KR20170134239A - Resin composition and cured film - Google Patents

Abstract

The present invention relates to a resin composition which comprises a resin (A) and a solvent. The resin (A) is a copolymer comprising: a form unit (Aa) derived from (meth)acrylic acid alkyl ester including an alkyl group having 2 or more carbon atoms; a form unit (Ab) derived from an unsaturated compound including a ring-type ether structure having 2-4 carbon atoms; and a form unit (Ac) derived from at least one type of compounds selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydrides. A ratio of the form unit (Aa) is 10 mol% higher with respect to the total amount of structural units forming the resin (A). The weight-average molecular weight of the resin (A) is 5,000-20,000.

Description

RESIN COMPOSITION AND CURED FILM [0001]

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

In recent liquid crystal display devices, a curable resin composition is used to form a cured film such as a photo-spacer or an overcoat.

(Aa) and / or a compound (Ab) copolymerizable with the unsaturated carboxylic acid anhydride (Aa) and / or an unsaturated carboxylic acid anhydride (Aa) and / or an unsaturated carboxylic acid anhydride (Ac) having a cyclic ether group of a cyclic ether group (for example, Japanese Patent Application Laid-Open No. 2010-106154).

The cured film can be formed by applying a curable resin composition to a substrate and heating it. In realizing fine display in a liquid crystal display device, it is preferable that the cured film such as a photo spacer or an overcoat is flat. However, since the substrate on which the colored pattern is formed has irregularities, when the curable resin composition is applied to the substrate and heated to obtain a cured film, the level required for overcoat can not be obtained in some cases.

The present invention includes the following inventions.

[1] A resin composition comprising a resin (A) and a solvent,

The resin (A) is obtained by copolymerizing a constituent unit (Aa) derived from a (meth) acrylic acid alkyl ester having an alkyl group having 2 or more carbon atoms and a constituent unit (Ab) derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms , A structural unit (Ac) derived from at least one compound selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride,

The proportion of the structural unit (Aa) is preferably higher than 10 mol% with respect to the total structural units constituting the resin (A)

Wherein the resin (A) has a weight average molecular weight of 5,000 to 20,000.

[2] The resin composition according to [1], wherein the resin (A) is a resin comprising a constituent unit (Aa), a constituent unit (Ab) and a constituent unit (Ac).

[3] The resin composition according to [1] or [2], wherein the proportion of the structural unit (Aa) is higher than 10 mol% and 35 mol% or lower with respect to the total structural units constituting the resin (A).

[4] The resin composition according to any one of [1] to [3], wherein the structural unit (Aa) is a structural unit derived from a (meth) acrylic acid alkyl ester having a linear alkyl group having 2 to 10 carbon atoms.

[5] The resin composition according to any one of [1] to [3], wherein the structural unit (Aa) is a structural unit derived from a (meth) acrylic acid alkyl ester having a linear alkyl group having 2 to 6 carbon atoms.

[6] A cured film formed from the resin composition according to any one of [1] to [5].

According to the present invention, it is possible to provide a resin composition capable of forming a cured film having a high surface flatness.

1 is a view showing a cross-sectional shape of an evaluation sample of Example 1. Fig. Specifically, the profile of the cross-sectional shape of the cured film and the evaluation substrate is shown.
Fig. 2 is a view showing the cross-sectional shape of the evaluation sample of Example 2. Fig. Specifically, the profile of the cross-sectional shape of the cured film and the evaluation substrate is shown.
3 is a view showing a cross-sectional shape of an evaluation sample of Comparative Example 1. Fig. Specifically, the profile of the cross-sectional shape of the cured film and the evaluation substrate is shown.
4 is a view showing the cross-sectional shape of the evaluation sample of Comparative Example 2. Fig. Specifically, the profile of the cross-sectional shape of the cured film and the evaluation substrate is shown.

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

The resin composition of the present invention comprises a resin (A) and a solvent (E).

The resin (A) is obtained by copolymerizing a constituent unit (Aa) derived from a (meth) acrylic acid alkyl ester having an alkyl group having 2 or more carbon atoms and a constituent unit (Ab) derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms , A structural unit (Ac) derived from at least one compound selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride,

The proportion of the constituent unit (Aa) is higher than 10 mol% based on the total amount of the structural units constituting the resin (A), and the weight average molecular weight of the resin (A) is 5000 to 20,000.

Hereinafter, the (meth) acrylic acid alkyl ester is referred to as "compound (Aa)", the unsaturated compound having a cyclic ether structure of 2 to 4 carbon atoms is referred to as "compound (Ab)", and the unsaturated carboxylic acid and unsaturated carboxyl And at least one compound selected from the group consisting of acid anhydrides may be referred to as " compound (Ac) ".

In the present specification, the term "(meth) acrylic acid" refers to at least one kind of compound selected from the group consisting of acrylic acid and methacrylic acid. Acrylate "," (meth) acryloyl "and" (meth) acrylate "have the same meaning.

The resin composition of the present invention may further contain at least one compound selected from the group consisting of a glycidyl ether type epoxy resin and a glycidyl ester type epoxy resin (hereinafter sometimes referred to as " epoxy resin (C) " ), A reactive monomer (B), an antioxidant (F), and a surfactant (H).

The resin composition of the present invention may further comprise at least one compound selected from the group consisting of a polymerization initiator (D), a polymerization initiator (D1), a thiol compound (T), a polycarboxylic acid anhydride and a polyvalent carboxylic acid (Hereinafter may be referred to as " polyvalent carboxylic acid (G) ") or an imidazole compound (J).

≪ Resin (A) >

The resin (A) is preferably a thermosetting resin, more preferably a thermosetting resin at 60 ° C or higher, and more preferably a resin derived from a (meth) acrylic acid alkyl ester (Aa) having an alkyl group having 2 or more carbon atoms At least one compound selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (Ac (meth) acrylate), a structural unit derived from an unsaturated compound (Ab) having a cyclic ether structure of 2 to 4 carbon atoms, ). ≪ / RTI >

The copolymer can also be copolymerized with the compound (Aa), the compound (Ab) or the compound (Ac) and can also be derived from the compound (Ad) other than the compound (Aa) Or may have a constituent unit.

(1) a structural unit derived from the compound (Aa)

In the present invention, the resin (A) is a copolymer containing a constituent unit derived from the compound (Aa), whereby the flatness of the film obtained by applying the resin composition can be improved.

As the compound (Aa), there can be mentioned, for example, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) (Meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isobutyl Acrylate, and the like. The number of carbon atoms of the alkyl group in the compound (Aa) is preferably 10 or less, more preferably 8 or less, since the peeling of the film obtained by applying the resin composition on the substrate can be suppressed under high temperature and high humidity conditions , And more preferably 6 or less. The alkyl group of the compound (Aa) may be a linear or branched type, but is preferably a linear type.

(2) a structural unit derived from a compound (Ab)

The compound (Ab) refers to an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one member selected from the group consisting of oxiran ring, oxetane ring and tetrahydrofuran ring). The compound (Ab) is preferably a compound having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

As the compound (Ab), for example, a compound (Ab1) having an oxylanyl group and an ethylenic unsaturated bond (hereinafter sometimes referred to as "(Ab1)"), a compound having an oxetanyl group and an ethylenic unsaturated bond (Hereinafter sometimes abbreviated as "(Ab2)"), a compound (Ab3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes abbreviated as "Ab3") .

(Ab1) (hereinafter sometimes referred to as "(Ab1-1)") having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized, And a compound (Ab1-2) having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized (hereinafter sometimes referred to as "(Ab1-2)").

(Ab1-1) may include glycidyl (meth) acrylate,? -Methyl glycidyl (meth) acrylate,? -Ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, Vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5- Styrenes such as 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, (Glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) .

(Ab1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000 manufactured by Daicel Chemical Industries Ltd.), 3,4-epoxycyclohexyl (Meth) acrylate (for example, CYRAMER A400 manufactured by Daicel Chemical Industries Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate Ltd.), a compound represented by the formula (I) and a compound represented by the formula (II).

In the formulas (I) and (II), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group 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 the binding hand with O.]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl. Examples of the alkyl group in which the hydrogen atom is substituted with hydroxy include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, Hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group and the like can be given .

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 include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane- And a 1,6-diyl group.

X ^b1 and X ^b2 are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O-, * -CH ₂ CH ₂ -O-, more preferably a single bond, * - CH ₂ CH ₂ -O-. * Denotes the binding hand with O.

Examples of the compound represented by the formula (I) include a compound represented by any one of the formulas (I-1) to (I-15). Among them, the compound represented by the formula (I-1), the compound represented by the formula (I-3), the compound represented by the formula (I-5), the compound represented by the formula (I- ), And compounds represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15) are more preferable.

Examples of the compound represented by formula (II) include compounds represented by any one of formulas (II-1) to (II-15).

Among them, the compound represented by the formula (II-1), the compound represented by the formula (II-3), the compound represented by the formula (II-5), the compound represented by the formula ) Is more preferable and a compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) is more preferable.

The compound represented by formula (I) and the compound represented by formula (II) may be used either singly or in any combination. When used in combination, the content of the compound represented by formula (I) and the compound represented by formula (II) is preferably 5:95 to 95: 5, more preferably 10:90 to 90: 10, and more preferably 20:80 to 80:20. For example, there is a mixture (commercially available product "E-DCPA" (manufactured by Daicel Co., Ltd.) containing 50:50 of the compound represented by the formula (I-1) and the compound represented by the formula ) Can be used.

(Ab2) is more preferably a compound having an oxetanyl group and a (meth) acryloyloxy group. (Ab2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3- 3-ethyl-3-acryloyloxyethyl oxetane, and the like.

(Ab3), a compound having a tetrahydrofuryl group and a (meth) acryloyloxy group is preferable. (Ab3) include tetrahydrofurfuryl acrylate (for example, Viscot V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

The compound (Ab) is preferably (Ab1) in that the reliability of heat resistance, chemical resistance and the like of the obtained cured film can be further increased. Further, (Ab1-2) is more preferable because of the excellent storage stability of the resin composition.

(3) a structural unit derived from a compound (Ac)

Examples of the compound (Ac) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m- and p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, 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- 5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept- Cyclo [2.2.1] hept-2-ene, and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride Unsaturated dicarboxylic acid anhydrides such as dimethyl tetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-eno anhydride; mono [2- (meth) acryloyloxyethyl] succinate, Unsaturated mono [(meth) acryloyloxyalkyl] esters of a divalent or higher polyvalent carboxylic acid such as phthalic acid mono [2- (meth) acryloyloxyethyl];

 unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule, such as? - (hydroxymethyl) acrylic acid;

And the like.

Of these, (meth) acrylic acid and maleic anhydride are preferable from the viewpoint of copolymerization reactivity and solubility in an aqueous alkali solution, and (meth) acrylic acid is more preferable.

(4) a structural unit derived from a compound (Ad)

Examples of the compound (Ad) include methyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (referred to in the art as "dicyclopentanyl (meth) acrylate"

(Tricyclodecyl (meth) acrylate), tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (referred to in the art as " (Meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (Meth) acrylic acid esters such as propyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate and benzyl (meth) acrylate;

(Meth) acrylic acid esters having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;

2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [ 2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept- 2,1-hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept- Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 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- Cycarbonylbicyclo [ 2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bee [ Cyclo [2.2.1] hept-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as 6-maleimide caproate, N-succinimidyl-3-maleimidepropionate and N- (9-acridinyl) maleimide;

But are not limited to, styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide , Vinyl acetate, 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene.

Of these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo [2.2.1] hept-2-ene are preferable from the viewpoint of copolymerization reactivity and heat resistance .

(5) Ratio of each constituent unit

The resin (A) is the following resin [K1] or [K2].

Resin [K1]: copolymer of compound (Aa), compound (Ab) and compound (Ac);

Resin [K2]: Copolymer of compound (Aa), compound (Ab), compound (Ac) and compound (Ad).

In the resin [K1], the ratio of each constituent unit is preferably such that the total constituent units constituting the resin [K1]

5 to 40 mol% of a constituent unit derived from the compound (Aa)

, 5 to 90 mol% of a constituent unit derived from the compound (Ab)

, A constituent unit derived from the compound (Ac), preferably from 5 to 40 mol%

10 to 35 mol% of a constituent unit derived from the compound (Aa)

A structural unit derived from the compound (Ab); 10 to 80 mol%

And more preferably 10 to 35 mol% of a constituent unit derived from the compound (Ac).

The proportion of the structural unit (Aa) in the resin (A) is higher than 10 mol% and further 35 mol% or less, and the constitutional unit derived from the compound (Ab) is 10 mol% or more and less than 80 mol% Is more preferable.

When the ratio of the constituent unit constituting the resin [K1] is within the above range, there is a tendency that the storage stability of the resin composition, the chemical resistance of the obtained cured film, the heat resistance and the mechanical strength are excellent.

Resin [K1] can be synthesized by, for example, the method described in "Experimental Method of Polymer Synthesis" (published by Otsu Takayuki Co., Ltd., first edition, 1st edition, published on March 1, 1972) Can be produced by referring to the cited document.

Specifically, a predetermined amount of a compound (Aa), a compound (Ab) and a compound (Ac), a polymerization initiator and a solvent are placed in a reaction vessel and oxygen is replaced by, for example, nitrogen, , And a method of heating and keeping warm while stirring. The polymerization initiator, solvent and the like to be used herein are not particularly limited and those conventionally used in the art can be used. Examples of the polymerization initiator include azo compounds (such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and the like) and organic peroxides (such as benzoyl peroxide And the like. The solvent may be any one that dissolves the respective monomers, and includes a solvent to be used in the resin composition, which will be described later.

In the resin obtained by the above method, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used, or it may be taken out as a solid (powder) by a method such as re-precipitation. Particularly, by using a solvent used for the resin composition of the present invention as a 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.

In the resin [K2], the ratio of the respective constitutional units is such that, among all the constitutional units constituting the resin [K2]

, 5 to 40 mol% of a constituent unit derived from the structural unit (Aa)

, 5 to 90 mol% of constitutional units derived from the structural unit (Ab)

(Ac); 5 to 40 mol%

(Ad) derived from a structural unit derived from an unsaturated carboxylic acid, preferably 1 to 40 mol%

10 to 35 mol% of a constituent unit derived from the structural unit (Aa)

(Ab), 10 to 80 mol%

(Ac), 10 to 35 mol%

More preferably from 5 to 35 mol% of the structural unit derived from the structural unit (Ad).

When the ratio of the constituent unit of the resin [K2] is within the above range, there is a tendency that the storage stability of the resin composition, the chemical resistance of the obtained cured film, the heat resistance and the mechanical strength are excellent.

The resin [K2] can be produced by the same method as the resin [K1]. As described above, the proportion of the structural unit (Aa) in the resin (A) is higher than 10 mol% and 35 mol% or lower and the constitutional unit derived from the compound (Ab) is 10 mol% or higher And more preferably less than 80 mol%.

Specific examples of the resin [K1] include a copolymer of an ethyl (meth) acrylate / a compound of the formula (I-1) / a (meth) acrylic acid, a compound of an ethyl (meth) acrylate / (Meth) acrylate / a compound of the formula (I-4) / (meth) acrylate, a copolymer of the ethyl (meth) acrylate / A copolymer of ethyl (meth) acrylate, a compound of formula (I-5) / a copolymer of (meth) acrylic acid, a compound of ethyl (meth) acrylate / Copolymer of ethyl (meth) acrylate / compound of formula (I-7) / copolymer of (meth) acrylic acid, compound of formula (I-8) / copolymer of (meth) (Meth) acrylate / compound of formula (I-10) / copolymer of (meth) acrylic acid, ethyl (meth) Ethyl (meth) (Meth) acrylate / compound of formula (I-12) / copolymer of (meth) acrylic acid, ethyl (meth) acrylate / (Meth) acrylate / compound of formula (I-14) / copolymer of (meth) acrylic acid, ethyl (meth) acrylate / (Meth) acrylate / compound of formula (II-1) / (meth) acrylic acid, a copolymer of ethyl (meth) acrylate / (Meth) acrylate / (II-3) / (meth) acrylic acid / (meth) acrylate / (Meth) acrylate / (meth) acrylate / (meth) acrylate / (meth) acrylate copolymer of formula (II) Unity / (Meth) acrylic acid / ethyl (meth) acrylate / compound of formula (II-7) / copolymer of (meth) (Meth) acrylate, a compound of formula (II-9) / a copolymer of (meth) acrylic acid, a copolymer of ethyl (meth) acrylate / (Meth) acrylate / a compound of the formula (II-12) / (meth) acrylate, a copolymer of an ethyl (meth) acrylate / a compound of the formula (Meth) acrylate / compound of formula (II-13) / copolymer of (meth) acrylic acid, ethyl (meth) acrylate / compound of formula (Meth) acrylate / compound of formula (II-15) / copolymer of (meth) acrylic acid, ethyl (meth) acrylate / compound of formula (I- (Meth) (Meth) acrylate / a compound of the formula (II-1) / (meth) acrylate / butyl (meth) acrylate / a compound of the formula (Meth) acrylate / compound of the formula (I-1) / compound of the formula (II-2) / copolymer of the (meth) (Meth) acrylate / compound of formula (I-1) / (meth) acrylate / copolymer of maleic acid, butyl (meth) acrylate / (Meth) acrylate / (meth) acrylate / copolymer of formula (I-1) / copolymer of (meth) acrylic acid, butyl (meth) acrylate / (Meth) acrylate / compound of formula (II-1) / copolymer of maleic acid, butyl (meth) acrylate / compound of formula (II-1) / Met) arc (Meth) acrylate / a compound of the formula (II-1) / (meth) acrylate / a copolymer of the (meth) acrylate / maleic anhydride, (Meth) acrylate / compound of formula (I-1) / compound of formula (II-2) / copolymer of (meth) acrylic acid, compound of propyl (Meth) acrylate / compound of formula (I-1) / copolymer of maleic acid, propyl (meth) acrylate / compound of formula (I-1) (Meth) acrylate / propyl (meth) acrylate / compound of formula (I-1) / copolymer of (meth) acrylic acid, propyl (meth) acrylate (Meth) acrylate / compound of formula (II-1) / maleic acid copolymer, propyl (meth) acrylate / (Meth) acrylate / compound of formula (I-1) / copolymer of (meth) acrylic acid, hexyl (meth) acrylate / (Meth) acrylate / compound of formula (II-1) / copolymer of (meth) acrylic acid, hexyl (meth) acrylate / compound of formula (I- (Meth) acrylate / compound of formula (I-1) / copolymer of maleic acid, hexyl (meth) acrylate / (Meth) acrylate / compound of formula (I-1) / copolymer of (meth) acrylic acid / maleic anhydride, copolymer of hexyl (meth) acrylate / butyl (Meth) acrylic acid, a copolymer of hexyl (meth) acrylate / compound of formula (II-1) / copolymer of crotonic acid, a compound of formula (II) coalescence, (Meth) acrylate / compound of formula (II-1) / copolymer of (meth) acrylic acid / maleic anhydride, 2-ethylhexyl (Meth) acrylate / compound of formula (II-1) / copolymer of (meth) acrylic acid, 2-ethylhexyl (Meth) acrylate / a compound of formula (I-1) / a crotonic acid copolymer, a copolymer of 2-ethylhexyl (meth) acrylate / (Meth) acrylate / compound of formula (I-1) / copolymer of (meth) acrylic acid / maleic anhydride, 2 (Meth) acrylate / (meth) acrylate / copolymer of the formula (I-1) / copolymer of (meth) acrylic acid, 2-ethylhexyl Compound / crotonic acid copolymer, 2-ethyl (Meth) acrylate / compound of formula (II-1) / copolymer of maleic acid, 2-ethylhexyl (meth) acrylate / compound of formula (II-1) / Copolymers and the like.

As the resin [K2], the resin [K1] exemplified above may further include a structural unit derived from the compound (Ad).

The weight average molecular weight (Mw) of the resin (A) in terms of polystyrene 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 5,000 to 10,000. When the weight average molecular weight (Mw) of the resin (A) is within the above range, the coating property of the resin composition tends to be good.

The dispersion degree (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 cured film tends to have excellent chemical resistance.

The acid value of the resin (A) is preferably 30 mgKOH / g or more and 180 mgKOH / g or less, more preferably 40 mgKOH / g or more and 150 mgKOH / g or less, still more preferably 50 KOH / g or more and 135 mg-KOH / g or less, particularly preferably 50 mg-KOH / g or more and 100 mg-KOH / g or less.

The acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin, and can be obtained by titration using an aqueous potassium hydroxide solution. When the acid value of the resin (A) is within the above range, the resulting cured film tends to have excellent adhesion with the substrate.

When the resin composition of the present invention contains a component other than the resin (A) and the solvent (E) such as the reactive monomer (B), the content of the resin (A) is not particularly limited, , Preferably 30 to 90 mass%, more preferably 35 to 80 mass%, and still more preferably 40 to 70 mass%, based on the total mass of the composition.

When the content of the resin (A) is within the above range, the cured film obtained is excellent in heat resistance and tends to have excellent adhesion with the substrate and chemical resistance.

Here, the solid content of the resin composition refers to the amount excluding the content of the solvent (E) from the total amount of the resin composition of the present invention.

≪ Reactive monomer (B) >

The reactive monomer (B) is a monomer which reacts by the action of heat or the polymerization initiator (D). As the monomer, for example, a compound having an ethylenically unsaturated bond can be mentioned, , A compound (B1), and more preferably a compound having at least one group selected from the group consisting of an acryloyl group and a methacryloyl group.

Examples of the (meth) acrylic compound having one (meth) acryloyl group include (meth) acrylic acid alkyl ester, phenoxylated polyethylene glycol ester of (meth) acrylic acid, alkoxylated polyethylene glycol ester of (meth) (Meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxybutyl , Tetrahydrofurfuryl (meth) acrylate, and the like.

Examples of the (meth) acryl compound having two (meth) acryloyl groups include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, Acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di Acrylate, polyethylene glycol diacrylate, bis (acryloyloxyethyl) ether of bisphenol A, ethoxylated bisphenol A di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate, ethoxylated neopentyl Glycol di (meth) acrylate, and 3-methylpentanediol di (meth) acrylate.

(Meth) acryloyl groups having three or more (meth) acryloyl groups include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2-hydroxyethyl) (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylated trimethylol propane tri Acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tetra (meth) acrylate, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) (Meth) acrylate, pentaerythritol tri (meth) acrylate and acid anhydride, a reaction product of pentaerythritol tri (meth) A reaction product of dipentaerythritol penta (meth) acrylate and an acid anhydride, a reaction product of tripentaerythritol hepta (meth) acrylate and an acid anhydride, caprolactone-modified trimethylol propane tri (meth) acrylate, caprolactone modified pentaerythritol (Meth) acrylate, caprolactone modified tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol (Meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol tetra (meth) acrylate, caprolactone-modified tripentaerythritol penta (meth) Lactone-modified tripentaerythritol hexa (meth) acrylate, caprolactone-modified tripentaerythritol Caprolactone-modified dipentaerythritol penta (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate and acid anhydride, caprolactone-modified dipentaerythritol penta (meth) acrylate, A reaction product of an acrylate and an acid anhydride, and a reaction product of caprolactone-modified tripentaerythritol (meth) acrylate and an acid anhydride.

As the (meth) acrylic compound (B1), a (meth) acrylic 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 the (meth) acrylic compound (B1), the content thereof is preferably 20 to 100 parts by mass, more preferably 25 to 100 parts by mass based on 100 parts by mass of the resin (A) 70 parts by mass. When the content of the (meth) acrylic compound (B1) is within the above range, the chemical resistance and mechanical strength of the resulting cured film can be improved.

As a suitable example of the reactive monomer (B), a compound represented by formula (1) (hereinafter, the compound may be referred to as "compound (B2)" in some cases).

Wherein R ¹ to R ³ independently represent a group represented by formula (a) or a group represented by formula (b), and at least one of R ¹ to R ³ is a group represented by formula (b) Lt; / RTI >

(In the formulas (a) and (b), R ⁴ and R ⁵ independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.)

Examples of the alkyl group having 1 to 8 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group and an octyl group.

R ⁴ is preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

R ⁵ is preferably a hydrogen atom or a methyl group.

It is preferable that at least one of R ¹ to R ³ is a group represented by formula (a).

Examples of the compound (B2) include compounds represented by the formulas (1-1) to (1-6). Is preferably a compound represented by any one of formulas (1-1) to (1-4).

When the resin composition of the present invention contains the compound (B2), the content thereof is preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass, per 100 parts by mass of the resin (A) . When the content of the compound (B2) is within the above range, the heat resistance of the resulting cured film can be improved.

≪ Epoxy resin (C) >

As the epoxy resin (C), for example, glycidyl ether type epoxy resin and glycidyl ester type epoxy resin (C) may be used as the epoxy resin (C) At least one kind of compound selected from the group consisting of

The glycidyl ether type epoxy resin is an epoxy resin having a glycidyl ether structure and can be synthesized by reacting epichlorohydrin with phenols, polyhydric alcohols and the like. Examples of the glycidyl ether type epoxy resin include epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, phenol novolak type epoxy resin, o-cresol novolak type epoxy resin, And epoxy-methoxy-type epoxy resins.

The glycidyl ester type epoxy resin is an epoxy resin having a glycidyl ester structure and is synthesized by reacting epichlorohydrin with a carbonyl group such as a phthalic acid derivative or a fatty acid. Examples of the glycidyl ester type epoxy resin include glycidyl ester type epoxy resins derived from aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid and terephthalic acid.

The epoxy resin (C) is a glycidyl ether type epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, o-cresol novolak type epoxy resin and polyphenol type epoxy resin . Among them, a bisphenol A type epoxy resin is particularly preferable.

The glycidyl ether type epoxy resin can be synthesized by condensing the corresponding phenol compound and epichlorohydrin in the presence of a strong alkali by a conventionally known method. Such a reaction can be carried out by a conventionally known method for a person skilled in the art.

As the glycidyl ether type epoxy resin, a commercially available product may be used. Examples of commercial products of bisphenol A type epoxy resin include jER157S70, Epicote 1001, Epicote 1002, Epicote 1003, Epicote 1004, Epicote 1007, Epicote 1009, Epicote 1010, Epicote 828 (manufactured by Mitsubishi Chemical Corporation) ) And the like. Examples of commercially available bisphenol F epoxy resins include Epikote 807 (manufactured by Mitsubishi Chemical Corporation) and YDF-170 (manufactured by Toto Chemical Industry Co., Ltd.). Eponote 152, Epikote 154 (manufactured by Mitsubishi Chemical Corporation), EPPN-201, PPN-202 (manufactured by Nippon Kayaku Co., Ltd.) and DEN-438 (manufactured by Dow Chemical Co., Ltd.) as commercial products of phenol novolac epoxy resin And the like. Examples of commercially available o-cresol novolac epoxy resins include EOCN-125S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.). Examples of commercially available polyphenol type epoxy resins include Epikote 1032H60 and Epikote YX-4000 (manufactured by Mitsubishi Chemical Corporation).

The epoxy equivalent of the epoxy resin (C) is preferably 100 to 500 g / eq, more preferably 150 to 400 g / eq. Here, the epoxy equivalent is defined by the molecular weight of the epoxy resin per epoxy group. The epoxy equivalent can be measured, for example, by the method prescribed in JIS K7236.

The acid value of the epoxy resin (C) is usually less than 30 mg-KOH / g, preferably 10 mg-KOH / g or less. The weight average molecular weight of the epoxy resin (C) is preferably 300 to 10,000, more preferably 400 to 6,000, and still more preferably 500 to 4,800.

When the resin composition of the present invention contains the epoxy resin (C), the content thereof is preferably 1 to 60 parts by mass, more preferably 1 to 60 parts by mass, per 100 parts by mass of the total content of the resin (A) and the reactive monomer (B) Is 5 to 50 parts by mass. When the content of the epoxy resin (C) is within the above range, the cured film obtained tends to have excellent adhesion with the substrate.

≪ Polymerization initiator (D) >

As the polymerization initiator (D), any known polymerization initiator can be used without particular limitation, as long as it is a compound capable of generating an active radical or an acid by the action of light or heat and capable of initiating polymerization of the reactive monomer (B) . As the polymerization initiator (D), a polymerization initiator containing at least one member selected from the group consisting of O-acyloxime compounds, alkylphenone compounds, triazine compounds, acylphosphine oxide compounds and imidazole compounds is preferable, and O -Acyloxime compound is more preferable.

These polymerization initiators tend to have a high sensitivity and a high transmittance in the visible light region.

The O-acyloxime compound is a compound having a structure represented by formula (d1). Herein, * denotes a combined hand.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethan- 1-imine, N- acetoxy- 1- [ 3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethan- 1-imine, N- acetoxy- 1- [ Benzoyloxy) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbaldehyde 3-yl] -3-cyclopentylpropan-1-one-2-imine. Commercially available products such as Irgacure (registered trademark) OXE01, OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used.

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

Examples of the compound having a structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- (4-morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) Butan-1-one. And commercially available products such as Irgacure (registered trademark) 369, 907 and 379 (manufactured by BASF). Also, a polymerization initiator having a group capable of chain transfer described in Japanese Patent Publication No. 2002-544205 may be used. Examples of the compound having the structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2- Hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, an oligomer of 2-hydroxy- ,?,? -diethoxyacetophenone, and benzyldimethylketal. From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by formula (d2).

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (5-methylfuran-1-yl) Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- Triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- L-methylethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. A commercially available product such as Irgacure 819 (manufactured by BASF Japan K.K.) may be used.

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis -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'-tetra (alkoxy) Phenyl) imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) ) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (Japanese Patent Publication No. 48-38403, Japanese Unexamined Patent Publication No. 62-174204 etc.), 4,4'5 , Imidazole compounds in which the phenyl group at the 5'-position is substituted by a carboalkoxy group (see JP-A-7-10913, etc.).

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

As the polymerization initiator (D), an acid generating system can be used. Examples of the acid generator include, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p- 4-acetoxyphenyl methyl benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate , Diphenyl iodonium hexafluoroantimonate, and the like, and nitrobenzyl tosylate and benzoin tosylate.

When the resin composition of the present invention contains the polymerization initiator (D), its content is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 30 parts by mass, per 100 parts by mass of the total content of the resin (A) and the reactive monomer (B) 0.5 to 15 parts by mass, more preferably 1 to 8% by mass. When the content of the polymerization initiator (D) is within the above range, high sensitivity is obtained and the exposure time tends to be shortened, so that the productivity is improved and the visible light transmittance of the resulting pattern tends to be high.

≪ Polymerization Initiator (D1) >

The polymerization initiator (D1) is used together with the polymerization initiator (D) to accelerate the polymerization of the polymerizable compound (for example, the (meth) acrylic compound (B)) initiated by the polymerization initiator Or a sensitizer.

Examples of the polymerization initiation auxiliary (D1) include a thiazoline compound, an amine compound, an alkoxyanthracene compound, a thiazonone compound, and a carboxylic acid compound.

Examples of the thiazoline compound include compounds represented by formulas (III-1) to (III-3) and compounds described in JP-A No. 2008-65319.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethyl para-toluidine, 4,4'-bis (dimethylamino) benzophenone (collectively, Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4 , 4'-bis (ethylmethylamino) benzophenone, and the like, among which 4,4'-bis (diethylamino) benzophenone is preferable. And commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

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

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

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, Chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

When the resin composition of the present invention contains the polymerization initiator (D1), the content thereof is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 30 parts by mass based on 100 parts by mass of the total content of the resin (A) and the reactive monomer (B) And preferably 0.2 to 10 parts by mass. When the amount of the polymerization initiator (D1) is within the above range, the sensitivity tends to become higher when the pattern is formed.

≪ Thiol compound (T) >

The thiol compound (T) is a compound having a sulfanyl group (-SH) in the molecule. Among them, a compound having two or more sulfanyl groups is preferable, and a compound having two or more sulfanyl groups bonded to carbon atoms of an aliphatic hydrocarbon structure is more preferable. The thiol compound (T) is preferably used together with the polymerization initiator (D).

Examples of the thiol compound (T) include hexane dithiol, decane dithiol, 1,4-bis (methylsulfanyl) benzene, butanediol bis (3-sulfanylpropionate), butanediol bis Acetate), ethylene glycol bis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediol bis (3-sulfanyl propionate), trimethylolpropane tris (3-sulfanyl propionate ), Trimethylolpropane tris (3-sulfanyl acetate), pentaerythritol tetrakis (3-sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl acetate), tris hydroxyethyl tris (3- Sulfanyl propionate), pentaerythritol tetrakis (3-sulfanyl butyrate), and 1,4-bis (3-sulfanylbutyloxy) butane.

When the resin composition of the present invention contains the thiol compound (T) together with the polymerization initiator (D), the content thereof is preferably 10 to 90 parts by mass, more preferably 10 to 90 parts by mass, per 100 parts by mass of the polymerization initiator (D) And preferably 15 to 70 parts by mass. When the content of the thiol compound (T) is within the above range, sensitivity tends to be high and developability tends to be good.

≪ Antioxidant (F) >

Examples of the antioxidant (F) include a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant and an amine-based antioxidant. Among them, a phenol-based antioxidant is preferable in that the cured film is less colored.

Examples of the phenolic antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -3,5-di-tert-butylphenyl) ethyl] -4,6-di-tert-pentylphenyl acrylate, 3,9-bis [2- {3- (3- Methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, 2,2'-methylenebis (6-tert- Methylphenol), 4,4'-butylidenebis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (2-tert- Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5 -Triazine-2,4,6 (1H, 3H, 5H) -trione, 3,3 ', 3 ", 5,5' Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2 , 6-di-tert-butyl-4-methylphenol and 6- [3- (3-tert- Methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1,3,2] dioxaphosphper. As the phenolic antioxidant, a commercially available product may be used. Examples of commercially available phenolic antioxidants include water-soluble risers BHT, GM, GS and GP (all manufactured by Sumitomo Chemical Co., Ltd.), Irganox (registered trademark) 1010, 1076, 1330 and 3114 (all manufactured by BASF).

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

Examples of the phosphorus antioxidant include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, tris (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra (tridecyl) -1 , And 1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane diphosphite. As the phosphorus antioxidant, a commercially available product may be used. Examples of commercially available phosphorus antioxidants include Irgafos (registered trademark) 168, 12 and 38 (all of which are manufactured by BASF), Adekastab 329K, Adekastab PEP36 Manufactured by ADEKA).

Examples of the amine-based antioxidant include N, N'-di-sec-butyl-p-phenylenediamine, N, N'-diisopropyl- Hexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine and N, N'-bis (2-naphthyl) -p-phenylenediamine. As the amine antioxidant, a commercially available product may be used. Commercially available amine antioxidants include, for example, watertight riser (registered trademark) BPA, BPA-M1 and 4ML (all manufactured by Sumitomo Chemical Co., Ltd.).

When the resin composition of the present invention contains the antioxidant (F), its content is preferably 0.1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the total content of the resin (A) and the reactive monomer (B) More preferably 0.5 part by mass or more and 3 parts by mass or less. When the content of the antioxidant (F) is within the above range, the resulting cured film tends to have excellent heat resistance and pencil hardness.

≪ Surfactant (H) >

Examples of the surfactant (H) include a silicone surfactant (having no fluorine atom), a fluorinated surfactant (having no siloxane bond), and a silicon surfactant having a fluorine atom.

Examples of the silicone surfactant include a surfactant having a siloxane bond. Concretely, it is possible to use a silicone oil such as Torensilicon DC3PA, SH7PA, Copper DC11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Polyether Modified Silicone Oil SH8400 (trade name: Toray Dow Corning) KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (Momentive Performance Materials Japan Co., Ltd.) And the like.

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain.

Concretely, there may be mentioned Fludin (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Ltd.), Megapack (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177, copper F183, copper F552, (Registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Material Electronics Corporation (registered trademark)), F555, F555, F556, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Co., Ltd.).

Examples of the silicone surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specific examples thereof include Megapac (registered trademark) R08, Copper BL20, Copper F475, Copper F477, Copper F443 (manufactured by DIC Corporation). And preferably Megapak (registered trademark) F475.

When the resin composition of the present invention contains the surfactant (H), the content thereof is usually 0.001% by mass or more and 0.2% by mass or less, preferably 0.002% by mass or more and 0.1% by mass or less based on the total amount of the resin composition of the present invention % Or less, more preferably 0.01 mass% or more and 0.05 mass% or less. When the content of the surfactant (H) is within the above range, the flatness of the cured film can be improved.

≪ The polycarboxylic acid (G)

The polyvalent carboxylic acid (G) is at least one compound selected from the group consisting of polyvalent carboxylic anhydrides and polyvalent carboxylic acids.

The polycarboxylic acid is a compound having two or more carboxyl groups, and the polycarboxylic anhydride is an anhydride of a polycarboxylic acid. Further, the polyvalent carboxylic acid (G) is distinguished from the reactive monomer (B) in that it does not have a polymerizable substituent such as a carbon-carbon double bond.

The molecular weight of the polycarboxylic acid (G) is preferably 3000 or less, more preferably 1000 or less.

Examples of the polycarboxylic anhydrides include maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhydride, 2-dodecylsuccinic anhydride, 2- Enyl) succinic anhydride, 2- (2,4,6-trimethylnona-3-enyl) succinic anhydride, tricarbalic acid anhydride and 1,2,3,4-butanetetracarboxylic acid dianhydride. Carboxylic anhydrides, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hexahydrophthalic 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 acid anhydride, methylbicyclo [2.2.1] hept- Pentanetetracarboxylic acid dianhydride, and other alicyclic polycarboxylic acid anhydrides such as phthalic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic acid dianhydride (Anhydrotrimellitate), glycerin tris (anhydrotrimellitate), glycerin bis (anhydrotrimellitate), glycerin bis (anhydrotrimellitate), glycerin bis Monoacetate, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) And aromatic dicarboxylic acid anhydrides such as dione. (Manufactured by ADEKA), ricardide-HH, copper-TH, copper-MH, copper MH-700 (manufactured by Shin-Nippon Electric Co., Ltd.) Commercially available products such as Nia 126, Dong YH-306 and Dong DX-126 (manufactured by Yucca Shell Epoxy Co., Ltd.) may be used.

Examples of the polyvalent carboxylic acid include polyvalent carboxylic acids such as oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, and polycarboxylic acids derived from a chain type polycarboxylic acid anhydride. Alicyclic polycarboxylic acids such as cyclohexane dicarboxylic acid, and polycarboxylic acid derived from cycloaliphatic dicarboxylic acid anhydride; aromatic dicarboxylic acids such as isophthalic acid, terephthalic acid, 1,4,5,8-naphthalenetetracarboxylic acid, And aromatic polycarboxylic acids such as polyvalent carboxylic acids which derive aromatic polycarboxylic anhydrides.

Of these, chain-like carboxylic acid anhydrides and alicyclic polycarboxylic acid anhydrides are preferable because they are excellent in heat resistance of the cured film and in particular, transparency in the visible light region is unlikely to deteriorate, and alicyclic polycarboxylic acid anhydrides are more preferable desirable.

When the resin composition of the present invention contains a polyvalent carboxylic acid (G), its content is preferably from 1 to 30 parts by mass, more preferably from 1 to 30 parts by mass, based on 100 parts by mass of the total content of the resin (A) and the reactive monomer (B) More preferably 2 to 20 parts by mass, and still more preferably 2 to 15 parts by mass. When the content of the polyvalent carboxylic acid (G) is within the above range, the cured film has excellent heat resistance and adhesion.

≪ Imidazole compound (J) >

The imidazole compound (J) is not particularly limited as long as it is a compound having an imidazole skeleton and includes, for example, a compound known as an epoxy curing agent. Among them, the compound represented by the formula (2) is preferable.

[In the formula (2), R ¹¹ 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 ¹² to R ¹⁴ 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, Or may be substituted with a hydroxyl group.]

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isobutyl, butyl, tert-butyl, hexyl, heptyl, , And 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 a formyl group, an acetyl group, a propionyl group, an isobutyryl group, a valeryl group, an isovaleryl group, a pivaloyl group, a lauroyl group, a myristyl group, .

Examples of the imidazole compound (J) include 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, 5- Methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methyl Imidazole, 4-hydroxymethyl-2-phenylimidazole, 2-phenylimidazole, 2-phenyl-2-hydroxymethylimidazole, 1-benzyl- Benzyl-5-hydroxymethylimidazole, 2- (p-hydroxyphenyl) imidazole, 1-cyanomethyl Methylimidazole, 1- (2-cyanoethyl) -2-hydroxymethylimidazole, 2,4-diphenylimidazole, 1-cyanomethyl-2-undecylimidazole Methylimidazole, 1-cyanomethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl- You can lift the ball. Among them, 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 the imidazole compound (J), its content is preferably 0.1 part by mass or more and 25 parts by mass or less, more preferably 0.1 parts by mass or more, More preferably 0.2 parts by mass or more and 15 parts by mass or less, and still more preferably 0.5 parts by mass or more and 5 parts by mass or less. When the content of the imidazole compound (J) is within the above range, the resulting cured film tends to have excellent 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 composition, 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 ethers such as ethylene glycol monoalkyl ether;

Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether;

Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate and 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, and methoxypentyl acetate;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and 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 and 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 and propylene glycol butyl ether propionate;

Butyldiol monoalkyl ethers such as methoxybutyl alcohol, ethoxybutyl alcohol, propoxybutyl alcohol and butoxybutyl alcohol;

Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate and butoxybutyl acetate;

Butanediol monoalkyl ether propionate such as methoxy butyl propionate, ethoxy butyl propionate, propoxy butyl propionate and butoxy butyl propionate;

Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropyl glycol methyl ethyl ether;

Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene;

Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone;

Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin;

Examples of the solvent include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy- , Hydroxybutyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, Methyl methoxyacetate, methyl methoxyacetate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate, ethoxyacetate, ethoxyacetate, propoxy Methyl acetate, ethyl propoxyacetate, propoxy propylacetate, butyl propoxyacetate, methyl butoxyacetate, Methoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-methoxypropionate, Ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 3-butoxypropionate, Ethoxypropionate, propyl 3-ethoxypropionate, propyl 3-methoxypropionate, propyl 3-methoxypropionate, methyl 3-methoxypropionate, Propoxy propionate, methyl 3-butoxypropionate, butyl 3-propoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, Propyl 3-butoxypropionate, butyl 3-butoxypropionate and the like;

Cyclic ethers such as tetrahydrofuran and pyran;

cyclic esters such as? -butyrolactone; and the like.

Among the above-mentioned solvents, organic solvents having a boiling point of 100 to 200 DEG C in the above solvents are preferable from the viewpoints of coatability and drying property. Specific examples of the organic solvent having a boiling point of 100 to 200 ° C include alkylene glycol alkyl ether acetates, alcohols such as methoxybutanol and ethoxybutanol, ketones such as cyclohexanone, ethyl 3-ethoxypropionate and 3- Methoxybutyl acetate, ethyl 3-ethoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutanol, - methyl 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 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, and 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>

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

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) and 2,2'-azobis (2,4-dimethylvaleronitrile). Examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxybenzophenone. Examples of the chain transfer agent include dodecanethiol, 2,4-diphenyl-4-methyl-1-pentene and the like.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxy Silane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane , N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, -Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane and the like.

The resin composition of the present invention is preferably substantially free of a coloring agent such as a pigment and a dye. That is, in the resin composition of the present invention, the content of the colorant in the entire composition is usually less than 1% by mass, preferably less than 0.5% by mass.

&Lt; Production method of resin composition &gt;

The resin composition of the present invention comprises the resin (A) and the solvent (E), and the (meth) acrylic compound (B), the epoxy resin (C), the polymerization initiator (D) ), An antioxidant (F), a surfactant (H), a polycarboxylic acid (G), an imidazole compound (J) and other components in a known manner. After mixing, it is preferable to filter with a filter having a pore diameter of about 0.05 to 1.0 mu m.

&Lt; Process for producing a cured film &

The cured film can be produced by applying the resin composition of the present invention on a substrate, drying and then curing by heat. More specifically, the method for producing a cured film 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): Step of forming the composition layer by drying the applied resin composition under reduced pressure

Step (3): Step of heating the composition layer

When the resin composition of the present invention contains the polymerization initiator (D), a cured film having a pattern can be produced by the following steps.

Step (1): a step of applying the resin composition of the present invention to a substrate

Step (2): Step of forming the composition layer by drying the applied resin composition under reduced pressure

Step (2a): Step of exposing the composition layer through a photomask

Step (2b): Step of developing the composition layer after exposure

Step (3a): Step of heating the composition layer after development

Step (1) is a step of applying the resin composition of the present invention to a substrate. The substrate may be glass, metal, plastic, or the like, and a color filter, an insulating film, a conductive film and / or a driving circuit may be formed on the substrate. The coating on the substrate is preferably carried out using a coating device such as a spin coater, slit & spin coater, slit coater, ink jet, roll coater, dip coater and the like.

Step (2) is a step of drying the applied resin composition under reduced pressure to form a composition layer. By carrying out the process, volatile components such as a solvent in the resin composition are removed. The reduced-pressure drying is preferably carried out at a temperature of 20 to 25 캜 under a pressure of 50 to 150 Pa. (Pre-baking) may be carried out before or after the drying under reduced pressure. The heating and drying are carried out usually using a heating apparatus such as an oven or a hot plate. The temperature for the heat drying is preferably 30 to 120 占 폚, more preferably 50 to 110 占 폚. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

Step (3) is a step (post-baking) of heating the composition layer. By heating, the composition layer is cured to form a cured film. Heating is usually carried out using a heating apparatus such as an oven or a hot plate. The heating temperature is preferably 130 to 270 占 폚, more preferably 150 to 260 占 폚, and still more preferably 200 to 250 占 폚. If the heating temperature is 200 to 250 占 폚, unnecessary solvent can be prevented from remaining in the cured 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 composition layer formed by the step (2) through a photomask. The photomask is formed with a light shielding portion corresponding to a portion of the composition layer to be removed. The shape of the light shielding portion is not particularly limited and can be selected according to the intended use. As the light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light having a wavelength of less than 350 nm may be cut using a filter that cuts the wavelength band, a band-pass filter may be used to extract light in the vicinity of 436 nm, around 408 nm, and around 365 nm Or may be selectively taken out. Examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp. It is preferable to use an exposure apparatus such as a mask aligner or a stepper because it is possible to uniformly irradiate the entire exposure surface with a parallel light beam and precisely align the photomask with the composition layer.

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

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

The cured film thus obtained is excellent in the flatness of the surface, and thus is useful as a protective film or an overcoat for a color filter substrate or a touch panel used in, for example, a liquid crystal display device, an organic EL display device or an electronic paper.

With the resin composition of the present invention, it becomes possible to manufacture a display device having a high-quality cured film. Even in the case of a color filter substrate having unevenness of the color pattern on its surface, the overcoat is formed by the resin composition of the present invention, whereby the flatness of the surface can be improved.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. In the examples, &quot;% &quot; and &quot; part &quot;

(Synthesis Example 1: Resin (A1))

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, 140 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 70 DEG C with stirring. Then, 25 parts of methacrylic acid, a mixture of the monomer of the formula (I-1) and the monomer of the formula (II-1) (the molar ratio of the monomer of the formula (I-1) } And 145 parts of ethyl methacrylate in 190 parts of propylene glycol monomethyl ether acetate was prepared and this solution was dropped into a flask kept at 70 ° C for 4 hours by using a dropping pump .

On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 240 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over 5 hours using another dropping pump . After completion of the dropwise addition of the polymerization initiator solution, the solution was maintained at 70 캜 for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin (A1)) having a solid content of 30%. The resin A1 thus obtained had a weight average molecular weight (Mw) of 9600, a dispersion degree (Mw / Mn) of 1.9 and an acid value in terms of solid content of 60 mg-KOH / g. The resin (A1) has the following constitutional unit.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the obtained resin were measured by the GPC method under the following conditions.

Apparatus: K2479 (manufactured by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 DEG C

Solvent: tetrahydrofuran (THF)

Flow rate: 1.0 ml / min

Detector: RI

Standard materials for calibration: 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 the number average molecular weight in terms of polystyrene obtained as described above was dispersed.

(Synthesis Example 2: Resin (A2))

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, 140 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 70 DEG C with stirring. Then, 25 parts of methacrylic acid, a mixture of the monomer of the formula (I-1) and the monomer of the formula (II-1) (the molar ratio of the monomer of the formula (I-1) }, And 75 parts of butyl methacrylate in 190 parts of propylene glycol monomethyl ether acetate was prepared, 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 polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 240 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over 5 hours using another dropping pump . After completion of the dropwise addition of the polymerization initiator solution, the solution was kept at 70 캜 for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin (A2)) having a solid content of 30%. The resin A1 thus obtained had a weight average molecular weight (Mw) of 9000, a degree of dispersion (Mw / Mn) of 1.9 and an acid value in terms of solid content of 61 mg-KOH / g. Resin (A2) has the following constitutional unit.

(Synthesis Example 3: Resin (A3))

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, 140 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 70 DEG C with stirring. Then, 25 parts of methacrylic acid, a mixture of the monomer of the formula (I-1) and the monomer of the formula (II-1) (the molar ratio of the monomer of the formula (I-1) And 145 parts of methyl methacrylate were dissolved in 190 parts of propylene glycol monomethyl ether acetate. This solution was dropped into a flask kept at 70 ° C. for 4 hours by using a dropping pump .

On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 240 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over 5 hours using another dropping pump . After the dropwise addition of the polymerization initiator solution was completed, the solution was kept at 70 캜 for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin (A3)) having a solid content of 30%. The resin A1 thus obtained had a weight average molecular weight (Mw) of 9200, a degree of dispersion (Mw / Mn) of 1.9 and an acid value in terms of solid content of 61 mg-KOH / g. The resin (A3) has the following constitutional unit.

(Synthesis Example 4: Resin (A4))

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to make a nitrogen atmosphere, 140 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 70 DEG C with stirring. 40 parts of methacrylic acid and a mixture of a monomer of the formula (I-1) and a monomer of the formula (II-1), wherein the molar ratio of the monomer of the formula (I- 50} was dissolved in 190 parts of propylene glycol monomethyl ether acetate, and this solution was dropped into a flask kept at 70 DEG C for 4 hours by using a dropping pump.

On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 240 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over 5 hours using another dropping pump . After the dropwise addition of the polymerization initiator solution was completed, the solution was kept at 70 캜 for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin (A4)) having a solid content of 42.3%. The obtained resin Aa had a weight average molecular weight (Mw) of 8000, a degree of dispersion (Mw / Mn) of 1.91 and an acid value in terms of solid content of 60 mg-KOH / g. Resin (A4) has the following constitutional unit.

[Examples 1 and 2 and Comparative Examples 1 and 2]

&Lt; Preparation of Resin Composition &gt;

The resin (A1) to the resin (A4) were mixed in propylene glycol monomethyl ether acetate as the solvent (E) so as to have a solid content of 15% by mass and Megafac (registered trademark) F554 DIC Co., Ltd.) was added in an amount of 0.1 part by mass based on 100 parts by mass of the resin (A), thereby obtaining a resin composition.

&Lt; Preparation of substrate for evaluation &gt;

A glass substrate (Eagle XG; manufactured by Corning) having an aspect ratio of 2 inches was sequentially washed with a neutral detergent, water and isopropanol, and then dried. On this substrate, a colored photosensitive resin composition having the following composition was spin-coated so as to have a thickness of 2.0 mu m after post-baking.

Next, in a clean oven, prebaked at 100 DEG C for 3 minutes to form a colored composition layer. After cooling down, 100 mJ / cm &lt; 2 &gt; was formed by using an exposure apparatus (TME-150RSK; manufactured by Topcon Co., Ltd., light source: ultra high pressure mercury lamp) at an interval of 100 mu m between the colored composition layer on the substrate and the quartz glass photomask, (Based on 365 nm). This light irradiation was conducted by passing the radiation from the ultra-high pressure mercury lamp through an optical filter (UV-31; manufactured by Asahi Techno Glass Co., Ltd.). As the photomask, a photomask for forming a line-and-space pattern with a line width of 30 mu m was used.

After the light irradiation, the coloring composition layer was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 DEG C for 60 seconds and developed. After washing with water, To prepare an evaluation substrate on which a line and space colored pattern having a line width of 30 mu m was formed.

(Composition of colored photosensitive resin composition)

Pigment: about 40% (note: ratio of green pigment in total pigment amount: about 90%, yellow colorant in total pigment amount: 10%),

Epoxy resin: 3%,

Acrylic monomer: 14%,

Polymerization initiator: 10%

Adhesion improver: 1%,

Surfactant: 600 ppm

The film thickness of the formed coloring pattern was measured using a contact type film thickness measuring device (DEKTAK6M; manufactured by ULVAC Co., Ltd.) under the conditions of a measuring width of 500 mu m and a measuring speed of 10 seconds and the profile of the cross- , Outline). The average value of the film thickness of the colored pattern was calculated from the profile. The average value of the film thickness was 2.0 탆.

&Lt; Preparation of cured film and evaluation of flatness &

The resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were applied to the evaluation substrate by spin coating under the condition that the film thickness after post-baking (film thickness from the surface of the colored pattern) became 1.0 탆 . Thereafter, the mixture was dried under reduced pressure at a rotary pump rotational speed of 1000 rpm, a booster pump rotational speed of 700 rpm and a room temperature of 25 캜 by a vacuum dryer (VCD Microtec Co., Ltd.) until the reduced pressure reached 66 Pa, And prebaked on a plate at a temperature of 100 DEG C for 3 minutes. After cooling, post-baking was performed at a temperature of 230 캜 for 30 minutes to form a cured film.

The film thickness of the cured film on the evaluation substrate was measured under the conditions of a measurement width of 500 mu m and a measurement speed of 10 seconds using a contact type film thickness measurement device (DEKTAK6M, manufactured by ULVAC Co., Ltd.) . As a result of calculating the average value of the film thickness of the cured film from the profile, the average value of the film thickness from the colored pattern surface was 1.0 占 퐉.

Figs. 1 to 4 show the cross-sectional shapes of the cured films obtained from the compositions of Examples 1 and 2 and Comparative Examples 1 and 2 together with the cross-sectional shape of the evaluation substrate. Figs. 1 to 4 each show profiles of respective cross-sectional shapes.

The abscissa represents the position in the plane direction, and the ordinate represents the position in the height direction. One convex portion in the cross-sectional shape of the coloring pattern corresponds to one coloring cell.

The average height difference of the concavo-convex pattern on the surface of the cured film was calculated from the sectional shape of the obtained cured film. The results are shown in Table 1.

According to the present invention, it is possible to provide a resin composition capable of forming a cured film having a high surface flatness. The cured film obtained from the curable resin composition has excellent flatness and can therefore be suitably used for display devices and the like.

Claims (6)

A resin composition comprising a resin (A) and a solvent,
The resin (A) is obtained by copolymerizing a constituent unit (Aa) derived from a (meth) acrylic acid alkyl ester having an alkyl group having 2 or more carbon atoms and a constituent unit (Ab) derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms , A structural unit (Ac) derived from at least one compound selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride,
The proportion of the structural unit (Aa) is preferably higher than 10 mol% with respect to the total structural units constituting the resin (A)
The resin (A) has a weight average molecular weight of 5000 to 20,000,
Resin composition. The method according to claim 1,
The resin (A) is a resin comprising a constituent unit (Aa), a constituent unit (Ab) and a constituent unit (Ac). The method according to claim 1,
Wherein the proportion of the structural unit (Aa) is higher than 10 mol% and 35 mol% or lower with respect to the total structural units constituting the resin (A). The method according to claim 1,
The structural unit (Aa) is a structural unit derived from a (meth) acrylic acid alkyl ester having a linear alkyl group having 2 to 10 carbon atoms. The method according to claim 1,
The structural unit (Aa) is a structural unit derived from a (meth) acrylic acid alkyl ester having a linear alkyl group having 2 to 6 carbon atoms. A cured film formed from the resin composition according to claim 1 or 2.

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