TWI765948B - Resin composition for liquid crystal display device, film and copolymer for liquid crystal display device - Google Patents

Abstract

A resin composition for a liquid crystal display device, contains a resin (A), a solvent, and a leveling agent, the resin (A) is a copolymer containing a constituent unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms and a constituent unit (Ab) having an active methylene group or an active methine group, and not containing any constituent unit (Ac) derived from a compound belonging to the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride.

Description

Resin composition for liquid crystal display device, film for liquid crystal display device, and copolymer

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, resin compositions have been used to form films such as overcoat layers. The resin composition described in Japanese Patent Laid-Open No. 2008-181087 is a resin composition containing a copolymer obtained by polymerizing methacrylic acid and 3,4-epoxytricyclo[ ^5.2.1.02.6 ]decyl acrylate.

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

An object of the present invention is to provide a resin composition for liquid crystal display devices which can form a flat film even when formed on a base or substrate having a step difference, and a copolymer suitable as a material for the resin composition.

The present invention includes the following inventions.

[1] A resin composition for a liquid crystal display device, comprising a resin (A), a solvent and a leveling agent, wherein the resin (A) comprises a structural unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms and A copolymer having a constituent unit (Ab) of an active methylene group or an active methine group without a constituent unit (Ac) derived from a compound belonging to the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride.

[2] The resin composition for a liquid crystal display device according to the item [1], wherein the acid value of the resin (A) is 0 mg-KOH/g to 5 mg-KOH/g.

[3] The resin composition for a liquid crystal display device according to the item [1] or [2], wherein the resin (A) is composed of a structural unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms and A copolymer formed by a constituent unit (Ab) having an active methylene group or an active methine group.

[4] The resin composition for a liquid crystal display device according to any one of [1] to [3], wherein the structural unit (Aa) is composed of a compound having an oxirane group and an ethylenically unsaturated bond A unit derived from a monomer.

[5] The resin composition for a liquid crystal display device according to any one of [1] to [4], wherein the structural unit (Aa) is represented by formula (Aa-1) or formula (Aa-2) constituent unit.

[式(Aa-1)及式(Aa-1)中，R^b1及R^b2係表示氫原子或碳數1至4的烷基，該烷基中所含的氫原子可用羥基取代。

[In formula (Aa-1) and formula (Aa-1), 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 may be substituted with a hydroxyl group.

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

R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms.

* indicates 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] A copolymer comprising a constituent unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms and a constituent unit (Ab) having an active methylene group or an active methine group, but not derived from The structural unit (Ac) of the compound of the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride, the said structural unit (Aa) contains the structural unit represented by formula (Aa-1) or formula (Aa-2).

[式(Aa-1)及式(Aa-2)中，R^b1及R^b2係表示氫原子或碳數1至4的烷基，該烷基中所含的氫原子可用羥基取代。

[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 may be substituted with a hydroxyl group.

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

R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms.

* indicates a bond with O. ]

According to the resin composition for liquid crystal display devices of the present invention, since the level difference of the base or the substrate can be reduced, a flat film can be formed even on the base or the substrate having the level difference.

1‧‧‧glass substrate

2‧‧‧Line and Space Patterns

2a‧‧‧interval

2b‧‧‧line

3‧‧‧Film

FIG. 1 is a schematic view showing a state in which a line pattern and a film are laminated on a glass substrate.

In the present specification, the compounds exemplified as the respective components may be used alone or in combination of several unless otherwise specified.

[Resin composition for liquid crystal display device]

Hereinafter, the resin composition for liquid crystal display devices of the present invention is also referred to as "the 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) contains a structural unit having a cyclic ether structure having 2 to 4 carbon atoms ( Hereinafter, it is 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).) do not contain components derived from unsaturated carboxylic acid and unsaturated A copolymer of a structural unit (hereinafter, referred to as a structural unit (Ac)) of the group consisting of a carboxylic acid anhydride. In the resin composition of the present invention, since the resin (A) contains the structural unit (Aa) and the structural unit (Ab), but does not contain the structural unit (Ac), the flatness of the film formed from the resin composition can be improved.

The resin composition of the present invention preferably contains the polymerizable compound (C). When a polymerizable compound (C) is contained, it is preferable to contain a polymerization initiator (D). At the same time, the resin composition of the present invention may contain other components, antioxidants (F), hardeners (G), and the like. As a hardening|curing agent (G), a polyhydric carboxylic acid (G1), an imidazole compound (G2), etc. can be illustrated, for example.

<Resin (A)>

The resin (A) is a curable resin, preferably a thermosetting resin, and more preferably a resin cured by heat at 60° C. or higher. Resin (A) is a copolymer which contains a structural unit (Aa) and a structural unit (Ab), and does not contain a structural unit (Ac). The copolymer may further copolymerize with the structural unit (Aa) or the structural unit (Ab), and may have structural units derived from compounds other than the structural units (Aa), (Ab) and (Ac) (hereinafter, referred to as Constituent unit (Ad)).

In this specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. Designations such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning. The resin (A) contains a structural unit (Aa), a structural unit (Ab), and a structural unit (Ad), and each of two or more types may be contained.

[1] Constituent unit (Aa)

The constituent unit (Aa) is composed of 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 has vinyl properties Units derived from unsaturated compounds with unsaturated bonds. The constituent unit (Aa) can be obtained by polymerizing the unsaturated compound. The structural unit (Aa) can also be obtained by reacting and polymerizing other structural units (Aa') with a compound having a cyclic ether structure having 2 to 4 carbon atoms.

The unsaturated compound derived from the structural unit (Aa) includes, for example, a monomer having an oxirane group and an ethylenically unsaturated bond (hereinafter referred to as a monomer (Aa1)), an oxetanyl group A monomer having an ethylenically unsaturated bond (hereinafter, referred to as a monomer (Aa2)), and a monomer having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter, referred to as a monomer (Aa3)).

The monomer (Aa1) includes, for example, a monomer having a linear or branched unsaturated aliphatic hydrocarbon-based epoxidized structure and an ethylenically unsaturated bond (hereinafter, referred to as monomer (Aa1-1)) ), and a monomer having an epoxidized structure of an unsaturated alicyclic hydrocarbon group and an ethylenically unsaturated bond (hereinafter, referred to as monomer (Aa1-2)).

Examples of the monomer (Aa1-1) include (meth)acrylate dehydrated glyceride, (meth)acrylate β-methyl dehydrated glyceride, (meth)acrylate β-ethyl dehydrated glyceride, and (meth)acrylate dehydrated glycerol Ethyl vinyl ether, o-vinylbenzyl anhydrous, m-vinylbenzyl anhydrous, p-vinylbenzyl anhydrous, alpha-methyl-o-vinylbenzene Methyl deglyceryl ether, α-methyl-m-vinylbenzyl anhydroglycerol, α-methyl-p-vinylbenzyl anhydroglycerol, 2,3-bis(dehydrated glycerol) oxymethyl)styrene, 2,4-bis(dehydroglyceryloxymethyl)styrene, 2,5-bis(dehydroglyceryloxymethyl)styrene, 2,6-bis (Dehydroglyceryloxymethyl)styrene, 2,3,4-paras(deglyceryloxymethyl)styrene, 2,3,5-paraffin(desglyceryloxymethyl) Styrene, 2,3,6-paraffin (dehydroglyceryloxymethyl) styrene, 3,4,5-paraffin (dehydroglyceryloxymethyl) styrene, 2,4,6-paraffin (Dehydroglyceryloxymethyl)styrene and the like.

Examples of the monomer (Aa1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by Daicel), (methyl) 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer A 400; manufactured by (stock) Daicel), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer M 100; ( Co., Ltd.) Daicel Co., Ltd.), the compound represented by the formula (I), the compound represented by the formula (II), and the like.

[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 may be substituted with a hydroxyl group.

X ^b1 and X ^b2 independently represent a single bond, *-R ^b3 -, *-R ^b3 -O-, *-R ^b3 -S- or *-R ^b3 -NH-.

R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms.

* indicates a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl and the like.

Examples of the alkyl group in which the hydrogen atom is substituted with a hydroxyl group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy-1- Methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc.

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

Examples of the alkanediyl having 1 to 6 carbon atoms include methylene, ethylidene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane- 1,5-diyl, hexane-1,6-diyl, etc.

Preferred examples of X ^b1 and X ^b2 include single bond, methylene group, ethylidene group, *-CH ₂ -O-, *-CH ₂ CH ₂ -O-, and more preferred examples include single bond, *-CH _2CH2 - _O- . * is a bond with O.

As the compound represented by the formula (I), the compound represented by any one of the formulae (I-1) to (I-15), and the like can be exemplified. 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) ) is preferable, and the compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15) is more preferable.

As the compound represented by the formula (II), the compound represented by any one of the formulae (II-1) to (II-15), and the like can be exemplified. 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) ) is preferable, and the compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) is more preferable.

The compound represented by the formula (I) and the compound represented by the formula (II) may be used independently, respectively, or may be mixed in an arbitrary ratio and used. When used in combination, the content ratio of the compound represented by the formula (I) and the compound represented by the formula (II) is based on moles, preferably 5:95 to 95:5, more preferably 10:90 to 90: 10, and even better is 20:80 to 80:20. For example, a mixture (commercially available under the trade name "E-DCPA" ((stock) Manufactured by Daicel)).

The monomer (Aa2) is more preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group. Examples of the monomer (Aa2) include 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3-acryloyloxymethyl oxetane, 3-ethyl Alkyl-3-methacryloyloxymethyl oxetane, 3-ethyl-3-propenyloxymethyl oxetane, 3-methyl-3-methacryloyloxy Ethyl oxetane, 3-methyl-3-propenyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3- Ethyl-3-propenyloxyethyl oxetane, etc.

The monomer (Aa3) is preferably a monomer having a tetrahydrofuran group and a (meth)acryloyloxy group. As the monomer (Aa3), tetrahydrofuran acrylate (for example, Viscoat V #150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) can be mentioned.

The constituent unit (Aa) is derived from the monomer (Aa1) so that the storage stability of the resin composition, the chemical resistance, heat resistance and mechanical strength of the obtained film tend to be excellent, and excellent flatness can be obtained. The structural unit of is preferable, and the structural unit derived from the monomer (Aa1-2) is more preferable, and the structural unit represented by the formula (Aa1-1) and the formula (Aa1-2) is even more preferable.

The structural unit represented by the formula (Aa1-1) can be derived from the compound represented by the formula (I), and the structural unit represented by the formula (Aa1-2) can be derived from the compound represented by the formula (II).

[In formula (Aa1-1) and formula (Aa1-2), 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 may be substituted with a hydroxyl group.

X ^b1 and X ^b2 represent mutually independent single bonds, *-R ^b3 -, *-R ^b3 -O-, *-R ^b3 -S- or *-R ^b3 -NH-.

R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms.

* indicates a bond with O. ]

[2] Constituent unit (Ab)

The constituent unit (Ab) is a constituent 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 refers to the structural unit of the unsaturated compound in the copolymer obtained by polymerizing the unsaturated compound. This structural unit can be obtained by polymerizing an unsaturated compound having an active methylene group or an active methine group. Alternatively, it can be obtained by reacting another constituent unit (Ab') with a compound (Ab") having an active methylene group or an active methine group.

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

R ¹¹ -XR ¹² -R ¹³ -CH ₂ -R ¹⁴ (III)

[In formula (III) and formula (VI), R ¹¹ represents a hydrogen atom or a hydrocarbon group having 1 to 24 carbon atoms which may contain 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 of the formulae (1-1) to (1-3).

R ¹⁴ represents a group represented by any of the formulae (1-4) to (1-7). ]

[R ¹⁴ represents a hydrogen atom or a hydroxyl group having 1 to 24 carbon atoms which may contain a hetero atom. X represents a divalent group represented by any of the formulae (1-8) to (1-10). ]

R ¹¹ and R ¹⁵ are preferably 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 or the like.

R ¹¹ and R ¹⁵ are independent of each other, and are represented by 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 the groups represented by the formula (1-11) to the formula (1-13) are preferable, and a hydrogen atom or a methyl group is more preferable.

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 represented by a single bond, methylene, ethylidene, propanediyl, butanediyl, hexanediyl, cyclohexanediyl, octanediyl, decanediyl, dodecanediyl , The group represented by the following formula (* represents a bond.) is preferable, and a single bond, a methylene group, and an ethylidene group are more preferable.

The compound represented by the formula (III) specifically includes 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 methyl. Similarly, R The compound in which ¹¹ is substituted with a hydrogen atom can also be exemplified as the compound represented by the formula (III) or the compound represented by the 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. ]

As a compound which derives the structural unit represented by formula (Ab-1), for example, 2-(methacryloyloxy)ethyl acetonitrile [compound represented by formula (III-1)] can be mentioned.

[3] Structural unit (Ac)

The constitutional unit (Ac) is a constitutional unit derived from a compound belonging to the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. Compounds belonging to the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides include, for example, acrylic acid, methacrylic acid, crotonic acid, o-vinyl benzoic acid, m-vinyl benzoic acid, p-vinyl benzoic acid Isounsaturated monocarboxylic acids; maleic acid, fumaric acid, citraconic acid, methyl fumaric acid (or mesaconic acid), itaconic acid, 3-vinylphthalic acid, 4-Vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1 ,4-cyclohexene dicarboxylic acid and other unsaturated dicarboxylic acids; methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 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]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2- Bicyclic unsaturated compounds containing carboxyl groups such as alkene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5 ,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1 ] Unsaturated dicarboxylic anhydrides such as hept-2-ene anhydride; mono[2-(meth)acryloyloxyethyl] succinate, mono[2-(meth)acrylooxyethyl phthalate] Unsaturated mono[(meth)acryloyloxyalkyl]esters of polycarboxylic acids with a valence of divalent or more, such as hydroxy] esters; unsaturated acrylic acids containing hydroxyl and carboxyl groups in the same molecule, such as α-(hydroxymethyl)acrylic acid esters, etc.

[4] Structural unit (Ad)

As a compound which derives the structural unit (Ad), the following compounds are mentioned, for example.

Methyl (meth)acrylate, 2nd butyl (meth)acrylate, 3rd butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, ( Cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[ ^5.2.1.02.6 ]decan-8-yl (meth)acrylate (In this technical field, it is commonly called "dicyclopentyl (meth)acrylate. At the same time, it is also called "tricyclodecyl (meth)acrylate.), (meth)acrylate tricyclo[[5.2 .1.0 ^2.6 ] Decen-8-yl ester (in this technical field, commonly known as "(meth)acrylic acid dicyclopentenyl ester.), (meth)acrylic acid dicyclopentenyloxyethyl ester, Isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propynyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylate (meth)acrylates such as naphthyl acrylate and benzyl (meth)acrylate; (meth)acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate ) acrylates; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconic acid; bicyclo[2.2.1]hept-2-ene, 5- Methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5- Hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1 ]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis( Hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(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-th Tributoxycarbonylbicyclo[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] Bicyclic unsaturated compounds such as hept-2-ene; N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide , N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimide yl-6-cis-butene Dicarbonyl imine derivatives such as imide acetate, N-succinimidyl-3-maleimide propionate, N-(9-acridyl) maleimide, etc. compounds; styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, paraffin Dichloroethylene, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene, etc.

In terms of copolymerization reactivity and heat resistance, among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, and N- - Benzylmaleimide is preferred.

[5] Ratio of each constituent unit

The resin (A) is the following resin [K1] or [K2]. Resin [K1]: A copolymer composed of a structural unit (Aa) and a structural unit (Ab); Resin [K2]: A copolymer composed of a structural unit (Aa), a structural unit (Ab), and a structural unit (Ad) thing.

The resin composition of the present invention preferably contains resin [K1].

In the resin [K1], the ratios of the respective constituent units with respect to the total constituent units constituting the resin [K1] are as follows: constituent unit (Aa): 5 to 95 mol %, constituent unit (Ab): 5 to 95 mol % More preferably, the constituent unit (Aa): 30 to 90 mol %, and the constituent unit (Ab): 10 to 70 mol %.

The ratio of the constituent units constituting the resin [K1] is preferably within the above-mentioned range, since the storage stability of the resin composition, the chemical resistance, heat resistance, and mechanical strength of the obtained film tend to be excellent, and excellent flatness.

For resin [K1], for example, the method described in the document "Experimental Method for Polymer Synthesis" (Published by Takashi Otsu: (stock) Chemical Doujin 1st Edition No. 1 Issued on March 1, 1972) and reference to this document can be referred to. Manufactured from the cited references.

Specifically, a predetermined amount of the structural unit (Aa) and the structural unit (Ab), a polymerization initiator, a solvent, etc. are put into a reaction vessel, and the oxygen-deoxidized environment is replaced by nitrogen, for example, and stirring is performed. A method of heating and keeping warm. In addition, the polymerization initiator, solvent and the like used here are not particularly limited, and those commonly used in this field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxides ( benzyl peroxide, etc.); the solvent is a solvent that can be used in the resin composition as long as it can dissolve each monomer, and the like can be mentioned later.

As the obtained resin, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used, or one obtained as a solid (powder) by a method such as reprecipitation may be used. By using the solvent used in the resin composition of the present invention as a polymerization solvent, the solution after the reaction can be directly used in the production of the resin composition, so that the production steps of the resin composition can be simplified.

In the resin [K2], among the total structural units constituting the resin [K2], the ratio of each structural unit is as follows: structural unit (Aa): 5 to 90 mol %, structural unit (Ab): 5 to 90 mol % Ear %, structural unit (Ad): 1 to 40 mol %, and structural unit (Aa): 17 to 80 mol %, structural unit (Ab): 17 to 80 mol %, structural unit (Ad) : 3 to 35 moles is better.

It is preferable that the ratio of the constituent units constituting the resin [K2] be within the above-mentioned range, because the storage stability of the resin composition, the chemical resistance, heat resistance and mechanical strength of the obtained film can be excellent, and excellent resin can be obtained. Flatness. Resin [K2] can be produced by the same method as resin [K1].

The polystyrene-converted weight average molecular weight (Mw) of the resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, more preferably 5,000 to 20,000, and still more preferably 5,000 to 10,000. When the weight average molecular weight (Mw) of the resin (A) is within the aforementioned range, the coatability of the resin composition can be improved.

The degree of dispersion [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 aforementioned range, the obtained film tends to be excellent in chemical resistance.

The acid value of resin (A) is preferably 0 mg-KOH/g or more and 135 mg-KOH/g or less, more preferably 0 mg-KOH/g or more and 50 mg-KOH/g or less, and 0 mg-KOH/g or more and 5 mg -KOH/g or less is more preferable, and 0 mg-KOH/g is more preferable.

When the acid value of the resin (A) is within the above-mentioned range, the obtained film and the substrate tend to have excellent adhesion.

In this specification, the above-mentioned acid value is an acid value converted into solid content, and can be obtained by the following procedure.

Steps: Add 70 mL of tetrahydrofuran [THF] and 10 mL of distilled water to 1 g of resin solution, then add 2 to 3 drops of phenolphthalein solution, and stir until uniform. The resulting resin solution was titrated with 0.1N-NaOH aqueous solution until the indicator was colored. The amount of 0.1N-NaOH aqueous solution required for the titration was A (mL). Similarly, titrate a mixture of 70 mL of THF, 10 mL of distilled water and 2 to 3 drops of phenolphthalein solution with 0.1N-NaOH aqueous solution, and the amount of 0.1N-NaOH aqueous solution required for titration of the mixture is set as B (mL). Then, the acid value of the resin was calculated by 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 mass %, more preferably 25 to 100 mass %, and still more preferably 30 to 100 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-mentioned range, the obtained film tends to be excellent in heat resistance, and tends to be excellent in adhesion and chemical resistance with the substrate. Here, the solid content of the resin composition means the amount excluding the content of the solvent (E) from the total amount of the resin composition of the present invention.

<Leveler (B)>

The leveling agent (B) includes polysiloxane-based surfactants, fluorine-based surfactants, and polysiloxane-based surfactants having a fluorine atom, and fluorine-based surfactants are preferred. These levelers may have a polymerizable group in the side chain.

The polysiloxane-based surfactant includes a surfactant having a siloxane bond in the molecule, and the like. Specifically, Toray polysiloxane DC3PA, the same SH7PA, the same DC11PA, the same SH21PA, the same SH28PA, the same SH29PA, the same SH30PA, the same SH8400 (trade name, manufactured by Toray Dow Corning Co., Ltd.), KP 321 , KP 322, KP 323, KP 324, KP 326, KP 340, KP 341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF 400, TSF 401, TSF 410, TSF 4300, TSF 4440, TSF 4445, TSF 4446, TSF 4452 and TSF 4460 (manufactured by Momentive High Performance Materials Co., Ltd., a joint venture in Japan), etc.

As said fluorine-type surfactant, the surfactant etc. which have a fluorocarbon chain in a molecule|numerator are mentioned. Specifically, Fluorad (registered trademark)) FC 430, the same FC 431 (manufactured by Sumitomo 3M Co., Ltd.); Megafac (registered trademark) F142D, the same F171, the same F172, the same F173, the same F177, the same F183, the same F554 ; same R30, same RS-718-K (manufactured by DIC Corporation), F-Top (registered trademark) EF301, same EF303, same EF351, same EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.); Surflon (registered trademark) ) S381, the same S382, the same SC101, the same SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by (stock) Daikin Fine Chemicals Research Institute), etc.

Examples of the polysiloxane-based surfactant having a fluorine atom include those having a siloxane bond and a fluorocarbon chain in the molecule, and the like. Specifically, Megafac (registered trademark) R08, the same BL20, the same F475, the same F477, and the same F443 (manufactured by DIC Corporation), etc. are mentioned.

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

<Polymerizable compound (C)>

The polymerizable compound (C) is a monomer reacted by heat or by the action of the polymerization initiator (D). Examples of the monomer include compounds having an ethylenically unsaturated bond, preferably (meth)acrylic compounds. , and more preferably a compound having at least one group selected from the group consisting of acrylyl and methacryloyl.

Examples of the (meth)acrylic compound having one (meth)acryloyl group include alkyl (meth)acrylate, phenoxy polyethylene glycol ester of (meth)acrylic acid, and alkoxylated poly(meth)acrylic acid. Ethylene glycol ester, isobornyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-(meth)acrylate Hydroxy-3-phenoxypropyl ester, tetrahydrofuryl (meth)acrylate, etc.

Examples of the (meth)acrylic compound having two (meth)acryloyl groups include 1,3-butanediol di(meth)acrylate, 1,3-butanediol (meth)acrylate, 1,3-butanediol (meth)acrylate, and 1,3-butanediol (meth)acrylate. 6-Hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethyl Glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bis(acrylooxyethyl) ether of bisphenol A, epoxidized bisphenol A Di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, 3-methylpentanediol di(meth)acrylate Wait.

Examples of the (meth)acrylic compound having three or more (meth)acryloyl groups include trimethylolpropane tri(meth)acrylate, neotaerythritol tri(meth)acrylate, gins(2-hydroxyl) Ethyl) neocyanurate tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, neopentyltetrakis Alcohol Tetra(meth)acrylate, Dipiveaerythritol Penta(meth)acrylate, Dipiveaerythritol Hex(meth)acrylate, Tripivalerythritol Tetra(meth)acrylate, Sanxin Pentaerythritol penta(meth)acrylate, Trinetaerythritol hexa(meth)acrylate, Trinetaerythritol hepta(meth)acrylate, Trinetaerythritol octa(meth)acrylate, The reaction product of neopentaerythritol tri(meth)acrylate and acid anhydride, the reaction product of dipeutaerythritol penta(meth)acrylate and acid anhydride, the reaction product of trinetaerythritol hepta(meth)acrylate and acid anhydride Reactants, caprolactone-modified trimethylolpropane tri(meth)acrylate, caprolactone-modified neopentaerythritol tri(meth)acrylate, caprolactone-modified ginseng (2-hydroxyethyl) ) New cyanurate tri(meth)acrylate, caprolactone-modified neopentaerythritol tetra(meth)acrylate, caprolactone-modified dipivalerythritol penta(meth)acrylate, Caprolactone-modified dipivoerythritol hexa(meth)acrylate, caprolactone-modified trinepentaerythritol tetra(meth)acrylate, caprolactone-modified trinepentaerythritol penta(methyl)acrylate ) Acrylate, caprolactone-modified trinepentaerythritol hexa(meth)acrylate, caprolactone-modified trinepentaerythritol hepta(meth)acrylate, caprolactone-modified trinepentaerythritol Octa(meth)acrylate, caprolactone-modified neotaerythritol tri(meth)acrylate and acid anhydride reactant, caprolactone-modified dipivalerythritol penta(meth)acrylate and acid anhydride Reactant, caprolactone-modified trinepentaerythritol hepta(meth)acrylate and acid anhydride reactant, etc.

The polymerizable compound (C) is preferably a (meth)acrylic compound having three or more (meth)acryloyl groups, and is more preferably dipivoerythritol hexa(meth)acrylate.

When the resin composition of the present invention contains the polymerizable compound (C), the compound (C) is preferably 20 to 80 parts by mass, more preferably 25 to 70 parts by mass, relative to 100 parts by mass of the resin (A). When the content of the polymerizable compound (C) is within the aforementioned range, the obtained film tends to be excellent in chemical resistance and mechanical strength, and flatness can be obtained.

<Polymerization initiator (D)>

化合物、醯基勝氧化物化合物及二咪唑化合物所組成之群組的至少1種之聚合起始劑為佳，並以含有O-醯肟化合物的聚合起始劑更佳。此等聚合起始劑傾向於高感度，且可見光域中的透過率高。 The polymerization initiator (D) generates active radicals, acids, etc. by the action of light or heat, and is not particularly limited as long as it is a compound that can start the polymerization of the polymerizable compound (C), and known polymerization can be used. starter. The polymerization initiator (D) is selected from the group consisting of O-hydroxyoxime compounds, alkyl phenone compounds,

At least one polymerization initiator from the group consisting of a compound, an acyl oxide compound and a diimidazole compound is preferred, and a polymerization initiator containing an O-oxime compound is more preferred. These polymerization initiators tend to have high sensitivity and high transmittance in the visible light region.

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

Examples of the O-oxime compound include N-benzyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzyloxy-1 -(4-Phenylthiophenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane -1-keto-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]ethane- 1-Imine, N-Acetyloxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolane Methoxy)benzyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzene Carboxylic)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzyloxy-1-[9-ethyl-6-(2-methyl) benzyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (the above, manufactured by BASF Corporation), and N-1919 (manufactured by ADEKA Corporation) can also be used.

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

Compounds having a partial structure represented by formula (D2-1) include, for example, 2-methyl-2-morpholino-1-(4-methylthiophenyl)propan-1-one, 2-di Methylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl) Methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one. Commercially available products such as Irgacure (registered trademark) 369, 907, and 379 (the above, manufactured by BASF Corporation) can be used. At the same time, a polymerization initiator having a chain transfer-generating group described in Japanese Patent Application Laid-Open No. 2002-544205 can also be used. Compounds having a partial structure represented by formula (D2-2) include, for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4 -(2-Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1 -Oligomers of ketones, α,α-diethoxyacetophenone, benzyl dimethyl ketal. In terms of sensitivity, the alkyl phenone compound is preferably a compound having a partial structure represented by formula (D2-2).

化合物可列舉：例如2,4-雙(三氯甲 基)-6-(4-甲氧基苯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基萘基)-1,3,5-三

、2,4-雙(三氯甲基)-6-胡椒基-1,3,5-三

、2,4-雙(三氯甲基)-6-(4-甲氧基苯乙烯基)-1,3,5-三

、2,4-雙(三氯甲基)-6-〔2-(5-甲基呋喃-2-基)乙烯基〕-1,3,5-三

、2,4-雙(三氯甲基)-6-〔2-(呋喃-2-基)乙烯基〕-1,3,5-三

、2,4-雙(三氯甲基)-6-〔2-(4-二乙基胺基-2-甲基苯基)乙烯基〕-1,3,5-三

、2,4-雙(三氯甲基)-6-〔2-(3,4-二甲氧基苯基)乙烯基〕-1,3,5-三

。 three

Examples of compounds include: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tris

, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-tris

, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-tri

, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-tri

.

As an acylphosphine oxide compound, 2,4,6- trimethylbenzyldiphenylphosphine oxide etc. are mentioned. Commercially available products such as Irgacure 819 (manufactured by Japan BASF Co., Ltd.) can be used.

As a diimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2,3-dichlorophenyl) Phenyl)-4,4',5,5'-tetraphenyldiimidazole (refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2'-bis(2 -Chlorophenyl)-4,4',5,5'-tetraphenyldiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(alkoxy) phenyl)diimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)diimidazole, 2,2'-bis( 2-Chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)diimidazole (refer to Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.). ), a diimidazole compound in which the phenyl group at the 4,4', 5,5'-position is substituted with a carbon alkoxy group (refer to Japanese Patent Laid-Open No. 7-10913, etc.).

In addition, the polymerization initiator (D) includes benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl o-benzylbenzoate, 4 -Phenylbenzophenone, 4-benzyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone , 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds; 10-butyl-2-chloroacridine pyridone, benzyl, methyl phenylglyoxylate, titanocene compounds, etc. These compounds can be used in combination with a polymerization initiator (H) (especially, an amine) to be described later.

Moreover, an acid generator can also be used as a polymerization initiator (D). Examples of acid generators include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-acetoxyphenyldimethylene. Sulfonium p-toluenesulfonate, 4-acetyloxyphenyl/methyl/benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium Onium salts such as hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyltoluenesulfonate, and benzoin tosylate.

When the resin composition of the present invention contains the polymerization initiator (D), the content of the polymerization initiator (D) is 0.01 to 100 parts by mass relative to the total content of the resin (A) and the polymerizable compound (C). It is preferably 30 parts by mass, more preferably 0.02 to 15 parts by mass, and more preferably 0.03 to 8 parts by mass. When content of a polymerization initiator (D) is in the said range, the visible light transmittance of the obtained pattern tends to become high.

<Polymerization Initiating Auxiliary (H)>

The polymerization initiator (H) can be used together with the polymerization initiator (D), and the polymerization initiator (H) is a polymerizable compound (C) for accelerating the initiation of polymerization by the polymerization initiator (D). Compounds or sensitizers used for polymerization.

The polymerization initiator (H) includes thiazoline compounds, amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, and the like.

As a thiazoline compound, the compound represented by Formula (H1-1) - Formula (H1-3), the compound described in Unexamined-Japanese-Patent No. 2008-65319, etc. are mentioned.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzene Isoamyl formate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis (Dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethyl) methylamino) benzophenone and the like, among which 4,4'-bis(diethylamino) benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10 - Diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

Examples of the thioxanthone compound include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4 -Propoxy thioxanthone, etc.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxybenzene thioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthalene glycine, naphthoxyacetic acid, etc.

When the resin composition of the present invention contains a polymerization initiator (H), the content of the polymerization initiator (H) is 100 parts by mass relative to the total content of the resin (A) and the polymerizable compound (C). 0.1 to 30 parts by mass is preferable, and 0.2 to 10 parts by mass is more preferable. When the amount of the polymerization initiation aid (H) is within the aforementioned range, a pattern tends to be formed with higher sensitivity.

<Antioxidant (F)>

The antioxidant (F) includes a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, and an amine-based antioxidant. Among them, a phenolic antioxidant is preferable in terms of making the obtained film less colored.

-2,4,6(1H,3H,5H)-三酮、3,3’,3”,5,5’,5”-六-第三丁基-a,a’,a”-(均三甲苯-2,4,6-三基)三-對-甲酚、新戊四醇肆[3-(3,5-二-第三丁基-4-羥基苯基)丙酸酯]、2,6-二-第三丁基-4-甲基酚及6-[3-(3-第三丁基-4-羥基-5-甲基苯基)丙氧基]-2,4,8,10-四-第三丁基二苯并[d,f][1,3,2]二氧雜磷雜庚英(phosphepine)。前述酚系抗氧化劑也可使用市售品。市售的酚系抗氧化劑可列舉：例如Sumilizer(註冊商標)BHT、GM、GS、GP(以上，全是住友化學(股)製造)、Irganox(註冊商標)1010、1076、1330、3114(以上，全是BASF公司製造)。 Phenolic antioxidants include, for example, 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 ester, 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-methylphenol), 4,4'-butylenebis(6-tert-butyl-3-methylphenol) , 4,4'-thiobis(2-tert-butyl-5-methylphenol), 2,2'-thiobis(6-tert-butyl-4-methylphenol), 1,3 ,5-Sham(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-tri

-2,4,6(1H,3H,5H)-trione, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(both Trimethylol-2,4,6-triyl)tris-p-cresol, neotaerythritol tetra[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-butyldibenzo[d,f][1,3,2]dioxaphosphepine (phosphepine). Commercially available products can also be used as the aforementioned phenolic antioxidants. Commercially available Examples of phenolic antioxidants include: Sumilizer (registered trademark) BHT, GM, GS, GP (all of which are manufactured by Sumitomo Chemical Co., Ltd.), Irganox (registered trademark) 1010, 1076, 1330, 3114 (all of which are above, all It is made by BASF Corporation).

Examples of sulfur-based antioxidants include dilauryl 3,3'-thiodipropionate, dimyristine 3,3'-thiodipropionate, and dihard 3,3'-thiodipropionate. Fatty acid ester, tetra(3-laurylthiopropionic acid) neopentaerythritol ester. A commercial item can also be used for the said sulfur-type antioxidant. Commercially available sulfur-based antioxidants include, for example, Sumilizer (registered trademark) TPL-R and TP-D (the above are all manufactured by Sumitomo Chemical Co., Ltd.).

Examples of phosphorus-based antioxidants include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, gins(nonylphenyl) phosphite, and distearyl neopentaerythritol diphosphite. , tetrakis (tridecyl)-1,1,3-para(2-methyl-5-tert-butyl-4-hydroxyphenyl) butane diphosphite. A commercial item can also be used for the said phosphorus antioxidant. Commercially available phosphorus-based antioxidants include, for example, Irgafos (registered trademark) 168, 12, and 38 (all of which are manufactured by BASF), Adekastab 329K, and Adekastab PEP36 (all of which are manufactured by ADEKA).

Amine-based antioxidants include, for example, N,N'-di-2-butyl-p-phenylenediamine, N,N'-di-isopropyl-p-phenylenediamine, N,N'- Dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine. A commercial item can also be used for the said amine type antioxidant. Commercially available amine-based antioxidants include, for example, Sumilizer (registered trademark) BPA, BPA-M1, and 4ML (all of which are manufactured by Sumitomo Chemical Co., Ltd.).

When the resin composition of the present invention contains the antioxidant (F), the content of the antioxidant (F) is 0.1 part by mass or more and 5 parts by mass relative to 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). The content is preferably less than or equal to 0.5 parts by mass or more and less than or equal to 3 parts by mass. When the content of the antioxidant (F) is within the aforementioned range, the obtained film tends to be excellent in heat resistance and pencil hardness.

<Polycarboxylic 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 polycarboxylic acid refers to a compound having two or more carboxyl groups; the polycarboxylic acid anhydride refers to the anhydrate of the polycarboxylic acid. The molecular weight of the polyvalent carboxylic acid (G1) is preferably 3,000 or less, and more preferably 1,000 or less.

The aforementioned polycarboxylic acid anhydrides include, for example, maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhydride, 2-dodecylsuccinic anhydride, 2-(2-oct-3-enyl ) Chain polyvalent anhydride such as succinic anhydride, 2-(2,4,6-trimethylnon-3-enyl)succinic anhydride, glyceric anhydride, 1,2,3,4-butanetetracarboxylic dianhydride Carboxylic anhydrides; 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride Dicarboxylic 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]hept-5-ene-2,3 - Alicyclic polycarboxylic acid anhydrides such as dicarboxylic acid anhydride and cyclopentanetetracarboxylic acid dianhydride; phthalic anhydride, 3-ethylene phthalic anhydride, 4-ethylene phthalic anhydride, pyromellitic anhydride , trimellitic anhydride, benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, ethylene glycol bis(anhydrotrimellitate), glycerol (anhydro trimellitate), glycerol bis (anhydro trimellitate) monoacetate, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-di Aromatic polycarboxylic acid anhydrides such as pendant oxy-3-furyl)naphthalene[1,2-c]furan-1,3-dione.

Adekahadna (registered trademark)-EH-700 (trade name (hereinafter the same), manufactured by (stock) ADEKA), Rikasidd (registered trademark)-HH, same BT-W, same-TH, same-MH, same MH can also be used Commercial products such as -700 (manufactured by Nippon Rika Co., Ltd.), Epikinia 126, the same YH-306, and the same DX-126 (manufactured by Petrochemical Shell Epoxy Co., Ltd.).

The aforementioned polybasic carboxylic acids can include chain polycarboxylic acids derived from chain polycarboxylic acid anhydrides (for example, oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, etc.); Alicyclic polycarboxylic acids (such as cyclohexanedicarboxylic acid) derived from alicyclic polycarboxylic acid anhydrides; aromatic polycarboxylic acids (such as isophthalic acid, terephthalic acid) derived from aromatic polycarboxylic acid anhydrides formic acid, 1,4,5,8-naphthalenetetracarboxylic acid, etc.).

Among them, chain polycarboxylic acid anhydrides and alicyclic polycarboxylic acid anhydrides are preferable, and alicyclic polycarboxylic acid anhydrides are more preferable in terms of making the obtained film excellent in heat resistance, and in particular, the transparency in the visible light region is not easily reduced. good.

When the resin composition of the present invention contains a polyvalent carboxylic acid (G1), the polyvalent carboxylic acid (G1) is 1 to 30 parts by mass relative to 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). Preferably, it is 2 to 20 parts by mass, and it is still more preferably 2 to 15 parts by mass. If the content of the polyvalent carboxylic acid (G1) is within the aforementioned range, the obtained film will be excellent in heat resistance and adhesiveness.

<Imidazole compound (G2)>

The imidazole compound (G2) is not particularly limited as long as it has an imidazole skeleton, and examples thereof include compounds known as epoxy curing agents. Among them, the compound represented by the formula (G2-1) is preferable.

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

R ³² to R ³⁴ independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a nitro group, or an acyl group having 1 to 20 carbon atoms, and the alkyl group and the phenyl group contained in the phenyl group The hydrogen atoms can be replaced by hydroxyl groups. ]

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isobutyl, butyl, tert-butyl, hexyl, heptyl, octyl, nonyl, decyl, heptadecanyl base, undecyl.

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

As a halogen atom, a fluorine atom, a chlorine atom, and a bromine atom are mentioned, for example.

Examples of the acyl group having 1 to 20 carbon atoms include methylyl, acetyl, propionyl, isobutyryl, pentamyl, isopentyl, neopentyl, lauryl, myristyl, Stearyl.

The imidazole compound (G2) includes, for example, 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, and 5-hydroxymethyl-4-methyl Imidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-hydroxymethyl- 2-phenylimidazole, 2-phenylimidazole, 2-phenyl-hydroxymethylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl-4-phenylimidazole, 1-benzyl yl-5-hydroxymethylimidazole, 2-(p-hydroxyphenyl)imidazole, 1-cyanomethyl-2-methylimidazole, 1-(2-cyanoethyl)-2-hydroxymethylimidazole , 2,4-diphenylimidazole, 1-cyanomethyl-2-undecylimidazole, 1-cyanomethyl-2-ethyl-4-methylimidazole, 1-cyanomethyl- 2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole. Among them, 1-benzyl-4-phenylimidazole, 2-ethyl-4-methylimidazole and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole are preferred.

When the resin composition of the present invention contains the imidazole compound (G2), the content of the imidazole compound (G2) is 0.1 part by mass or more and 25 mass parts relative to 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). part is preferably not more than 0.2 parts by mass, more preferably not less than 0.2 parts by mass but not more than 15 parts by mass, and still more preferably not less than 0.5 parts by mass and not more than 5 parts by mass. When the content of the imidazole compound (G2) is within the aforementioned range, the obtained film tends to be excellent in transparency in the visible light region.

<Solvent (E)>

The resin composition of this invention contains a solvent (E). The solvent (E) includes various organic solvents used in the field of resin compositions, and specific examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether. Ethylene glycol monoalkyl ether of ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, etc. Ethylene glycol dialkyl ethers; ethylene glycol alkyl ethers such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate, etc. acid esters; propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxyamyl acetate and other alkyl glycol alkyl ethers Ester; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether and other propylene glycol monoalkyl ethers; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propyl ether Methyl ether, propylene glycol ethyl propyl ether and other propylene glycol dialkyl ethers; propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate and other propylene glycol alkyl ether propionates; Methoxy Butyl butanol, ethoxybutanol, propoxybutanol, butoxybutanol and other butanediol monoalkyl ethers; methoxybutyl acetate, ethoxybutyl acetate, propoxy Butylene glycol monoalkyl ether acetates such as butyl acetate and butoxybutyl acetate; methoxybutyl propionate, ethoxybutyl propionate, propoxybutyl propionic acid Butylene glycol monoalkyl ether propionate such as ester, butoxybutyl propionate; dipropylene glycol dialkyl ether such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether; benzene, toluene, xylene , aromatic hydrocarbons such as mesitylene; methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones; ethanol, propanol, butanol, hexanol, cyclohexanol, Ethylene glycol, glycerin and other alcohols; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methyl propionate, 2-hydroxy-2 -Ethyl methylpropionate, methyl glycolate, ethyl glycolate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, 3-hydroxyl Ethyl Propionate, Propionate 3-Hydroxypropionate, Butyl 3-Hydroxypropionate, Methyl 2-Hydroxy-3-Methylbutyrate, Methyl Methoxyacetate, Ethyl Methoxyacetate, Methoxyacetate propyl acetate, butyl methoxy acetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxy acetate, propoxy acetate Ethyl acetate, propyl propoxy acetate, butyl propoxy acetate, methyl butoxy acetate, ethyl butoxy acetate, propyl butoxy acetate, butyl butoxy acetate, 2-methoxyacetate methyl propionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2-ethoxypropionate Ethyl propionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxypropionate Propionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate , 3-methoxypropionate, 3-methoxypropionate, 3-methoxypropionate, 3-ethoxypropionate, 3-ethoxypropionate, 3-ethoxypropionate, 3-ethoxypropionate, 3-ethoxypropionate , butyl 3-propoxy propionate, methyl 3-propoxy propionate, ethyl 3-propoxy propionate, propyl 3-propoxy propionate, butyl 3-propoxy propionate , methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate, etc.; cyclic tetrahydrofuran, pyran, etc. ethers; cyclic esters such as γ-butyrolactone, etc.

Among the above-mentioned solvents, organic solvents having a boiling point of 100 to 200° C. in the above-mentioned solvents are preferably mentioned in terms of coating properties and drying properties. Organic solvents with a boiling point of 100 to 200°C, specifically: alkanediol alkyl ether acetate, alcohols such as methoxybutanol and ethoxybutanol, ketones such as cyclohexanone, 3-ethoxypropane Acid ethyl ester and methyl 3-methoxypropionate and other esters, preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutanol, methoxybutyl Ethyl acetate, ethyl 3-ethoxypropionate and methyl 3-methoxypropionate. These solvents (E) may 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% by mass, more preferably 70 to 95% by mass, relative to 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 rate of the solvent (E) is in the above-mentioned range, the flatness of the film obtained by coating the resin composition tends to be high.

<other ingredients>

The resin composition of the present invention may optionally contain additives known in the technical field such as fillers, other polymer compounds, thermal radical generators, ultraviolet absorbers, chain transfer agents, and adhesion promoters.

Glass, silica, alumina, etc. are mentioned as a filler.

Other polymer compounds include thermosetting resins such as maleimide resins, and thermoplastics such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane. resin, etc.

The thermal radical generator includes 2,2'-azobis(2-methylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), and the like.

The ultraviolet absorber includes 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxybenzophenone, and the like.

The chain transfer agent includes dodecyl mercaptan, 2,4-diphenyl-4-methyl-1-pentene, and the like.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, 3-dehydroglyceryloxypropyltrimethoxysilane, 3-Deglyceryloxypropylmethyldimethoxysilane, 3-Deglyceryloxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethyl Oxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-thiolpropyltrimethoxysilane Oxysilane, 3-Hydrothiopropyltrimethoxysilane, 3-Isocyanatopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxy Silane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3 -aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane Ethoxysilane, etc.

In addition, when the resin composition of the present invention is filled in a quartz vial with an optical path length of 1 cm, and the transmittance is measured by a spectrophotometer under the conditions of a measurement wavelength of 400 to 700 nm, the average transmittance is preferably 70% or more, and More than 80% is better.

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. The average transmittance is an average value when measured with a spectrophotometer on a film having a thickness of 2 μm after heat curing (100 to 250° C., 5 minutes to 3 hours) at a measurement wavelength of 400 to 700 nm. Thereby, a film excellent in transparency in the visible light region can be provided.

<Manufacturing method of resin composition>

In the resin composition of the present invention, the resin (A), the leveling agent (B), the solvent (E), and optionally the polymerizable compound (C), the polymerization initiator (D), The polymerization initiator (H), antioxidant (F), hardener (G), and other components are mixed and produced. After mixing, it is preferably filtered through a filter having a pore size of about 0.05 to 1.0 µm.

<The manufacturing method of the film for liquid crystal display devices>

The film for liquid crystal display devices of the present invention is hereinafter also referred to as "the film of the present invention" or "film".

The film of this invention can be manufactured by apply|coating the resin composition of this invention on a board|substrate, drying, and heating. More specifically, the method for producing the film of the present invention includes the following steps (1) to (3). Step (1): the step of coating the resin composition of the present invention on the substrate, step (2): the step of drying the coated resin composition under reduced pressure and/or heating to form a composition layer, step (3) ): the step of heating the composition layer.

When the resin composition of this invention contains a polymerizable compound (C) and a polymerization initiator (D), a cured film can be manufactured by carrying out the following procedure. Step (1): the step of coating the resin composition of the present invention on the substrate, step (2): the step of drying the coated resin composition under reduced pressure and/or heating to form a composition layer, step (2a) ): a step of exposing the resin composition layer, step (2b): a step of developing the exposed resin composition layer, step (3a): a step of heating the developed resin composition layer.

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, etc., and a color filter, an insulating film, a conductive film, and/or a driving circuit, etc. may be formed on the substrate. The coating on the substrate is preferably carried out using a coating apparatus such as a spin coater, a slit and spin coater, a slit coater, an ink jet, a roll coater, and a dip coater. When the resin composition of the present invention is formed on the substrate on which the color filter, insulating film, and conductive film are formed, the resin composition is applied on the color filter, insulating film, conductive film, and the like.

Step (2) is a step of forming a resin composition layer after drying the coated resin composition under reduced pressure and/or heating. Volatile components such as solvents in the resin composition are removed by performing this step. The vacuum drying system is preferably carried out under a pressure of 50 to 150 Pa and a temperature range of 20 to 25°C. Before or after drying under reduced pressure, heat drying (prebaking) may also be performed. Heating drying is usually performed using a heating device such as an oven and a hot plate. The temperature for heating and drying is preferably 30 to 120°C, and more preferably 50 to 110°C. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

Step (3) is a step of heating the resin composition layer (post-baking). Heating is usually performed using a heating device such as an oven and 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, unnecessary solvents can be prevented from remaining in the film. The heating time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes.

The step (2a) is a step of exposing the resin composition layer formed in the step (2). The light source used for exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. For example, a filter for cutting this wavelength range is used to cut light below 350 nm, and a band pass filter for selecting and extracting these wavelength ranges can also be used to extract light around 436 nm, around 408 nm, and around 365 nm. Examples of the light source include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.

Step (2b) is a step of developing the exposed resin composition layer. By contacting the exposed resin composition layer with the developer, the unexposed part of the resin composition layer is dissolved in the developer and removed, so that the patterned resin composition layer can be formed on the substrate. The developing solution is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide. The concentration of the aqueous solution of these basic compounds is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. In addition, the developer may contain a surfactant. The developing method may be any of a paddle method, a dipping method, a spray method, and the like. In addition, the substrate can be tilted at any angle during development. It is better to wash with water after developing.

Step (3a) is a step of heating the developed resin composition layer. The patterned film can be formed on the substrate by curing the patterned composition layer by heating in the same manner as in the aforementioned step (3).

The film thus obtained is excellent in surface flatness, and thus can be used as a color filter substrate, a protective film or an overcoat layer for a touch panel, for example, in a liquid crystal display device, an organic EL display device, or electronic paper. Therefore, a display device with a high-quality film can be manufactured. In the color filter substrate having a concave-convex coloring pattern on the surface, the surface flatness can also be improved by forming an overcoat layer with 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 surface to be coated has unevenness, the film thickness from the surface of the convex portion) is preferably 0.5 μm or more and 5 μm or less, and more preferably 0.5 μm or more and 3 μm or less. . When the surface to be coated 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 difference in height of the irregularities on the surface to be coated. The overcoat layer obtained from the resin composition of the present invention can improve the flatness of the surface even if the film thickness is thin. By forming the overcoat layer using the resin composition of the present invention, the unevenness of the surface of the overcoat layer can be made to be 50% or less of the unevenness of the surface to be coated.

[Copolymer]

The copolymer of the present invention is a resin (A) which contains a structural unit (Aa) and a structural unit (Ab) but does not contain a structural unit (Ac), and the structural unit (Aa) contains the above formula (Aa-1) or the above formula The constituent unit represented by (Aa-2). The copolymer of the present invention can be used as a material of a resin composition for liquid crystal display devices, such as an overcoat layer of a color resist. The structural unit (Aa) in the copolymer of the present invention may be a structural unit represented by the above formula (Aa-1) or the above formula (Aa-2).

[Example]

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

[Examples 1 to 5 and Comparative Example 1]

<Preparation of resin composition>

Resin (A), polymerizable compound (C), polymerization initiator (D), hardener (G), and leveling agent (B) were mixed in the proportions shown in Table 1, and the solid content concentration was as shown in Table 1. 1 was mixed with propylene glycol monomethyl ether acetate as a solvent (E) to obtain each resin composition. In Table 1, the parts of each component represent parts by mass 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, Polymerizable Compound (c1): Dipivalerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Japan Kayaku Co., Ltd.), polymerizable compound (c2): ethylene glycol-modified dipivoerythritol hexaacrylate (KAYARAD (registered trademark) DP-3060; Nippon Kayaku Co., Ltd. product), polymerization start Agent (d1): N-benzyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF Corporation) , polycarboxylic acid (g1): 1,2,3,4-butane tetracarboxylic acid (Rikasidd (registered trademark) BT-W; manufactured by Nippon Chemical Co., Ltd.), leveling agent (b1): Megafac (registered trademark) trademark) F554; manufactured by DIC (stock)).

(Synthesis Example 1: Resin (a1))

Nitrogen gas was sufficiently poured into the flask equipped with a reflux cooler, a dropping funnel, and a stirrer to obtain a nitrogen atmosphere, 260 parts of diethylene glycol ethyl methyl ether was added, and the mixture was heated to 85°C while stirring. Next, 77 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) (the molar ratio of the two compounds in the mixture is 50:50) ) 278 parts of mixed solution and 155 parts of diethylene glycol ethyl methyl ether were dropped into the flask which was kept at 85°C over 4 hours.

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

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained resin was carried out by GPC under the following conditions.

Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.)

Column: TSK-GELG2000HXL

Column temperature: 40℃

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0mL/min

Measured liquid and solid concentration: 0.001 to 0.01% by mass

Injection volume: 50 μL

Detector: RI

Standard material for calibration: TSK standard polystyrene (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 the number average molecular weight of the converted polystyrene obtained above was used as the degree of dispersion.

(Synthesis Example 2: Resin (a2))

Nitrogen gas was sufficiently poured into a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to create a nitrogen atmosphere, 140 parts of diethylene glycol ethyl methyl ether was added, and the mixture was heated to 70°C while stirring. Next, 40 parts of methacrylic acid, 360 parts of a mixture of the monomer represented by the formula (I-1) and the monomer represented by the formula (II-1) (the molar ratio of the two compounds in the mixture is 50:50) were dissolved A solution was prepared in 190 parts of diethylene glycol ethyl methyl ether, and this solution was dropped into a flask that was kept at 70° C. by a drip pump over 4 hours.

On the other hand, 30 parts of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in 240 parts of diethylene glycol ethyl methyl ether using a separate drip pump. The solution was dropped into the flask over 5 hours. After the dropwise addition of the polymerization initiator solution was completed, the solution was kept at 70° C. for 4 hours, and then cooled to room temperature to obtain a solution of the copolymer (resin (a2)) having a solid content of 42%. The weight average molecular weight (Mw) of the obtained resin (a2) was 7,800, the degree of dispersion (Mw/Mn) was 2.0, and the acid value in terms of solid content was 61 mg-KOH/g. The resin (a2) has the following structural units.

(Synthesis Example 3: Resin (a3))

In Synthesis Example 1, except that 136 parts of the compound represented by the formula (III-1), the mixture of the compound represented by the formula (I-1) and the compound represented by the formula (II-1) (the molar ratio of the two compounds in the mixture) were used. 50:50) except 218 parts, it reacted by the same method as Synthesis Example 1, and obtained the resin (a3) of 26.2 weight% of solid content, weight average molecular weight (Mw) 7,750, and dispersion degree 1.8. The acid value of the resin (a3) in terms of solid content is 0 mg-KOH/g.

(Synthesis Example 4: Resin (a4))

In Synthesis Example 1, except that 177 parts of the compound represented by the formula (III-1), the mixture of the compound represented by the formula (I-1) and the compound represented by the formula (II-1) (the molar ratio of the two compounds in the mixture) were used. Except for 50:50) 177 parts, the reaction was carried out in the same manner as in Synthesis Example 1 to obtain a resin (a4) having a solid content of 24.6% by weight, a weight average molecular weight (Mw) of 7,960 and a degree of dispersion of 1.8. The acid value of the resin (a4) in terms of solid content is 0 mg-KOH/g.

<Production of Evaluation Board>

A 2-inch square glass substrate (Eagle XG: manufactured by Corning Incorporated) was washed with a neutral detergent, water, and isopropyl alcohol in this order, and then dried. A commercially available photosensitive resin composition (trade name: Diebright (registered trademark)) was spin-coated on the above-mentioned substrate so that the film thickness after post-baking was 2.0 μm. Next, the composition layer was formed by prebaking at 100° C. for 3 minutes in a clean oven. After cooling, the distance between the composition layer on the substrate and the mask made of quartz glass was 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd., light source; ultra-high pressure mercury lamp) was used under atmospheric pressure at 100 mJ/cm Light irradiation was performed at an exposure amount of ² (365 nm reference). In addition, this light irradiation was performed by making the light emitted from an ultra-high pressure mercury lamp pass through an optical filter (UV-313; manufactured by Technoglass Co., Ltd.). In addition, the photomask used for forming a 1:1 line and space pattern with a line width of 20 μm was used. The light-irradiated composition layer was immersed in an aqueous developing solution containing 0.12% nonionic surfactant and 0.04% potassium hydroxide for 60 seconds at 23°C for development, washed with water, and then carried out in an oven at 230°C After post-baking for 15 minutes, a substrate for evaluation in which a pattern of lines and spaces with a line width of 20 μm (10 lines and spaces, respectively) was formed was produced.

<Production of Film (Condition 1)>

Each resin of Examples 1 to 3, 6 to 7, and Comparative Example 1 was coated by a spin coater under the condition that the film thickness after post-baking (film thickness measured from the surface of the line pattern of the evaluation substrate) was 1.0 μm. The composition was coated on the aforementioned evaluation substrate. Then, it was dried under reduced pressure until the degree of reduced pressure reached 66Pa, pre-baked at 100°C for 3 minutes on a hot plate. After standing to cool, a film was formed by post-baking at a temperature of 230°C for 30 minutes. Using a contact film thickness measuring device (DEKTAK6M; manufactured by ULVAC Co., Ltd.), the film thickness of the film on the evaluation substrate was measured under the conditions of a measurement width of 500 μm and a measurement rate of 10 seconds, and the outline of the film surface shape was obtained.

Moreover, the average value of the film thickness of a film was calculated from this profile, and the average value of the film thickness measured from the line pattern surface of the substrate for evaluation was 1.0 μm.

<Production of Film (Condition 2)>

The resin compositions of Examples 4 and 5 were coated on the aforementioned substrate for evaluation by a spin coater under the condition that the film thickness after post-baking (the film thickness measured from the surface of the line pattern of the substrate for evaluation) was 1.0 μm. superior. Then, use a decompression dryer (manufactured by VCD Micro-Technology Co., Ltd.), with the rotation speed of the rotary pump at 1000 rpm, the rotation speed of the booster pump at 700 rpm, and the conditions of normal temperature 25 ° C, make it dry under reduced pressure until the decompression degree reaches 66 Pa, The hot plate was pre-baked at a temperature of 100°C for 3 minutes. After standing to cool, light irradiation was performed at an exposure amount (365 nm standard) of 25 mJ/cm ² under atmospheric pressure using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd., light source; ultra-high pressure mercury lamp). The composition layer after light irradiation was immersed in an aqueous developing solution containing 0.12% non-ionic surfactant and 0.04% potassium hydroxide 0.04% at 23°C for 60 seconds for development, and after washing with water, in an oven at 230°C A film was formed by post-baking for 15 minutes. Using a contact film thickness measuring device (DEKTAK6M; manufactured by ULVAC Co., Ltd.), the film thickness of the film on the evaluation substrate was measured with a measurement width of 500 μm and a measurement rate of 10 seconds to obtain the outline of the film surface shape. The average value of the film thickness of the film was calculated from the profile, and the average value of the film thickness measured from the line pattern surface of the substrate for evaluation was 1.0 μm.

<Flatness Evaluation>

For the film formed on the aforementioned evaluation substrate, the surface profile of the film formed on the line and space pattern of the evaluation substrate was measured using a stylus type film thickness meter (trade name: DEKTAK3; manufactured by Nippon Vacuum Co., Ltd.). As shown in the schematic cross-sectional view shown in FIG. 1, the difference Δ(μm) between the maximum film thickness and the minimum film thickness in the state where the line and space pattern 2 (space 2a, line 2b) and the film 3 on the substrate 1 are laminated is measured. , to evaluate flatness. The measurement results are shown in Table 1. The smaller the value of the difference Δ, the smoother the film formed.

With the resin composition of the present invention, a flat film can be formed even on a base or a substrate having a level difference. Since the film obtained from this resin composition is excellent in flatness, it can be applied to a display device and the like.

Since the diagrams in this case are only examples and are not representative, there is no designated representative diagram in this case.

Claims (6)

A resin composition for a liquid crystal display device, comprising a resin (A), a solvent and a leveling agent, wherein the resin (A) comprises a structural unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms and a reactive subunit (Aa). A copolymer of a structural unit (Ab) of a methyl group or an active methine group without a structural unit (Ac) from a compound belonging to the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, the aforementioned structural unit (Aa) contains a structural unit represented by formula (Aa-1) or formula (Aa-2);

In formula (Aa-1) and formula (Aa-1), 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 can be substituted with a hydroxyl group; X ^b1 and X ^b2 represents a single bond, *-R ^b3 -, *-R ^b3 -O-, *-R ^b3 -S- or *-R ^b3 -NH-; R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms ; * represents the bond with O The aforementioned structural unit (Ab) is 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. The resin composition for a liquid crystal display device according to claim 1, wherein the acid value of the resin (A) is 0 mg-KOH/g to 5 mg-KOH/g. The resin composition for a liquid crystal display device according to claim 1 or 2, wherein the resin (A) is composed of a structural unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms and a reactive subunit (Aa). A copolymer formed by the structural unit (Ab) of methyl group or active methine group. The resin composition for liquid crystal display devices according to claim 1 or 2, wherein the leveling agent is a fluorine-based surfactant. A film for a liquid crystal display device formed from the resin composition for a liquid crystal display device described in any one of claims 1 to 4 of the patent application. A copolymer containing a constituent unit (Aa) having a cyclic ether structure with a carbon number of 2 to 4 and a constituent unit (Ab) having an active methylene group or an active methine group, but not derived from an unsaturated carboxyl group. The constituent unit (Ac) of the compound of the group consisting of acid and unsaturated carboxylic acid anhydride, the aforementioned constituent unit (Aa) comprises the constituent unit represented by formula (Aa-1) or 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 can be substituted with a hydroxyl group; X ^b1 and X ^b2 represents a single bond, *-R ^b3 -, *-R ^b3 -O-, *-R ^b3 -S- or *-R ^b3 -NH-; R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms ; * represents the bond with O The aforementioned structural unit (Ab) is 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.

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