JP2018106172A - Resin composition for liquid crystal display devices, film for liquid crystal display devices, and copolymer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition for liquid crystal display devices that can form a flat film even on an undercoat or substrate with steps.SOLUTION: A resin composition for liquid crystal display devices contains a resin (A), a solvent, and a leveling agent. The resin (A) is a copolymer that contains a constitutional unit having a C2-4 cyclic ether structure (Aa) and a constitutional unit having an active methylene group or an active methine group (Ab), and does not contain constitutional units derived from compounds belonging to the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (Ac).SELECTED DRAWING: None

Description

  The present invention relates to a resin composition for a liquid crystal display device, a film for a liquid crystal display device, and a copolymer.

In recent liquid crystal display devices, a resin composition is used to form a film such as an overcoat. Japanese Patent Application Laid-Open No. 2008-181087 discloses a resin composition containing a copolymer obtained by polymerizing methacrylic acid and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate. A composition is described.

JP 2008-181087 A

  Even when the overcoat in the liquid crystal display device is formed on a base or substrate having a step, the overcoat is required to be flat.

  The present invention provides a resin composition for a liquid crystal display device capable of forming a flat film even when formed on a substrate or substrate having a step, and a copolymer suitable as a material for the resin composition. With the goal.

The present invention includes the following inventions.
[1] Including resin (A), solvent, and leveling agent,
The resin (A) includes a structural unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms and a structural unit (Ab) having an active methylene group or an active methine group, and includes an unsaturated carboxylic acid and an unsaturated carboxylic acid. The resin composition for liquid crystal display devices which is a copolymer which does not contain the structural unit (Ac) derived from the compound which belongs to the group which consists of a saturated carboxylic acid anhydride.
[2] The resin composition for a liquid crystal display device according to [1], wherein the resin (A) has an acid value of 0 mg-KOH / g to 5 mg-KOH / g.
[3] The resin (A) is a copolymer composed of a structural unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms and a structural unit (Ab) having an active methylene group or an active methine group. The resin composition for a liquid crystal display device according to [1] or [2].
[4] The liquid crystal display according to any one of [1] to [3], wherein the structural unit (Aa) is a structural unit derived from a monomer having an oxiranyl group and an ethylenically unsaturated bond. Resin composition for apparatus.
[5] The liquid crystal display according to any one of [1] to [4], wherein the structural unit (Aa) is a structural unit represented by the formula (Aa-1) or the formula (Aa-2). Resin composition for apparatus.

[In Formula (Aa-1) and Formula (Aa-2), 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 a hydroxy group. May be substituted.
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. ]
[6] The resin composition for a liquid crystal display device according to any one of [1] to [5], wherein the leveling agent is a fluorine-based surfactant.
[7] A film for a liquid crystal display device formed from the resin composition for a liquid crystal display device according to any one of [1] to [6].
[8] An unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride comprising a structural unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms and a structural unit (Ab) having an active methylene group or an active methine group Does not include a structural unit (Ac) derived from a compound belonging to the group consisting of
The said structural unit (Aa) is a copolymer containing the structural unit represented by a formula (Aa-1) or a formula (Aa-2).

[In Formula (Aa-1) and Formula (Aa-2), 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 a hydroxy group. May be substituted.
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. ]

  According to the resin composition for a liquid crystal display device of the present invention, the level difference between the base and the substrate can be reduced, so that a flat film can be formed on the base and the substrate having the level difference.

It is sectional drawing which shows typically the state by which the line pattern and film | membrane on a glass substrate were laminated | stacked.

  In this specification, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination of multiple types.

[Resin composition for liquid crystal display]
Hereinafter, the resin composition for a liquid crystal display device of the present invention may be referred to as “resin composition of the present invention” or “resin composition”.
The resin composition of the present invention is a resin composition containing a resin (A), a solvent (E) and a leveling agent (B), and the resin (A) is a structural unit having a cyclic ether structure having 2 to 4 carbon atoms. (Hereinafter referred to as a structural unit (Aa)) and a structural unit having an active methylene group or an active methine group (hereinafter referred to as a structural unit (Ab)), and an unsaturated carboxylic acid and an unsaturated carboxylic acid. The copolymer does not contain a structural unit derived from a compound belonging to the group consisting of acid anhydrides (hereinafter referred to as a structural unit (Ac)). In the resin composition of the present invention, the resin (A) includes the structural unit (Aa) and the structural unit (Ab), and does not include the structural unit (Ac), whereby the flatness of the film formed from the resin composition is obtained. Can be improved.

  The resin composition of the present invention preferably contains a polymerizable compound (C). When the polymerizable compound (C) is included, it is preferable that the polymerization initiator (D) is also included. Moreover, the resin composition of this invention may contain the other component, antioxidant (F), hardening | curing agent (G), etc. Examples of the curing agent (G) include polyvalent carboxylic acids (G1) and imidazole compounds (G2).

<Resin (A)>
The resin (A) is a curable resin, preferably a thermosetting resin, and more preferably a resin curable by heat of 60 ° C. or higher. The resin (A) is a copolymer containing the structural unit (Aa) and the structural unit (Ab) and not including the structural unit (Ac). The copolymer further can be copolymerized with the structural unit (Aa) or (Ab) and is derived from a compound other than the structural units (Aa), (Ab), and (Ac) (hereinafter, (Referred to as a structural unit (Ad)).
In the present specification, “(meth) acrylic acid” means 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. Resin (A) may contain 2 or more types about each of a structural unit (Aa), a structural unit (Ab), and a structural unit (Ad).

[1] Structural unit (Aa)
The structural unit (Aa) is derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms (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. It is a structural unit. The structural unit (Aa) can be obtained by polymerizing the unsaturated compound. The structural unit (Aa) can also be obtained by reacting and polymerizing a compound having a cyclic ether structure having 2 to 4 carbon atoms with another structural unit (Aa ′).

  Examples of the unsaturated compound for deriving the structural unit (Aa) include a monomer having an oxiranyl group and an ethylenically unsaturated bond (hereinafter referred to as a monomer (Aa1)), an oxetanyl group and an ethylenically unsaturated group. A monomer having a bond (hereinafter referred to as monomer (Aa2)) and a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as monomer (Aa3)). It is done.

  As the monomer (Aa1), for example, a monomer having a structure in which a linear or branched unsaturated aliphatic hydrocarbon group is epoxidized and an ethylenically unsaturated bond (hereinafter referred to as a single amount) Body (Aa1-1)), and a monomer having an unsaturated alicyclic hydrocarbon group epoxidized and an ethylenically unsaturated bond (hereinafter referred to as monomer (Aa1-2)) For example).

  As the monomer (Aa1-1), 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 (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, 2,4,6 -Tris (glycidyloxymethyl) styrene etc. are mentioned.

  As the monomer (Aa1-2), vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (For example, Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), a compound represented by Formula (I) and a formula Examples include compounds represented by (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. Also good.
X ^b1 and X ^b2 are each independently 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 a hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, 1- Examples thereof include a hydroxy-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, more preferably a hydrogen atom and a methyl group.

  Examples of the alkanediyl group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5. -A diyl group, a hexane-1, 6-diyl group, etc. are mentioned.

X ^b1 and X ^b2 are preferably a single bond, a methylene group, an ethylene group, * —CH ₂ —O—, * —CH ₂ CH ₂ —O—, and 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 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), or formula (I-11) to formula (I-15) A compound represented by formula (I-1), formula (I-7), formula (I-9) or 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) or formula (II-11) to formula (II-15) A compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (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. 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 (as a commercial product, trade name “E-DCPA” (stock) Daicel) can be used.

  As the monomer (Aa2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. As the monomer (Aa2), 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyl Examples include oxymethyl oxetane, 3-methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, and 3-ethyl-3-acryloyloxyethyl oxetane. It is done.

  As the monomer (Aa3), a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is preferable. Examples of the monomer (Aa3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

As the structural unit (Aa), the monomer (Aa1) is excellent in that the storage stability of the resin composition, the chemical resistance, the heat resistance, and the mechanical strength of the resulting film are excellent, and that excellent flatness can be obtained. Is preferably a structural unit derived from the monomer (Aa1-2), more preferably a structural unit represented by the formula (Aa-1) or the formula (Aa-2). More preferably.
The structural unit represented by the formula (Aa-1) is derived from the compound represented by the formula (I), and the structural unit represented by the formula (Aa-2) is derived from the compound represented by the formula (II). It is burned.

[In Formula (Aa-1) and Formula (Aa-2), 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 a hydroxy group. May be substituted.
X ^b1 and X ^b2 are each independently 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. ]

[2] Structural unit (Ab)
The structural unit (Ab) is a structural unit derived from an unsaturated compound having an active methylene group or an active methine group. The structural unit derived from an unsaturated compound having an active methylene group or an active methine group means a structural unit derived from the unsaturated compound in a copolymer obtained by polymerizing the unsaturated compound. The structural unit can be obtained by polymerizing an unsaturated compound having an active methylene group or an active methine group. Or it can also obtain by making the compound (Ab '') which has an active methylene group or an active methine group react with another structural unit (Ab ').

The unsaturated compound from which the structural unit (Ab) is derived is represented by the formula (III), and the unsaturated compound having an active methine group includes a compound represented by the formula (IV).

[In Formula (III) and Formula (VI), R ¹¹ represents a hydrocarbon group having 1 to 24 carbon atoms which may contain a hydrogen atom or a hetero atom.
R ¹² represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms.
R ¹³ represents a divalent group represented by any one of formulas (1-1) to (1-3).
R ¹⁴ represents a group represented by any one of formulas (1-4) to (1-7). ]



[R ¹⁵ is a hydrocarbon group having 1 to 24 carbon atoms which may contain a hydrogen atom or a hetero atom. X represents a divalent group represented by any one of formulas (1-8) to (1-10). ]

As R ¹¹ and R ¹⁵ , an alkyl group having 1 to 8 carbon atoms which may have an oxygen atom or a nitrogen atom, a cycloalkyl group having 3 to 10 carbon atoms which may have an oxygen atom or a nitrogen atom, a hydrogen atom, etc. Is preferred.
R ¹¹ and R ¹⁵ are independently of each other preferably hydrogen atom, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclohexyl group, methoxy group, ethoxy group, propoxy group, hexyloxy group, cyclohexyloxy group Or it is group represented by Formula (1-11)-Formula (1-13), More preferably, it is a hydrogen atom or a methyl group.

R ¹² is preferably a single bond, an alkanediyl group having 1 to 20 carbon atoms (preferably 1 to 4 carbon atoms), or a cycloalkanediyl group having 3 to 10 carbon atoms. R ¹² is preferably a single bond, a methylene group, an ethylene group, a propanediyl group, a butanediyl group, a hexanediyl group, a cyclohexanediyl group, an octanediyl group, a decandidiyl group, a dodecandiyl group, or a group represented by the following formula ( * Represents a bond.), More preferably a single bond, a methylene group, or an ethylene group.

Specific examples of the compound represented by the formula (III) include the following compounds.

Specific examples of the compound represented by the formula (IV) include the following compounds.

Formulas (III-1) to (III-7), (III-16), (IV-1), (IV-2) and (IV-5) are compounds in which R ¹¹ is a methyl group, Similarly, a compound in which R ¹¹ is replaced with a hydrogen atom is also exemplified as a compound represented by formula (III) or a compound represented by formula (IV).

The structural unit (Ab) is preferably a structural unit represented by the formula (Ab-1).

[In Formula (Ab-1), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]

Examples of the compound that leads to the structural unit represented by the formula (Ab-1) include 2- (methacryloyloxy) ethyl acetoacetate [compound represented by the formula (III-1)].

[3] Structural unit (Ac)
The structural unit (Ac) is a structural unit derived from a compound belonging to the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. Examples of the compound belonging to the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride include acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid and the like. Unsaturated monocarboxylic acids;
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 [2.2.1] bicyclounsaturated compounds containing a carboxy group such as 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 anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] ;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.

[4] Structural unit (Ad)
Examples of the compound that derives the structural unit (Ad) include the following compounds.
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 this technical field, commonly referred to as “dicyclopentanyl (meth) acrylate”) Also, it may be referred to as “tricyclodecyl (meth) acrylate”), tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (conventional in the art) As a name "dicyclopentenyl (meth) acrylate" Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl ( (Meth) acrylic acid esters such as (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, 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 [2.2 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, etc. 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, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3 -Butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

  Of these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide and N-benzylmaleimide are preferable from the viewpoint of copolymerization reactivity and heat resistance.

[5] Ratio of each structural unit The resin (A) is the following resin [K1] or [K2].
Resin [K1]: a copolymer composed of the structural unit (Aa) and the structural unit (Ab);
Resin [K2]: a copolymer composed of the structural unit (Aa), the structural unit (Ab), and the structural unit (Ad).
The resin composition of the present invention preferably contains a resin [K1].

In the resin [K1], the ratio of each structural unit is relative to all the structural units constituting the resin [K1].
Structural unit (Aa); 5-95 mol%,
The structural unit (Ab) is preferably 5 to 95 mol%,
Structural unit (Aa); 30 to 90 mol%,
The structural unit (Ab) is more preferably 10 to 70 mol%.

  When the ratio of the structural units constituting the resin [K1] is within the above range, the storage stability of the resin composition, the chemical resistance, heat resistance and mechanical strength of the resulting film are excellent, and further excellent flatness. Is preferable in that it can be obtained.

  Resin [K1] is, for example, a method described in the document “Experimental Methods for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., first edition, first edition, published on March 1, 1972) It can manufacture with reference to the cited reference described in 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 a reaction vessel, for example, by substituting oxygen with nitrogen to obtain a deoxygenated atmosphere, A method of heating and keeping warm while stirring is mentioned. 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. Examples of the polymerization initiator include 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 thereof include a solvent described later used for the 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 is used. May be. By using the solvent used for the resin composition of the present invention as the polymerization solvent, the solution after the reaction can be used as it is for the production of the resin composition, so that the production process of the resin composition can be simplified. it can.

In the resin [K2], the ratio of each structural unit is the structural unit (Aa) in all the structural units constituting the resin [K2];
Structural unit (Ab); 5-90 mol%,
Structural unit (Ad); preferably 1 to 40 mol%,
Structural unit (Aa); 17-80 mol%,
Structural unit (Ab); 17-80 mol%,
Structural unit (Ad); 3-35 mol%,
It is more preferable that

  When the ratio of the structural unit of the resin [K2] is within the above range, the storage stability of the resin composition, the chemical resistance, heat resistance and mechanical strength of the resulting film are excellent, and further excellent flatness is obtained. It is preferable in that it can be performed. Resin [K2] can be manufactured by the same method as 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 applicability of the 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 resulting film tends to be excellent in chemical resistance.

The acid value of the resin (A) is preferably from 0 mg-KOH / g to 135 mg-KOH / g, more preferably from 0 mg-KOH / g to 50 mg-KOH / g, still more preferably from 0 mg-KOH / g to 5 mg. -KOH / g or less, Especially preferably, it is 0 mg-KOH / g.
When the acid value of the resin (A) is within the above range, the resulting film tends to have excellent adhesion to the substrate.
In this specification, said acid value is an acid value of solid content conversion, and is calculated | required by the following procedure.
Procedure: To 1 g of the resin solution, add 70 mL of tetrahydrofuran [THF] and 10 mL of distilled water, add 2 to 3 drops of a phenolphthalein solution, and stir to make uniform. The obtained resin solution is titrated with an aqueous 0.1N NaOH solution until the indicator is colored. Let A (mL) be the amount of 0.1N NaOH aqueous solution required for titration. A mixture of 70 mL of THF, 10 mL of distilled water, and 2 to 3 drops of phenolphthalein solution was titrated in the same manner with a 0.1 N NaOH aqueous solution, and the amount of the 0.1 N NaOH aqueous solution required for titration of the mixture was B (mL ). And the acid value of resin is computed from the following formula.
Acid value (mg-KOH / g) = [(A-B) × 5.6 × (resin concentration of resin solution (%))] / 100

The content of the resin (A) is preferably 20 to 100% by mass, more preferably 25 to 100% by mass, and further preferably 30 to 100% by mass with respect to the solid content of the resin composition of the present invention.
When the content of the resin (A) is within the above range, the resulting film tends to be excellent in heat resistance and excellent in adhesion to the substrate and chemical resistance. Here, solid content of a resin composition means the quantity remove | excluding the content of the solvent (E) from the total amount of the resin composition of this invention.

<Leveling agent (B)>
Examples of the leveling agent (B) include silicone surfactants, fluorine surfactants, silicone surfactants having a fluorine atom, and the like, and fluorine surfactants are preferred. 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, TSF4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan GK) .

  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.

  The content of the leveling agent (B) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass with respect to the total amount of the resin composition. Or less, more preferably 0.005 mass% or more and 0.07 mass% or less. When the content of the leveling agent (B) is within the above range, the flatness of the film can be further improved.

<Polymerizable compound (C)>
The polymerizable compound (C) is a monomer that reacts by the action of heat or a polymerization initiator (D). Examples of the monomer include compounds having an ethylenically unsaturated bond, and preferably a (meth) acrylic. A 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 (meth) acrylic compounds having one (meth) acryloyl group include (meth) acrylic acid alkyl esters, (meth) acrylic acid phenoxylated polyethylene glycol esters, (meth) acrylic acid alkoxylated polyethylene glycol esters, and isobornyl. (Meth) 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 A bis (acryloyloxyethyl) ether, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl glycol (Meth) acrylate, 3-methyl-pentanediol di (meth) acrylate.

  Examples of the (meth) acrylic compound having three or more (meth) acryloyl groups include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, Ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripenta Erythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripen Erythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride, Reaction product of pentaerythritol hepta (meth) acrylate and acid anhydride, caprolactone-modified trimethylolpropane tri (meth) 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, caprola Ton 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 tripentaerythritol hepta (Meth) acrylate, caprolactone modified tripentaerythritol octa (meth) acrylate, reaction product of caprolactone modified pentaerythritol tri (meth) acrylate and acid anhydride, caprolactone modified dipentaerythritol penta (meth) acrylate and acid anhydride Reaction of reaction product, caprolactone-modified tripentaerythritol hepta (meth) acrylate with acid anhydride Thing etc. are mentioned.

  As the polymerizable compound (C), a (meth) acryl compound having three or more (meth) acryloyl groups is preferable, and dipentaerythritol hexa (meth) acrylate is more preferable.

  When the resin composition of the present invention contains a polymerizable compound (C), the content thereof is preferably 20 to 80 parts by mass, more preferably 25 to 70 parts by mass with respect to 100 parts by mass of the resin (A). is there. When the content of the polymerizable compound (C) is in the above range, the chemical resistance and mechanical strength of the resulting film can be improved and flatness can be obtained.

<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 of the polymerizable compound (C). An agent 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. More preferred is a polymerization initiator containing a sulfur compound. These polymerization initiators tend to be highly sensitive and have high transmittance in the visible light region.

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. 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 (D2-1) or a partial structure represented by the formula (D2-2). In these partial structures, the benzene ring may have a substituent.

  Examples of the compound having a partial structure represented by the formula (D2-1) 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] butane-1 -ON. 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 (D2-2) 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- Examples include diethoxyacetophenone and benzyldimethyl ketal. In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (D2-1).

  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 Ethenyl] -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 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 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 (trialkoxyphene) B) Biimidazole (see JP-B-48-38403, JP-A-62-174204, etc.), the phenyl group at the 4,4 ′, 5,5′-position is substituted with a carboalkoxy group. And biimidazole compounds (see JP-A-7-10913, etc.).

  Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl Benzophenone compounds such as -4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone Quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These can be used in combination with the polymerization initiation assistant (H) (particularly amine) described below.

  An acid generator can also 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, benzoin Tosylate.

  When the resin composition of this invention contains a polymerization initiator (D), the content is preferably 0.01 with respect to 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). -30 mass parts, More preferably, it is 0.02-15 mass parts, More preferably, it is 0.03-8 mass%. When the content of the polymerization initiator (D) is within the above range, the visible light transmittance of the resulting pattern tends to be high.

<Polymerization initiation aid (H)>
The polymerization initiation assistant (H) is used together with the polymerization initiator (D), and is used to accelerate the polymerization of the polymerizable compound (C) whose polymerization has been initiated by the polymerization initiator (D), or to increase the polymerization initiator (D). It is a sensitizer.

  Examples of the polymerization initiation assistant (H) include thiazoline compounds, amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, and the like.

Examples of the thiazoline compound include compounds represented by formulas (H1-1) to (H1-3), 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 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, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

  When the resin composition of the present invention contains a polymerization initiation assistant (H), the content thereof is preferably 0.00 with respect to 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). 1-30 mass parts, More preferably, it is 0.2-10 mass parts. When the amount of the polymerization initiation assistant (H) is within the above range, it tends to be more sensitive when forming a pattern.

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

  Examples of phenolic antioxidants 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, 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 "- (Mesitylene-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, [1,3,2] Dioxaphosphepine As the phenolic antioxidant, a commercially available product may be used. (Registered Trademarks) BHT, GM, GS, GP (all are manufactured by Sumitomo Chemical Co., Ltd.), Irganox (Registered Trademarks) 1010, 1076, 1330, 3114 (all are manufactured by BASF).

  Examples of the sulfur-based antioxidant include dilauryl 3,3′-thiodipropionate, dimyristyl 3,3′-thiodipropionate, distearyl 3,3′-thiodipropionate, pentaerythrityl tetrakis (3 -Lauryl thiopropionate). A commercially available product may be used as the sulfur-based antioxidant. Examples of commercially available sulfur-based antioxidants include Sumilizer (registered trademark) TPL-R and TP-D (all manufactured by Sumitomo Chemical Co., Ltd.).

  Examples of phosphorus antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) -1,1, An example is 3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butanediphosphite. A commercially available product may be used as the phosphorus-based antioxidant. Examples of commercially available phosphorus antioxidants include Irgaphos (registered trademark) 168, 12, and 38 (all manufactured by BASF), Adeka Stub 329K, and Adeka Stub PEP36 (all manufactured by ADEKA Corporation). It is done.

  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 include diamine, N, N′-diphenyl-p-phenylenediamine, and N, N′-bis (2-naphthyl) -p-phenylenediamine. A commercially available product may be used as the amine-based antioxidant. Examples of commercially available amine-based antioxidants include Sumilizer (registered trademark) BPA, BPA-M1, 4ML (all manufactured by Sumitomo Chemical Co., Ltd.).

  When the resin composition of the present invention contains an antioxidant (F), its content is preferably 0.1 with respect to 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). It is not less than 5 parts by mass and more preferably not less than 0.5 parts by mass and not more than 3 parts by mass. When the content of the antioxidant (F) is within the above range, the resulting film tends to be excellent in heat resistance and pencil hardness.

<Polyvalent carboxylic acid (G1)>
The polyvalent carboxylic acid (G1) is at least one compound selected from the group consisting of a polyvalent carboxylic acid anhydride and a polyvalent carboxylic acid. The polyvalent carboxylic acid is a compound having two or more carboxy groups, and the polyvalent carboxylic acid anhydride is an anhydride of a 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 anhydride, 2-dodecyl succinic anhydride, 2- (2-octa -3-enyl) succinic anhydride, 2- (2,4,6-trimethylnon-3-enyl) succinic anhydride, tricarballylic anhydride, 1,2,3,4-butanetetracarboxylic acid Linear polycarboxylic 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 anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, bicyclo [2 2.1] Heptane-2,3-dicarboxylic anhydride, bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride, methylbicyclo [2.2.1] hepta-5 -Cycloaliphatic polycarboxylic acid anhydrides such as ene-2,3-dicarboxylic acid anhydride and cyclopentanetetracarboxylic acid dianhydride; phthalic anhydride, 3-vinylphthalic acid anhydride, 4-vinylphthalic acid anhydride, Pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfonetetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate), Glycerin tris (anhydro trimellitate), glycerin bis (anhydro trimellitate) monoacetate, 1,3,3a, 4,5,9b-hexahydro Aromatic polycarboxylic anhydrides such as -5- (tetrahydro-2,5-dioxo-3-furanyl) naphtho [1,2-c] furan-1,3-dione;
ADEKA HARDNA (registered trademark) -EH-700 (trade name (hereinafter the same), manufactured by ADEKA Corporation), Rikacid (registered trademark) -HH, BT-W, same-TH, same-MH, same MH-700 ( Commercial products such as Shin Nippon Rika Co., Ltd.), Epikinia 126, YH-306, DX-126 (Oilized Shell Epoxy) may be used.

Examples of the polyvalent carboxylic acid include a chain polyvalent carboxylic acid that leads to a chain polyvalent carboxylic acid anhydride (for example, oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, etc.); Cycloaliphatic polycarboxylic acids that lead to cyclic polycarboxylic anhydrides (eg cyclohexanedicarboxylic acid); aromatic polycarboxylic acids that lead to aromatic polycarboxylic anhydrides (eg isophthalic acid, terephthalic acid, 1, 4,5,8-naphthalenetetracarboxylic acid).

  Among them, chain polyvalent carboxylic acid anhydrides and alicyclic polyvalent carboxylic acid anhydrides are preferred because of the excellent heat resistance of the resulting film, and transparency in the visible light region is particularly difficult to decrease. A polyvalent carboxylic acid anhydride is more preferable.

When the resin composition of the present invention contains a polyvalent carboxylic acid (G1), the content thereof is preferably 1 to 100 parts by mass with respect to the total content of the resin (A) and the polymerizable compound (C). 30 mass parts, More preferably, it is 2-20 mass parts, More preferably, it is 2-15 mass parts. When the content of the polyvalent carboxylic acid (G1) is within the above range, the resulting film has excellent heat resistance and adhesion.

<Imidazole compound (G2)>
The imidazole compound (G2) is not particularly limited as long as it has a imidazole skeleton, and examples thereof include compounds known as epoxy curing agents. Among these, a compound represented by Formula (G2-1) is preferable.


Wherein (2), R ³¹ represents an alkyl group, a phenyl group, a benzyl group, or a cyanoalkyl group having 2 to 5 carbon atoms having 1 to 20 carbon atoms.
R ^{32 to} R ³⁴ each 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 methyl group, ethyl group, propyl group, isobutyl group, butyl group, tert-butyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and heptadecyl group. And an undecyl group.
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 formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristolyl group, and 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-sia Methyl-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. Of these, 1-benzyl-4-phenylimidazole, 2-ethyl-4-methylimidazole, and 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole are preferable.

  When the resin composition of the present invention contains an imidazole compound (G2), the content thereof is preferably 0.1 mass with respect to 100 mass parts of the total content of the resin (A) and the polymerizable compound (C). Or more and 25 parts by mass or less, more preferably 0.2 to 15 parts by mass, and still more preferably 0.5 to 5 parts by mass. When the content of the imidazole compound (G2) is in the above range, the resulting film tends to be excellent in transparency in the visible light region.

<Solvent (E)>
The resin composition of the present invention contains a solvent (E). Examples of the solvent (E) include various organic solvents used in the field of resin compositions. Specific examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol. Ethylene glycol monoalkyl ethers such as monobutyl ether;
Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether;
Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate;
Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate;
Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether;
Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl methyl ether, propylene glycol ethyl propyl ether;
Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate;
Butanediol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol, butoxybutyl alcohol;
Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate, butoxybutyl acetate;
Butanediol monoalkyl ether propionates such as methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionate, butoxybutyl propionate;
Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether;
Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene;
Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone;
Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin;
Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxyethyl acetate, hydroxy Butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3-methylbutane Methyl acetate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxyacetate Ethyl acetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2- Butyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxy Propyl propionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3- Methyl toxipropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxy Esters such as butyl propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate;
Cyclic ethers such as tetrahydrofuran and pyran;
and cyclic esters such as γ-butyrolactone.

Among the above-mentioned solvents, an organic solvent having a boiling point of 100 to 200 ° C. is preferable among the above solvents from the viewpoints of coating properties and drying properties. As an organic solvent having a boiling point of 100 to 200 ° C., specifically, alkylene glycol alkyl ether acetate, alcohol such as methoxybutanol and ethoxybutanol, ketone such as cyclohexanone,
And esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutanol, methoxybutyl acetate, 3-ethoxypropionic acid Examples include ethyl and methyl 3-methoxypropionate. These solvents (E) can be used alone or in combination of two or more.

  The content of the solvent (E) in the resin composition of the present invention is preferably 60 to 95 mass%, more preferably 70 to 95 mass%, based on the total amount of the resin composition. In other words, the solid content of the 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 in the above range, the flatness of the film obtained by applying the resin composition tends to be high.

<Other ingredients>
In the resin composition of the present invention, additives known in the technical field, such as fillers, other polymer compounds, thermal radical generators, ultraviolet absorbers, chain transfer agents, adhesion promoters, and the like are added to the resin composition of the present invention as necessary. You may contain.

Examples of the filler include glass, silica, and alumina.
Examples of other polymer compounds include thermosetting resins such as maleimide resins, and thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane.
Examples of the thermal radical generator include 2,2′-azobis (2-methylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), and the like.
Examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole, alkoxybenzophenone and the like.
Examples of the chain transfer agent include dodecanethiol and 2,4-diphenyl-4-methyl-1-pentene.

  As adhesion promoters, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyl Methyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltri Methoxysilane, 3-sulfanylpropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- ( Minoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3 -Aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane and the like.

  In addition, when the 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 under a measurement wavelength of 400 to 700 nm using a spectrophotometer, the average transmittance is Preferably it is 70% or more, more preferably 80% or more.

  When a film is formed using the resin composition of the present invention, the average transmittance of the film is preferably 90% or more, more preferably 95% or more. This average transmittance was measured using a spectrophotometer on a film having a thickness of 2 μm after heat curing (100 to 250 ° C., 5 minutes to 3 hours) under a measurement wavelength of 400 to 700 nm. Is the average value. Thereby, the film | membrane excellent in transparency in visible region can be provided.

<Method for producing resin composition>
The resin composition of the present invention comprises a resin (A), a leveling agent (B) and a solvent (E), and, if necessary, a polymerizable compound (C), a polymerization initiator (D), a polymerization initiation assistant ( H), an antioxidant (F), a hardening | curing agent (G), and another component can be manufactured by mixing by a well-known method. After mixing, it is preferable to filter with a filter having a pore size of about 0.05 to 1.0 μm.

<Method for Manufacturing Liquid Crystal Display Film>
Hereinafter, the film for a liquid crystal display device of the present invention may be referred to as “film of the present invention” or “film”.
The film of the present invention can be produced by applying the resin composition of the present invention on a substrate, drying and heating. More specifically, the film manufacturing method of the present invention includes the following steps (1) to (3).
Step (1): a step of applying the resin composition of the present invention to a substrate,
Step (2): a step of forming a composition layer by drying the resin composition after coating under reduced pressure and / or drying by heating,
Step (3): A step of heating the composition layer.

When the resin composition of the present invention contains a polymerizable compound (C) and a polymerization initiator (D), a cured film can be produced by performing the following steps.
Step (1): a step of applying the resin composition of the present invention to a substrate,
Step (2): a step of forming a resin composition layer by drying the resin composition after coating under reduced pressure and / or heat drying,
Step (2a): a step of exposing the resin composition layer,
Step (2b): a step of developing the resin composition layer after exposure,
Step (3a): A step of heating the resin composition layer after development.

  Step (1) is a step of applying the resin composition of the present invention to a substrate. Examples of the substrate include glass, metal, plastic, and the like, and a color filter, an insulating film, a conductive film, and / or a drive circuit may be formed over the substrate. The coating on the substrate is preferably performed using a coating apparatus such as a spin coater, a slit & spin coater, a slit coater, an ink jet, a roll coater, or a dip coater. When the resin composition of the present invention is formed on a substrate on which a color filter, an insulating film, a conductive film and the like are formed, the resin composition is applied on the color filter, the insulating film, the conductive film and the like.

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

  Step (3) is a step (post-bake) for heating the resin composition layer. The heating is usually performed using a heating device such as an oven or a hot plate. The heating temperature is preferably 130 to 270 ° C, more preferably 150 to 260 ° C, and still more preferably 200 to 250 ° C. When the heating temperature is 200 to 250 ° C., it is possible to prevent unnecessary solvents from remaining in the film. The heating time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

  Step (2a) is a step of exposing the resin composition layer formed in step (2). 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. Examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.

  Step (2b) is a step of developing the resin composition layer after exposure. By developing the exposed resin composition layer in contact with the developer, the unexposed portion of the resin composition layer is removed by dissolution in the developer, and a resin composition layer having a pattern is formed on the substrate. Is done. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide. 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. It is preferable to wash with water after development.

  Step (3a) is a step of heating the resin composition layer after development. By heating in the same manner as in the step (3), the composition layer having a pattern is cured, and a film having the pattern is formed on the substrate.

  The film thus obtained is excellent in surface flatness, and thus is useful as, for example, a color filter substrate used in a liquid crystal display device, a protective film for a touch panel, or an overcoat. As a result, a liquid crystal display device having a high-quality film can be manufactured. Even in a color filter substrate having colored pattern irregularities on the surface, the flatness of the surface can be improved by forming an overcoat from the resin composition of the present invention. The film thickness of the overcoat layer formed from the resin composition of the present invention (when the coated surface has irregularities, the film thickness from the surface of the convex part) is preferably 0.5 μm or more and 5 μm or less, more preferably 0. .5 μm or more and 3 μm or less. When the coated surface has irregularities, the film thickness of the overcoat layer formed from the resin composition of the present invention is preferably 30% or more of the height difference of the irregularities on the coated surface. Even if the overcoat layer obtained from the resin composition of the present invention is thin, the surface flatness can be improved. By forming the overcoat layer using the resin composition of the present invention, the height difference of the unevenness on the surface of the overcoat layer can be 50% or less of the height difference of the unevenness on the surface to be coated.

[Copolymer]
The copolymer of the present invention is a resin (A) containing a structural unit (Aa) and a structural unit (Ab) and not containing a structural unit (Ac), and the structural unit (Aa) A structural unit represented by the formula (Aa-1) or the above formula (Aa-2) is included. The copolymer of the present invention is useful as a material for a resin composition for a liquid crystal display device such as an overcoat layer of a color resist. In the copolymer of the present invention, the structural unit (Aa) may be a structural unit represented by the above formula (Aa-1) or the above formula (Aa-2).

  Hereinafter, the present invention will be described in more detail with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

[Examples 1 to 7 and Comparative Example 1]
<Preparation of resin composition>
Resin (A), polymerizable compound (C), polymerization initiator (D), curing agent (G), and leveling agent (B) are mixed in the proportions shown in Table 1, and the solid content concentration is shown in Table 1. Each resin composition was obtained by mixing propylene glycol monomethyl ether acetate as the solvent (E). In Table 1, the number of parts of each component represents a mass part in terms of solid content.

Each component in Table 1 is as follows.
Resin (a1): Resin obtained by Synthesis Example 1
Resin (a2): Resin obtained by Synthesis Example 2
Resin (a3): Resin obtained in Synthesis Example 3
Resin (a4): Resin obtained by Synthesis Example 4
Polymerizable compound (c1): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.),
Polymerizable compound (c2): ethylene glycol-modified dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DP-3060; manufactured by Nippon Kayaku Co., Ltd.),
Polymerization initiator (d1): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF Corporation)
Polyvalent carboxylic acid (g1): 1,2,3,4-butanetetracarboxylic acid (Licacid (registered trademark) BT-W; manufactured by Shin Nippon Rika Co., Ltd.),
Leveling agent (b1): Megafac (registered trademark) F554; manufactured by DIC Corporation).

(Synthesis Example 1: Resin (a1))
Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was sufficiently passed to form a nitrogen atmosphere, and 260 parts of diethylene glycol ethyl methyl ether was added and heated to 85 ° C. with stirring. Subsequently, 77 parts of the compound represented by the formula (III-1) and a mixture of the compound represented by the formula (I-1) and the compound represented by the formula (II-1) (of the two compounds in the mixture) A mixture of 278 parts of a molar ratio of 50:50) and 155 parts of diethylene glycol ethyl methyl ether was dropped into a flask kept at 85 ° C. for 4 hours.

On the other hand, a solution in which 23 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) was dissolved in 208 parts of diethylene glycol ethyl methyl ether was dropped into the flask over 5 hours. After completion of the dropwise addition of the polymerization initiator solution, the mixture was kept at 85 ° C. for 3 hours, and then cooled to room temperature to obtain a copolymer (resin (a1)) having a B-type viscosity (23 ° C.) of 28 mPas and a solid content of 35.7%. ) Was obtained. The weight average molecular weight (Mw) of the obtained resin (a1) was 6.3 × 10 ³ , the dispersity (Mw / Mn) was 1.80, and the acid value in terms of solid content was 0 mg-KOH / g. Resin (a1) has the following structural units.

The weight average molecular weight (Mw) and number average molecular weight (Mn) of the obtained resin were measured using the GPC method under the following conditions.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: THF (tetrahydrofuran)
Flow rate: 1.0 mL / min
Test liquid solid concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector: RI
Calibration standard materials: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio (Mw / Mn) of the weight average molecular weight and number average molecular weight obtained above in terms of polystyrene was defined as the dispersity.

(Synthesis Example 2: Resin (a2))
Into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was sufficiently passed to make a nitrogen atmosphere, 140 parts of diethylene glycol ethyl methyl ether was added, and the mixture was heated to 70 ° C. with stirring. Subsequently, 40 parts of methacrylic acid, a monomer represented by formula (I-1) and a mixture of monomers represented by formula (II-1) (molar ratio of two monomers in the mixture is 50:50) 360 parts of was dissolved in 190 parts of diethylene glycol ethyl methyl ether, and this solution was dropped into a flask kept at 70 ° C. for 4 hours using a dropping pump.

  On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 240 parts of diethylene glycol ethyl methyl ether was placed in a flask over another 5 hours using another dropping pump. It was dripped. After completion of the dropwise addition of the polymerization initiator solution, the solution was kept at 70 ° C. for 4 hours and then cooled to room temperature to obtain a copolymer (resin (a2)) solution having a solid content of 42%. The weight average molecular weight (Mw) of the obtained resin (a2) was 7800, the dispersity (Mw / Mn) was 2.0, and the acid value in terms of solid content was 61 mg-KOH / g. Resin (a2) has the following structural units.

(Synthesis Example 3: Resin (a3))
In Synthesis Example 1, 136 parts of the compound represented by the formula (III-1), a mixture of the compound represented by the formula (I-1) and the compound represented by the formula (II-1) (two in the mixture) The reaction was carried out in the same manner as in Synthesis Example 1 except that 218 parts of the molar ratio of the two compounds were 50:50). The solid content was 26.2% by weight, the weight average molecular weight Mw was 7750, and the degree of dispersion was 1.80. Of resin (a3) was obtained. Resin (a3) had an acid value in terms of solid content of 0 mg-KOH / g.

(Synthesis Example 4: Resin (a4))
In Synthesis Example 1, 177 parts of the compound represented by the formula (III-1), a mixture of the compound represented by the formula (I-1) and the compound represented by the formula (II-1) (two in the mixture) The reaction was carried out in the same manner as in Synthesis Example 1 except that 177 parts of the molar ratio of the two compounds was 50:50). The solid content was 24.6% by weight, the weight average molecular weight Mw was 7960, and the degree of dispersion was 1.80. Of resin (a4) was obtained. Resin (a4) had an acid value in terms of solid content of 0 mg-KOH / g.

<Production of evaluation substrate>
A 2-inch square glass substrate (Eagle XG; manufactured by Corning) was sequentially washed with a neutral detergent, water and isopropanol and then dried. On this board | substrate, the commercially available photosensitive resin composition (Brand name: Dybright (trademark)) was spin-coated so that the film thickness after a post-baking might be set to 2.0 micrometers. Next, a composition layer was formed by pre-baking at 100 ° C. for 3 minutes in a clean oven. After standing to cool, the distance between the composition layer on the substrate and the quartz glass photomask was set to 100 μm, and using an exposure machine (TME-150RSK; manufactured by Topcon Corporation, light source: ultrahigh pressure mercury lamp), Light irradiation was performed at an exposure amount of 100 mJ / cm ² (based on 365 nm). In addition, this light irradiation performed the radiated light from an ultrahigh pressure mercury lamp through the optical filter (UV-31; Asahi Techno Glass Co., Ltd. product). As the photomask, a photomask for forming a 1: 1 line and space pattern having a line width of 20 μm was used. The composition layer after light irradiation was developed by immersing it in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23 ° C. for 60 seconds, washed with water, and then in an oven. Then, post-baking was performed at 230 ° C. for 15 minutes to prepare an evaluation substrate on which a line-and-space pattern (having 10 lines and spaces each) was formed with a line width of 20 μm.

<Production of Film (Condition 1)>
Examples 1 to 3 and 6 to 7 and comparison were performed on the evaluation substrate by spin coating under a condition that the film thickness after post-baking (film thickness from the line pattern surface of the evaluation substrate) was 1.0 μm. Each resin composition of Example 1 was applied. Then, it is dried under reduced pressure with a vacuum dryer (VCD Microtech Co., Ltd.) under the conditions of a rotary pump speed of 1000 rpm, a booster pump speed of 700 rpm, and a room temperature of 25 ° C. until the degree of vacuum reaches 66 Pa. And prebaking at a temperature of 100 ° C. for 3 minutes. After cooling, a film was formed by post-baking at a temperature of 230 ° C. for 30 minutes. The film thickness on the evaluation substrate was measured using a contact-type film thickness measuring device (DEKTAK6M; manufactured by ULVAC, Inc.) under the conditions of a measurement width of 500 μm and a measurement speed of 10 seconds. Got.
Moreover, when the average value of the film thickness of a film | membrane was computed from the said profile, the average value of the film thickness from the line pattern surface of the board | substrate for evaluation was 1.0 micrometer.

<Production of film (Condition 2)>
Each resin composition of Examples 4 and 5 was spin-coated on the evaluation substrate under the condition that the film thickness after post-baking (film thickness from the line pattern surface of the evaluation substrate) was 1.0 μm. Applied. Then, it is dried under reduced pressure with a vacuum dryer (VCD Microtech Co., Ltd.) under the conditions of a rotary pump speed of 1000 rpm, a booster pump speed of 700 rpm, and a room temperature of 25 ° C. until the degree of vacuum reaches 66 Pa. And prebaking at a temperature of 100 ° C. for 3 minutes. After allowing to cool, light exposure was performed using an exposure machine (TME-150RSK; manufactured by Topcon Corporation, light source; ultrahigh pressure mercury lamp) at an exposure amount of 25 mJ / cm ² (based on 365 nm) in an air atmosphere. The resin composition layer after light irradiation is developed by immersing it in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 60 seconds, washing with water, A film was formed by post-baking at 230 ° C. for 15 minutes. The film thickness on the evaluation substrate was measured using a contact-type film thickness measuring device (DEKTAK6M; manufactured by ULVAC, Inc.) under the conditions of a measurement width of 500 μm and a measurement speed of 10 seconds. Got.
When the average value of the film thickness of the film was calculated from the profile, the average value of the film thickness from the surface of the line pattern of the evaluation substrate was 1.0 μm.

<Evaluation of flatness>
About the film | membrane formed on the said board | substrate for evaluation, the surface profile of the film | membrane formed on the line and space pattern of the board | substrate for evaluation is a stylus-type film thickness meter (brand name: DEKTAK3; made by Nippon Vacuum Co., Ltd.). It was measured. As shown in the schematic cross-sectional view of FIG. 1, the difference Δ () between the maximum film thickness and the minimum film thickness in a state where the line and space pattern 2 (space 2a, line 2b) and the film 3 on the substrate 1 are laminated. μm) was measured and the flatness was evaluated. Table 1 shows the measurement results. As the value of the difference Δ is smaller, a flatter film is formed.

  According to the resin composition of the present invention, a flat film can be formed even on a base or substrate having a step. Since a film obtained from the resin composition is excellent in flatness, it can be suitably used for a display device or the like.

1 glass substrate, 2 line and space pattern, 2a space, 2b line 3 film.

Claims (8)

Including resin (A), solvent, and leveling agent,
The resin (A) includes a structural unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms and a structural unit (Ab) having an active methylene group or an active methine group, and includes an unsaturated carboxylic acid and an unsaturated carboxylic acid. The resin composition for liquid crystal display devices which is a copolymer which does not contain the structural unit (Ac) derived from the compound which belongs to the group which consists of a saturated carboxylic acid anhydride.   The resin composition for a liquid crystal display device according to claim 1, wherein the resin (A) has an acid value of 0 mg-KOH / g to 5 mg-KOH / g.   The resin (A) is a copolymer composed of a structural unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms and a structural unit (Ab) having an active methylene group or an active methine group. The resin composition for liquid crystal display devices according to claim 1 or 2.   4. The resin composition for a liquid crystal display device according to claim 1, wherein the structural unit (Aa) is a structural unit derived from a monomer having an oxiranyl group and an ethylenically unsaturated bond. 5. . The resin composition for liquid crystal display devices according to any one of claims 1 to 4, comprising a structural unit represented by formula (Aa-1) or formula (Aa-2) as the structural unit (Aa). .

[In Formula (Aa-1) and Formula (Aa-2), 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 a hydroxy group. May be substituted.
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. ]   The said leveling agent is a resin composition for liquid crystal display devices in any one of Claims 1-5 which is a fluorine-type surfactant.   The film | membrane for liquid crystal display devices formed from the resin composition for liquid crystal display devices of any one of Claims 1-6. It comprises a structural unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms and a structural unit (Ab) having an active methylene group or an active methine group, and comprises an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. Not including a structural unit (Ac) derived from a compound belonging to the group,
The said structural unit (Aa) is a copolymer containing the structural unit represented by a formula (Aa-1) or a formula (Aa-2).

[In Formula (Aa-1) and Formula (Aa-2), 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 a hydroxy group. May be substituted.
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. ]