is irradiated with light through a photomask having a shape corresponding to the pattern shape of the cured resin film to be produced, and photocured.
In the exposure step, a known light source can be used for light irradiation. Specific examples of light sources include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, xenon lamps, and metal halide lamps.
The irradiation amount of light (exposure amount) in the exposure step is not particularly limited, and is appropriately set according to the pattern shape of the photomask, the composition of the photosensitive resin composition, the thickness of the coating film, and the like.

(Development process)
In the development step, the unexposed portion of the coating film after the exposure step is dissolved and removed using a developer.
As the developer, a known alkaline developer used for developing photosensitive compositions can be used. Specifically, for example, as an alkaline developer, aqueous solutions of sodium carbonate, potassium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide, etc.; aqueous solutions of amine compounds such as ethylamine, diethylamine, dimethylethanolamine; Aqueous solutions of quaternary ammonium salts such as methylammonium; 3-methyl-4-amino-N,N-diethylaniline, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl -4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluene An aqueous solution of a p-phenylenediamine compound such as a sulfonate can be used. Among these alkaline developers, it is preferable to use an aqueous solution of a p-phenylenediamine compound.

Additives such as antifoaming agents and surfactants may be added to the alkali developer as needed.
Development conditions such as development temperature and development time in the development step can be appropriately determined according to the composition of the photosensitive resin composition, the composition of the developer, the thickness of the coating film, and the like.
In the developing step, it is preferable to develop the coating by dissolving the unexposed portion of the coating film using the alkaline developer, followed by washing with water and drying.

(Post-baking process)
In the post-baking process, the coating film after the developing process is heated.
In the post-baking step, as a method for heating the coating film after the developing step, a known method such as a method using a hot plate can be used.

The heating temperature in the post-baking step can be appropriately determined according to the composition of the photosensitive resin composition, the base material on which the coating film is formed, or the underlying material. The heating temperature can be, for example, 130.degree. C. to 250.degree.
The heating time in the post-baking step can be appropriately determined according to the composition of the photosensitive resin composition, the thickness of the coating film, and the like. The heating time can be, for example, 10 minutes to 60 minutes.
Through the above steps, a cured resin film having a predetermined pattern shape is obtained.

The cured resin film of this embodiment consists of a cured product obtained by curing the photosensitive resin composition of this embodiment. Therefore, it has high hardness, good adhesion to the substrate and/or base, good water resistance, high temperature and high humidity resistance, and transparency. Further, when the cured resin film of the present embodiment has a predetermined pattern shape formed by a photolithography method, it is formed using the photosensitive resin composition of the present embodiment having good developability. Therefore, it is highly accurate. For these reasons, the cured resin film of the present embodiment is suitable as an insulating film and/or protective film provided in an image display device such as a touch panel.

[Image display device]
The image display device of this embodiment includes the cured resin film of this embodiment. It is particularly preferable that the image display device of the present embodiment is a touch panel. The cured resin film in the image display device of the present embodiment is preferably one selected from the group consisting of a protective film and an insulating film, and is particularly preferably a protective film or insulating film of a touch panel.
The image display device of this embodiment can be manufactured using a conventionally known method.

The image display device of the present embodiment includes the cured resin film of the present embodiment, which has high hardness, good adhesion to the substrate and / or base, water resistance, high temperature and high humidity resistance, and transparency, Excellent reliability and durability.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. It should be noted that the following examples are intended to facilitate understanding of the content of the present invention. The invention is not limited to only these examples.
[(A) Synthesis of alkali-soluble resin]
Alkali-soluble resins (A) of Synthesis Examples 1 to 8, Comparative Synthesis Examples 1 and 2 were produced by the methods shown below.

[Synthesis Example 1 (Sample No. A1)]
A flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube is charged with the solvent shown in Table 1 so that the solid content concentration in the sample containing (A) an alkali-soluble resin is 30% by mass. 700.0 g of propylene glycol monomethyl ether acetate was added, and the mixture was stirred while being replaced with nitrogen gas, and heated to 120°C.

Then, 142.6 g (0.45 mol) of benzyl methacrylate, which are the monomers (ma-1) to (ma-3) shown in Table 1, 69.7 g (0.45 mol) of methacrylic acid, and 39 of dicyclopentanyl methacrylate .6 g (0.1 mol) of raw material monomers were mixed to obtain a monomer mixture.

4.5 g (1.8 parts by mass) of t-butylperoxy-2-ethylhexanoate, which is a polymerization initiator, was added to the monomer mixture, and added to the solvent at 120° C. that was being stirred in the above flask. was added dropwise over 1 hour using a dropping funnel to obtain a reaction solution. The obtained reaction liquid was further stirred at 120° C. for 2 hours to carry out a copolymerization reaction to produce a reaction liquid containing a resin precursor which is a copolymer.

Next, the inside of the flask in which the resin precursor was generated was replaced with 6% oxygen gas, and the reaction liquid containing the resin precursor in the flask was added with glycidyl methacrylate 38.5, which is the monomer (ma-5) shown in Table 1. 3 g (0.15 mol), 0.871 g of triphenylphosphine as a catalyst, and 0.871 g of methylhydroquinone as a polymerization inhibitor are added, and an addition reaction is performed at 120° C. for 6 hours to convert the side chain of the resin precursor to A sample (Sample No. A1) containing the modified (A) alkali-soluble resin of Synthesis Example 1 was obtained.

[Synthesis Example 2 to Synthesis Example 8, Comparative Synthesis Example 1 and Comparative Synthesis Example 2 (Sample Nos. A2 to A10)] Instead of the monomer used in the monomer mixture in Synthesis Example 1, the monomer (ma-1) shown in Table 1 In the same manner as in Synthesis Example 1, except that ~ (ma-4) was used in the proportion shown in Table 1 and the amount of polymerization initiator added was as shown in Table 1, Synthesis Examples 2 to 8, A reaction solution containing the resin precursors of Comparative Synthesis Example 1 and Comparative Synthesis Example 2 was produced.

Thereafter, in the same manner as in Synthesis Example 1, except that the monomer (ma-5) shown in Table 1 was added to the reaction solution containing the resin precursor in the flask at the ratio shown in Table 1, the resin precursor side Samples containing (A) the alkali-soluble resin of Synthesis Examples 2 to 8, Comparative Synthesis Example 1 and Comparative Synthesis Example 2 (Sample Nos. A2 to A10) having modified chains were obtained.

In Table 1, the compounds used are as follows.
BZMA: benzyl methacrylate St: styrene PQMA: 4-hydroxyphenyl methacrylate MAA: methacrylic acid TCDMA: dicyclopentanyl methacrylate THFMA: tetrahydrofurfuryl methacrylate GMA: glycidyl methacrylate TBO: t-butylperoxy-2-ethylhexanoate (Product name: Perbutyl O, manufactured by NOF Corporation)
PGMEA: propylene glycol monomethyl ether acetate

The numerical values of the monomers (ma-1) to (ma-4) in Table 1 indicate the ratio (mol%) of each monomer to the total amount of the monomers (ma-1) to (ma-4) used in the resin precursor. show.
The numerical value of the monomer (ma-5) in Table 1 indicates the amount (parts by mass) added to the total 100 parts by mass of the monomers (ma-1) to (ma-4) used in the resin precursor.
The numerical value of the solvent in Table 1 indicates the content (% by mass) in the sample containing (A) the alkali-soluble resin.
The numerical values of the polymerization initiator shown in Table 1 indicate the amount (parts by mass) added to 100 parts by mass in total of the monomers (ma-1) to (ma-4) used in the resin precursor.

The weight average molecular weight (Mw) and the acid value of (A) the alkali-soluble resins of Synthesis Examples 1 to 8, Comparative Synthesis Examples 1 and 2 thus obtained were measured by the methods described above. , the ethylenically unsaturated group equivalent was calculated by the method shown below. Table 1 shows the results.

(Ethylenically unsaturated group equivalent)
(A) From the charged amount of the monomers (ma-1) to (ma-5) used in producing the alkali-soluble resin, (A) alkali-soluble resin per 1 mol of unsaturated bond in (A) alkali-soluble resin The mass of (A) was calculated as the ethylenically unsaturated group equivalent (g/mol) of the alkali-soluble resin.

[(B) Synthesis of alkoxysilyl group-containing resin]
The alkoxysilyl group-containing resins (B) of Synthesis Examples 9 to 13 were produced by the method shown below.

[Synthesis Example 9 (Sample No. B1)]
A solvent shown in Table 2 was added to a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube so that the solid content concentration in the sample containing (B) the alkoxysilyl group-containing resin was 40% by mass. 600 g of 3-methoxy-1-butanol was added, and the mixture was stirred while being replaced with nitrogen gas, and the temperature was raised to 105°C.

Then, 327.0 g (0.8 mol) of 3-methacryloyloxypropylmethyldiethoxysilane, which is the monomers (mb-1) and (mb-2) shown in Table 2, and 27.0 g (0.2 mol) of methacrylic acid were added. were mixed to form a monomer mixture. To the monomer mixture, 46.0 g (13 parts by mass) of 2,2′-azobis(isobutyrate)dimethyl, which is a polymerization initiator, was added, and the dropping funnel was added to the solvent at 105° C. that was being stirred in the flask. was added dropwise to obtain a reaction solution. The obtained reaction solution was further stirred at 105° C. for 2 hours to carry out a copolymerization reaction to obtain a sample (Sample No. B1) containing the (B) alkoxysilyl group-containing resin of Synthesis Example 9, which is a copolymer.

[Synthesis Example 10 to Synthesis Example 13 (Sample Nos. B2 to B5)]
Instead of the monomers used in the monomer mixture in Synthesis Example 9, the monomers (mb-1) to (mb-3) shown in Table 2 were used in the proportions shown in Table 2, and the polymerization initiator shown in Table 2 was used. Samples (Sample Nos. B2 to B5) containing the (B) alkoxysilyl group-containing resins of Synthesis Examples 10 to 13 were obtained in the same manner as in Synthesis Example 9, except that the added amount was changed.

In Table 2, the compounds used are as follows.
KBE-502: 3-methacryloyloxypropylmethyldiethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
KBE-503: 3-methacryloyloxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
MAA: methacrylic acid AA: acrylic acid St: styrene GMA: glycidyl methacrylate AIBME: 2,2'-azobis(isobutyrate) dimethyl MB: 3-methoxy-1-butanol

The numerical values of the monomers (mb-1) to (mb-3) in Table 2 are the ratio of each monomer to the total amount of the monomers (mb-1) to (mb-3) used in the alkoxysilyl group-containing resin (B). (mol%).
The numerical value of the solvent in Table 2 indicates the content (% by mass) in the sample containing the (B) alkoxysilyl group-containing resin.
The numerical values of the polymerization initiator shown in Table 2 indicate the amount (parts by weight) added to 100 parts by weight in total of the monomers (mb-1) to (mb-3) used in the alkoxysilyl group-containing resin (B).

For the (B) alkoxysilyl group-containing resins of Synthesis Examples 9 to 13 thus obtained, the weight average molecular weight (Mw), acid value, and silyl group equivalent were measured by the methods described above. Table 2 shows the results.

(Storage stability)
Next, the (B) alkoxysilyl group-containing resins (specimen) collected from the samples containing the (B) alkoxysilyl group-containing resins (sample numbers B1 to B5) of Synthesis Examples 9 to 13 were prepared by the following method. was used to evaluate the storage stability. Table 2 shows the results.

For each specimen, the weight average molecular weight (Mw) was measured using GPC (GPC-101, manufactured by Shodex). In addition, the viscosity at 25° C. was measured for each specimen by the method described above.
10 g of each test sample was weighed into a 20 ml glass container, sealed, and placed in a thermostat kept at 40° C. for 1 month for preservation test.
The weight average molecular weight (Mw) and the viscosity at 25° C. of each specimen after the storage test were measured again by the above method.

Using the weight average molecular weight (Mw) before and after the storage test and the viscosity at 25°C before and after the storage test, the rate of increase in the weight average molecular weight and the increase in viscosity at 25°C are calculated by the following formula (I). The rate was obtained and evaluated according to the following criteria. The results are shown in Tables 2 to 7.
Increase rate (%) = ((before storage test - after storage test) / before storage test) x 100 (I) "Evaluation criteria"
○ (acceptable): both the rate of increase in molecular weight and the rate of increase in viscosity are less than 10% × (impossible): one or both of the rate of increase in molecular weight and the rate of increase in viscosity is 10% or more

As shown in Table 2, the (B) alkoxysilyl group-containing resins (Sample Nos. B1 to B5) of Synthesis Examples 9 to 13 were all evaluated for storage stability as ◯ (acceptable), indicating excellent storage. It was confirmed that it has stability.

<Examples 1 to 16, Comparative Examples 1 to 5>
[Preparation of photosensitive resin composition]
(A) alkali-soluble resins (sample numbers A1 to A10) of Synthesis Examples 1 to 8, Comparative Synthesis Examples 1 and 2, and (B) alkoxysilyl group-containing resins of Synthesis Examples 9 to 13 ( Sample numbers B1 to B5), (C) reactive diluents shown in Tables 3 to 7, (D) photoradical polymerization initiators, (E) solvents, and (F) silane coupling agents, By mixing at the ratios shown in Tables 3 to 7, photosensitive resin compositions of Examples 1 to 16 and Comparative Examples 1 to 5 were prepared.

The compounds used in Tables 3 to 7 are as follows.
DPHA: dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd.)
OXE-01: 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone (manufactured by BASF Japan)
PGMEA: propylene glycol monomethyl ether acetate MB: 3-methoxy-1-butanol KBE-503: 3-methacryloyloxypropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)

The numerical values of (A) alkali-soluble resin shown in Tables 3 to 7 include the solvent Contains only other ingredients and does not contain solvents.
The numerical values of the (B) alkoxysilyl group-containing resin shown in Tables 3 to 7 include only the components other than the solvent in the samples containing the (B) alkoxysilyl group-containing resin synthesized in Synthesis Examples 9 to 13. contains no solvents.

(A) an alkali-soluble resin, (B) an alkoxysilyl group-containing resin, (C) a reactive diluent, (D) a photoradical polymerization initiator, and (F) a silane coupling agent in Tables 3 to 7. The compounding amount indicates the content (parts by mass) of each of components (A) to (D) and (F) with respect to 100 parts by mass of (A) to (C) in total.
(E) The blending amount of the solvent indicates the content (parts by mass) per 100 parts by mass of the above (A) to (D) and (F).

(Storage stability)
Among the formulations of Examples 1 to 16 and Comparative Examples 1 to 5 shown in Tables 3 to 7, (C) a reactive diluent, (D) a photoradical polymerization initiator and (E) a silane cup Storage stability was evaluated in the same manner as in the storage stability tests of Synthesis Examples 9 to 13 under the condition that no ring agent was added. The results are shown in Tables 3-7.

As shown in Tables 3 to 7, the photosensitive resin compositions of Examples 1 to 16 and Comparative Examples 1 to 5 were all evaluated for storage stability as ◯ (acceptable), indicating excellent storage stability. I was able to confirm that I had sex.

Next, for the cured resin films obtained by curing the photosensitive resin compositions of Examples 1 to 16 and Comparative Examples 1 to 5, (1) hardness (pencil hardness), (2) transmittance (transparency properties), (3) adhesion, (4) water resistance, (5) resistance to high temperature and high humidity, (6) developability, and (7) overall evaluation were evaluated by the following methods.

(1) Hardness (pencil hardness)
A coating film was formed by coating the photosensitive resin composition on a glass substrate (non-alkali glass substrate) of 5 cm long and 5 cm wide using a spin coater. By heating the glass substrate on which the coating film was formed on a hot plate at 100°C for 3 minutes, the content of the solvent (E) contained in the coating film was reduced to form a coating film on the glass substrate. . Next, the coating film was irradiated with light having a wavelength of 365 nm at an exposure amount of 200 mJ/cm ² to be photocured. Next, the glass substrate having the photo-cured coating film was heated at 230° C. for 30 minutes in a dryer to obtain a cured resin film having a thickness of 2.0 μm.

The pencil hardness of the cured resin film thus prepared was measured according to JIS K5600-5-4 using a pencil hardness tester (No. 553-M, manufactured by Yasuda Seiki Seisakusho). The results are shown in Tables 4-6.

(2) transmittance (transparency)
For a glass substrate having a cured resin film prepared in the same manner as in (1) hardness evaluation, the spectral transmittance at 400 to 800 nm was measured using a spectrophotometer (UV-1650PC, manufactured by Shimadzu Corporation). . Then, the transmittance at a wavelength of 400 nm was evaluated according to the criteria shown below. The results are shown in Tables 3-7.
"Evaluation criteria"
○ (acceptable): 98% or more × (impossible): less than 98%

(3) Adhesion (to glass, ITO, metal mesh (Cu, Ag), Mo)
A glass substrate having a cured resin film was prepared as a test piece in the same manner as in (1) Evaluation of hardness.
Further, in place of the glass substrate, a glass substrate on which an indium tin oxide (ITO) film is formed, a substrate on which a metal mesh (Cu, Ag) is formed, and a glass substrate on which a molybdenum (Mo) film is formed are used. A cured resin film was prepared as a test sample in the same manner as in (1) Hardness evaluation, except that it was used.

Adhesion of the cured resin film was evaluated by the cross-cut method of JIS K5600-5-6 on the specimens having the cured resin film thus prepared. Specifically, the number of peeled pieces in 100 grids was counted and evaluated according to the following criteria. The results are shown in Tables 3-7.
"criterion"
○ (possible): 0 peeled pieces × (impossible): 1 or more peeled pieces

(4) Water Resistance A glass substrate having a cured resin film was prepared in the same manner as in (1) hardness evaluation, and immersed in water at a temperature of 100° C. for 1 hour.
The adhesion of the cured resin film was evaluated by the cross-cut method of JIS K5600-5-6 on the glass substrate having the cured resin film thus prepared. Specifically, the number of peeled pieces in 100 grids was counted and evaluated according to the following criteria. The results are shown in Tables 3-7.
"criterion"
○ (possible): 0 peeled pieces × (impossible): 1 or more peeled pieces

(5) High Temperature and High Humidity Resistance A photosensitive resin composition was applied by a spin coater onto a molybdenum (Mo) substrate having a length of 5 cm and a width of 5 cm to form a coating film (coating step). By heating the molybdenum substrate on which the coating film is formed for 3 minutes on a hot plate at 100 ° C. (pre-baking process), the content of (E) solvent contained in the coating film is reduced, and the molybdenum substrate is coated. A film was formed. Next, a photomask having a line-and-space pattern with a width of 3 to 100 μm was arranged with a distance of 100 μm from the surface of the coating film. Then, the coating film was irradiated with light of 200 mJ/cm ² from an extra-high pressure mercury lamp through a photomask to be photocured (exposure step).

Thereafter, the unexposed portion of the coated film after exposure was dissolved and removed using a developer (development step). As the developer, semi-clean DL-A10 developer (product (manufactured by Yokohama Yushi Kogyo Co., Ltd.) diluted 75 times was used. Development was carried out by spraying the developer onto the exposed coating film at a temperature of 23° C. and a pressure of 0.1 MPa for 30 to 60 seconds.
Then, the glass substrate having the photo-cured coating film was heated in a dryer at 230° C. for 30 minutes (post-baking step).
Through the above steps, a cured resin film having a line-and-space pattern with a film thickness of 2.0 μm and a width of 3 to 100 μm was produced on the molybdenum substrate.

The molybdenum substrate having the cured resin film prepared in this way was allowed to stand for 1000 hours in a thermo-hygrostat at a temperature of 85° C. and a relative humidity of 85% RH. Thereafter, the molybdenum substrate having the cured resin film was taken out, and the presence or absence of discoloration of the cured resin film was visually evaluated according to the following criteria. The results are shown in Tables 3-7.
"criterion"
○ (acceptable): no discoloration × (impossible): slightly discolored to blue

(6) Developability In the same manner as in (5) Evaluation of high-temperature and high-humidity resistance, except that a glass substrate (non-alkali glass substrate) having a length of 5 cm and a width of 5 cm was used instead of the molybdenum substrate. A cured resin film having a line-and-space pattern with a thickness of 2.0 μm and a width of 3 to 100 μm was prepared.

For the glass substrate having the resin cured film thus prepared, a microscope (trade name; RH-2000, manufactured by Hylox Co., Ltd.) was used to observe the resin cured film at a magnification of 500 times, and the resolved minimum The line width (minimum development dimension) was measured. The results are shown in Tables 3-7. The above cured resin film was observed with a microscope by the above method, and the presence or absence of residues in unexposed areas between resolved patterns was evaluated according to the following criteria. The results are shown in Tables 3-7.
"criterion"
○ (possible): no residue in the unexposed area between patterns × (impossible): residue in the unexposed area between patterns

(7) Comprehensive Judgment Evaluation was made according to the criteria shown below. The results are shown in Tables 3-7.
"Evaluation criteria"
○ (Possible): Satisfies all of the following items.
(1) Pencil hardness in terms of hardness is 4H or more (2) Transmittance is 98% or more (3) The number of peeled pieces in adhesion is 0 (4) The number of peeled pieces in water resistance is 0 (5) High temperature resistance and high temperature There is no discoloration in the wetness evaluation (6) The minimum development dimension in developability is 20 μm or less, and there is no residue in the unexposed area between patterns × (impossible): Any of the s items indicated by the above ○ (possible) or 1 or more.

As shown in Tables 3 to 6, the cured resin films of Examples 1 to 16 had (1) a pencil hardness of 4H or 5H, (2) transmittance (transparency), (3 ) Adhesion, (4) Water resistance, (5) High temperature and high humidity resistance, (6) Developability (residue) are all evaluated as ○ (acceptable), and (6) Minimum development size in developability is 20 μm. (7) Comprehensive judgment was ◯ (acceptable).

On the other hand, as shown in Table 7, the cured resin films of Comparative Examples 1 to 5 were all evaluated as (7) overall judgment of x (improper).
More specifically, (B) the cured resin films of Comparative Examples 1 and 2, which did not contain an alkoxysilyl group-containing resin, had (1) a pencil hardness of H, and sufficient hardness was not obtained. . In addition, the resin cured films of Comparative Examples 1 and 2 were evaluated as (5) high temperature and high humidity resistance x (improper), and the high temperature and high humidity resistance was also insufficient.

(A) The cured resin film of Comparative Example 3, which does not contain an alkali-soluble resin, has (6) a minimum developable dimension of 50 μm in developability, and compared with the cured resin films of Examples 1 to 16, the developed It was of poor quality.

(A) The resin cured film of Comparative Example 4 having a low content of the structural unit (a-1) derived from the ethylenically unsaturated group-containing compound (ma-1) having an aromatic group in the total repeating structure of the alkali-soluble resin (4) water resistance and (5) high temperature and high humidity resistance were evaluated as x (improper), and the water resistance and high temperature and high humidity resistance were insufficient. In addition, the cured resin film of Comparative Example 4 had a minimum development size of 30 μm in (6) developability, and was inferior in developability compared to the cured resin films of Examples 1 to 16. .

(A) The resin cured film of Comparative Example 5 in which the ethylenically unsaturated group equivalent of the alkali-soluble resin is 2500 g / mol or more is evaluated as (5) high temperature and high humidity resistance × (impossible), and high temperature and high humidity resistance was insufficient. The cured resin film of Comparative Example 5 had a minimum developable dimension of 30 μm, and was inferior in developability to the cured resin films of Examples 1 to 16.

According to the present invention, the storage stability is good, the resin cured film having a highly accurate pattern shape can be formed by photolithography, and the resin has good developability. Provided is a photosensitive resin composition capable of obtaining a resin cured film having excellent adhesion to a substrate and/or an underlayer, water resistance, resistance to high temperature and high humidity, and transparency. The photosensitive resin composition can be preferably used as a material for protective films and insulating films of touch panels.

Claims

(A) an alkali-soluble resin;
(B) an alkoxysilyl group-containing resin;
(C) a reactive diluent;
(D) a radical photopolymerization initiator;
(E) a solvent, and
The (A) alkali-soluble resin contains a structural unit (a-1) derived from an ethylenically unsaturated group-containing compound (ma-1) having an aromatic group, and has an acid group and a (meth)acryloyloxy group. and the ethylenically unsaturated group equivalent is 400 g / mol or more and 2500 g / mol or less,
Containing 15 mol% or more and 60 mol% or less of the structural unit (a-1) in all the repeating structural units of the alkali-soluble resin (A),
A photosensitive resin composition, wherein the (B) alkoxysilyl group-containing resin comprises a structural unit (b-1) derived from an ethylenically unsaturated group-containing compound (mb-1) having an alkoxysilyl group.
The photosensitive resin composition according to claim 1, wherein the mass ratio of (A) the alkali-soluble resin and (B) the alkoxysilyl group-containing resin is 40:60 to 99:1.
The photosensitive resin composition according to claim 1 or claim 2, wherein the content of said structural unit (b-1) in all repeating structural units of said (B) alkoxysilyl group-containing resin is 45 mol% or more.
The (A) alkali-soluble resin comprises the structural unit (a-1), a structural unit (a-2) derived from an unsaturated monobasic acid (ma-2), and an ethylenic having an alicyclic hydrocarbon group. Part of the carboxy groups of the copolymer containing the unsaturated group-containing compound (ma-3)-derived structural unit (a-3) is an epoxy group-containing (meth)acrylate (ma-5)-derived structural unit ( 3. The photosensitive resin composition according to claim 1, which is a resin modified by a-5).
The photosensitive resin composition according to claim 1 or claim 2, wherein (A) the alkali-soluble resin has an acid value of 20 mg KOH/g to 200 mg KOH/g.
The photosensitive resin composition according to claim 1 or claim 2, wherein (A) the alkali-soluble resin has a weight average molecular weight (Mw) of 1,000 to 50,000.
The (B) alkoxysilyl group-containing resin contains a structural unit (b-2) derived from an unsaturated monobasic acid (mb-2),
3. The photosensitive resin composition according to claim 1, which has an acid value of 150 KOHmg/g or less.
The photosensitive resin composition according to claim 1 or claim 2, wherein the (B) alkoxysilyl group-containing resin has a weight average molecular weight (Mw) of 1,000 to 20,000.
With respect to a total of 100 parts by mass of the (A) alkali-soluble resin, the (B) alkoxysilyl group-containing resin, and the (C) reactive diluent,
Containing 5 to 75 parts by mass of the (C) reactive diluent,
3. The photosensitive resin composition according to claim 1, containing 0.1 to 20 parts by mass of (D) the radical photopolymerization initiator.
The (E) solvent contains one or more alcohols selected from primary alcohols having 3 to 10 carbon atoms and secondary alcohols having 3 to 10 carbon atoms,
3. The photosensitive resin composition according to claim 1, wherein the total alcohol content in all solvents is 15 to 100% by mass.
(F) The photosensitive resin composition according to claim 1 or 2, further comprising a silane coupling agent.
The photosensitive resin composition according to claim 11, wherein the (F) silane coupling agent has one or more functional groups selected from (meth)acrylic groups, vinyl groups and styryl groups.
With respect to a total of 100 parts by mass of the (A) alkali-soluble resin, the (B) alkoxysilyl group-containing resin, and the (C) reactive diluent,
12. The photosensitive resin composition according to claim 11, containing 0.1 to 20 parts by mass of the (F) silane coupling agent.
A cured resin film comprising a cured product of the photosensitive resin composition according to claim 1.
An image display device comprising the cured resin film according to claim 14.
The image display device according to claim 15, which has a protective film made of the cured resin film.
The image display device according to claim 15, which has an insulating film made of the cured resin film.