JP6135063B2 - Curable resin composition - Google Patents

Description

  The present invention relates to a curable resin composition.

The liquid crystal display device is provided with a protective film for a photo spacer or a color filter, and these are formed from a curable resin composition. As such a curable resin composition, a composition containing a copolymer of methacrylic acid and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate is known as a resin. (Patent Document 1).

JP 2008-181087 A

  Conventionally known curable resin compositions have not always been sufficiently satisfactory in the linearity of the pattern obtained by the curable resin composition.

［式（ｘ）中、Ｒ^ａ１は、水素原子又は炭素数１〜４のアルキル基を表す。
Ｒ^ａ２は、炭素数１〜２０の脂肪族炭化水素基を表す。］
で表される単量体に由来する構造単位とを有する共重合体を含む樹脂であり、
式（ｘ）で表される単量体に由来する構造単位の含有量が、該共重合体を構成する構造単位全量に対して、０．１モル％以上１０モル％以下である硬化性樹脂組成物。
［２］ さらに、重合開始剤を含む［１］記載の硬化性樹脂組成物。
［３］ ［１］又は［２］記載の硬化性樹脂組成物により形成される塗膜。
［４］ ［１］又は［２］記載の硬化性樹脂組成物により形成されるパターン。
［５］ ［３］記載の塗膜及び［４］記載のパターンからなる群から選ばれる少なくとも１種を含む表示装置。 The present invention includes the following inventions.
[1] including a resin and a polymerizable compound,
A monomer having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond A structural unit derived from the formula (x)

[In formula (x), R ^a1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ^a2 represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms. ]
A resin containing a copolymer having a structural unit derived from a monomer represented by:
Curable resin whose content of the structural unit derived from the monomer represented by the formula (x) is 0.1 mol% or more and 10 mol% or less with respect to the total amount of the structural unit constituting the copolymer. Composition.
[2] The curable resin composition according to [1], further comprising a polymerization initiator.
[3] A coating film formed from the curable resin composition according to [1] or [2].
[4] A pattern formed from the curable resin composition according to [1] or [2].
[5] A display device comprising at least one selected from the group consisting of the coating film according to [3] and the pattern according to [4].

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the curable resin composition which can form the pattern which is excellent in linearity.

［式（ｘ）中、Ｒ^ａ１は、水素原子又は炭素数１〜４のアルキル基を表す。
Ｒ^ａ２は、炭素数１〜２０の脂肪族炭化水素基を表す。］
で表される単量体に由来する構造単位とを有する共重合体を含む樹脂であり、
式（ｘ）で表される単量体に由来する構造単位の含有量は、該共重合体を構成する構造単位全量に対して、０．１モル％以上１０モル％以下である。
本発明の硬化性樹脂組成物は、さらに重合開始剤（Ｄ）を含むことが好ましく、さらに溶剤（Ｅ）を含むことがより好ましい。
また、本発明の硬化性樹脂組成物は、必要に応じて、重合開始助剤（Ｄ１）、チオール化合物（Ｔ）、界面活性剤（Ｆ）及び酸化防止剤（Ｇ）からなる群から選ばれる少なくとも１種を含んでもよい。
尚、本発明の硬化性樹脂組成物は、実質的に着色剤を含まない。 The curable resin composition of the present invention includes a resin (B) and a polymerizable compound (C),
The resin (B) has a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having 2 to 4 carbon atoms, and an ethylenically unsaturated bond. A structural unit derived from a monomer and the formula (x)

[In formula (x), R ^a1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ^a2 represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms. ]
A resin containing a copolymer having a structural unit derived from a monomer represented by:
The content of the structural unit derived from the monomer represented by the formula (x) is 0.1 mol% or more and 10 mol% or less with respect to the total amount of the structural unit constituting the copolymer.
The curable resin composition of the present invention preferably further contains a polymerization initiator (D), and more preferably contains a solvent (E).
Moreover, the curable resin composition of this invention is chosen from the group which consists of a polymerization start adjuvant (D1), a thiol compound (T), surfactant (F), and antioxidant (G) as needed. At least one kind may be included.
In addition, the curable resin composition of this invention does not contain a coloring agent substantially.

［式（ｘ）中、Ｒ^ａ１は、水素原子又は炭素数１〜４のアルキル基を表す。
Ｒ^ａ２は、炭素数１〜２０の脂肪族炭化水素基を表す。］
で表される単量体（以下「（ｘ）」という場合がある）に由来する構造単位とを有する共重合体（以下「共重合体（Ａ）」という場合がある）を含み、（ｘ）に由来する構造単位の含有量は、該共重合体（Ａ）を構成する構造単位全量に対して、０．１モル％以上１０モル％以下である。 <Resin (B)>
The resin (B) is a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), and has 2 to 4 carbon atoms. A structural unit derived from a monomer having a cyclic ether structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”), and the formula (x)

[In formula (x), R ^a1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ^a2 represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms. ]
And a copolymer having a structural unit derived from a monomer represented by (hereinafter sometimes referred to as “(x)”) (hereinafter sometimes referred to as “copolymer (A)”), and (x The content of the structural unit derived from) is 0.1 mol% or more and 10 mol% or less with respect to the total amount of the structural unit constituting the copolymer (A).

Examples of the alkyl group having 1 to 4 carbon atoms representing R ^a1 include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group.
R ^a1 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms representing R ^a2 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a dodecyl group. Straight chain aliphatic hydrocarbon groups such as tetradecyl group, hexadecyl group, octadecyl group, octadecenyl group, icosyl group; branched chain aliphatic carbonization such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group A hydrogen group;
R ^a2 is preferably a hydrogen atom or an aliphatic hydrocarbon group having 5 to 20 carbon atoms, more preferably an aliphatic hydrocarbon group having 6 to 18 carbon atoms, and an aliphatic hydrocarbon group having 7 to 18 carbon atoms. It is more preferable that it is an aliphatic hydrocarbon group having 7 to 9 carbon atoms, and an aliphatic hydrocarbon group having 8 carbon atoms is particularly preferable.

Examples of (x) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, isodecyl (meth) acrylate, 2,4,6-trimethylheptyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate Etc.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

Specific examples of (a) 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-cyclohexene dicarboxylic 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 Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene, 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, and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hymic acid anhydride);

Unsaturated mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid and maleic anhydride are preferred from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution.

  (B) is, for example, a polymerizable compound having a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say. (B) is preferably a monomer having a C2-C4 cyclic ether and a (meth) acryloyloxy group.

  Examples of (b) include a monomer (a1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b3)”), etc. Can be mentioned.

  (B1) may be, for example, a monomer (b1-1) having a structure obtained by epoxidizing a linear or branched unsaturated aliphatic hydrocarbon (hereinafter referred to as “(b1-1)”) ), A monomer (b1-2) having a structure obtained by epoxidizing an unsaturated alicyclic hydrocarbon (hereinafter sometimes referred to as “(b1-2)”).

  As (b1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, 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 (glycidyloxymethyl) styrene 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene and 2,4,6- Examples include tris (glycidyloxymethyl) styrene.

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate ( For example, Cyclomer A400 (manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Chemical Industries, Ltd.), represented by formula (I) Examples thereof include compounds and compounds represented by formula (II).

[In Formula (I) and Formula (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.
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, and a tert-butyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy Examples include a -1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
R ^b1 and R ^b2 are preferably 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.

Examples of alkanediyl groups include methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane- Examples include 1,6-diyl group.
As X ^b1 and X ^b2 , a single bond, a methylene group, an ethylene group, * —CH ₂ —O— and * —CH ₂ CH ₂ —O— are preferable, and a single bond and * —CH ₂ CH ₂ —O— are preferable. More preferred. * Represents a bond with O.

  Examples of the compound represented by the formula (I) include compounds represented by any one of the formulas (I-1) to (I-15). Among them, Formula (I-1), Formula (I-3), Formula (I-5), Formula (I-7), Formula (I-9), and Formula (I-11) to Formula (I-15) A compound represented by any one of formula (I-1), formula (I-7), formula (I-9) and formula (I-15) is more preferred.

  Examples of the compound represented by the formula (II) include compounds represented by any one of the formulas (II-1) to (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) and formula (II-11) to formula (II-15) A compound represented by any one of formulas (II-1), (II-7), (II-9) and (II-15) is more preferred.

  The compound represented by the formula (I) and the compound represented by the formula (II) may be used singly or as a mixture in any ratio. When used as a mixture, the content ratio of the compound represented by the formula (I) and the compound represented by the formula (II) is preferably 5:95 to 95: 5, more preferably 10:90 to 5 on a molar basis. 90:10, more preferably 20:80 to 80:20.

  As the monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth) acryloyloxy group is preferable. (B2) includes 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

  As the monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

  (B) is preferably (b1) from the viewpoint that the reliability of the obtained coating film and pattern, such as heat resistance and chemical resistance, can be further increased. Furthermore, (b1-2) is more preferable in that the storage stability of the curable resin composition is excellent.

Further, the copolymer (A) is different from (a), (b) and (x) and is derived from a monomer copolymerizable with these (hereinafter sometimes referred to as “(c)”). You may have a structural unit.
Examples of (c) include cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, and tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth). Acrylate (in this technical field, it is referred to as “dicyclopentanyl (meth) acrylate” as a common name. It may also be referred to as “tricyclodecyl (meth) acrylate”), tricyclo [5.2.1 .0 ^2,6] (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) decene-8-yl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate , Isobornyl (meth) acrylate, adamantyl (meth) acrylate, phenyl (meth) a (Meth) acrylic acid esters such as acrylate, naphthyl (meth) acrylate, 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, diethyl itaconate;

  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] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2′-hydroxyethyl) bicyclo [2.2. 1] hept-2-ene, 5,6-dimethoxybicyclo [2. .1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene Bicyclo unsaturated compounds;

  N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate and N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, and 2,3-dimethyl-1,3-butadiene.
Of these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo [2.2.1] hept-2-ene are preferred from the viewpoints of copolymerization reactivity and heat resistance. Styrene, vinyltoluene and N-cyclohexylmaleimide are more preferred.

When the copolymer (A) is a copolymer comprising a structural unit derived from (x), a structural unit derived from (a), and a structural unit derived from (b), The content ratio is based on the total amount of structural units constituting the copolymer.
Structural unit derived from (x); 0.1 to 10 mol%
Structural unit derived from (a); 2 to 50 mol%
Structural unit derived from (b); 40-97.9 mol%
Is preferred,
Structural unit derived from (x); 0.3 to 8 mol%
Structural unit derived from (a); 5-45 mol%
Structural unit derived from (b); 47-94.7 mol%
Is more preferable. The content molar ratio of the structural unit can be calculated from the mass ratio of the monomers used for the production of the copolymer.
When the ratio of each structural unit is within the above range, the resulting pattern tends to be excellent in linearity.

The copolymer (A) is a copolymer comprising a structural unit derived from (x), a structural unit derived from (a), a structural unit derived from (b), and a structural unit derived from (c). In this case, the content ratio of the structural units derived from each is based on the total amount of structural units constituting the copolymer,
Structural unit derived from (x); 0.1 to 10 mol%
Structural unit derived from (a); 2 to 50 mol%
Structural unit derived from (b); 10-92.9 mol%
Structural unit derived from (c); 5-87.9 mol%
Is preferred,
Structural unit derived from (x); 0.3 to 8 mol%
Structural unit derived from (a); 5-45 mol%
Structural unit derived from (b); 20-70 mol%
Structural unit derived from (c); 10-70 mol%
Is more preferable.
When the ratio of each structural unit is within the above range, the resulting pattern tends to be excellent in linearity. Furthermore, the dried product of the curable resin composition tends to be excellent in solubility in an organic solvent. Therefore, even if the dry matter is generated at the discharge unit of the coating apparatus, the curable resin composition or the cleaning liquid supplied to the discharge unit dissolves quickly, and foreign matter generated on the substrate is reduced.

  The copolymer (A) is prepared by, for example, the method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, Publishing Co., Ltd., Chemical Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and It can manufacture with reference to the cited reference described in the said literature.

  Specifically, a predetermined amount of (x), (a), (b) and, if necessary, (c), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and, for example, nitrogen is substituted with oxygen. Thus, there is a method of heating and keeping warm while stirring in a deoxygenated atmosphere. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and those usually used in the field can be used. For example, as polymerization initiators, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.) As the solvent, any solvent that dissolves each monomer may be used, and examples of the solvent for the curable resin composition include a solvent (E) described later.

  In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using a solvent (E) described later as a solvent in the polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.

The polystyrene equivalent weight average molecular weight of the copolymer (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. It is. When the molecular weight is in the above range, the hardness of the pattern and the coating film is improved, the residual film ratio is high, the solubility in the developer in the unexposed area is good, and the resolution tends to be improved.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the copolymer (A) is preferably 1.1 to 6, and more preferably 1.2 to 4.

  The acid value of the copolymer (A) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150, still more preferably 70 to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin, and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

The resin (B) may contain a resin different from the copolymer (A) (hereinafter sometimes referred to as “resin (B ′)”). The resin (B ′) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B ′) include the following resins [K1] to [K6].
Resin [K1]: Copolymer of (a) and (b);
Resin [K2]: Copolymer of (a), (b) and (c);
Resin [K3]: Copolymerization of (a) with a monomer copolymerizable with (a) and different from (a) and (b) (hereinafter sometimes referred to as “(c ′)”) Coalescence;
Resin [K4]: a resin obtained by reacting (b) with a copolymer of (a) and (c ′);
Resin [K5]: a resin obtained by reacting (a) with a copolymer of (b) and (c ′);
Resin [K6]: A resin obtained by reacting (a) with a copolymer of (b) and (c ′) and further reacting with a carboxylic acid anhydride.
Here, examples of (c ′) include the monomers exemplified in the above (x) and (c).

In the resin [K1], the ratio of the structural units derived from each is relative to all the structural units constituting the resin [K1].
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (b); 40-98 mol%
Is preferred,
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (b); 50-90 mol%
Is more preferable.
When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability of the curable resin composition, the developability when forming the pattern, and the solvent resistance of the resulting pattern and coating film are excellent. Tend.
Resin [K1] can be produced, for example, in the same manner as described in the method for producing copolymer (A).

In the resin [K2], the ratio of the structural units derived from each of the structural units in the resin [K2]
Structural unit derived from (a); 2-45 mol%
Structural unit derived from (b); 2 to 95 mol%
Structural unit derived from (c); 1 to 65 mol%
It is preferable that
Structural unit derived from (a); 5 to 40 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (c); 5 to 60 mol%
It is more preferable that
When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the curable resin composition, the developability when forming a pattern, and the solvent resistance of the resulting pattern and coating film, There is a tendency to be excellent in heat resistance and mechanical strength.
Resin [K2] can be produced, for example, in the same manner as described in the method for producing copolymer (A).

In the resin [K3], the proportion of structural units derived from each of the structural units constituting the resin [K3]
Structural unit derived from (a); 2 to 60 mol%
Structural unit derived from (c ′); 40 to 98 mol%
It is preferable that
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (c ′); 50-90 mol%
It is more preferable that
Resin [K3] can be produced, for example, in the same manner as described in the method for producing copolymer (A).

Resin [K4] obtains a copolymer of (a) and (c ′), and (b) has a carboxylic acid and / or carboxylic acid anhydride having (a) a cyclic ether having 2 to 4 carbon atoms. It can be manufactured by adding to a product.
First, a copolymer of (a) and (c ′) is produced in the same manner as the method described as the production method of the copolymer (A). In this case, it is preferable that the ratio of the structural units derived from each is the same as that described for the resin [K3].

Next, the C2-C4 cyclic ether which (b) has is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer.
Subsequent to the production of the copolymer of (a) and (c ′), the atmosphere in the flask is replaced with nitrogen to air, and (b) a reaction catalyst (for example, tris) of carboxylic acid or carboxylic anhydride and cyclic ether is used. (Dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (eg, hydroquinone, etc.) are placed in a flask and reacted, for example, at 60-130 ° C. for 1-10 hours to produce resin [K4]. Can do.
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By using this range, the storage stability of the curable resin composition, the developability when forming a pattern, and the solvent and heat resistance, mechanical strength, and sensitivity of the resulting pattern and coating film are well balanced. Tend to be. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c ′). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c ′).
The reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, and the like.

Resin [K5] obtains a copolymer of (b) and (c ′) as the first step, as in the method described as the method for producing copolymer (A). Similarly to the above, the obtained copolymer may be used as it is after the reaction, or may be a concentrated or diluted solution, or may be solid (powder) by a method such as reprecipitation. You may use what was taken out as.
The ratio of the structural units derived from (b) and (c ′) is preferably in the following range with respect to the total number of moles of all structural units constituting the copolymer.
Structural unit derived from (b); 5-95 mol%
Structural unit derived from (c ′); 5-95 mol%
It is preferable that
Structural unit derived from (b); 10-90 mol%
Structural unit derived from (c ′); 10 to 90 mol%
It is more preferable that

Furthermore, the carboxylic acid or carboxylic acid possessed by (a) is added to the cyclic ether derived from (b) possessed by the copolymer of (b) and (c ′) under the same conditions as in the resin [K4] production method. Resin [K5] can be obtained by reacting an anhydride.
As for the usage-amount of (a) made to react with the said copolymer, 5-80 mol is preferable with respect to 100 mol of (b). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K5], and (b1-1) is more preferable.

Resin [K6] is a resin obtained by further reacting carboxylic anhydride with resin [K5]. Carboxylic anhydride is reacted with a hydroxy group generated by reaction of cyclic ether with carboxylic acid or carboxylic anhydride.
Carboxylic anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (highmic acid anhydride) and the like. It is done. As for the usage-amount of carboxylic acid anhydride, 0.5-1 mol is preferable with respect to 1 mol of usage-amount of (a).

Specifically, as the resin (B ′), 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^{2 .6} ] Resin such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (Meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3 -Resin such as (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / (Meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer resin [K3]; glycidyl (meth) acrylate added to benzyl (meth) acrylate / (meth) acrylic acid copolymer Resin, resin obtained by adding glycidyl (meth) acrylate to tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) Resin [K4] such as resin obtained by adding glycidyl (meth) acrylate to acrylic acid copolymer; (meth) acrylic acid was reacted with tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate copolymer Resin, of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resin [K5] such as a resin obtained by reacting a copolymer with (meth) acrylic acid; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid Furthermore, resin [K6] such as a resin obtained by reacting tetrahydrophthalic anhydride may be used.
These resins may be used alone or in combination of two or more.

  Among these, as the resin (B ′), the resin [K1], the resin [K2], and the resin [K3] are preferable.

The polystyrene equivalent weight average molecular weight of the resin (B ′) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. is there. When the molecular weight is in the above range, the hardness of the pattern and the coating film is improved, the residual film ratio is high, the solubility in the developer in the unexposed area is good, and the resolution tends to be improved.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B ′) is preferably 1.1 to 6, and more preferably 1.2 to 4.

  The acid value of the resin (B ′) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150, and still more preferably 70 to 135 mg-KOH / g.

  The resin (B ′) may not be contained, but the content of the resin (B ′) is preferably 70% by mass or less, more preferably 50% by mass or less with respect to the total amount of the resin (B). is there.

The content of the resin (B) is preferably 25 to 70% by mass and more preferably 35 to 60% by mass with respect to the total amount of the solid content. When the content of the resin (B) is within the above range, the resolution of the pattern and the remaining film rate tend to be improved.
Here, the “total amount of solids” in this specification refers to an amount obtained by removing the content of the solvent from the total amount of the curable resin composition. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by heat or an active radical and / or acid generated from the polymerization initiator (D). For example, a compound having a polymerizable ethylenically unsaturated bond is used. Preferably, it is a (meth) acrylic acid ester compound.

As the polymerizable compound (C), a polymerizable compound having three or more ethylenically unsaturated bonds is preferable. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) ) Isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol Hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Is mentioned. These polymerizable compounds may be used alone or in combination of two or more.
Of these, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

  The weight average molecular weight of the polymerizable compound (C) is preferably from 150 to 2,900, more preferably from 250 to 1,500.

  The content of the polymerizable compound (C) is preferably 25 to 70% by mass and more preferably 35 to 60% by mass with respect to the total amount of the solid content. When the content of the polymerizable compound (C) is in the above range, the pattern remaining film ratio and chemical resistance tend to be improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an O-acyl oxime compound, an alkylphenone compound, a triazine compound, an acyl phosphine oxide compound, and a biimidazole compound. A polymerization initiator containing an acyloxime compound is more preferable. These polymerization initiators tend to be highly sensitive and have high transmittance in the visible light region.

Ｏ−アシルオキシム化合物としては、例えば、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）−３−シクロペンチルプロパン−１−オン−２−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−｛２−メチル−４−（３，３−ジメチル−２，４−ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−イミン、Ｎ−ベンゾイルオキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−オン−２−イミン等が挙げられる。イルガキュア（登録商標）ＯＸＥ０１、ＯＸＥ０２（以上、ＢＡＳＦ社製）、Ｎ−１９１９（ＡＤＥＫＡ社製）等の市販品を用いてもよい。 The O-acyl oxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane- 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4) -Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9 Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl)- 9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) may be used.

The alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In these partial structures, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4 -Morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one Etc. Commercial products such as Irgacure (registered trademark) 369, 907 and 379 (manufactured by BASF) may be used. Moreover, you may use the polymerization initiator which has the group which can raise | generate chain transfer described in the Japanese translations of PCT publication No. 2002-544205 gazette.
Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2 -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxy Examples include acetophenone and benzyl dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy Naphthyl) -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- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2) -Methylphenyl) Thenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercial products such as Irgacure 819 (manufactured by Ciba Japan) 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 and JP-A-6-75373), 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 (for example, see JP-B-48-38403, JP-A-62-174204, etc.), and the phenyl group at the 4,4′5,5′-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (for example, see JP-A-7-10913).

  Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 Benzophenone compounds such as '-methyldiphenyl sulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2 -Quinone compounds such as ethyl anthraquinone and camphor quinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like. These are preferably used in combination with a polymerization initiation assistant (D1) (particularly amines) described later.

Furthermore, an acid generator can be used as the polymerization initiator (D).
Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl. Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, Examples thereof include benzoin tosylate.

  The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is -15 mass parts, More preferably, it is 1-8 mass%. If the content of the polymerization initiator (D) is in the above range, the sensitivity is increased and the exposure time tends to be shortened, so that the productivity is improved and the visible light transmittance of the resulting pattern tends to be high. There is.

  In addition to the polymerization initiator (D), a polymerization initiation assistant (D1) may further be included. The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the photopolymerizable compound that has been polymerized by the polymerization initiator.

  Examples of the polymerization initiation aid (D1) include thiazoline compounds, amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

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

  Examples of amine compounds 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, and 4,4′-bis (diethylamino) benzophenone is preferred. Commercial products such as EAB-F (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. Anthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

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

Carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.
The polymerization initiation assistant (D1) may be used alone or in combination of two or more.

  When these polymerization initiation assistants (D1) are used, the amount used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Preferably it is 1-20 mass parts. When the amount of the polymerization initiation assistant (D1) is within this range, the sensitivity tends to be higher when forming a pattern.

<Thiol compound (T)>
The thiol compound (T) is a compound having a sulfanyl group (—SH) in the molecule. Among them, a compound having two or more sulfanyl groups is preferable, and a compound having two or more sulfanyl groups bonded to a carbon atom of an aliphatic hydrocarbon structure is more preferable.

  Examples of the thiol compound (T) include hexanedithiol, decanedithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanylpropionate), butanediol bis (3-sulfanyl acetate), ethylene Glycol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanylpropionate), trimethylolpropane tris (3-sulfanylpropionate), trimethylolpropane tris ( 3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanyl acetate), trishydroxyethyl Squirrel (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate), 1,4-bis (3-sulfanyl-butyloxy) include butane and the like.

  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 within this range, the sensitivity tends to be high and the developability tends to be good.

<Solvent (E)>
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. Examples of the solvent (E) include ester solvents (solvents containing —COO— in the molecule and not containing —O—), ether solvents (solvents containing —O— in the molecule and not containing —COO—). , Ether ester solvents (solvents containing —COO— and —O— in the molecule), ketone solvents (solvents containing —CO— in the molecule and not containing —COO—), alcohol solvents, aromatic hydrocarbon solvents Amide solvent and dimethyl sulfoxide.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, 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, and γ-butyrolactone.

  Ether solvents 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, propylene glycol monoethyl ether , Propylene 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, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, include phenetol and methyl anisole and the like.

  Examples of ether ester solvents 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, dipropylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate, and the like.

  Examples of 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. Etc.

  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.

These solvents may be used alone or in combination of two or more.
Among the above solvents, an organic solvent having a boiling point at 1 atm of 120 ° C. or higher and 180 ° C. or lower is preferable from the viewpoints of coating properties and drying properties. Among these, ethyl lactate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol methyl ethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol and a mixed solvent containing these are preferable.

  Content of a solvent (E) becomes like this. Preferably it is 60-95 mass% with respect to the total amount of curable resin composition, More preferably, it is 70-95 mass%. In other words, the solid content of the curable resin composition is preferably 5 to 40% by mass, and more preferably 5 to 30% by mass. Here, solid content means the quantity remove | excluding the solvent (E) from curable resin composition. If the content of the solvent (E) is in the above range, the flatness of the film coated with the curable resin composition tends to be high.

<Surfactant (F)>
Examples of the surfactant (F) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade names: 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, TSF-4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) Can be mentioned.

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

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be given.

These surfactants may be used alone or in combination of two or more.
The content of the surfactant (F) is preferably 0.001% by mass to 0.2% by mass, and preferably 0.002% by mass to 0.1%, based on the total amount of the curable resin composition. It is not more than mass%, more preferably not less than 0.01 mass% and not more than 0.05 mass%. By containing the surfactant in this range, the flatness of the coating film can be improved.

<Antioxidant (G)>
The curable resin composition of the present invention may contain an antioxidant (G).
Examples of the antioxidant (G) include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2- [1- (2- Hydroxy-3,5-di-tert-pentylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy ] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphine, 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′-methyl Renbis (6-tert-butyl-4-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 4,4′-thiobis (2-tert-butyl-5-methylphenol) ), 2,2′-thiobis (6-tert-butyl-4-methylphenol), dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′- Thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), 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 "-(mesitichi -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, etc. Commercial products such as IRGANOX 3114 (manufactured by Ciba Japan) may be used.

  The content of the antioxidant (G) is preferably 0.1 parts by mass or more and 5 parts by mass or less, and 0.5 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). More preferred is 3 parts by mass or less. When the content of the antioxidant (G) is within the above range, the resulting coating film tends to be excellent in heat resistance and pencil hardness.

<Other ingredients>
The curable resin composition of the present invention may contain additives known in the art, such as fillers, other polymer compounds, adhesion promoters, light stabilizers, and chain transfer agents, as necessary.

  The curable resin composition of the present invention does not substantially contain colorants such as pigments and dyes. That is, in the curable resin composition of the present invention, the content of the colorant relative to the whole composition is usually less than 1% by mass, preferably less than 0.5% by mass.

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

  When the curable resin composition of the present invention is used as a coating film, the average transmittance of the coating 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 for a coating film having a thickness of 3 μm after heat curing (for example, 100 to 250 ° C., 5 minutes to 3 hours). It is an average value when measured by. Thereby, the coating film excellent in transparency in the visible light region can be provided.

<Method for producing curable resin composition>
The curable resin composition of the present invention includes, for example, a resin (B), a polymerizable compound (C), a polymerization initiator (D) used as necessary, a polymerization initiation assistant (D1), a surfactant (F ), Antioxidant (G) and other components can be prepared by mixing with solvent (E). The mixed curable resin composition is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

<Method for producing coating film and pattern>
Examples of the method for producing a pattern from the curable resin composition of the present invention include a photolithographic method, an ink jet method, and a printing method. Of these, the photolithographic method is preferable. The photolithographic method is a method in which the curable resin composition is applied to a substrate and dried to form a composition layer, and the composition layer is exposed through a photomask and developed. In the photolithographic method, a coating film that is a cured product of the composition layer can be formed by not using a photomask and / or not developing during exposure.
The film thickness of the coating film and pattern to be produced is not particularly limited, and can be appropriately adjusted according to the purpose and application, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, more preferably 0. .5-6 μm.

  As a substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate such as soda lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the substrate In addition, an aluminum, silver, silver / copper / palladium alloy thin film or the like is used. On these substrates, a color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

Formation of the pattern by the photolithographic method can be performed by a known or conventional apparatus or conditions. For example, it can be produced as follows.
First, a curable resin composition is applied on a substrate, dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth composition layer is obtained.
Examples of the coating method include spin coating, slit coating, and slit and spin coating.
30-120 degreeC is preferable and the temperature in the case of performing heat drying has more preferable 50-110 degreeC. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
When performing vacuum drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.
The film thickness of the composition layer is not particularly limited, and can be appropriately adjusted depending on the material used, application, and the like. The composition layer is formed so that the film thickness of the resulting pattern or coating film is, for example, 0.1 to 20 μm, preferably 0.5 to 6 μm.

Next, the composition layer is exposed through a photomask. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specific examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.
It is preferable to use an exposure apparatus such as a mask aligner or a stepper because the entire exposure surface can be irradiated with parallel light rays uniformly and the photomask and substrate can be accurately aligned.

By developing the exposed composition layer in contact with a developer, a structure, that is, a pattern (photocuring pattern) is formed on the substrate. By the development, the unexposed portion of the composition layer is dissolved and removed in the developer. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, 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 paddle method, dipping method, 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.

  Furthermore, it is preferable to post-bake the obtained pattern (photocuring pattern). Curing of the pattern (photocuring pattern) proceeds by post-baking, and a pattern (thermosetting pattern) with improved hardness and durability is obtained. The post-bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-bake time is preferably 0.5 to 120 minutes, more preferably 1 to 60 minutes.

  The patterns and coating films thus obtained are transparent films, patterns, photo spacers, overcoats, insulating films, projections for controlling liquid crystal alignment, micro lenses, coat layers, etc. constituting part of the color filter substrate and / or array substrate. Useful as. In addition, a color filter substrate, an array substrate, and the like provided with these coating films or patterns as a part of their constituent parts, and a display device including these color filter substrate and / or array substrate, for example, a liquid crystal display device, an organic It can be used for EL devices, electronic paper, and the like.

  Next, the present invention will be described more specifically with reference to examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.

一方、重合開始剤２，２’−アゾビス（２，４−ジメチルバレロニトリル）３０部をプロピレングリコールモノメチルエーテルアセテート１０５部に溶解した溶液を、別の滴下ロートを用いて４時間かけてフラスコ内に滴下した。重合開始剤の溶液の滴下が終了した後、４時間、７０℃に保持し、その後室温まで冷却して、重量平均分子量Ｍｗが１．０１×１０^４、分子量分布が２．０、固形分が３７％、固形分酸価が１１０ｍｇ−ＫＯＨ／ｇの共重合体Ａ１溶液を得た。共重合体Ａ１は、以下の構造単位を有する。

[Synthesis Example 1]
Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, and 165 parts of propylene glycol monomethyl ether acetate was added and heated to 70 ° C. with stirring. Subsequently, 39 parts of acrylic acid, 5.2 parts of 2-ethylhexyl acrylate, 57 parts of p-vinyltoluene and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (formula (I-1 ) And the compound represented by formula (II-1) are mixed at a molar ratio of 50:50) 159 parts are dissolved in 140 parts of propylene glycol monomethyl ether acetate to prepare a solution, This solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping funnel.

On the other hand, a solution obtained by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 105 parts of propylene glycol monomethyl ether acetate was placed in a flask over 4 hours using another dropping funnel. It was dripped. After dropping of the solution of the polymerization initiator is completed, the temperature is kept at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight Mw is 1.01 × 10 ⁴ , the molecular weight distribution is 2.0, and the solid content is A copolymer A1 solution having 37% and a solid content acid value of 110 mg-KOH / g was obtained. Copolymer A1 has the following structural units.

[Synthesis Example 2]
Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, and 160 parts of propylene glycol monomethyl ether acetate was added and heated to 70 ° C. with stirring. Next, 52 parts of acrylic acid, 5.2 parts of 2-ethylhexyl acrylate, 57 parts of p-vinyltoluene and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (formula (I-1 ) And the compound represented by formula (II-1) in a molar ratio of 50:50) 146 parts are dissolved in propylene glycol monomethyl ether acetate 140 parts to prepare a solution, This solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping funnel.
On the other hand, a solution obtained by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 105 parts of propylene glycol monomethyl ether acetate was placed in a flask over 4 hours using another dropping funnel. It was dripped. After dropping of the solution of the polymerization initiator is completed, the temperature is kept at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight Mw is 1.01 × 10 ⁴ , the molecular weight distribution is 2.0, and the solid content is A copolymer A2 solution having 38% and a solid content acid value of 143 mg-KOH / g was obtained. Copolymer A2 has the following structural units.

[Synthesis Example 3]
Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, and 255 parts of propylene glycol monomethyl ether acetate was added and heated to 70 ° C. with stirring. Subsequently, 46 parts of acrylic acid, 4.1 parts of 2-ethylhexyl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and 225 parts of the compound represented by the formula (II-1) are mixed at a molar ratio of 50:50) and dissolved in 160 parts of propylene glycol monomethyl ether acetate to prepare a solution. Was added dropwise to the flask kept at 70 ° C. over 4 hours.
On the other hand, a solution obtained by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 295 parts of propylene glycol monomethyl ether acetate was placed in a flask for 4 hours using another dropping funnel. It was dripped. After completion of the dropwise addition of the polymerization initiator solution, the temperature is maintained at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight Mw is 9.74 × 10 ³ , the molecular weight distribution is 2.1, the solid content is A copolymer A3 solution having 26% solid acid value of 127 mg-KOH / g was obtained. Copolymer A3 has the following structural units.

[Synthesis Example 4]
Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, and 160 parts of propylene glycol monomethyl ether acetate was added and heated to 70 ° C. with stirring. Then 47 parts acrylic acid, 3.9 parts lauryl acrylate, 57 parts p-vinyltoluene and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (in formula (I-1) The compound represented by formula (II-1) and the compound represented by formula (II-1) are mixed at a molar ratio of 50:50) 152 parts are dissolved in 140 parts of propylene glycol monomethyl ether acetate to prepare a solution. The liquid was dropped into a flask kept at 70 ° C. for 4 hours using a dropping funnel.
On the other hand, a solution obtained by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 105 parts of propylene glycol monomethyl ether acetate was placed in a flask over 4 hours using another dropping funnel. It was dripped. After dropping of the solution of the polymerization initiator is completed, the temperature is kept at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight Mw is 1.05 × 10 ⁴ , the molecular weight distribution is 2.0, and the solid content is A copolymer A4 solution having a solid acid value of 38 mg-KOH / g was obtained in an amount of 38%. Copolymer A4 has the following structural units.

[Synthesis Example 5]
Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, and 160 parts of propylene glycol monomethyl ether acetate was added and heated to 70 ° C. with stirring. Next, 47 parts of acrylic acid, 3.9 parts of stearyl acrylate, 57 parts of p-vinyltoluene and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (in formula (I-1) The compound represented by formula (II-1) and the compound represented by formula (II-1) are mixed at a molar ratio of 50:50) 152 parts are dissolved in 140 parts of propylene glycol monomethyl ether acetate to prepare a solution. The liquid was dropped into a flask kept at 70 ° C. for 4 hours using a dropping funnel.
On the other hand, a solution obtained by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 105 parts of propylene glycol monomethyl ether acetate was placed in a flask over 4 hours using another dropping funnel. It was dripped. After completion of the dropwise addition of the polymerization initiator solution, the temperature is maintained at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight Mw is 9.94 × 10 ³ , the molecular weight distribution is 2.0, and the solid content is A copolymer A5 solution having a solid acid value of 37% and a solid content acid value of 137 mg-KOH / g was obtained. Copolymer A5 has the following structural units.

[Synthesis Example 6]
Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, and 160 parts of propylene glycol monomethyl ether acetate was added and heated to 70 ° C. with stirring. Next, 47 parts of acrylic acid, 3.9 parts of 2,4,6-trimethylheptyl methacrylate, 57 parts of p-vinyltoluene and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate ( The compound represented by the formula (I-1) and the compound represented by the formula (II-1) are mixed at a molar ratio of 50:50) and 152 parts are dissolved in 140 parts of propylene glycol monomethyl ether acetate. A solution was prepared, and this solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping funnel.
On the other hand, a solution obtained by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 105 parts of propylene glycol monomethyl ether acetate was placed in a flask over 4 hours using another dropping funnel. It was dripped. After dropping of the solution of the polymerization initiator is completed, the temperature is maintained at 70 ° C. for 4 hours, and then cooled to room temperature. The weight average molecular weight Mw is 9.90 × 10 ³ , the molecular weight distribution is 2.0, and the solid content is A copolymer A6 solution having a solid acid value of 38% and a solid content acid value of 133 mg-KOH / g was obtained. Copolymer A6 has the following structural units.

[Synthesis Example 7]
In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was allowed to flow at 0.02 L / min to form a nitrogen atmosphere, and 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were added. Heat to 70 ° C. with stirring. Subsequently, 60 parts by mass of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate (a compound represented by the formula (I-1) and a formula (II-1) (Mix ratio of the compound to be prepared is a 50:50 mixture.) A solution is prepared by dissolving 240 parts by mass in 140 parts by mass of 3-methoxybutyl acetate, and the resulting solution is added over 4 hours using a dropping funnel. And dropped in a flask kept at 70 ° C. On the other hand, a solution in which 30 parts by mass of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 225 parts by mass of 3-methoxybutyl acetate was added to a flask over another 4 hours using another dropping funnel. It was dripped in. After dropping of the solution of the polymerization initiator is completed, the resin is kept at 70 ° C. for 4 hours and then cooled to room temperature, and has a solid content of 32.6% by mass and an acid value of 110 mg-KOH / g (in terms of solid content). A B′1 solution was obtained. The obtained resin Aa had a weight average molecular weight Mw of 13,400 and a molecular weight distribution of 2.50.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in the synthesis example were measured using the GPC method under the following conditions.
Apparatus; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shim-pack GPC-80M
Column temperature: 40 ° C
Solvent; THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Detector; RI
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The polystyrene-converted weight average molecular weight and number average molecular weight ratio (Mw / Mn) obtained above was defined as molecular weight distribution.

Example 1
(Preparation of curable resin composition)
Copolymer (A): Copolymer A1 (solid content conversion) 60 parts Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 40 parts Polymerization start Agent (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF; O-acyloxime compound) 5 parts Solvent (E): Ethyl lactate 266 parts Solvent (E): Propylene glycol monomethyl ether acetate 86 parts Leveling agent (F): Polyether-modified silicone oil (Toray Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.11 part By mixing, a curable resin composition was obtained.

[Average transmittance of composition]
Each of the obtained curable resin compositions was averaged at 400 to 700 nm using an ultraviolet-visible near-infrared spectrophotometer (V-650; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). The transmittance (%) was measured. The results are shown in Table 1.

[Formation of coating film]
A 2-inch square glass substrate (Eagle XG; manufactured by Corning) was sequentially washed with a neutral detergent, water and alcohol and then dried. The curable resin composition obtained above was spin-coated on this glass substrate so that the film thickness after post-baking was 3.0 μm, and then pre-baked at 90 ° C. for 3 minutes in a clean oven. Then, it heated at 230 degreeC for 20 minutes, and obtained the coating film.

[Transparency of coating film]
About the obtained coating film, the average transmittance | permeability (%) in 400-700 nm was measured using the microspectrophotometer (OSP-SP200; OLYMPUS company make). If the transmittance | permeability of a coating film is high, the transmittance | permeability will also be high in the pattern formed from the same curable resin composition. The results are shown in Table 1.

[Create pattern]
On a 2-inch square glass substrate (Eagle 2000; manufactured by Corning), the curable resin composition was applied by spin coating so that the film thickness after post-baking was 2.0 μm, and then at 100 ° C. A composition layer was formed by pre-baking for 3 minutes. After cooling, the distance between the substrate on which the composition layer is formed and the quartz glass photomask is set to 80 μm, and exposure is performed at 40 mJ / cm ^{2 in} an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). Light was irradiated in an amount (based on 365 nm). A photomask having a 50 μm line and space pattern was used. The composition layer after the light irradiation was developed by being immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C. for 60 seconds, washed with water, A pattern was obtained by post-baking at 20 ° C. for 20 minutes. About the obtained pattern, when the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd.), it was confirmed to be 2.0 μm.

[Evaluation of pattern linearity]
About the obtained pattern, using a scanning electron microscope (S-4000; manufactured by Hitachi High-Technologies Corporation), the shape was observed from the top surface at a magnification of 10,000 times, and the fluctuation width of the pattern edge (line edge roughness) Was measured. When the deflection width was 0.4 μm or less, “◎”, when it exceeded 0.4 μm and 0.8 μm or less, “◯”, and when it exceeded 0.8 μm, “×”. The results are shown in Table 1.
For example, when a pattern is used as a photospacer, if the fluctuation width is large, variations in the mechanical characteristics of the pattern become large, and thus display unevenness may occur in a liquid crystal display device including the pattern.

Example 2
A curable resin composition was obtained in the same manner as in Example 1 except that 60 parts of copolymer A1 (in terms of solid content) was replaced with 60 parts of copolymer A2 (in terms of solid content). The curable resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Reference example 3
A curable resin composition was obtained in the same manner as in Example 1, except that 60 parts of copolymer A1 (converted to solid content) was replaced with 60 parts of copolymer A3 (converted to solid content). The curable resin composition was evaluated in the same manner as in Example 1. The results are shown in Table 1.

Reference example 4
A curable resin composition is obtained in the same manner as in Example 1 except that 60 parts of copolymer A1 (in terms of solid content) is replaced with 60 parts of copolymer A4 (in terms of solid content). About this curable resin composition, operation similar to Example 1 was performed. The results are shown in Table 1.

Reference Example 5
A curable resin composition is obtained in the same manner as in Example 1 except that 60 parts of copolymer A1 (in terms of solid content) is replaced with 60 parts of copolymer A5 (in terms of solid content). About this curable resin composition, operation similar to Example 1 was performed. The results are shown in Table 1.

Reference Example 6
A curable resin composition is obtained in the same manner as in Example 1 except that 60 parts of the copolymer A1 (in terms of solid content) is replaced with 60 parts of the copolymer A6 (in terms of solid content). About this curable resin composition, operation similar to Example 1 was performed. The results are shown in Table 1.

Comparative Example 1
(Preparation of curable resin composition)
Resin (B): Resin B′1 (solid content conversion) 60 parts Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 40 parts Polymerization initiator ( D): N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine (Irgacure (registered trademark) OXE 02; manufactured by BASF) 2 Part Solvent (E): 3-methoxy-1-butanol 39 parts Solvent (E): Propylene glycol monomethyl ether acetate 161 parts Solvent (E): Ethyl 3-ethoxypropionate 78 parts Solvent (E): 3-methoxybutyl acetate 63 parts were mixed to obtain a curable resin composition. The same operation as in Example 1 was performed for evaluation. The results are shown in Table 1.

  From the above results, it was confirmed that the pattern formed by the curable resin composition of the present invention was excellent in linearity. From this, it turns out that according to this invention, the curable resin composition which can manufacture the display apparatus excellent in a display characteristic was able to be provided.

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the curable resin composition which can form the pattern which is excellent in linearity.
The pattern and coating film obtained from the curable resin composition of the present invention are a transparent film, pattern, photo spacer, overcoat, insulating film, and liquid crystal alignment control that constitute a part of the color filter substrate and / or array substrate. Useful as protrusions, microlenses, coat layers, etc., and color filter substrates, array substrates, etc., comprising these coating films or patterns as part of their constituent parts, and further comprising these color filter substrates and / or array substrates, etc. It can be suitably used for a display device such as a liquid crystal display device, an organic EL device, and electronic paper.

Claims (4)

A resin, a polymerization initiator and a polymerizable compound,
A structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, or a structural unit derived from p-methoxystyrene, a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond, and the formula (x)

[In formula (x), R ^a1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
R ^a2 represents an aliphatic hydrocarbon group having 7 to 9 carbon atoms. ]
A resin containing a copolymer having a structural unit derived from a monomer represented by:
The content of the structural unit derived from the monomer represented by the formula (x) is 0.3 mol% or more and 8 mol% or less with respect to the total amount of the structural unit constituting the copolymer,
A curable resin composition, wherein the polymerization initiator is a polymerization initiator containing an O-acyloxime compound. Coating film formed by using the curable resin composition of claim 1 Symbol placement. Pattern formed by using the curable resin composition of claim 1 Symbol placement. A display device comprising at least one selected from the group consisting of the coating film according to claim 2 and the pattern according to claim 3 .