TW201837068A - Resin composition and cured film - Google Patents

Abstract

A resin composition comprises a resin, a polymerizable compound, and a polymerization initiator, wherein the polymerizable compound comprises a polymerizable compound having a fluorene skeleton, and the content of the polymerizable compound having a fluorene skeleton is more than 10% by mass based on the total amount of the polymerizable compound.

Description

   Resin composition and cured film   

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

In recent years, a liquid crystal display device is a resin composition that can be used to form a pattern by development in a color filter or the like. Such a resin composition is described in JP2011-165396 specifically as a photosensitive composition including a polymerizable compound as a polymerizable compound of 9.4% by mass of a compound represented by the following formula.

The present invention includes the following inventions.

[1] A resin composition containing a resin, a polymerizable compound, and a polymerization initiator, wherein the polymerizable compound includes a polymerizable compound having a fluorene skeleton, and a content ratio of the polymerizable compound having a fluorene skeleton relative to the polymerizability The total amount of the compound exceeds 10% by mass.

[2] The resin composition according to [1], wherein the polymerizable compound having a fluorene skeleton is a compound represented by formula (VI).

[In formula (VI), L ¹ independently of each other represents a single bond or an alkanediyl group having 1 to 16 carbon atoms which may have a substituent, and the methylene group contained in the alkanediyl group may be substituted with an oxygen atom. However, the methylene group bonded with an oxygen atom is not substituted with an oxygen atom. R ¹¹ independently of each other represents a hydrogen atom or a methyl group. ]

[3] The resin composition according to [1] or [2], wherein the resin includes a structural unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms, and the structural unit (Aa) is composed of an unsaturated group. Alicyclic hydrocarbons are derived from epoxidized structural monomers.

[4] The resin composition according to any one of [1] to [3], wherein the resin includes a resin having a constituent unit of a carbazole ring.

[5] A cured film formed from the resin composition according to any one of [1] to [4].

In the present specification, the compounds exemplified for each component may be used alone or in combination of plural kinds unless otherwise specified.

[Resin composition]

The resin composition of the present invention includes a resin (hereinafter referred to as resin (A)), a polymerizable compound (hereinafter referred to as polymerizable compound (C)), and a polymerization initiator (hereinafter referred to as polymerization initiator (D)). . The polymerizable compound (C) includes a polymerizable compound having a fluorene skeleton.

The resin composition may further contain a solvent (hereinafter referred to as a solvent (E)). In addition, the resin composition of the present invention may contain other components such as a leveling agent (hereinafter referred to as a leveling agent (B)), an antioxidant (hereinafter referred to as an antioxidant (F)), and a hardener (hereinafter referred to as a hardening agent). (G)) and so on. Examples of the curing agent (G) include polycarboxylic acids (hereinafter referred to as polycarboxylic acids (G1)), imidazole compounds (hereinafter referred to as imidazole compounds (G2)), and the like.

<Polymerizable compound>

The polymerizable compound (C) is a monomer that reacts by the action of heat or a polymerization initiator (D), and includes a polymerizable compound having a fluorene skeleton (hereinafter referred to as a polymerizable compound (C1)). The content rate of the polymerizable compound (C1) is more than 10% by mass relative to the total amount of the polymerizable compound (C), preferably 12% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more. Still more preferably, it is 40% by mass or more. The polymerizable compound (C1) is usually 100% by mass or less based on the total amount of the polymerizable compound (C). By including the polymerizable compound (C1) in such a content ratio, the developability of the resin composition can be improved. By including the polymerizable compound (C1) in such a content ratio, the refractive index of the obtained film can be increased.

The polymerizable compound (C) may contain a polymerizable compound other than the polymerizable compound (C1). Examples of the other polymerizable compound include compounds having an ethylenically unsaturated bond, preferably a (meth) acrylic compound, and more preferably, a group selected from the group consisting of an acrylyl group and a methacrylmethyl group. A compound of at least one kind. In the present specification, "(meth) acrylic acid" means at least one compound selected from the group consisting of acrylic acid and methacrylic acid. The symbols "(meth) acrylfluorenyl" and "(meth) acrylate" have the same meaning.

[1] Polymerizable compound (C1)

The polymerizable compound (C1) is a compound having a fluorene skeleton, and is preferably a compound represented by formula (VI).

[In the formula (VI), L ¹ independently of each other represents a single bond or an alkanediyl group having 1 to 16 carbon atoms which may have a substituent, and the methylene group contained in the alkanediyl group may be substituted with an oxygen atom. However, the methylene group bonded to the oxygen atom is not substituted with an oxygen atom. R ¹¹ independently of each other represents a hydrogen atom or a methyl group. ]

Examples of the compound represented by formula (VI) include compounds represented by formula (VI-1) to formula (VI-3).

[In formula (VI-3), R ^12a and R ^12b independently represent a hydrogen atom or a methyl group, and m and n are integers of 0 or more. However, when m and n are 0, at least one of R ^12a and R ^12b is a methyl group. ]

The compound represented by formula (VI) is more preferably a compound represented by formula (VIa).

[In the formula (VIa), L ^2a and L ^2b each independently represent an alkyldiyl group having 1 to 6 carbon atoms which may be substituted. m and n independently represent integers from 0 to 8. But m + n is 0 to 16. When m and n are respectively 2 or more, the plural L ^2a and L ^2b may be the same or different. However, in m L ^2a and n L ^2b , the total carbon number is 0 to 30. R ^13a and R ^2b each independently represent a hydrogen atom or a methyl group. ]

[2] (meth) acrylic compounds

Examples of the (meth) acrylic compound having one (meth) acrylfluorenyl group include alkyl (meth) acrylate, phenoxylated polyethylene glycol (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, tetrahydrofurfuryl (meth) acrylate, and the like.

Examples of the (meth) acrylic compound having two (meth) acrylfluorenyl groups include 1,3-butanediol di (meth) acrylate, 1,3-butanediol (meth) acrylate, 1 , 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, three Ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol diacrylate, bis (acryloxyethyl) ether of bisphenol A, ethylene oxide Modified bisphenol A di (meth) acrylate, propylene oxide modified neopentyl glycol di (meth) acrylate, ethylene oxide modified 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, and tris (2- (Hydroxyethyl) isotricyanate tri (meth) acrylate, ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (methyl) Base) acrylate, neopentaerythritol tetra (meth) acrylate, dinepentaerythritol penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, trinepentaerythritol tetra ( (Meth) acrylic acid esters, trinepentaerythritol penta (meth) acrylate, trinepentaerythritol hexa (meth) acrylate, trinepentaerythritol hepta (meth) acrylate, trinepentaerythritol Octa (meth) acrylate, reactant of neopentaerythritol tri (meth) acrylate and anhydride, reactant of dipentaerythritol penta (meth) acrylate and anhydride, trinepentaerythritol seven ( Reactant of meth) acrylate and anhydride, caprolactone modified trimethylolpropane tri (meth) acrylate, caprolactone modified neopentaerythritol tri (meth) acrylate, caprolactone modified Tris (2-hydroxyethyl) iso Tricyanate tri (meth) acrylate, caprolactone modified neopentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol penta (meth) acrylate, caprolactone Ester modification dinepentaerythritol hexa (meth) acrylate, caprolactone modification trinepentaerythritol tetra (meth) acrylate, caprolactone modification trinepentaerythritol penta (meth) acrylic acid Ester, caprolactone modified trinepentaerythritol hexa (meth) acrylate, caprolactone modified trinepentaerythritol hexa (meth) acrylate, caprolactone modified trinepentaerythritol eight Methacrylate, Caprolactone Modified Reactant of Neopentaerythritol Tri (meth) acrylate and Anhydride, Caprolactone Modified Reactant of Dipentaerythritol Penta (meth) acrylate and Acid Anhydride 2. Caprolactone reformates the reaction product of tripentaerythritol hepta (meth) acrylate and anhydride.

The (meth) acrylic compound is preferably a (meth) acrylic compound having three or more (meth) acrylfluorenyl groups, and more preferably dineopentaerythritol hexa (meth) acrylate.

The content of the polymerizable compound (C) is preferably 20 to 200 parts by mass, and more preferably 30 to 150 parts by mass based on 100 parts by mass of the resin (A). When the content of the polymerizable compound (C) is within the aforementioned range, the obtained film can have good chemical resistance and mechanical strength.

<Resin (A)>

The resin (A) is not limited as long as it is a curable resin, but the resin (A) is preferably an alkali-soluble resin. The resin (A) is preferably a copolymer containing a constituent unit (hereinafter referred to as a constituent unit (Aa)) having a cyclic ether structure having a carbon number of 2 to 4, and derived from an unsaturated carboxylic acid and At least one constituent unit (hereinafter referred to as a constituent unit (Ac)) selected from the group consisting of unsaturated carboxylic anhydrides. The resin (A) preferably contains a constituent unit containing a condensed ring (hereinafter referred to as a constituent unit (Ab)). The resin (A) may have a constituent unit (hereinafter referred to as a constituent unit (Ad)) other than the constituent units (Aa), (Ab), and (Ac). The resin (A) may contain two or more kinds of constituent units (Aa) and constituent units (Ab), respectively.

[1] Component (Aa)

The structural unit (Aa) may be composed of an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an ethylene oxide ring, an oxetane ring, and a tetrahydrofuran ring). derivative. The constituent unit derived from an unsaturated compound having a cyclic ether structure having 2 to 4 carbon atoms can be obtained by using the unsaturated compound as a monomer and obtaining a copolymer. Alternatively, it can be obtained by reacting a compound having a cyclic ether structure having 2 to 4 carbon atoms in another constitutional unit (hereinafter referred to as constitutional unit (Aa ')).

Examples of the unsaturated compound derived from the structural unit (Aa) include a monomer having an oxirane group and an ethylenically unsaturated bond (hereinafter referred to as a monomer (Aa1)), an oxetanyl group, and an ethylenically unsaturated group. Bonded monomers (hereinafter referred to as monomers (Aa2)), monomers having a tetrahydrofuran group and ethylenically unsaturated bonds (hereinafter referred to as monomers (Aa3)).

The monomer (Aa1) includes, for example, a monomer having a structure in which an unsaturated aliphatic hydrocarbon having a linear or branched chain undergoes epoxidation (hereinafter referred to as a monomer (Aa1-1)) and an unsaturated alicyclic compound. Monomer of epoxidized hydrocarbon structure (hereinafter referred to as monomer (Aa1-2)). The monomer derived from the structural unit (Aa) is preferably a monomer (Aa1) because the reliability of the obtained film, such as heat resistance and chemical resistance, can be improved. From the viewpoint of excellent storage stability of the resin composition, the monomer (Aa1-2) is more preferred.

Examples of the monomer (Aa1-1) include glycidyl (meth) acrylate, beta-methylglycidyl (meth) acrylate, beta-ethylglycidyl (meth) acrylate, and epoxy Propyl vinyl ether, o-vinyl benzyl epoxy propyl ether, m-vinyl benzyl epoxy propyl ether, p-vinyl benzyl epoxy propyl ether, α-methyl-o-vinyl benzyl ring Oxypropyl ether, α-methyl-m-vinyl benzyl epoxy propyl ether, α-methyl-p-vinyl benzyl epoxy propyl ether, 2,3-bis (glycidyloxymethyl) Styrene), 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyl oxide) Methoxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2 , 3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (propylene oxide Oxymethyl) styrene and the like.

Examples of the monomer (Aa1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, celloxide 2000; manufactured by Daicel Corporation), and (methyl) 3,4-epoxycyclohexyl methyl acrylate (for example, cyclomer A400; manufactured by Daicel Co., Ltd.), 3,4-epoxy cyclohexyl methyl (meth) acrylate (for example, cyclomer M100; manufactured by Daicel Co., 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 hydroxy-substituted alkyl group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, and 1-hydroxy-1. -Methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

R ^b1 and R ^b2 include preferably 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.

Examples of the alkylenediyl group include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and pentane-1,5-diyl. Radical, hexane-1,6-diyl and the like.

X ^b1 and X ^b2 include preferably a single bond, methylene, ethylene, * -CH ₂ -O-, * -CH ₂ CH ₂ -O-, and more preferably a single bond, * -CH ₂ CH ₂ -O-. * 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). Preferred examples include the formula (I-1) and (I-3). , Compounds of formula (I-5), formula (I-7), formula (I-9), and formula (I-11) to formula (I-15), more preferably, formula (I-1) Compounds represented by Formula (I-7), Formula (I-9) and Formula (I-15).

Examples of the compound represented by formula (II) include compounds represented by any one of formula (II-1) to formula (II-15), and preferred examples include formula (II-1) and formula (II-3) , Compounds of formula (II-5), formula (II-7), formula (II-9), and formula (II-11) to formula (II-15), more preferably, formula (II-1) Compounds of Formula (II-7), Formula (II-9) and Formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of two or more kinds. When these are used in combination, the content ratio of these [compounds represented by formula (I): compounds represented by formula (II)] is preferably 5:95 to 95: 5, more preferably 20:80 to 80 on a Mohr basis. : 20. For example, a mixture containing a compound represented by the formula (I-1) and a compound represented by the formula (II-1) at 50:50 (commercially available product has a trade name "E-DCPA" (manufactured by Daicel Corporation)) can be used.

The monomer (Aa2) is more preferably a monomer having an oxetanyl group and a (meth) acryloxy group. Examples of the monomer (Aa2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, and 3- Ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-propenemethyloxetane, 3-methyl-3-methacryloxy Ethylethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methacryloxyethyloxetane, 3 -Ethyl-3-propenyloxyethyloxetane and the like.

The monomer (Aa3) is preferably a monomer having a tetrahydrofuranyl group and a (meth) acryloxy group. Examples of the monomer (Aa3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and tetrahydrofurfuryl methacrylate.

From the viewpoint of excellent storage stability of the resin composition, excellent chemical resistance, heat resistance, and mechanical strength of the obtained film and more excellent followability of the shape of the base substrate, the constituent unit (Aa) is preferably a monomer ( The structural unit derived from Aa1-2) is more preferably a structural unit represented by formula (Aa-1) or formula (Aa-2). The structural unit represented by formula (Aa-1) is derived from a compound represented by formula (I), and the structural unit represented by formula (Aa-2) is derived from a compound represented by formula (II).

[In the formula (Aa-1) and (Aa-2), R ^b1 and R ^b2 represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X ^b1 and X ^b2 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. ]

[2] Construction unit (Ab)

The constituent unit (Ab) having a condensed ring may be derived from an unsaturated compound having a condensed ring. Examples of the condensed ring include a naphthalene ring, an anthracene ring, and a carbazole ring. Among them, a carbazole ring is preferred. The structural unit having a carbazole ring is a structural unit derived from an unsaturated compound having a carbazole ring. The constitutional unit derived from an unsaturated compound having a carbazole ring can be obtained by using the unsaturated compound as a monomer and obtaining a copolymer. Alternatively, it can be obtained by reacting a compound (Ab ") having a carbazole ring due to other constitutional units (Ab ').

With the structural unit (Ab) having a carbazole ring, a film having high conformability to the shape of the base substrate can be formed. In addition, by having a carbazole ring-containing constituent unit (Ab), the refractive index of the obtained film can be increased.

The unsaturated compound derived from the structural unit (Ab) is preferably a compound represented by the formula (III).

[In formula (III), R ¹ represents a hydrogen atom, a methyl group, or a hydroxymethyl group.

R ² to R ⁹ each independently represent a hydrogen atom, a halogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with an alkoxy group or an aryl group.

X represents a single bond, an alkanediyl group having 1 or more carbon atoms, or a linear or branched chain represented by the following formula (V).

(In the formula (V), 1 represents an integer of 0 or more. M represents an integer of 1 or more.)]

Examples of the compound represented by formula (III) include N-vinylcarbazole, N-allylcarbazole, N- (meth) acrylfluorenylcarbazole, and (meth) acrylic acid 2- (9-carbazolyl) ) Ethyl ester, 2- (9-carbazolyl) ethoxyethyl (meth) acrylate, 2- (9-carbazolyl) -2-methylethyl (meth) acrylate, (methyl) 2- (9-carbazolyl) -1-methylethyl acrylate and the like are preferably exemplified by N-vinylcarbazole, N-allylcarbazole, and 2- (9-carb (meth) acrylate) (Oxazolyl) ethyl ester.

[3] Component (Ac)

Examples of the constitutional unit (Ac) include constitutional units derived from compounds belonging to the group of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter referred to as "constitutive units (Ac1)").

Compounds belonging to the group of unsaturated carboxylic acids and unsaturated carboxylic anhydrides include, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinyl benzoic acid; maleic acid, fumaric acid, Citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3 Unsaturated dicarboxylic acids such as 1,6-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 ] Hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy -6-ethylbicyclo [2.2.1] hept-2-ene and other bicyclic unsaturated compounds containing carboxyl groups; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-ethylene Phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-Dicarboxybicyclo [2.2. 1] Unsaturated dicarboxylic anhydrides such as hept-2-ene anhydride; succinate mono [2- (meth) propenyloxyethyl] ester, phthalic acid mono [2- (meth) propenyloxy] Unsaturated mono [(meth) acryloxyalkyl] esters of polyvalent carboxylic acids such as ethyl] esters; unsaturated acrylic esters containing hydroxyl and carboxyl groups in the same molecule, such as α- (hydroxymethyl) acrylic acid Wait.

[4] Component (Ad)

The structural unit (Ad) may be, for example, a structural unit derived from the following compounds.

Methyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, stearyl (meth) acrylate, ( Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (methyl) Acrylate (commonly known as "dicyclopentyl (meth) acrylate" in this technical field. Also known as "tricyclodecyl (meth) acrylate"), tricyclic [5.2.1.0 ^2,6 ] decane Ene-8-yl (meth) acrylate (commonly known in the technical field as "dicyclopentene (meth) acrylate"), dicyclopentyloxyethyl (meth) acrylate, (meth) ) Isoamyl acrylate, adamantane (meth) acrylate, allyl (meth) acrylate, propynyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, etc. ( (Meth) acrylates; hydroxyl-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; diethyl maleate, diethyl fumarate , Dicarboxylic acid diesters such as diethyl iconate; 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-hydroxymethyl Bicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene , 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, and other bicyclic unsaturated compounds; N-phenylmaleimide , N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4 -Maleimidine imine butyrate and other dicarbonylammine derivatives; styrene, α-methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, p-methoxy Styrene, (meth) acrylonitrile, vinyl chloride, vinylidene chloride, (meth) acrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2,3-dimethyl -1,3-butadiene and the like.

[5] Ratio of each constituent unit

Examples of the resin (A) include the following resins [K1] to [K4].

Resin [K1]: Copolymer composed of constitutional unit (Aa) and constitution unit (Ac); Resin [K2]: Copolymer composed of constitutional unit (Ab) and constitution unit (Ac); Resin [K3] : Copolymer composed of constitutional unit (Aa), constitutional unit (Ab), and constitutional unit (Ac); resin [K4]: constitutional unit (Aa), constitutional unit (Ab), constitutional unit (Ac), and constitution Copolymer of units (Ad).

The resin (A) is preferably a resin [K1] and a resin [K3].

In the resin [K1], the ratio of each constituent unit to the total constituent units constituting the resin [K1] is preferably constituent unit (Aa); 50 to 99 mol%, constituent unit (Ac); 1 to 50 mol %; More preferably a constitutional unit (Aa); 60 to 95 mol%, a constitutional unit (Ac); 5 to 40 mol%.

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 film, the heat resistance and the mechanical strength are excellent, and the followability to the shape of the base substrate can be formed more A high film is better at this point.

The resin [K1] can be referred to, for example, the method described in the document "Experimental Method of Polymer Synthesis" (by Otsu Takayuki, Publishing House: Chemical Dojin Co., Ltd., 1st edition, 1st brush, issued March 1, 1972) and It is manufactured by citing a document described in this document.

Specifically, the following methods can be enumerated: a specific amount of the structural unit (Aa) and the structural unit (Ac), a polymerization initiator, a solvent, and the like are added to a reaction vessel, and for example, nitrogen is used to replace oxygen to form a deoxidizing environment. Heat and keep warm while stirring. The polymerization initiator, solvent, and the like used here are not particularly limited, and ordinary users in this field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) or organic peroxides ( A benzamyl peroxide, etc.) may be used as long as the solvent dissolves each monomer, and examples of the solvent used in the resin composition are described below.

In addition, the obtained resin may be directly used as a solution after the reaction, a concentrated or diluted solution may be used, or a solid (powder) may be taken out by a method such as re-sinking. In particular, the solvent used in the resin composition of the present invention is used as a polymerization solvent, whereby 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.

In the resin [K2], the ratio of each constituent unit among all the constituent units constituting the resin [K2] is preferably the constituent unit (Ab); 50 to 99 mol%, and the constituent unit (Ac); 1 to 50 mol% ; More preferably constituting unit (Ab); 60 to 90 mole%, constituting unit (Ac); 5 to 40 mole%.

In the resin [K3], the ratio of each constituent unit among the total constituent units constituting the resin [K3] is preferably the constituent unit (Aa); 1 to 90 mol%, the constituent unit (Ab); 1 to 98 mol %, Constituting unit (Ac); 1 to 50 mol%; more preferably constituting unit (Aa); 3 to 70 mol%, constituting unit (Ab); 20 to 90 mol%, constituting unit (Ac); 3 to 40 mol%; still more preferred is constituent unit (Aa); 3 to 70 mol%, constituent unit (Ab); 50 to 90 mol%, constituent unit (Ac); 3 to 40 mol%.

In the resin [K4], the ratio of each constituent unit among the total constituent units constituting the resin [K4] is preferably the constituent unit (Aa); 1 to 70 mol%, the constituent unit (Ab); 5 to 90 mol %, Constituting unit (Ac); 1 to 50 moles, constituting unit (Ad); 1 to 40 moles, more preferably constituting unit (Aa); 3 to 50 moles, constituting unit (Ab); 10 to 90 mol%, constituting unit (Ac); 5 to 35 mol%, constituting unit (Ad); 1 to 30 mol%; still more preferably constituting unit (Aa); 3 to 50 mol%, Constituent unit (Ab); 50 to 90 mol%, constituent unit (Ac); 5 to 35 mol%, constituent unit (Ad); 1 to 30 mol%.

If the ratio of the constituent units of the resins [K2] to [K4] is within the above range, the storage stability of the resin composition, the chemical resistance of the resulting film, the heat resistance and mechanical strength are excellent, and excellent developability is obtained. It's better. The resins [K2] to [K4] can be produced by the same method as the resin [K1].

The polystyrene equivalent weight average molecular weight (Mw) of the resin (A) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 20,000, and particularly preferably 5,000 to 10,000. When the weight average molecular weight (Mw) of the resin (A) is within the above range, the coating property of the resin composition tends to be good.

The dispersion [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 be excellent in 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 still more preferably 50 mg-KOH / g or more and 135 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 obtained 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.

The content of the resin (A) is preferably 30 to 90% by mass, more preferably 35 to 80% by mass, and still more preferably 40 to 70% by mass based on the solid content of the resin composition of the present invention.

When the content ratio of the resin (A) is within the aforementioned range, the developability of the resin composition is excellent, and the resulting cured film tends to be excellent in heat resistance and excellent in adhesion to a substrate and chemical resistance. Here, the solid content of the resin composition refers to an amount obtained by subtracting the content of the solvent (E) from the total amount of the resin composition of the present invention.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate living radicals, acids, and the like by the action of light or heat and start polymerization of the polymerizable compound (C), and a known polymerization initiator can be used. . The polymerization initiator (D) is preferably at least one selected from the group consisting of an O-fluorenyl oxime compound, an alkyl phenone compound, a triazine compound, a fluorenyl phosphine oxide compound, and a diimidazole compound. The polymerization initiator is more preferably a polymerization initiator containing an O-fluorenyl oxime compound. With these polymerization initiators, there is a tendency that the sensitivity is high and the transmittance in the visible light region is increased.

The O-fluorenyl oxime compound is a compound having a structure represented by formula (D1). In the following, * indicates a bond.

Examples of O-fluorenyl oxime compounds include N-benzyloxy-1- (4-phenylhydrothiophenyl) butane-1-one-2-imine, N-benzyloxy 1- (4-phenylhydrothiophenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylhydrothiophenyl)- 3-cyclopentylpropane-1-one-2-imine, N-ethoxyl-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazole-3 -Yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-di Oxacyclopentylmethyloxy) benzamidine} -9H-carbazol-3-yl] ethane-1-imine, N-acetamyloxy-1- [9-ethyl-6- ( 2-methylbenzylidene) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzylideneoxy-1- [9-ethyl-6 -(2-methylbenzyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2-imine. Commercial products such as IRGACURE (registered trademark) OXE01, OXE02 (the above are manufactured by BASF Co., Ltd.), and N-1919 (made by ADEKA Co., Ltd.) can also be used.

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

Examples of the compound having a structure represented by the formula (D2-1) include 2-methyl-2-N-morpholinyl-1- (4-methylhydrothiophenyl) propane-1-one, 2-di Methylamino-1- (4-morpholinylphenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl Group] -1- [4- (4-morpholinyl) phenyl] butane-1-one. Commercial products such as IRGACURE (registered trademark) 369, 907, and 379 (above manufactured by BASF Co., Ltd.) can also be used. In addition, a polymerization initiator having a base capable of causing chain transfer described in Japanese Patent Application Publication No. 2002-544205 can also be used. Examples of the compound having a partial structure represented by the formula (D2-2) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1- [4- ( 2-hydroxyethoxy) phenyl] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one Oligomer, α, α-diethoxyacetophenone, benzyldimethylketal. From the viewpoint of sensitivity, the alkyl phenone compound is preferably a compound having a structure represented by the formula (D2-1).

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-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 fluorenylphosphine oxide compound include 2,4,6-trimethylbenzylfluorenyldiphenylphosphine oxide and the like. Commercial products such as IRGACURE 819 (manufactured by BASF. JAPAN Co., Ltd.) can also be used.

Examples of diimidazole compounds include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyldiimidazole, 2,2'-bis (2,3-dichlorobenzene) Radical) -4,4 ', 5,5'-tetraphenyldiimidazole (for example, refer to Japanese Unexamined Patent Publication No. 6-75372, Japanese Unexamined Patent Publication No. 6-75373, etc.), 2,2'-bis (2- (Chlorophenyl) -4,4 ', 5,5'-tetrakis (alkoxyphenyl) diimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'- Tetrakis (dialkoxyphenyl) diimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) diimidazole (see for example Japanese Patent Application Publication No. 48-38403, Japanese Patent Application Publication No. 62-174204, etc.), and a diimidazole compound in which a 4,4-', 5,5'-phenyl group is substituted with a carbonylalkoxy group (for example, refer to Japanese Patent Application Laid-open No. Hei. 7-10913, etc.).

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; diphenyl ketone and o-benzoyl benzoin Methyl ester, 4-phenyldiphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3 ', 4,4'-tetrakis (third butylperoxycarbonyl) ) Diphenyl ketone compounds such as diphenyl ketone, 2,4,6-trimethyldiphenyl ketone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone; 10-butyl -2-chloroacridone, diphenylethylene dione, methyl phenylglyoxylate, titanium cetoate and the like. These can be used in combination with a polymerization initiation aid (hereinafter referred to as a polymerization initiation aid (H)) (in particular, amines) described later.

Examples of the polymerization initiator (D) include an acid generator. Examples of the acid generator include 4-hydroxyphenyldimethylfluorene p-toluenesulfonate, 4-hydroxyphenyldimethylfluorene hexafluoroantimonate, and 4-acetoxyphenyldimethylfluorene Tosylate, 4-Ethyloxyphenyl. methyl. Oniums such as benzylfluorene hexafluoroantimonate, triphenylfluorene p-toluenesulfonate, triphenylfluorene hexafluoroantimonate, diphenylfluorene p-toluenesulfonate, diphenylfluorene hexafluoroantimonate Salt, nitrobenzyl tosylate, benzoin tosylate.

When the resin composition of the present invention contains a polymerizable compound (C) and a polymerization initiator (D), the content of the polymerization initiator (D) is 100 mass relative to the total content of the resin (A) and the polymerizable compound (C). The part is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 15 parts by mass, and even more preferably 1 to 8 parts by mass. When the content of the polymerization initiator (D) is within the aforementioned range, the visible light transmittance of the obtained cured film tends to be increased.

<Polymerization starter (H)>

The polymerization initiator (H) is used together with the polymerization initiator (D) to promote the polymerization of the polymerizable compound (C) which is polymerized by the polymerization initiator (D), or to enhance the polymerization. Agent.

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

Examples of the thiazoline compound include compounds represented by the formulae (H1-1) to (H1-3), 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-dimethylamino Isoamyl benzoate, 2-dimethylamino ethyl benzoate, 2-ethylhexyl 4-dimethylamino benzoate, N, N-dimethyl-p-toluidine, 4,4'- Bis (dimethylamino) diphenyl ketone (commonly known as Michelin), 4,4'-bis (diethylamino) diphenyl ketone, 4,4'-bis (ethylmethylamine) Group), diphenyl ketone and the like, and 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 the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9, 10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

Examples of thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro- 4-propoxythioxanthone and the like.

Examples of the carbonic acid compound include phenylhydrothioacetic acid, methylphenylhydrothioacetic acid, ethylphenylhydrothioacetic acid, methylethylphenylhydrothioacetic acid, and dimethylphenylhydrothioacetic acid. , Methoxyphenyl hydrothioacetic acid, dimethoxyphenyl hydrothioacetic acid, chlorophenylhydrothioacetic acid, dichlorophenylhydrothioacetic acid, N-phenylglycine, phenoxy Acetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

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

<Leveling agent (B)>

Examples of the leveling agent (B) include a polysiloxane-based surfactant, a fluorine-based surfactant, and a polysiloxane-based surfactant having a fluorine atom. These may have a polymerizable group in a side chain.

Examples of the polysiloxane-based surfactant include a surfactant having a siloxane bond in the molecule. Specific examples include Toray silicone DC3PA, the same as SH7PA, the same as DC11PA, the same as SH21PA, the same as SH28PA, the same as SH29PA, the same as SH30PA, and the same as SH8400 (trade name; manufactured by TORAY. DOW CORNING Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (made by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (made by Momentive Performance Materials Japan).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specific examples include Fluorad (registered trademark) FC430, same FC431 (made by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, same F171, same F172, same F173, same F177, same F183, same F554, same R30, same as RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, same as EF303, same EF351, same as EF352 (made by Mitsubishi Materials Electronic Chemicals Co., Ltd.), surflon (registered trademark) S381 , Same as S382, same SC101, same SC105 (made by Asahi Glass Co., Ltd.) and E5844 (made by DAIKIN Refinery Research Institute Co., Ltd.), etc.

Examples of the polysiloxane-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples include Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

When the leveling agent (B) is contained, its content ratio is preferably 0.001% by mass or more and 0.2% by mass or less with respect to the total amount of the resin composition, more preferably 0.002% by mass or more and 0.1% by mass or less, and still more preferably 0.005% by mass Above 0.07 mass%.

<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 preferable because the color of the obtained film is small.

Examples of the phenolic antioxidant include 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2- [1- (2-hydroxy-3,5-di-third-pentylphenyl) ethyl] -4,6-di-third-pentylphenyl acrylate, 3,9-bis [2- {3- (3- Tributyl-4-hydroxy-5-methylphenyl) propanyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] 11 Alkane, 2,2'-methylenebis (6-third-butyl-4-methylphenol), 4,4'-butylenebis (6-third-butyl-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"-(mesitylene-2,4,6-triyl) tri-p-cresol, neopentaerythritol tetra [ 3- (3,5-di-tertiary-butyl-4-hydroxyphenyl) propionate], 2,6-di-tertiary-butyl-4-methylphenol and 6- [3- (3-tertiary Butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxin Phosphateptane. Commercially available phenolic antioxidants can be used. Commercial phenolic antioxidants can be used. E.g. SUMILIZER (registered trademark) BHT, GM, GS, GP (manufactured by Sumitomo Chemical Co., Ltd. are all above), IRGANOX (registered trademark) 1010,1076,1330,3114 (the above are all manufactured by BASF Co.).

Examples of the sulfur-based antioxidant include 3,3'-thiodipropionate dilauryl, 3,3'-dipropionate dimyristyl, 3,3'-distearyl thiopropionate, neopentyl Tetraol tetra (3-laurylthiopropionate). 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, distearyl neopentaerythritol diphosphite, (Tridecyl) -1,1,3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane diphosphite. As the phosphorus-based antioxidant, a commercially available product can be used. Examples of commercially available phosphorus-based antioxidants include IRGAFOS (registered trademark) 168, 12, 38 (all of which are manufactured by BASF Co., Ltd.), ADEKASTAB 329K, and ADEKASTAB PEP36 (all of which are manufactured by ADEKA Corporation).

Examples of the amine-based antioxidant include N, N'-di second butyl-p-phenylenediamine, N, N'-diisopropyl-p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine Amine, 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-based 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 with respect to 100 parts by mass of the total content of the resin (A) and the polymerizable compound (C). 0.5 mass part or more and 3 mass parts or less. When the content of the antioxidant (F) is within the aforementioned range, the resulting film tends to be excellent in heat resistance and pencil hardness.

<Hardener (G)>

<Polycarboxylic acid (G1)>

The polycarboxylic acid (G1) 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, and a polycarboxylic acid anhydride is an anhydride of a polycarboxylic acid. The molecular weight of the polycarboxylic acid (G1) 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, 2- (2-oct-3-ene) succinic anhydride, 2 -(2,4,6-trimethylnon-3-ene) succinic anhydride, 1,2,3-propanetricarboxylic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride and other chain polycarboxylic acids Acid anhydride; 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, hexahydrophthalic acid 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-dicarboxylic anhydride, Cyclopentane tetracarboxylic dianhydride and other alicyclic polycarboxylic anhydrides; phthalic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, pyrolite anhydride, trimellitic anhydride, Phenylketone tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenylphosphonium tetracarboxylic dianhydride, ethylene glycol bis (anhydrotrimellitate), triglyceride (anhydromellitate Esters), glycerol bis (anhydrodecumenyl) Triester) monoacetate, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furyl) naphtho [1,2 -c] an aromatic polycarboxylic anhydride such as furan-1,3-dione. Adeka hardener (registered trademark) -EH-700 (trade name (the same below), made by ADEKA Co., Ltd.), RIKACID (registered trademark) -HH, same-TH, same-MH, same MH-700 (new (Made by Japan Physical and Chemical Co., Ltd.), Epikonia 126, same YH-306, and DX-126 (made by Yuka Shell Epoxy Co., Ltd.) and other commercially available products.

Examples of the polycarboxylic acid include chain polycarboxylic acids such as oxalic acid, malonic acid, adipic acid, sebacic acid, fumaric acid, tartaric acid, citric acid, and polycarboxylic acids derived from chain polycarboxylic anhydrides; cyclohexanedicarboxylic acid; Acid, alicyclic polycarboxylic acid such as polycarboxylic acid derived from alicyclic polycarboxylic anhydride; isophthalic acid, terephthalic acid, 1,4,5,8-naphthalenetetracarboxylic acid, derived aromatic polycarboxylic anhydride Aromatic polycarboxylic acids and the like.

From the viewpoint of excellent heat resistance of the obtained film, and particularly difficult to reduce the transparency of the visible light region, among them, a chain carboxylic acid anhydride and an alicyclic polycarboxylic acid anhydride are preferred, and an alicyclic polycarboxylic acid anhydride is more preferred.

When the resin composition of the present invention contains a polycarboxylic acid (G1), its content is preferably from 1 to 30 parts by mass, more preferably from 2 to 100 parts by mass relative to the total content of the resin (A) and the polymerizable compound (C). 20 parts by mass, and more preferably 2 to 15 parts by mass. When the content of the polycarboxylic acid (G1) is within the aforementioned range, the resulting film will have excellent heat resistance and adhesion.

<Imidazole compound (G2)>

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

[In the formula (G2-1), R ³¹ represents an alkyl group having 1 to 20 carbon atoms, a phenyl group, a benzyl group, or a cyanoalkyl group having 2 to 5 carbon atoms.

R ³² to R ³⁴ 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 hydrogen atom contained in the phenyl group Can be substituted by a hydroxyl group. ]

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isobutyl, butyl, third butyl, hexyl, heptyl, octyl, nonyl, decyl, and heptadecyl , Undecyl.

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

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

Examples of fluorenyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, propyl, isobutyl, pentyl, isopentyl, trimethylethyl, lauryl, and myristyl. , Stearyl group.

Examples of the imidazole compound (G2) include 1-methylimidazole, 2-methylimidazole, 2-hydroxymethylimidazole, 2-methyl-4-hydroxymethylimidazole, 5-hydroxymethyl-4-methylimidazole , 2-ethylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 4-hydroxymethyl-2 -Phenylimidazole, 2-phenylimidazole, 2-phenyl-2-hydroxymethylimidazole, 1-benzyl-4-methylimidazole, 1-benzyl-4-phenylimidazole, 1-benzyl- 5-hydroxymethylimidazole, 2- (p-hydroxyphenyl) imidazole, 1-cyanomethyl-2-methylimidazole, 1- (2-cyanoethyl) -2-hydroxymethylimidazole, 2, 4-diphenylimidazole, 1-cyanomethyl-2-undecylimidazole, 1-cyanomethyl-2-ethyl-4-methylimidazole, 1-cyanomethyl-2-benzene Imidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole. Among these, 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 an imidazole compound (G2), its content is preferably 0.1 parts by mass or more and 25 parts by mass or less with respect to the total content of the resin (A) and the polymerizable compound (C), more preferably 0.2 to 15 parts by mass, and more preferably 0.5 to 5 parts by mass. When the content of the imidazole compound (G2) is within the aforementioned range, the obtained film tends to have excellent transparency in the visible light region.

<Solvent (E)>

The resin composition of the present invention may contain a solvent (E). The solvent (E) is not particularly limited, and examples thereof include solvents generally used in this field. Examples include an ester solvent (a solvent containing -COO- and not containing -O- in the molecule), an ether solvent (a solvent containing -O- and not containing -COO- in the molecule), an ether ester solvent (containing -COO in the molecule) -And -O- solvents), ketone solvents (solvents containing -CO- and not -COO- in the molecule), alcohol solvents (containing OH in the molecule and -O-, -CO- and -COO- Solvents), aromatic hydrocarbon solvents, amidine solvents, dimethyl sulfene and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, and propyl Butyl ester, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl ethyl acetate, ethyl ethyl acetate, cyclohexanol Acetate and γ-butyrolactone.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and diethylene glycol. Monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3 -Methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl Ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether and methyl anisole.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and methyl 3-methoxypropionate. , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate , Propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy Ethyl-2-methylpropanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate Esters, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monoethyl ether Butyl ether acetate.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2-pentanone , Cyclopentanone, cyclohexanone and isophorone.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

Examples of the amidine solvent include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

From the viewpoints of coating properties and drying properties, the above solvents are preferably organic solvents having a boiling point of 100 ° C to 200 ° C in 1 atm. The solvent is preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethylene glycol ethyl methyl ether, cyclohexyl Ketones, methoxybutanol and methoxybutyl acetate, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol ethyl methyl ether, methoxybutanol and methyl acetate Oxybutyl ester.

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 ratio of the solvent (E) is within the above range, there is a tendency that the followability of the film obtained by coating the resin composition on the shape of the base substrate can be improved.

<Other ingredients>

The resin composition of the present invention may contain fillers, other polymer compounds, ultraviolet absorbers, chain transfer agents, adhesion promoters, colorants, pigment dispersants and other well-known additives in the technical field, as necessary.

In addition, when the resin composition of the present invention is filled in a quartz cell with an optical diameter of 1 cm and the transmittance is measured using a spectrophotometer at a measurement wavelength of 400 to 700 nm, the average transmittance is preferably 70% or more, more preferably 80 %the above.

When the resin composition of the present invention is used to form a film, the average transmittance of the film is preferably 90% or more, and more preferably 95% or more. This average transmittance is an average value when a film having a thickness of 2 m after heat curing (100 to 250 ° C, 5 minutes to 3 hours) is measured using a spectrophotometer at a measurement wavelength of 400 to 700 nm. This makes it possible to provide a film having excellent transparency in the visible light region.

<Manufacturing method of resin composition>

The resin composition of the present invention can be obtained by adjusting the resin (A), the polymerizable compound (C) and the polymerization initiator (D), and optionally the solvent (E), the polymerization initiator (H), and The leveling agent (B), the antioxidant (F), the hardener (G), and other components are produced by mixing in a known method. After mixing, it is preferably filtered with a filter having a pore size of 0.05 to 1.0 μm.

<Manufacturing method of cured film>

The cured film can be produced by applying the resin composition of the present invention to a substrate, drying it, and heating it. A patterned cured film can be manufactured by the following steps. Step (1): a step of coating the resin composition of the present invention on a substrate; step (2): a step of drying the coated resin composition under reduced pressure and / or heating to form a composition layer; step ( 2a): a step of exposing the composition layer through a photomask; step (2b): a step of developing the exposed composition layer; and 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 (base substrate). Examples of the substrate include glass, metal, and plastic. A color filter, an insulating film, a conductive film, and / or a driving circuit can be formed on the substrate. The coating on the substrate is preferably performed using a coating device such as a spin coater, a slit & spin coater, a slit coater, an inkjet, a roll coater, or a dip coater.

Step (2) is a step of drying the coated resin composition under reduced pressure and / or heating 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 temperature in the range of 20 to 25 ° C under a pressure of 50 to 150 Pa. Heat drying (pre-baking) may be performed before or after drying under reduced pressure. Heating and drying are usually performed using a heating device such as an oven or a hot plate. The temperature for heating and drying 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 (2a) is a step of exposing the composition layer formed in step (2) through a photomask. In this photomask, a light-shielding portion is formed in a portion corresponding to the composition layer to be removed. The shape of the light shielding portion is not particularly limited, and can be selected according to the intended use. 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, light below 350 nm can be blocked with a filter that blocks the wavelength range, and light near 436 nm, 408 nm, and 365 nm can be selectively removed with a band-pass filter that takes out these wavelength ranges. Examples of the light source include a mercury lamp, a light-emitting diode, a metal halide lamp, and a halogen lamp. Since the entire exposure surface can be uniformly irradiated with parallel light rays, and the mask and the composition layer can be correctly aligned, it is preferable to use a mask aligner, a stepper and other exposure devices.

Step (2b) is a step of developing the composition layer after exposure. By exposing the exposed composition layer to a developing solution, the unexposed portion of the composition layer is dissolved in the developing solution and removed to form a patterned composition layer on the substrate. The developing solution is preferably an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration in the aqueous solution of these basic compounds is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass. The developing solution 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, that is, a post-baking step. By heating in the same manner as the conventionally known post-baking step, the patterned composition layer is hardened, and a patterned film is formed on the substrate. The resin composition of the present invention used for pattern formation has excellent developability. Therefore, during development, the composition layer is not accidentally peeled off, and the pattern can be completely formed. The film thickness of the patterned film is preferably 0.3 μm or more and 10 μm or less, and more preferably 0.5 μm or more and 5 μm or less. With such a film thickness, developability can be further improved.

    (Example)    

Hereinafter, the present invention will be described in more detail through examples. "%" And "part" in the examples are mass% and mass part unless otherwise stated.

[Examples 1 to 11, Comparative Example 1]

<Preparation of resin composition>

The propylene glycol monomer containing the resin (A), the polymerizable compound (C), and the polymerization initiator (D) shown in Table 1 in a proportion shown in Table 1 is mixed with the solvent (E) so as to have a solid content concentration shown in Table 1. Methyl ether acetate to prepare a resin composition. In Tables 1 and 2, the parts of each component represent parts by mass in terms of solid content.

Each component in Table 1 and Table 2 is as follows.

Resin (a1): The resin obtained in Synthesis Example 1.

Resin (a2): The resin obtained in Synthesis Example 2.

Compound (c1): A compound represented by formula (VI-3) (OGSOL (registered trademark) EA-0200; manufactured by Osaka Gas Chemical Co., Ltd.).

Compound (c2): a bifunctional acrylate compound having a fluorene skeleton (OGSOL (registered trademark) EA-0300; manufactured by Osaka Gas Chemical Co., Ltd.).

Compound (c3): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.).

Starter (d1): N-benzyloxy-1- (4-phenylhydrothiophenyl) octan-1-one-2-imine (IRGACURE (registered trademark) OXE01; BASF shares Limited company).

(Synthesis Example 1: Preparation of Resin (a1))

In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was flowed and replaced with a nitrogen atmosphere. 280 parts of propylene glycol monomethyl ether acetate was added, and heated to 80 ° C while stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, and 3,4-epoxytricyclo [5.2.1.0 ² were added dropwise over 5 hours. ⁶ ] A mixed solution of 289 parts of a mixture of decane-9-yl acrylate (trade name "E-DCPA", manufactured by Daicel Co., Ltd.) and 125 parts of propylene glycol monomethyl ether acetate.

On the other hand, a mixed solution in which 33 parts of 2,2-azobis (2,4-dimethylvaleronitrile) was dissolved in 235 parts of propylene glycol monomethyl ether acetate was dropped over 6 hours. After the dropping was completed, the solution was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin (a1)) having a B-type viscosity (23 ° C) of 125 mPas and a solid content of 35.1%. The weight average molecular weight (Mw) of the obtained copolymer was 9200, the degree of dispersion was 2.08, and the acid value in terms of solid content was 77 mg-KOH / g. The resin (a1) has the following constituent units.

(Synthesis Example 2: Preparation of Resin (a2))

In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, an appropriate amount of nitrogen was passed and replaced with a nitrogen atmosphere. 324 parts of propylene glycol monomethyl ether acetate was added, and heated to 85 ° C while stirring. Then, 60 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, and 3,4-epoxytricyclo [5.2. 1.0 ^2,6 ] 30 parts of decane-9-yl acrylate mixture (trade name "E-DCPA", manufactured by Daicel Co., Ltd.), 210 parts of 9-vinylcarbazole, and propylene glycol monomethyl ether acetic acid A mixed solution of 190 parts of ester. On the other hand, a mixed solution in which 31 parts of 2,2-azobis (2,4-dimethylvaleronitrile) was dissolved in 155 parts of propylene glycol monomethyl ether acetate was dropped over 5 hours. After the dropping, the solution was kept at the same temperature for 3 hours and then cooled to room temperature to obtain a copolymer (resin (a1)) solution having a B-type viscosity (23 ° C) of 163 mPas and a solid content of 31.8%. The weight average molecular weight (Mw) of the obtained resin (a1) was 7,900, the degree of dispersion (Mw / Mn) was 1.99, and the acid value in terms of solid content was 107 mg-KOH / g. The resin (a2) has the following constituent units.

<Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn)>

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

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

Column: TSK-GELG2000HXL.

Column temperature: 40 ° C.

Vehicle: THF (tetrahydrofuran).

Flow rate: 1.0 mL / min.

Test solution solid content concentration: 0.001 to 0.01% by mass.

Injection volume: 50 μL.

Detector: RI.

Calibration reference materials: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by TOSOH Corporation).

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

<Production of hardened film>

A 2-inch square glass substrate (EAGLE XG; manufactured by Corning Corporation) was sequentially washed with a neutral detergent, water, and isopropyl alcohol, and then dried. The resin compositions of Examples 1 to 11 and Comparative Example 1 were spin-coated on the substrate such that the film thickness after baking was 1.0 μm. Next, a reduced pressure dryer (manufactured by VCD Microtek Co., Ltd.) was used to reduce the pressure of the rotary pump to 1,000 rpm, the pressure of the booster pump to 700 rpm, and reduce the pressure to 66 Pa at room temperature at 25 ° C to form a resin composition layer. . After leaving to cool, the distance between the resin composition layer on the substrate and the quartz glass mask was 100 μm, and an exposure machine (TME-150RSK; manufactured by topcon Co., Ltd., light source; ultra-high pressure mercury lamp) was used in an atmospheric environment at 100 mJ / The exposure amount of cm ² (365 nm standard) was irradiated with light. The light emitted from the ultra-high pressure mercury lamp was passed through a filter (UV-31; manufactured by Asahi Techno Glass Co., Ltd.) to irradiate the light. The photomask is a photomask for forming a 1: 1 line gap pattern with a line width of 100 μm. The resin composition layer after irradiation with light was immersed in a 1% aqueous solution of tetramethylammonium hydroxide at 23 ° C for 60 seconds and developed. After being washed with water, it was post-baked at 230 ° C for 15 minutes to form a line width of 100 μm. A hardened film with a 1: 1 line gap pattern.

<Evaluation of pattern formability>

The formed cured film was observed using a microscope (500x magnification; VF-7510; manufactured by Keyence Co., Ltd.). A 1: 1 line gap pattern that can be formed with a line width of 100 μm is “A” and cannot be formed as “C”. The results are shown in Tables 1 and 2.

When the resin composition of Examples 1 to 11 was used, a hardened film having a 1: 1 line gap pattern formed with a line width of 100 μm was prepared on a glass substrate. However, the resin composition of the comparative example was irradiated with light during development. The composition layer is peeled off, and a pattern cannot be formed on a glass substrate.

According to the present invention, there can be provided a resin composition capable of forming a patterned cured film on a glass substrate. This cured film can be suitably used for a display device and the like.

Claims (5)

    A resin composition comprising a resin, a polymerizable compound, and a polymerization initiator. The polymerizable compound includes a polymerizable compound having a fluorene skeleton. The content rate of the polymerizable compound having a fluorene skeleton is higher than that of the polymerizable compound. The total amount exceeds 10% by mass.     The resin composition according to item 1 of the patent application range, wherein the polymerizable compound having a fluorene skeleton is a compound represented by formula (VI), In formula (VI), L ¹ independently of each other represents a single bond or an alkanediyl group having 1 to 16 carbon atoms which may have a substituent. The methylene group contained in the alkanediyl group may be substituted with an oxygen atom, but the bond is oxygenated. The methylene group of the atom is not substituted with an oxygen atom, and R ¹¹ independently represent a hydrogen atom or a methyl group.     The resin composition according to item 1 or 2 of the scope of patent application, wherein the aforementioned resin contains a structural unit (Aa) having a cyclic ether structure having 2 to 4 carbon atoms, and the structural unit (Aa) is composed of an unsaturated alicyclic ring. Hydrocarbons are derived from epoxidized structural monomers.         The resin composition according to item 1 of the scope of patent application, wherein the aforementioned resin contains a resin having a constituent unit of a carbazole ring.         A hardened film formed of a resin composition as described in the first item of the patent application.