TW201815847A - 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 order to form a cured film of an optical spacer, an overcoat layer, and the like on a liquid crystal display device, a curable resin composition is used.

As a curable resin composition usable in a liquid crystal display device, there have been proposed, for example, an unsaturated carboxylic acid and / or an unsaturated carboxylic acid anhydride (Aa), a compound (Ab) polymerizable with the (Aa), and A curable resin composition of an adhesive resin formed by polymerizing a compound (Ac) having a cyclic ether group having 2 to 4 carbon atoms (for example, Japanese Patent Application Laid-Open No. 2010-106154).

The cured film system can be formed by applying a curable resin composition to a substrate and further heating it. In order to achieve fine display in a liquid crystal display device, it is preferable that the hardened film of the photo-isolator and the overcoat layer is flat. However, since the substrate on which the colored pattern is formed has irregularities, when the curable resin composition is applied to the substrate and further heated to obtain a cured film, the flatness required for the overcoat layer may not be obtained.

The present invention includes the following inventions.

[1] A resin composition comprising a resin (A) and a solvent, and the resin (A) contains a structural unit (Aa) derived from an alkyl (meth) acrylate having an alkyl group having 2 or more carbon atoms, Composition of a structural unit (Ab) derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms, and a structure derived from at least one compound selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride Unit (Ac), and the ratio of the constituent unit (Aa) is higher than 10 mol% relative to the total amount of the structural units constituting the resin (A), and the resin (A) is a copolymer having a weight average molecular weight of 5000 to 20,000.

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

[3] The resin composition according to item [1] or [2], wherein the ratio of the constituent unit (Aa) is higher than 10 mol% relative to the total amount of the constituent units constituting the resin (A) and is 35 mol% or less.

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

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

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

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

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

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

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

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

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

The resin composition of the present invention includes a resin (A) and a solvent (E). Resin (A) is an unsaturated compound derived from 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) and the structural unit (Ac) derived from at least one compound selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride, and the ratio of the structural unit (Aa) to the composition The total amount of the structural unit of the resin (A) is higher than 10 mol%, and the resin (A) is a copolymer having a weight average molecular weight of 5000 to 20,000.

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

In the present specification, "(meth) acrylic acid" means at least one compound selected from the group consisting of acrylic acid and methacrylic acid. The descriptions of "(meth) acrylfluorenyl" and "(meth) acrylate" also have the same meaning.

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

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

<Resin (A)>

Resin (A) is a hardening resin, preferably a thermosetting resin, and more preferably a resin hardened by heat at 60 ° C or higher. The resin (A) is derived from an alkyl group having a carbon number of 2 or more ( A structural unit derived from an alkyl meth) acrylate (Aa), a structural unit derived from an unsaturated compound (Ab) having a cyclic ether structure having 2 to 4 carbon atoms, and a component derived from an unsaturated carboxylic acid and an unsaturated carboxylic acid A copolymer of structural units of at least one compound (Ac) in the group of acid anhydrides.

The copolymer may be further copolymerized with the compound (Aa), the compound (Ab), or the compound (Ac), and may further have a compound (Ad) derived from the compound (Aa), the compound (Ab), and the compound (Ac). Building unit.

(1) Structural unit derived from compound (Aa)

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

Examples of the compound (Aa) include ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, Dodecyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isobutyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, and the like. Furthermore, since the film obtained by coating the resin composition on a substrate can suppress peeling under high temperature and high humidity, the number of carbon atoms of the alkyl group in the compound (Aa) is preferably 10 or less, and 8 or less. More preferably, it is even better if it is 6 or less. The alkyl group of the compound (Aa) may be linear or branched, and is preferably linear.

(2) Structural unit derived from compound (Ab)

Compound (Ab) refers to an unsaturated structure having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an ethylene oxide 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) acrylic acid group.

Examples of the compound (Ab) include a compound (Ab1) (hereinafter, sometimes referred to as "(Ab1)") having an epoxyethyl group and an ethylenically unsaturated bond, and an oxobutane group and an ethylenic unsaturated group. Compound (Ab2) of a saturated bond (hereinafter, sometimes referred to as "(Ab2)"), compound (Ab3) (hereinafter, sometimes referred to as "(Ab3)") having a tetrahydrofuryl group and an ethylenically unsaturated bond.

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

(Ab1-1) As an example, a glycidyl (meth) acrylate, (beta) -methyl-glycidyl (meth) acrylate, and (beta) -ethyl-glycidyl (meth) acrylate can be mentioned. , Epoxypropyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-ortho -Vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (Glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2 1,6-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-tris (epoxypropyloxymethyl) styrene and the like.

(Ab1-2), for example, vinyl cyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example: Celloxide 2000; Daicel Chemical Industry Co., Ltd.), (Meth) acrylic acid 3,4-epoxycyclohexyl methyl ester (for example: Cyclomer-A400; manufactured by Daicel Chemical Industry Co., Ltd.), (meth) acrylic acid 3,4-epoxy cyclohexyl methyl ester (Example: Cyclomer-M100; manufactured by Daicel Chemical Industries, Ltd.), a compound represented by formula (I), a compound represented by formula (II), and the like.

[In formulae (I) and (II), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

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

R ^b3 represents an alkanediyl group having 1 to 6 carbon atoms. * Indicates a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, and third butyl. Examples of the alkyl group having a hydrogen atom substituted with a hydroxyl group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1- Hydroxy-1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

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

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

In terms of X ^b1 and X ^b2 , preferred examples include single bonds, methylene, ethylidene, * -CH ₂ -O-, * -CH ₂ CH ₂ -O- 'with single bonds, *- CH ₂ CH ₂ -O- is more preferred. * Indicates a bond with O.

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

The compound represented by formula (II) includes, for example, a compound represented by any one of formula (II-1) to formula (II-15).

Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), or formula (II-11) to formula (II-15) The compound represented by) is more preferable, and the compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) is more preferable.

The compound represented by the formula (I) and the compound represented by the formula (II) may be used individually or in a mixture at any ratio. When used in combination, the content ratio of the compound represented by the formula (I) and the compound represented by the formula (II) is based on Mohr, 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 containing a compound represented by the formula (I-1) and a compound represented by the formula (II-1) (commercially available product has the trade name "E-DCPA" (Daicel (share) Manufacturing).

In terms of (Ab2), a compound having an oxycyclobutane group and a (meth) acrylfluorenyloxy group is more preferable. (Ab2) As examples, 3-methyl-3-methacrylmethyloxycyclobutane, 3-methyl-3-propylamyloxymethyloxycyclobutane, 3 -Ethyl-3-methylpropenyloxymethyloxycyclobutane, 3-ethyl-3-propenyloxymethyloxycyclobutane, 3-methyl-3-methacryl Ethoxyethyloxycyclobutane, 3-methyl-3-propenyloxyethyloxycyclobutane, 3-ethyl-3-methpropenyloxyethyloxycyclobutane, 3-ethyl-3-propenyloxyethyloxycyclobutane and the like.

In (Ab3), a compound having a tetrahydrofuranyl group and a (meth) acrylfluorenyloxy group is preferred. In (Ab3), tetrahydrofuran methyl acrylate (e.g., Viscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofuran methyl methacrylate, and the like can be mentioned.

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

(3) Structural unit derived from compound (Ac)

Examples of the compound (Ac) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; maleic acid, fumaric acid, Citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6- Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylic acid, 5 -Carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] heptane 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 bicyclic unsaturated compounds containing carboxyl groups; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinyl phthalic 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; amber Unsaturation of two or more polyvalent carboxylic acids such as acid mono [2- (meth) acrylfluorenyloxyethyl] ester and phthalic acid mono [2- (meth) acrylfluorenyloxyethyl] ester Mono [(meth) acryl fluorenyloxyalkyl] ester; α- (hydroxymethyl) acrylic acid and the like, unsaturated acrylates having a hydroxyl group and a carboxyl group in the same molecule.

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

(4) Structural unit derived from compound (Ad)

Examples of the compound (Ad) include methyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, Tricyclo [5.2.1.0 ^2.6 ] decane-8- (meth) acrylate (In the technical field, the common name is called "dicyclopentyl (meth) acrylate". It is also sometimes called "( Tricyclodecyl methacrylate ".), Tricyclo [5.2.1.0 ^2.6 ] decene-8-ester (in the technical field, the common name is" dicyclopentyl (meth) acrylate ""Allyl".), Dicyclopentyloxyethyl (meth) acrylate, Isoamyl (meth) acrylate, Adamantane (meth) acrylate, Allyl (meth) acrylate, (Methyl) ) (Meth) acrylates such as propargyl acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, (Meth) acrylic acid-containing (meth) acrylates such as 2-hydroxypropyl acrylate; dicarboxylic acids such as diethyl maleate, diethyl fumarate, diethyl itaconate Diester; 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] heptane- 2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxy Bicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-bis (hydroxymethyl) bicyclo [2.2.1] heptane -2-ene, 5,6-bis (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene 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-third 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 (third butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclic unsaturated compounds; N-phenyl-cis-butene-diimide, N-cyclohexyl-cis-butene-diimide, N-benzyl-cis-butene-diimide, N-succinimide -3-cis-butene diamidine Benzoate, N-succinimide-4-maleimide diimide butyrate, N-succinimide imino-6-maleimide diimide hexanoate, N-amber Fluorenimine-3-cis-butene difluorenimide propionate, N- (9-acridinyl) cis-butene difluorenimide and other dicarbonylfluorenimine derivatives; styrene, α-formaldehyde Styryl, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, dichloroethane, vinylidene chloride, acrylic fluorene Amines, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene.

Among them, from the viewpoints of copolymerization reactivity and heat resistance, styrene, vinyltoluene, N-phenylcis-butenedifluoreneimine, N-cyclohexylcisbutenedifluoreneimide, and N-benzyl Preference is given to cis-butene diamidine and bicyclo [2.2.1] hept-2-ene.

(5) Ratio of each constituent unit

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

Resin [K1]: copolymer of compound (Aa), compound (Ab) and compound (Ac); resin [K2]: copolymer of compound (Aa), compound (Ab), compound (Ac) and compound (Ad) .

The ratio of each constituent unit in the resin [K1] is a constituent unit derived from the compound (Aa) with respect to all the constituent units constituting the resin [K1]: 5 to 40 mol%, and a constituent derived from the compound (Ab) Unit: 5 to 90 mol%, constituent unit derived from compound (Ac): 5 to 40 mol% is preferred, and constituent unit derived from compound (Aa): 10 to 35 mol%, derived from compound ( Ab) constituting unit: 10 to 80 mol%, and constituting unit derived from compound (Ac): 10 to 35 mol%.

In the resin (A), the ratio of the constituent unit (Aa) is higher than 10 mol% and 35 mol% or less, and the constituent unit derived from the compound (Ab) is 10 mol% or more and less than 80 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, the chemical resistance of the obtained cured film, heat resistance, and mechanical strength tend to be excellent.

For the resin [K1], refer to the method described in the document "Experimental Method of Polymer Synthesis" (Otsu Takayuki Press: Chemical Dojin (Stock), 1st Edition, First Printing, March 1, 1972) and the method It is manufactured by citing documents described in the literature.

Specifically, the method may be, for example, adding a predetermined amount of the compound (Aa), the compound (Ab) and the compound (Ac), a polymerization initiator, a solvent, and the like into a reaction vessel, for example, by replacing oxygen with nitrogen, and deoxidizing In the environment, the method of heating and holding at the same time while stirring. The polymerization initiator, solvent, and the like used therein are not particularly limited, and those generally used in the technical field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) and organic compounds. As for the oxide (such as benzamyl peroxide) and the solvent, any monomer may be used as long as it can dissolve each monomer. For example, a solvent described later is used in the resin composition.

The resin obtained by the above method may be used directly after the reaction, a concentrated or diluted solution may be used, and a solid (powder) may be taken out by using a method such as reprecipitation. In particular, as the polymerization solvent, by using the solvent used in the resin composition of the present invention, the solution after the reaction can be directly used in the manufacture of the resin composition, and therefore the manufacturing steps of the resin composition can be simplified.

The ratio of each constituent unit in the resin [K2] is the constituent unit derived from (Aa) among all the constituent units constituting the resin [K2]: 5 to 40 mol%, and the constituent unit derived from (Ab): 5 to 90 mol%, constituent units derived from (Ac): 5 to 40 mol%, constituent units derived from (Ad): 1 to 40 mol% is preferred, and the composition 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 mole% is better.

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

Resin [K2] can be produced in the same manner as resin [K1]. As described above, in the resin (A), the ratio of the constituent unit (Aa) is higher than 10 mol% and 35 mol% or less, and the constituent unit derived from the compound (Ab) is 10 mol%. Those above and below 80% are more preferred.

Specific examples of the resin [K1] include ethyl (meth) acrylate / compound of formula (I-1) / (meth) acrylic acid copolymer, ethyl (meth) acrylate / formula (I- 2) Compound of compound / (meth) acrylic acid copolymer, ethyl (meth) acrylate / compound of formula (I-3) / (meth) acrylic acid copolymer, ethyl (meth) acrylate / formula ( I-4) compound / (meth) acrylic acid copolymer, ethyl (meth) acrylate / compound (I-5) compound / (meth) acrylic acid copolymer, ethyl (meth) acrylate / Compound of formula (I-6) / (meth) acrylic acid copolymer, ethyl (meth) acrylate / compound of formula (I-7) / (meth) acrylic acid copolymer, ethyl (meth) acrylate Esters / compounds of formula (I-8) / (meth) acrylic acid copolymers, ethyl (meth) acrylates / compounds of formula (I-9) / (meth) acrylic acid copolymers, (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, (formaldehyde Based) ethyl acrylate / compound of formula (I-12) / (meth) acrylic acid copolymer, ethyl (meth) acrylate / formula (I-13 ) Compound / (meth) acrylic acid copolymer, ethyl (meth) acrylate / compound of formula (I-14) / (meth) acrylic acid copolymer, ethyl (meth) acrylate / formula (I -15) compound / (meth) acrylic acid copolymer, ethyl (meth) acrylate / compound (II-1) compound / (meth) acrylic acid copolymer, ethyl (meth) acrylate / formula (II-2) compound / (meth) acrylic acid copolymer, ethyl (meth) acrylate / compound (II-3) compound / (meth) acrylic acid copolymer, ethyl (meth) acrylate / Compound of formula (II-4) / copolymer of (meth) acrylic acid, ethyl (meth) acrylate / compound of formula (II-5) / copolymer of (meth) acrylic acid, (meth) acrylic acid Ethyl ester / compound of formula (II-6) / (meth) acrylic acid copolymer, ethyl (meth) acrylate / compound of formula (II-7) / (meth) acrylic acid copolymer, (methyl ) Ethyl acrylate / compound of formula (II-8) / (meth) acrylic acid copolymer, ethyl (meth) acrylate / compound of formula (II-9) / (meth) acrylic acid copolymer, ( (Meth) ethyl acrylate / Compound of formula (II-10) / (meth) acrylic acid copolymer, (meth) propylene Ethyl ester / compound of formula (II-11) / (meth) acrylic acid copolymer, ethyl (meth) acrylate / compound of formula (II-12) / (meth) acrylic acid copolymer, (methyl ) Ethyl acrylate / compound of formula (II-13) / (meth) acrylic acid copolymer, ethyl (meth) acrylate / compound of formula (II-14) / (meth) acrylic acid copolymer, ( 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) / (Meth) acrylic copolymer, butyl (meth) acrylate / compound of formula (I-1) / (meth) acrylic copolymer, butyl (meth) acrylate / formula (II-1) Compound / (meth) acrylic acid copolymer, butyl (meth) acrylate / compound of formula (I-1) / compound of formula (II-2) / (meth) acrylic acid copolymer, (meth) ) Butyl acrylate / compound of formula (I-1) / crotonic acid copolymer, butyl (meth) acrylate / compound of formula (I-1) / maleic acid copolymer, (meth) Butyl acrylate / Compound of formula (I-1) / (meth) acrylic acid / maleic anhydride copolymer, ethyl (meth) acrylate / (formaldehyde) Base) butyl acrylate / compound of formula (I-1) / (meth) acrylic acid copolymer, butyl (meth) acrylate / compound of formula (II-1) / crotonic acid copolymer, (methyl ) Butyl acrylate / compound of formula (II-1) / copolymer of maleic acid, butyl (meth) acrylate / compound of formula (II-1) / (meth) acrylic acid / maleic acid Copolymer of anhydride, propyl (meth) acrylate / compound of formula (I-1) / copolymer of (meth) acrylic acid, propyl (meth) acrylate / compound of formula (II-1) / (formaldehyde) (Meth) acrylic acid copolymer, propyl (meth) acrylate / compound of formula (I-1) / compound of formula (II-2) / (meth) acrylic acid copolymer, propyl (meth) acrylate Compound / copolymer of formula (I-1) / crotonic acid, propyl (meth) acrylate / copolymer of compound of formula (I-1) / maleic acid, propyl (meth) acrylate / Compound of formula (I-1) / (meth) acrylic acid / maleic anhydride copolymer, ethyl (meth) acrylate / propyl (meth) acrylate / compound of formula (I-1) / (Meth) acrylic acid copolymer, propyl (meth) acrylate / compound of formula (II-1) / crotonic acid copolymer, (formaldehyde ) Acrylic acid acrylate / compound of formula (II-1) / copolymer of maleic acid, propyl (meth) acrylate / compound of formula (II-1) / (meth) acrylic acid / maleic acid Copolymer of anhydride, hexyl (meth) acrylate / compound of formula (I-1) / copolymer of (meth) acrylic acid, hexyl (meth) acrylate / compound of formula (II-1) / (formaldehyde) Base) copolymer of acrylic acid, hexyl (meth) acrylate / compound of formula (I-1) / compound of formula (II-2) / copolymer of (meth) acrylic acid, hexyl (meth) acrylate / Compound of formula (I-1) / crotonic acid copolymer, hexyl (meth) acrylate / compound of formula (I-1) / maleic acid copolymer, hexyl (meth) acrylate / formula Compound of (I-1) / (meth) acrylic acid / maleic anhydride copolymer, hexyl (meth) acrylate / butyl (meth) acrylate / compound of formula (I-1) / (formaldehyde Based) acrylic acid copolymer, hexyl (meth) acrylate / compound of formula (II-1) / crotonic acid copolymer, hexyl (meth) acrylate / compound of formula (II-1) / cis butene Copolymers of diacids, copolymers of hexyl (meth) acrylate / compounds of formula (II-1) / (meth) acrylic acid / maleic anhydride 2, -2-ethylhexyl (meth) acrylate / compound of formula (I-1) / copolymer of (meth) acrylic acid, 2-ethylhexyl (meth) acrylate / formula (II-1 ) Compound / (meth) acrylic acid copolymer, (meth) acrylic acid 2-ethylhexyl ester / compound of formula (I-1) / compound of formula (II-2) / (meth) acrylic acid Copolymer, 2-ethylhexyl (meth) acrylate / compound of formula (I-1) / crotonic acid copolymer, 2-ethylhexyl (meth) acrylate / formula (I-1) Copolymer of maleic acid / maleic acid, 2-ethylhexyl (meth) acrylic acid / compound of formula (I-1) / copolymer of (meth) acrylic acid / maleic anhydride, ( 2-ethylhexyl methacrylate / butyl (meth) acrylate / compound of formula (I-1) / (meth) acrylic acid copolymer, 2-ethylhexyl (meth) acrylate / Compound of formula (II-1) / copolymer of crotonic acid, 2-ethylhexyl (meth) acrylate / compound of formula (II-1) / copolymer of maleic acid, (methyl ) 2-ethylhexyl acrylate / compound of formula (II-1) / (meth) acrylic acid / maleic anhydride copolymer and the like.

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

The weight average molecular weight (Mw) of the resin (A) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, even more preferably 5,000 to 20,000, and particularly preferably 5,000 to 10,000. When the weight average molecular weight (Mw) of the resin (A) is within the aforementioned range, the coatability of the resin composition tends to be improved.

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

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

The acid value is a measurement value of the amount of potassium hydroxide (mg) required to neutralize 1 g of the resin, and can be determined by titration with an aqueous potassium hydroxide solution. When the acid value of the resin (A) is within the above range, the adhesiveness between the obtained cured film and the substrate tends to be excellent.

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

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

The solid content of the resin composition refers to an 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 the action of heat or a polymerization initiator (D). Examples of the single system include compounds having an ethylenically unsaturated bond, and (methyl) ) The acrylic compound (B1) is more preferred, and a compound selected from at least one group selected from the group consisting of acrylfluorenyl and methacrylfluorenyl is more preferred.

Examples of the (meth) acrylic compound having one (meth) acrylfluorenyl group include alkyl (meth) acrylate, phenoxy polyethylene glycol ester of (meth) acrylic acid, and (meth) acrylic acid Alkoxylated polyethylene glycol esters, isoamyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (formyl) Group) 2-hydroxy-3-phenoxypropyl acrylate, tetrahydrofuran methyl (meth) acrylate, and the like.

Examples of the (meth) acrylic compound having two (meth) acrylfluorenyl groups include di (meth) acrylic acid-1,3-butanediol, (meth) acrylic acid-1,3-butane Glycol ester, 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, di (meth) acrylic acid Pentylene glycol ester, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, bisphenol A bis (propyleneoxyethyl) 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 the (meth) acrylic compound having three or more (meth) acrylfluorenyl groups include trimethylolpropane tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, Tris (2-hydroxyethyl) isotricyanate tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri ( (Meth) acrylic acid esters, neopentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, tetra (meth) acrylic acid Tripentaerythritol ester, tripentaerythritol penta (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, octa (methyl) Trispentaerythritol acrylate, pentapentaerythritol tri (meth) acrylate and anhydride, reactant of dipentaerythritol penta (meth) acrylate and anhydride, hepta (methyl) Reactant of trinepentaerythyl acrylate and anhydride, caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone modified neopentaerythritol tri (meth) acrylate, caprolactone Ester Modified Tris (2-hydroxyl Base) isotricyanate tri (meth) acrylate, caprolactone modified neopentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate , Caprolactone modified dipentaerythritol hexa (meth) acrylate, caprolactone modified tripentaerythritol tetra (meth) acrylate, caprolactone modified tripentaerythritol penta (methyl) Base) acrylate, caprolactone modified trinepentaerythritol hexa (meth) acrylate, caprolactone modified trinepentaerythritol hexa (meth) acrylate, caprolactone modified trinepentaerythritol Alcohol octa (meth) acrylate, caprolactone modified neopentaerythritol tri (meth) acrylate and acid anhydride, caprolactone modified dipentaerythritol penta (meth) acrylate and acid anhydride Reactants of caprolactone, and reactants of tripentaerythritol hepta (meth) acrylate and acid anhydride.

As for the (meth) acrylic compound (B1), a (meth) acrylic compound having three or more (meth) acrylfluorenyl groups is preferred, and dipivalatetraol hexa (meth) acrylate is more preferred. .

When the resin composition of the present invention contains a (meth) acrylic compound (B1), the content thereof is preferably 100 to 100 parts by mass, and more preferably 25 to 70 parts by mass relative to the content of the resin (A). . When the content of the (meth) acrylic compound (B1) is within the above 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) includes a compound represented by the formula (1) (hereinafter, this compound may be referred to as "compound (B2)").

[In formula (1), R ¹ to R ³ independently of each other represent a base represented by formula (a) or a base represented by formula (b), and at least one of R ¹ to R ³ is represented by formula (b) The base. ]

[In formulae (a) and (b), R ⁴ and R ⁵ independently of each other represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ]

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

R ^{4 is} preferably a hydrogen atom or a methyl group, and 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 is preferably a base represented by formula (a).

Examples of the compound (B2) include compounds represented by the formula (1-1) to the formula (1-6). Compounds represented by formulae (1-1) to (1-4) are preferred.

When the resin composition of the present invention contains the compound (B2), the content thereof is preferably 5 to 60 parts by mass, and more preferably 10 to 50 parts by mass based on 100 parts by mass of the content 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 ethylene oxide group (however, it is different from the resin (A).). In the aspect of the epoxy resin (C), at least one kind of compound selected from the group consisting of a propylene oxide epoxy resin and a propylene oxide epoxy resin can be mentioned.

Glycidyl ether epoxy resin is an epoxy resin with a glycidyl ether structure. It can be synthesized by reacting phenols and polyols with epichlorohydrin. As for the epoxy propylene ether type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, phenol-phenol novolac type epoxy resin, ortho-cresol -Novolac epoxy resin, trihydroxyphenylmethane epoxy resin.

The propylene oxide epoxy resin is an epoxy resin having a propylene oxide structure, and can be synthesized by reacting a carbonyl group of a phthalic acid derivative and a fatty acid with epichlorohydrin. The propylene oxide epoxy resin includes propylene oxide epoxy resins derived from aromatic carboxylic acids such as p-hydroxybenzoic acid, m-hydroxybenzoic acid, and terephthalic acid.

Epoxy resin (C) is bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, o-cresol novolac epoxy resin, polyphenol epoxy resin, etc. A propylene oxide epoxy resin is preferred. Among them, bisphenol A type epoxy resin is particularly preferable.

The above epoxy propylene ether type epoxy resin can be synthesized by using a conventional conventional method, and the corresponding phenol compound and epichlorohydrin are condensed in the presence of a strong base. This reaction is performed by those with ordinary knowledge in the art using conventional methods.

As the glycidyl ether type epoxy resin, a commercially available product may be used. As for the commercially available products of bisphenol A epoxy resin, examples include: jER 157S70, Epikote 1001, Epikote 1002, Epikote 1003, Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, Epikote 828 (Mitsubishi Chemical Corporation) )Wait. Commercial products of bisphenol F-type epoxy resins include Epikote 807 (manufactured by Mitsubishi Chemical Corporation), YDF-170 (manufactured by Totsu Kasei Co., Ltd.), and the like. As for the commercially available products of the phenol-phenol novolac-type epoxy resin, examples include: Epikote 152, Epikote 154 (manufactured by Mitsubishi Chemical Corporation), EPPN-201, PPN-202 (manufactured by Nippon Kayaku Co., Ltd.), DEN -438 (manufactured by Dow Chemical Japan) As for the commercially available products of o-cresol-phenol novolac epoxy resin, examples include: EOCN-125S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (Japanese Chemicals (Stock ) Manufacturing) and so on. Examples of commercially available products of the polyphenol epoxy resin include Epikote 1032H60 and Epikote YX-4000 (manufactured by Mitsubishi Chemical Corporation).

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

The acid value of the epoxy resin (C) is generally less than 30 mg-KOH / g, and preferably 10 mg-KOH / g or less. 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 even more preferably from 500 to 4,800.

When the resin composition of the present invention contains epoxy resin (C), its content is preferably 1 to 60 parts by mass relative to 100 parts by mass of the total content of the resin (A) and the reactive monomer (B). It is more preferably 50 parts by mass. When the content of the epoxy resin (C) is within the foregoing range, the adhesiveness between the obtained cured film and the substrate tends to be excellent.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating active radicals, acids, and the like by the action of light and heat to start the polymerization of the reactive monomer (B), and it can be used as it is. Polymerization initiator. The polymerization initiator (D) is a polymerization agent containing at least one selected from the group consisting of an O-fluorenyl oxime compound, an alkylacetophenone compound, a triazine compound, a fluorenyl oxide compound, and a biimidazole compound. The initiator is preferred, and a polymerization initiator containing an O-fluorenyl oxime compound is more preferred.

Such a polymerization initiator tends to have high sensitivity and transmittance in the visible light region.

The O-fluorenyl oxime compound is a compound having a structure represented by formula (d1). In the following, * indicates a bond.

Examples of the O-fluorenyl oxime compound include: N-benzylideneoxy-1- (4-phenylmercaptophenyl) butane-1-one-2-imine, and N-benzylideneoxy 1- (4-phenylmercaptophenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylmercaptophenyl) -3-cyclopentyl Propane-1-one-2-imine, N-ethoxyl-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] ethyl Alkane-1-imine, N-ethoxyl-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxolane Methylmethyloxy) benzamidine} -9H-carbazol-3-yl] ethane-1-imine, N-ethoxymethyl-1- [9-ethyl-6- (2-methyl Benzamyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzyloxy-1- [9-ethyl-6- (2 -Methylbenzyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2-imine. Commercially available products such as Irgacure (registered trademark) OXE 01, OXE 02 (above, manufactured by BASF Japan (stock)), N-1919 (made by ADEKA (stock)) 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.

Examples of compounds having a structure represented by the formula (d2) include 2-methyl-2-N-morpholinyl-1- (4-methylmercaptophenyl) propane-1-one and 2-di Methylamino-1- (4-N-morpholinylphenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylbenzene Yl) methyl] -1- [4- (4-N-morpholinyl) phenyl] butane-1-one. Commercial products such as Irgacure (registered trademark) 369, 907, and 379 (above, manufactured by BASF) can also be used. At the same time, a polymerization initiator having a base capable of causing chain transfer, which is described in Japanese Patent Publication No. 2002-544205, can also be used. Examples of compounds having a structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1- Ketone oligomer, α, α-diethoxyacetophenone, benzophenone methyl dimethyl ketal. In terms of sensitivity, the alkylacetophenone compound is preferably a compound having a structure represented by formula (d2).

Examples of triazine compounds include: 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloro) (Methyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperyl-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) vinyl] -1,3,5-triazine .

Examples of the phosphonium oxide phosphine compounds include oxidized -2,4,6-trimethylbenzylidene diphenylphosphine and the like. Commercial products such as Irgacure 819 (manufactured by BASF Japan) can also be used.

As for the biimidazole compound, for example, 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 Laid-Open No. 6-75372, Japanese Patent Application Laid-Open No. 6-75373, etc.), 2,2'-di (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 Publication No. 48-38403, Japanese Patent Publication No. 62-174204 Gazette, etc.), and imidazole compounds in which a phenyl group at the 4,4 ', 5,5'-position is substituted with a alkoxy group (Reference: Japanese Patent Application Laid-Open No. 7-10913, etc.).

As for the polymerization initiator (D), benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether can be listed. Compounds; diphenyl ketones, methyl o-benzylidene benzoate, 4-phenyldiphenyl ketone, sulfurized 4-benzylidene-4'-methyldiphenyl, 3,3 ' Diphenyl ketone compounds such as 4,4'-tetrakis (third butylperoxycarbonyl) diphenyl ketone, 2,4,6-trimethyldiphenyl ketone; 9,10-phenanthrenequinone, 2- Quinone compounds such as ethyl anthraquinone and fluorenone; 10-butyl-2-chloroacridone, benzophenone, methyl phenylglyoxylate, titanocene compounds, and the like. These are preferably used in combination with a polymerization initiation aid (D1) (in particular, an amine compound) described later.

As the polymerization initiator (D), an acid generator may be used. Examples of the acid generator include p-toluenesulfonic acid-4-hydroxyphenyldimethylfluorene, hexafluoroantimonic acid-4-hydroxyphenyldimethylfluorene, and p-toluenesulfonic acid-4-ethylfluorenyloxybenzene. Dimethylpyrene, hexafluoroantimonate-4-ethoxyphenylphenyl, methyl, benzylpyrene, triphenylpyrene p-toluenesulfonate, triphenylpyrene hexafluoroantimonate, p-toluenesulfonic acid Onium salts such as diphenylphosphonium, diphenylphosphonium hexafluoroantimonate, nitrobenzyl tosylate, and benzoin tosylate.

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

<Polymerization starter (D1)>

The polymerization initiator (D1) can be used together with the polymerization initiator (D), and is used to promote a polymerizable compound (e.g., (meth) acrylic acid) to start polymerization with the polymerization initiator (D). Compound (B)) is a polymerized compound, or a sensitizer.

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

Examples of the thiazoline compound include compounds represented by formulae (III-1) to (III-3), compounds described in Japanese Patent Application Laid-Open No. 2008-65319, and the like.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamine. Isoamylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethyl-p-toluidine, 4,4'-bis (dimethylamino) diphenyl ketone (common name: Michler's ketone), 4,4'-bis (diethylamino) diphenyl ketone, 4, 4'-bis (ethylmethylamino) diphenyl ketone and the like, among them, 4,4'-bis (diethylamino) diphenyl ketone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

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

Examples of the thiathrone compounds include 2-isopropylthiaxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorosulfan Heteranthrone, 1-chloro-4-propoxythioanthrone, etc.

Examples of the carboxylic acid compound include phenylmercaptoacetic acid, methylphenylmercaptoacetic acid, ethylphenylmercaptoacetic acid, methylethylphenylmercaptoacetic acid, dimethylphenylmercaptoacetic acid, and methoxyphenyl. Thioglycolic acid, dimethoxyphenyl mercaptoacetic acid, chlorophenyl mercaptoacetic acid, dichlorophenyl mercaptoacetic acid, N-phenyllysine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthyllysine Acid, naphthyloxyacetic acid, etc.

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

<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 thiol groups is preferable, and a compound having two or more thiol groups which can be bonded to a carbon atom having an aliphatic hydrocarbon structure is more preferable. The thiol compound (T) is preferably used together with the polymerization initiator (D).

Examples of the thiol compound (T) include hexamethylene dithiol, sebacyl mercaptan, 1,4-bis (methylmercapto) benzene, butanediol bis (3-mercaptopropionate), and butanediol Di (3-mercaptoacetate), ethylene glycol bis (3-mercaptoacetate), trimethylolpropane tri (3-mercaptoacetate), butanediol bis (3-mercaptopropionate) , Trimethylolpropane tri (3-mercaptopropionate), trimethylol propane tri (3-mercaptoacetate), neopentyl tetraol (3-mercaptopropionate), neopentyl tetraol (3-mercaptoacetate), trihydroxyethyltris (3-mercaptopropionate), neopentaerythritol tetra (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). Preferably, 15 to 70 parts by mass is more preferable. When the content of the thiol compound (T) is within the above range, there is a tendency that the sensitivity is increased and the developability is improved.

<Antioxidant (F)>

Examples of the antioxidant (F) include phenol-based antioxidants, sulfur-based antioxidants, phosphorus-based antioxidants, and amine-based antioxidants. Among them, a phenol-based antioxidant is preferred from the viewpoint of less coloration of the cured film.

Examples of the phenol-based antioxidant include acrylic acid 2-third butyl-6- (3-third butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl ester, and acrylic acid -2- [1- (2-hydroxy-3,5-di-third-pentylphenyl) ethyl] -4,6-di-third-pentylphenyl ester, 3,9-di [2- { 3- (3-Third-butyl-4-hydroxy-5-methylphenyl) propanyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxa Spiro [5.5] undecane, 2,2'-methylenebis (6-thirdbutyl-4-methylphenol), 4,4'-butylenebis (6-thirdbutyl-3- Methylphenol), 4,4'-thiobis (2-third butyl-5-methylphenol), 2,2'-thiobis (6-third butyl-4-methylphenol) , 1,3,5-tris (3,5-di-third-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -Trione, 3,3 ', 3 ", 5,5', 5" -hexa-third-butyl-a, a ', a "-(trimethylbenzene-2,4,6-triyl) tri- P-cresol, neopentaerythritol tetra [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate], 2,6-di-third-butyl-4-methyl Phenol and 6- [3- (3-third-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenzo [ d, f] [1,3,2] Dioxaphosphacycloheptane. Commercially available phenolic antioxidants can be used. Commercially available Examples of phenolic antioxidants include: SUMILIZER (registered trademark) BHT, GM, GS, GP (above, all manufactured by Sumitomo Chemical Co., Ltd.), IRGANOX (registered trademark) 1010, 1076, 1330, 3114 (above, (All are manufactured by BASF Japan).

For sulfur-based antioxidants, examples include: 3,3'-dithiopropionate dilauryl, 3,3'-dipropionate dimyristyl, and 3,3'-thiodipropionate distearyl Tetrakis (3-laurylthiopropionate) neopentaerythritol ester. As the sulfur-based antioxidant, a commercially available product can be used. Examples of commercially available sulfur-based antioxidants include SUMILIZER (registered trademark) TPL-R and TP-D (all of which are manufactured by Sumitomo Chemical Co., Ltd.).

Examples of the phosphorus-based antioxidant include trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, tris (nonylphenyl) phosphite, and distearyl neopentyl tetraol diphosphite. , Butane diphosphite tetrakis (tridecyl) -1,1,3-tris (2-methyl-5-third butyl-4-hydroxyphenyl ester). As the phosphorus-based antioxidant, a commercially available product can be used. For commercially available phosphorus-based antioxidants, examples include: IRGAFOS (registered trademark) 168, 12, 38 (above, all manufactured by BASF), ADK STAB 329K, ADK STAB PEP36 (above, all ADEKA (shares) ) Manufacturing).

Examples of the amine-based antioxidant 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'-bis (2-naphthyl) -p-phenylenediamine. As the amine-based antioxidant, a commercially available product can be used. Examples of commercially available amine antioxidants include SUMILIZER (registered trademark) BPA, BPA-M1, and 4ML (all of which are manufactured by Sumitomo Chemical Co., Ltd.).

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

<Surfactant (H)>

As for the surfactant (H), polysiloxane-based surfactants (without fluorine atoms), fluorine-based surfactants (without siloxane bonds), and polysiloxanes with fluorine atoms are exemplified. Surfactant.

Examples of the polysiloxane-based surfactant include: a surfactant having a siloxane bond. Specifically, examples include: Toray Silicone DC3PA, the same series of SH7PA, the same series of DC11PA, the same series of SH21PA, the same series of SH28PA, the same series of SH29PA, the same series of SH30PA, polyether modified silicone oil SH8400 (trade name: Dow Corning Toray ( Manufacturing), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (made by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, TSF4460 (Momentive Performance Materials Japan Contract (share) manufacturing) and so on.

Examples of the fluorine-containing surfactant include a surfactant having a fluorocarbon chain. Specifically, examples include: Fluorinert (registered trademark) FC430, same series FC431 (manufactured by Sumitomo 3M), 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 (stock)), EFTOP (registered trademark) EF301, Same series EF303, same series EF351, same series EF352 (manufactured by Mitsubishi Materiale), Surflon (registered trademark) S381, same series S382, same series SC101, same series SC105 (made by Asahi Glass (stock)), E5844 (Manufactured by Daikin Fine Chemical Research Institute).

Examples of the polysiloxane-based surfactant having a fluorine atom include surfactants such as a siloxane bond and a fluorocarbon chain. Specifically, examples include: MEGAFAC (registered trademark) R08, same series BL20, same series F475, same series F477, same series F443 (manufactured by DIC). MEGAFAC (registered trademark) F475 is preferred.

When the resin composition of the present invention contains a surfactant (H), its content rate is generally 0.001% by mass or more and 0.2% by mass or less, and 0.002% by mass or more and 0.1% by mass relative to the total amount of the resin composition of the present invention. The following is preferable, and more preferably 0.01% by mass or more and 0.05% by mass or less. When the content of the surfactant (H) is within the aforementioned range, the flatness of the cured film can be improved.

<Polycarboxylic acid (G)>

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

A polycarboxylic acid is a compound having two or more carboxyl groups, a polycarboxylic acid anhydride, and an anhydride of a polycarboxylic acid. The polycarboxylic acid (G) is different 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 3,000 or less, and more preferably 1,000 or less.

Examples of the polycarboxylic acid anhydride include maleic anhydride, succinic anhydride, glutaric anhydride, citraconic anhydride, itaconic anhydride, 2-dodecylsuccinic anhydride, and 2- (2-oct-3-ene Succinic anhydride, 2- (2,4,6-trimethylnon-3-enyl) succinic anhydride, glyceric anhydride, 1,2,3,4-butanetetracarboxylic dianhydride, etc. Chain polycarboxylic anhydride; 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hexahydrobenzene Formic anhydride, 4-methylhexahydrophthalic anhydride, norbornene dicarboxylic anhydride, methylbicyclo [2.2.1] heptane-2,3-dicarboxylic anhydride, bicyclo [2.2.1] heptane -2,3-dicarboxylic anhydride, bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride, methylbicyclo [2.2.1] hept-5-ene-2,3-di Alicyclic polycarboxylic anhydrides such as carboxylic anhydride, cyclopentanetetracarboxylic dianhydride; phthalic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, pyromellitic anhydride, trimellitic anhydride , Diphenylketone tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, ethylene glycol bis (trimellitic anhydride ester), glycerol tris (trimellitic anhydride) Ester), glycerol bis (trimellitic anhydride) (Ester) monoacetate, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furyl) naphtho [1,2-c ] Aromatic polycarboxylic anhydrides such as furan-1,3-dione. You can also use ADEKA HARDENER-EH-700 (brand name (the same below), made by ADEKA), RIKACID-HH, the same series -TH, the same series -MH, the same series MH-700 (New Japan Physical and Chemical Co., Ltd.) (Manufactured), Epikinia 126, the same series YH-306, and the same series DX-126 (made by Petrochemical Shell Epoxy).

The aforementioned polycarboxylic acids include chains such as oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, and polycarboxylic acids derived from linear polycarboxylic anhydrides. Polycarboxylic acids; cycloaliphatic dicarboxylic acids, alicyclic polycarboxylic acids derived from polycarboxylic acids derived from alicyclic polycarboxylic anhydrides, etc .; isophthalic acid, terephthalic acid, 1,4,5,8- Aromatic polycarboxylic acids such as naphthalenetetracarboxylic acid and polycarboxylic acids derived from aromatic polycarboxylic anhydrides.

Among them, from the viewpoint that the cured film is excellent in heat resistance, particularly in the visible light region, it is not easy to reduce transparency, and chain carboxylic anhydrides and alicyclic polycarboxylic anhydrides are preferred, and alicyclic polycarboxylic anhydrides are more preferred.

When the resin composition of the present invention contains a polycarboxylic acid (G), its content is preferably 100 parts by mass with respect to the total content of the resin (A) and the reactive monomer (B), preferably 1 to 30 parts by mass, and 2 It is more preferably 20 parts by mass, and even more preferably 2 to 15 parts by mass. When the content of the polycarboxylic acid (G) is within the above range, the heat resistance and adhesion of the 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 as conventional epoxy hardeners. Among them, a compound represented by the formula (2) is preferred.

[In the formula (2), R ¹¹ represents an alkyl group having 1 to 20 carbon atoms, a phenyl group, a benzyl group, or a cyanoalkyl group having 2 to 5 carbon atoms.

R ¹² to R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a phenyl group, a nitro group, or a fluorenyl group having 1 to 20 carbon atoms, and the alkyl group and the phenyl group contain The hydrogen atom may be substituted by a hydroxyl group. ]

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

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

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

In the case of fluorenyl groups having 1 to 20 carbon atoms, examples include: methyl fluorenyl, ethyl fluorenyl, propyl fluorenyl, isobutyl fluorenyl, pentyl fluorenyl, isopentyl fluorenyl, trimethylethyl fluorenyl, and lauryl fluorenyl , Myristyl, stearyl.

As for the imidazole compound (J), 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-hydroxymethyl 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 100 parts by mass with respect to the total content of the resin (A) and the reactive monomer (B), preferably 0.1 parts by mass or more and 25 parts by mass or less. 0.2 mass part or more and 15 mass parts or less is more preferable, and 0.5 mass part or more and 5 mass parts or less is more preferable. When the content of the imidazole compound (J) is within the above range, the resulting cured film tends to have excellent transparency in the visible light region.

<Solvent (E)>

The resin composition of the present invention contains a solvent (E). As for the solvent (E), various organic solvents used in the field of resin composition can be listed, and specific examples thereof include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol. Monobutyl ethers such as monobutyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol dipropyl ether, diethylene glycol diethylene glycol Diethylene glycol dialkyl ethers such as butyl ether; ethylene glycol alkyls such as methyl ethyl acetate, ethyl ethyl acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoethyl ether acetate Ether acetates; 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. Acetic acid esters; propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether; propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether, propylene glycol propylene Propylene glycol dialkyl ethers such as methyl ether, propylene glycol ethyl propyl ether; propylene glycol methyl ether propionate, propylene glycol ether propionate Propylene glycol alkyl ether propionates such as propylene glycol propyl ether propionate, propylene glycol butyl ether propionate; butylene glycol such as methoxybutanol, ethoxybutanol, propoxybutanol, butoxybutanol Monoalkyl ethers; Butyl glycol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate, butoxybutyl acetate; methoxybutyl propionate Esters, ethoxybutyl propionate, propoxybutyl propionate, butoxybutyl propionate, etc. butanediol monoalkyl ether propionate; dipropylene glycol dimethyl ether, dipropylene glycol diethyl Dipropylene glycol dialkyl ethers such as methyl ether, dipropylene glycol methyl ethyl ether; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene; methyl ethyl ketone, acetone, methyl pentanone, methyl isopropyl Ketones such as methyl ethyl ketone, cyclohexanone; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerol, etc .; methyl acetate, ethyl acetate, propyl acetate, butyl acetate Esters, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl glycolate, ethyl glycolate, butyl glycolate Lactate Ester, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy- Methyl 3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxylate Propyl ethoxyacetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, Ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate , Butyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate , Methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate Ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, Propyl 3-propoxypropionate, butyl 3-propoxypropionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, Esters such as butyl 3-butoxypropionate; cyclic ethers such as tetrahydrofuran and pyran; cyclic esters such as γ-butyrolactone.

Among the above-mentioned solvents, from the viewpoints of coating properties and drying properties, the aforementioned solvents are preferably organic solvents having a boiling point of 100 to 200 ° C. Organic solvents having a boiling point of 100 to 200 ° C. Specific examples include: alkanediol alkyl ether acetates, alcohols such as methoxybutanol and ethoxybutanol, ketones such as cyclohexanone, 3- Esters of ethyl ethoxypropionate and methyl 3-methoxypropionate are propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutanol, Methoxybutyl acetate, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate are preferred. Each of these solvents (E) can be used alone or as a mixture 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, and more preferably 70 to 95% by mass with respect 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, and 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 radical generators, ultraviolet absorbers, chain transfer agents, adhesion promoters, and the like, as needed, additives known in the technical field. .

Examples of the filler include glass, silica, and alumina. Other polymer compounds include thermosetting resins such as cis-butene diimide resin, polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, and polyester. , Polyamine fingers and other thermoplastic resins. The thermal radical generator includes, for example, 2,2'-azobis (2-methylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), and the like. Examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzotriazole and alkoxydiphenyl ketone. Examples of the chain transfer agent include dodecanethiol and 2,4-diphenyl-4-methyl-1-pentene.

Examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2methoxyethoxy) silane, and 3-glycidoxypropyltrimethoxysilane. Silane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethyl Oxysilane, 2- (3,4-ethoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methyl Allyl propyl methoxypropyltrimethoxysilane, 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-aminopropyltriethyl Silane-yl and the like.

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

<Manufacturing method of resin composition>

In the resin composition of the present invention, the resin (A), the solvent (E), and the (meth) acrylic compound (B), the epoxy resin (C), and the polymerization initiator (D) can be used if necessary. ), A polymerization initiation aid (D1), an antioxidant (F), a surfactant (H), a polycarboxylic acid (G), an imidazole compound (J), and other components, and mixed and produced by a conventional method. 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 then curing it by heating. More specifically, the method for producing a cured film of the present invention includes the following steps (1) to (3).

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

Step (2): a step of drying the coated resin composition under reduced pressure to form a composition layer

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

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

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

Step (2): a step of drying the coated resin composition under reduced pressure to form a composition layer

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

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

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

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

Step (2) is a step of drying the coated 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 performed at a pressure of 50 to 150 Pa and a temperature range of 20 to 25 ° C. Heating drying (pre-baking) may be performed before or after reduced-pressure drying. Heating drying is generally performed using a heating device such as a heating box or a hot plate. The heating and drying temperature is preferably 30 to 120 ° C, and more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

Step (3) is a step of heating the composition layer (post-baking). The composition layer is hardened by heating to form a cured film. Heating is generally performed using a heating device such as a heating box or a hot plate. The heating temperature is preferably 130 to 270 ° C, more preferably 150 to 260 ° C, and even more preferably 200 to 250 ° C. When the heating temperature is 200 to 250 ° C, unnecessary solvents in the cured film can be prevented. The heating time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes.

Step (2a) is a step of exposing the composition layer formed in step (2) through a photomask. This photomask is used to form a light-shielding portion corresponding to a portion where the composition layer is to be removed. The shape of the light-shielding portion is not particularly limited and may be selected depending on the intended use. The light source used for the exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, for light less than 350nm, you can use a filter that filters out the wavelength range, and light near 436nm, 408nm, and 365nm. You can also selectively use bandpass filtering that filters out these wavelength ranges. Light device. Examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp. In order to make the entire exposure surface uniformly irradiate parallel light and align the photomask and the composition layer at the correct position, it is preferable to use a photomask alignment exposure machine, a stepper, and other exposure devices.

Step (2b) is a step of developing the composition layer after exposure. After the exposed composition layer is developed by contact with the developing solution, the unexposed portion of the composition layer can be dissolved in the developing solution and removed to form a composition layer having a pattern on the substrate. As for the developing solution, an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide is preferable. The concentration in the alkaline compound aqueous solution is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. Meanwhile, the developing liquid system may contain a surfactant. The development method may be any of a paddle method, a dipping method, and a spray method. In addition, the substrate can be tilted at any angle during development. After development, washing with water is preferred.

Step (3a) is a step of heating the developed composition layer. By performing the same heating as in the step (3), the composition layer having a pattern can be hardened, and a cured film having a pattern can be formed on the substrate.

Since the cured film obtained in this way has excellent surface flatness, it can be used as a protective film and an overcoat for a liquid crystal display device, a color filter substrate used in an organic EL display device, and an electronic paper display, and a touch panel. .

With the resin composition of the present invention, a display device having a high-quality cured film can be manufactured. Even if the color filter substrate has unevenness on the surface of the coloring pattern, the resin composition of the present invention can form an overcoat layer, thereby improving the flatness of the surface.

    [Example]    

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

(Synthesis Example 1: Resin (A1))

In a flask equipped with a circulating condenser, a dropping funnel, and a stirrer, nitrogen was introduced into the flask at 0.02 L / min to form a nitrogen atmosphere. 140 parts of propylene glycol monomethyl ether acetate was added, and heated to 70 ° C while stirring. Next, 25 parts of methacrylic acid; a mixture of a monomer of formula (I-1) and a monomer of formula (II-1) {the mole of the monomer of formula (I-1) and the monomer of formula (II-1) 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 the solution was dripped in using a drip pump over 4 hours. In a flask maintained at 70 ° C.

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

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

Installation: K2479 (manufactured by Shimadzu Corporation)

Column: SHIMADZU Shim-pack GPC-80M

Column temperature: 40 ℃

Solvent: Tetrahydrofuran (THF)

Flow rate: 1.0mL / min

Detector: RI

Calibration Standards: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

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

(Synthesis Example 2: Resin (A2))

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

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

(Synthesis Example 3: Resin (A3))

In a flask equipped with a circulating condenser, a dropping funnel, and a stirrer, nitrogen was introduced into the flask at 0.02 L / min to form a nitrogen atmosphere. 140 parts of propylene glycol monomethyl ether acetate was added, and heated to 70 ° C while stirring. Next, 25 parts of methacrylic acid; a mixture of a monomer of formula (I-1) and a monomer of formula (II-1) {the mole of the monomer of formula (I-1) and the monomer of formula (II-1) Ratio = 50: 50} 145 parts; and 75 parts of methyl methacrylate, dissolved in 190 parts of propylene glycol monomethyl ether acetate, and prepared into a solution, and the solution was dropped into 70 with a drip pump for 4 hours. The flask was kept at ℃.

On the other hand, a solution of 30 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 240 parts of propylene glycol monomethyl ether acetate was used, and another drop was used. The liquid pump was dropped into the flask over 5 hours. After the completion of dropping of the polymerization initiator solution, the solution was kept at 70 ° C. for 4 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin (A3)) having a solid content of 30%. The weight average molecular weight (Mw) of the obtained resin A1 was 9,200, the degree of dispersion (Mw / Mn) was 1.9, and the acid value in terms of solid content was 61 mg-KOH / g. The resin (A3) has the following constituent units.

(Synthesis example: Resin (A4))

In a flask equipped with a circulating condenser, a dropping funnel, and a stirrer, nitrogen was introduced into the flask at 0.02 L / min to form a nitrogen atmosphere. 140 parts of propylene glycol monomethyl ether acetate was added, and heated to 70 ° C while stirring. Next, 40 parts of methacrylic acid; and a mixture of a monomer of formula (I-1) and a monomer of formula (II-1) {molecular formula (I-1) monomer and 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 maintained at 70 ° C. for 4 hours using a dropping pump.

On the other hand, a solution of 30 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 240 parts of propylene glycol monomethyl ether acetate was used, and another drop was used. The liquid pump was dropped into the flask over 5 hours. After the completion of the dropping of the polymerization initiator solution, the solution was kept at 70 ° C. for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin (A4)) having a solid content of 42.3%. The weight average molecular weight (Mw) of the obtained resin Aa was 8000, the degree of dispersion (Mw / Mn) was 1.91, and the acid value in terms of solid content was 60 mg-KOH / g. The resin (A4) has the following constituent units.

    [Examples 1, 2 and Comparative Examples 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) was mixed with propylene glycol monomethyl ether acetate in the solvent (E), and then the amount of the surfactant (H) MEGAFAC (registered trademark) F554 (manufactured by DIC Corporation) was added at 0.1 parts by mass to 100 parts by mass of the resin (A) to obtain a resin composition.

<Making of Evaluation Board>

A 2-inch square glass substrate (EAGLE XG; manufactured by Corning) was sequentially washed with a neutral detergent, water, and isopropyl alcohol, and then dried. Spin coating was performed on the substrate so that a colored photosensitive resin composition having the following composition was used, and the film thickness after baking was 2.0 μm.

Next, a colored composition layer was formed by pre-baking at 100 ° C for 3 minutes in a dust-free heating box. After cooling, the distance between the colored composition layer on the substrate and the mask made of quartz glass was made 100 μm, and an exposure machine (TME-150RSK; manufactured by TOPCON, light source: ultra-high-pressure mercury lamp) was used. Under atmospheric conditions, Light was irradiated at an exposure amount (based on 365 nm) of 100 mJ / cm ² . The irradiation of the light is performed by an optical filter (UV31; manufactured by Asahi Glass Co., Ltd.) using light emitted from an ultra-high pressure mercury lamp. For the photomask, a photomask having a line / space pattern with a line width of 30 μm was used.

Then, the coloring composition layer after irradiation with light is immersed in a water-based imaging solution containing 0.12% of a non-ionic surfactant and 0.04% of potassium hydroxide for 60 seconds at 23 ° C. for development. After washing with water, it is heated in a heating cabinet. After that, post-baking was performed at 230 ° C. for 30 minutes, and a substrate for evaluation was formed to form a colored pattern with a line width / space of 30 μm.

(Composition of colored photosensitive resin composition)

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

The film thickness of the colored pattern formed was measured using a contact-type film thickness measuring device (DEKTAK 6M; manufactured by ULVAC, Inc.) under conditions of a measurement width of 500 μm and a measurement speed of 10 seconds to obtain a cross-section of the cross-sectional shape of the colored pattern ( (I.e., outline drawing). Then, the average value of the film thickness of the colored pattern was calculated from the cross section. The average film thickness was 2.0 μm.

<Production of Hardened Film and Evaluation of Flatness>

The substrates for evaluation described above were spin-coated under conditions such that the film thickness (film thickness from the surface of the colored pattern) after baking was 1.0 m, and the resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2 were applied. Then, the vacuum pump was used to reduce the pressure of the rotary pump to 1,000 rpm, the pressure of the booster pump to 700 rpm, and reduced pressure to 66 Pa at room temperature at 25 ° C, and then heated under reduced pressure, and then heated. The plate was prebaked at a temperature of 100 ° C for 3 minutes. After being left to cool, a temperature of 230 ° C. was followed by baking for 30 minutes to form a cured film.

The film thickness of the cured film on the substrate for evaluation is measured using a contact film thickness measuring device (DEKTAK 6M; manufactured by ULVAC), under conditions of a measurement width of 500 μm and a measurement speed of 10 seconds to obtain a cross-sectional shape of the cured film. section. Then, the average value of the film thickness of the cured film was calculated from the cross section, and the average value of the film thickness from the surface of the colored 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 FIGS. 1 to 4 are summarized as the cross-sectional shape of the substrate for evaluation. Each of FIGS. 1 to 4 shows a cross section of each cross section shape.

The horizontal axis indicates the position in the plane direction, and the vertical axis indicates 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 cross-sectional shape of the obtained cured film, the average height difference of the uneven 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 having a high surface flatness can be provided. Since the cured film obtained from this curable resin composition is excellent in flatness, it is suitable for use in a display device and the like.

Claims (6)

    A resin composition comprising a resin (A) and a solvent, and the resin (A) comprises: a structural unit (Aa) derived from an alkyl (meth) acrylate having an alkyl group having 2 or more carbon atoms; Structural unit (Ab) of an unsaturated compound having a cyclic ether structure of 2 to 4 and structural unit (Ac) derived from at least one compound selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride And, with respect to the total amount of the structural units constituting the resin (A), the ratio of the structural units (Aa) is higher than 10 mol%, and the resin (A) is a copolymer having a weight average molecular weight of 5000 to 20,000.         The resin composition according to item 1 of the scope of patent application, wherein the resin (A) is a resin composed of a constituent unit (Aa), a constituent unit (Ab), and a constituent unit (Ac).         The resin composition according to item 1 of the scope of patent application, wherein the ratio of the constituent unit (Aa) is higher than 10 mol% and less than 35 mol% with respect to the total amount of the structural units constituting the resin (A). .         The resin composition according to item 1 of the scope of patent application, wherein the constituent unit (Aa) is a constituent unit derived from an alkyl (meth) acrylate having a linear alkyl group having 2 to 10 carbon atoms.         The resin composition according to item 1 of the scope of patent application, wherein the constituent unit (Aa) is a constituent unit derived from an alkyl (meth) acrylate having a linear alkyl group having 2 to 6 carbon atoms.         A hardened film formed from a resin composition as described in the first or second scope of the patent application.