JP2020164800A - Curable resin composition and cured film - Google Patents

Abstract

To provide a curable resin composition capable of forming a cured product excellent in heat-resistant adhesion to a substrate.SOLUTION: The curable resin composition contains: a resin being a copolymer which contains a constituent unit derived from at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a constituent unit derived from a compound having a C2-4 cyclic ether structure and an ethylenically unsaturated bond; a polymerizable compound which has a condensed polycyclic aromatic skeleton and at least one selected from the group consisting of an acryloyl group and a methacryloyl group; a polymerization initiator; and a thiol compound.SELECTED DRAWING: None

Description

The present invention relates to a curable resin composition and a cured film.

A cured film such as a color filter protective film is used as a member in a liquid crystal display device or the like. A curable resin composition is used to form such a cured film.

As the curable resin composition, for example, a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride, and a structural unit derived from an unsaturated compound having an oxylanyl group. A curable resin composition containing an addition polymer containing, a dipentaerythritol hexaacrylate and a polymerization initiator is known (for example, Japanese Patent Application Laid-Open No. 2013-10938).

Japanese Unexamined Patent Publication No. 2013-10938

In a liquid crystal display device or the like, a cured film formed from a curable resin composition can be used as a spacer for maintaining the spacing between substrates. When a spacer is formed on a substrate by using a conventional curable resin composition, there is a problem that heat resistance and adhesion are not sufficient. Such a problem was remarkable when the spacer was formed on the substrate containing the conductive film so as to be in contact with the conductive film.

An object of the present invention is to provide a curable resin composition capable of forming a cured product having excellent heat-resistant adhesion to a substrate, and a cured film formed from the curable resin composition.

The present invention includes the following inventions.
[1] A structural unit derived from at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond. A resin that is a copolymer containing a constituent unit derived from a compound having
A polymerizable compound having a condensed polycyclic aromatic skeleton and at least one selected from the group consisting of acryloyl groups and methacryloyl groups;
Polymerization initiator; and
A curable resin composition containing a thiol compound.
[2] The curable resin composition according to [1], wherein the polymerizable compound has a fluorene skeleton as the condensed polycyclic aromatic skeleton.
[3] The curable resin composition according to [1] or [2], wherein the polymerizable compound is contained in an amount of 30 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the resin.
[4] A cured film formed from the curable resin composition according to any one of [1] to [3].

According to the curable resin composition of the present invention, it is possible to form a cured product having excellent heat-resistant adhesion to a substrate.

In the present specification, the compounds exemplified as each component may be used alone or in combination of a plurality of types unless otherwise specified.

[Curable resin composition]
The curable resin composition of the present invention includes a resin (hereinafter referred to as resin (A)), a polymerizable compound (hereinafter referred to as a polymerizable compound (B)), and a polymerization initiator (hereinafter referred to as a polymerization initiator (hereinafter referred to as a polymerization initiator). D) and a thiol compound (hereinafter referred to as a thiol compound (T)) are included. In the curable resin composition of the present invention, the resin (A) contains at least the resin (A1), and the polymerizable compound (B) contains at least the polymerizable compound (B1). In the present specification, the resin (A1) has a structural unit (Aa) derived from at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and has 2 to 4 carbon atoms. It is a copolymer containing a structural unit (Ab) derived from a compound having a cyclic ether structure and an ethylenically unsaturated bond. As used herein, the polymerizable compound (B1) has a condensed polycyclic aromatic skeleton and at least one selected from the group consisting of acryloyl groups and methacryloyl groups.

The curable resin composition of the present invention may further contain a solvent (hereinafter, referred to as a solvent (E)). Further, the curable resin composition of the present invention has other components such as a leveling agent (hereinafter referred to as a leveling agent (I)), an antioxidant (hereinafter referred to as an antioxidant (F)), and the like. A curing agent (hereinafter, referred to as a curing agent (G)) or the like may be contained. The curing agent (G) is referred to as a polyvalent carboxylic acid (G1). ), An imidazole compound (hereinafter, referred to as an imidazole compound (G2)) and the like.

<Polymerizable compound (B)>
The polymerizable compound (B) is a monomer that reacts by heat or the action of the polymerization initiator (D). The polymerizable compound (B) contains at least the polymerizable compound (B1). The polymerizable compound (B1) has a condensed polycyclic aromatic skeleton and at least one selected from the group consisting of an acryloyl group and a methacryloyl group. The weight average molecular weight of the polymerizable compound (B) is preferably 150 or more and 2,900 or less, and more preferably 250 to 1,500 or less.

The content of the polymerizable compound (B1) is 10% by mass or more, preferably 30% by mass or more, and more preferably 50% by mass or more with respect to the total amount of the polymerizable compound (B). The content of the polymerizable compound (B1) is 100% by mass or less with respect to the total amount of the polymerizable compound (B). By containing the polymerizable compound (B1) at such a content, the heat-resistant adhesion between the obtained cured film and the substrate can be improved.

The polymerizable compound (B) may contain a polymerizable compound (B1) and a polymerizable compound (polymerizable compound (B2)) different from the polymerizable compound (B1). Examples of the other polymerizable compound include compounds having an ethylenically unsaturated bond and not having a condensed polycyclic aromatic skeleton, preferably a (meth) acrylic compound, and more preferably an acryloyl group and a methacryloyl group. Examples thereof include compounds having at least one group selected from the group consisting of. In addition, in this specification, "(meth) acrylic acid" represents at least one compound selected from the group consisting of acrylic acid and methacrylic acid. Notations such as "(meth) acryloyl" and "(meth) acrylate" have the same meaning.

[1] Polymerizable compound (B1)
The polymerizable compound (B1) has a condensed polycyclic aromatic skeleton and at least one selected from the group consisting of an acryloyl group and a methacryloyl group. The condensed polycyclic aromatic skeleton means a structure (skeleton) in which two or more aromatic rings are condensed. The condensed polycyclic aromatic skeleton may be a condensed polycyclic aromatic hydrocarbon skeleton such as fluorene, naphthalene, anthracene, phenanthrene, pyrene, or the above aromatic ring such as quinoline, quinoxaline, benzofuran, benzimidazole, benzothiophene. It may be a skeleton in which at least one of is a heterocycle. The condensed polycyclic aromatic skeleton may or may not have a substituent attached to the aromatic ring. The polymerizable compound (B1) is preferably a compound having a condensed polycyclic aromatic hydrocarbon skeleton as the condensed polycyclic aromatic skeleton, preferably fluorene, from the viewpoint of improving the heat-resistant adhesion between the obtained cured film and the substrate. Compounds having a skeleton are more preferred.

The polymerizable compound (B1) having a fluorene skeleton is preferably a compound represented by the formula (VI).

[In the formula (VI), L ¹ represents an alkanediyl group having 1 to 16 carbon atoms which may have a single bond or a substituent independently of each other, and the methylene group contained in the alkanediyl group is oxygen. It may be replaced with an atom. However, the methylene group to which the oxygen atom is bonded does not replace the oxygen atom.
R ¹¹ represents a hydrogen atom or a methyl group independently of each other. ]
Examples of the compound represented by the formula (VI) include compounds represented by the formulas (VI-1) to (VI-3).

[In the formula (VI-3), R ^12a and R ^12b represent a hydrogen atom or a methyl group independently of each other, and m and n are integers of 0 or more. However, when m and n are 0, at least one of R ^12a and R ^12b is a methyl group. ]
As the compound represented by the formula (VI), the compound represented by the formula (VIa) is more preferable.

[In formula (VIa), L ^2a and L ^2b represent an alkanediyl group having 1 to 6 carbon atoms which may be substituted independently of each other.
m and n represent integers 0 to 8 independently of each other. However, m + n is 0 to 16. When m and n are 2 or more, respectively, the plurality of L ^2a and L ^2b may be the same or different.
However, the total number of carbon atoms of m L ^2a and n L ^2b is 0 to 30.
R ^13a and R ^13b represent a hydrogen atom or a methyl group independently of each other. ]

[2] Polymerizable compound (B2)
The polymerizable compound (B) may contain a polymerizable compound (polymerizable compound (B2)) different from the polymerizable compound (B1), and the polymerizable compound (B2) has an ethylenically unsaturated bond. However, it is a compound that does not have a condensed polycyclic aromatic skeleton. The polymerizable compound (B2) is preferably a (meth) acrylic compound, and more preferably a compound having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group.

Examples of the (meth) acrylic compound having one (meth) acryloyl group include (meth) acrylic acid alkyl ester, (meth) acrylic acid phenoxylated polyethylene glycol ester, (meth) acrylic acid alkoxylated polyethylene glycol ester, and isobornyl. (Meta) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc. Can be mentioned.

Examples of the (meth) acrylic compound having two (meth) acryloyl groups include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, and 1,6-hexanediol di (meth). Acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, bisphenol Bis (acryloyloxyethyl) ether of A, ethylene oxide-modified bisphenol A di (meth) acrylate, propylene oxide-modified neopentyl glycol di (meth) acrylate, ethylene oxide-modified neopentyl glycol di (meth) acrylate, 3-methylpentanediol di ( Meta) acrylate and the like can be mentioned.

Examples of the (meth) acrylic compound having three or more (meth) acryloyl groups include trimethylpropantri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, and the like. Ethylene oxide-modified trimethylol propanetri (meth) acrylate, propylene oxide-modified trimethylol propanetri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri Pentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, pentaerythritol tri (meth) Reaction product of acrylate and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, reaction product of tripentaerythritol hepta (meth) acrylate and acid anhydride, caprolactone-modified trimethylpropantri (Meta) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, caprolactone-modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol penta (meth) acrylate ) Acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) acrylate, caprolactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tri Pentaerythritol hepta (meth) acrylate, caprolactone-modified tripentaerythritol octa (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride reaction product, caprolactone-modified dipentaerythritol penta (meth) acrylate and acid anhydride Reactants with substances, caprolactone-modified tripentaerythritol hepta (meth) acrylate Examples thereof include a reaction product of g and acid anhydride.

As the (meth) acrylic compound, a (meth) acrylic compound having three or more (meth) acrylic loyl groups is preferable, and dipentaerythritol hexa (meth) acrylate is more preferable.

The content of the polymerizable compound (B) is preferably 20 to 200 parts by mass, more preferably 30 to 150 parts by mass with respect to 100 parts by mass of the resin (A). When the content of the polymerizable compound (B) is within the above range, it is preferable from the viewpoint that the heat-resistant adhesion between the obtained cured film and the substrate can be improved. The content of the polymerizable compound (B1) is preferably 20 to 200 parts by mass, more preferably 30 to 150 parts by mass, and further preferably 30 to 80 parts by mass with respect to 100 parts by mass of the resin (A).

<Resin (A)>
The resin (A) is not limited as long as it is a curable resin, but the resin (A) is preferably an alkali-soluble resin. The resin (A) contains at least the resin (A1). The resin (A1) is a structural unit (Aa) derived from at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, a cyclic ether structure having 2 to 4 carbon atoms, and ethylene. It is a copolymer containing a structural unit (Ab) derived from a compound having a sex unsaturated bond. The resin (A) further has a structural unit (hereinafter, referred to as a structural unit (Ac)) derived from a monomer copolymerizable with the structural unit (Aa) and (Ab). May be.

[1] Structural unit (Aa)
The structural unit (Aa) is a structural unit derived from at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides.

Examples of compounds belonging to the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexendicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo A bicyclounsaturated compound containing a carboxy group such as [2.2.1] hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride; monosuccinate [2-( Meta) acryloyloxyethyl], mono [2- (meth) acryloyloxyethyl] and other unsaturated mono-[(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.

[2] Structural unit (Ab)
The structural unit (Ab) is derived from a compound having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond. The structural unit (Ab) is derived from a compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxylan ring, an oxetane ring and a tetrahydrofuran ring) and an unsaturated bond made of ethylene. Can be done.

Examples of the compound that derives the structural unit (Ab) include a monomer having an oxylanyl group and an ethylenically unsaturated bond (hereinafter referred to as a monomer (Ab1)), an oxetanyl group and an ethylenically unsaturated bond. Examples thereof include a monomer having the above (hereinafter referred to as a monomer (Ab2)) and a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as a monomer (Ab3)). ..

The monomer (Ab1) is, for example, a monomer having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter, referred to as a monomer (Ab1-1)). ), And a monomer having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter, referred to as a monomer (Ab1-2)). The monomer (Ab1) is preferable as the monomer that leads to the structural unit (Ab) in that the heat-resistant adhesion between the obtained cured film and the substrate can be improved. Further, the monomer (Ab1-2) is more preferable in that the curable resin composition has excellent storage stability.

Examples of the monomer (Ab1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, and m-vinylbenzyl glycidyl. Ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxy) Methyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxy) Methyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4 Examples thereof include 6-tris (glycidyloxymethyl) styrene.

Examples of the monomer (Ab1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, celloxide 2000; manufactured by Daicel Co., Ltd.), and 3,4-epoxycyclohexylmethyl (meth) acrylate. (For example, Cyclomer A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Co., Ltd.), the compound represented by the formula (I) and the formula. Examples thereof include the compound represented by (II).

[In formulas (I) and (II), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. May be good.

X ^b1 and ^{X b2} represents a single ^{bond, * - R b3 -, *} - R b3 -O -, * - R b3 -S- or ^* -R b3 represents a -NH-.

R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]
Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like.

The alkyl groups in which the hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group and 1-hydroxy. Examples thereof include -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 4-hydroxybutyl group.

^Examples of R ^b1 and R ^b2 include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

The alkanediyl group includes methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, and hexane-. Examples include 1,6-diyl group.

The X ^b1 and ^{X b2,} preferably a single bond, a methylene group, an ethylene _{group, * - CH 2 -O -,} * - CH 2 CH 2 -O- and the like, more preferably a single bond, * - CH ₂ CH _2- O- can be mentioned. * Represents a bond with O.

Examples of the compound represented by the formula (I) include compounds represented by any of the formulas (I-1) to (I-15), preferably formulas (I-1) and (I). -3), formula (I-5), formula (I-7), formula (I-9) and compounds represented by formulas (I-11) to (I-15) are mentioned, more preferably. Examples thereof include compounds represented by formulas (I-1), formulas (I-7), formulas (I-9) and formulas (I-15).

Examples of the compound represented by the formula (II) include compounds represented by any of the formulas (II-1) to (II-15), and the compounds represented by the formulas (II-1) and (II-15) are preferable. -3), formula (II-5), formula (II-7), formula (II-9) and compounds represented by formulas (II-11) to (II-15) are mentioned, more preferably. Examples thereof include compounds represented by formulas (II-1), formulas (II-7), formulas (II-9) and formulas (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of two or more. When these are used in combination, their content ratios [compound represented by formula (I): compound represented by formula (II)] are based on molars, preferably 5:95 to 95: 5, more preferably 20. : 80 to 80:20. For example, a mixture containing a compound represented by the formula (I-1) and a compound represented by the formula (II-1) at a ratio of 50:50 (commercially available, trade name "E-DCPA" (Co., Ltd.) There is (made by Daicel)) can be used.

As the monomer (Ab2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of the monomer (Ab2) include 3-methyl-3-methacrylloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, and 3-ethyl-3-acryloyl. Oxymethyloxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, etc. Be done.

As the monomer (Ab3), a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is preferable. Examples of the monomer (Ab3) include tetrahydrofurfuryl acrylate (for example, Viscort V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate and the like.

As the structural unit (Ab), a structural unit derived from the monomer type (Ab1-2) is preferable because it is excellent in storage stability of the curable resin composition and heat-resistant adhesion between the obtained cured film and the substrate. It is more preferable that the structural unit is represented by the formula (Ab-1) or the formula (Ab-2). The structural unit represented by the formula (Ab-1) is derived from the compound represented by the formula (I), and the structural unit represented by the formula (Ab-2) is derived from the compound represented by the formula (II). Be taken.

[In the formula (Ab-1) and the formula (Ab-2), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms independently of each other, and the hydrogen atom contained in the alkyl group is , May be substituted with a hydroxy group.

X ^b1 and ^{X b2} represents a single ^{bond, * - R b3 -, *} - R b3 -O -, * - R b3 -S- or ^* -R b3 represents a -NH-.

R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

[3] Structural unit (Ac)
As the structural unit (Ac), for example, the following compound:
Methyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2- Methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in the art, it is commonly referred to as "dicyclopentanyl (meth) acrylate". (Also referred to as "tricyclodecyl (meth) acrylate"), tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate (as a common name in the art). It is called "dicyclopentenyl (meth) acrylate"), dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate. , (Meta) acrylic acid esters such as phenyl (meth) acrylate and benzyl (meth) acrylate; hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate. ;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2] .1] Bicyclounsaturated compounds such as hept-2-ene;
Dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate;
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, vinyl acetate, 1,3- Examples thereof include structural units derived from butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

[4] Ratio of each structural unit Examples of the resin (A) include the following resins [K1] and [K2].
Resin [K1]: A copolymer composed of a structural unit (Aa) and a structural unit (Ab);
Resin [K2]: A copolymer composed of a structural unit (Aa), a structural unit (Ab), and a structural unit (Ac).

In the resin [K1], the ratio of each structural unit is relative to all the structural units constituting the resin [K1].
Constituent unit (Aa); 5-60 mol%,
Constituent unit (Ab); preferably 40-95 mol%
Constituent unit (Aa); 10-50 mol%,
Constituent unit (Ab); more preferably 50-90 mol%.

When the ratio of the constituent units constituting the resin [K1] is within the above range, the curable resin composition tends to be excellent in storage stability, chemical resistance of the obtained film, heat resistance and mechanical strength.

The resin [K1] is, for example, the method described in the document "Experimental Method for Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku-Dojin Co., Ltd., 1st edition, 1st print, published on March 1, 1972) and the above. It can be manufactured with reference to the cited references described in the literature.

Specifically, a predetermined amount of the structural unit (Aa) and the structural unit (Ab), a polymerization initiator, a solvent and the like are placed in the reaction vessel, and for example, oxygen is replaced with nitrogen to create an oxygen scavenging atmosphere. Examples thereof include a method of heating and keeping warm while stirring. The polymerization initiator, solvent, and the like used here are not particularly limited, and those usually used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). The solvent may be any solvent that dissolves each monomer, and examples thereof include the solvents described below used in the curable resin composition.

As the obtained resin, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a resin taken out as a solid (powder) by a method such as reprecipitation may be used. You may use it. In particular, by using the solvent used in the curable resin composition of the present invention as the polymerization solvent, the solution after the reaction can be used as it is in the production of the curable resin composition, so that the curable resin composition The manufacturing process can be simplified.

In the resin [K2], the ratio of each constituent unit is the constituent unit (Aa); 2 to 40 mol%, among all the constituent units constituting the resin [K2].
Constituent unit (Ab); 2-95 mol%,
Constituent unit (Ac); preferably 1-65 mol%
Constituent unit (Aa); 5-35 mol%,
Constituent unit (Ab); 5-80 mol%,
Constituent unit (Ac); more preferably 1-60 mol%.

When the ratio of the constituent units of the resin [K2] is within the above range, the curable resin composition tends to be excellent in storage stability, chemical resistance of the obtained film, heat resistance and mechanical strength. The resin [K2] can be produced by the same method as the resin [K1].

The polystyrene-equivalent weight average molecular weight (Mw) of the resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 20,000, and particularly preferably. Is 5,000 to 10,000. When the weight average molecular weight (Mw) of the resin (A) is within the above range, the coatability of the curable resin composition tends to be good.

The dispersity [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (A) is preferably 1.1 to 6.0, more preferably 1.2 to 4.0. When the degree of dispersion is within the above range, the obtained cured film tends to have excellent chemical resistance.

The acid value of the resin (A) is preferably 30 mg-KOH / g or more and 180 mg-KOH / g or less, more preferably 40 mg-KOH / g or more and 150 mg-KOH / g or less, and further preferably 50 mg-KOH / g or more and 135 mg. -KOH / g or less. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined by titrating with an aqueous potassium hydroxide solution. When the acid value of the resin (A) is within the above range, the obtained cured film tends to have excellent adhesion to the transparent conductive substrate.

The content of the resin (A) is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, still more preferably 40 to 70% by mass, based on the solid content of the curable resin composition of the present invention. is there. When the content of the resin (A) is within the above range, the obtained cured film tends to have excellent heat resistance and excellent adhesion to the substrate. Here, the solid content of the curable resin composition means an amount obtained by subtracting the content of the solvent (E) from the total amount of the curable resin composition of the present invention.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating active radicals, acids, etc. by the action of light or heat and initiating the polymerization of the polymerizable compound (B), and is known to initiate polymerization. Agents can be used. As the polymerization initiator (D), a polymerization initiator containing at least one selected from the group consisting of an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound and a biimidazole compound is preferable, and an O-acyloxy compound is preferable. A polymerization initiator containing a compound compound is more preferable. These polymerization initiators tend to have high sensitivity and high transmittance in the visible light region.

The O-acyloxime compound is a compound having a structure represented by the formula (D1). Hereinafter, * represents a bond.

Examples of the O-acyloxym compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-. 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4) −Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-Il] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropane-1 −On-2-imine can be mentioned. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (all manufactured by BASF Corporation) and N-1919 (manufactured by ADEKA Corporation) may be used.

The alkylphenone compound is a compound having a structure represented by the formula (D2-1) or a structure represented by the formula (D2-2). In these structures, the benzene ring may have a substituent.

Examples of the compound having a structure represented by the formula (D2-1) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1-(. 4-Morphorinophenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1- On is mentioned. Commercially available products such as Irgacure (registered trademark) 369, 907 and 379 (all manufactured by BASF Limited) may be used. Further, a polymerization initiator having a group capable of causing chain transfer, which is described in JP-A-2002-544205, may be used. Examples of the compound having a partial structure represented by the formula (D2-2) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4-]. (2-Hydroxyethoxy) phenyl] Propane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, α, α- Examples thereof include diethoxyacetophenone and benzyldimethyl ketal. In terms of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by the formula (D2-1).

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-methoxy). Naftyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) )-1,3,5-Triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- [2- (fran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2) −Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine Be done.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercially available products such as Irgacure 819 (manufactured by BASF Japan Ltd.) may be used.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl) -4. , 4', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4, 4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis ( 2-Chlorophenyl) -4,4', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxy) Phenyl) Biimidazole (see, for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), the phenyl group at the 4,4', 5,5'-position is substituted with a carboalkoxy group. Examples thereof include biimidazole compounds (see, for example, Japanese Patent Application Laid-Open No. 7-10913).

Further, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl- Benzoin compounds such as 4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrene quinone, Kinone compounds such as 2-ethylanthraquinone and benzoin; 10-butyl-2-chloroacrydone, benzyl, methylphenylglycoxylate, titanosen compounds and the like can be mentioned. These can be used in combination with a polymerization initiator (hereinafter, referred to as a polymerization initiator (H)) (particularly amines) described later.

The polymerization initiator (D) also includes an acid generator. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethyl. Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyltosylate, benzoin Tosilate can be mentioned.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 0.5, based on 100 parts by mass of the total content of the resin (A) and the polymerizable compound (B). It is ~ 15 parts by mass, more preferably 1 to 8 parts by mass. When the content of the polymerization initiator (D) is within the above range, the visible light transmittance of the obtained cured film tends to be high.

<Polymerization initiator (H)>
The polymerization initiator (H) is a compound used together with the polymerization initiator (D) and used to promote the polymerization of the polymerizable compound (B) initiated by the polymerization initiator (D), or an increase. It is a sensitive agent.

Examples of the polymerization initiator (H) include thiazolin compounds, amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the thiazolin compound include compounds represented by formulas (H1-1) to (H1-3), compounds described in JP-A-2008-65319, and the like.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4-. 2-Ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis ( Ethylmethylamino) benzophenone and the like can be mentioned, with 4,4′-bis (diethylamino) benzophenone being preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-dibutoxy. Examples thereof include anthracene and 2-ethyl-9,10-dibutoxyanthracene.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone and the like.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, and N. -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.

When the curable resin composition of the present invention contains a polymerizable compound (B), a polymerization initiator (D) and a polymerization initiator (H), the content of the polymerization initiator (H) is the resin (A). The total content of the polymer (B) and the polymerizable compound (B) is 100 parts by mass, preferably 0.1 to 30 parts by mass, and more preferably 0.2 to 10 parts by mass.

<Thiol compound (T)>
The thiol compound (T) is a compound having a sulfanil group (mercapto group; -SH) in the molecule. Of these, a compound having two or more sulfanyl groups is preferable, and a compound having two or more sulfanyl groups bonded to a carbon atom having an aliphatic hydrocarbon structure is more preferable. The curable resin composition of the present invention tends to have high sensitivity at the time of exposure because it contains the thiol compound (T).

Examples of the thiol compound (T) include hexanedithiol, decandithiol, 1,4-bis (methylsulfanyl) benzene, butanediolbis (3-sulfanyl propionate), butanediolbis (3-sulfanyl acetate), and ethylene. Glycolbis (3-sulfanyl acetate), trimethylolpropanthris (3-sulfanyl acetate), butanediol bis (3-sulfanyl propionate), trimethylol propanthris (3-propionate), trimethylolpropanthris (3-sulfanyl) Acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyethyltris (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate), 1 , 4-Bis (3-sulfanylbutyloxy) butane.

The content of the thiol compound (T) is preferably 10 to 90 parts by mass, more preferably 15 to 70 parts by mass with respect to 100 parts by mass of the polymerization initiator (D). When the content of the thiol compound (T) is in this range, the sensitivity during exposure tends to be high.

<Leveling agent (I)>
Examples of the leveling agent (I) include a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the silicone-based surfactant include surfactants having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (manufactured by Momentive Performance Materials Japan GK) and the like. ..

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Megafuck (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F554. R30, RS-718-K (manufactured by DIC Corporation), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, Examples thereof include S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include MegaFvck (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).

When the leveling agent (I) is contained, the content thereof is preferably 0.001% by mass or more and 0.2% by mass or less, and more preferably 0.002% by mass, based on the total amount of the curable resin composition. % Or more and 0.1% by mass or less, more preferably 0.005% by mass or more and 0.07% by mass or less.

<Antioxidant (F)>
Examples of the antioxidant (F) include a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, and an amine-based antioxidant. Of these, phenolic antioxidants are preferred in that the resulting film is less colored.

Examples of the phenolic antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate and 2- [1- (2-hydroxy). -3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5) -Methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis (6-tert-butyl-4-methyl) Phenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (2-tert-butyl-5-methylphenol), 2,2'-thiobis (6-) tert-Butyl-4-methylphenol), 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 3,3', 3 ", 5,5', 5" -hexa-tert-butyl-a, a', a "-(mesitylen-2,4,6-triyl) tri- p-cresol, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol and 6- [3-( 3-tert-Butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosfepine As the phenol-based antioxidant, a commercially available product may be used. Examples of the commercially available phenol-based antioxidant include Sumilyzer (registered trademark) BHT, GM, GS, GP (all of the above). Examples thereof include Sumitomo Chemical Co., Ltd.) and Irganox (registered trademark) 1010, 1076, 1330, 3114 (all manufactured by BASF Co., Ltd.).

Examples of the sulfur-based antioxidant include dilauryl 3,3'-thiodipropionate, dimyristyl 3,3'-thiodipropionate, disstearyl 3,3'-thiodipropionate, and pentaerythrityl tetrakis (3). -Laurylthiopropionate). As the sulfur-based antioxidant, a commercially available product may be used. Examples of commercially available sulfur-based antioxidants include Sumilyzer (registered trademark) TPL-R and TP-D (all manufactured by Sumitomo Chemical Co., Ltd.).

Examples of phosphorus-based antioxidants include trioctyl phosphite, trilauryl phosphite, tridecylphosphite, tris (nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra (tridecyl) -1,1, Examples thereof include 3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphosphite. As the phosphorus-based antioxidant, a commercially available product may be used. Examples of commercially available phosphorus-based antioxidants include Irgaphos (registered trademark) 168, 12, 38 (all manufactured by BASF Corporation), ADEKA STAB 329K, and ADEKA STAB PEP36 (all manufactured by ADEKA Corporation). Can be mentioned.

Examples of amine-based antioxidants include N, N'-di-sec-butyl-p-phenylenediamine, N, N'-di-isopropyl-p-phenylenediamine, and N, N'-dicyclohexyl-p-phenylene. Examples thereof include diamine, N, N'-diphenyl-p-phenylenediamine and N, N'-bis (2-naphthyl) -p-phenylenediamine. As the amine-based antioxidant, a commercially available product may be used. Examples of commercially available amine-based antioxidants include Sumilyzer (registered trademark) BPA, BPA-M1, and 4ML (all manufactured by Sumitomo Chemical Co., Ltd.).

When the curable resin composition of the present invention contains an antioxidant (F), the content thereof is preferably 0 with respect to 100 parts by mass of the total content of the resin (A) and the polymerizable compound (B). .1 part by mass or more and 5 parts by mass or less, more preferably 0.5 parts by mass or more and 3 parts by mass or less. When the content of the antioxidant (F) is within the above range, the obtained cured film tends to have excellent heat resistance.

<Curing agent (G)>
[1] Polyvalent carboxylic acid (G1)
The polyvalent carboxylic acid (G1) is at least one compound selected from the group consisting of polyvalent carboxylic acid anhydrides and polyvalent carboxylic acids. The polyvalent carboxylic acid is a compound having two or more carboxy groups, and the polyvalent carboxylic acid anhydride is an anhydride of the polyvalent carboxylic acid. The molecular weight of the polyvalent carboxylic acid (G1) is preferably 3000 or less, more preferably 1000 or less.

Examples of the polyvalent carboxylic acid anhydride include maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, itaconic acid anhydride, 2-dodecylsuccinic anhydride, 2- (2-octa). -3-Enyl) succinic anhydride, 2- (2,4,6-trimethylnona-3-enyl) succinic anhydride, tricarbaryl anhydride, 1,2,3,4-butanetetracarboxylic acid anhydride Chain polyvalent carboxylic acid anhydrides such as anhydrides; 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hexahydro Phthalic anhydride, 4-methylhexahydrophthalic anhydride, norbornene dicarboxylic acid anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic acid anhydride, bicyclo [2.2.1] heptane -2,3-Dicarboxylic acid anhydride, bicyclo [2.2.1] hepta-5-en-2,3-dicarboxylic acid anhydride, methylbicyclo [2.2.1] hepta-5-en-2, Alicyclic polyvalent carboxylic acid anhydrides such as 3-dicarboxylic acid anhydride and cyclopentanetetracarboxylic acid dianhydride; phthalic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, pyromellitic anhydride , Trimellitic anhydride, benzophenone tetracarboxylic acid anhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic acid anhydride, ethylene glycol bis (anhydrotrimeritate), glycerintris (anhydro) Trimeritate), glycerinbis (anhydrotrimericate) monoacetate, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1, 2-c] Aromatic polyvalent carboxylic acid anhydrides such as furan-1,3-dione; Adeka Hardna (registered trademark) -EH-700 (trade name (same below), manufactured by ADEKA Corporation), Ricacid (registered trademark) -HH, -TH, -MH, MH-700 (Shin Nihon Rika Co., Ltd.) ), Epikinia 126, YH-306, DX-126 (manufactured by Yuka Shell Epoxy Co., Ltd.) and the like.

Examples of the polyvalent carboxylic acid include chain polyvalent carboxylic acids such as oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, and polyvalent carboxylic acids that lead to chain polyvalent carboxylic acid anhydrides. Acids; alicyclic polyvalent carboxylic acids such as cyclohexanedicarboxylic acid, polyvalent carboxylic acid leading to alicyclic polyvalent carboxylic acid anhydrides; isophthalic acid, terephthalic acid, 1,4,5,8-naphthalenetetracarboxylic acid, Aromatic polyvalent carboxylic acids such as polyvalent carboxylic acids that lead to aromatic polyvalent carboxylic acid anhydrides; and the like.

Among them, chain carboxylic acid anhydrides and alicyclic polyvalent carboxylic acid anhydrides are preferable, and alicyclic polyvalents are preferable because the obtained film has excellent heat resistance and the transparency in the visible light region does not easily decrease. Carboxylic anhydride is more preferred.

When the curable resin composition of the present invention contains a polyvalent carboxylic acid (G1), the content thereof is preferably 100 parts by mass based on the total content of the resin (A) and the polymerizable compound (B). It is 1 to 30 parts by mass, more preferably 2 to 20 parts by mass, and further preferably 2 to 15 parts by mass. When the content of the polyvalent carboxylic acid (G1) is within the above range, the obtained cured film is excellent in heat resistance and adhesion.

［式（２）中、Ｒ^３１は、炭素数１〜２０のアルキル基、フェニル基、ベンジル基又は炭素数２〜５のシアノアルキル基を表す。 [2] Imidazole compound (G2)
The imidazole compound (G2) is not particularly limited as long as it is a compound having an imidazole skeleton, excluding the biimidazole compound which is the polymerization initiator (D), and examples thereof include compounds known as epoxy curing agents. Of these, the compound represented by the formula (G2-1) is preferable.

[In the formula (2), R ³¹ represents an alkyl group having 1 to 20 carbon atoms, a phenyl group, a benzyl group or a cyanoalkyl group having 2 to 5 carbon atoms.

R ^{32 to} R ³⁴ independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a nitro group, or an acyl group having 1 to 20 carbon atoms, and the alkyl group and the phenyl group. The hydrogen atom contained in may be substituted with a hydroxy group. ]
Examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isobutyl group, a butyl group, a tert-butyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and a heptadecyl group. , Undecyl group is mentioned.

Examples of the cyanoalkyl group having 2 to 5 carbon atoms include a cyanomethyl group, a cyanoethyl group, a cyanopropyl group, a cyanobutyl group and a cyanopentyl group.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the acyl group having 1 to 20 carbon atoms include a formyl group, an acetyl group, a propionyl group, an isobutyryl group, a valeryl group, an isovaleryl group, a pivaloyl group, a lauroyl group, a myristolyl group and a stearoyl group.

Examples of the imidazole compound (G2) include 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, 5-hydroxymethyl-4-methylimidazole, and 2-ethylimidazole. , 2-Undecylimidazole, 2-Heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-hydroxymethyl-2-phenylimidazole, 2-phenylimidazole, 2-phenyl-2- Hydroxymethylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl-4-phenylimidazole, 1-benzyl-5-hydroxymethylimidazole, 2- (p-hydroxyphenyl) imidazole, 1-cyanomethyl-2-methylimidazole , 1- (2-Cyanoethyl) -2-hydroxymethylimidazole, 2,4-diphenylimidazole, 1-cyanomethyl-2-undecylimidazole, 1-cyanomethyl-2-ethyl-4-methylimidazole, 1-cyanomethyl-2 -Phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole can be mentioned. Of these, 1-benzyl-4-phenylimidazole, 2-ethyl-4-methylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole are preferable.

When the curable resin composition of the present invention contains an imidazole compound (G2), the content thereof is preferably 0, based on 100 parts by mass of the total content of the resin (A) and the polymerizable compound (B). It is 1 part by mass or more and 25 parts by mass or less, more preferably 0.2 parts by mass or more and 15 parts by mass or less, and further preferably 0.5 parts by mass or more and 5 parts by mass or less. When the content of the imidazole compound (G2) is in the above range, the obtained cured film tends to have excellent transparency in the visible light region.

<Solvent (E)>
The curable resin composition of the present invention may contain a solvent (E). The solvent (E) is not particularly limited, and examples thereof include solvents usually used in the art. For example, ester solvent (solvent containing -COO- in the molecule and not containing -O-), ether solvent (solvent containing -O- in the molecule and not containing -COO-), ether ester solvent (solvent in the molecule). Solvent containing -COO- and -O-), Ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing OH in the molecule, -O-,- CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. , Propropylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl Examples thereof include ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyletol and methyl anisole.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy. Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl Examples thereof include ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate.

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone and isophorone. And so on.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol and glycerin.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and mesitylene.

Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

Among the above solvents, an organic solvent having a boiling point of 100 ° C. or higher and 200 ° C. or lower at 1 atm is preferable from the viewpoint of coatability and drying property. As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethylene glycol ethyl methyl ether, cyclohexanone, methoxybutanol and methoxybutyl acetate are preferable, and propylene glycol monomethyl ether More preferred are acetate, propylene glycol monomethyl ether, ethylene glycol ethyl methyl ether, methoxybutanol and methoxybutyl acetate.

The content of the solvent (E) in the curable resin composition of the present invention is preferably 60 to 95% by mass, more preferably 70 to 95% by mass, based on the total amount of the curable resin composition. In other words, the solid content of the curable resin composition of the present invention is preferably 5 to 40% by mass, more preferably 5 to 30% by mass. When the content of the solvent (E) is within the above range, the coatability of the curable resin composition is improved.

<Other ingredients>
The curable resin composition of the present invention is known in the art such as a filler, other polymer compounds, an ultraviolet absorber, a chain transfer agent, an adhesion accelerator, a colorant, a pigment dispersant, etc., if necessary. It may contain an additive.

Further, the curable resin composition of the present invention is filled in a quartz cell having an optical path length of 1 cm, and when the transmittance is measured under the condition of a measurement wavelength of 400 to 700 nm using a spectrophotometer, the average transmittance thereof. The rate is preferably 70% or more, more preferably 80% or more.

When a cured film is formed using the curable resin composition of the present invention, the average transmittance of the cured film is preferably 90% or more, more preferably 95% or more. This average transmittance is measured under the conditions of a measurement wavelength of 400 to 700 nm using a spectrophotometer on a cured film having a thickness of 2 μm after heat curing (100 to 250 ° C., 5 minutes to 3 hours). It is the average value when This makes it possible to provide a cured film having excellent transparency in the visible light region.

<Manufacturing method of curable resin composition>
The curable resin composition of the present invention comprises a resin (A), a polymerizable compound (B), a polymerization initiator (D) and a thiol compound (T), and, if necessary, a solvent (E) polymerization initiator (. It can be produced by mixing H), a leveling agent (I), an antioxidant (F), a curing agent (G) and other components by a known method. After mixing, it is preferable to filter with a filter having a pore size of about 0.05 to 1.0 μm.

<Manufacturing method of cured film>
The cured film can be produced by applying the curable resin composition of the present invention on a substrate, drying the film, and then heating the film. A cured film can be produced by the following steps. Step (2a) and step (2b) are steps required when forming a cured film having a pattern.
Step (1): A step of applying the curable resin composition of the present invention to a substrate,
Step (2): A step of forming a composition layer by drying the curable resin composition after coating under reduced pressure and / or heating and drying.
Step (2a): A step of exposing the composition layer through a photomask.
Step (2b): A step of developing the composition layer after exposure,
Step (3): A step of heating the composition layer after development.

The step (1) is a step of applying the curable resin composition of the present invention to a substrate (base substrate). Examples of the substrate include glass, metal, plastic, and the like, and a color filter, an insulating film, a conductive film, and / or metal wiring may be formed on the substrate. Examples of the conductive film include an ITO (Indiumu Tin Oxide) film which is a transparent conductive film. When a cured film was formed on a substrate containing an ITO film as a transparent conductive film so as to be in contact with the ITO film, it was particularly difficult to improve the heat-resistant adhesion, but according to the curable resin composition of the present invention. A cured film having high heat-resistant adhesion can be formed even on such a substrate.

The curable resin composition is preferably applied onto the substrate by using a coating device such as a spin coater, a slit & spin coater, a slit coater, an inkjet, a roll coater, or a dip coater.

The step (2) is a step of forming a composition layer by drying the curable resin composition after coating under reduced pressure and / or heating and drying. By performing this step, volatile components such as a solvent in the curable resin composition are removed. The vacuum drying is preferably carried out under a pressure of 50 to 150 Pa in a temperature range of 20 to 25 ° C. Heat drying (pre-baking) may be performed before or after vacuum drying. Heat drying is usually performed using a heating device such as an oven or a hot plate. The heat-drying temperature is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

The step (2a) is a step of exposing the composition layer formed by the step (2) through a photomask. As the photomask, a photomask having a light-shielding portion formed corresponding to a portion of the composition layer to be removed is used. The shape of the light-shielding portion is not particularly limited and can be selected according to the intended use. As the light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light less than 350 nm is cut by using a filter that cuts this wavelength range, and light near 436 nm, 408 nm, and 365 nm is selectively extracted by using a bandpass filter that extracts these wavelength ranges. You may do it. Examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp and the like. It is preferable to use an exposure device such as a mask aligner or a stepper because it is possible to uniformly irradiate the entire exposed surface with parallel rays and to accurately align the photomask and the composition layer.

Step (2b) is a step of developing the composition layer after exposure. By bringing the exposed composition layer into contact with a developing solution for development, the unexposed portion of the composition layer is dissolved in the developing solution and removed, and a composition layer having a pattern is formed on the substrate. As the developing solution, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant. The developing method may be any of a paddle method, a dipping method, a spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development. After development, it is preferable to wash with water.

Step (3) is a step of heating the composition layer after development. By heating in the same manner as in the above step (2), the composition layer is cured and a cured film is formed on the substrate. The film thickness of the cured film is preferably 0.3 μm or more and 10 μm or less, and more preferably 0.5 μm or more and 5 μm or less.

Hereinafter, the present invention will be described in more detail by way of examples. Unless otherwise specified, "%" and "part" in the example are mass% and parts by mass.

(Synthesis Example 1)
Nitrogen was flowed at 0.02 L / min into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to create a nitrogen atmosphere, 140 parts of diethylene glycol ethyl methyl ether was added, and the mixture was heated to 70 ° C. with stirring. Then 40 parts of methacrylic acid; and a mixture of monomer (I-1) and monomer (II-1) {monomer (I-1) in the mixture: molar ratio of monomer (II-1) A solution prepared by dissolving 360 parts of = 50: 50} in 190 parts of diethylene glycol ethyl methyl ether was prepared, and this solution was added dropwise to a flask kept at 70 ° C. over 4 hours using a dropping pump.

On the other hand, a solution prepared by dissolving 30 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 240 parts of diethylene glycol ethyl methyl ether was placed in a flask over 5 hours using another dropping pump. Dropped. After the dropping of the polymerization initiator solution was completed, the mixture was kept at 70 ° C. for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin (a1)) having a solid content of 42.6%. The weight average molecular weight (Mw) of the obtained resin (a1) was 8000, the molecular weight distribution (Mw / Mn) was 1.91, and the acid value was 60 mg-KOH / g (acid value in terms of solid content). The resin (a1) has the following structural units.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin obtained above were measured by using the GPC method under the following conditions.
Equipment: K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shima-pack GPC-80M
Column temperature; 40 ° C
Solvent; THF (tetrahydrofuran)
Flow velocity; 1.0 mL / min
Detector; RI
Calibration standard material; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight and the number average molecular weight obtained above was used as the molecular weight distribution.

(Examples 1 to 3 and Comparative Examples 1 and 2)
Each component shown in Table 1 was mixed to obtain each curable resin composition.

Unless otherwise noted in Table 1, the unit is "part". The number of parts contained in the resin (A) represents a mass part in terms of solid content. Each component shown in Table 1 is as follows.

Resin (A); a1; Resin (a1) obtained in Synthesis Example 1
Polymerizable compound (B); b11; 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene (A-BPEF; manufactured by Shin Nakamura Chemical Industry Co., Ltd .; polymerizable compound (B1))

Polymerizable compound (B); b12; OGSOL® EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd .; polymerizable compound (B1))

Polymerizable compound (B); b13; OGSOL® GA-5060P (manufactured by Osaka Gas Chemical Co., Ltd .; polymerizable compound (B1))

Polymerizable compound (B); b21; dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd .; (meth) acrylic compound; polymerizable compound (B2))

Polymerizable compound (B); b22; EBECRYL® 11 (manufactured by Daicel Ornex Co., Ltd .; (meth) acrylic compound; polymerizable compound (B2))

Polymerization Initiator (D); d1; N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure® OXE 01; BASF; oxime compound)
Polymerization Initiator (D); d2; 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole (B-CIM; Hodogaya Chemical Co., Ltd.) Made by Co., Ltd.)
Polymerization Initiator (H); h1; 2-Isopropylthioxanthone (manufactured by IHT)

Imidazole compound (G2); g2; 1-benzyl-2-phenylimidazole (Curesol 1B2PZ; manufactured by Shikoku Chemicals Corporation)

Thiol compound (T); t1; pentaerythritol tetrakis (3-sulfanyl propionate) (PEMP (pentaerythritol tetrakis (3-mercaptopropionate)); manufactured by SC Organic Chemistry Co., Ltd.)
Antioxidant (F); f1; 1,3,5-tris (4-hydroxy-3,5-di-tert-butylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H) , 5H) -Trione (IRGANOX® 3114; manufactured by BASF Japan Ltd.)
Solvent (E); e1; Propropylene glycol monomethyl ether acetate Solvent (E); e2; 3-methoxy-1-butanol Solvent (E); e3; Diethylene glycol ethyl methyl ether Solvent (E) is a solid curable resin composition. The mixture is mixed so that the amount is "solid content (%)" in Table 1, and the values of the solvent components (e1) to (e3) in the solvent (E) represent the mass ratio in the solvent (E).

<Preparation of cured film>
A 2-inch square glass substrate (Eagle XG; manufactured by Corning Inc.) was washed successively with a neutral detergent, water and 2-propanol, and then dried. ITO was vapor-deposited on this glass substrate by sputtering to form an ITO film. A curable resin composition was spin-coated on the surface of the substrate on which the ITO film was formed so that the film thickness after post-baking was about 4 μm (1 second at 0 rpm, and then at 400, 350, or 300 rpm. 5 seconds), then prebaked at 100 ° C. for 3 minutes in a clean oven. Next, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd., light source; ultra-high pressure mercury lamp), the coating film after prebaking was exposed under an atmospheric atmosphere with an exposure amount of 100 mJ / cm ² (365 nm standard). .. In this exposure, the synchrotron radiation from the ultra-high pressure mercury lamp was irradiated through an optical filter (UV-33; manufactured by Asahi Techno Glass Co., Ltd.). After the exposure, it was heated at 230 ° C. for 30 minutes and post-baked to obtain a cured film.

<Heat adhesion>
The substrate on which the cured film was formed was heated at 250 ° C. for 90 minutes in a clean oven as a heat resistance test. After that, following the method of the adhesive grid tape of 8.5.3 of JIS K5400 1990, cuts were made with a cutter knife at 1 mm intervals so as to form a 10 × 10 grid square, and cellophane tape was attached. It was later peeled off, and the number of grids in which 95% or more of the cured film remained in close contact with the substrate without peeling was observed. The results are shown in Table 1.

Claims (4)

A compound having a structural unit derived from at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond. A resin that is a copolymer containing the derived building blocks;
A polymerizable compound having a condensed polycyclic aromatic skeleton and at least one selected from the group consisting of acryloyl groups and methacryloyl groups;
Polymerization initiator; and
A curable resin composition containing a thiol compound. The curable resin composition according to claim 1, wherein the polymerizable compound has a fluorene skeleton as the condensed polycyclic aromatic skeleton. The curable resin composition according to claim 1 or 2, wherein the polymerizable compound is contained in an amount of 30 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the resin. A cured film formed from the curable resin composition according to any one of claims 1 to 3.