TWI778963B - Resin composition and cured film - Google Patents

Abstract

The present invention is a resin composition which comprises a resin (A) and a solvent, wherein the resin (A) comprises a structural unit (Aa) derived from an alkyl (meth) acrylate having an alkyl group having 2 or more carbon atoms, a structural unit (Ab) derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms, and 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, and the proportion of the structural unit (Aa) is higher than 10 mol% with respect to the total amount of the structural units constituting the resin (A). The resin (A) is a copolymer having a weight average molecular weight of 5,000 to 20,000.

Description

Resin composition and cured film

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

In recent years, in liquid crystal display devices, curable resin compositions have been used to form cured films such as optical spacers and overcoat layers.

As a curable resin composition that can be used in a liquid crystal display device, it has been proposed to include, for example, an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride (A-a), a compound (Ab) that can be polymerized with the (A-a), and / or a curable resin composition of a binder resin formed by polymerizing a compound (Ac) having a cyclic ether group having 2 to 4 carbon atoms (for example: Japanese Patent Application Publication No. 2010-106154).

The cured film can be formed by coating the curable resin composition on the substrate and heating it further. In order to realize a fine display in a liquid crystal display device, it is preferable that the cured film of the optical spacer and the overcoat layer be flat. However, since the substrate on which the coloring pattern is formed has unevenness, when the curable resin composition is coated on the substrate and further heated to obtain a cured film, the flatness required for the overcoat layer may not be obtained in some cases.

The present invention includes the following inventions.

[1] A resin composition comprising a resin (A) and a solvent, wherein the resin (A) comprises: a structural unit (Aa) derived from an alkyl (meth)acrylate having an alkyl group having 2 or more carbon atoms, A constitutional unit (Ab) derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms and a compound derived from at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides Unit (Ac), and relative to the total amount of structural units constituting the resin (A), the ratio of the constituting unit (Aa) is higher than 10 mol%. The resin (A) is a copolymer with a weight average molecular weight of 5,000 to 20,000.

[2] The resin composition according to item [1], wherein the resin (A) is a resin composed of a structural unit (Aa), a structural unit (Ab), and a structural unit (Ac).

[3] The resin composition as described in [1] or [2], wherein the ratio of the structural unit (Aa) to the total amount of the structural units constituting the resin (A) is higher than 10 mol % and is Below 35 mol%.

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

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

[6] A cured film formed of the resin composition described in any one of the above items [1] to [5].

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

Fig. 1 shows a cross-sectional shape of an evaluation sample in Example 1. Specifically, it is a cross-sectional view showing the cured film and the cross-sectional shape of the evaluation substrate.

Fig. 2 shows a cross-sectional shape of an evaluation sample of Example 2. Specifically, it is a cross-sectional view showing the cured film and the cross-sectional shape of the evaluation substrate.

Fig. 3 is a diagram showing the cross-sectional shape of the evaluation sample of Comparative Example 1. Specifically, it is a cross-sectional view showing the cured film and the cross-sectional shape of the evaluation substrate.

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

In this specification, the compounds exemplified by each component are not particularly limited, and may be used alone or in combination of plural kinds.

The resin composition of the present invention includes resin (A) and solvent (E). Resin (A) comprising: a structural unit (Aa) derived from an alkyl (meth)acrylate having an alkyl group having 2 or more carbon atoms, and an unsaturated compound derived from a cyclic ether structure having 2 to 4 carbon atoms The structural unit (Ab) of and the structural unit (Ac) derived from at least one compound selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride, and the ratio of the structural unit (Aa) relative to the constituent The total amount of the structural units of the resin (A) is higher than 10 mol%, and the resin (A) is a copolymer with a weight average molecular weight of 5,000 to 20,000.

Hereinafter, the above-mentioned alkyl (meth)acrylate is referred to as "compound (Aa)", and the unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms is referred to as "compound (Ab)". A compound of at least one kind selected from the group consisting of an unsaturated carboxylic anhydride and an unsaturated carboxylic acid anhydride is referred to as "compound (Ac)".

Moreover, in this specification, "(meth)acrylic acid" means the compound of at least 1 sort(s) chosen from the group which consists of acrylic acid and methacrylic acid. Descriptions such as "(meth)acryl" and "(meth)acrylate" have the same meaning.

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

The resin composition of the present invention may further comprise a polymerization initiator (D), a polymerization initiation aid (D1), a thiol compound (T), at least One type of compound (hereinafter sometimes referred to as "polycarboxylic acid (G)"), and an imidazole compound (J).

<Resin (A)>

Resin (A) is a curable resin, preferably a thermosetting resin, more preferably a resin that can be cured by heat above 60°C, and contains: ( A constituent unit of alkyl meth)acrylate (Aa), a constituent unit derived from an unsaturated compound (Ab) having a cyclic ether structure having 2 to 4 carbon atoms, and a constituent unit derived from an unsaturated carboxylic acid and an unsaturated carboxylic acid A copolymer of structural units of at least one compound (Ac) of the group consisting of acid anhydrides.

This copolymer may further be copolymerized with compound (Aa), compound (Ab) or compound (Ac), and may have Constituent unit.

(1) Structural unit derived from compound (Aa)

In the present invention, since the resin (A) is a copolymer containing structural units derived from the compound (Aa), the flatness of a film obtained by coating with the resin composition can be improved.

Compound (Aa) includes, for example, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, Lauryl (meth)acrylate, Heptyl (meth)acrylate, Octyl (meth)acrylate, Nonyl (meth)acrylate, Decyl (meth)acrylate, Isobutyl (meth)acrylate , 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, etc. Furthermore, since the film obtained by coating the resin composition on the substrate can suppress peeling under high temperature and high humidity, the carbon number of the alkyl group in the compound (Aa) is preferably 10 or less, and 8 or less. Even better, less than 6 is even better. The alkyl group of the compound (Aa) may be a straight chain or a branched chain, preferably a straight chain.

(2) Constituent units derived from compound (Ab)

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

As for the compound (Ab), for example, a compound (Ab1) having an oxirane group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "(Ab1)"), a compound having an oxetane group and an ethylenically unsaturated bond, A compound (Ab2) having a saturated bond (hereinafter, sometimes referred to as "(Ab2)"), a compound (Ab3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "(Ab3)").

(Ab1) includes, for example: a compound (Ab1-1) having a structure in which a linear or branched unsaturated aliphatic hydrocarbon is epoxidized (hereinafter sometimes referred to as "(Ab1-1)"), and a compound (Ab1-2) having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized (hereinafter, may be referred to as "(Ab1-2)").

(Ab1-1), for example, glycidyl (meth)acrylate, -β-methylglycidyl (meth)acrylate, -β-ethylglycidyl (meth)acrylate , Glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o -Vinylbenzylglycidyl ether, α-methyl-m-vinylbenzylglycidyl ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-di (Glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2 ,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxy methyl) styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4 , 6-three (glycidyloxymethyl) styrene and so on.

(Ab1-2), for example: vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example: Celloxide 2000; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example: Cyclomer-A400; manufactured by Daicel Chemical Industry Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (Example: Cyclomer-M100; manufactured by Daicel Chemical Industry Co., Ltd.), compounds represented by formula (I), compounds represented by 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 by 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 bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, and tert-butyl group. In terms of the alkyl group in which the hydrogen atom is replaced by a hydroxyl group, examples include: hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxypropyl, Hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc.

R ^b1 and R ^b2 are preferably, for example, hydrogen atom, methyl group, hydroxymethyl group, 1-hydroxyethyl group and 2-hydroxyethyl group, more preferably hydrogen atom and methyl group.

In terms of alkanediyl, preferred ones include: methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane Alkane-1,5-diyl, hexane-1,6-diyl, etc.

In terms of X ^b1 and X ^b2 , preferred ones include: single bond, methylene, ethylidene, *-CH ₂ -O-, *-CH ₂ CH ₂ -O-' with single bond, *- CH2CH2 _{- O-} is more preferred. *Indicates the bond with O.

The compound represented by formula (I) includes, for example, a compound represented by any one of formula (I-1) to formula (I-15). Wherein, with formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) to formula (I-15 ) is preferably a compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15) is more preferred.

As for the compound represented by the formula (II), for example, a compound represented by any one of the formula (II-1) to the formula (II-15) and the like are exemplified.

Among them, with formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15 ) is preferably a compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) is more preferred.

The compound represented by formula (I) and the compound represented by formula (II) may be used alone or in combination at any ratio. When used in combination, the content ratio of the compound represented by formula (I) and the compound represented by formula (II) is based on moles, preferably 5:95 to 95:5, and 10:90 to 90: 10 is better, and 20:80 to 80:20 is even better. For example, a 50:50 mixture of a compound represented by formula (I-1) and a compound represented by formula (II-1) can be used (the commercially available strain has a trade name "E-DCPA" (Daicel (stock) manufacturing).

(Ab2) is more preferably a compound having an oxetanyl group and a (meth)acryloxy group. In terms of (Ab2), examples include: 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3 -Ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-methyl-3-methacryl Oxytidine, 3-methyl-3-acryloxyethyl oxetane, 3-ethyl-3-methacryloxyethyl oxetane, 3-Ethyl-3-acryloyloxyethyloxyetane, etc.

(Ab3) is preferably a compound having a tetrahydrofuryl group and a (meth)acryloxy group. (Ab3) includes, for example, tetrahydrofuryl methyl acrylate (for example: Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofuryl methyl methacrylate, and the like.

As for the compound (Ab), (Ab1) is preferable from the viewpoint that the reliability such as heat resistance and chemical resistance of the obtained cured film can be further improved. At the same time, (Ab1-2) is more preferable from the viewpoint of excellent storage stability of the resin composition.

(3) Structural unit derived from compound (Ac)

Compound (Ac) includes, for example: unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, 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, 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, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]heptene -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-ene and other carboxyl-containing bicyclic unsaturated compounds; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, dehydration Anhydrides of unsaturated dicarboxylic acids such as 5,6-dicarboxybicyclo[2.2.1]hept-2-ene; mono[2-(meth)acryloxyethyl]succinate, phthalic acid Unsaturated mono[(meth)acryloxyalkyl]esters of divalent or higher polycarboxylic acids such as mono[2-(meth)acryloxyethyl]ester; α-(hydroxymethyl ) Acrylic acid, etc., containing hydroxyl and carboxyl groups in the same molecule, such as unsaturated acrylates.

Among them, (meth)acrylic acid, maleic anhydride, and the like are preferable, and (meth)acrylic acid is more preferable from the viewpoint of copolymerization reactivity and solubility in an alkaline aqueous solution.

(4) Constituent units derived from compound (Ad)

Compound (Ad) includes, for example, methyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, Tricyclo[5.2.1.0 ^2.6 ]decane-8-(meth)acrylate (in this technical field, the commonly used name is called "dicyclopentyl (meth)acrylate". Also, it is sometimes called "( Tricyclodecyl meth)acrylate."), Tricyclo[5.2.1.0 ^2.6 ]decen-8-(meth)acrylate (in this technical field, the commonly used name is "dicyclopentanyl (meth)acrylate) Enyl ester".), Dicyclopentyloxyethyl (meth)acrylate, Isobornyl (meth)acrylate, Adamantyl (meth)acrylate, Allyl (meth)acrylate, (Meth) ) propargyl acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate and other (meth)acrylates; 2-hydroxyethyl (meth)acrylate, Hydroxyl-containing (meth)acrylates such as 2-hydroxypropyl (meth)acrylate; dicarboxylic acids such as diethyl maleate, diethyl fumarate, and diethyl itaconate Diesters; 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-dihydroxydi Cyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo [2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2 -ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl -5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2 .1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept- Bicyclic unsaturated compounds such as 2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenylmaleimide, N- Cyclohexylmaleimide, N-Benzylmaleimide, N-Succinimido-3-maleimide Benzoate, N-Succinimidyl Amino-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-succinimidyl-3-maleyl diimide propionate , N-(9-acridyl)maleimide and other dicarbonylimide derivatives; styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p- -Vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, dichloroethane, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butyl Diene, isoprene and 2,3-dimethyl-1,3-butadiene, etc.

Among them, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyl toluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzyl Preferred are maleimide and bicyclo[2.2.1]hept-2-ene.

(5) The 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 structural unit is based on the structural unit derived from the compound (Aa): 5 to 40 mol %, the structure derived from the compound (Ab) with respect to all the structural units constituting the resin [K1] Units: 5 to 90 mol%, constituent units derived from compound (Ac): preferably 5 to 40 mol%, constituent units derived from compound (Aa): 10 to 35 mol%, derived from compound ( The structural unit of Ab): 10 to 80 mol%, the structural unit derived from the compound (Ac): 10 to 35 mol%, more preferably.

In addition, in the resin (A), the ratio of the structural unit (Aa) is more than 10 mol % and 35 mol % or less, and the structural unit derived from the compound (Ab) is 10 mol % or more and less than 80 mol %. Mole% is better.

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

Resin [K1] can refer to the method and the method recorded in the document "Experimental Method of Polymer Synthesis" (Otsu Takayuki Publishing House: Chemical Doujin (Stock) 1st Edition, 1st Printing, March 1, 1972) Manufactured by citing references recorded in the literature.

Specifically, for example, adding a predetermined amount of compound (Aa), compound (Ab) and compound (Ac), polymerization initiator and solvent etc. into the reaction vessel, for example by replacing oxygen with nitrogen, during deoxidation Under the environment, the method of heating and keeping warm at the same time while stirring. In addition, the polymerization initiator and solvent used therein are not particularly limited, and those commonly used in the technical field can be used. Examples of polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides. Oxides (benzoyl peroxide, etc.), and solvents, as long as they can dissolve each monomer, for example, the solvents described later are used in the resin composition.

The resin obtained by the above method can be used directly as a solution after the reaction, or as a concentrated or diluted solution, or as a solid (powder) obtained by reprecipitation and other methods. In particular, 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, thus simplifying the production steps of the resin composition.

In the resin [K2], the ratio of each structural unit is, among all the structural units constituting the resin [K2], the structural unit derived from (Aa): 5 to 40 mol%, and the structural unit derived from (Ab): 5 to 90 mol%, the constituent unit derived from (Ac): 5 to 40 mol%, the constituent unit derived from (Ad): 1 to 40 mol%, preferably, the constituent derived from (Aa) Unit: 10 to 35 mol%, Constituent unit derived from (Ab): 10 to 80 mol%, Constituent unit derived from (Ac): 10 to 35 mol%, Constituent unit derived from (Ad): 5 to 35 mol% is more preferable.

When the ratio of the constituent units of the resin [K2] is within the above range, the storage stability of the resin composition and the chemical resistance, heat resistance and mechanical strength of the obtained cured film tend to be excellent.

Resin [K2] can be produced in the same manner as resin [K1]. Also, as described above, in the resin (A), the ratio of the structural unit (Aa) is higher than 10 mol % and 35 mol % or less, and the structural unit derived from the compound (Ab) is 10 mol % Above but less than 80 mole% is better.

Specific examples of the resin [K1] include: (meth)ethyl acrylate/copolymer of compound/(meth)acrylic acid of formula (I-1), ethyl (meth)acrylate/formula (I-1) 2) compound/(meth)acrylic acid copolymer, (meth)ethyl acrylate/formula (I-3) compound/(meth)acrylic acid copolymer, (meth)acrylate ethyl ester/formula ( I-4) compound/copolymer of (meth)acrylic acid, ethyl (meth)acrylate/compound of formula (I-5)/copolymer of (meth)acrylic acid, ethyl (meth)acrylate/ Compound of formula (I-6)/copolymer of (meth)acrylic acid, ethyl (meth)acrylate/compound of formula (I-7)/copolymer of (meth)acrylic acid, ethyl (meth)acrylate Copolymer of ester/compound of formula (I-8)/(meth)acrylic acid, ethyl (meth)acrylate/compound of formula (I-9)/copolymer of (meth)acrylic acid, (meth) Copolymer of ethyl acrylate/compound of formula (I-10)/(meth)acrylic acid, copolymer of ethyl (meth)acrylate/compound of formula (I-11)/(meth)acrylic acid, (meth)acrylic acid Base) copolymer of ethyl acrylate/compound of formula (I-12)/(meth)acrylic acid, copolymer of ethyl (meth)acrylate/compound of formula (I-13)/(meth)acrylic acid, Copolymer of ethyl (meth)acrylate/compound of formula (I-14)/(meth)acrylic acid, copolymer of ethyl (meth)acrylate/compound of formula (I-15)/(meth)acrylic acid Copolymer of ethyl (meth)acrylate/compound of formula (II-1)/(meth)acrylic acid, ethyl (meth)acrylate/compound of formula (II-2)/(meth)acrylic acid Copolymer of ethyl (meth)acrylate/compound of formula (II-3)/copolymer of (meth)acrylic acid, ethyl (meth)acrylate/compound of formula (II-4)/(methyl ) copolymer of acrylic acid, ethyl (meth)acrylate/compound of formula (II-5)/copolymer of (meth)acrylic acid, ethyl (meth)acrylate/compound of formula (II-6)/( Copolymer of meth)acrylic acid, ethyl (meth)acrylate/compound of formula (II-7)/copolymer of (meth)acrylic acid, ethyl (meth)acrylate/compound of formula (II-8) /Copolymer of (meth)acrylic acid, ethyl (meth)acrylate/compound of formula (II-9)/copolymer of (meth)acrylic acid, ethyl (meth)acrylate/formula (II-10) Compound/copolymer of (meth)acrylic acid, ethyl (meth)acrylate/compound of formula (II-11)/copolymer of (meth)acrylic acid, ethyl (meth)acrylate/copolymer of formula (II- 12) compound/(meth)acrylic acid copolymer, (meth)ethyl acrylate/formula (II-13) compound/(meth)acrylic acid copolymer, (meth)acrylate ethyl ester/formula ( II-14) compound/copolymer of (meth)acrylic acid, Ethyl (meth)acrylate/compound of formula (II-15)/copolymer of (meth)acrylic acid, ethyl (meth)acrylate/compound of formula (I-1)/compound of formula (II-1) Copolymer of compound/(meth)acrylic acid, butyl (meth)acrylate/compound of formula (I-1)/copolymer of (meth)acrylic acid, butyl (meth)acrylate/formula (II-1 ) compound/copolymer of (meth)acrylic acid, butyl (meth)acrylate/compound of formula (I-1)/compound of formula (II-2)/copolymer of (meth)acrylic acid, (meth)acrylic acid base) copolymer of butyl acrylate/compound of formula (I-1)/crotonic acid, copolymer of butyl (meth)acrylate/compound of formula (I-1)/maleic acid, (methyl ) butyl acrylate/copolymer of formula (I-1)/(meth)acrylic acid/maleic anhydride, (meth)ethyl acrylate/(meth)butyl acrylate/formula (I-1 ) compound/copolymer of (meth)acrylic acid, butyl (meth)acrylate/compound of formula (II-1)/copolymer of crotonic acid, butyl (meth)acrylate/formula (II-1) Compound/copolymer of maleic acid, butyl (meth)acrylate/compound of formula (II-1)/copolymer of (meth)acrylic acid/maleic anhydride, acrylic acid (meth)acrylic acid ester/compound of formula (I-1)/copolymer of (meth)acrylic acid, (meth)propyl ester/compound of formula (II-1)/copolymer of (meth)acrylic acid, (meth) Propyl acrylate/compound of formula (I-1)/compound of formula (II-2)/copolymer of (meth)acrylic acid, compound of (meth)propyl acrylate/compound of formula (I-1)/ Copolymer of crotonic acid, (meth)propyl acrylate/compound of formula (I-1)/maleic acid copolymer, (meth)propyl acrylate/compound of formula (I-1)/( Copolymer of meth)acrylic acid/maleic anhydride, copolymer of ethyl (meth)acrylate/propyl (meth)acrylate/compound of formula (I-1)/(meth)acrylic acid, (meth)acrylic acid base) copolymer of propyl acrylate/compound of formula (II-1)/crotonic acid, copolymer of (meth)propyl acrylate/compound of formula (II-1)/maleic acid, (methyl ) propyl acrylate/compound of formula (II-1)/copolymer of (meth)acrylic acid/maleic anhydride, (meth)hexyl acrylate/compound of formula (I-1)/(methyl) Acrylic acid copolymer, (meth)hexyl acrylate/compound/(meth)acrylic acid copolymer, (meth)hexyl acrylate/formula (I-1) compound/formula ( II-2) compound/copolymer of (meth)acrylic acid, (meth)hexyl acrylate/copolymer of compound/crotonic acid of formula (I-1), (meth)hexyl acrylate/formula (I -1) compound/copolymer of maleic acid, (meth)hexyl acrylate/compound of formula (I-1)/(meth)propylene Copolymer of acid/maleic anhydride, hexyl (meth)acrylate/butyl (meth)acrylate/compound of formula (I-1)/copolymer of (meth)acrylic acid, (meth)acrylic acid Copolymer of hexyl ester/compound of formula (II-1)/crotonic acid, hexyl (meth)acrylate/compound of formula (II-1)/copolymer of maleic acid, hexyl (meth)acrylate Copolymer of ester/compound of formula (II-1)/(meth)acrylic acid/maleic anhydride, (meth)acrylic acid-2-ethylhexyl ester/compound of formula (I-1)/(form base) acrylic acid copolymer, (meth)acrylate-2-ethylhexyl ester/compound of formula (II-1)/(meth)acrylic acid copolymer, (meth)acrylate-2-ethylhexyl ester /compound of formula (I-1)/compound of formula (II-2)/copolymer of (meth)acrylic acid, (meth)acrylic acid-2-ethylhexyl ester/compound of formula (I-1)/ Copolymer of crotonic acid, (meth)acrylate-2-ethylhexyl ester/compound of formula (I-1)/maleic acid copolymer, (meth)acrylate-2-ethylhexyl ester/ Compound of formula (I-1)/copolymer of (meth)acrylic acid/maleic anhydride, 2-ethylhexyl (meth)acrylate/butyl (meth)acrylate/formula (I-1 ) compound/(meth)acrylic acid copolymer, (meth)acrylic acid-2-ethylhexyl ester/formula (II-1) compound/crotonic acid copolymer, (meth)acrylic acid-2-ethylhexyl Hexyl ester/compound of formula (II-1)/copolymer of maleic acid, (meth)acrylic acid-2-ethylhexyl ester/compound of formula (II-1)/(meth)acrylic acid/ Copolymer of maleic anhydride, etc.

As for the resin [K2], for example, the resin [K1] exemplified above further includes a constituent unit derived from the compound (Ad).

The polystyrene-equivalent weight average molecular weight (Mw) of the resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, more preferably 5,000 to 20,000, especially preferably 5,000 to 10,000. When the weight average molecular weight (Mw) of resin (A) is in the said range, there exists a tendency for the applicability of a resin composition to become favorable.

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

The acid value of the resin (A) is preferably from 30mg-KOH/g to 180mg-KOH/g, more preferably from 40mg-KOH/g to 150mg-KOH/g, and from 50mg-KOH/g to 135mg-KOH It is more preferably not more than 50 mg-KOH/g and not more than 100 mg-KOH/g.

The acid value is the measured value of the amount of potassium hydroxide (mg) required to neutralize 1 g of the resin, and can be determined 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 to the substrate.

When the resin composition of the present invention contains components other than resin (A) and solvent (E) such as reactive monomer (B), the content of resin (A) is not particularly limited, but relative to the present invention The solid content of the resin composition is preferably 30 to 90 mass%, more preferably 35 to 80 mass%, and more preferably 40 to 70 mass%.

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

Here, the solid content of the resin composition refers to the amount obtained by dividing the total amount of the resin composition of the present invention by the content of the solvent (E).

<Reactive monomer (B)>

The reactive monomer (B) is a monomer that reacts by heat or the action of the polymerization initiator (D). The monomer system can include, for example: a compound having an ethylenically unsaturated bond, and (methyl ) Acrylic compound (B1) is preferred, and a compound having at least one group selected from the group consisting of acryl and methacryl is more preferred.

(Meth)acrylic compounds having one (meth)acryl group include, for example, alkyl (meth)acrylates, phenoxypolyethylene glycol esters of (meth)acrylic acid, (meth)acrylic acid Alkoxylated polyethylene glycol ester, isocamphoryl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, (meth)acrylate base) 2-hydroxy-3-phenoxypropyl acrylate, tetrahydrofuryl methyl (meth)acrylate, etc.

Examples of (meth)acrylic compounds having two (meth)acrylic acid groups include: 1,3-butylene di(meth)acrylate, 1,3-butylene (meth)acrylate Glycol ester, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, new di(meth)acrylate Pentylene glycol ester, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol diacrylate, bisphenol A (acryloxyethyl) ether, ethoxylated bisphenol A di(meth)acrylate, propoxylated neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, 3 - Methylpentanediol di(meth)acrylate and the like.

Examples of (meth)acrylic compounds having three or more (meth)acryl groups include trimethylolpropane tri(meth)acrylate, neopentylitol tri(meth)acrylate, Tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate Meth)acrylate, neopentylthritol tetra(meth)acrylate, dipentylpentylpenta(meth)acrylate, dipentylthritol hexa(meth)acrylate, tetra(meth)acrylic acid Tri-neopentylthritol, penta(meth)acrylate, hexa(meth)acrylate, hepta(meth)acrylate, octa(methyl) ) Tri-Neopentylthritol Acrylate, The Reactant of Penta-Neopentylthritol Tri(Meth)acrylate and Anhydride, The Reactant of Di-Neopentylthritol Penta(Meth)acrylate and Anhydride, Hepta(methyl) Reactant of tri-neopentylthritol acrylate and acid anhydride, caprolactone-modified trimethylolpropane tri(meth)acrylate, caprolactone-modified neopentylthritol tri(meth)acrylate, caprolactone Ester-modified tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, caprolactone-modified neopentylitol tetra(meth)acrylate, caprolactone-modified dipentyl Tetrol penta(meth)acrylate, caprolactone-modified dipenteoerythritol hexa(meth)acrylate, caprolactone-modified tri-neopentylthritol tetra(meth)acrylate, caprolactone-modified Tri-Neopentylthritol Penta(Meth)acrylate, Caprolactone-modified Tri-Neopentylthritol Hexa(meth)acrylate, Caprolactone-modified Tri-Neopentylthritol Hepta(meth)acrylate, Caprolactone-modified tri-neopentylthritol octa(meth)acrylate, caprolactone-modified neopentylthritol tri(meth)acrylate and anhydride reactant, caprolactone-modified dipenteoerythritol The reactant of penta(meth)acrylate and acid anhydride, the reactant of caprolactone-modified trineopentaerythritol hepta(meth)acrylate and acid anhydride, etc.

(Meth)acrylic compound (B1) is preferably a (meth)acrylic compound having 3 or more (meth)acryl groups, more preferably dipentylthritol hexa(meth)acrylate .

When the resin composition of the present invention contains the (meth)acrylic compound (B1), its content is preferably 20 to 100 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 (meth)acrylic compound (B1) is within the aforementioned range, the chemical resistance and mechanical strength of the obtained cured film can be improved.

One of the preferable examples of the reactive monomer (B) further includes a compound represented by formula (1) (hereinafter, this compound may be referred to as "compound (B2)").

[式(1)中，R¹至R³互相獨立地表示式(a)所示之基或式(b) 所示之基，R¹至R³之至少1者為式(b)所示之基。]

[In formula (1), R ¹ to R ³ independently represent the base shown in formula (a) or the base shown in formula (b), and at least one of R ¹ to R ³ is represented by formula (b) foundation. ]

[式(a)及式(b)中，R⁴及R⁵互相獨立地表示氫原子或碳數1至8之烷基。]

[In formula (a) and formula (b), R ⁴ and R ⁵ independently represent a hydrogen atom or an alkyl group with 1 to 8 carbons. ]

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

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.

Among R ¹ to R ³ , at least one of them is preferably a group represented by formula (a).

As for the compound (B2), for example, compounds represented by the formula (1-1) to the formula (1-6) and the like are exemplified. Compounds represented by formula (1-1) to formula (1-4) are preferred.

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

<Epoxy resin (C)>

The epoxy resin (C) has an oxirane group (however, it is different from the resin (A).). As for the epoxy resin (C), for example, at least one compound selected from the group consisting of glycidyl ether type epoxy resins and glycidyl ester type epoxy resins can be mentioned.

Glycidyl ether type epoxy resin is an epoxy resin with a glycidyl ether structure, which can be synthesized by reacting phenols and polyols with epichlorohydrin. Glycidyl ether type epoxy resins include, for example, bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, phenol-novolak type epoxy resins, o-cresol - Novolak-type epoxy resins, trishydroxyphenylmethane-type epoxy resins.

Glycidyl ester type epoxy resin is an epoxy resin with a glycidyl ester structure, which can be synthesized by reacting carbonyl groups of phthalic acid derivatives and fatty acids with epichlorohydrin. As the glycidyl epoxy resin, for example, a glycidyl epoxy resin derived from an aromatic carboxylic acid such as p-hydroxybenzoic acid, m-hydroxybenzoic acid, or terephthalic acid may be mentioned.

Epoxy resin (C) is based on bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, o-cresol-novolac type epoxy resin, polyphenol type epoxy resin, etc. Glycidyl ether type epoxy resin is preferred. Among them, bisphenol A type epoxy resin is particularly preferable.

The above-mentioned glycidyl ether type epoxy resin can be synthesized by condensation of the corresponding phenolic compound and epichlorohydrin in the presence of a strong base using a conventional known method. The reaction can be performed by conventional methods known to those skilled in the art.

A commercial item can also be used as said glycidyl ether type epoxy resin. Examples of commercially available bisphenol A epoxy resins include jER 157S70, Epikote 1001, Epikote 1002, Epikote 1003, Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, Epikote 828 (manufactured by Mitsubishi Chemical Co., Ltd. )Wait. Commercially available bisphenol F-type epoxy resins include, for example, Epikote 807 (manufactured by Mitsubishi Chemical Co., Ltd.), YDF-170 (manufactured by Tohto Chemical Co., Ltd.), and the like. Commercially available phenol-novolak epoxy resins include, for example, Epikote 152, Epikote 154 (manufactured by Mitsubishi Chemical Co., Ltd.), EPPN-201, PPN-202 (manufactured by Nippon Kayaku Co., Ltd.), DEN -438 (manufactured by Dow Chemical Japan Co., Ltd.), etc. Commercially available o-cresol-novolak epoxy resins include, for example: EOCN-125S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (Nippon Kayaku Co., Ltd. ) Manufacturing) etc. Examples of commercially available polyphenol epoxy resins include Epikote 1032H60 and Epikote YX-4000 (manufactured by Mitsubishi Chemical Co., Ltd.).

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 one epoxy group. The epoxy equivalent can be measured by the method prescribed|regulated by JIS K7236, for example.

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

When the resin composition of the present invention includes epoxy resin (C), its content, relative to the total content of resin (A) and reactive monomer (B) 100 mass parts, is preferably 1 to 60 mass parts, preferably 5 More preferably to 50 parts by mass. When content of an epoxy resin (C) exists in the said range, there exists a tendency for the obtained cured film and the adhesiveness of a board|substrate to be excellent.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by the action of light and heat to initiate polymerization of the reactive monomer (B). Polymerization initiator. The polymerization initiator (D) is a polymer comprising at least one compound selected from the group consisting of O-acyl oxime compounds, alkyl acetophenone compounds, triazine compounds, acyl phosphine oxide compounds and biimidazole compounds. The initiator is preferred, and the polymerization initiator comprising O-acyl oxime compound is more preferred.

Such polymerization initiators tend to have high sensitivity and increase the light transmittance in the visible light region.

The O-acyl oxime compound is a compound having a structure represented by formula (d1). Hereinafter, * represents a bonding key.

O-acyl oxime compounds, such as: N-benzoyloxy-1-(4-phenylmercaptophenyl) butane-1-one-2-imine, N-benzoyloxy Base-1-(4-phenylmercaptophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylmercaptophenyl)-3-cyclopentyl Propan-1-one-2-imine, N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethyl Alkane-1-imine, N-acetyloxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolane methyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl-6-(2-methyl N-benzoyloxy)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2 -methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine. Commercially available products such as Irgacure (registered trademark) OXE 01 and OXE 02 (above, manufactured by BASF Japan Co., Ltd.), N-1919 (manufactured by ADEKA Co., Ltd.) can be used.

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

With respect to the compound of the structure shown in formula (d2), can enumerate such as: 2-methyl-2-N-morpholino-1-(4-methylmercaptophenyl) propan-1-one, 2-di Methylamino-1-(4-N-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylbenzene base)methyl]-1-[4-(4-N-morpholinyl)phenyl]butan-1-one. Commercially available products such as Irgacure (registered trademark) 369, 907, and 379 (above, manufactured by BASF Co., Ltd.) can also be used. Meanwhile, a polymerization initiator having a group capable of causing chain transfer described in JP 2002-544205 A can also be used. With respect to the compound of the structure shown in formula (d3), can enumerate such as: 2-hydroxyl-2-methyl-1-phenylpropane-1-ketone, 2-hydroxyl-2-methyl-1-[4- (2-Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1- Ketone oligomers, α,α-diethoxyacetophenone, dibenzoylmethyl dimethyl ketal. From the viewpoint of sensitivity, the alkylacetophenone compound is preferably a compound having a structure represented by formula (d2).

In terms of triazine compounds, for example: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) Methyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine , 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[ 2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl) Vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]- 1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine .

Examples of the acylphosphine oxide compound include oxy-2,4,6-trimethylphenacyldiphenylphosphine and the like. Commercially available products such as Irgacure 819 (manufactured by BASF Japan Co., Ltd.) can also be used.

Biimidazole compounds, such as: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (reference: Japanese Patent Application Publication No. 6-75372, Japanese Patent Application Publication No. 6-75373, etc.), 2,2'- (2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra( Alkoxyphenyl) biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'- Bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (Reference: Japanese Patent Application Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204 Gazette, etc.), imidazole compounds in which the 4,4',5,5'-position phenyl is substituted by carboalkoxy (reference: JP-A No. 7-10913, etc.).

In terms of the polymerization initiator (D), for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. Indium compounds; diphenyl ketone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, sulfide-4-benzoyl-4'-methyldiphenyl, 3,3' ,4,4'-Tetrakis(tertiary butylperoxycarbonyl)diphenyl ketone, 2,4,6-trimethyldiphenyl ketone and other diphenyl ketone compounds; 9,10-phenanthrenequinone, 2- Quinone compounds such as ethyl anthraquinone and camphor quinone; 10-butyl-2-chloroacridone, dibenzoyl, methyl phenylglyoxylate, titanocene compounds, etc. These are preferably used in combination with a polymerization initiation aid (D1) (especially an amine compound) described later.

As the polymerization initiator (D), an acid generator can also be used. Acid generators, such as: p-toluenesulfonic acid-4-hydroxyphenyldimethylconium, hexafluoroantimonic acid-4-hydroxyphenyldimethylconium, p-toluenesulfonic acid-4-acetyloxybenzene Dimethyl columium hexafluoroantimonate, 4-acetyloxyphenyl‧methyl‧benzyl columium hexafluoroantimonate, triphenyl columium p-toluenesulfonate, triphenyl columium hexafluoroantimonate, p-toluenesulfonic acid Onium salts such as diphenyliodonium and diphenyliodonium hexafluoroantimonate, nitrobenzyl toluenesulfonate, and benzoin toluenesulfonate.

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

<Polymerization Initiation Auxiliary (D1)>

A polymerization initiation aid (D1), which can be used together with a polymerization initiator (D), is a polymerizable compound (such as (meth)acrylic acid) used to promote the initiation of polymerization through the polymerization initiator (D). Compound (B)) A polymerized compound, or a sensitizer.

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

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

Amine compounds, such as: triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate Isoamylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)diphenylketone (common name: Michler's ketone), 4,4'-bis(diethylamino)diphenylketone, 4, 4'-bis(ethylmethylamino)diphenyl ketone, etc., among which 4,4'-bis(diethylamino)diphenyl ketone is preferred. Commercial items such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) can also be used.

Alkoxyanthracene compounds, such as: 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl -9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

Thioxanthone compounds include, for example: 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone Xanthone, 1-chloro-4-propoxythioxanthone, etc.

Carboxylic acid compounds include, for example: phenylthioglycolic acid, methylphenylthioglycolic acid, ethylphenylthioglycolic acid, methylethylphenylthioglycolic acid, dimethylphenylthioglycolic acid, methoxyphenylthioglycolic acid, Thioglycolic acid, dimethoxyphenylthioglycolic acid, chlorophenylthioglycolic acid, dichlorophenylthioglycolic acid, N-phenyllysine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthyl thioglycolic acid acid, naphthyloxyacetic acid, etc.

When the resin composition of the present invention contains the polymerization initiation aid (D1), its content is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the total content of the resin (A) and the reactive monomer (B). , more preferably 0.2 to 10 parts by mass. When the amount of the polymerization initiation aid (D1) is within the aforementioned range, the sensitivity tends to be higher when forming a pattern.

<Thiol compound (T)>

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

As the thiol compound (T), examples include: hexanedithiol, decanedithiol, 1,4-bis(methylmercapto)benzene, butanediol bis(3-mercaptopropionate), butanediol Bis(3-mercaptoacetate), Ethylene glycol bis(3-mercaptoacetate), Trimethylolpropane tris(3-mercaptoacetate), Butylene glycol bis(3-mercaptopropionate) , Trimethylolpropane Tris(3-Mercaptopropionate), Trimethylolpropane Tris(3-Mercaptoacetate), Neopentylthritol Tetrakis(3-Mercaptopropionate), Neopentylthritol Tetra (3-mercaptoacetate), trihydroxyethyl tris(3-mercaptopropionate), neopentylthritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyloxy ) butane.

When the resin composition of the present invention contains the thiol compound (T) together with the polymerization initiator (D), the content thereof is 10 to 90 parts by mass relative to 100 parts by mass of the content of the polymerization initiator (D). Best, more preferably 15 to 70 parts by mass. When content of a thiol compound (T) exists in the said range, it exists in the tendency which makes sensitivity high and image development becomes favorable.

<Antioxidant (F)>

As an antioxidant (F), a phenolic antioxidant, a sulfur antioxidant, a phosphorus antioxidant, and an amine antioxidant are mentioned, for example. Among them, phenolic antioxidants are preferable from the viewpoint of less coloring of the cured film.

In terms of phenolic antioxidants, such as: acrylic acid-2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl ester, acrylic acid -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-tetraoxa Spiro[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-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H) -Triketone, 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(trimethylbenzene-2,4,6-triyl)tri- p-cresol, neopentylthritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methanol Basephenol and 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[ d, f] [1,3,2] dioxaphosphopane. The aforementioned phenolic antioxidants can use commercially available products. Commercially available phenolic antioxidants, such as: SUMILIZER (registered trademark ) BHT, GM, GS, GP (all of the above are manufactured by Sumitomo Chemical Co., Ltd.), IRGANOX (registered trademark) 1010, 1076, 1330, 3114 (all of the above are manufactured by BASF Japan Co., Ltd.).

In terms of sulfur-based antioxidants, examples include: 3,3'-dilauryl thiodipropionate, 3,3'-dimyristyl thiodipropionate, and distearyl 3,3'-thiodipropionate , Tetrakis (3-laurylthiopropionate) neopentylthritol ester. As the aforementioned sulfur-based antioxidant, commercially available products can be used. Commercially available sulfur-based antioxidants include, for example, SUMILIZER (registered trademark), TPL-R, and TP-D (all of the above are manufactured by Sumitomo Chemical Co., Ltd.).

In terms of phosphorus antioxidants, for example: trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, tris(nonylphenyl) phosphite, distearyl neopentylthritol diphosphite , Butanediphosphite tetrakis(tridecyl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl ester). As the above-mentioned phosphorus-based antioxidant, commercially available products can be used. In terms of commercially available phosphorus antioxidants, for example: IRGAFOS (registered trademark) 168, 12, 38 (above, all manufactured by BASF (stock)), ADK STAB 329K, ADK STAB PEP36 (above, all manufactured by ADEKA (stock) )manufacture).

In terms of amine antioxidants, examples include: N,N'-di-second-butyl-p-phenylenediamine, N,N'-diisopropyl-p-phenylenediamine, N,N'-dicyclohexyl -p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-di(2-naphthyl)-p-phenylenediamine. As the aforementioned amine-based antioxidant, commercially available products can be used. Examples of commercially available amine antioxidants include SUMILIZER (registered trademark) BPA, BPA-M1, and 4ML (all of the above are manufactured by Sumitomo Chemical Co., Ltd.).

When the resin composition of the present invention contains an antioxidant (F), the content thereof is preferably not less than 0.1 parts by mass and not more than 5 parts by mass relative to 100 parts by mass of the total content of the resin (A) and the reactive monomer (B). More preferably, it is not less than 0.5 parts by mass and not more than 3 parts by mass. When content of antioxidant (F) is in the said range, there exists a tendency for the heat resistance and pencil hardness of the obtained cured film to be excellent.

<Surfactant (H)>

Surfactants (H) include, for example: polysiloxane-based surfactants (without fluorine atoms), fluorine-based surfactants (without siloxane bonds), and polysiloxane-based surfactants with fluorine atoms. Surfactant.

Examples of the polysiloxane-based surfactant include surfactants having a siloxane bond. Specifically, examples include: Toray Silicone DC3PA, same series SH7PA, same series DC11PA, same series SH21PA, same series SH28PA, same series SH29PA, same series SH30PA, polyether modified silicone oil SH8400 (trade name: Dow Corning Toray ( Stock) Manufacturing), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Shin-Etsu Chemical Industry Co. contract (share) manufacturing), etc.

As the above-mentioned fluorine-containing surfactant, for example, a surfactant having a fluorocarbon chain can be mentioned. Specifically, examples include: Fluorinert (registered trademark) FC430, same series FC431 (manufactured by Sumitomo 3M Co., Ltd.), MEGAFAC (registered trademark) F142D, same series F171, same series F172, same series F173, same series F177, Same series F183, same series F552, same series F553, same series F554, same series F555, same series F556, same series F558, same series F559, same series R30 (manufactured by DIC), EFTOP (registered trademark) EF301, Same series EF303, same series EF351, same series EF352 (manufactured by Mitsubishi Materiale Electronic Chemical Co., Ltd.), Surflon (registered trademark) S381, same series S382, same series SC101, same series SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.), etc.

Examples of polysiloxane-based surfactants having fluorine atoms include surfactants with siloxane bonds and fluorocarbon chains. Specifically, MEGAFAC (registered trademark) R08, BL20 of the same series, F475 of the same series, F477 of the same series, F443 of the same series (manufactured by DIC Co., Ltd.), etc. are mentioned, for example. MEGAFAC (registered trademark) F475 is preferable.

When the resin composition of the present invention contains a surfactant (H), its content is generally not less than 0.001% by mass and not more than 0.2% by mass, and preferably not less than 0.002% by mass and not more than 0.1% by mass, relative to the total amount of the resin composition of the present invention. It is preferably not more than 0.01% by mass and more preferably not more than 0.05% by mass. When the content of the surfactant (H) is within the aforementioned range, the flatness of the cured film can be improved.

<Polycarboxylic acid (G)>

Polyvalent carboxylic acid (G) is at least 1 sort(s) of compound chosen from the group which consists of polyhydric carboxylic acid anhydride and polyvalent carboxylic acid.

A polycarboxylic acid refers to a compound having two or more carboxyl groups, and a polycarboxylic acid anhydride refers to an anhydride of a polycarboxylic acid. Also, the polyvalent carboxylic acid (G) is distinguished from the reactive monomer (B) in that it does not contain 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.

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-ene base) succinic anhydride, 2-(2,4,6-trimethylnon-3-enyl) succinic anhydride, propanetricarboxylic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, etc. Chain polycarboxylic acid anhydride; 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hexahydrophthalic anhydride Formic anhydride, 4-methylhexahydrophthalic anhydride, norcamphene 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-di Alicyclic polycarboxylic acid anhydrides such as carboxylic acid anhydride and cyclopentane tetracarboxylic dianhydride; phthalic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, pyromellitic anhydride, and trimellitic anhydride , diphenyl ketone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, ethylene glycol bis(benzenetricarboxylic anhydride ester), glycerol tri(benzenetricarboxylic anhydride ester), glycerol bis(benzenetricarboxylic anhydride ester) monoacetate, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3- Aromatic polycarboxylic acid anhydrides such as furyl)naphtho[1,2-c]furan-1,3-dione. ADEKA HARDENER-EH-700 (trade name (same below), manufactured by ADEKA Co., Ltd.), RIKACID-HH, same series-TH, same series-MH, same series MH-700 (Nippon Rika Co., Ltd.) can also be used manufactured), Epikinia 126, the same series YH-306, the same series DX-126 (manufactured by Shell Epoxy Co., Ltd.), etc. are commercially available.

As for the aforementioned polycarboxylic acid, for example, chains of polycarboxylic acids derived from oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, and linear polycarboxylic anhydrides can be cited. Cyclohexanedicarboxylic acid, polycarboxylic acid derived from alicyclic polycarboxylic acid anhydride, etc.; alicyclic polycarboxylic acid; isophthalic acid, terephthalic acid, 1,4,5,8- Aromatic polycarboxylic acids such as naphthalene tetracarboxylic acid, polycarboxylic acids derived from aromatic polycarboxylic acid anhydrides, etc.

Among them, chain carboxylic acid anhydrides and alicyclic polyhydric carboxylic acid anhydrides are preferable, and alicyclic polyhydric carboxylic acid anhydrides are more preferable because the heat resistance of the cured film is excellent, and especially in the visible light region, the transparency is not easily lowered.

When the resin composition of the present invention contains polycarboxylic acid (G), its content is preferably 1 to 30 parts by mass, preferably 2 to 100 parts by mass of the total content of resin (A) and reactive monomer (B). More preferably to 20 parts by mass, more preferably 2 to 15 parts by mass. When content of polyhydric carboxylic acid (G) exists in the said range, the heat resistance and adhesiveness of a cured film are excellent.

<Imidazole compound (J)>

The imidazole compound (J) is not particularly limited as long as it is a compound having an imidazole skeleton, and examples thereof include compounds that are conventional epoxy curing agents. Among them, the compound represented by formula (2) is preferred.

[In formula (2), R ¹¹ represents an alkyl group with 1 to 20 carbons, phenyl, benzyl or cyanoalkyl with 2 to 5 carbons.

R ¹² to R ¹⁴ independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 20 carbons, a phenyl group, a nitro group or an acyl group with 1 to 20 carbons, and the alkyl group and the phenyl group contained The hydrogen atoms in the hydrogen atoms may be substituted by hydroxyl groups. ]

As for the alkyl group having 1 to 20 carbon atoms, examples include: methyl, ethyl, propyl, isobutyl, butyl, tert-butyl, hexyl, heptyl, octyl, nonyl, decyl, Heptadecyl, Undecyl.

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

The halogen atom includes, for example, a fluorine atom, a chlorine atom, and a bromine atom.

Examples of acyl groups having 1 to 20 carbon atoms include formyl, acetyl, propionyl, isobutyryl, pentyl, isopentyl, trimethylacetyl, and lauryl. , Myristyl, Stearyl.

As for the imidazole compound (J), examples include: 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, 5-hydroxymethyl-4- Methylimidazole, 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-hydroxymethylimidazole Base-2-phenylimidazole, 2-phenylimidazole, 2-phenyl-2-hydroxymethylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl-4-methylimidazole, 1-Benzyl-4-phenylimidazole, 1-benzyl-5-hydroxymethylimidazole, 2-(p-hydroxyphenyl)imidazole, 1-cyanomethyl-2-methylimidazole, 1 -(2-cyanoethyl)-2-hydroxymethylimidazole, 2,4-diphenylimidazole, 1-cyanomethyl-2-undecylimidazole, 1-cyanomethyl-2- Ethyl-4-methylimidazole, 1-cyanomethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole. 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 (J), its content is preferably at least 0.1 parts by mass and at most 25 parts by mass relative to 100 parts by mass of the total content of the resin (A) and the reactive monomer (B). More preferably, it is 0.2 to 15 parts by mass, and more preferably 0.5 to 5 parts by mass. When content of an imidazole compound (J) exists in the said range, there exists a tendency for the transparency of the obtained cured film to be excellent in the visible light region.

<Solvent (E)>

The resin composition of the present invention contains a solvent (E). As for the solvent (E), examples can be given of various organic solvents used in the field of resin compositions, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol Ethylene glycol monoalkyl ether such as monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, diethylene glycol di Diethylene glycol dialkyl ethers such as butyl ether; ethylene glycol alkyls such as methyl cellosuloacetate, ethyl cellosuloacetate, ethylene glycol monobutyl ether acetate, and ethylene glycol monoethyl ether acetate Ether acetate; alkyl glycol alkyl ethers of propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate, etc. Acetate; 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 propylene Propylene glycol dialkyl ether such as methyl ether, propylene glycol ethyl propyl ether, etc.; Propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether propionate, etc. ; Methoxybutanol, ethoxybutanol, propoxybutanol, butoxybutanol and other butanediol monoalkyl ethers; methoxybutyl acetate, ethoxybutyl acetate, propoxyl acetate Butyl butyl ester, butoxy butyl acetate and other butanediol monoalkyl ether acetate; methoxy butyl propionate, ethoxy butyl propionate, propoxy butyl propionate, butoxy butyl propionate Butane glycol monoalkyl ether propionate, such as butyl ester; Dipropylene glycol dialkyl ether, such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol methyl ethyl ether, etc.; Benzene, toluene , xylene, mesitylene and other aromatic hydrocarbons; methyl ethyl ketone, acetone, methyl pentanone, methyl isobutyl ketone, cyclohexanone and other ketones; ethanol, propanol, butanol, hexanol, cyclohexanol, etc. Alcohols such as hexanol, ethylene glycol, and glycerin; methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate , 2-Hydroxy-2-methylpropionate ethyl ester, methyl glycolate, ethyl glycolate, butyl glycolate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, 3-hydroxypropionate Methyl ester, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, methyl 2-hydroxy-3-methylbutyrate, methyl methoxyacetate, methoxy Ethyl acetate, methoxypropyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate, ethoxypropyl acetate, ethoxybutyl acetate, propoxyacetic acid Methyl ester, propoxy ethyl acetate, propoxy propyl acetate, propoxy butyl acetate, butoxy methyl acetate, butoxy ethyl acetate, butoxy propyl acetate, butoxy butyl acetate ester, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, methyl 2-ethoxypropionate ester, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate Esters, Propyl 2-butoxypropionate, Butyl 2-butoxypropionate, 3-Methoxypropionate Methyl ester, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate Ethyl ester, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, 3-propoxypropionate Propyl ester, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, 3-butoxypropionate Esters such as butyl esters; cyclic ethers such as tetrahydrofuran and pyran; cyclic esters such as γ-butyrolactone, etc.

Among the above-mentioned solvents, organic solvents with a boiling point of 100 to 200° C. are preferred from the viewpoint of coating properties and drying properties. Organic solvents with a boiling point of 100 to 200°C, specific examples include: alkanediol alkyl ether acetate, alcohols such as methoxybutanol and ethoxybutanol, ketones such as cyclohexanone, 3- Esters of ethyl ethoxy propionate and methyl 3-methoxy propionate, such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutanol, Methoxybutyl acetate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate are preferred. These solvents (E) can be used alone or in combination of two or more.

The content of the solvent (E) in the resin composition of the present invention is preferably 60 to 95% 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 of the solvent (E) is within the above range, the flatness of the film obtained by coating with the resin composition tends to be high.

<other ingredients>

The resin composition of the present invention may further contain fillers, other polymer compounds, thermal free radical generators, ultraviolet absorbers, chain transfer agents, adhesion promoters, etc., as required, additives known in this technical field .

Examples of fillers include glass, silicon oxide, aluminum oxide, and the like. Other polymer compounds include thermosetting resins such as maleimide resins, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester , Polyamine refers to other thermoplastic resins, etc. As a thermal radical generating agent, 2,2'- azobis(2-methylvaleronitrile), 2,2'- azobis(2,4-dimethylvaleronitrile), etc. are mentioned, for example. As the ultraviolet absorber, 2-(3-tert-butyl-2-hydroxy-5-methylphenyl)-5-chlorobenzotriazole, alkoxydiphenone, etc. are mentioned, for example. As a chain transfer agent, dodecanethiol, 2,4-diphenyl-4-methyl-1-pentene, etc. are mentioned, for example.

Adhesion promoters, etc., such as: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2methoxyethoxy)silane, 3-glycidoxypropyl trimethoxy 3-Glycidoxypropylmethyldimethoxysilane, 3-Glycidoxypropylmethyldimethoxysilane, 3-Glycidoxypropylmethyldimethoxysilane, 3-Glycidoxypropylmethyldimethoxysilane Oxysilane, 2-(3,4-ethoxycyclohexyl)ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methoxysilane Acryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, N-2-(amino Ethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, N-2-(amino Ethyl)-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane , 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, etc.

The resin composition of the present invention is preferably substantially free of coloring agents such as pigments and dyes. That is, in the resin composition of the present invention, the content of the coloring agent relative to the entire composition is generally less than 1% by mass, preferably less than 0.5% by mass.

<Manufacturing method of resin composition>

The resin composition of the present invention can be obtained by mixing resin (A) and solvent (E), and optionally used (meth)acrylic acid compound (B), epoxy resin (C), polymerization initiator (D ), polymerization initiation aid (D1), antioxidant (F), surfactant (H), polycarboxylic acid (G), imidazole compound (J) and other components are mixed and manufactured by known methods. After mixing, it is better to filter through a filter membrane with a pore size of about 0.05 to 1.0 μm.

<Manufacturing method of cured film>

The cured film can be produced by coating the resin composition of the present invention on a substrate, drying it, and curing it by heating. More specifically, the manufacturing method of the cured 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 to form a composition layer

Step (3): The step of heating the composition layer

Moreover, when the resin composition of this invention contains a polymerization initiator (D), the cured film containing a pattern 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 to form a composition layer

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

Step (2b): The step of developing the exposed composition layer

Step (3a): the step of heating the developed composition layer

Step (1) is a step of coating the resin composition of the present invention on a substrate. As for the substrate, for example, glass, metal, plastic, etc. may be mentioned, and a filter layer, an insulating film, a conductive film and/or a driving circuit may also be formed on the substrate. Coating on the substrate is preferably carried out using coating devices such as spin coaters, slit and spin coaters, slit coaters, inkjet printers, roll coaters, and dip coaters.

Step (2) is a step of drying the applied resin composition under reduced pressure to form a composition layer. By performing this step, volatile components such as solvents in the resin composition are removed. Drying under reduced pressure is preferably carried out at a pressure of 50 to 150 Pa and a temperature range of 20 to 25°C. Heat drying (prebaking) can also be performed before or after reduced-pressure drying, and heat drying is generally performed using heating devices such as a heating box and a heating plate. The heating and drying temperature is preferably 30 to 120°C, more preferably 50 to 110°C. At the same time, the heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.

Step (3) is a step of heating the composition layer (post-baking). The composition layer is cured by heating to form a cured film. Heating is generally carried out using heating devices such as heating boxes and heating plates. The heating temperature is preferably 130 to 270°C, more preferably 150 to 260°C, more preferably 200 to 250°C. When the heating temperature is 200 to 250°C, unnecessary excess solvent in the cured film can be prevented. The heating time is preferably from 1 to 120 minutes, more preferably from 10 to 60 minutes.

Step (2a) is a step of exposing the composition layer formed in step (2) through a photomask. The mask is used to form a light-shielding portion corresponding to the portion where the composition layer is to be removed. The shape of the light-shielding portion is not particularly limited, and can be selected depending on the intended use. The light source used for exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. For example, light that does not reach 350nm can be filtered with a filter that filters out this wavelength range, and light around 436nm, 408nm, and 365nm can also be selectively filtered out using a bandpass filter that filters out these wavelength ranges. optical device. As a light source, for example, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned. In order to uniformly irradiate the entire exposure surface with parallel light rays and align the mask and the composition layer in the correct position, it is better to use exposure devices such as a mask alignment exposure machine and a stepper.

Step (2b) is a step of developing the exposed composition layer. The exposed composition layer is developed by contacting with a developing solution, and the unexposed part of the composition layer can be dissolved in the developing solution and removed, forming a patterned composition layer on the substrate. As for the developing solution, an aqueous solution of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide is preferred. The concentration in the aqueous solution of the basic compound is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. At the same time, the imaging solution system may contain a surfactant. The image development method may be any of paddle method, dipping method, spray method and the like. Moreover, the substrate can be tilted at any angle during imaging. After developing, it is better to wash with water.

Step (3a) is a step of heating the developed composition layer. By performing the same heating as in the aforementioned step (3), the patterned composition layer can be cured to form a patterned cured film on the substrate.

The cured film obtained in this way has excellent surface flatness, so it can be used as a protective film and overcoat layer for color filter substrates and touch panels used in liquid crystal display devices, organic EL display devices, and electronic paper displays. .

A display device having a high-quality cured film can be manufactured with the resin composition of the present invention. Even on a color filter substrate having unevenness of a colored pattern on the surface, the resin composition of the present invention can be used to form an overcoat layer, thereby improving the flatness of the surface.

[Example]

Hereinafter, the present invention will be further described in detail according to the examples. "%" and "parts" in the examples mean % by mass and parts by mass unless otherwise specified.

(Synthesis Example 1: Resin (A1))

Into a flask equipped with a circulating condenser, a dropping funnel, and a stirrer, 0.02 L/min of nitrogen gas was passed through to form a nitrogen atmosphere, and 140 parts of propylene glycol monomethyl ether acetate was added, and heated to 70° C. while stirring. Then 25 parts of methacrylic acid; the mixture of the monomer of formula (I-1) and the monomer of formula (II-1) {the mole of monomer of formula (I-1) and formula (II-1) monomer Ratio = 50:50} 145 parts; and 75 parts of ethyl methacrylate, dissolved in 190 parts of propylene glycol monomethyl ether acetate to prepare a solution, and then use a drip pump to drip the solution in 4 hours In a flask insulated at 70°C.

On the other hand, dissolve 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in a solution of 240 parts of propylene glycol monomethyl ether acetate, and use another drop The liquid was pumped dropwise into the flask over 5 hours. After the polymerization initiator solution was dropped, it was kept at 70° C. for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin (A1)) with a solid content of 30%. The obtained resin A1 had a weight average molecular weight (Mw) of 9600, a degree of dispersion (Mw/Mn) of 1.9, and an acid value of 60 mg-KOH/g in terms of solid content. Resin (A1) has the following structural units.

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

Device: K2479 (manufactured by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40°C

Solvent: Tetrahydrofuran (THF)

Flow rate: 1.0mL/min

Detector: RI

Calibration standard: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

The degree of dispersion was defined as the ratio (Mw/Mn) of the weight average molecular weight and number average molecular weight obtained above in terms of polystyrene.

(Synthesis Example 2: Resin (A2))

Into a flask equipped with a circulating condenser, a dropping funnel, and a stirrer, 0.02 L/min of nitrogen gas was passed through to form a nitrogen atmosphere, and 140 parts of propylene glycol monomethyl ether acetate was added, and heated to 70° C. while stirring. Then 25 parts of methacrylic acid; the mixture of the monomer of formula (I-1) and the monomer of formula (II-1) {the mole of monomer of formula (I-1) and formula (II-1) monomer Ratio = 50:50} 145 parts; and 75 parts of butyl methacrylate, dissolved in 190 parts of propylene glycol monomethyl ether acetate to form a solution, and then the solution was dripped into the In a flask insulated at 70°C.

On the other hand, dissolve 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in a solution of 240 parts of propylene glycol monomethyl ether acetate, and use another drop The liquid was pumped dropwise into the flask over 5 hours. After dropping the polymerization initiator, it was kept at 70° C. for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin (A2)) with a solid content of 30%. The obtained resin A1 had a weight average molecular weight (Mw) of 9000, a degree of dispersion (Mw/Mn) of 1.9, and an acid value of 61 mg-KOH/g in terms of solid content. Resin (A2) has the following structural units.

(Synthesis Example 3: Resin (A3))

Into a flask equipped with a circulating condenser, a dropping funnel, and a stirrer, 0.02 L/min of nitrogen gas was passed through to form a nitrogen atmosphere, and 140 parts of propylene glycol monomethyl ether acetate was added, and heated to 70° C. while stirring. Then 25 parts of methacrylic acid; the mixture of the monomer of formula (I-1) and the monomer of formula (II-1) {the mole of monomer of formula (I-1) and formula (II-1) monomer Ratio = 50:50} 145 parts; and 75 parts of methyl methacrylate, dissolved in 190 parts of propylene glycol monomethyl ether acetate to prepare a solution, and the solution was dripped at 70 ℃ insulated flask.

On the other hand, dissolve 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in a solution of 240 parts of propylene glycol monomethyl ether acetate, and use another drop The liquid was pumped dropwise into the flask over 5 hours. After the polymerization initiator solution was dropped, it was kept at 70° C. for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin (A3)) with a solid content of 30%. The obtained resin A1 had a weight average molecular weight (Mw) of 9200, a degree of dispersion (Mw/Mn) of 1.9, and an acid value of 61 mg-KOH/g in terms of solid content. Resin (A3) has the following structural units.

(Synthesis example: Resin (A4))

Into a flask equipped with a circulating condenser, a dropping funnel, and a stirrer, 0.02 L/min of nitrogen gas was passed through to form a nitrogen atmosphere, and 140 parts of propylene glycol monomethyl ether acetate was added, and heated to 70° C. while stirring. Then 40 parts of methacrylic acid; and the mixture of the monomer of formula (I-1) and the monomer of formula (II-1); Ear ratio=50:50} 360 parts; dissolved in 190 parts of propylene glycol monomethyl ether acetate to prepare a solution, and then the solution was dripped into a flask kept at 70°C for 4 hours using a drip pump.

On the other hand, dissolve 30 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) in a solution of 240 parts of propylene glycol monomethyl ether acetate, and use another drop The liquid was pumped dropwise into the flask over 5 hours. After the polymerization initiator solution was dripped, it was kept at 70° C. for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin (A4)) with 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 of 60 mg-KOH/g in terms of solid content. Resin (A4) has the following structural units.

[Example 1, 2 and Comparative Example 1, 2]

<Preparation of resin composition>

In order to make the solid content 15% by mass, any one of the resin (A1) to the resin (A4) is mixed in the propylene glycol monomethyl ether acetate of the solvent (E), and then the surfactant (H) MEGAFAC (trademark) F554 (manufactured by DIC Co., Ltd.) was added in an amount of 0.1 parts by mass with respect to 100 parts by mass of the resin (A) to obtain a resin composition.

<Preparation of substrates for evaluation>

A 2-inch square glass substrate (EAGLE XG; manufactured by Corning Co., Ltd.) was washed with a neutral detergent, water, and isopropanol in sequence, and then dried. On this board|substrate, the colored photosensitive resin composition which has the following composition was spin-coated so that the film thickness after post-baking might become 2.0 micrometers.

Next, in a dust-free heating box, pre-bake at 100° C. for 3 minutes to form a colored composition layer. After cooling, the distance between the coloring composition layer on the substrate and the quartz glass mask is made 100 μm, and an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd., light source: ultra-high-pressure mercury lamp) is used to expose in the atmosphere. Light was irradiated at an exposure amount of 100 mJ/cm ² (based on 365 nm). In addition, this light irradiation was performed by passing the light radiated from the ultra-high pressure mercury lamp through an optical filter (UV31; manufactured by Asahi Tech Glass Co., Ltd.). Also, as a photomask, a photomask formed with a line/space pattern with a line width of 30 μm was used.

Then immerse the colored composition layer after irradiating light with an aqueous developer solution containing 0.12% non-ionic surfactant and 0.04% potassium hydroxide at 23°C for 60 seconds, wash with water, and place in a heating box. In the process, post-baking was performed at 230° C. for 30 minutes to prepare a substrate for evaluation on which a colored pattern of line/space with a line width of 30 μm was formed.

(Composition of Colored Photosensitive Resin Composition)

Pigment: about 40% (note: the ratio of green pigment in the total amount of pigment: about 90%, the yellow colorant in the total amount of pigment: 10%), epoxy resin: 3%, acrylic monomer: 14% , Polymerization initiator: 10%, Adhesion improver: 1%, Surfactant: 600ppm

The film thickness of the formed coloring pattern was measured using a contact film thickness measuring device (DEKTAK 6M; manufactured by ULVAC Co., Ltd.) with a measurement width of 500 μm and a measurement speed of 10 seconds to obtain a profile of the cross-sectional shape of the coloring pattern ( That is, contour plots). Then, the average value of the film thickness of the colored pattern was calculated from the section. The average value of the film thickness was 2.0 μm.

<Formation of cured film and evaluation of flatness>

The aforementioned substrate for evaluation was spin-coated under the condition that the film thickness after post-baking (film thickness from the surface of the colored pattern) was 1.0 µm, and the resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were applied. Then, use a decompression dryer (manufactured by VCD Micron Technology Co., Ltd.) to dry the rotary pump at 1000 rpm, the booster pump at 700 rpm, and a normal temperature of 25°C until the decompression is 66 Pa, and then heat Prebake at 100°C for 3 minutes on the plate. After standing to cool, it was baked for 30 minutes at a temperature of 230° C. to form a cured film.

The film thickness of the cured film on the evaluation substrate is measured using a contact film thickness measuring device (DEKTAK 6M; manufactured by ULVAC Co., Ltd.) with a measurement width of 500 μm and a measurement speed of 10 seconds to obtain the cross-sectional shape of the cured film. profile. Then, the average value of the film thickness of the cured film was calculated from the section, and the average value of the film thickness on the surface of the self-coloring pattern was 1.0 μm.

The cross-sectional shapes of the cured films obtained from the compositions of Examples 1 and 2 and Comparative Examples 1 and 2 shown in Fig. 1 to Fig. 4 are summarized as the cross-sectional shapes of the substrates for evaluation. In FIGS. 1 to 4, the cross-sections of the respective cross-sectional shapes are described.

The horizontal axis represents the position in the planar direction, and the vertical axis represents the position in the height direction. A protruding part in the cross-sectional shape of the coloring pattern corresponds to a coloring unit.

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

According to the present invention, a resin composition capable of forming a cured film with high surface flatness can be provided. Since the cured film obtained with this curable resin composition is excellent in flatness, it is suitable for use in a display device etc.

Since the picture in this case is the test data, it is not a representative picture of this case.

Therefore, there is no designated representative figure in this case.

Claims (6)

A resin composition comprising a resin (A) and a solvent, the resin (A) is composed of a constituent unit (Aa) derived from an alkyl (meth)acrylate having a carbon number of 2 or more, derived from a The structural unit (Ab) of an unsaturated compound having a cyclic ether structure of 2 to 4, and the structural unit (Ac) derived from at least one compound selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides Composed resin, and relative to the total amount of structural units constituting the resin (A), the ratio of the constituent unit (Aa) is higher than 10 mole %; the resin (A) is a copolymer with a weight average molecular weight of 5000 to 20000; the resin ( The dispersity of A) [weight average molecular weight (Mw)/number average molecular weight (Mn)] is 1.1 to 6.0; the acid value of the resin (A) is more than 30 mg-KOH/g and less than 180 mg-KOH/g. The resin composition as described in item 1 of the scope of the patent application, wherein the aforementioned unsaturated compound having a cyclic ether structure with 2 to 4 carbon atoms is a compound represented by the following formula (I) and the following formula (II) ) at least one compound selected from the compounds shown in ); relative to the total amount of structural units constituting the resin (A), the ratio of the constituent unit (Aa) is 10 to 35 mol%, and the ratio of the constituent unit (Ab) is 10 to 80 mole%, the ratio of the constituent unit (Ac) is 10 to 35 mole%;

In formula (I) and formula (II), R ^b1 and R ^b2 represent a hydrogen atom, or an alkyl group with 1 to 4 carbons, and the hydrogen atom contained in the alkyl group can be substituted by a hydroxyl group; X ^b1 and X ^b2 represent Single bond, -Rb ³ -, *-Rb ³ -O-, *-R ^b3 -S- or *-R ^b3 -NH-; R ^b3 represents an alkanediyl group with 1 to 6 carbons, and * represents the difference between Bond key. The resin composition as described in claim 1, wherein, relative to the total amount of structural units constituting the resin (A), the ratio of the structural unit (Aa) is higher than 10 mol% and 35 mol% or less . The resin composition as described in claim 1 or 2, wherein the constituent unit (Aa) is a constituent unit derived from an alkyl (meth)acrylate having a linear alkyl group having 2 to 10 carbons. The resin composition as described in claim 1 or 2, wherein the constituent unit (Aa) is a constituent unit derived from an alkyl (meth)acrylate having a linear alkyl group having 2 to 6 carbons. A cured film formed of the resin composition as described in claim 1 or 2 of the patent application.

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