Primer composition, laminate, and method for producing laminate

Abstract

To provide a primer composition capable of improving adhesion between a substrate and a cured product layer composed of a cured product of a photosensitive composition regardless of the type of the substrate, a laminate having a primer layer derived from the primer composition, and a method for producing the same.SOLUTION: Wherein the polymerizable compound (A1) is a compound capable of polymerizing by a polymerization mechanism other than radical polymerization, and the compound (B) has a functional group capable of forming a covalent bond by a reaction with an ethylenically unsaturated double bond-containing group in the photocurable compound (a) in the photosensitive composition, and the polymerizable compound (A2) is a compound capable of polymerizing by a polymerization mechanism other than radical polymerization, and the polymerizable compound (A2) is a compound capable of polymerizing by a polymerization mechanism other than radical polymerization.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a primer composition, a laminate, and a method for producing the laminate. [Background technology]

[0002] Negative photosensitive compositions that can be cured by exposure to light are widely used in the production of functional layers such as insulating layers in various semiconductor elements, and in the production of insulating layers and various optically functional layers in image display panels such as liquid crystal display panels and organic EL display panels.

[0003] As such a photosensitive composition, for example, a photosensitive composition containing an acrylic resin, a silane coupling agent with a specific structure, and a polymerizable compound has been proposed (see Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2015 / 194639 Summary of the Invention [Problem to be solved by the invention]

[0005] Conventional photosensitive compositions have the problem of insufficient adhesion to substrates, resulting in peeling. To address this issue, a silane coupling agent has been used to improve adhesion, as in Patent Document 1. However, there have been problems in that this method can only be applied to substrates having silanol groups on the surface, and even for substrates having silanol groups on the surface, sufficient effects cannot be obtained depending on the amount of silanol groups.

[0006] The present invention has been made in view of the above circumstances, and aims to provide a primer composition that can improve adhesion between a substrate and a cured layer made of a cured product of a photosensitive composition, regardless of the type of substrate, a laminate including a primer layer derived from the primer composition, and a method for producing the same. [Means for solving the problem]

[0007] In order to solve the above problems, the present inventors have conducted extensive research and have found that a primer composition containing a predetermined base material component (A), a predetermined compound (B), and a solvent (S) can solve the above problems, leading to the completion of the present invention. Specifically, the present invention provides the following.

[0008] A first aspect is a primer composition used to form a primer layer between a substrate and a cured product layer made of a cured product of a photosensitive composition when the cured product layer is formed on the substrate, the primer composition comprising: the photosensitive composition contains a photocurable compound (a) having an ethylenically unsaturated double bond-containing group and a photopolymerization initiator (b); The primer composition comprises a substrate component (A), a compound (B), and a solvent (S), the base component (A) is a compound that does not form a covalent bond by reaction with the ethylenically unsaturated double bond-containing group in the photocurable compound (a), the base component (A) contains a resin (A1) and / or a polymerizable compound (A2), the polymerizable compound (A2) is a compound that can be polymerized by a polymerization mechanism other than radical polymerization, the compound (B) has a functional group capable of forming a covalent bond by reaction with the ethylenically unsaturated double bond-containing group in the photocurable compound (a), In the primer composition, the functional group in the compound (B) is at least one selected from the group consisting of an ethylenically unsaturated double bond-containing group, an amino group, a hydrosilyl group, and a thiol group.

[0009] A second aspect is a laminate comprising a substrate, the primer layer derived from the primer composition of the first aspect, and the cured product layer.

[0010] A third aspect of the present invention is a method for forming a primer layer by applying the primer composition of the first aspect to a substrate and drying it; applying the photosensitive composition onto the substrate on which the primer layer has been formed to form a photosensitive composition layer; exposing the photosensitive composition layer to light to form the cured product layer; Including, In a second aspect of the method for producing a laminate, when components in the primer composition other than the compound (B) can be polymerized or crosslinked, the components in the primer composition other than the compound (B) are polymerized or crosslinked before the application of the photosensitive composition. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a primer composition that can improve adhesion between a substrate and a cured layer made of a cured product of a photosensitive composition regardless of the type of substrate, a laminate including a primer layer derived from the primer composition, and a method for producing the same. DETAILED DESCRIPTION OF THE INVENTION

[0012] Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited to the following embodiments and can be practiced with appropriate modifications within the scope of the object of the present invention.

[0013] <Primer composition> The primer composition is used to form a primer layer between a substrate and a cured product layer formed from a cured product of a photosensitive composition on a substrate. The photosensitive composition contains a photocurable compound (a) having an ethylenically unsaturated double bond-containing group and a photopolymerization initiator (b). The primer composition contains a base component (A), a compound (B), and a solvent (S). The base component (A) is a compound that does not form a covalent bond upon reaction with the ethylenically unsaturated double bond-containing group in the photocurable compound (a), and contains a resin (A1) and / or a polymerizable compound (A2). The polymerizable compound (A2) is a compound that can be polymerized by a polymerization mechanism other than radical polymerization. The compound (B) has a functional group capable of forming a covalent bond upon reaction with the ethylenically unsaturated double bond-containing group in the photocurable compound (a), and the functional group is at least one selected from the group consisting of an ethylenically unsaturated double bond-containing group, an amino group, a hydrosilyl group, and a thiol group.

[0014] The primer composition can improve the adhesion between the substrate and the cured product layer regardless of the type of substrate. This effect is presumably achieved for the following reasons. Compound (B) has a specific functional group capable of forming a covalent bond by reaction with the ethylenically unsaturated double bond-containing group in the photocurable compound (a) in the photosensitive composition, thereby forming a covalent bond between the primer layer and the cured product layer. Furthermore, since the primer composition also contains the base component (A), the formed thin film (primer layer) has a thickness of several nanometers to several tens of nanometers, resulting in excellent uniformity. These factors synergistically improve adhesion between the substrate and the cured product layer, thereby improving adhesion between the substrate and the cured product layer regardless of the type of substrate.

[0015] <Base material component (A)> The base component (A) is a compound that does not form a covalent bond by reaction with the ethylenically unsaturated double bond-containing group in the photocurable compound (a) in the photosensitive composition (specifically, for example, a compound that does not have an ethylenically unsaturated double bond-containing group, an amino group, a hydrosilyl group, or a thiol group). The base component (A) contains a resin (A1) and / or a polymerizable compound (A2).

[0016] [Resin (A1)] The resin (A1) is not particularly limited as long as it is a resin material that imparts shaping properties such as film-forming properties to the primer composition. For example, a water-soluble resin (A1-1) or a phenolic hydroxyl group-containing resin (A1-2) is preferred.

[0017] (Water-soluble resin (A1-1)) The water-soluble resin (A1-1) is poorly soluble in solvents such as propylene glycol monomethyl ether acetate (PM), which are commonly used in photosensitive compositions. Therefore, when the photosensitive composition is applied onto the primer layer, mixing is less likely to occur between the primer layer and the coating film of the photosensitive composition, which makes it easier to improve adhesion between the substrate and the cured layer. In this specification, "water-soluble" means that 0.5 g or more of the solute (water-soluble resin) dissolves in 100 g of water or alkaline aqueous solution at 25°C.

[0018] Examples of the water-soluble resin (A1-1) include vinyl resins, polysaccharides, polyethylene oxide, polyglycerin, and water-soluble nylon. The vinyl resin is not particularly limited as long as it is a homopolymer or copolymer of a monomer having a vinyl group and is a water-soluble resin. Examples of vinyl resins include polyvinyl alcohol resins, such as polyvinyl alcohol, polyvinyl acetal (including vinyl acetate copolymers), butenediol-vinyl alcohol copolymers, polyvinyl alcohol-polyacrylic acid block copolymers, and polyvinyl alcohol-polyacrylic acid ester block copolymers. Other examples of vinyl resins include polyvinylpyrrolidone, polyacrylamide, poly(N-alkylacrylamide), polyallylamine, poly(N-alkylallylamine), partially amidated polyallylamine, poly(diallylamine), allylamine-diallylamine copolymer, and polyacrylic acid. Examples of polysaccharides include cellulose-based resins, dextrin, and dextran. The cellulose-based resins are not particularly limited as long as they are water-soluble cellulose derivatives. Examples of cellulose-based resins include methyl cellulose, ethyl cellulose, and hydroxypropyl cellulose. These may be used alone or in combination of two or more. As the water-soluble resin (A1-1), vinyl resins and polysaccharides are preferred, and polyvinyl alcohol, polyvinylpyrrolidone, polysaccharides and poly(meth)acrylic acid are more preferred.

[0019] The weight average molecular weight (Mw) of the water-soluble resin (A1-1) is not particularly limited, but is, for example, 1,000 or more and 100,000 or less, or 1,000 or more and 50,000 or less.

[0020] The solubility parameter (SP value) of the water-soluble resin (A1-1) is, for example, 10 or more and 20 or less. The difference in SP value between the water-soluble resin (A1-1) and the solvent (S1) in the photosensitive composition is preferably 2.30 or more. When the SP value is 2.30 or more, mixing between the primer layer and the coating film of the photosensitive composition is unlikely to occur when the photosensitive composition is applied onto the primer layer, which makes it easier to improve the adhesion between the substrate and the cured product layer. In this specification, the SP value is a value calculated by the method of Fedors (RF Fedors: “A Method for Estimating Both the Solubility Parameters and Molar Volumes of Liquids”, Polym. Eng. Sci., Vol. 14, No. 2, 147-154 (1974)).

[0021] The content of the water-soluble resin (A1-1) is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, based on 100% by mass of the total mass (total solids) of the primer composition excluding the mass of the solvent (S) described below. The content is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less. Within the above numerical range, good adhesion is likely to be obtained.

[0022] (Phenolic hydroxyl group-containing resin (A1-2)) The phenolic hydroxyl group-containing resin (A1-2) can be crosslinked with a cyclic ether group-containing compound (A2-1) or a methylol-type crosslinking agent (C) described below to form a curable primer layer. Examples of the phenolic hydroxyl group-containing resin (A1-2) include resins containing structural units derived from hydroxystyrene which may have a substituent, resins containing structural units derived from a (meth)acrylic acid ester having a hydroxyphenyl group which may have a substituent, and novolac resins.

[0023] When the phenolic hydroxyl group-containing resin (A1-2) is a resin containing structural units derived from hydroxystyrene which may have a substituent, or a resin containing structural units derived from a (meth)acrylic acid ester having a hydroxyphenyl group which may have a substituent, the amount of structural units having a phenolic hydroxyl group in the resin is preferably 50 mol % or more, more preferably 70 mol % or more, even more preferably 90 mol % or more, and most preferably 100 mol % based on all structural units.

[0024] As the structural unit derived from hydroxystyrene which may have a substituent, a structural unit represented by the following formula (a1-2-1) is preferred. [ka] (In formula (a1-2-1), R d1 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. d2is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, or a cyano group. n is an integer of 0 to 4. When n is an integer of 2 to 4, multiple R d2 may be the same or different.)

[0025] The alkyl group having from 1 to 6 carbon atoms is, for example, a linear or branched alkyl group having from 1 to 6 carbon atoms. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, and a neopentyl group. The alkoxy group having 1 to 6 carbon atoms is, for example, a linear or branched alkoxy group having 1 to 6 carbon atoms. Examples of the linear or branched alkyl group include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a tert-butyloxy group, an n-pentyloxy group, an isopentyloxy group, an eth ... Examples of the aryloxy group include a pentyloxy group and a neopentyloxy group. Halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0026] Specific preferred examples of the monomer that provides the structural unit represented by formula (a1-2-1) include 4-hydroxystyrene, 3-hydroxystyrene, 2-hydroxystyrene, α-methyl-4-hydroxystyrene, α-methyl-3-hydroxystyrene, α-methyl-2-hydroxystyrene, α-ethyl-4-hydroxystyrene, α-ethyl-3-hydroxystyrene, and α-ethyl-2-hydroxystyrene, etc. Among these, 4-hydroxystyrene, 3-hydroxystyrene, α-methyl-4-hydroxystyrene, and α-methyl-3-hydroxystyrene are preferred, with 4-hydroxystyrene being more preferred.

[0027] As a structural unit derived from a (meth)acrylic acid ester having a hydroxyphenyl group which may have a substituent, a structural unit represented by the following formula (a1-2-2) is preferred. [ka] (In formula (a1-2-2), R d2 and n are the same as those in formula (a1-2-2). d3 is a hydrogen atom or a methyl group. d4 is a single bond or an alkylene group having 1 to 4 carbon atoms.

[0028] R d4 Examples of the alkylene group include a methylene group, an ethane-1,2-diyl group (ethylene group), an ethane-1,1-diyl group, a propane-1,3-diyl group, a propane-1,2-diyl group, a propane-2,2-diyl group, a propane-3,3-diyl group, and a butane-1,4-diyl group. Among these, a methylene group, an ethylene group, a propane-1,3-diyl group, and a butane-1,4-diyl group are preferred, and a methylene group and an ethylene group are more preferred.

[0029] Specific preferred examples of monomers that provide the structural unit represented by formula (a1-2-2) include phenolic hydroxyl group-containing acrylates such as 4-hydroxyphenyl acrylate, 3-hydroxyphenyl acrylate, 2-hydroxyphenyl acrylate, 4-hydroxybenzyl acrylate, 3-hydroxybenzyl acrylate, 2-hydroxybenzyl acrylate, 4-hydroxyphenethyl acrylate, 3-hydroxyphenethyl acrylate, and 2-hydroxyphenethyl acrylate, as well as phenolic hydroxyl group-containing methacrylates such as 4-hydroxyphenyl methacrylate, 3-hydroxyphenyl methacrylate, 2-hydroxyphenyl methacrylate, 4-hydroxybenzyl methacrylate, 3-hydroxybenzyl methacrylate, 2-hydroxybenzyl methacrylate, 4-hydroxyphenethyl methacrylate, 3-hydroxyphenethyl methacrylate, and 2-hydroxyphenethyl methacrylate. Among these, 4-hydroxyphenyl acrylate, 3-hydroxyphenyl acrylate, Preferred are acrylate, 4-hydroxybenzyl acrylate, 3-hydroxybenzyl acrylate, 4-hydroxyphenyl methacrylate, 3-hydroxyphenyl methacrylate, 4-hydroxybenzyl methacrylate, and 3-hydroxybenzyl methacrylate, including 4-hydroxyphenyl acrylate, 4-hydroxybenzyl acrylate, 4-hydroxyphenyl methacrylate, and 4-hydroxybenzyl methacrylate.

[0030] When the phenolic hydroxyl group-containing resin (A1-2) is a polymer of a monomer having an unsaturated bond, the phenolic hydroxyl group-containing resin (A1-2) may be a copolymer of a monomer having a phenolic hydroxyl group and another monomer not having a phenolic hydroxyl group. Examples of such other monomers include known radical polymerizable compounds and anion polymerizable compounds. Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives having a carboxy group and an ester bond such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. (meth)acrylic acid hydroxyalkyl esters such as acrylate; (meth)acrylic acid aryl esters such as phenyl (meth)acrylate and benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene and vinyltoluene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and the like.

[0031] The novolac resin is not particularly limited, and various conventionally known novolac resins can be used. Examples of novolac resins include resins obtained by addition condensation of aromatic compounds having a phenolic hydroxyl group (hereinafter simply referred to as "phenols") and aldehydes in the presence of an acid catalyst.

[0032] (phenols) Examples of phenols used in producing novolac resins include phenol; cresols such as o-cresol, m-cresol, and p-cresol; xylenols such as 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol; ethylphenols such as o-ethylphenol, m-ethylphenol, and p-ethylphenol; 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol, o-butylphenol, m-butylphenol, p-butylphenol, and Examples of suitable phenols include alkylphenols such as p-tert-butylphenol, trialkylphenols such as 2,3,5-trimethylphenol and 3,4,5-trimethylphenol, polyhydric phenols such as resorcinol, catechol, hydroquinone, hydroquinone monomethyl ether, pyrogallol and phloroglucinol, alkylpolyhydric phenols such as alkylresorcinol, alkylcatechol and alkylhydroquinone (all alkyl groups having 1 to 4 carbon atoms), α-naphthol, β-naphthol, hydroxydiphenyl, and bisphenol A. These phenols may be used alone or in combination of two or more.

[0033] (aldehydes) Examples of aldehydes used in producing novolac resins include formaldehyde, paraformaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde. These aldehydes may be used alone or in combination of two or more.

[0034] The phenolic hydroxyl group-containing resin (A1-2) described above is preferably a resin having a structural unit derived from hydroxystyrene which may have a substituent, more preferably a resin having a structural unit derived from hydroxystyrene, even more preferably a homopolymer of hydroxystyrene, and particularly preferably a homopolymer of 4-hydroxystyrene.

[0035] The Mw of the phenolic hydroxyl group-containing resin (A1-2) is not particularly limited, but is, for example, 1,000 or more and 100,000 or less, 1,000 or more and 50,000 or less, or 1,000 or more and 10,000 or less.

[0036] The content of the phenolic hydroxyl group-containing resin (A1-2) is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, based on 100% by mass of the total mass (total solids) of the primer composition excluding the mass of the solvent (S) described below. The content is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less. Within the above numerical range, good adhesion is likely to be obtained.

[0037] [Polymerizable compound (A2)] The polymerizable compound (A2) is a compound that can be polymerized by a polymerization mechanism other than radical polymerization. As the polymerizable compound (A2), a cyclic ether group-containing compound (A2-1) is preferred.

[0038] (Cyclic ether group-containing compound (A2-1)) Examples of the cyclic ether group-containing compound (A2-1) include epoxy compounds and oxetane compounds.

[0039] The epoxy compounds include aromatic epoxy compounds, alicyclic epoxy compounds, and aliphatic epoxy compounds.

[0040] Examples of aromatic epoxy compounds include glycidyl ethers of mono- or polyhydric phenols having at least one aromatic ring (phenol, biphenol, bisphenol A, bisphenol F, phenol novolac, cresol novolac, and brominated products thereof or alkylene oxide adducts thereof), and glycidyl esters (diglycidyl phthalate, diglycidyl-3-methylphthalate, etc.) of mono- or polycarboxylic acids having at least one aromatic ring (phthalic acid, 3-methylphthalic acid, etc.).

[0041] Alicyclic epoxy compounds include compounds obtained by epoxidizing a compound having at least one cyclohexene or cyclopentene ring with an oxidizing agent (3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, cyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexanemetadioxane, bis(3,4-epoxycyclohexylmethyl)adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylenebis(3,4-epoxycyclohexane), dicyclopentadiene diepoxide, and ethylenebis(3,4-epoxycyclohexanecarboxylate).

[0042] Examples of aliphatic epoxy compounds include polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts (1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, and hexaglycidyl ether of dipentaerythritol, etc.), polyglycidyl esters of aliphatic polybasic acids (diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, and diglycidyl hexahydro-3-methylphthalate, etc.), epoxidized products of long-chain unsaturated compounds (epoxidized soybean oil and epoxidized polybutadiene, etc.), glycidyl group-containing polymers (homopolymers of glycidyl (meth)acrylate or copolymers thereof with other unsaturated monomers, etc.), and polyfunctional epoxides having a dimethylsiloxane skeleton (Journal of Polym. Sci., Part 1, pp. 111-114, 2003). A, Polym. Chem., Vol. 28, 497 (1990)).

[0043] Examples of oxetane compounds include 3-ethyl-3-hydroxymethyloxetane, (3-ethyl-3-oxetanylmethoxy)methylbenzene, [1-(3-ethyl-3-oxetanylmethoxy)ethyl]phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-ethyl-3-oxetanylmethyl) ether, 2-ethylhexyl (3-ethyl-3-oxetanylmethyl) ether, and 1-methylphenyl ether. 2-Tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, ethyl diethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether 2-Hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-Hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, Butoxyethyl (3-ethyl-3-oxetanylmethyl) ether, Pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 3,3'-(1,3-(2-methyleneyl)propanediylbis(oxymethylene))bis-(3-ethyloxetane), 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-Bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene(3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether hexakis(3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, 3-ethyl-3-phenoxymethyloxetane , 3-ethyl-3-(4-methylphenoxy)methyloxetane, 3-ethyl-3-(4-fluorophenoxy)methyloxetane, 3-ethyl-3-(1-naphthoxy)methyloxetane, 3-ethyl-3-(2-naphthoxy)methyloxetane, 3-ethyl-3-{[3-(ethoxysilyl)propoxy]methyl}oxetane, oxetanylsilsesquioxetane, and phenol novolac oxetane.

[0044] The content of the cyclic ether group-containing compound (A2-1) is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, based on 100% by mass of the total mass (total solids) of the primer composition excluding the mass of the solvent (S) described below. The content is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less. Within the above numerical range, good adhesion is likely to be obtained.

[0045] (Other base ingredients) Other base component (A) includes materials for forming thermosetting polyurethane (polyols and diisocyanates) and polyamic acids.

[0046] The content of the base component (A) is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, based on 100% by mass of the mass (total solids content) of the primer composition excluding the mass of the solvent (S) described below. The content is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less. Within the above numerical range, good adhesion is likely to be obtained.

[0047] <Compound (B)> Compound (B) has a functional group capable of forming a covalent bond by reaction with the ethylenically unsaturated double bond-containing group in photocurable compound (a). The functional group in compound (B) is at least one selected from the group consisting of an ethylenically unsaturated double bond-containing group, an amino group, a hydrosilyl group, and a thiol group.

[0048] Examples of the ethylenically unsaturated double bond-containing group include a vinyl group and a (meth)acryloyl group. As the compound (B) having an ethylenically unsaturated double bond-containing group, a compound having a (meth)acryloyl group such as a (meth)acrylate compound or a (meth)acrylamide compound is preferred, and a (meth)acrylate compound is more preferred. The compound (B) having an ethylenically unsaturated double bond-containing group includes monofunctional compounds and polyfunctional compounds.

[0049] Examples of the monofunctional compound having an ethylenically unsaturated double bond-containing group include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, N-methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth) Examples of suitable monofunctional compounds include acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerin mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylamino (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and half (meth)acrylates of phthalic acid derivatives. These monofunctional compounds may be used alone or in combination of two or more.

[0050] Examples of polyfunctional compounds having an ethylenically unsaturated double bond-containing group include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexaacrylate, (Meth)acrylate, 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, Examples of suitable polyfunctional compounds include glycerin polyglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., tolylene diisocyanate), a reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, and 2-hydroxyethyl (meth)acrylate, methylene bis(meth)acrylamide, (meth)acrylamide methylene ether, and a condensation product of a polyhydric alcohol and N-methylol (meth)acrylamide, as well as triacryl formal. These polyfunctional compounds may be used alone or in combination of two or more.

[0051] As the compound (B) having an amino group, an olefin polymer containing a structural unit derived from an olefin having an amino group and polyethyleneimine are preferred, and polyethyleneimine is more preferred.

[0052] With regard to the olefin polymer containing a structural unit derived from an olefin having an amino group, examples of the olefin having an amino group include allylamine, 3-butenylamine, 4-pentenylamine, and 5-hexenylamine. The content of the structural units derived from an olefin having an amino group in the olefin-based polymer is not particularly limited, and is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 100% by mass. For the olefin polymer, other olefins that may be copolymerized with the olefin having an amino group include chain olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-dodecene, and cyclic olefins such as cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclohexadiene, cycloheptadiene, and cyclooctadiene.

[0053] Polyethyleneimine is a polymer having the following partial structure: As the polyethyleneimine, either branched-chain polyethyleneimine or linear-chain polyethyleneimine can be used. [ka]

[0054] The compound (B) having a hydrosilyl group includes an organosiloxane compound having a hydrosilyl group. Examples of organosiloxane compounds having a hydrosilyl group include organosiloxanes in which the main chain of a cyclic compound or a linear or branched chain compound is composed solely of siloxane units (—Si—O—).

[0055] The organosiloxane compound having a hydrosilyl group is obtained by hydrolysis and condensation of one or more organosilanes represented by the following formula, and has at least one hydrosilyl group and the following R 4 and hydrolysis condensates having at least one monovalent organic group having 1 to 50 carbon atoms in one molecule, which is derived from the above. [ka] (In the formula, R 4 is a hydrogen atom or a monovalent organic group having 1 to 50 carbon atoms, and R 5 is a monovalent organic group, and x is an integer of 0 or more and 2 or less. The hydrolysis condensate belongs to the above-mentioned organosiloxane whose main chain is composed only of siloxane units (—Si—O—).

[0056] Here, examples of the monovalent organic group include an alkyl group, an aryl group, an allyl group, and a glycidyl group, and among these, an alkyl group and an aryl group are preferred. R 4 The monovalent organic group having 1 to 50 carbon atoms as the aryl group is preferably an alkyl group or an aryl group having 1 to 20 carbon atoms. The number of carbon atoms in the alkyl group is preferably 1 to 5, and specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, and a butyl group. The alkyl group may be linear or branched, and a hydrogen atom in the alkyl group may be substituted with a fluorine atom. The aryl group is preferably a group having 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

[0057] The compound (B) having a thiol group includes a polyfunctional thiol compound. Specific examples of the polyfunctional thiol compound (B) include 1,2-benzenedithiol, 1,3-benzenedithiol, 1,4-benzenedithiol, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris(mercaptomethyl)benzene, 1,2,4-tris(mercaptomethyl)benzene, 1,3,5-tris(mercaptomethyl)benzene, 1,2,3-tris(mercaptoethyl)benzene, 1,2,4-tris(mercaptoethyl)benzene, 1,3,5-tris(mercaptomethyl)benzene, (mercaptoethyl)benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 1,3-di(p-methoxyphenyl)propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di(p-mercaptophenyl)pentane, 1,2-bis(mercaptoethylthio)benzene, 1,3-bis(mercaptoethylthio)benzene, 1,4-bis(mercaptoethylthio)benzene, 1,2,3-tris(mercaptomethylthio)benzene, 1,2,4-tris(mercaptomethylthio)benzene, 1,3,5-tris(mercaptomethylthio)benzene, 1,2,3-tris(mercaptoethylthio)benzene, 1,2,4-tris(mercaptoethylthio)benzene, and 1,3,5-tris(mercaptoethylthio)benzene.

[0058] The content of compound (B) is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more, based on 100% by mass of the total mass (total solids) of the primer composition excluding the mass of the solvent (S) described below. The content is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less. Within the above numerical range, good adhesion is likely to be obtained.

[0059] The content of compound (B) is preferably 20 parts by mass or more, more preferably 50 parts by mass or more, and even more preferably 80 parts by mass or more, per 100 parts by mass of base component (A). The content is preferably 500 parts by mass or less, more preferably 200 parts by mass or less, and even more preferably 125 parts by mass or less. Within the above numerical range, good adhesion is likely to be obtained.

[0060] <Methylol-type crosslinker (C)> When the primer composition contains the phenolic hydroxyl group-containing resin (A1-2), it preferably further contains a methylol-type crosslinking agent (C). The methylol crosslinking agent (C) is a crosslinking agent having two or more crosslinkable groups selected from a methylol group and an alkoxymethyl group.

[0061] Examples of the methylol-type crosslinking agent (C) include melamine-based crosslinking agents, urea-based crosslinking agents, alkylene urea-based crosslinking agents, glycoluril-based crosslinking agents, and phenol-based crosslinking agents. In the following description, "lower" means having 1 to 5 carbon atoms.

[0062] Examples of melamine-based crosslinking agents include compounds obtained by reacting melamine with formaldehyde to substitute the hydrogen atoms of the amino groups with hydroxymethyl groups, and compounds obtained by reacting melamine, formaldehyde, and a lower alcohol to substitute the hydrogen atoms of the amino groups with lower alkoxymethyl groups. Specific examples include hexamethoxymethylmelamine, hexaethoxymethylmelamine, hexapropoxymethylmelamine, and hexabutoxybutylmelamine. Of these, hexamethoxymethylmelamine is preferred.

[0063] Examples of urea-based crosslinking agents include compounds in which urea and formaldehyde are reacted to replace the hydrogen atoms of the amino groups with hydroxymethyl groups, and compounds in which urea, formaldehyde, and a lower alcohol are reacted to replace the hydrogen atoms of the amino groups with lower alkoxymethyl groups. Specific examples include bismethoxymethylurea, bisethoxymethylurea, bispropoxymethylurea, and bisbutoxymethylurea. Among these, bismethoxymethylurea is preferred.

[0064] The alkylene urea crosslinking agent may be a compound represented by the following formula (CA-1).

[0065] [ka] (In formula (CA-1), Rc 1 and Rc 2 Rc is independently a hydroxyl group or a lower alkoxy group. 3 and Rc 4 are each independently a hydrogen atom, a hydroxyl group, or a lower alkoxy group, and vc is an integer of 0 or more and 2 or less.

[0066] Rc 1 and Rc 2 When Rc is a lower alkoxy group, it is preferably an alkoxy group having 1 to 4 carbon atoms, and may be linear or branched. 1 and Rc 2 and may be the same or different from each other, and are more preferably the same. Rc 3 and Rc 4 When Rc is a lower alkoxy group, it is preferably an alkoxy group having 1 to 4 carbon atoms, and may be linear or branched. 3 and Rc 4 and may be the same or different from each other, and are more preferably the same. vc is preferably 0 or 1. As the alkylene urea crosslinking agent, a compound in which vc is 0 (ethylene urea crosslinking agent) and / or a compound in which vc is 1 (propylene urea crosslinking agent) are particularly preferred.

[0067] The compound represented by the above formula (CA-1) can be obtained by condensing alkylene urea with formalin and then reacting the resulting product with a lower alcohol.

[0068] Specific examples of alkylene urea-based crosslinking agents include ethylene urea-based crosslinking agents such as mono- and / or dihydroxymethylated ethylene urea, mono- and / or dimethoxymethylated ethylene urea, mono- and / or diethoxymethylated ethylene urea, mono- and / or dipropoxymethylated ethylene urea, and mono- and / or dibutoxymethylated ethylene urea; propylene urea-based crosslinking agents such as mono- and / or dihydroxymethylated propylene urea, mono- and / or dimethoxymethylated propylene urea, mono- and / or diethoxymethylated propylene urea, mono- and / or dipropoxymethylated propylene urea, and mono- and / or dibutoxymethylated propylene urea; 1,3-di(methoxymethyl)-4,5-dihydroxy-2-imidazolidinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone, and the like.

[0069] Examples of glycoluril crosslinking agents include glycoluril derivatives in which the N-position is substituted with one or both of a hydroxyalkyl group and an alkoxyalkyl group having from 1 to 4 carbon atoms. The glycoluril derivatives can be obtained by condensation reaction of glycoluril with formalin and then by reacting the product with a lower alcohol. Specific examples of glycoluril-based crosslinking agents include mono-, di-, tri-, and / or tetrahydroxymethylated glycoluril; mono-, di-, tri-, and / or tetramethoxymethylated glycoluril; mono-, di-, tri-, and / or tetraethoxymethylated glycoluril; mono-, di-, tri-, and / or tetrapropoxymethylated glycoluril; and mono-, di-, tri-, and / or tetrabutoxymethylated glycoluril.

[0070] The phenol-based crosslinking agent is not particularly limited, and any compound having multiple phenol nucleus structures in the same molecule can be selected and used. The presence of multiple phenol nucleus structures improves crosslinking reactivity. The number of phenol nucleus structures is preferably 2 or more and 5 or less, more preferably 2 or more and 4 or less, and even more preferably 2 or 3.

[0071] Specific examples of glycoluril-based crosslinking agents or phenol-based crosslinking agents are shown below.

[0072] [ka]

[0073] In the primer composition, the methylol crosslinking agent (C) may be used alone or in combination of two or more kinds.

[0074] The content of the methylol crosslinking agent (C) is preferably 0.5% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, based on 100% by mass of the mass (total solids content) of the primer composition excluding the mass of the solvent (S) described below. The content is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. Within the above numerical range, good adhesion is likely to be obtained.

[0075] The content of the methylol crosslinking agent (C) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 10 parts by mass or more, per 100 parts by mass of the phenolic hydroxyl group-containing resin (A1-2). The content is preferably 60 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 30 parts by mass or less. Within the above numerical range, good adhesion is likely to be obtained.

[0076] <Acid generator (D)> When the primer composition contains a cyclic ether group-containing compound (A2-1) or when the primer composition contains a phenolic hydroxyl group-containing resin (A1-2) and a cyclic ether group-containing compound (A2-1) and / or a methylol-type crosslinking agent (C), it is preferable that the primer composition further contains an acid generator (D).

[0077] The acid generator (D) is a compound that generates an acid when irradiated with actinic rays or radiation, and is not particularly limited as long as it is a compound that generates an acid directly or indirectly when exposed to light. Preferred examples of acid generators that can be suitably used will be described below.

[0078] A first example of a suitable acid generator is a compound represented by the following formula (a1).

[0079] [ka]

[0080] In the above formula (a1), X 1arepresents a sulfur atom or iodine atom with a valence of g, where g is 1 or 2. h represents the number of repeating units of the structure in parentheses. R 1a is X 1a and represents an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an alkynyl group having 2 to 30 carbon atoms, and R 1a R may be substituted with at least one selected from the group consisting of alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthiocarbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro, and halogen. 1a The number of is g+h(g-1)+1, and R 1a may be the same or different from each other. 1a are directly connected to each other, or -O-, -S-, -SO-, -SO2-, -NH-, -NR 2a -, -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group; 1a may form a ring structure containing R 2a is an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.

[0081] X 2a is a structure represented by the following formula (a2).

[0082] [ka]

[0083] In the above formula (a2), X 4arepresents an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent group of a heterocyclic compound having 8 to 20 carbon atoms; X 4a X may be substituted with at least one selected from the group consisting of alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, aryl having 6 to 10 carbon atoms, hydroxy, cyano, nitro, and halogen. 5a -O-, -S-, -SO-, -SO2-, -NH-, -NR 2a represents -, -CO-, -COO-, -CONH-, an alkylene group having 1 to 3 carbon atoms, or a phenylene group. h represents the number of repeating units of the structure in parentheses. h+1 X 4a and h X's 5a may be the same or different. 2a is the same as defined above.

[0084] X 3a- is a counter ion of the onium, and examples thereof include a fluorinated alkylfluorophosphate anion represented by the following formula (a17) or a borate anion represented by the following formula (a18).

[0085] [ka]

[0086] In the above formula (a17), R 3a represents an alkyl group in which 80% or more of the hydrogen atoms are substituted with fluorine atoms. j represents the number of R groups, and is an integer of 1 to 5. 3a may be the same or different.

[0087] [ka]

[0088] In the above formula (a18), R 4a ~R 7aeach independently represents a fluorine atom or a phenyl group, and some or all of the hydrogen atoms of the phenyl group may be substituted with at least one selected from the group consisting of a fluorine atom and a trifluoromethyl group.

[0089] Examples of the onium ion in the compound represented by the formula (a1) include triphenylsulfonium, tri-p-tolylsulfonium, 4-(phenylthio)phenyldiphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, 4-(4-benzoyl-2-chlorophenylthio)phenylbis (4-Fluorophenyl)sulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-(4-benzoylphenylthio)phenyldiphenyl sulfonium, diphenylphenacylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylphenacylsulfonium, phenyl[4-(4-biphenylthio)phenyl]4-biphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]3-biphenylsulfonium, [4-(4-acetophenylthio)phenyl]diphenylsulfonium, octadecylmethylphenacylsulfonium, diphenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octyloxyphenyl)phenyliodonium, bis(4-decyloxy)phenyliodonium, 4-(2-hydroxytetradecyloxy)phenylphenyliodonium, 4-isopropylphenyl(p-tolyl)iodonium, or 4-isobutylphenyl(p-tolyl)iodonium.

[0090] Of the onium ions in the compound represented by the above formula (a1), preferred onium ions include sulfonium ions represented by the following formula (a19).

[0091] [ka]

[0092] In the above formula (a19), R 8a X each independently represents a group selected from the group consisting of a hydrogen atom, alkyl, hydroxy, alkoxy, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, a halogen atom, an aryl which may have a substituent, and an arylcarbonyl which may have a substituent. 2a is X in the above formula (a1). 2a It has the same meaning as:

[0093] Specific examples of the sulfonium ion represented by the above formula (a19) include 4-(phenylthio)phenyldiphenylsulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyldiphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]4-biphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]3-biphenylsulfonium, [4-(4-acetophenylthio)phenyl]diphenylsulfonium, and diphenyl[4-(p-terphenylthio)phenyl]diphenylsulfonium.

[0094] In the fluorinated alkylfluorophosphate anion represented by the above formula (a17), R 3arepresents an alkyl group substituted with a fluorine atom, preferably having 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The proportion of hydrogen atoms in the alkyl group substituted with fluorine atoms is usually 80% or more, preferably 90% or more, and more preferably 100%. If the fluorine atom substitution rate is less than 80%, the acid strength of the onium fluorinated alkylfluorophosphate represented by formula (a1) will be reduced.

[0095] Particularly preferred R 3a is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and a fluorine atom substitution rate of 100%, and specific examples include CF3, CF3CF2, (CF3)2CF, CF3CF2CF2, CF3CF2CF2CF2, (CF3)2CFCF2, CF3CF2(CF3)CF, and (CF3)3C. 3a The number j is an integer of 1 or more and 5 or less, preferably 2 or more and 4 or less, and particularly preferably 2 or 3.

[0096] A specific example of a preferred fluorinated alkyl fluorophosphate anion is [(CF3CF2)2PF4] - , [(CF3CF2)3PF3] - , [((CF3)2CF)2PF4] - , [((CF3)2CF)3PF3] - , [(CF3CF2CF2)2PF4] - , [(CF3CF2CF2)3PF3] - , [((CF3)2CFCF2)2PF4] - , [((CF3)2CFCF2)3PF3] - , [(CF3CF2CF2CF2)2PF4] - , or [(CF3CF2CF2)3PF3] - Among these, [(CF3CF2)3PF3]- , [(CF3CF2CF2)3PF3] - , [((CF3)2CF)3PF3] - , [((CF3)2CF)2PF4] - , [((CF3)2CFCF2)3PF3] - , or [((CF3)2CFCF2)2PF4] - is particularly preferred.

[0097] A preferred example of the borate anion represented by the formula (a18) is tetrakis(pentafluorophenyl)borate ([B(C6F5)4] - ), tetrakis[(trifluoromethyl)phenyl]borate ([B(C6H4CF3)4] - ), difluorobis(pentafluorophenyl)borate ([(C6F5)2BF2] - ), trifluoro(pentafluorophenyl)borate ([(C6F5)BF3] - ), tetrakis(difluorophenyl)borate ([B(C6H3F2)4] - Among these, tetrakis(pentafluorophenyl)borate ([B(C6F5)4] - ) is particularly preferred.

[0098] Second examples of suitable acid generators include 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-ethyl-2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-propyl-2-furyl)ethenyl]-s-triazine, 2,4 -Bis(trichloromethyl)-6-[2-(3,5-dimethoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-diethoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dipropoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-ethoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-propoxyphenyl)ethenyl]-s-triazine 2,4-bis(trichloromethyl)-6-[2-(3,4-methylenedioxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-(3,4-methylenedioxyphenyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine Azine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(2-furyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(5-methyl-2-furyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,Examples of halogen-containing triazine compounds include 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methylenedioxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, tris(1,3-dibromopropyl)-1,3,5-triazine, and tris(2,3-dibromopropyl)-1,3,5-triazine, as well as halogen-containing triazine compounds represented by the following formula (a3), such as tris(2,3-dibromopropyl)isocyanurate.

[0099] [ka]

[0100] In the above formula (a3), R 9a , R 10a , R 11a each independently represents a halogenated alkyl group.

[0101] A third example of a suitable acid generator includes α-(p-toluenesulfonyloxyimino)-phenylacetonitrile, α-(benzenesulfonyloxyimino)-2,4-dichlorophenylacetonitrile, α-(benzenesulfonyloxyimino)-2,6-dichlorophenylacetonitrile, α-(2-chlorobenzenesulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, 2-[2-(propylsulfonyloxyimino)thiophen-3(2H)-ylidene]-2-(2-methylphenyl)acetonitrile, and oxime sulfonate compounds such as compounds represented by the following formula (a4) containing an oxime sulfonate group:

[0102] [ka]

[0103] In the above formula (a4), R 12a represents a monovalent, divalent, or trivalent organic group; R 13a represents a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic compound group, and n represents the number of repeating units of the structure in the parentheses.

[0104] In the above formula (a4), the aromatic compound group refers to a group of a compound that exhibits physical and chemical properties specific to aromatic compounds, and examples thereof include aryl groups such as phenyl and naphthyl groups, and heteroaryl groups such as furyl and thienyl groups. These may have one or more suitable substituents on the ring, such as halogen atoms, alkyl groups, alkoxy groups, and nitro groups. In addition, R 13a is particularly preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group. 12a is an aromatic compound group, and R 13a is an alkyl group having 1 to 4 carbon atoms.

[0105] The photoacid generator represented by the above formula (a4) is, when n=1, 12a is a phenyl group, a methylphenyl group, or a methoxyphenyl group, and R 13a is a methyl group, specifically α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylphenyl)acetonitrile, α-(methylsulfonyloxyimino)-1-(p-methoxyphenyl)acetonitrile, [2-(propylsulfonyloxyimino)-2,3-dihydroxythiophen-3-ylidene](o-tolyl)acetonitrile, etc. When n=2, specific examples of the photoacid generator represented by the above formula (a4) include acid generators represented by the following formula:

[0106] [ka]

[0107] A fourth example of a suitable acid generator is an onium salt having a naphthalene ring in the cation moiety. "Having a naphthalene ring" here means having a structure derived from naphthalene, and means that at least two ring structures and their aromaticity are maintained. The naphthalene ring may have a substituent such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. The structure derived from the naphthalene ring may be a monovalent group (having one free valence) or a divalent group (having two or more free valences), but a monovalent group is preferable (however, in this case, the free valence is counted excluding the portion bonded to the above-mentioned substituent). The number of naphthalene rings is preferably 1 to 3.

[0108] The cation moiety of such an onium salt having a naphthalene ring at the cation moiety is preferably a structure represented by the following formula (a5).

[0109] [ka]

[0110] In the above formula (a5), R 14a , R 15a , R 16a At least one of R represents a group represented by the following formula (a6), and the rest represent a linear or branched alkyl group having from 1 to 6 carbon atoms, a phenyl group which may have a substituent, a hydroxyl group, or a linear or branched alkoxy group having from 1 to 6 carbon atoms. 14a , R 15a , R 16a One of the groups is a group represented by the following formula (a6), and the remaining two groups are each independently a linear or branched alkylene group having from 1 to 6 carbon atoms, and the ends of these groups may be bonded to form a ring.

[0111] [ka]

[0112] In the above formula (a6), R 17a , R 18a each independently represents a hydroxyl group, a linear or branched alkoxy group having from 1 to 6 carbon atoms, or a linear or branched alkyl group having from 1 to 6 carbon atoms; R 19a represents a single bond or a linear or branched alkylene group having 1 to 6 carbon atoms which may have a substituent. l and m each independently represent an integer of 0 to 2, and l+m is 3 or less. However, R 17a When there are multiple R, they may be the same or different. 18a When there are a plurality of groups, they may be the same or different.

[0113] Above R 14a , R 15a , R 16a Among these, the number of groups represented by the above formula (a6) is preferably one from the viewpoint of compound stability, and the rest are linear or branched alkylene groups having from 1 to 6 carbon atoms, the ends of which may be bonded to form a ring. In this case, the two alkylene groups, including the sulfur atom, form a 3- to 9-membered ring. The number of atoms (including the sulfur atom) constituting the ring is preferably 5 to 6.

[0114] Furthermore, examples of the substituent that the alkylene group may have include an oxygen atom (which in this case forms a carbonyl group together with the carbon atom that constitutes the alkylene group), a hydroxyl group, and the like.

[0115] In addition, examples of the substituent that the phenyl group may have include a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a linear or branched alkyl group having 1 to 6 carbon atoms.

[0116] Suitable examples of these cation moieties include those represented by the following formulae (a7) and (a8), and the structure represented by the following formula (a8) is particularly preferred.

[0117] [ka]

[0118] Such a cation moiety may be either an iodonium salt or a sulfonium salt, but from the standpoint of acid generation efficiency and the like, a sulfonium salt is preferred.

[0119] Therefore, anions that can form sulfonium salts are preferred as the anion moiety of onium salts having a naphthalene ring in the cation moiety.

[0120] The anion moiety of such an acid generator is a fluoroalkylsulfonate ion or an arylsulfonate ion in which some or all of the hydrogen atoms have been fluorinated.

[0121] The alkyl group in the fluoroalkylsulfonate ion may be linear, branched, or cyclic and have from 1 to 20 carbon atoms, and preferably has from 1 to 10 carbon atoms in view of the bulkiness of the generated acid and its diffusion distance. Branched and cyclic groups are particularly preferred because they have a short diffusion distance. Furthermore, preferred groups include methyl, ethyl, propyl, butyl, and octyl groups because they can be synthesized inexpensively.

[0122] The aryl group in the arylsulfonate ion is an aryl group having from 6 to 20 carbon atoms, and examples thereof include a phenyl group and a naphthyl group which may or may not be substituted with an alkyl group or a halogen atom. In particular, an aryl group having from 6 to 10 carbon atoms is preferred because it can be synthesized inexpensively. Specific examples of preferred groups include a phenyl group, a toluenesulfonyl group, an ethylphenyl group, a naphthyl group, and a methylnaphthyl group.

[0123] In the above-mentioned fluoroalkylsulfonate ions or arylsulfonate ions, when some or all of the hydrogen atoms are fluorinated, the fluorination rate is preferably 10% or more and 100% or less, more preferably 50% or more and 100% or less, and in particular, those in which all the hydrogen atoms are substituted with fluorine atoms are preferred because they have a stronger acid strength. Specific examples of such fluorine ions include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctane sulfonate, and perfluorobenzenesulfonate.

[0124] Among these, preferred anion moieties include those represented by the following formula (a9).

[0125] [ka]

[0126] In the above formula (a9), R 20a are groups represented by the following formulae (a10), (a11), and (a12).

[0127] [ka]

[0128] In the formula (a10), x represents an integer of 1 or more and 4 or less. In the formula (a11), R 21a represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having from 1 to 6 carbon atoms, or a linear or branched alkoxy group having from 1 to 6 carbon atoms, and y represents an integer of from 1 to 3. Among these, trifluoromethanesulfonate and perfluorobutanesulfonate are preferred from the viewpoint of safety.

[0129] The anion moiety may also be one containing nitrogen and represented by the following formulas (a13) and (a14).

[0130] [ka]

[0131] In the above formulas (a13) and (a14), X a represents a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the alkylene group has 2 to 6 carbon atoms, preferably 3 to 5 carbon atoms, and most preferably 3 carbon atoms. a , Z a each independently represents a linear or branched alkyl group in which at least one hydrogen atom has been substituted with a fluorine atom, and the alkyl group has 1 or more and 10 or less carbon atoms, preferably 1 or more and 7 or less, and more preferably 1 or more and 3 or less carbon atoms.

[0132] X a The number of carbon atoms in the alkylene group, or Y a , Z a The smaller the number of carbon atoms in the alkyl group, the better the solubility in organic solvents, and therefore the more preferable.

[0133] Also, X a or an alkylene group of Y a , Z a In the alkyl group, the greater the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, which is preferable. The proportion of fluorine atoms in the alkylene group or alkyl group, i.e., the fluorination rate, is preferably 70% or more and 100% or less, more preferably 90% or more and 100% or less, and most preferably a perfluoroalkylene group or perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms.

[0134] Preferred onium salts having a naphthalene ring in the cation moiety include compounds represented by the following formulae (a15) and (a16).

[0135] [ka]

[0136] A sixth example of a suitable acid generator includes bissulfonyldiazomethanes such as bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, and bis(2,4-dimethylphenylsulfonyl)diazomethane; nitrobenzyl derivatives such as 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzyl sulfonate, nitrobenzyl carbonate, and dinitrobenzyl carbonate; pyrogallol trimesylate, pyrogallol tritosylate, benzyl tosylate, benzyl sulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, and N-methylsulfonyloxysuccinimide. trifluoromethanesulfonic acid esters such as N-hydroxyphthalimide and N-hydroxynaphthalimide; onium salts such as diphenyliodonium hexafluorophosphate, (4-methoxyphenyl)phenyliodonium trifluoromethanesulfonate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, and (p-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonate; benzoin tosylates such as benzoin tosylate and α-methylbenzoin tosylate; other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts, and benzyl carbonate.

[0137] Other examples of acid generators include bis(p-toluenesulfonyl)diazomethane, methylsulfonyl-p-toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1-(1,1-dimethylethylsulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(1-methylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, bis(4-ethylphenylsulfonyl)diazomethane, bis(3-methylphenylsulfonyl)diazomethane, and bis(4-methoxyphenylsulfonyl). bissulfonyldiazomethanes such as bis(4-tert-butylphenylsulfonyl)diazomethane, bis(4-fluorophenylsulfonyl)diazomethane, bis(4-chlorophenylsulfonyl)diazomethane, and bis(4-tert-butylphenylsulfonyl)diazomethane; sulfonylcarbonylalkanes such as 2-methyl-2-(p-toluenesulfonyl)propiophenone, 2-(cyclohexylcarbonyl)-2-(p-toluenesulfonyl)propane, 2-methanesulfonyl-2-methyl-(p-methylthio)propiophenone, and 2,4-dimethyl-2-(p-toluenesulfonyl)pentan-3-one;1-p-toluenesulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-methylsulfonyl-4-phenyl-2-butanone, 1-cyclohexylsulfonyl-1-cyclohexylcarbonyldiazomethane, 1-diazo-1-cyclohexylsulfonyl-3,3-dimethyl-2-butanone, 1-diazo-1-(1,1-dimethylethylsulfonyl)-3,3-dimethyl-2-butanone, 1-acetyl-1-(1-methylethylsulfonyl)diazomethane, 1-diazo-1-(p-toluenesulfonyl) 1-Diazo-1-benzenesulfonyl-3,3-dimethyl-2-butanone, 1-Diazo-1-(p-toluenesulfonyl)-3-methyl-2-butanone, 2-Diazo-2-(p-toluenesulfonyl)cyclohexyl acetate, 2-Diazo-2-benzenesulfonylacetate-tert-butyl, 2-Diazo-2-methanesulfonylacetate isopropyl, 2-Diazo-2-benzenesulfonylacetate-cyclohexyl, 2-Diazo-2-(p-toluenesulfonyl)acetic acid-tert- butyl etc.; nitrobenzyl derivatives such as 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, 2,4-dinitrobenzyl p-trifluoromethylbenzenesulfonate etc.; methanesulfonate ester of pyrogallol, benzenesulfonate ester of pyrogallol, p-toluenesulfonate ester of pyrogallol, p-methoxybenzenesulfonate ester of pyrogallol, mesitylenesulfonate ester of pyrogallol, pyrogallol Examples include esters of polyhydroxy compounds with aliphatic or aromatic sulfonic acids, such as benzylsulfonate ester of rogalol, methanesulfonate ester of alkyl gallate, benzenesulfonate ester of alkyl gallate, p-toluenesulfonate ester of alkyl gallate, p-methoxybenzenesulfonate ester of alkyl gallate (the alkyl group has 1 to 15 carbon atoms), mesitylenesulfonate ester of alkyl gallate, and benzylsulfonate ester of alkyl gallate; These acid generators can be used alone or in combination of two or more.

[0138] The content of the acid generator (C) is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 3% by mass or more, based on 100% by mass of the total mass (total solids) of the primer composition excluding the mass of the solvent (S) described below. The content is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less. Within the above numerical range, good adhesion is likely to be obtained.

[0139] The content of the acid generator (C) is preferably 1 part by mass or more, more preferably 5 parts by mass or more, and even more preferably 8 parts by mass or more, per 100 parts by mass of the base component (A). The content is preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 20 parts by mass or less. Within the above numerical range, good adhesion is likely to be obtained.

[0140] <Solvent (S)> The type of solvent (S) is not particularly limited, but is typically an organic solvent. The type of organic solvent is not particularly limited as long as it can uniformly dissolve or disperse the components contained in the primer composition.

[0141] Examples of organic solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol (Poly)alkylene glycol monoalkyl ethers such as glycol monomethyl ether and tripropylene glycol monoethyl ether; (poly)alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone; alkyl lactate esters such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate;Ethyl 2-hydroxy-2-methylpropionate, Methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, Ethyl 3-ethoxypropionate, Ethoxyethyl acetate, Ethyl hydroxyacetate, Methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, Ethyl acetate, n-propyl acetate, Isopropyl acetate, n-butyl acetate, Isobutyl acetate, n-pentyl formate Examples of suitable esters include butyl acetate, isopentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; amides such as N-methylpyrrolidone, N,N-dimethylformamide, and N,N-dimethylacetamide; and alcohols such as ethanol, isopropyl alcohol, and butanol. These may be used alone or in combination of two or more.

[0142] The content of the solvent (S) is not particularly limited. In terms of film-forming properties, the solvent is used so that the solid content concentration is preferably 0.1% by mass or more and 99% by mass or less, more preferably 0.1% by mass or more and 50% by mass or less, when the mass of the primer composition excluding the mass of the solvent (E) is taken as the solid content.

[0143] <Other ingredients> The primer composition may contain various additives in addition to the components described above. Preferred additives include dispersants, adhesion promoters such as silane coupling agents, antioxidants, anti-aggregation agents, and anti-foaming agents.

[0144] <Application> The primer composition is used to form a primer layer between a substrate and a cured product layer formed from a cured product of a photosensitive composition when the cured product layer is formed on the substrate. The photosensitive composition contains a photocurable compound (a) having an ethylenically unsaturated double bond-containing group and a photopolymerization initiator (b).

[0145] Examples of the ethylenically unsaturated double bond-containing group in the photocurable compound (a) include a vinyl group and a (meth)acryloyl group.

[0146] As the photocurable compound (a) having an ethylenically unsaturated double bond-containing group, a compound having a (meth)acryloyl group such as a (meth)acrylate compound or a (meth)acrylamide compound is preferred, and a (meth)acrylate compound is more preferred. The photocurable compound (a) having an ethylenically unsaturated double bond-containing group includes monofunctional compounds and polyfunctional compounds.

[0147] Examples of the monofunctional compound include (meth)acrylamide, methylol (meth)acrylamide, methoxymethyl (meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, N-methylol (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethyl (meth)acrylate, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, methyl ... Examples of the monofunctional compounds include ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropyl phthalate, glycerin mono(meth)acrylate, tetrahydrofurfuryl (meth)acrylate, dimethylamino (meth)acrylate, glycidyl (meth)acrylate, 2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, and half (meth)acrylates of phthalic acid derivatives. These monofunctional compounds may be used alone or in combination of two or more.

[0148] Examples of polyfunctional compounds include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexane glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate. , 2,2-bis(4-(meth)acryloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloxypolyethoxyphenyl)propane, 2-hydroxy-3-(meth)acryloyloxypropyl (meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, phthalic acid diglycidyl ester di(meth)acrylate, glycerin triacrylate, glycerin poly Examples of suitable polyfunctional compounds include triglycidyl ether poly(meth)acrylate, urethane (meth)acrylate (i.e., tolylene diisocyanate), a reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate, and 2-hydroxyethyl (meth)acrylate, methylene bis(meth)acrylamide, (meth)acrylamide methylene ether, and a condensation product of a polyhydric alcohol and N-methylol (meth)acrylamide, as well as triacryl formal. These polyfunctional compounds may be used alone or in combination of two or more.

[0149] Examples of the photopolymerization initiator (b) include the same compounds as the acid generator (D) in the primer composition.

[0150] The photosensitive composition may contain a solvent (S1). Examples of the solvent (S1) include compounds similar to those used as the solvent (S) in the primer composition.

[0151] The SP value of the solvent (S1) is not particularly limited, but is, for example, 7 or more and 11 or less.

[0152] <Laminate> The laminate includes a substrate, a primer layer derived from a primer composition, and a cured product layer made of a cured product of a photosensitive composition.

[0153] <Substrate> Examples of the substrate include substrates used for manufacturing semiconductor devices (for example, various inorganic substrates and organic substrates). Examples of materials for the inorganic substrate include various metals such as copper, aluminum, iron, and tungsten, alloys thereof, silicon, and glass. Examples of materials for the organic substrate include various resin materials such as polyester resins such as PET resin and PBT resin, various nylons, polyimide resins, polyamide-imide resins, polyolefins such as polyethylene and polypropylene, polystyrene, (meth)acrylic resins, and polycarbonate resins. Among these, a substrate made of silicon, polycarbonate resin, or glass is preferable.

[0154] The thickness of the primer layer is, for example, 5 nm or more and 50 nm or less. The thickness of the cured layer is, for example, 10 nm or more and 200 μm or less.

[0155] <Method of manufacturing laminate> Examples of methods for producing laminates include a method comprising the steps of applying a primer composition to a substrate and drying it to form a primer layer (hereinafter also referred to as a "primer layer forming step"); applying a photosensitive composition to the substrate on which the primer layer has been formed to form a photosensitive composition layer (hereinafter also referred to as a "photosensitive composition layer forming step"); and exposing the photosensitive composition layer to form a cured layer (hereinafter also referred to as a "cured layer forming step"). In the above method, if components other than compound (B) in the primer composition can be polymerized or crosslinked, the components other than compound (B) in the primer composition are polymerized or crosslinked before the application of the photosensitive composition.

[0156] [Primer layer formation process] The method for applying the primer composition is not particularly limited. For example, a coating film can be formed by applying the primer composition to a substrate to a desired thickness using a contact transfer coating device such as a roll coater, reverse coater, bar coater, or slit coater, or a non-contact coating device such as a spinner (rotary coating device) or curtain flow coater. Alternatively, a coating film can be formed by a method such as dip coating or various printing methods such as inkjet printing or gravure printing.

[0157] The method for drying the coating film is not particularly limited, and conventionally known methods such as natural drying and heat drying can be used.

[0158] When the components in the primer composition other than the compound (B) can be polymerized or crosslinked, the components in the primer composition other than the compound (B) are polymerized or crosslinked. The method is not particularly limited; if the components other than the compound (B) are photocurable, the coating film can be exposed to light, or if the components are thermocurable, the coating film can be heated to obtain a cured primer layer. The conditions for exposing the coating film are not particularly limited as long as the curing proceeds well. The exposure is carried out, for example, by irradiating with active energy rays such as ultraviolet light or excimer laser light. The amount of energy radiation to be irradiated is not particularly limited, but may be, for example, 30 mJ / cm. 2 More than 5000mJ / cm2 The following are included:

[0159] [Photosensitive composition layer forming process] The method for applying the photosensitive composition to form the photosensitive composition layer is not particularly limited, and may be the same as the method for applying a primer composition or the method for drying a coating film.

[0160] [Cured material layer formation process] The method for exposing the photosensitive composition layer is not particularly limited. The exposure conditions are not particularly limited as long as the curing proceeds well. The exposure is carried out by irradiating with active energy rays such as ultraviolet rays and excimer laser light. The amount of energy radiation to be irradiated is not particularly limited, but is, for example, 30 mJ / cm. 2 More than 5000mJ / cm 2 The following are included:

[0161] The formed cured product layer may be patterned as necessary. The patterning method is not particularly limited, and examples include a method of position-selectively exposing the photosensitive composition layer (photolithography) and a method comprising pressing a mold having a concave-convex pattern against the photosensitive composition layer to transfer the concave-convex pattern to the photosensitive composition layer, exposing the photosensitive composition layer with the transferred concave-convex pattern while pressing the mold against the photosensitive composition layer to form a cured product layer, and peeling the mold from the cured product layer (photonanoimprint lithography). The primer composition can improve adhesion between the substrate and the cured product layer made of a cured product of the photosensitive composition regardless of the type of substrate, and is therefore particularly useful for photonanoimprint lithography, in which the cured product layer is likely to peel off when the mold is peeled from the cured product layer.

[0162] As described above, the present inventors provide the following (1) to (10). (1) A primer composition used to form a primer layer between a substrate and a cured product layer of a photosensitive composition when the cured product layer is formed on the substrate, the primer composition comprising: the photosensitive composition contains a photocurable compound (a) having an ethylenically unsaturated double bond-containing group and a photopolymerization initiator (b); The primer composition comprises a substrate component (A), a compound (B), and a solvent (S), the base component (A) is a compound that does not form a covalent bond by reaction with the ethylenically unsaturated double bond-containing group in the photocurable compound (a), the base component (A) contains a resin (A1) and / or a polymerizable compound (A2), the polymerizable compound (A2) is a compound that can be polymerized by a polymerization mechanism other than radical polymerization, the compound (B) has a functional group capable of forming a covalent bond by reaction with the ethylenically unsaturated double bond-containing group in the photocurable compound (a), A primer composition, wherein the functional group in the compound (B) is at least one selected from the group consisting of an ethylenically unsaturated double bond-containing group, an amino group, a hydrosilyl group, and a thiol group. (2) The ethylenically unsaturated double bond-containing group in the compound (B) is a vinyl group or a (meth)acryloyl group, The primer composition according to (1), wherein the ethylenically unsaturated double bond-containing group in the photocurable compound (a) is a vinyl group or a (meth)acryloyl group. (3) The primer composition according to (1) or (2), wherein the base component (A) contains a water-soluble resin (A1-1) as the resin (A1). (4) The primer composition according to (3), wherein the base component (A) contains, as the water-soluble resin (A1-1), at least one selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, polysaccharides, and poly(meth)acrylic acid. (5) The primer composition according to any one of (1) to (4), wherein the base component (A) contains a cyclic ether group-containing compound (A2-1) as the polymerizable compound (A2). (6) The primer composition according to (5), further comprising an acid generator (D). (7) The primer composition according to any one of (1) to (6), comprising a phenolic hydroxyl group-containing resin (A1-2) as the resin (A1), a cyclic ether group-containing compound (A2-1) as the polymerizable compound (A2), and / or a methylol-type crosslinking agent (C), and an acid generator (D). (8) A laminate comprising a substrate, the primer layer derived from the primer composition according to any one of (1) to (7), and the cured product layer. (9) Applying the primer composition according to any one of (1) to (7) onto a substrate and drying it to form a primer layer; applying the photosensitive composition onto the substrate on which the primer layer has been formed to form a photosensitive composition layer; exposing the photosensitive composition layer to light to form the cured product layer; Including, (8) The method for producing a laminate according to (8), wherein, when a component in the primer composition other than the compound (B) can be polymerized or crosslinked, the component in the primer composition other than the compound (B) is polymerized or crosslinked before coating of the photosensitive composition. [Example]

[0163] The present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

[0164] The various chemicals used in the examples and comparative examples will be collectively described below.

[0165] <Primer composition> A-1: Kuraray PVA-505C (polyvinyl alcohol, SP value: 19.01) A-2: jER1007 (bisphenol A epoxy resin) manufactured by Mitsubishi Chemical Corporation A-3: PVP K 15 (polyvinylpyrrolidone) manufactured by Tokyo Chemical Industry Co., Ltd. A-4: Sigma-Aldrich PAA (polyacrylic acid) A-5: M-313 (isocyanuric acid EO-modified di- and triacrylate) manufactured by Toagosei Co., Ltd. A-6: Mitsubishi Chemical Corporation's jER157S70 (bisphenol A novolac epoxy resin) A-7: VP-2500 (poly(p-hydroxystyrene), Mw: 2400) manufactured by Nippon Soda Co., Ltd. B-1: KAYARAD DPHA (a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) manufactured by Nippon Kayaku Co., Ltd. B-2: Polyethyleneimine 10000 (polyethyleneimine) manufactured by Junsei Chemical Co., Ltd. C-1: Nikalac MW-100LM (methylol crosslinker represented by the following formula) manufactured by Sanwa Chemical Co., Ltd. [ka] D-1: Irgacure 290 manufactured by BASF (a photoacid generator represented by the following formula) [ka] D-2: Irgacure PAG103 manufactured by BASF (a photoacid generator represented by the following formula) [ka] E-1: KBM-503 (3-methacryloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. PE: Propylene glycol monomethyl ether PM: Propylene glycol monomethyl ether acetate

[0166] <Photosensitive composition> F-1: A-DCP (tricyclodecane dimethanol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd. G-1: KBM-503 (3-methacryloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. G-2: PF-656 manufactured by Omnova (a fluorosurfactant represented by the following formula) [ka] H-1: Omnirad 651 (2,2-dimethoxy-2-phenylacetophenone, photoacid generator) manufactured by IGM Resins PM: Propylene glycol monomethyl ether acetate (SP value: 8.73)

[0167] <Substrate> S-1: Made of silicone S-2: Made of polycarbonate S-3: Glass (Corning EAGLE XG)

[0168] <Examples and Comparative Examples> The components of the types and amounts (parts by mass) shown in Table 1 were mixed with the solvent shown in Table 1 (in the case of mixed solvents, the mass ratio is also shown) to give the solids concentration (concentration of components other than the solvent) (mass %) shown in Table 1, to obtain primer compositions for the examples and comparative examples. The obtained primer composition was applied to the substrate shown in Table 1 using a spin coater (MS-B200 manufactured by Mikasa Co., Ltd.), and the applied film was heated at 100°C for 1 minute to form a primer layer. In Examples 4 and 5, the applied film was heated at 100°C for 1 minute, and then exposed to light at an exposure dose of 1 J / cm using an exposure device (HMW-532D manufactured by Oak Manufacturing Co., Ltd., ultra-high pressure mercury lamp). 2 The film was then heated at 100° C. for 1 minute to form a primer layer. The thickness of the formed primer layer was measured by spectroscopic ellipsometry. The results are shown in Table 1. Note that, since Examples 2 and 3 were not silicon substrates, the thickness was not measured by spectroscopic ellipsometry. However, since the primer composition and application method used were the same as those of Example 1, the thicknesses of Examples 2 and 3 were evaluated to be the same as those of Example 1.

[0169] 100 parts by mass of F-1, 5 parts by mass of G-1, 0.25 parts by mass of G-2, and 5 parts by mass of H-1 were mixed with PM so that the solid concentration (concentration of components other than the solvent) was 20% by mass, thereby obtaining a photosensitive composition. The photosensitive composition was applied onto the substrate on which the primer layer had been formed using a spin coater (MS-B200 manufactured by Mikasa Co., Ltd.), and the applied film was heated at 100°C for 1 minute. Thereafter, an imprinting device (ST-200 manufactured by Shibaura Machine Co., Ltd.) was used to apply the photosensitive composition to the substrate at an exposure dose of 1 J / cm. 2 The coating was exposed to light (under a vacuum atmosphere of 200 Pa) to form a cured layer.

[0170] <Adhesion> A lattice-shaped cut (cross cut) having a width of 1 mm was made in the cured product layer on the substrate. The laminates with cuts in the cured layer were subjected to a tape peel test according to ASTM-D3359-09e2 to observe whether or not each grid had peeled off. The results of the tape peel test were evaluated according to the following criteria. The results are shown in Table 1. A (Rank 5B): No peeling at all. B (Rank 4B): The ratio of the number of peeled off cured material layers to the total number of cured material layers divided by the lattice-shaped cuts was 5% or less. C (Rank 3B): The ratio of the number of peeled off cured material layers to the total number of cured material layers divided by the lattice-shaped cuts was more than 5% and 15% or less. D (rank 2B to 0B): The ratio of the number of peeled cured material layers to the total number of resin films divided by the lattice-shaped cuts was 15% or more.

[0171] [Table 1]

[0172] As shown in Table 1, when the primer compositions of Examples were used, the adhesion of the cured material layer was good, whereas when the primer compositions of Comparative Examples were used, the adhesion of the cured material layer was poor. In particular, the results of Examples 1 to 3 showed that the adhesion of the cured material layer was good regardless of the type of substrate.

Claims

1. A primer composition used to form a primer layer between a substrate and a cured product layer made of a cured product of a photosensitive composition when the cured product layer is formed on the substrate, the primer composition comprising: the photosensitive composition contains a photocurable compound (a) having an ethylenically unsaturated double bond-containing group and a photopolymerization initiator (b), The primer composition comprises a substrate component (A), a compound (B), and a solvent (S), the base component (A) is a compound that does not form a covalent bond by reaction with the ethylenically unsaturated double bond-containing group in the photocurable compound (a), the base component (A) contains a resin (A1) and / or a polymerizable compound (A2), the polymerizable compound (A2) is a compound that can be polymerized by a polymerization mechanism other than radical polymerization, the compound (B) has a functional group capable of forming a covalent bond by reaction with the ethylenically unsaturated double bond-containing group in the photocurable compound (a), a primer composition, wherein the functional group in the compound (B) is at least one selected from the group consisting of an ethylenically unsaturated double bond-containing group, an amino group, a hydrosilyl group, and a thiol group.

2. the ethylenically unsaturated double bond-containing group in the compound (B) is a vinyl group or a (meth)acryloyl group, The primer composition according to claim 1, wherein the ethylenically unsaturated double bond-containing group in the photocurable compound (a) is a vinyl group or a (meth)acryloyl group.

3. 2. The primer composition according to claim 1, wherein the base component (A) contains a water-soluble resin (A1-1) as the resin (A1).

4. 4. The primer composition according to claim 3, wherein the base component (A) contains, as the water-soluble resin (A1-1), at least one selected from the group consisting of polyvinyl alcohol, polyvinylpyrrolidone, polysaccharides, and poly(meth)acrylic acid.

5. 2. The primer composition according to claim 1, wherein the base component (A) contains a cyclic ether group-containing compound (A2-1) as the polymerizable compound (A2).

6. The primer composition according to claim 5 , further comprising an acid generator (D).

7. 2. The primer composition according to claim 1, comprising: a phenolic hydroxyl group-containing resin (A1-2) as the resin (A1); a cyclic ether group-containing compound (A2-1) as the polymerizable compound (A2); and / or a methylol-type crosslinking agent (C); and an acid generator (D).

8. A laminate comprising a substrate, the primer layer derived from the primer composition according to any one of claims 1 to 7, and the cured product layer.

9. Applying the primer composition according to any one of claims 1 to 7 onto a substrate and drying it to form a primer layer; applying the photosensitive composition onto the substrate on which the primer layer has been formed to form a photosensitive composition layer; exposing the photosensitive composition layer to light to form the cured product layer; Including, 9. The method for producing a laminate according to claim 8, wherein, when a component in the primer composition other than the compound (B) can be polymerized or crosslinked, the component in the primer composition other than the compound (B) is polymerized or crosslinked before application of the photosensitive composition.

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