TW202115132A - Polymerizable composition, method for manufacturing coated structure, coated structure and coating material - Google Patents

Abstract

The main purpose of the present invention is to provide a polymerizable composition which is capable of forming a coating material having an excellent ability to capture an acid component and high adhesive power. The present invention pertains to a polymerizable composition which contains a first polymerizable compound having an amide group and an ethylenically unsaturated group and which is to be used for coating an acid component-containing member. Preferably, the first polymerizable compound comprises at least one compound selected from the group consisting of an acrylamide compound having a structure in which an amide group is directly bonded to an ethylenically unsaturated group, a urethane compound having a urethane bond and an ethylenically unsaturated group and an isocyanuric ring-containing compound having an isocyanuric ring and an ethylenically unsaturated group.

Description

Polymerizable composition, manufacturing method of covering structure, covering structure and covering material

The present invention relates to a polymerizable composition for forming a coating material for coating a member containing an acid component.

The cured product formed by curing the cation polymerizable component with an acid generator is used in various applications, such as a member for forming an optical waveguide or a member for manufacturing an optical filter.

When an acid generator is used to produce a hardened product, there are cases where the acid generator remains in the finished hardened product. In this case, there is a risk that the acid generated by the acid generator oozes out of the hardened substance and corrodes surrounding components.

In order to prevent corrosion of the members existing around the hardened product with the acid generator remaining, the following operation is performed: the hardened product with the acid generator remaining is covered with a coating material containing an acid trapping material. For example, Patent Document 1 describes that a resin containing an amine compound such as imidazole is laminated on a cured product in which an acid generator remains. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-225019

However, the resin layer described in Patent Document 1 has a problem that it cannot sufficiently capture the acid generated by the acid generator. In addition, the resin layer described in this document has the problem of weak adhesion to the cured product.

Therefore, the subject of the present invention is to provide a coating material capable of capturing the acid component in a member containing an acid component and having high adhesion to the member containing the acid component, that is, to provide a coating material capable of forming an excellent acid component capture property and adhesive force. The material of the higher covering material.

The inventors of the present invention worked diligently to solve the above-mentioned problems. As a result, they found that the above-mentioned problems can be solved by using a composition containing a specific polymerizable compound to form a coating material that coats a member containing an acid component, thereby completing the present invention.

That is, the present invention relates to a polymerizable composition containing a first polymerizable compound having an amide group and an ethylenically unsaturated group, and Used to coat components containing acid.

In addition, the present invention relates to a method of manufacturing a covering structure, which has a step of covering a member containing an acid component with a covering material, The coating material includes a polymer having a structural unit derived from a first polymerizable compound having an amide group and an ethylenically unsaturated group.

In addition, the present invention relates to a covering structure having a member containing an acid component and a covering material covering the member, The coating material includes a polymer having a structural unit derived from a first polymerizable compound having an amide group and an ethylenically unsaturated group.

In addition, the present invention relates to a coating material comprising a polymer having a structural unit derived from a first polymerizable compound having an amide group and an ethylenically unsaturated group, and the coating material is used for coating and containing an acid Components of ingredients.

The present invention relates to a polymerizable composition, a coating structure containing a coating material containing a polymer of the polymerizable composition, a method for manufacturing the coating structure, and a coating material. Hereinafter, the present invention will be described in detail.

A. Polymerizable composition The polymerizable composition of the present invention contains a first polymerizable compound having an amide group and an ethylenically unsaturated group, and is used to coat a member containing an acid component.

The polymerizable composition of the present invention contains a first polymerizable compound having an amide group and an ethylenically unsaturated group. The polymer of the polymerizable composition containing the first polymerizable compound can form a coating material with excellent acid trapping properties and high adhesive force. Here, the reason why such a coating material with excellent acid trapping properties and high adhesive force can be formed is not clear, but it is estimated as follows. That is, the polymer of the polymerizable composition includes the polymer of the first polymerizable compound. In addition, the polymer has a structural unit containing -(C=O)-N- derived from the first polymerizable compound. -(C=O)-N- in this structural unit can efficiently capture acid components. As a result, the following effects can be exerted: it is possible to suppress the corrosion of the components located around the covered structure caused by the acid component; it is possible to suppress the decomposition of the components contained in the component containing the acid component covered by the above-mentioned coating material due to the acid component, etc. . More specifically, the amide group possessed by the above polymer can stabilize the acid component so that a complex between the nitrogen atom and the carbonyl group and the acid component can be formed. This mechanism is different from the mechanism in which basic groups such as imidazole compounds capture acid components. Therefore, the acid component capturing ability of the basic group is less reduced due to the capturing and neutralization of the acid component, and the acid component can be captured more efficiently. In addition, since the polymer has an amide group, the amide group that captures the acid component is stably fixed in the polymer. As a result, the acid component can be stably captured. Thereby, the polymer containing the above-mentioned polymer can stably capture the acid component in the acid component-containing member in the polymer, and stably suppress the corrosion of the member around the acid component-containing member. Furthermore, the polymer contained in the polymer of the above-mentioned polymerizable composition has an ethylenically unsaturated group and therefore has a high adhesive force to the cured product. As a result, the member containing the acid component and the coating material are not easily peeled off. More specifically, the above-mentioned polymerizable composition can form a polymer including a polymer in which the first polymerizable compounds are polymerized in a network form via an ethylenically unsaturated group. As a result, it is possible to produce a coating material with high adhesion to the member containing the acid component. In addition, since the polymer of the above-mentioned polymerizable composition has an amide group, it has excellent affinity with the cation curable component contained in the cation curable composition. As a result, it is possible to form a coating material having a high adhesive force with a member containing an acid component, such as a cured product of a cationic curable composition.

1. The first polymerizable compound The first polymerizable compound contained in the polymerizable composition has an amide group and an ethylenically unsaturated group, and has at least one amide group and at least one ethylenically unsaturated group in one molecule. The amide group and the ethylenically unsaturated group may be directly bonded, or may be bonded via a divalent linking group. When the first polymerizable compound has a plurality of amide groups in one molecule, the plural amide groups may be bonded in a linear manner via a linking group or not through a linking group, and may also be linked through a linking group or not through a linking group. The base is bonded in a ring. The ethylenically unsaturated group may be any one having radical polymerizability, and it may, for example, be an acryloyl group, a methacryloyl group, or a vinyl group. As such a first polymerizable compound, for example: An acrylamide compound with a structure in which an amide group and an ethylenically unsaturated group are directly bonded, A urethane compound having a urethane bond and an ethylenically unsaturated group, and An isocyanuric acid ring-containing compound having an isocyanuric acid ring and an ethylenically unsaturated group.

(1) Acrylic amide compound The acrylamide compound is a compound having a structure in which an amide group and an ethylenically unsaturated group are directly bonded. Among such acrylamide compounds, it is preferred that the ethylenic unsaturated group is directly bonded to the carbonyl group in the amide group to form an acrylamide group or a methyl group in terms of easy polymerization reaction and excellent availability. Acrylic acrylamide or methacrylamide. As such an acrylamide compound, it is preferable to use the one represented by the following formula (A1) in terms of being able to form a polymer that can more effectively capture the acid component and easily form a coating material with a higher adhesive force.

[化1]

In the formula, n represents an integer of 1 or 2. When n is an integer of ¹ , R 1 and R ² each independently represent a hydrogen atom, a group represented by the following formula (a), a monovalent hydrocarbon group having 1 to 30 carbon atoms, and 2 to 30 carbon atoms A monovalent heterocyclic group, or one or more methylene groups in the hydrocarbon group or the heterocyclic group is substituted with a divalent group selected from the following group (I), wherein in 2 When more than one methylene group is substituted with a divalent group selected from the following group (I), the divalent group is not adjacent, and R ¹ and R ² may be bonded to each other to form a heterocyclic ring, and R ³ represents Hydrogen atom or methyl group. When n is an integer of 2, R ¹ represents a direct bond, a divalent hydrocarbon group with 1 to 30 carbon atoms, a divalent heterocyclic group with 2 to 30 carbon atoms, or the hydrocarbon group or the heterocyclic group One or more methylene groups are substituted with a divalent group selected from the following group (I), wherein two or more methylene groups are substituted with a divalent group selected from the following group (I) In the case of a divalent group, the divalent group is not adjacent, and R ² represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 30 carbon atoms, a monovalent heterocyclic group containing 2 to 30 carbon atoms, or the hydrocarbon group Or one or more methylene groups in the heterocyclic group are substituted with divalent groups selected from the following group (I), wherein two or more methylene groups are substituted with In the case of the divalent group of the following group (I), the divalent group is not adjacent, R ² can bond with the adjacent nitrogen atom to form a heterocyclic ring containing two nitrogen atoms, and R ³ represents a hydrogen atom or methyl The two groups of R ² and R ³ may be the same or different.

[化2]

In the formula, R ⁴ represents a hydrogen atom or a monovalent hydrocarbon group with 1 to 30 carbon atoms, R ⁵ represents a hydrogen atom or a methyl group, and X represents a direct bond, a divalent hydrocarbon group with 1 to 30 carbon atoms, and 2 carbon atoms. ~30 divalent heterocyclic group, or one or more methylene groups in the hydrocarbon group or the heterocyclic group is substituted with a divalent group selected from the following group (I), wherein, When two or more methylene groups are substituted with a divalent group selected from the following group (I), the divalent group is not adjacent, and there are plural in the compound represented by the general formula (A1) In the case of the base represented by the above general formula (a), there are a plurality of R ⁴ , R ⁵ and X which may be the same or different, respectively, and * represents a bonding bond. Group (I): -O-, -S-, -NR ⁶ -, -NR ⁶ -(C=O)-O-, -CO-, -(C=O)-O-, -O-(C =O)-, -O-(C=O)-O- R ⁶ represents a hydrogen atom or a monovalent hydrocarbon group with 1 to 30 carbon atoms.

In the present invention, the hydrocarbon group means a group consisting of an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and an aromatic ring-containing hydrocarbon group formed by combining these groups. In the present invention, the heterocyclic group-containing group means a group consisting of a heterocyclic group and a group in which one or more hydrogen atoms in the hydrocarbon group are substituted with a heterocyclic group. The heterocyclic group-containing group only needs to include a heterocyclic ring, and may include an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Furthermore, the above-mentioned concepts of hydrocarbon groups and heterocyclic groups also include the case where more than one hydrogen atom in the group is substituted by a substituent.

^{The monovalent hydrocarbon group with 1 to 30 carbon atoms represented by R 1} , R ² , R ⁴ and R ⁶ in the formula (A1) is not particularly limited. For example, the number of carbon atoms that may have a substituent 1-30 alkyl, optionally substituted alkenyl with 2-30 carbon atoms, optionally substituted alkynyl with 2-30 carbon atoms, optionally substituted ring with 3-30 carbon atoms Alkyl group, optionally substituted aliphatic hydrocarbon group such as cycloalkylalkyl having 4 to 30 carbon atoms; optionally substituted aromatic hydrocarbon group such as aryl group with 6 to 30 carbon atoms; An optionally substituted aromatic ring-containing hydrocarbon group such as an aralkyl group having 7 to 30 carbon atoms and an optionally substituted alkenyl aryl group having 8 to 30 carbon atoms.

^{When R 1} , R ² , R ⁴ and R ⁶ in the formula (A1) are an alkyl group having 1 to 30 carbon atoms, the alkyl group may be linear or branched. Examples of linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, and n-decyl. Monoalkyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl and n-eicosyl. Examples of branched alkyl groups include isopropyl, isobutyl, second butyl, tertiary butyl, isopentyl, tertiary pentyl, isooctyl, 2-ethylhexyl, and tertiary octyl. Base, isononyl and isodecyl, etc.

In formula (A1), the ^{alkenyl group with 2 to 30 carbon atoms used in R 1} , R ² , R ⁴ and R ⁶ has an unsaturated double bond, and one or more of the saturated aliphatic hydrocarbon groups can be used. The methyl group is substituted with an unsaturated double bond. Examples of saturated aliphatic hydrocarbon groups include the above-mentioned alkyl groups with 1 to 30 carbon atoms which may have substituents, cycloalkyl groups with 3 to 30 carbon atoms which may have substituents, and those which may have substituents. Cycloalkylalkyl groups having 4 to 30 carbon atoms, etc. The alkenyl group may have one unsaturated double bond, or may have two or more unsaturated double bonds. The above-mentioned alkenyl group may be chain-like or may have a cyclic structure. In the present invention, from the viewpoint of further improving the acid component trapping properties of the obtained polymer, it is preferably chain-like. When the alkenyl group is chain-like, the alkenyl group may be linear or branched. When the alkenyl group is chain-like, it may be a terminal alkenyl group having an unsaturated double bond at the end, or an internal alkenyl group having an unsaturated double bond inside. In the present invention, the terminal alkenyl group is preferred from the viewpoint of further improving the acid component capture property of the polymer obtained. In addition, as the terminal alkenyl group, *-CH=CH ₂ or *-C(CH ₃ )=CH ₂ (* represents a bonding bond). Furthermore, when the saturated aliphatic hydrocarbon group used to form the alkenyl group has a branched structure, the alkenyl group may have an unsaturated double bond at each end of the branched structure. That is, as the alkenyl group, an alkenyl group having two or more unsaturated double bonds at the end can be used. As the linear terminal alkenyl group having 2 to 30 carbon atoms, for example, -(CH ₂ ) _p1 -CH=CH ₂ (p1 represents an integer of 0 to 28). As the branched terminal alkenyl group having 2 to 30 carbon atoms, for example, -(CH ₂ ) _p2 -C(CH ₃ )=CH ₂ (p2 represents an integer of 0 to 27). In the present invention, as the alkenyl group, both a linear terminal unsaturated double bond structure and a branched terminal unsaturated double bond structure can be used, and a linear terminal unsaturated double bond structure is preferred. The reason is that this makes the polymerization rate of the first polymerizable compound faster. As a specific example of a terminal alkenyl group, a vinyl group, 2-propenyl group, 3-butenyl group, 4-pentenyl group, 5-hexenyl group, etc. are mentioned, for example. Examples of internal alkenyl groups include 2-butenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 2-heptenyl, 3-heptenyl, and 4-heptene. Group, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, etc. The cyclic alkenyl group may, for example, be 3-cyclohexenyl, 2,5-cyclohexadienyl-1-methyl, 4,8,12-tetradecatrienylallyl, and the like.

In formula (A1), the ^{alkynyl group with 2 to 30 carbon atoms used in R 1} , R ² , R ⁴ and R ⁶ has an unsaturated triple bond, and one or more of the saturated aliphatic hydrocarbon groups can be used. The methyl group is substituted with an unsaturated triple bond. The alkynyl group may have one unsaturated triple bond, or may have two or more unsaturated triple bonds. The above-mentioned alkynyl group may be chain-like or may have a cyclic structure. In the present invention, from the viewpoint of further improving the acid component trapping properties of the obtained polymer, it is preferably chain-like. When the alkynyl group is chain-like, it can be a group with a terminal unsaturated triple bond structure, that is, a group with an unsaturated triple bond structure at the end, or a group with an internal unsaturated triple bond structure, that is, a group with an internal unsaturated triple bond structure. The base of unsaturated triple bond structure. When the alkynyl group is chain-like, the alkynyl group may be linear or branched. Examples of the alkynyl group having 2 to 30 carbon atoms include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1 -Octynyl, 1-decynyl, 1-octadecynyl, etc.

^{Examples of the cycloalkyl group having 3 to 30 carbon atoms represented by R 1} , R ² , R ⁴ and R ⁶ in the formula (A1) include: a group obtained by removing one hydrogen atom from a cycloalkane, or One or two or more hydrogen atoms in the cycloalkane are substituted with the above-mentioned alkyl group, alkenyl group, and/or alkynyl group, and a group obtained by removing one hydrogen atom from the cycloalkane contained in the compound. As such a cycloalkyl group having 3 to 30 carbon atoms, a saturated monocyclic or saturated polycyclic alkyl group having 3 to 30 carbon atoms as a whole may be mentioned. As a saturated monocyclic alkyl group, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, etc. are mentioned, for example. As a saturated polycyclic alkyl group, adamantyl, decahydronaphthyl, octahydrocyclopentadiene, bicyclo[1.1.1]pentyl, tetradecahydroanthryl, etc. are mentioned, for example.

^{The cycloalkylalkyl group having 4 to 30 carbon atoms represented by R 1} , R ² , R ⁴ and R ⁶ in the formula (A1) means that the hydrogen atom of the alkyl group is substituted with a cycloalkyl group and has 4 to 4 as a whole. A base of 30 carbon atoms. The cycloalkyl group in the cycloalkylalkyl group may be monocyclic or polycyclic.

The cycloalkyl group is a monocyclic cycloalkylalkyl group having 4 to 30 carbon atoms, for example, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, and cycloheptyl Cycloalkylmethyl such as methyl, cyclooctylmethyl, cyclononylmethyl and cyclodecylmethyl; 2-cyclobutylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 2-cyclononylethyl, 2-cyclodecylethyl and other cycloalkylethyls; 3-cyclobutylpropyl, 3-cyclopentyl Cycloalkylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 3-cyclooctylpropyl, 3-cyclononylpropyl and 3-cyclodecylpropyl; 4 -Cyclobutylbutyl, 4-cyclopentylbutyl, 4-cyclohexylbutyl, 4-cycloheptylbutyl, 4-cyclooctylbutyl, 4-cyclononylbutyl, 4-cyclodecyl Cycloalkylbutyl groups such as butyl group. The cycloalkyl group is a polycyclic cycloalkylalkyl group having 4 to 20 carbon atoms, for example: bicyclo[1.1.0]butyl, bicyclo[1.1.1]pentyl, bicyclo[2.1.0]pentyl Bicyclo[3.1.0]hexyl, bicyclo[2.1.1]hexyl, bicyclo[2.2.0]hexyl, bicyclo[4.1.0]heptyl, bicyclo[3.2.0]heptyl, bicyclo[3.1.1] Heptyl, bicyclo[2.2.1]heptyl, bicyclo[5.1.0]octyl, bicyclo[4.2.0]octyl, bicyclo[4.1.1]octyl, bicyclo[3.3.0]octyl, bicyclo[ 3.2.1]octyl, bicyclo[2.2.2]octyl, spiro[4,4]nonyl, spiro[4,5]decyl, decahydronaphthalene, tricyclodecyl, tetracyclododecyl and Cedarol, cyclododecyl 3-3-adamantyl propyl and decahydronaphthyl propyl, etc.

Furthermore, as the aliphatic hydrocarbon group, a cycloalkylalkylene group in which the methylene group of an alkyl group in a cycloalkylalkyl group is substituted with -CH=CH-, that is, a cycloalkylalkylene group can also be used.

^{Examples of the aryl group having 6 to 30 carbon atoms used for R 1} , R ² , R ⁴ and R ⁶ in the formula (A1) include: a group formed by removing one hydrogen atom from an aromatic hydrocarbon ring, Or one or two or more hydrogen atoms in the aromatic hydrocarbon ring are substituted with the above-mentioned aliphatic hydrocarbon group by removing one hydrogen atom from the aromatic hydrocarbon ring contained in the compound. As an aromatic hydrocarbon ring, a monocyclic structure, a condensed ring structure, a polycyclic structure, etc. are mentioned. The polycyclic structure is one formed by linking two or more monocyclic structures and/or condensed aromatic hydrocarbon rings, as long as it has aromaticity. More specifically, as the polycyclic structure, there can be exemplified: those formed by connecting a single ring structure and a single ring structure, those formed by connecting a single ring structure and a condensed ring structure, and a condensed ring structure and a condensed ring structure are connected Winners and so on. Examples of the group that connects the aromatic hydrocarbon rings of the monocyclic structure and/or the condensed ring structure to each other include a direct bond, -S-, -O-, -CO-, -CR ¹⁰¹ R ¹⁰² -. R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. As the aryl group having a monocyclic structure, for example, a phenyl group may be mentioned. As the aryl group having 6 to 30 carbon atoms, for example, tolyl, xylyl, ethylphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-tris Monocyclic aryl groups such as methylphenyl. As the aryl group having a condensed ring structure, for example, a naphthyl group, an anthryl group, a phenanthryl group, etc. may be mentioned. As an aryl group having a polycyclic structure, for example, a biphenyl group, a benzophenone group, etc. may be mentioned.

^{The aralkyl group having 7 to 30 carbon atoms represented by R 1} , R ² , R ⁴ and R ⁶ in the formula (A1) means that one or more hydrogen atoms of the alkyl group are substituted with the above-mentioned aryl group base. Examples of aralkyl groups having 7 to 30 carbon atoms include benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, α-dimethylbenzyl, 2 -Phenylalkyl such as phenylethyl, 2-phenylpropyl, 3-phenylpropyl, diphenylmethyl, triphenylmethyl and triphenylpropyl; and naphthalene such as naphthylpropyl基alkyl.

^{The alkenyl aryl group having 8 to 30 carbon atoms represented by R 1} , R ² , R ⁴ and R ⁶ in the formula (A1) means that one or more hydrogen atoms of the alkenyl group are substituted with the above-mentioned aryl group The base. Examples of alkenyl aryl groups having 8 to 30 carbon atoms include phenylpropenyl, phenylbutenyl, phenylpentynyl or tolylpropenyl, tolylbutenyl and tolylpentynyl Base and so on.

^{As the hydrocarbon group used for R 1} , R ² , R ⁴ and R ⁶ in the formula (A1), a hydrocarbon group having an unsaturated double bond (hereinafter, also referred to as an unsaturated double bond-containing group) may also be used. Here, the unsaturated double bond-containing group should just have an unsaturated double bond other than the aromatic ring and it does not contain a heterocyclic ring. As the above-mentioned unsaturated double bond-containing group, one having 2 to 30 carbon atoms can be used, and examples thereof include an alkenyl group, or a combination of an alkenyl group, a cycloalkyl group, a cycloalkylene group, or an aromatic hydrocarbon group. As a group formed by combining an alkenyl group with a cycloalkyl group, a cycloalkylene group or an aromatic hydrocarbon group, one or more of the hydrogen atoms in the cycloalkyl group, cycloalkylene group or aromatic hydrocarbon group is substituted with an alkene A group in which one or more of the hydrogen atoms in an alkenyl group is substituted with a cycloalkyl group, a cycloalkylene group, or an aromatic hydrocarbon group, or the like. The number of unsaturated double bonds possessed by the above-mentioned unsaturated double bond-containing group may be one or more, preferably 1-2, and more preferably one. The reason for this is that the first polymerizable compound can easily form a coating material with a small curing shrinkage and a high adhesive force.

基、二苯并呋喃基、1,3-二氧雜環戊烷基及環氧乙烷基等環中具有氧原子之雜環基；噻吩基、苯并噻吩基、硫代呋喃基、二苯并噻吩基及四氫噻吩基等環中具有硫原子之雜環基；㗁唑基、苯并㗁唑基、異㗁唑基、𠰌啉基及㗁唑啶等環中具有氮原子及氧原子之雜環基；噻唑基、噻二唑基、苯并噻唑基、異噻唑基及硫代𠰌啉基等環中具有氮原子及硫原子之雜環基；上述2個以上之雜環基經由直接鍵、-S-、-O-、-CO-或-CR¹⁰³ R¹⁰⁴ -連結而成的基。R¹⁰³ 及R¹⁰⁴ 分別獨立地表示氫原子或碳原子數1～4之烷基。In the present invention, the heterocyclic group may be a group including a heterocyclic ring, may be a group obtained by removing one hydrogen atom in the ring of the heterocyclic ring, and replacing one or more hydrogen atoms in the heterocyclic ring with the above The aliphatic hydrocarbon group is composed of one hydrogen atom in the heterocyclic ring of the compound, or the hydrogen atom in the hydrocarbon group is substituted with a heterocyclic group. In the present invention, the heterocyclic group includes an unsubstituted heterocyclic group and a substituted heterocyclic group. Examples of the monovalent heterocyclic group containing 2 to 30 carbon atoms represented ^{by R 1} , R ² and R ⁴ in the formula (A1) include: pyrrolidinyl, pyridyl, pyridine, and piperidine Group, piperidine group, pyrazoline group, pyrimidinyl group, titanyl group, trisyl group, hexahydrotrisyl group, carbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, pyrrolyl group, indole There are nitrogen atoms in the ring, such as phenyl, aziridinyl, imidazolyl, benzimidazolyl, pyrazolyl, quinolinyl, isoquinolinyl, pyrrolidinone, piperidinone and dioxyimidazolidinyl The heterocyclic group; piperanyl, furanyl, benzofuranyl, tetrahydrofuranyl, chromanyl dihydropyranyl, 𠮿

Group, dibenzofuranyl, 1,3-dioxolane and oxiranyl and other heterocyclic groups with oxygen atoms in the ring; thienyl, benzothienyl, thiofuranyl, two Heterocyclic groups with sulfur atoms in the ring such as benzothienyl and tetrahydrothienyl; oxazolyl, benzoazolyl, isooxazolyl, pyrolinyl and azolidine have nitrogen atoms and oxygen in the ring Heterocyclic groups of atoms; thiazolyl, thiadiazolyl, benzothiazolyl, isothiazolyl, and thiothiolinyl and other heterocyclic groups having a nitrogen atom and a sulfur atom in the ring; the above two or more heterocyclic groups A group formed by a direct bond, -S-, -O-, -CO- or -CR ¹⁰³ R ¹⁰⁴ -. R ¹⁰³ and R ¹⁰⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

^{The heterocyclic ring formed by the bonding of R 1} and R ² in the formula (A1) may be a ring containing a nitrogen atom and a carbon atom, or a ring containing a nitrogen atom, a heteroatom other than a nitrogen atom, and a carbon atom. As the hetero atom, an oxygen atom or a sulfur atom may be mentioned. From the standpoint of further improving the acid component capture property of the obtained polymer, the heterocyclic ring is preferably a ring containing a nitrogen atom, a heteroatom other than a nitrogen atom, and a carbon atom, and preferably contains a nitrogen atom and an oxygen atom. And a ring of carbon atoms. The aforementioned heterocyclic ring may be a five-membered ring or a six-membered ring. From the viewpoint of further improving the acid component capturing properties of the obtained polymer, the heterocyclic ring is preferably a six-membered ring. Examples of the five-membered ring heterocycle containing nitrogen and carbon atoms include: pyrrole ring, pyrrolidine ring, imidazole ring, imidazole ring, imidazoline ring, pyrazole ring, pyrazole ring, piperidine ring, etc. . Examples of the six-membered heterocyclic ring containing a nitrogen atom and a carbon atom include piperidine ring, pyridine ring, pyrimidine ring, pyrimidine ring and pyrimidine ring. The six-membered heterocyclic ring containing a nitrogen atom, an oxygen atom, and a carbon atom may, for example, be a pholine ring. The six-membered heterocyclic ring containing a nitrogen atom, a sulfur atom and a carbon atom may, for example, be a thiocyclic ring. The ^{heterocyclic ring formed by the bonding of R 1} and R ² also includes one in which one or more hydrogen atoms in the ring of the heterocyclic ring are substituted with an aliphatic hydrocarbon group having 1 to 30 carbon atoms.

^{As a heterocyclic ring containing 2 nitrogen atoms formed by n being 2 and R 2} bonding with adjacent nitrogen atoms in the formula (A1), piperazine and the like can be mentioned. Furthermore, when R ² is bonded to an adjacent nitrogen atom to form a heterocyclic ring containing two nitrogen atoms, R ² functions as a divalent group. For example, in the compound represented by (1-19) below, both R ¹ and R ² are divalent hydrocarbon groups bonded to the nitrogen atom of the other. In addition, in the compound represented by (1-19), both R ¹ and R ² are divalent hydrocarbon groups with a total number of carbon atoms of 9, including a terminal alkenyl group and having a branched structure, and the methylene group is substituted It is a divalent group of -O-, -NR ⁶ -CO-, and -CO-O-, and R ⁶ is a hydrogen atom.

^{In the case where R 1} when n is 2 in formula (A1) and X are a divalent hydrocarbon group having 1 to 30 carbon atoms, the hydrocarbon group may be exemplified by the above-mentioned monovalent hydrocarbon group having 1 to 30 carbon atoms A divalent group formed by removing one hydrogen atom. In the present invention, from the viewpoint of further improving the acid component trapping properties of the obtained polymer, an alkylene group having 1 to 30 carbon atoms is preferred. The alkylene group may be linear or branched. Examples of linear alkylene groups include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl. , N-undecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl and other straight-chain alkyl end carbon atoms removed 1 A divalent group formed by hydrogen atoms. Examples of branched alkylene groups include isopropyl, isobutyl, second butyl, tertiary butyl, isopentyl, tertiary pentyl, isooctyl, and 2-ethylhexyl. , Tertiary octyl, isononyl and isodecyl and other branched alkylenes are divalent groups formed by removing one hydrogen atom from a carbon atom in a branched alkylene group.

^{When R 1} and X in the formula (A1) are a divalent heterocyclic ring-containing group having 2 to 30 carbon atoms, examples of the hydrocarbon group include the above-mentioned monovalent heterocyclic ring-containing group having 2 to 30 carbon atoms. A divalent group formed by removing one hydrogen atom.

The above-mentioned monovalent hydrocarbon group with 1 to 30 carbon atoms, the above-mentioned monovalent hydrocarbon group with 1 to 30 carbon atoms, the above-mentioned divalent hydrocarbon group with 1 to 30 carbon atoms, and the above-mentioned divalent heterocyclic ring-containing group with 2 to 30 carbon atoms One or more hydrogen atoms in the heterocyclic ring formed by bonding between R ¹ and R ^{2 and} the heterocyclic ring formed by bonding between R ² and adjacent nitrogen atoms and containing two nitrogen atoms may be substituted. As a substituted monovalent or divalent hydrocarbon group with a substituent, a monovalent or divalent heterocyclic group with a substituent, a heterocyclic ring formed by the bonding ^{of R 1} and R ^{2 with a substituent, and R 2} and adjacent The substituent of the hydrogen atom in the heterocyclic ring containing 2 nitrogen atoms formed by the bonding of the nitrogen atom may, for example, be a halogen atom, a cyano group, a nitro group, a hydroxyl group, a thiol group, -COOH or -SO ₂ H . As a halogen atom, fluorine, chlorine, bromine, iodine, etc. are mentioned. Furthermore, in this specification, when a hydrogen atom of a group with a specific number of carbon atoms is substituted with a substituent containing a carbon atom, the carbon atom of the substituent, including the carbon atom of the substituent, satisfies the requirement of the specific number of carbon atoms. Therefore, when a hydrocarbon with 1 to 30 carbon atoms is based on the case where the hydrogen atom in the group is substituted with a substituent containing carbon atoms, the number of carbon atoms from 1 to 30 refers to the number of carbon atoms after the hydrogen atom is substituted, and does not mean The number of carbon atoms in the group before the hydrogen atom is replaced. In addition, the number of carbon atoms in a group formed by substituting a methylene group with a specific number of carbon atoms with a divalent group is the same as the number of carbon atoms contained in the group before the substitution. Therefore, the number of carbon atoms of the group in which the methylene group in the hydrocarbon group having 1-30 carbon atoms is substituted with a divalent group also satisfies 1-30.

In the present invention, when n=1, R ¹ and R ² in formula (A1) are preferably hydrogen atoms, the group represented by the above formula (a), and those with 1 to 30 carbon atoms. A monovalent hydrocarbon group or one or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the above group (I), or they are bonded to each other to form a heterocyclic ring. Among them, R ¹ and R ^{2 are} preferably a hydrogen atom, a group represented by the above formula (a), an alkyl group having 1 to 30 carbon atoms which may have a substituent, and a carbon atom number of 2 to which may have a substituent. 30 unsaturated double bond-containing groups, or one or more methylene groups in the unsaturated double bond-containing groups are substituted with divalent groups selected from the above group (I), or are bonded to each other It forms a heterocyclic ring, particularly preferably a hydrogen atom, a group represented by the above formula (a), a substituted alkyl group having 1 to 20 carbon atoms, and a substituted group containing 2 to 20 carbon atoms. Unsaturated double bond group, or one or more methylene groups in the unsaturated double bond-containing group are substituted with divalent groups selected from the above group (I), or are bonded to each other to form a heterocyclic ring Among them, a hydrogen atom, the group represented by the above formula (a), an alkyl group having 1 to 10 carbon atoms which may have a substituent, and an alkenyl group having 2 to 10 carbon atoms which may have a substituent are particularly preferable Or one or more methylene groups in the alkenyl group are substituted with divalent groups selected from the above group (I), or they are bonded to each other to form a heterocyclic ring. Among them, a hydrogen atom, the above-mentioned The group represented by the formula (a), the alkyl group having 1 to 4 carbon atoms which may have substituents, or the methylene group of one or more of the alkenyl groups having 3 to 10 carbon atoms which may have substituents It is substituted with a divalent group selected from the above group (I), or is bonded to each other to form a heterocyclic ring. The reason is that the above-mentioned polymerizable composition easily forms a coating material having excellent acid component capturing properties. One or more methylene groups in the unsaturated double bond-containing groups used by R ¹ and R ² are substituted with divalent groups selected from the above group (I), and the substituted methylene groups are selected from The divalent group of the above group (I) is preferably selected from the group consisting of -O-, -NR ⁶ -(C=O)-O-, -CO-, and -(C=O)-O- the group, which preferably comprises a ^{-NR 6 - (C = O)} -O- , particularly preferably comprising ^{-NR 6 - (C = O)} -O- and - (C = O) -O-. The reason is that the above-mentioned polymerizable composition easily forms a coating material having excellent acid component capturing properties.

In the present invention, when n=2, R ¹ in formula (A1) is preferably a divalent hydrocarbon group having 1 to 30 carbon atoms, a divalent heterocyclic group containing 2 to 30 carbon atoms, or One or more methylene groups in the hydrocarbon group or the heterocyclic group are substituted with a divalent group selected from the above group (I), and among them, a divalent group having 1 to 30 carbon atoms is preferred A hydrocarbon group or a group in which one or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the above group (I), and it is particularly preferably a hydrocarbon group having 1 to 30 carbon atoms which may have substituents. An alkyl group, one or more methylene groups in the alkylene group is substituted with a divalent group selected from the above group (I) (hereinafter referred to as a methylene substituted alkylene group), own When having a substituent, a divalent group formed by removing one hydrogen atom from an unsaturated double bond-containing group with 2 to 30 carbon atoms, or a divalent group formed by removing one hydrogen atom from the unsaturated double bond-containing group One or more of the methylene groups are substituted with divalent groups selected from the above group (I) (hereinafter, sometimes referred to as divalent methylene substituted unsaturated double bond-containing groups), especially further Preferably, a divalent methylene group having 1 to 30 carbon atoms is substituted with an unsaturated double bond-containing group. The reason is that the above-mentioned polymerizable composition easily forms a coating material having excellent acid component capturing properties. The divalent group formed by removing one hydrogen atom from the unsaturated double bond-containing group which may have substituents in the R ¹ system, or the methylene group in the above-mentioned unsaturated double bond-containing group is substituted to be selected from the above group ( In the case of a divalent group formed from the divalent group of I), the above-mentioned R ^{1 is} preferably a branched group, and among them, a group having a terminal unsaturated double bond structure is preferable. The reason for this is that this makes it easy for the polymerizable composition to form a coating material with excellent acid trapping properties. When R ¹ is a divalent hydrocarbon group or when one or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the above group (I), the number of carbon atoms of the hydrocarbon group is preferably 1-25, among them, 3-20 are preferred, and 5-15 are particularly preferred. The reason for this is that this makes it easy for the polymerizable composition to form a coating material with excellent acid trapping properties. When R ¹ is an alkylene group sometimes having substituents or a methylene group substituted alkylene group sometimes having substituents, the number of carbon atoms of the alkylene group and the methylene substituted alkylene group is preferable It is 1-25, preferably 3-20, especially more preferably 5-15. The reason for this is that this makes it easy for the polymerizable composition to form a coating material with excellent acid trapping properties. In addition, the reason is that this makes it easy for the polymerizable composition to form a coating material with a high adhesive force.

When ^{one or more methylene groups in the divalent hydrocarbon group of R 1} are substituted with a divalent group selected from the above group (I), it is selected from the divalent group (I) The number of methylene groups substituted by the group is preferably 1-6, more preferably 2-5. In the case where R ¹ is a methylene substituted alkylene group sometimes having a substituent, the number of methylene groups substituted with a divalent group selected from the above group (I) is preferably 1 to 6, wherein, Preferably it is 2-5. The reason for this is that this makes it easy for the polymerizable composition to form a coating material with excellent acid trapping properties.

In addition, when ^{one or more methylene groups in the divalent hydrocarbon group of R 1} are substituted with a group selected from the divalent group of the above group (I), it is selected from two of the group (I) The valence group preferably includes ^{at least one group selected from the group consisting of -O-, -NR 6} -(C=O)-O-, -CO-, -(C=O)-O-, wherein , Preferably contains -O-. The reason for this is that this makes it easy for the polymerizable composition to form a coating material with excellent acid trapping properties.

In the present invention, when n=2, R ² in formula (A1) is preferably a hydrogen atom, a monovalent hydrocarbon group having 1 to 30 carbon atoms, and a monovalent heterocyclic ring containing 2 to 30 carbon atoms. Group, or one or more methylene groups in the hydrocarbon group or the heterocyclic group are substituted with divalent groups selected from the above group (I), or are bonded to adjacent nitrogen atoms to form a group containing A heterocyclic ring with 2 nitrogen atoms, wherein R ^{2 is} preferably a hydrogen atom, or is bonded to an adjacent nitrogen atom to form a heterocyclic ring containing 2 nitrogen atoms, and a hydrogen atom is particularly preferred. The reason for this is that this makes it easy for the polymerizable composition to form a coating material with excellent acid trapping properties. When R ² is bonded to an adjacent nitrogen atom, that is ^{, a nitrogen atom bonded via R 1} to form a heterocyclic ring having two nitrogens, R ² can preferably be the same as R when the above compound n is 2. ^{1 The} same base. When the above-mentioned R ² forms a heterocyclic ring containing 2 nitrogen atoms, R ^{2 is} preferably a divalent group obtained by removing one hydrogen atom from an unsaturated double bond-containing group which may have a substituent, or the above-mentioned alkene The methylene group in the group is substituted with a divalent group selected from the group (I). The reason for this is that this makes it easy for the polymerizable composition to form a coating material with excellent acid trapping properties.

X in the group represented by the above formula (a) is preferably a divalent hydrocarbon group with 1 to 30 carbon atoms, a divalent heterocyclic group with 2 to 30 carbon atoms, or the hydrocarbon group or the heterocyclic group One or more methylene groups are substituted with divalent groups selected from the above group (I). Among them, a divalent hydrocarbon group with 1 to 30 carbon atoms or a divalent hydrocarbon group with 2 to 30 carbon atoms is preferred. The divalent heterocyclic group is particularly preferably a divalent hydrocarbon group having 1 to 30 carbon atoms, and among them, an alkylene group having 1 to 30 carbon atoms is particularly more preferred, and among these, a divalent hydrocarbon group having 1 to 30 carbon atoms is more preferred. The alkylene group of 10 is particularly preferably an alkylene group having 1 to 4 carbon atoms. The reason for this is that this makes it easy for the polymerizable composition to form a coating material with excellent acid trapping properties. Also, the reason is that it is so easy to obtain. When X is a divalent alkylene group having 1 to 30 carbon atoms, the alkylene group is preferably a straight chain. In addition, the alkylene group may have a substituent, but preferably has no substituent. The reason is that it is so easy to obtain.

^{R 3} in the above formula (A1) ^{and R 5} in the formula (a) are a hydrogen atom or a methyl group, preferably a hydrogen atom. The reason is that this makes the polymerization rate of the first polymerizable compound faster. ^{R 4} in the above formula (a) is a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms, preferably a hydrogen atom. The reason is that this makes the polymerization rate of the first polymerizable compound faster. When the compound represented by the above formula (A1), the symbols R ² and R ^3, R ^4, R ⁵ and X presence of a plurality of case, there are a plurality of R ² and R ^3, R ^4, R ⁵ and X may be They are the same or different, but from the viewpoint of ease of synthesis, they are preferably the same.

In the present invention, the compound represented by formula (A1) preferably contains a compound selected from the group consisting of the following compounds A1-1, A1-2, and compounds from the viewpoint of further improving the acid component capturing property of the obtained polymer At least one compound in the group consisting of A1-3, compound A1-4 and compound A1-5. Compound A1-1: The compound in formula (A1) where n is 1 and R ¹ and R ² are bonded to each other to form a heterocyclic ring. Compound A1-2: In formula (A1), n is 1 and R ¹ and R ² are respectively Independently a hydrogen atom, or an alkyl group having 1 to 30 carbon atoms that may have a substituent, or one or more methylene groups in the alkyl group are substituted with a divalent group selected from the above group (I), and Compound A1-3: In formula (A1), n is 1, R ¹ is a hydrogen atom and R ² is an unsaturated double bond-containing group which may have substituents, or the unsaturated double bond-containing group Compounds in which one or more methylene groups are substituted with divalent groups selected from the above group (I) Compound A1-4: In formula (A1), n is 1 and R ¹ and R ² are respectively Compound A1-5 independently of the above group (a): n in formula (A1) is 2, R ¹ is a divalent hydrocarbon group with 1-30 carbon atoms, and a divalent heterocyclic ring-containing group with 2-30 carbon atoms One or more methylene groups in the hydrocarbon group or the heterocyclic group is substituted with a divalent group selected from the above group (I), and R ² is a hydrogen atom and has a carbon number of 1 to A 30 monovalent hydrocarbon group, a monovalent heterocyclic group containing 2 to 30 carbon atoms, or one or more methylene groups in the hydrocarbon group or the heterocyclic group is substituted with two selected from the above group (I) Valence base compound

Among them, in the present invention, the above-mentioned acrylamide compound preferably includes the above-mentioned compound A1-1. As the content of the compound A1-1, in 100 parts by mass of the acrylamide compound, 30 parts by mass or more are preferable, among them, 40 parts by mass or more are preferable, and 50 parts by mass or more are more preferable, and among them, more preferably 60 parts by mass or more, particularly preferably 70 parts by mass or more, particularly preferably 80 parts by mass or more, particularly preferably 90 parts by mass or more, and particularly preferably 100 parts by mass. The reason is that, by setting the content of the compound A1-1 in the above range, the polymerizable composition can easily form a coating material having excellent acid component trapping properties.

In the above compound A1-1, the heterocyclic ring is preferably a ring containing a nitrogen atom, a heteroatom other than a nitrogen atom, and a carbon atom, and is preferably a ring containing a nitrogen atom, an oxygen atom, and a carbon atom. The reason is that this makes it easy for the polymerizable composition to form a coating material having excellent acid component capturing properties and high adhesiveness. Furthermore, the heterocyclic ring is preferably a five-membered ring or a six-membered ring, more preferably a six-membered ring. The reason is that this makes it easy for the polymerizable composition to form a coating material having excellent acid component capturing properties and high adhesiveness. Also, the reason is that it is so easy to obtain. Regarding the above-mentioned heterocyclic ring, one or more hydrogen atoms in the ring may be substituted by a substituent, but it is preferably unsubstituted. The reason is that this will further improve the acid component trapping properties of the obtained polymer. Also, the reason is that it is so easy to obtain. As a compound used as said compound A1-1, the compound represented by following formula (A1-1) can be mentioned specifically,.

In the above compound A1-2, an alkyl group having 1 to 30 carbon atoms which may have a substituent is used, or one or more methylene groups in the alkyl group are substituted with two selected from the above group (I) When the group formed of a valence group ^{is any one of R 1} and R ² , the number of carbon atoms of the above-mentioned alkyl group is preferably 1-20, more preferably 1-10, and particularly preferably 1-4. In addition, the alkyl group may be linear or branched. The alkyl group may be substituted or unsubstituted, and is preferably unsubstituted. The reason for this is that this makes it easy for the polymerizable composition to form a coating material with excellent acid trapping properties. In the above compound A1-2, R ¹ and R ² are each independently a hydrogen atom, or an alkyl group having 1 to 30 carbon atoms which may have a substituent, or one or more methylene groups in the alkyl group are substituted It is a group selected from the divalent group of the above group (I). As ^{examples of preferable combinations of R 1} or R ² , the following examples are preferable. The reason for this is that this makes it easy for the polymerizable composition to form a coating material with excellent acid trapping properties.・Combination 1: R ¹ and R ² are each independently a linear alkyl group. Among them, a linear alkyl group with 1 to 20 carbon atoms is preferred, and a linear alkyl group with 1 to 10 carbon atoms is particularly preferred. , Particularly preferably a straight chain alkyl group with 1 to 4 carbon atoms. The alkyl group is preferably unsubstituted. The reason is that this will further improve the acid component trapping properties of the obtained polymer. Also, the reason is that it is so easy to obtain.・Combination 2: R ¹ is a hydrogen atom, R ² is a branched alkyl group, wherein R ^{2 is} preferably a branched alkyl group with 1 to 20 carbon atoms, and particularly preferably a branched alkyl group with 1 to 10 carbon atoms Among them, a branched alkyl group having 1 to 4 carbon atoms is particularly preferred. The alkyl group is preferably unsubstituted. The reason is that this will further improve the acid component trapping properties of the obtained polymer. Also, the reason is that it is so easy to obtain. As a compound used as the said compound A1-2, the compound represented by following formula (A1-2), a formula (A1-3), and (A1-4) can be mentioned specifically,.

The number of unsaturated double bonds contained in the unsaturated double bond-containing group used ^{in R 2} in the above compound A1-3 may be 1 or more, preferably 1 to 2, and particularly preferably 1. The reason is that, by setting the above-mentioned amount, the above-mentioned compound can be easily obtained. ^{As R 2} in the above compound A1-3, an unsaturated double bond-containing group sometimes having a substituent, or the methylene group in the above unsaturated double bond-containing group is substituted to be selected from the above group (I) Any of the divalent groups (hereinafter, sometimes simply referred to as methylene-substituted unsaturated double bond-containing groups). Among them, unsubstituted unsaturated double bond-containing groups are preferred The methylene group in is substituted with a divalent group selected from the above group (I). The reason for this is that this makes it easy for the polymerizable composition to form a coating material with excellent acid trapping properties. From the viewpoint of further improvement of the acid component capturing property of the obtained polymer, the number of carbon atoms of the unsaturated double bond-containing group or methylene-substituted unsaturated double bond-containing group used in ^{R 2 is preferably 2-20} , More preferably 2～10. The reason for this is that this makes it easy for the polymerizable composition to form a coating material with excellent acid trapping properties. The ^{unsaturated double bond-containing group or methylene-substituted unsaturated double bond-containing group used by R 2} is preferably a group having a terminal unsaturated double bond structure, that is, an unsaturated double bond at the end. The terminal unsaturated double bond structure may be linear or branched, preferably linear. The reason is that this will make the polymerization rate of the above-mentioned compound A1-3 faster. The methylene-substituted unsaturated double bond-containing group is preferably two or more methylene groups substituted with a divalent group selected from the above group (I). The reason for this is that this makes it easy for the polymerizable composition to form a coating material with excellent acid trapping properties. The methylene substituted divalent group substituted by the methylene group in the unsaturated double bond-containing group is preferably selected from -O-, -NR ⁶ -(C=O)-O-, -CO-, -( The base in the group of C=O)-O-, wherein, preferably includes -NR ⁶ -(C=O)-O-. R ^{6 is} preferably a hydrogen atom. The reason for this is that this makes it easy for the polymerizable composition to form a coating material with excellent acid trapping properties. As a specific example of such a compound A1-3, the compounds represented by the following (1-1) to (1-15) can be mentioned.

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In addition, as a compound used as the above-mentioned compound A1-3, specifically, a compound represented by the following formula (A1-7) may also be exemplified.

In the above compound A1-4, R ⁴ in the formula (a) is preferably a hydrogen atom. X in the formula (a) is preferably a divalent hydrocarbon group having 1 to 30 carbon atoms or a divalent heterocyclic group containing 2 to 30 carbon atoms, more preferably an alkylene group having 1 to 30 carbon atoms, and further It is preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 1 to 4 carbon atoms. The alkylene group is preferably straight chain. In addition, the alkylene group preferably does not have a substituent. As a compound used as the said compound A1-4, the compound represented by following formula (A1-6) can be mentioned specifically,.

In the above compound A1-5, R ^{1 is} preferably a divalent hydrocarbon group having 1 to 30 carbon atoms, or one or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the above group (I). Among them, it is more preferred that an alkylene group having 1 to 30 carbon atoms which may have a substituent, or one or more methylene groups in the alkylene group are substituted to be selected from the above group (I) A divalent group (hereinafter referred to as a methylene substituted alkylene group), or an unsaturated double bond-containing group with 2 to 30 carbon atoms that may have substituents by removing one hydrogen atom The divalent group (hereinafter, sometimes referred to as a divalent unsaturated double bond-containing group), or one or more methylene groups in the divalent group formed by removing one hydrogen atom from the above-mentioned unsaturated double bond-containing group A group substituted with a divalent group selected from the above group (I) (hereinafter, sometimes referred to as a divalent methylene-substituted unsaturated double bond-containing group), particularly preferably having 1 to 30 carbon atoms The methylene substituted alkylene. The reason is that the above-mentioned polymerizable composition easily forms a coating material having excellent acid component capturing properties. Also, easy to obtain. In addition, the compounds represented by the following formulas (1-16) to (1-22) represent the following examples: R ¹ is substituted with a methylene group in an unsaturated double bond-containing group which may have a substituent The divalent group formed by removing one hydrogen atom from the divalent group selected from the above group (I) is a branched group and a group having a terminal unsaturated double bond structure. In addition, it shows an example in which R ¹ is a group having two terminal unsaturated double bond structures. In the above compound A1-5, when R ¹ is a divalent hydrocarbon group, the number of carbon atoms of the hydrocarbon group is preferably 1-25, of which 3-20 is preferred, and 5-15 is particularly preferred. When R ¹ is an alkylene group sometimes having substituents or a methylene group substituted alkylene group sometimes having substituents, the number of carbon atoms of the alkylene group and the methylene substituted alkylene group is preferable It is 1-25, preferably 3-20, especially more preferably 5-15. The reason is that the above-mentioned polymerizable composition easily forms a coating material having excellent acid component capturing properties. In addition, the above-mentioned polymerizable composition is easy to form a coating material having a high adhesive force. ^{When one or more methylene groups in the R 1} divalent hydrocarbon group used in the above compound A1-5 are substituted with a group selected from the divalent group of the above group (I), it is selected from The number of methylene groups substituted by divalent groups in the group (I) is preferably 1-6, more preferably 2-5. ^{When R 1} used in the above compound A1-5 is sometimes substituted with a substituted methylene group, the number of methylene groups substituted with the divalent group selected from the above group (I) Preferably it is 1-6, and among them, it is preferably 2-5. ^{In addition, R 1} used in the above compound A1-5 is a divalent hydrocarbon group in which one or more methylene groups in the hydrocarbon group are substituted with a divalent group selected from the above group (I) In case, the above-mentioned divalent group preferably contains at least one group selected from -O-, -NR ⁶ -(C=O)-O-, -CO-, -(C=O)-O-, Among them, it is preferable to include -O-. The reason for this is that this makes it easy for the polymerizable composition to form a coating material with excellent acid trapping properties. In the above compound A1-5, R ² is preferably a hydrogen atom, and R ¹ is an alkylene group sometimes having a substituent or a methylene-substituted alkylene group sometimes having a substituent, and the methylene group is substituted for the alkylene group. The divalent group substituted by the methylene group in the alkyl group includes -O-. As such a compound A1-5, for example, a compound represented by the following formula (A1-5) can also be exemplified. Among the above compounds A1-5, R ² is a hydrogen atom, or R ² is bonded to an adjacent nitrogen atom, that is ^{, a nitrogen atom bonded via R 1} to form a heterocyclic ring with two nitrogens. . As a specific example of such a compound A1-5, the compound represented by following formula (1-16)-(1-22) is mentioned, for example.

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The above-mentioned various acrylamides can be used individually by 1 type or in combination of 2 or more types.

(2) Urethane compound The aforementioned urethane compound is a compound having a urethane bond and an ethylenically unsaturated group. Furthermore, compounds containing a urethane bond and further having a structure in which an amide group and an ethylenically unsaturated group are directly bonded are acrylamide compounds and are not included in the urethane compound.

The number of ethylenically unsaturated groups contained in the urethane compound may be 1 or more, preferably 2 or more and 20 or less, more preferably 2 or more and 15 or less, and still more preferably 3 or more and 10 or less. The reason is that this makes it easy for the polymerizable composition to form a coating material having excellent acid component capturing properties and high adhesiveness.

Among the urethane compounds, in terms of easy progress of the polymerization reaction and excellent availability, the ethylenically unsaturated group is preferably an acrylic urethane or methacrylate group. Methacrylate urethane.

The molecular weight of the urethane compound should just be able to obtain the required acid component trapping properties and adhesive force, and is preferably 200 or more and 30,000 or less, more preferably 300 or more and 10,000 or less, and still more preferably 400 or more and 5,000 or less. The reason is that this allows the polymerizable composition to form a coating material having excellent acid component capturing properties and high adhesiveness.

As the urethane compound that can be preferably used in the present invention, for example, a compound represented by the following formula (10) or (11) can be mentioned.

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In the formula, R ¹¹ , R ¹² and R ¹³ each independently represent a monovalent hydrocarbon group having 1 to 30 carbon atoms, a monovalent heterocyclic group containing 2 to 30 carbon atoms, or the hydrocarbon group or the heterocyclic group containing One or more methylene groups are substituted with divalent groups selected from the following group (Ia), and at least one of ^{R 11} , R ¹² or R ^{13 has one or more hydrogen atoms} Is substituted with an acrylate group or a methacrylate group, X ¹ , X ² and X ³ each independently represent a divalent hydrocarbon group with 1 to 30 carbon atoms, a divalent heterocyclic group containing 2 to 30 carbon atoms, Or one or more methylene groups in the hydrocarbon group or the heterocyclic group are substituted with a divalent group selected from the following group (Ia), wherein two or more methylene groups are substituted In the case of a divalent group selected from the following group (Ia), the divalent group is not adjacent. Group (Ia): -O-, -S-, -NR ¹⁴ -, -NR ¹⁴ -(C=O)-O-, -CO-, -(C=O)-O-, -O-(C =O)-, -O-(C=O)-O- R ¹⁴ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms.

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In the formula, R ¹⁵ and R ¹⁶ each independently represent a monovalent hydrocarbon group having 1 to 30 carbon atoms, a monovalent heterocyclic group containing 2 to 30 carbon atoms, or one of the hydrocarbon group or the heterocyclic group containing The above methylene group is substituted with a divalent group selected from the following group (Ib), in which at least one of ^{R 15} or R ^{16 is substituted with an acrylate group} Or a methacrylate group, X ⁴ represents a divalent hydrocarbon group with 1 to 30 carbon atoms, a divalent heterocyclic group with 2 to 30 carbon atoms, or one or more of the hydrocarbon group or the heterocyclic group The methylene group is substituted with a divalent group selected from the following group (Ib), wherein two or more methylene groups are substituted with a divalent group selected from the following group (Ib) When, the divalent groups are not adjacent. Group (Ib): -O-, -S-, -NR ¹⁷ -, -NR ¹⁷ -(C=O)-O-, -CO-, -(C=O)-O-, -O-(C =O)-, -O-(C=O)-O- R ¹⁷ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms.

As the monovalent hydrocarbon group with 1 to 30 carbon atoms represented ^{by R 11} , R ¹² , R ¹³ and R ¹⁴ in formula (10), it ^{can be combined with R 1} , R ² , R ⁴ and R 4 in the above formula (A1) The monovalent hydrocarbon groups with 1 to 30 carbon atoms represented by ^{R 6 are the same.} As the monovalent heterocyclic group containing 2 to 30 carbon atoms represented ^{by R 11} , R ¹² and R ¹³ in formula (10), it ^{can be combined with R 1} , R ² and R ⁴ in formula (A1). The indicated monovalent heterocyclic group containing 1-30 carbon atoms and 2-30 carbon atoms is the same. Furthermore, the monovalent hydrocarbon group with 1-30 carbon atoms and the monovalent heterocyclic ring-containing group with 1-30 carbon atoms and 2-30 carbon atoms used for ^{R 11} , R ¹² and R ¹³ in formula (10) The group may include an alkenyl structure such as an internal alkenyl structure having an unsaturated double bond inside the group, a terminal alkenyl structure having an unsaturated bond at the end, but usually does not include an alkenyl structure. As the divalent hydrocarbon group with 1 to 30 carbon atoms and the divalent heterocyclic group with 2 to 30 carbon atoms represented ^{by X 1} , X ² and X ³ in the formula (10), it can be combined with the formula (A1) The divalent hydrocarbon group having 1 to 30 carbon atoms and the divalent heterocyclic group containing 2 to 30 carbon atoms represented by R ^{1 and X are the same.}

As the monovalent hydrocarbon group with 1 to 30 carbon atoms represented ^{by R 15} , R ¹⁶ and R ¹⁷ in the formula (11), it ^{can be combined with R 1} , R ² , R ⁴ and R ^{6 in the above formula (A1)} The indicated monovalent hydrocarbon groups with 1 to 30 carbon atoms are the same. As the monovalent heterocyclic group containing 2 to 30 carbon atoms represented ^{by R 15} and R ¹⁶ in the formula (11), it can be combined with the carbon represented by ^{R 1} , R ² and R ^{4 in the above formula (A1)} The monovalent heterocyclic group having 1 to 30 carbon atoms and 2 to 30 carbon atoms is the same. Furthermore, the monovalent hydrocarbon group with 1-30 carbon atoms and the monovalent heterocyclic group with 2-30 carbon atoms with 1-30 carbon atoms used ^{in R 15} and R ¹⁶ in formula (11) may include The group has an alkenyl structure such as an internal alkenyl structure having an unsaturated bond inside, and a terminal alkenyl structure having an unsaturated bond at the end, but usually does not include an alkenyl structure. As the divalent hydrocarbon group with 1 to 30 carbon atoms and the divalent heterocyclic group with 2 to 30 carbon atoms represented ^{by X 4} in formula (11), it ^{can be combined with R 1} and X in formula (A1) The indicated divalent hydrocarbon group having 1 to 30 carbon atoms and the divalent heterocyclic ring-containing group having 2 to 30 carbon atoms are the same.

In the present invention, R ¹¹ , R ¹² and R ¹³ in formula (10) are preferably a monovalent hydrocarbon group having 1 to 30 carbon atoms, or one or more methylene groups in the hydrocarbon group are substituted with the above group The group formed by (Ia) is more preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent, or one or more methylene groups in the alkyl group are substituted with the above group (Ia) The group (methylene-substituted alkyl group) is more preferably a methylene-substituted alkyl group having 1 to 30 carbon atoms which may have a substituent. The reason is that this makes it easy to form a coating material that has excellent acid trapping properties and high adhesiveness. When R ¹¹ , R ^12, and R ¹³ are alkyl groups or methylene substituted alkyl groups, from the viewpoint of easily forming a coating material with excellent acid trapping properties and high adhesiveness, the alkyl group or the alkyl group The number of carbon atoms of the methyl-substituted alkyl group is preferably 1-20, more preferably 2-10, and still more preferably 3-8. From the viewpoint of easily forming a coating material with excellent acid trapping properties and high adhesive force, it is preferable that two or more hydrogen atoms of the alkyl group or the methylene substituted alkyl group are acrylate groups or methacrylic acid groups. Ester group substitution, more preferably 2-7 hydrogen atoms are substituted with acrylate group or methacrylate group, and more preferably 3-6 hydrogen atoms are substituted with acrylate group or methacrylate group. From the viewpoint of easily forming a coating material having excellent acid component capturing properties and high adhesiveness, it is preferable that all of R ¹¹ , R ¹² and R ¹³ are substituted with an acrylate group or a methacrylate group. From the viewpoint of easily forming a coating material having excellent acid component capturing properties and high adhesiveness, the divalent group substituted by the methylene group in the methylene substituted alkyl group preferably contains -O-.

^{In the present invention, R 15} and R ¹⁶ in the formula (11) are preferably a monovalent hydrocarbon group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent. The reason is that this makes it easy to form a coating material that has excellent acid trapping properties and high adhesiveness. In the case where R ¹⁵ and R ¹⁶ are alkyl groups that may have substituents, from the viewpoint of easily forming a coating material with excellent acid trapping properties and high adhesiveness, the number of carbon atoms of the alkyl group is preferably 1-20, more preferably 2-15. The alkyl group is more preferably branched. From the viewpoint of easily forming a coating material with excellent acid trapping properties and high adhesion, it is preferable that 1 to 5 hydrogen atoms in the alkyl group are substituted with acrylate groups or methacrylate groups, and more preferably 2 to 4 hydrogen atoms are substituted with acrylate groups or methacrylate groups. From the viewpoint of easily forming a coating material having excellent acid component capturing properties and high adhesiveness, it is preferable that both R ¹⁵ and R ¹⁶ are substituted with an acrylate group or a methacrylate group. ^{In addition, X 4} in the formula (11) is preferably a divalent hydrocarbon group having 1 to 30 carbon atoms, more preferably an arylene group having 6 to 30 carbon atoms that may have a substituent, and more preferably sometimes The substituted arylene group having 6 to 20 carbon atoms is particularly preferably a phenylene group or a tolylene group. The reason is that this makes it easy to form a coating material that has excellent acid trapping properties and high adhesiveness.

As the urethane compound that can be used as the first polymerizable compound, for example, the derivatization of a reactive compound such as acrylic acid or hydroxyethyl acrylate and an isocyanate by addition reaction with a diisocyanate such as isophorone diisocyanate Things and so on. These derivatives can be extended by using caprolactone or polyols. As a urethane compound, you may use a commercial item. As such commercially available products, for example, U-122P, U-3, 40P, U-4HA, U-1084A (the above are manufactured by Shinnakamura Chemical Industry); KRM7595, KRM7610, KRM7619 (the above are Daicel-Cytec Manufacturing) and so on. A urethane compound can be used individually by 1 type or in combination of 2 or more types.

(3) Compounds containing isocyanuric acid ring The isocyanuric acid ring-containing compound is a compound having an isocyanuric acid ring and an ethylenically unsaturated group, and has an amide group derived from the isocyanuric acid ring. Furthermore, compounds having an isocyanuric acid ring and a structure in which an amide group and an ethylenically unsaturated group are directly bonded are acrylamide compounds, and are not included in the isocyanuric acid ring-containing compound. In addition, compounds that have an isocyanuric acid ring and a urethane bond, and do not have a structure in which an amide group and an ethylenically unsaturated group are directly bonded are urethane compounds, and are not included in the Polycyanate ring compound.

The number of ethylenically unsaturated groups contained in the isocyanuric acid ring-containing compound may be 1 or more, more preferably 1 or more and 15 or less, still more preferably 2 or more and 9 or less, and particularly preferably 3 or more 6 or less. The reason is that the polymerizable composition is easy to form a coating material having excellent acid component capturing properties and high adhesive force.

Among the isocyanuric acid ring-containing compounds, in terms of easy progress of the polymerization reaction and excellent availability, preferred are isocyanuric acid ring-containing acrylates in which the ethylenically unsaturated group is an acrylate group, Or the ethylenically unsaturated group is a methacrylate group containing isocyanuric acid ring methacrylate.

As the molecular weight of the isocyanuric acid ring-containing compound, as long as it can obtain the required acid trapping properties and adhesion, it is preferably 200 or more and 5000 or less, more preferably 300 or more and 3000 or less, and particularly preferably 400 or more and 2000 the following. The reason is that this makes it easy for the polymerizable composition to form a coating material having excellent acid component capturing properties and high adhesiveness.

As an isocyanuric acid ring-containing compound, the compound represented by following formula (12) can be mentioned.

[化27]

In the formula, R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a monovalent hydrocarbon group having 1 to 30 carbon atoms, a monovalent heterocyclic group containing 2 to 30 carbon atoms, or the hydrocarbon group or the heterocyclic group containing One or more methylene groups are substituted with divalent groups selected from the following group (Ic), and at least one hydrogen atom of at least one of ^{R 18} , R ¹⁹ and R ^{20 is} Substituted with an acrylate group or a methacrylate group, X ⁵ , X ⁶ and X ⁷ each independently represent a direct bond, a divalent hydrocarbon group with 1-30 carbon atoms, and a divalent heterocyclic ring-containing group with 2-30 carbon atoms Group, or one or more methylene groups in the hydrocarbon group or the heterocyclic group is substituted with a divalent group selected from the following group (Ia), wherein more than two methylene groups When substituted with a divalent group selected from the following group (Ic), the divalent group is not adjacent. Group (Ic): -O-, -S-, -NR ²²¹ -, -NR ²²¹ -(C=O)-O-, -CO-, -(C=O)-O-, -O-(C =O)-or -O-(C=O)-O-. R ²²¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms.

As the monovalent hydrocarbon group with 1 to 30 carbon atoms represented ^{by R 18} , R ¹⁹ , R ²⁰ and R ²²¹ in formula (12), it ^{can be combined with R 1} , R ² , R ⁴ and R 4 in the above formula (A1) The monovalent hydrocarbon groups with 1 to 30 carbon atoms represented by ^{R 6 are the same.} As the monovalent heterocyclic group containing 2 to 30 carbon atoms represented ^{by R 18} , R ¹⁹ and R ²⁰ in the formula (12), it ^{can be combined with R 1} , R ² and R ^{4 in the above formula (A1)} The indicated monovalent heterocyclic group containing 1-30 carbon atoms and 2-30 carbon atoms is the same. Furthermore, the monovalent hydrocarbon group with 1-30 carbon atoms and the monovalent heterocyclic ring with 1-30 carbon atoms and 2-30 carbon atoms used ^{in R 18} , R ¹⁹ and R ²⁰ in the formula (12) The group may include an alkenyl structure such as an internal alkenyl structure having an internal unsaturated double bond structure group, and a terminal alkenyl structure having an unsaturated bond at the end, but usually does not include an alkenyl structure. As the divalent hydrocarbon group with 1 to 30 carbon atoms and the divalent heterocyclic group with 2 to 30 carbon atoms represented ^{by X 5} , X ⁶ and X ⁷ in the formula (12), it can be combined with the formula (A1) The divalent hydrocarbon group having 1 to 30 carbon atoms and the divalent heterocyclic group containing 2 to 30 carbon atoms represented by R ^{1 and X are the same.}

In the present invention, R ¹⁸ , R ¹⁹ and R ^{20 are} preferably a monovalent hydrocarbon group having 1 to 30 carbon atoms, or one or more methylene groups in the hydrocarbon group are substituted with the above group (Ic) The group is more preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent, or a group in which one or more methylene groups in the alkyl group are substituted with the above group (Ic) (methylene group) Substituted alkyl group), and more preferably an alkyl group having 1 to 30 carbon atoms which may have a substituent. The reason is that this makes it easy to form a coating material that has excellent acid trapping properties and high adhesiveness. When R ¹⁸ , R ¹⁹ and R ²⁰ are sometimes substituted alkyl groups, the number of carbon atoms in the alkyl group is Preferably it is 1-20, more preferably 2-8. From the viewpoint of easily forming a coating material with excellent acid trapping properties and high adhesiveness, it is preferable that one or more hydrogen atoms at the terminal of the alkyl group are substituted with acrylate groups or methacrylate groups. More preferably, one hydrogen atom is substituted with an acrylate group or a methacrylate group. From the viewpoint of easily forming a coating material with excellent acid component capturing properties and high adhesiveness, it is preferable ^{that two or more of R 18} , R ¹⁹ and R ²⁰ are substituted with an acrylate group or a methacrylate group, More preferably, all of R ¹⁸ , R ¹⁹ and R ²⁰ are substituted with an acrylate group or a methacrylate group. ^{In addition, X 5} , X ⁶ and X ⁷ in formula (12) are preferably direct bonds or divalent hydrocarbon groups having 1 to 30 carbon atoms, more preferably direct bonds or sometimes substituted carbon atoms having 6 to The alkylene group of 30 is more preferably a direct bond. The reason is that this makes it easy to form a coating material that has excellent acid trapping properties and high adhesiveness.

As the isocyanuric acid ring-containing compound, a commercially available product may also be used. As such a commercially available product, for example, A-9300 and A93003CL (the above are manufactured by Shinnakamura Chemical Industry Co., Ltd.). As the acrylate compound, it is preferable to use tris(2-propenoxyethyl) isocyanurate represented by the following formula (A1-8). The reason is that this makes it easy for the polymerizable composition to form a coating material having excellent acid component capturing properties and high adhesiveness.

The above-mentioned isocyanuric acid ring-containing compound can be used individually by 1 type or in combination of 2 or more types.

(4) Other The first polymerizable compound contained in the polymerizable composition of the present invention may be composed only of an acrylamide compound, may be composed only of a urethane compound, or may be composed only of an isocyanuric acid ring-containing compound. The compound is composed. Alternatively, the first polymerizable compound may include two or more selected from the group consisting of acrylamide compounds, urethane compounds, and isocyanuric ring-containing compounds. In particular, from the viewpoint of easily forming a coating material having excellent acid component capturing properties and high adhesiveness, the first polymerizable compound preferably contains at least an acrylamide compound. In this case, the content of the acrylamide compound in the total 100 parts by mass of the first polymerizable compound is preferably 40 parts by mass or more, more preferably 50-100 parts by mass, and still more preferably 70-100 parts by mass, More preferably, it is 80-100 mass parts, More preferably, it is 90-100 mass parts, Especially preferably, it is 95-100 mass parts. By setting the content of the acrylamide compound in the above range, the curing rate of the polymerizable composition is excellent, which is preferable. In addition, from the viewpoint of making it have more excellent acid component trapping properties, the first polymerizable compound is preferably at least one of an acrylamide compound, a urethane compound, and an isocyanuric ring-containing compound These are used in combination, and among them, a urethane compound is preferably used in combination. When used in combination, the content of the acrylamide compound is preferably 40 parts by mass or more in the total 100 parts by mass of the first polymerizable compound, more preferably 50 to 99 parts by mass, and still more preferably 60 to 97 parts by mass It is more preferably 70 to 95 parts by mass, and still more preferably 85 to 93 parts by mass.

The content of the first polymerizable compound in the polymerizable composition of the present invention is preferably 10 parts by mass or more, and more preferably 20 parts by mass or more in 100 parts by mass of the solid content of the polymerizable composition. The reason is that this makes it easy for the polymerizable composition to form a coating material having excellent acid component capturing properties and high adhesiveness. From the viewpoint of excellent curability, the content of the first polymerizable compound in 100 parts by mass of the solid content of the polymerizable composition is preferably 70 parts by mass or more, and more preferably 90 parts by mass or more. In addition, from the viewpoint of making the acid component capturing properties particularly excellent, it is preferably 95 parts by mass or more, and more preferably 100 parts by mass. The reason is that, by setting the above content, the step of applying the polymerizable composition to the member and the step of polymerizing the first polymerizable compound in the polymerizable composition are adopted as the method of manufacturing the coated structure. In the case (hereinafter, the manufacturing method of the coating structure having the coating step and the polymerization step is sometimes referred to as the first manufacturing method), it is easy to form a coating material with a high adhesive force. In addition, the content of the first polymerizable compound in 100 parts by mass of the solid content of the polymerizable composition is preferably 20 parts by mass or more and 50 parts by mass or less, more preferably 25 parts by mass or more and 35 parts by mass or less. The reason is that by setting the above content, the step of polymerizing the first polymerizable compound in the polymerizable composition to form a coating material and the coating material obtained in the step of forming the coating material and the acid component are used In the case where the step of contacting the member is used as the manufacturing method of the covering structure (hereinafter, the method of manufacturing the covering structure using the covering material forming step and the contacting step is sometimes referred to as the second manufacturing method), the covering material is easy to adhere to the acid-containing Components of ingredients. In addition, the solid component refers to the one containing all the components of the polymerizable composition excluding the solvent. Furthermore, in more detail, the above-mentioned first manufacturing method may be the same as the first method described in "1. Coating step" in the item of "C. Manufacturing method of covered structure" below, and in more detail, the above The second manufacturing method can be the same as the second method described in "1. Coating Step" in the section of "C. Manufacturing Method of Coated Structure" below.

2. The second polymerizable compound The polymerizable composition of the present invention may further contain a second polymerizable compound in addition to the first polymerizable compound. The second polymerizable compound is a compound having an ethylenically unsaturated group other than the first polymerizable compound. By making it contain the second polymerizable compound in addition to the first polymerizable compound, the cured product obtained has a high adhesive force.

In the present invention, as the second polymerizable compound, for example, a compound having an ethylenically unsaturated group such as an acrylic group, a methacryl group, and a vinyl group and not having an amide group can be used, and it is not particularly limited. The second polymerizable compound may be a monofunctional compound having one ethylenically unsaturated group, or may be a multifunctional compound having two or more ethylenically unsaturated groups. As the second polymerizable compound, a known compound can be used. For example, the compound described in International Publication No. 2018/012383, the polymerizable organic substance described in International Publication No. 2014/021023, and the like can be used as the second polymerizable compound.

As the second polymerizable compound, for example, a hydrocarbon having 1 to 30 carbon atoms, or a compound in which one or more methylene groups in the hydrocarbon are substituted with a divalent group selected from the following group a One or more of the hydrogen atoms is substituted with an acrylate group or a methacrylate group. However, when two or more methylene groups of the above-mentioned hydrocarbon are substituted with a divalent group selected from the following group (I), the divalent group is not adjacent. In addition, the above-mentioned hydrocarbon may have a substituent. The substituent may, for example, be a monovalent hydrocarbon group having 1 to 30 carbon atoms. The hydrocarbon group may be the same as the monovalent hydrocarbon group having 1 to 30 carbon atoms ^{in R 1} , R ² , R ³ , and R ^{4 in the formula (A1).} Group a: -O-, -CO-, -(C=O)-O-, -O-(C=O)- or -O-(C=O)-O-.

The second polymerizable compound to be combined with the first polymerizable compound can be appropriately determined according to the use of the acid component-containing member coated with the polymer of the polymerizable composition of the present invention. When the above-mentioned polymerizable composition is used in the first manufacturing method as the manufacturing method of the covering structure, as the second polymerizable compound, it is possible to easily form a covering material with excellent acid trapping properties and high adhesiveness. From the aspect, it is preferable to use a monofunctional compound, for example, phenoxy polyalkylene glycol acrylate such as phenoxy polyethylene glycol acrylate. From the viewpoint of easy formation of a coating material with excellent acid component capturing properties and high adhesiveness, it is also preferable to use as the second polymerizable compound: for example, 1,9-nonanediol diacrylate and 1,10- Acrylate compounds of glycols such as decanediol diacrylate; and bifunctional second polymerizable compounds such as polyalkylene glycol diacrylates such as polyethylene glycol diacrylate and polypropylene glycol diacrylate.

When the polymerizable composition is used in the second manufacturing method as the manufacturing method of the coated structure, from the viewpoint that the coating material containing the polymer of the polymerizable composition is easily attached to the member containing the acid component, the first 2 The polymerizable compound is preferably a compound represented by the following formula (13).

[化28]

In the formula, Al represents a chain-like or alicyclic alkyl group having 1 to 30 carbon atoms which may have a substituent, and R ²¹² represents a hydrogen atom or a methyl group.

As the chain-like or alicyclic alkyl group with 1-30 carbon atoms used for Al, the carbon number 1 used for R ¹ , R ² , R ³ , and R ^{4 in the above formula (A1) can be used} An exemplary group of -30 aliphatic hydrocarbon groups. Specific examples of such alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl. Linear or branched chain alkyl such as alkyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, cycloheptyl, cyclooctyl Cycloalkyl and cycloalkylalkyl such as cyclononyl.

In the present invention, the number of carbon atoms of the alkyl group represented by Al is preferably from 1 to 20, more preferably from 1 to 10, and still more preferably from 1 to from the viewpoint of easy formation of a coating material with high adhesive force. 5. From the viewpoint of easy formation of a coating material with high adhesive force, the alkyl group represented by Al is preferably chain-like. From the viewpoint of easily forming a coating material with high adhesive force, the alkyl group is preferably unsubstituted.

As the compound represented by the formula (13), alkyl acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate are preferably used. The reason is that by using the first polymerizable compound together with the alkyl acrylate, when the above-mentioned polymerizable composition is used in the second manufacturing method as the manufacturing method of the covered structure, the polymerization of the polymerizable composition is included. The coating material of the object is easy to adhere to the member containing the acid component, and can be preferably used as an adhesive sheet.

The glass transition temperature (Tg) of the second polymerizable compound is preferably 0°C or lower, more preferably -20°C or lower, and still more preferably -30°C to -50°C. The reason is that by using the second polymerizable compound whose glass transition temperature is within the above-mentioned range, when the above-mentioned polymerizable composition is used in the second manufacturing method of the manufacturing method of the covered structure, the polymerizable composition is included The polymer coating material is easy to adhere to the member containing the acid component. The glass transition temperature means, for example, the Tg of the homopolymer of the second polymerizable compound. The Tg of the homopolymer can be measured according to the method specified in JIS K7121:2012.

The second polymerizable compound may be used singly or in combination of two or more kinds.

When the polymerizable composition of the present invention contains the first polymerizable compound and the second polymerizable compound, the content of the first polymerizable compound is more than 100 parts by mass of the total of the first polymerizable compound and the second polymerizable compound. It is preferably 20 parts by mass or more, more preferably 20 to 50 parts by mass, and even more preferably 25 to 35 parts by mass. The reason is that by setting the content of the first polymerizable compound in the above range, when the polymerizable composition is used in the second manufacturing method as a method for manufacturing a covered structure, the polymerized composition is included. The polymer coating material is easy to adhere to the member containing the acid component.

3. Free radical polymerization initiator The polymerizable composition of the present invention may further contain a radical polymerization initiator. By containing a radical polymerization initiator, the polymerization of the first polymerizable compound is facilitated. The radical initiator may, for example, be a photo radical polymerization initiator or a thermal radical polymerization initiator. As the photo radical polymerization initiator and the thermal radical polymerization initiator, a known radical polymerization initiator can be used, and there is no particular limitation. As the radical polymerization initiator, it is particularly preferable to use a photoradical polymerization initiator. The reason is that this will further improve the polymerizability of the polymerizable composition. As the photoradical polymerization initiator, preferred acetophenone-based compounds, acylphosphine-based compounds, and the like can be exemplified. As such a photoradical polymerization initiator, the compounds described in Japanese Patent Application Publication No. 2018-172495, Japanese Patent Application Publication No. 2018-127527, and Japanese Patent Application Publication No. 2017-098290 may be mentioned.

The content of the radical polymerization initiator in the polymerizable composition of the present invention is preferably 1-20 parts by mass, more preferably 1-10 parts by mass relative to 100 parts by mass of the total of the first polymerizable compound and the second polymerizable compound Mass parts. By setting the content of the polymerization initiator to 1 part by mass or more, it is easy to prevent poor curing caused by insufficient curing sensitivity. Therefore, it is preferably set to 20 parts by mass or less to suppress the generation of volatiles during light irradiation or heating. .

4. Solvent The polymerizable composition of the present invention may contain a solvent. The solvent is liquid at normal temperature (25°C) and atmospheric pressure, and is capable of dispersing or dissolving each component of the polymerizable composition. Therefore, even if the first polymerizable compound, the second polymerizable compound, the acid generator, and the sensitizer described below are liquid at normal temperature (25° C.) and atmospheric pressure, they are not included in the solvent. As the above-mentioned solvent, both water and organic solvents can be used. In the present invention, the above-mentioned solvent is preferably an organic solvent. The reason is that it is easy to dissolve or disperse the first polymerizable compound and the second polymerizable compound in this way.

Examples of organic solvents include: carbonates such as propylene carbonate and diethyl carbonate; ketones such as acetone and 2-heptanone; ethylene glycol, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and dipropylene glycol mono Polyols and derivatives such as monomethyl ether or monophenyl ether of acetate; cyclic ethers such as dioxane; esters such as ethyl formate and 3-methyl-3-methoxybutyl acetate Classes; aromatic hydrocarbons such as toluene and xylene; lactones such as γ-caprolactone and δ-caprolactone, etc.

The content of the solvent in the polymerizable composition is preferably 80 parts by mass or less in 100 parts by mass of the polymerizable composition. Furthermore, when the polymerizable composition contains a solvent, the content of the solvent is more preferably 5 parts by mass or more and 50 parts by mass or less, and still more preferably 10 parts by mass or more and 40 parts by mass or less. The reason is that by setting the content of the solvent in the above range, the coatability of the polymerizable composition becomes good.

5. Sensitizer The polymerizable composition of the present invention may contain a sensitizer. As this sensitizer, the compound described as a spectral sensitizer in Japanese Patent Application Publication No. 2008-506749 may be mentioned, for example. The content of the above-mentioned sensitizer only needs to be able to form a coating material with excellent acid component capturing properties and high adhesive force. The above-mentioned sensitizer is preferably 0.1 parts by mass or more and 50 parts by mass relative to 100 parts by mass of the radical polymerization initiator Part or less, more preferably 1 part by mass or more and 10 parts by mass or less.

6. Additives In addition to the first polymerizable compound, the second polymerizable compound, a radical polymerization initiator, a solvent, and a sensitizer, the polymerizable composition of the present invention may also contain customary additives, such as polymerizable compounds, polymerizable compounds, and sensitizers. Initiators, colorants, inorganic compounds, latent additives, organic polymers, chain transfer agents, surfactants, silane coupling agents, melamine compounds, thermal polymerization inhibitors; plasticizers; adhesion promoters; fillers; Foaming agent; leveling agent; surface regulator; antioxidant; ultraviolet absorber; dispersing aid; anti-cohesive agent; catalyst; effect accelerator; crosslinking agent; tackifier, etc.

The content of the above-mentioned additives in the polymerizable composition of the present invention can be appropriately determined according to the types of additives. From the viewpoint of being able to form a coating material with excellent acid component capturing properties and high adhesion, the total content of the above-mentioned additives in 100 parts by mass of the polymerizable composition is preferably 30 parts by mass or less, more preferably 20 parts by mass Below, it is especially preferable that it is 10 mass parts or less.

7. The component containing the acid component The polymerizable composition of the present invention is used to coat the component containing the acid component. In the present invention, the acid component may be one that can supply protons (H ⁺ ). Examples of such acid components include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, as well as organic acids such as carboxylic acids (aromatic carboxylic acid and aliphatic carboxylic acid, etc.), and organic acids such as sulfonic acid and sulfinic acid. _{Acid, FeCl 3} , AlCl ₃ , Fe(OTs) ₃ , PF ₅ , AsF ₅ , SbF ₅ , BF ₃ , BCl ₃ , BBr ₃ that can supply protons in the presence _{of water (H 2} O) that can penetrate from the outside , And SO ₃ and other Lewis acids. The acid component contained in the above-mentioned member may be contained in advance as a forming material of the above-mentioned member, or may be generated when the above-mentioned member is formed. As for the content of the above-mentioned acid component, it is sufficient that corrosion of peripheral components, modification of other components in the component containing the acid component, etc. occur in the absence of the above-mentioned coating material due to defects caused by the acid component, for example, In 100 parts by mass of the above-mentioned acid component-containing member, it may be 0.001 part by mass or more and 5 parts by mass or less. In the present invention, the above-mentioned acid component-containing member is preferably a member containing a hardened product of a cation hardening composition containing an acid generator and a cation hardening component, that is, the acid generator in the above-mentioned cation hardening composition An acid component is generated, whereby the above-mentioned cation curable components are hardened to each other. The reason is that it has the following advantages: it is easy to form a member of a desired shape; it is easy to form a member at the required time. In addition, the coating may cover the entire component containing the acid component, or a part of it. For example, the upper surface of the coating film may be covered for a specific area of the coating film in a plan view, or the upper surface of the coating film may not be covered, but formed in a frame shape so as to cover only the side surface of the coating film. In addition, the coating is not limited to the case where it is placed directly in contact with the member containing the acid component, and it also includes the case where it is placed through other members. Among them, in the present invention, in terms of being able to effectively capture the acid component in the above-mentioned member, it is preferable to arrange it directly in contact with the above-mentioned member.

(1) Cationic curable composition The cationic curable composition contains an acid generator and a cationic curable component. Hereinafter, the cationic curable composition will be described in detail.

(1-1) Cationic hardening ingredients As the cation curable component contained in the cation curable composition, as long as it is a compound that causes the polymerization or crosslinking reaction by the acid generated by the acid generator, it can be used without particular limitation. As the cation curable component, for example, epoxy compounds, oxetane compounds, cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, spiroorthoester compounds, vinyl compounds, etc. can be used. The cationic curable component can be used singly or in combination of two or more kinds. As an example of a cationic curable composition containing two or more types of cationic curable components, those containing two or more types of cationic curable components different in structure, molecular weight, etc. can be mentioned.

As a combination of cationic curable components with different structures, for example, an epoxy compound, an oxetane compound, a cyclic lactone compound, a cyclic acetal compound, a cyclic thioether compound, and a spiroorthoester may be mentioned. A combination of two or more of different classifications such as a compound and a vinyl compound, for example, includes a combination of an epoxy compound and an oxetane compound. Specifically, a combination of two or more selected from aromatic epoxy compounds, alicyclic epoxy compounds, and aliphatic epoxy compounds can be exemplified, such as containing aliphatic epoxy compounds as epoxy compounds and Those containing alicyclic epoxy compounds, those containing aliphatic epoxy compounds and aromatic epoxy compounds as epoxy compounds, those containing aromatic epoxy compounds and alicyclic epoxy compounds, and the like.

As a combination of cationic curable components having different molecular weights, for example, a combination of two types of aliphatic epoxy compounds having different molecular weights as epoxy compounds can be mentioned.

In the present invention, from the viewpoint of improving the adhesion between the polymer of the polymerizable composition and the cured product, the cationic curable component preferably contains at least one selected from epoxy compounds and oxetane compounds .

As long as the epoxy compound used as the cationic curable component contains an epoxy structure, the type is not particularly limited. For example, a compound containing both an epoxy structure and an oxetane structure is an epoxy compound. As such an epoxy compound, an aromatic epoxy compound, an alicyclic epoxy compound, an aliphatic epoxy compound, etc. are mentioned, for example. In the present invention, the epoxy compound particularly preferably contains at least an alicyclic epoxy compound.

(1-1-1) Alicyclic epoxy compound The alicyclic epoxy compound has an epoxy cycloalkyl group in which an alicyclic ring and an epoxy ring share a part of the ring structure. Furthermore, when it contains both an aromatic ring and an epoxy cycloalkyl group, it belongs to an alicyclic epoxy compound. As the alicyclic epoxy compound, an epoxycyclohexane or epoxycyclopentane-containing compound obtained by epoxidizing a compound containing a cyclohexene ring or a cyclopentene ring with an oxidizing agent can be exemplified.

As an alicyclic epoxy compound, for example, 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexyl methyl ester, 3,4-epoxy-1-methylcyclohexyl-3 ,4-Epoxy-1-methylhexane carboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexane carboxylate, 3,4-Epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexane carboxylate, 3,4-epoxy-5-methylcyclohexylmethyl- 3,4-Epoxy-5-methylcyclohexane carboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta Alkyl, bis(3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexylcarboxylate, methylene bis(3,4-epoxycyclohexyl) Alkane), dicyclopentadiene diepoxide, ethylenebis(3,4-epoxycyclohexane carboxylate), dioctyl epoxyhexahydrophthalate, epoxyhexahydrophthalate Di(2-ethylhexyl) dicarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane, 1,2-epoxy-2-epoxyethylcyclohexane, acrylic acid 3,4 -Epoxycyclohexyl methyl ester, 3,4-epoxycyclohexyl methyl methacrylate, etc. As the alicyclic epoxy compound, from the viewpoint of excellent curability, 3,4-epoxycyclohexanecarboxylic acid 3,4-epoxycyclohexyl methyl ester and 3,4-epoxy-1 are particularly preferred -Methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, etc. Moreover, when the cationic curable composition contains a dye, it is preferable from the viewpoint that a cured product having excellent light absorption in the desired wavelength region can be obtained. Epoxy compounds containing both aliphatic and aromatic rings belong to alicyclic epoxy compounds.

As an alicyclic epoxy compound, you may use a commercial item. As such a commercially available product, for example, those described in Japanese Patent No. 6103653, etc. may be mentioned.

As the alicyclic epoxy compound, the compound represented by formula (21) can also be preferably used.

[化29]

In the formula, n1 represents an integer of 1 or 2. When n1 is 1, A represents a monovalent hydrocarbon group with 1 to 30 carbon atoms, or one or more methylene groups in the hydrocarbon group are substituted to be selected from the following A group composed of a divalent group of the group (II), wherein when two or more methylene groups are substituted with a divalent group selected from the following group (I), the divalent group is not adjacent , One or more hydrogen atoms in the hydrocarbyl group may be substituted by an epoxy group. When n1 is 2, A represents a divalent hydrocarbyl group with 1 to 30 carbon atoms, or one or more of the divalent hydrocarbyl groups The methylene group is substituted with a divalent group selected from the following group (II), wherein two or more methylene groups are substituted with a divalent group selected from the following group (I) In this case, the divalent groups are not adjacent, and more than one hydrogen atom in the divalent hydrocarbon group may be substituted by epoxy groups. Group (II): -O-, -S-, -NR ³¹ -, -NR ³¹ -(C=O)-O-, -CO-, -(C=O)-O-, -O-(C =O)-or -O-(C=O)-O-. R ³¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms.

As the monovalent hydrocarbon group with 1 to 30 carbon atoms represented ^{by A and R 31} in formula (21), it ^{can be combined with R 1} , R ² and R ³ in the above general formula (A1), and in the group (a) The monovalent hydrocarbon groups with 1 to 30 carbon atoms represented by R ^{4 are the same.} As the divalent hydrocarbon group with 1 to 30 carbon atoms represented by A in the formula (21), it can be used with the divalent hydrocarbon group with 1 to 30 carbon atoms represented by ^{R 1 when n1 = 2 in the general formula (A1).} The hydrocarbon groups are the same. In addition, regarding the above-mentioned monovalent hydrocarbon group with 1 to 30 carbon atoms and a divalent hydrocarbon group with 1 to 30 carbon atoms, when the hydrogen atom in the group is substituted by a substituent, as the substituent, the above general formula can be used (A1) Exemplary groups and epoxy groups etc. of the substituents substituted by hydrogen atoms in the hydrocarbon groups used for ^{R 1} etc. in (A1).

In the present invention, when n1 in formula (21) is 1, A is preferably a monovalent hydrocarbon group having 1 to 30 carbon atoms, and among these, it is preferably a monovalent hydrocarbon group having 1 to 30 carbon atoms which may have a substituent. The alkyl group of 30. The reason is that it is easy to further improve the adhesion between the polymer of the polymerizable composition and the cured product. When n is 1, the number of carbon atoms of A is preferably 1-20, and among them, it is preferably 1-10, and particularly preferably 1-4. As the substituent for substituting one or more hydrogen atoms in the monovalent hydrocarbon group used in A, an epoxy group can be preferably used. The reason is that it is easy to further improve the adhesion between the polymer of the polymerizable composition and the cured product.

In the present invention, when n1 in formula (21) is 2, A is preferably a divalent hydrocarbon group having 1 to 30 carbon atoms. One or more methylene groups are substituted to be selected from the above group ( II) is a group consisting of a divalent group, and among them, it is preferable that the methylene group in the alkylene group having 1 to 30 carbon atoms that may have a substituent is substituted with a divalent group selected from the above group (II) It is preferable that the divalent group substituted for the methylene group in the alkylene having 1 to 30 carbon atoms which may have a substituent includes -O-(C=O)- or -O-( C=O)-O-. When n is 2, the number of carbon atoms of A is preferably 1-20, and among them, 2-10 is preferable. The reason is that it is easy to further improve the adhesion between the polymer of the polymerizable composition and the cured product.

The content of the alicyclic epoxy compound contained in the cationic curable composition is, for example, preferably 40 parts by mass or more in 100 parts by mass of the cationic curable component, and among them, it is preferably 50 parts by mass or more, and more preferably 60 parts by mass. Parts by mass or more and 90 parts by mass or less. The reason is that it is easy to further improve the adhesion between the polymer of the polymerizable composition and the cured product.

(1-1-2) Aromatic epoxy compound The aromatic epoxy compound should just be an epoxy compound which has an aromatic ring, and is an epoxy compound which does not contain an epoxy cycloalkyl group. As a specific example of such an aromatic epoxy compound, a polyphenol having at least one aromatic ring, or a polyglycidyl ether of an alkylene oxide adduct thereof, such as bisphenol A, bisphenol F, Or the glycidyl etherate or phenol novolak type epoxy compound of a compound obtained by adding alkylene oxide to it; resorcinol, hydroquinone, catechol, etc. have two or more phenolic hydroxyl groups Glycidyl ethers of aromatic compounds; polyglycidyl ethers of aromatic compounds with more than two alcoholic hydroxyl groups such as benzenedimethanol, benzenediethanol, and benzenedibutanol; phthalic acid, terephthalic acid, Trimellitic acid and other polyglycidyl esters of aromatic compounds with more than two carboxylic acids, benzoic acid or toluic acid, naphthoic acid and other benzoic acid polyglycidyl esters, benzoic acid glycidyl esters, benzene oxide Epoxides of ethylene or divinylbenzene, etc. Among them, preferred are polyglycidyl ethers containing polyglycidyl ethers selected from phenols, aromatic compounds having two or more alcoholic hydroxyl groups, polyglycidyl ethers of polyphenols, and polyglycidyls of benzoic acid. At least one of glycerides and polyglycidyl esters of polybasic acids is particularly preferably a polyglycidyl etherate of an aromatic compound having two or more alcoholic hydroxyl groups.

As the aromatic compound epoxy compound, a compound represented by formula (22) can be preferably used.

[化30]

Wherein, R ^a represents a methylene _{group, -CH (CH 3) -,} - C (CH 3) 2 -, or -CH (R ^d), R ^b represents a number of 1 to 4 carbon atoms, alkyl of stretch, R ^c represents a direct bond or -O-, R ^d represents a group represented by the following formula (b), and n2 represents an integer of 1-4.

[化31]

Wherein, R ^{a 'represents} a methylene group, -CH (CH ₃₎ -, or _{-C (CH 3) 2 -,} R b' represents a number of 1 to 4 carbon atoms, alkyl of stretch, R ^{c 'represents} a direct bond Or -O-, n2' represents an integer from 1 to 4, and * represents a bonding bond.

The alkylene group having 1 to 4 carbon atoms represented by ^{R b} and R ^b'may be one having 1 to 4 carbon atoms in the alkylene group having 1 to 30 carbon atoms represented by ^{R 1.}

As the aromatic epoxy compound, commercially available products may also be used. As such a commercially available product, for example, those described in Japanese Patent No. 6103653, etc. may be mentioned.

The content of the aromatic epoxy compound is not particularly limited. For example, in 100 parts by mass of the cationic curable component, it can be set to 0 parts by mass or more and 60 parts by mass or less. When the above-mentioned cationic curable component contains an aromatic epoxy compound, the content of the aromatic epoxy compound in 100 parts by mass of the cationic curable component is preferably 1 part by mass or more and 50 parts by mass or less, and among them, it is preferably 5 Parts by mass or more and 20 parts by mass or less. The reason is that, by setting the content in this range, the balance between the coatability and curability of the cationic curable composition is excellent.

(1-1-3) Aliphatic epoxy compound The aliphatic epoxy compound may be an epoxy compound that does not contain an aromatic ring and an epoxycycloalkyl group, and examples include: polyglycidyl ether of a polyol having at least one aliphatic ring, and aliphatic polyvalent Homopolymer synthesized by vinyl polymerization of polyglycidyl ether of alcohol or its alkylene oxide adduct, polyglycidyl ester of aliphatic long-chain polybasic acid, glycidyl acrylate or glycidyl methacrylate; glycidyl acrylate Copolymers of glycerol ester or glycidyl methacrylate and other vinyl monomers through vinyl polymerization.

As a representative aliphatic epoxy compound, for example, hydrogenated bisphenol A diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol ter Glycidyl ether, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, etc. Glycidyl ether of alcohol; In addition, polyglycidyl ether of polyether polyol obtained by adding one or more kinds of alkylene oxide to aliphatic polyols, such as propylene glycol, trimethylolpropane, glycerol, etc., Diglycidyl ester of aliphatic long-chain dibasic acid. Further examples include: monoglycidyl ether of aliphatic higher alcohols or phenol, cresol, butyl phenol; in addition, monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxide to them, and glycidyls of higher fatty acids Glycerides, epoxidized soybean oil, epoxy octyl stearate, epoxy butyl stearate, epoxidized polybutadiene, etc. Furthermore, the aliphatic epoxy resin may not contain an aliphatic ring and an aromatic ring.

The content of the aliphatic epoxy compound is not particularly limited. For example, in 100 parts by mass of the cationic curable component, it can be set to 0 parts by mass or more and 60 parts by mass or less. When the above-mentioned cationic curable component contains an aliphatic epoxy compound, the content of the aliphatic epoxy compound in 100 parts by mass of the cationic curable component is preferably 1 part by mass or more and 50 parts by mass or less, and particularly preferably 5 More than 40 parts by mass and less than 40 parts by mass. The reason is that, by setting the content in this range, the balance between the coatability and curability of the cationic curable composition is excellent. As an aliphatic epoxy compound, you may use a commercial item. As such a commercially available product, for example, those described in Japanese Patent No. 6103653, etc. may be mentioned.

The total content of the various epoxy compounds contained in the cationic curable component is preferably 50 parts by mass or more in 100 parts by mass of the cationic curable component, more preferably 60 parts by mass or more, and still more preferably 80 parts by mass or more. The reason is that this will make the cationic curable composition have an excellent balance between coatability and curability.

As the cationic curable component contained in the cationic curable composition, as described above, an oxetane compound can also be used. As an oxetane compound, what has an oxetane structure and does not contain an epoxy structure may be sufficient. As such an oxetane compound, the compound described in Japanese Patent No. 6103653 etc. can be mentioned, for example.

The content of the oxetane compound is not particularly limited. For example, in 100 parts by mass of the cationic curable component, it can be set to 0 parts by mass or more and 40 parts by mass or less. When the cation curable component contains an oxetane compound, the content of the oxetane compound is preferably 10 parts by mass or more and 30 parts by mass or less. The reason is that this will make the cationic curable composition have an excellent balance between coatability and curability.

As the cation curable component contained in the cation curable composition, in addition to the above, a thiane compound, a thietane compound, and the like may also be exemplified. Furthermore, cyclic lactone compounds, cyclic acetal compounds, cyclic thioether compounds, spiroorthoester compounds, and vinyl compounds such as vinyl ether compounds and ethylenically unsaturated compounds can also be used as cation curable components. . The details of these cationic curable components may be the same as those described in International Publication No. 2013/172145.

The cationic curable component contained in the cationic curable composition may be any one of a low molecular weight compound and a high molecular weight compound. From the viewpoint of easy coating of the cationic curable composition, the cationic curable component is preferably a low molecular weight compound. In addition, the low-molecular-weight compound is excellent in dispersibility, solubility, etc. in the cation curable composition, so it is possible to obtain a cured product having excellent transparency, which is also advantageous in this respect. On the other hand, from the viewpoint of improving the adhesion of the cured product of the cationic curable composition, the cationic curable component is preferably a high molecular weight compound.

From the viewpoint of coatability and the like, the cationic curable composition preferably contains at least a low molecular weight compound as the cationic curable component. However, from the viewpoint of the balance between the ease of coating of the cationic curable composition and the adhesion of the cured product obtained from the cationic curable composition, the cationic curable composition may also include low molecular weight compounds and high molecular weight compounds Both.

The molecular weight of the low-molecular-weight compound may be as long as the desired coatability and the like can be obtained. For example, it can be set to 1000 or less, preferably 50 or more and 500 or less, and among them, 50 or more and 300 or less. On the other hand, the molecular weight of the high-molecular-weight compound may be as long as the desired adhesiveness and the like can be obtained. For example, it may be greater than 1,000, preferably 1,000 or more and 50,000 or less, and among them, 1,000 or more and 10,000 or less. In this specification, the molecular weight means the weight average molecular weight (Mw) when the compound is a polymer. The weight average molecular weight can be calculated by gel permeation chromatography (GPC) in terms of standard polystyrene. Specifically, for the weight average molecular weight Mw, for example, GPC (LC-2000plus series) manufactured by JASCO Corporation can be used, the elution solvent is tetrahydrofuran, and the polystyrene standard for the calibration curve is Mw1110000, 707000, 397000 , 189000, 98900, 37200, 13700, 9490, 5430, 3120, 1010, 589 (TSKgel standard polystyrene manufactured by Tosoh Corporation), set the measuring column to KF-804, KF-803, KF-802 (Manufactured by Showa Denko Co., Ltd.). The measurement temperature can be set to 40°C, and the flow rate can be set to 1.0 mL/min.

The content of the low-molecular-weight compound contained in the cationic curable composition is not particularly limited. For example, it is preferably 10 parts by mass or more in 100 parts by mass of the cationic curable component, and more preferably 30 parts by mass or more, particularly It is 50 parts by mass or more, preferably 60 parts by mass or more. The reason for this is that by setting the above content within the above range, the cationic curable composition has an excellent balance between coatability and curability.

The content of the cationic curable component in the cationic curable composition is not particularly limited. For example, in 100 parts by mass of the solid component of the cationic curable composition, it can be 50 parts by mass or more, preferably 50 parts by mass or more 99 parts by mass or less, among them, 70 parts by mass or more and 96 parts by mass or less are preferable, and among them, 85 parts by mass or more and 95 parts by mass or less are preferable. The reason for this is that by setting the above content within the above range, the cationic curable composition has an excellent balance between coatability and curability.

In addition, the content of the cationic curable component in 100 parts by mass of the resin component in the cationic curable composition can be 50 parts by mass or more, preferably 80 parts by mass or more, and among them, 90 parts by mass or more, especially Preferably, it is 95 parts by mass or more. Moreover, it may be 100 parts by mass, that is, only the cationic curable component may be contained as the resin component. The reason for this is that by setting the above content within the above range, the cationic curable composition has an excellent balance between coatability and curability.

(1-2) Acid generator As the acid generator contained in the curable composition together with the cation curable component, there is no problem in any of them as long as it is a compound that can generate an acid under specific conditions, and is not particularly limited. As such an acid generator, for example, a photoacid generator that can generate acid by light irradiation such as ultraviolet irradiation, and a thermal acid generator that can generate acid by heat can be used. As the acid generator, at least one of a photoacid generator and a thermal acid generator can be used. From the viewpoint of ease of hardening, the ability to reduce thermal damage to peripheral members used adjacent to the cationic curable composition during hardening, and the viewpoint of increasing the freedom of choice of peripheral members, a photoacid generator is preferred. In addition, the photoacid generator also has the advantage of a faster curing speed. On the other hand, the acid generator is preferably a thermal acid generator from the viewpoint that a hardened product is easily formed at a position hard to reach by light. In addition, since the thermal acid generator has a relatively slow curing speed, it can be easily bonded to other members after being subjected to a curing treatment (heat treatment) with the thermal acid generator.

The content of the acid generator contained in the cation curable composition is singly or the total amount of plural kinds, in 100 parts by mass of the solid content of the cationic curable composition, it can be set to 0.01 parts by mass or more and 10 parts by mass or less Among them, it is preferably not less than 0.1 parts by mass and not more than 5 parts by mass. The reason for this is that it is possible to more effectively exhibit the excellent acid component trapping effect of the present invention.

In the cationic curable composition, the use ratio of the acid generator to the cationic curable component is not particularly limited, as long as it is used at a generally normal use ratio within a range that does not hinder the purpose of the present invention. For example, relative to 100 parts by mass of the cationic curable component, the acid generator is preferably 0.05 parts by mass or more and 10 parts by mass or less, preferably 0.5 parts by mass or more and 8 parts by mass or less, preferably 1 part by mass or more and 7 parts by mass or less . The reason is that by setting the use ratio in the above range, the cationic curable component can be sufficiently hardened, and the effect of the present invention of excellent acid component trapping properties can be more effectively exhibited.

As a photoacid generator used as an acid generator contained in a cation curable composition, a well-known thing can be used without a restriction|limiting in particular. In the present invention, in terms of sensitivity, the aromatic sulfonium salt represented by the following formula (2) is more preferable. In addition, the reason is that by using the above-mentioned aromatic sulfonium salt as the photoacid generator, the above-mentioned aromatic sulfonium salt is excellent in acid generation efficiency, and therefore the excellent acid component trapping effect of the present invention can be exerted more effectively.

[化32]

(In the formula, R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ and R ³⁴ each independently represent hydrogen Atoms, halogen atoms, sometimes substituted alkyl groups with 1 to 10 carbon atoms, and methylene groups other than the end of the bonding site in the alkyl group are substituted under the condition that oxygen atoms are not adjacent to each other. A group formed from a divalent group of the above group (I), an alkoxy group having 1 to 10 carbon atoms that may have a substituent, and the methylene group in the alkoxy group is not adjacent to oxygen atoms A group substituted with a divalent group selected from the above group (I), an ester group with 1 to 10 carbon atoms that may have a substituent, or the methylene group in the above ester group is not adjacent to an oxygen atom It is substituted with a divalent group selected from the above group (I) under the conditions, R ³⁵ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms that may have a substituent, the alkyl group Among them, the methylene group other than the end of the bonding site is substituted with a divalent group selected from the above group (I) under the condition that the oxygen atom is not adjacent, or is selected from the following formula (A) Any of the substituents in ~(C), An ^q- represents an anion of q valence, q represents an integer of 1 or 2, and p represents a coefficient that makes the charge neutral)

[化33]

In the formula, * represents the bonding bond.

(In the formula, R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , R ¹³⁰ , R ¹³¹ , R ¹³² , R ¹³³ , R ¹³⁴ , R ¹³⁶ , R ¹³⁷ , R ¹³⁸ , R ¹³⁹ , R ¹⁴⁰ , R ¹⁴¹ , R ¹⁴² , R ¹⁴³ and R ¹⁴⁴ , R ¹⁴⁵ , R ¹⁴⁶ , R ¹⁴⁷ , R ¹⁴⁸ and R ¹⁴⁹ each independently represent a hydrogen atom, a halogen atom, and sometimes have The substituent is an alkyl group having 1 to 10 carbon atoms, and the methylene group in the alkyl group other than the end of the bonding site is substituted with the two selected from the above group (I) under the condition that the oxygen atom is not adjacent A group consisting of a valence group, an alkoxy group having 1 to 10 carbon atoms which may have a substituent, and the methylene group in the alkoxy group is substituted to be selected from the above group under the condition that the oxygen atom is not adjacent to each other ( I) a divalent group, sometimes a substituted ester group with 1 to 10 carbon atoms, or the methylene group in the ester group is substituted under the condition that the oxygen atom is not adjacent to selected from The base formed by the divalent base of the above group (I), *represents the bonding position with S in formula (2))

In the compound represented by the above formula (2), as R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , R ¹³⁰ , R ¹³¹ , R ¹³² , R ¹³³ , R ¹³⁴ , The halogen atoms represented by R ¹³⁶ , R ¹³⁷ , R ¹³⁸ , R ¹³⁹ , R ¹⁴⁰ , R ¹⁴¹ , R ¹⁴² , R ¹⁴³ , R ¹⁴⁴ , R ¹⁴⁵ , R ¹⁴⁶ , R ¹⁴⁷ , R ¹⁴⁸ and R ^{149 can be exemplified} : Fluorine, chlorine, bromine, iodine, etc.

In the compound represented by the above formula (2), R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , R ¹³⁰ , R ¹³¹ , R ¹³² , R ¹³³ , R ¹³⁴ , R ¹³⁶ , R ¹³⁷ , R ¹³⁸ , R ¹³⁹ , R ¹⁴⁰ , R ¹⁴¹ , R ¹⁴² , R ¹⁴³ , R ¹⁴⁴ , R ¹⁴⁵ , R ¹⁴⁶ , R ¹⁴⁷ , R ¹⁴⁸ and R ¹⁴⁹ have 1 to 10 carbon atoms Examples of the alkyl group include the number of carbon atoms of the group used for ^{R 2} in the general formula (A1) described in the item of "(1) acrylamide compound" in the above "1. First polymerizable compound" 1-30 alkyl, 3-30 cycloalkyl, 4-30 cycloalkylalkyl, and 1 or more methylene groups in these groups (bonding site side end Except) is substituted with the divalent group represented by the above group (I) (in addition, the divalent group represented by the above group (I) is not adjacent) satisfying the specified number of carbon atoms. In addition, as the substituent for substituting the hydrogen atom in the alkyl group having 1 to 10 carbon atoms which may have a substituent, the above-mentioned "1. The first polymerizable compound" can be exemplified by "(1) acrylic acid Exemplary groups of substituents substituted by hydrogen atoms in the hydrocarbon groups described in the section of "amine compounds". Examples of the alkyl groups used for such R ²¹ and the like include methyl, ethyl, propyl, isopropyl, butyl, second butyl, tertiary butyl, isobutyl, pentyl, and isopropyl. Pentyl, tertiary pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, ethyloctyl, 2-methoxyethyl, 3-methoxypropyl, 4-methoxybutyl , 2-butoxyethyl, methoxyethoxyethyl, methoxyethoxyethoxyethyl, 3-methoxybutyl, 2-methylthioethyl, fluoromethyl, Difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl, tribromomethyl, difluoroethyl, trichloroethyl, dichloro Difluoroethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, decafluoropentyl, tridecafluorohexyl, pentafluoroheptyl, heptafluorooctyl, methoxymethyl, 1, 2-Ethoxyethyl, methoxyethyl, methoxyethoxymethyl, methylthiomethyl, ethoxyethyl, butoxymethyl, tertiary butylthiomethyl, 4- Pentenyloxymethyl, trichloroethoxymethyl, bis(2-chloroethoxy)methyl, methoxycyclohexyl, 1-(2-chloroethoxy)ethyl, 1-methyl -1-Methoxyethyl, ethyldithioethyl, trimethylsilylethyl, tert-butyldimethylsilyloxymethyl, 2-(trimethylsilyl)ethoxy Methyl, tertiary butoxycarbonylmethyl, ethyloxycarbonylmethyl, ethylcarbonylmethyl, tertiary butoxycarbonylmethyl, acryloxyethyl, methacryloxyethyl , 2-Methyl-2-adamantyloxycarbonylmethyl, acetylethyl, 2-methoxy-1-propenyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, 2 -Hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl, 1,2-dihydroxyethyl, etc.

In the compound represented by the above formula (2), as R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , R ¹³⁰ , R ¹³¹ , R ¹³² , R ¹³³ , R ¹³⁴ , R ¹³⁶ , Alkoxy with 1 to 10 carbon atoms represented by R ¹³⁷ , R ¹³⁸ , R ¹³⁹ , R ¹⁴⁰ , R ¹⁴¹ , R ¹⁴² , R ¹⁴³ and R ¹⁴⁴ , R ¹⁴⁵ , R ¹⁴⁶ , R ¹⁴⁷ , R ¹⁴⁸ and R ¹⁴⁹ The group may, for example, be a group in which -O- is bonded to a methylene group at the end of the bonding site of an alkyl group. As the alkyl group constituting the above-mentioned alkoxy group, examples of the alkyl group ^{used in the above-mentioned R 21 and the like can be used.} As the alkoxy group used for such R ²¹ and the like, specifically, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butyloxy group, a second butyloxy group, Tertiary butyloxy, isobutyloxy, pentyloxy, isopentyloxy, tertiary pentyloxy, hexyloxy, cyclohexyloxy, cyclohexylmethyloxy, tetrahydrofuranyloxy Group, tetrahydropiperanyloxy, 2-methoxyethyloxy, 3-methoxypropoxy, 4-methoxybutyloxy, 2-butoxyethyloxy, methyl Oxyoxyethoxyethyloxy, methoxyethoxyethoxyethyloxy, 3-methoxybutyloxy, 2-methylthioethyloxy, trifluoromethyloxy Wait.

In the compound represented by the above formula (2), as R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ¹²¹ , R ¹²² , R ¹²³ , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁸ , R ¹²⁹ , R ¹³⁰ , R ¹³¹ , R ¹³² , R ¹³³ , R ¹³⁴ , R ¹³⁶ , R ¹³⁷ , R ¹³⁸ , R ¹³⁹ , R ¹⁴⁰ , R ¹⁴¹ , R ¹⁴² , R ¹⁴³ and R ¹⁴⁴ , R ¹⁴⁵ , R ¹⁴⁶ , R ¹⁴⁷ , R ¹⁴⁸ and R ¹⁴⁹ represent ester groups with 2 to 10 carbon atoms , As long as it is a group having an ester bond (-CO-O- or -O-CO-) at the end of the bonding site, and an ester bond may be bonded to the methylene group at the end of the bonding site of the alkyl group. Chengzhiji. As the alkyl group constituting the above-mentioned ester group, ^{those exemplified as the alkyl group used in the above-mentioned R 21} and the like can be used. As the ester group used for such R ²¹ etc., specifically, a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, a phenoxycarbonyl group, an acetoxy group, and a propoxy group may be mentioned. , Butyroxy, chloroacetoxy, dichloroacetoxy, trichloroacetoxy, trifluoroacetoxy, tert-butylcarbonyloxy, methoxyacetoxy, benzene Formaldehyde and so on.

In the present invention, the above-mentioned R ^{35 is} preferably selected from the above-mentioned chemical formulae (A) to (C), and among them, it is preferably selected from the above-mentioned formula (A) or (B). By making the said R ³⁵ have the said structure, the acid generating efficiency of the said acid generator is excellent. The reason for this is that it is thereby possible to more effectively exhibit the excellent acid component trapping effect of the present invention.

R ²¹ , R ²² , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ and R ^{34 are} preferably hydrogen atoms, halogen atoms, and sometimes substituted ones The alkyl group having 1 to 10 carbon atoms is particularly preferably a hydrogen atom. By being the above-mentioned functional group, the acid generation efficiency of the above-mentioned acid generator is excellent. The reason for this is that it is thereby possible to more effectively exhibit the excellent acid component trapping effect of the present invention. Among them, R ²³ and R ^{28 are} preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms, and particularly preferably a hydrogen atom or a halogen atom. By being the above-mentioned functional group, the acid generation efficiency of the above-mentioned acid generator is excellent. The reason for this is that it is thereby possible to more effectively exhibit the excellent acid component trapping effect of the present invention.

R ¹²¹ , R ¹²² , R ¹²⁴ , R ¹²⁵ , R ¹²⁶ , R ¹²⁷ , R ¹²⁹ , R ¹³⁰ , R ¹³¹ , R ¹³² , R ¹³³ , R ¹³⁴ , R ¹³⁷ , R ¹³⁸ , R ¹³⁹ , R ¹⁴⁰ , R ¹⁴¹ , R ¹⁴² , R ¹⁴³ , R ¹⁴⁴ , R ¹⁴⁵ , R ¹⁴⁶ , R ¹⁴⁷ , R ¹⁴⁸ and R ^{149 are} preferably a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, and a hydrogen atom is particularly preferred. By being the above-mentioned functional group, the acid generation efficiency of the above-mentioned acid generator is excellent. The reason for this is that it is thereby possible to more effectively exhibit the excellent acid component trapping effect of the present invention. R ¹²³ , R ¹²⁸ and R ^{136 are} preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 10 carbon atoms, and among them, a hydrogen atom or a halogen atom is preferred. By being the above-mentioned functional group, the acid generation efficiency of the above-mentioned acid generator is excellent. The reason for this is that it is thereby possible to more effectively exhibit the excellent acid component trapping effect of the present invention.

In the compound represented by the above formula (2), as ^{the q-valent anion represented by An q-} , for example, tetrakis (pentafluorophenyl) borate [(C ₆ F ₅ ) ₄ B] ^- , tetrakis Fluoroborate (BF ₄ ) ^- , hexafluorophosphate (PF ₆ ) ^- , hexafluoroantimonate (SbF ₆ ) ^- , hexafluoroarsenate (AsF ₆ ) ^- , hexachloroantimonate (SbCl ₆ ) ^- , three (Pentafluoromethyl) trifluorophosphate ion (FAP anion) perchlorate ion (ClO ₄ ) ^- , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ^- , fluorosulfonate ion (FSO ₃ ) ^- , Tosylate anion, trinitrobenzenesulfonate anion, camphorsulfonate, nonafluorobutanesulfonate, hexadecafluorooctanesulfonate, tetraarylborate, tetrakis(pentafluorophenyl)borate, etc.

As the compound represented by the formula (2), the compounds represented by the following formulas (F-1) to (F-4) and (F-6) described in the following examples are preferably used.

As long as the thermal acid generator used as the acid generator contained in the cation curable composition is a compound that can generate an acid by heat, there will be no problem and there is no particular limitation. Regarding the thermal acid generator, in terms of the heat resistance of the cured product formed by curing the resin composition, the onium salt of the Lewis acid is released by heat, that is, the double salt, or a derivative thereof. In the present invention, it is preferable to use a salt represented by the following formula (14). The reason is that as a thermal acid generator, the curability of the resin is good, and the cured product obtained from the cationic curable composition has high heat resistance. In addition, the acid generator described above has excellent acid generation efficiency. As a result, the excellent acid component trapping effect of the present invention can be exerted more effectively.

[化34]

(In the formula, R ²²⁵ represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 6 to 20 carbon atoms which may have a substituent, and a carbon number of 7 to 30 aralkyl groups, hydroxyl groups, nitro groups, sulfonyl groups and cyano groups. One or more hydrogen atoms of the alkyl groups, aryl groups and aralkyl groups may be independently substituted with hydroxyl groups, halogen atoms, and carbon atoms. 1-10 alkyl group, 6-20 aryl group, 7-30 aralkyl group, nitro group, sulfonyl group or cyano group, R ²²⁶ represents a hydrogen atom, sometimes substituted carbon An alkyl group having 1 to 10 atoms, an aryl group having 6 to 20 carbon atoms that may have a substituent, or an aralkyl group having 7 to 30 carbon atoms that may have a substituent, the alkyl group, aryl group, and One or more hydrogen atoms of an aralkyl group are sometimes independently substituted with a hydroxyl group, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aromatic group having 6 to 20 carbon atoms, and a carbon number of 7 to 30. An aralkyl group, a nitro group, a sulfonyl group or a cyano group, R ²²⁷ represents an alkyl group with 1 to 10 carbon atoms in which the methylene group sometimes constituted is substituted with the group represented by -O- or S-, An ^q''- means q'' valence anion, q'' means 1 or 2, p'' means the coefficient to keep the charge as neutral)

In the compound represented by the above formula (14), as the halogen atom represented by ^{R 225} and the halogen atom sometimes substituted with one or more of the hydrogen atoms of the group represented by ^{R 225} , R ²²⁶ and R ^{227, and R 225} , R ^226, and R ²²⁷ represents an alkyl group with 1 to 10 carbon atoms, and sometimes replaces one or more of the hydrogen atoms of the group represented by ^{R 225} , R ^226, and R ^{227 with 1 to 10 carbon atoms} a halogen atom of the alkyl group used in the formulas, may be related to those "(1-2) photoacid generator" described in the (2) of the other of R ^21, the same alkyl group. The aryl group and aralkyl group having 6 to 20 carbon atoms represented by R ²²⁵ and R ²²⁶ , and the number of carbon atoms in which one or more hydrogen atoms of the group represented by ^{R 225} and R ^{226 may be substituted with 6 to} The aryl group and aralkyl group of 20 can be exemplified as the ones described in the item of "(1) acrylamide compound" of the above-mentioned "1. The first polymerizable compound" are used as R ^{2 in the general formula (A1)} One or more of the aryl group with 6 to 30 carbon atoms and the aralkyl group with 7 to 30 carbon atoms, as well as the methylene group in these groups (except for the end at the bonding site side) are substituted with Among the groups formed by the divalent groups represented by the group (I) (in addition, the divalent groups represented by the group (I) are not adjacent), those satisfying the specified number of carbon atoms. Specific examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, and an anthryl group.

^{As the q'or q'valent anion} represented by p'An q'- and p''An ^q''- in the above formula (13), there can be exemplified: methanesulfonate anion, dodecylsulfonate Anion, benzenesulfonate anion, tosylate anion, triflate anion, naphthalenesulfonate anion, diphenylamine-4-sulfonate anion, 2-amino-4-methyl-5-chlorobenzenesulfonate anion , 2-Amino-5-nitrobenzenesulfonate anion, Japanese Patent Laid-Open No. 10-235999, Japanese Patent Laid-Open No. 10-337959, Japanese Patent Laid-Open No. 11-102088, Japanese Patent Laid-Open 2000- 108510, Japanese Patent Application Publication No. 2000-168233, Japanese Patent Application Publication No. 2001-209969, Japanese Patent Application Publication No. 2001-322354, Japanese Patent Application Publication No. 2006-248180, Japanese Patent Application Publication 2006- Sulfonate anions described in 297907, Japanese Patent Laid-open No. 8-253705, Japanese Patent Special Publication No. 2004-503379, Japanese Patent Laid-Open No. 2005-336150, International Publication No. 2006/28006, etc. Organic sulfonate anion, in addition, can be exemplified: chloride ion, bromide ion, iodide ion, fluoride ion, chlorate ion, thiocyanate ion, perchlorate ion, hexafluorophosphate ion, antimony hexafluoro Acid ion, tetrafluoroborate ion, octyl phosphate ion, dodecyl phosphate ion, octadecyl phosphate ion, phenyl phosphate ion, nonyl phenyl phosphate ion, tris(pentafluoromethyl) Group) trifluorophosphate ion (FAP anion), 2,2'-methylene bis(4,6-di-tert-butylphenyl) phosphonate ion, tetrakis(pentafluorophenyl) borate ion, with The quenching anion that de-excites (quenches) the active molecule in the excited state, or the ferrocene and ruthenium with anionic groups such as carboxyl, phosphonic acid and sulfonic acid groups on the cyclopentadienyl ring And other metallocene compound anions. Among them, in terms of high heat resistance, hexafluorophosphate ion, hexafluoroantimonate ion, and tetrakis(pentafluorophenyl)borate ion are preferred.

The temperature range in which the above-mentioned thermal acid generator can generate acid by heat to harden the composition is not particularly limited. In terms of obtaining a cured product with better heat resistance, and in terms of good thermal stability in the manufacturing process, it is more It is preferably 50°C or higher and 250°C or lower, more preferably 100°C or higher and 220°C or lower, more preferably 130°C or higher and 200°C or lower, and still more preferably 150°C or higher and 180°C or lower. The reason is that this makes it easy to form a hardened product of the above-mentioned composition.

As the thermal acid generator used for the cationic curable composition, a commercially available product can also be used. As such a commercially available product, for example, San-Aid SI-B2A, San-Aid SI-B3A, San-Aid SI-B3, San-Aid SI-B4, San-Aid SI-60, San-Aid SI-80, San-Aid SI-100, San-Aid SI-110, San-Aid SI-150 (the above are manufactured by Sanxin Chemical Industry Co., Ltd.), Adekaopton CP-66, Adekaopton CP-77 (the above is ADEKA (Stock) Manufacturing) and so on. These can be used individually by 1 type or in combination of 2 or more types.

(1-3) Other The cationic curable composition contains a cationic curable component and an acid generator, but may contain a solvent and other components as needed. As the solvent, an organic solvent, water, etc. can be used. As a solvent containing an organic solvent and water, a solvent that is liquid at normal temperature (25° C.) and atmospheric pressure and can be dried and removed when a cured product is formed from a cationic curable composition is generally used. As other components, various additives may be mentioned. Such organic solvents and various additives may be the same as those described as solvents, additives, etc. in International Publication No. 2017/098996. The above-mentioned organic solvent is one capable of dispersing or dissolving each component of the cationic curable composition. Therefore, even if the cation curable component, acid generator, and sensitizer described below are liquid at normal temperature (25°C) and atmospheric pressure, they are not included in the solvent. As the above-mentioned organic solvent, specifically, methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone, methyl isobutyl ketone, cyclohexanone, Ketones such as 2-heptanone; methanol, ethanol, isopropanol or n-propanol, isobutanol or n-butanol, pentanol, diacetone alcohol and other alcoholic solvents; ethylene glycol monomethyl ether acetate, ethyl Glycol monoethyl ether acetate, propylene glycol-1-monomethyl ether-2-acetate (PGMEA), dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethoxyethyl propionate , 1-tertiary butoxy-2-propanol, 3-methoxybutyl acetate, cyclohexanediol acetate and other ether ester solvents; benzene and other BTX (Benzene-Toluene-Xylene, benzene-toluene-two Toluene) solvents; aliphatic hydrocarbon solvents such as hexane; terpene hydrocarbon oils such as turpentine; paraffin wax solvents such as mineral spirits; halogenated aliphatic hydrocarbon solvents such as carbon tetrachloride; halogenated aromatic hydrocarbons such as chlorobenzene Solvent; Carbitol-based solvents, etc. These solvents can be used singly or in the form of a mixed solvent of two or more kinds. In addition, in 100 parts by mass of the cationic curable composition, the content of the solvent is preferably 20 parts by mass or more and 80 parts by mass or less. The reason is that this makes the coatability excellent. The cationic curable composition can use a sensitizer together with an acid generator. As such a sensitizer, a well-known sensitizer can be used, and specifically, the compound described in the item of "5. Sensitizer" of the above-mentioned "1. First polymerizable compound" can be used.

The cationic curable composition contains a cationic curable component as a resin component, but may optionally contain a resin component other than the cationic curable component (hereinafter, may be referred to as other resin component). As other resin components, well-known components used in the technical field to which the present invention belongs can be used within a range that does not impair the effects of the present invention.

染料、三芳基甲烷染料等。作為該等陽離子染料，例如可使用日本專利特開2017-068221號公報所記載之花青系色素、部花青系色素、吡咯甲川系色素、偶氮系色素、四氮雜卟啉系色素、𠮿

系色素、三芳基甲烷系色素等之示例。 又，作為吡咯甲川染料，亦可使用日本專利特開2006-189751號公報中之通式(1)所表示之化合物、日本專利特開2011-174036號公報中之通式(1)所表示之化合物等。作為四氮雜卟啉染料，亦可使用日本專利特開2017-68221號公報中之通式(1)所表示之化合物。 再者，上述染料之含量相對於上述陽離子硬化性成分100質量份可設為0.01質量份以上10質量份以下。 硬化物之製造方法只要能夠使硬化物形成為所需形狀，則並無特別限定。作為此種製造方法，例如可與下述「C.被覆構造體的製造方法」之項所記載之內容相同，故而省略此處之說明。The cationic curable composition may optionally contain components that are easily decomposed and modified in the presence of acid components. The reason for this is that it is possible to effectively exhibit the excellent effect of capturing the acid component of the above-mentioned coating material. As such a component that is easily decomposed and degraded in the presence of an acid component, for example, dyes and the like can be mentioned. As the above-mentioned dyes, cationic dyes can be preferably used. Cationic dyes are sometimes decomposed or modified in the presence of acid components, which changes the transmittance in the desired wavelength range. In contrast, when the coating material formed of the above-mentioned polymerizable composition is used for coating, it is easy to suppress the decomposition and modification of the dye, so that the transmittance in the desired wavelength range is less changed. Examples of such cationic dyes include cyanine dyes, merocyanine dyes, pyrromethene dyes, azo dyes, porphyrazine dyes, and

Dyes, triarylmethane dyes, etc. As these cationic dyes, for example, cyanine dyes, merocyanine dyes, pyrromethine dyes, azo dyes, porphyrazine dyes, etc. described in Japanese Patent Laid-Open No. 2017-068221 can be used. 𠮿

Examples of dyes, triarylmethane dyes, etc. In addition, as the pyrromethene dye, the compound represented by the general formula (1) in Japanese Patent Laid-Open No. 2006-189751 and the compound represented by the general formula (1) in Japanese Patent Laid-Open No. 2011-174036 can also be used. Compound etc. As the porphyrazine dye, the compound represented by the general formula (1) in JP 2017-68221 A can also be used. Furthermore, the content of the dye can be set to 0.01 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the cationic curable component. The method of manufacturing the hardened product is not particularly limited as long as it can form the hardened product into a desired shape. As such a manufacturing method, for example, the content described in the section of "C. Manufacturing Method of Covered Structure" below can be the same, so the description here is omitted.

(2) Components containing acid As the application of the above-mentioned acid component-containing member, any application that requires the acid component capture property of the coating material may be used. For example, the following various applications can be exemplified: filter; printing plate; insulating varnish; insulating sheet; laminate Boards; printed substrates; sealants, such as semiconductor devices, LED (Light Emitting Diode) packages, liquid crystal injection ports, organic electroluminescence (EL), optical components, electrical insulation, electronics For parts, or separation film, etc.; and molding materials; interlayer insulating film; protective film; printed circuit board, color TV, PC (personal computer, personal computer) display, portable information terminal, CCD (Charge Coupled Device) , Charge Coupled Device) The color filter of the image sensor or the electrode material for the plasma display panel.

As the above-mentioned filter, it can be one that requires a change in the spectral shape of the light that passes through the filter. For example, it can be used for liquid crystal display devices (LCD), plasma display panels (PDP), electroluminescence displays (ELD), and cathode tube displays. Device (CRT), CCD image sensor, CMOS (complementary metal oxide semiconductor) sensor, fluorescent display tube, field emission display and other image display devices, analytical devices, semiconductor device manufacturing Use, astronomical observation, optical communication, spectacle lenses, windows, etc. In the use of the above-mentioned member containing the acid component, the site where the effect of the acid component capturing property of the coating material is exerted may be the inside of the member containing the acid component itself, or the outside of the member containing the acid component. As a specific example of the member containing the acid component inside the site where the effect of the acid component capturing property is exerted, a dye-containing filter can be exemplified. In this case, by the above-mentioned coating material, it is possible to suppress the decomposition and deterioration of the dye in the optical filter, which is a member containing an acid component. As a specific example of a member containing an acid component in the external part where the effect of the acid component capturing effect is exerted, there can be mentioned: a printed circuit board with wiring containing metals, metal oxides, etc., or an electronic board with electronic components arranged on the printed circuit board The insulating substrate supporting the wiring, the insulating film covering the wiring, and the interlayer insulating film arranged in the wiring room. In addition, as a specific example of the above-mentioned member whose acid component capture property is externally located, for example, the various members included in the above-mentioned optical filter, printed circuit board, and electronic substrate may be used to fix the optical filter, Adhesive layers, adhesive layers, etc. for printed circuit boards and electronic substrates. As a specific example of the above-mentioned member in which the part where the acid component capture property is exerted is inside, a resin molded body such as pellets containing ingredients such as a drug that is easily affected by deterioration or decomposition by the acid component can also be exemplified.

The shape of the member containing the acid component in plan view is appropriately set according to the use of the member containing the acid component, etc., when the member containing the acid component is formed on the substrate, it may be in the form of a film covering the entire surface of the substrate. It may also be a pattern formed on a part of the substrate. The above-mentioned components containing acid components are used in the filters of image display devices such as color pixels, color adjustment layers, etc. included in color filters, plasma display panels, electroluminescence displays, and other image display devices In this case, the plan view shape of the above-mentioned acid component-containing member may be a pattern shape. When the member containing the acid component is used as, for example, an adhesive layer for fixing two members, the shape of the member containing the acid component in plan view may be a film shape. When the acid component-containing member is, for example, a resin composition containing a dye or a drug, the shape of the acid component-containing member may be granular. The film thickness of the above-mentioned acid component-containing member is appropriately set according to the use of the above-mentioned acid component-containing member, etc. When the above-mentioned member is used in an optical filter or an adhesive layer, etc., it can be set to 0.01 μm or more and 10 mm or less . When the above-mentioned acid component-containing member is used in, for example, an optical filter of an image display device, the film thickness of the above-mentioned acid component-containing member is preferably 0.05 μm or more and 300 μm or less, preferably 0.1 μm or more and 100 μm or less , Preferably 1 μm or more and 20 μm or less. The reason for this is that by setting the film thickness as described above, the effect of capturing the acid component of the coating material and the like can be effectively exhibited.

B. Covered structure The covering structure of the present invention has a member containing an acid component and a covering material covering the member. The coating material includes a polymer containing a polymer having a structural unit derived from a first polymerizable compound, and the first polymerizable compound has an amide group and an ethylenically unsaturated group.

1. Coating material The polymer contained in the coating material may contain repeating units derived from the first polymerizable compound. The above-mentioned polymer may be a homopolymer containing repeating units derived from the first polymerizable compound, or may include repeating units derived from the first polymerizable compound (first repeating unit), and derived from other than the first polymerizable compound. The compound having an ethylenically unsaturated group other than the compound is a copolymer of the repeating unit (second repeating unit) of the second polymerizable compound. As such a coating material, it is preferable to use, for example, a polymer of a polymerizable composition containing the first polymerizable composition. The reason is that it is easy to form a coating material in this way. The content of the above-mentioned first polymerizable compound, second polymerizable compound, and polymerizable composition may be the same as the content described in the item of the above-mentioned "A. Polymerizable composition". The types and content ratios of the first repeating unit and the second repeating unit may be the same as those of the first polymerizable compound and the second polymerizable compound in the polymerizable composition. For example, in the case where the above-mentioned polymer contains the second repeating unit, the content of the first repeating unit in 100 parts by mass of the total of the first repeating unit and the second repeating unit may be the same as the above-mentioned "A. Polymerizable composition". The content of the first polymerizable compound in the total 100 parts by mass of the first polymerizable compound and the second polymerizable compound described above is the same. In addition, the types and content ratios of the first repeating unit and the second repeating unit may vary depending on the manufacturing method of the covering structure. For example, when the manufacturing method of the covering structure is the above-mentioned first manufacturing method, the types and contents of the first repeating unit and the second repeating unit are preferably the same as those described in the section of "A. Polymerizable composition" above. The types and contents of the first polymerizable compound and the second polymerizable compound preferably used in the first production method are the same. The reason is that it is easy to form a coating material in this way. Similarly, when the manufacturing method of the covering structure is the above-mentioned second manufacturing method, the types and contents of the first repeating unit and the second repeating unit are preferably the same as those described in the section of "A. Polymerizable composition" above. The type and content of the first polymerizable compound and the second polymerizable compound preferably used in the second manufacturing method are the same. The reason is that it is easy to form a coating material in this way.

The said coating material and the member containing an acid component can contact|abut. Alternatively, another member may be interposed between the above-mentioned coating material and the member containing the acid component. From the viewpoint of more reliably capturing the acid generated from the member containing the acid component, it is preferable that the coating material and the member containing the acid component are in contact with each other. In addition, when the site where the effect of capturing the acid component is outside the member containing the acid component, the formation site of the coating material may be between the site where the effect is exerted and the member containing the acid component, or not between them. For example, when wiring and an acid component-containing member are sequentially formed as a printed circuit board, the formation location of the coating material may not be a position sandwiched between the wiring and the acid component-containing member. Parts of acid components and coating materials.

The thickness of the coating material is not particularly limited, and can be appropriately determined according to the application of the coating structure. The thickness of the above-mentioned coating material may be 0.01 μm or more and 300 μm or less. When the acid component-containing member of the coating object is an optical filter, the thickness of the coating material is preferably 0.01-100 μm, more preferably 0.1-50 μm, and particularly preferably 1-20 μm. The reason is that by setting the above thickness to the above range, it is possible to effectively exhibit excellent acid trapping properties and obtain a high adhesive force effect.

Regarding the formation method of the coating material, as long as the method can dispose the acid component-containing member so as to cover the acid component-containing member, it can be combined with the following "C. Method of Manufacturing Coated Structure". The recorded content is the same.

2. Components containing acid The above-mentioned acid component-containing member may be the same as the content described in the section of the above-mentioned "A. Polymerizable composition", so the description here is omitted.

2. Other The use of the above-mentioned covered structure may be the same as the use of the member containing the acid component described in the item of "A. Polymerizable composition".

C. Manufacturing method of covered structure The manufacturing method of the coated structure of the present invention includes a step of coating a member containing an acid component with a coating material. Hereinafter, the coating material forming step will be described in detail.

1. Covering steps The coating step in the present invention is a step of coating a member containing an acid component with a coating material. In addition, the coating material includes a polymer having a structural unit derived from a first polymerizable compound having an amide group and an ethylenically unsaturated group. In this step, as a method of coating a member containing an acid component with a coating material, as long as the method can form a coating structure, it is not particularly limited. As a coating method, the following 1st method, 2nd method, etc. are mentioned specifically,. ・The first method It is a method with the following steps: The step of applying the polymerizable composition containing the first polymerizable compound to the above-mentioned acid component-containing member, The step of polymerizing the first polymerizable compound in the polymerizable composition. ・The second method It is a method with the following steps: The step of polymerizing the first polymerizable compound in the polymerizable composition to form the first polymerizable compound as a coating material, A step of contacting the coating material obtained in the above coating material forming step so as to coat the member containing the acid component. Hereinafter, this step is divided into the first method and the second method and will be described.

(1) Method 1 The first method of this step has the steps of: applying a polymerizable composition containing a first polymerizable compound to the above-mentioned acid component-containing member, and polymerizing the first polymerizable compound in the above-mentioned polymerizable composition. step. (1-1) Coating steps The application of the polymerizable composition in this step to the above-mentioned member is not limited to the form in which it is applied directly in contact with the above-mentioned member, and also includes the form in which it is interposed and connected to other members. In this step, as the coating method of the polymerizable composition, examples include: spin coater, roll coater, bar coater, die coater, curtain coater, various Known methods such as printing and dipping. Regarding the thickness of the coating film of the polymerizable composition applied in this step, as long as it can form a coating material of a desired thickness, it is appropriately set according to the type of the acid component-containing member and the like. In addition, the content of the above-mentioned first polymerizable compound and polymerizable composition may be the same as the content described in the item of the above-mentioned "A. Polymerizable composition", so the description here is omitted. Among them, in this step, the polymerizable composition is preferably the content that is preferably used in the first manufacturing method as a method of manufacturing a covered structure in the item of "A. Polymerizable composition" described above.

(1-2) Polymerization step As the polymerization method of the first polymerizable compound in this step, as long as the first polymerizable compounds can be polymerized with each other to form a polymer having structural units derived from the first polymerizable compound, a known method can be used, such as Examples include: a method of irradiating the coating film of the polymerizable composition with energy rays, a method of heating the coating film of the polymerizable composition, and the like. In the case where the above-mentioned polymerizable composition contains a radical polymerization initiator, such a polymerization method is preferably determined according to the kind of the radical polymerization initiator. Specifically, when the polymerizable composition contains a photo-radical polymerization initiator as the radical polymerization initiator, the method of irradiating energy rays can be preferably used. When the polymerizable composition contains a thermal radical polymerization initiator, When the initiator is used as a radical polymerization initiator, a heating method can be preferably used. The reason is that it is easy to polymerize the above-mentioned first polymerizable compound.

In this step, as the light source of the energy line used to polymerize the first polymerizable compound, ultra-high-pressure mercury lamps, high-pressure mercury lamps, medium-pressure mercury lamps, low-pressure mercury lamps, mercury vapor arc lamps, xenon arc lamps, and carbon arc lamps can be used. , Metal halide lamps, fluorescent lamps, tungsten filament lamps, excimer lamps, germicidal lamps, light-emitting diodes, CRT (cathode-ray tube, cathode ray tube) light source, etc., obtained by electromagnetic waves with a wavelength of 2000 angstroms to 7000 angstroms Energy or high-energy lines such as electron beams, X-rays, and radiation. It is preferable to use ultra-high pressure mercury lamps, mercury vapor arc lamps, carbon arc lamps, xenon arc lamps, light-emitting diodes, etc. that emit light with a wavelength of 300-450 nm. The reason is that it is easy to polymerize the first polymerizable compound.

The irradiation amount of energy rays is not particularly limited, and can be appropriately determined according to the composition of the polymerizable composition. From the viewpoint of preventing deterioration of the components in the polymerizable composition, the above-mentioned irradiation amount is preferably 100 mJ/cm ² to 2000 mJ/cm ² .

As a method of heating the coating film of the polymerizable composition in this step, a method of using a hot plate such as a hot plate, or an atmospheric oven, an inert gas oven, a vacuum oven, a hot air circulation type oven, etc. can be exemplified. The heating temperature at the time of heating the coating film is not particularly limited. From the viewpoint of easy polymerization of the first polymerizable compound, it is preferably 70°C or higher and 200°C or lower, and more preferably 90°C or higher and 150°C or lower. The heating time when heating the coating film is not particularly limited, but in terms of improving productivity, it is preferably 1 to 60 minutes, more preferably 1 to 30 minutes.

In this step, the above-mentioned polymerization method is preferably a method combining an energy ray irradiation method and a heating method, and more specifically, it is preferable to perform an energy ray irradiation method and a heating method sequentially. The reason is that the first polymerizable compound can be efficiently polymerized.

(2) Method 2 The second method in this step is a method having the following steps: polymerizing the first polymerizable compound in the polymerizable composition to form the first polymerizable compound as a coating material, and coating the member containing the acid component The coating material obtained in the above coating material forming step is in contact with it.

(2-1) Steps for forming coating material As a method of polymerizing the first polymerizable compound in this step to form a coating material, as long as the first polymerizable compounds are polymerized with each other to form a polymer having structural units derived from the first polymerizable compound, the coating The material may be formed on the above-mentioned member so as to cover the above-mentioned member. As such a method, from the viewpoint of improving workability and easy contact with the coating material, a method of polymerizing the polymerizable composition after coating the substrate is preferred. Regarding the polymerization method of the first polymerizable compound, the polymerizable composition, and the first polymerizable compound, the same method as described in the item "(1) First Method" above can be used, so the description here is omitted. . Among them, in this step, the polymerizable composition is preferably the content that is preferably used in the second manufacturing method as a method of manufacturing a covered structure in the item of "A. Polymerizable composition" described above.

(2-2) Contact steps As a method of bringing the coating material in this step into contact with the member containing the acid component, as long as the coating material can be brought into contact with the above-mentioned member to obtain the desired acid component capture property. In this step, the contact with the above-mentioned member is not limited to the method of directly connecting with the above-mentioned member, and may also be a method of interposing other members in contact, that is, a method of contacting other members adjacent to the above-mentioned member. Examples of the contact method include: a method of bonding a coating material to the member via an adhesive; a method of bonding the coating material to the member using the adhesive force of the coating material when the coating material has adhesive force. In this step, the above-mentioned contact method is preferably a method of attaching to the above-mentioned member by using the adhesive force of the covering material. The reason is easy access. When the covering material is brought into contact, the above-mentioned contact method may press the covering material against the above-mentioned member, or may heat it. As heating conditions, temperature conditions of 60°C or more and 150°C or less can be set. In the case where the coating material is formed on the substrate, the contact method may be a method of contacting a laminate including the substrate and the coating material with the member, or the coating material may be peeled from the substrate and the coating material may be brought into contact with the member. The contact method of the above-mentioned components.

(3) Other Regarding the polymerizable composition, the acid component-containing member, and the first polymerizable compound in the above-mentioned coating step, other related content may be the same as the content described in the item "A. Polymerizable composition" above, so it is omitted The description here. The content of the coating material formed by this step can be the same as the content of the coating material described in the item "B. Coating structure" above, so the description here is omitted.

2. Other steps The manufacturing method of the covered structure of the present invention has a covering step, but may also have other steps as needed.

D. Coating material The coating material of the present invention contains a polymer derived from a first polymerizable compound having an amide group and an ethylenically unsaturated group. In addition, it is used to coat a member containing an acid component. Regarding such a coating material, its manufacturing method, and the member containing an acid component, the contents described in the section of "B. Coating Structure" above can be the same. [Example]

Hereinafter, the present invention will be described in further detail with examples and the like, but the present invention is not limited to these examples. In addition, unless otherwise specified, the numerical values in Tables 1 and 2 mean parts by mass.

[Examples 1-1 to 1-16 and Comparative Examples 1-1 to 1-2, Examples 2-1 to 2-29 and Comparative Examples 2-1 to 2-5] 1. Preparation of polymerizable composition (Examples 1-1 to 1-16 and Comparative Examples 1-1 to 1-2) The components described in Table 1 below were mixed at the ratio described in the table to prepare a polymerizable composition. The symbols in Table 1 indicate the following components. In addition, the obtained polymerizable compositions (compositions 1-1 to 1-16 and comparative compositions 1-1 to 1-2) were evaluated using the following Examples 2-1 to 2-29 and Comparative Example 2 -1 to 2-5 of the covered structure manufactured.

[Table 1] Example 1-1 Example 1-2 Example 1-3 Example 1-4 Example 1-5 Example 1-6 Example 1-7 Example 1-8 Example 1-9 Example 1-10 Example 1-11 Example 1-12 Example 1-13 Example 1-14 Example 1-15 Example 1-16 Comparative example 1-1 Comparative example 1-2 1st polymerizable compound A1-1 100 40 50 50 90 90 90 50 70 50 90 90 90 50 30 A1-2 60 A1-3 50 A1-4 50 A1-5 10 A1-6 10 A1-7 10 A1-8 10 A1-9 10 A1-10 10 20 100 2nd polymerizable compound A2-1 50 30 70 100 A2-2 30 A2-3 50 100 Polymerization initiator B-1 5 5 7 3 3 3 3 3 2 1 3 2.5 3 3 3 3 B-2 9 3 3 3 5 3 3 4 3 3 2.5 3 1 3 3 Leveling agent C-1 0.25 0.25 0.1 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 C-2 0.1 0.2 Sensitizer D-1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Imidazole compounds D-2 5

[First polymerizable compound] A1-1: The acrylamide compound (Compound A1-1) represented by the following formula (A1-1) A1-2: The acrylamide compound (Compound A1-2) represented by the following formula (A1-2) A1-3: The acrylamide compound (Compound A1-2) represented by the following formula (A1-3) A1-4: The acrylamide compound (Compound A1-2) represented by the following formula (A1-4) A1-5: The acrylamide compound (Compound A1-5) represented by the following formula (A1-5) A1-6: The acrylamide compound (Compound A1-4) represented by the following formula (A1-6) A1-7: An acrylamide compound (Compound A1-3) represented by the following formula (A1-7) A1-8: Isocyanuric ring-containing compound represented by the following formula (A1-8) (ethoxylated isocyanuric acid triacrylate, A-9300, manufactured by Shinnakamura Chemical Co., Ltd.) A1-9: Compound containing isocyanuric acid ring (caprolactone modified tris(2-propenoxyethyl) isocyanurate A9300-1CL, manufactured by Shinnakamura Chemical Co., Ltd.) A1-10: Urethane compound (Acrylic urethane, U-9H manufactured by Shinnakamura Chemical Co., Ltd., 9 functions)

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[Second polymerizable compound] A2-1: Phenoxy polyethylene glycol acrylate (AMP-20GY, manufactured by Shinnakamura Chemical) A2-2: Polypropylene glycol diacrylate (APG-200, manufactured by Shinnakamura Chemical) A2-3: 1,9-nonanediol diacrylate (A-NOD-N, manufactured by Shinnakamura Chemical)

[Other ingredients] B-1: Photo radical polymerization initiator (Lucirin TPO, manufactured by BASF) B-2: Light radical polymerization initiator (Irg907, manufactured by BASF) C-1: Leveling agent (SH-29PA, manufactured by Dow Toray) C-2: Leveling agent (FZ-2110, manufactured by Dow Toray) D-1: Sensitizer (DETX, manufactured by Nippon Kayaku) D-2: Imidazole compound (2-ethyl-4-methylimidazole)

2. Manufacture of covering structure (Examples 2-1 to 2-29 and Comparative Examples 2-1 to 2-5) (1) Formation of acid component-containing member The components described in Table 2 below are used in this table Mix at the stated ratio to prepare a mixture. The prepared mixture was passed through a 5 μm membrane filter to remove insoluble components to obtain cationic curable compositions 1-14. The symbols in Table 2 indicate the following components. The cationic curable composition is applied to a substrate (indium tin oxide (ITO) coated glass slide, manufactured by Sigma-Aldrich) to obtain a substrate with a coating film. As the base material, a length of 10 cm and a width of 3 cm are used. The coating system adopts bar coating method. The coating is carried out in the following way: in the center of the substrate, the coating length of the cationic curable composition is 5 cm (the long side direction of the substrate), and the coating width is 3 cm (the short side direction of the substrate), namely , The ITO surface of the substrate with a length of 10 cm is divided by the coating film of the cationic curable composition with a width of 5 cm in the plan view, and two side portions without the coating film of the cationic curable composition are formed on the substrate ( ITO surface). Adjust the coating thickness of the cationic curable composition so that the film thickness after curing of the cationic curable composition is 3 to 5 μm. The substrate with the coating film was placed on a hot plate, and the coating film was dried at 90°C for 1 minute. For the coating film formed by using cationic curable compositions 1-1 to 1-5 and 1-7 to 1-14, use UV-LED (Ultraviolet-Light Emitting Diode) at 3000 mJ/cm ² Irradiate the dried coating film with 365 nm ultraviolet rays to harden the coating film, thereby forming a cured product of the cationic curable composition (a member containing an acid component) on the substrate. In addition, for the coating film formed using the cationic curable composition 1-6, heat treatment in an oven at 120°C for 15 minutes to harden the coating film to form a cured product of the cationic curable composition (containing The building block of the acid component).

(2) Formation of coating structure: Cured products obtained by curing the cationic curable compositions 1-1 to 1-14 formed on the substrate (in Tables 3 to 4, simply referred to as cured products 1-1 to 1-14) The surface of 1-14) is treated with corona discharge to obtain a laminated substrate with a substrate (glass slide, ITO) and a cured product of the corona discharge-treated cationic curable composition (member containing acid) . In Examples 2-1 to 2-29 and Comparative Examples 2-4 to 2-5, the polymerizable composition prepared in Examples 1-1 to 1-16 was applied to the laminated base material (in the table, simple Described as compositions 1-1 to 1-16) and the polymerizable compositions prepared in Comparative Examples 1-1 to 1-2 (in the table, simply referred to as comparative compositions 1-1 to 1-2).涂膜。 Coating. The coating system adopts bar coating method. Regarding the coating of the polymerizable composition, the coating length is set to 5 cm (the long side direction of the substrate), and the coating width is set to 3 cm (the short side direction of the substrate), and the film thickness after curing is Adjust the coating thickness of the polymerizable composition by 3 to 5 μm. In addition, the application site is a site that covers the entire surface of the cured product of the cationic curable composition in a plan view. That is, the application site of the polymerizable composition is the same as the formation site of the cured product (member containing an acid component) of the cationic curable composition. Then, for the coating film formed using the polymerizable composition prepared in Examples 1-1 to 1-16 and the polymerizable composition prepared in Comparative Examples 1-1 to 1-2, UV-LED was used to 3000 mJ/cm ^{2 is} irradiated with 365 nm ultraviolet rays to polymerize the polymerizable composition. Thereby, the covering structure (Examples 2-1 to 2-29 and Comparative Examples 2-4 to 2-5) containing the polymer of the polymerizable composition, the cured product of the cation curable composition, and the substrate was produced. In addition, except that the acid component-containing member (cured product of the cationically polymerizable composition) was not formed, Comparative Example 2-1 in which a polymer with a polymerizable composition layered on a substrate was produced in the same manner as in Example 2-1 and the like ～2-4 covered structure.

(3) Evaluation Corrosion tests and adhesion tests were performed on the coated structures obtained in Examples 2-1 to 2-29 and Comparative Examples 2-1 to 2-5.

[Corrosion Test] The resistance value (initial resistance value) of the indium tin oxide at the part where the hardened substance is not formed on the base material of the prepared covered structure was measured. Specifically, the terminals of the tester are respectively set on the two sides of the base material where the hardened material is not formed, and the resistance value of the base material is measured. The terminals of the tester are respectively arranged at a position about 1 cm away from the end of the hardened object in the longitudinal direction of the base material. After that, the covered structure was left in a constant temperature and humidity bath for 1 week. Set the temperature of the constant temperature and humidity tank to 60°C and the humidity to 90%RH. Measure the resistance value of the covered structure statically placed in a constant temperature and humidity tank. The resistance value was measured using a commercially available megohm tester (insulation resistance meter). Using the resistance value and the initial resistance value after being placed in a constant temperature and humidity tank, the rate of change of the resistance value is calculated from the following formula. The results are shown in Tables 3 and 4 below. The smaller the value of the rate of change, it means that the corrosion of indium tin oxide is suppressed, and it has excellent acid trapping properties. Change rate (%) = initial resistance value/resistance value after standing in a constant temperature and humidity tank×100

[Adhesion test] A peel test was performed on the covered structure. Specifically, for the coated structures obtained in the examples and comparative examples, cutting blades were used to cross each other at an angle of 30° to cut out the cured product (member containing acid component) reaching the cationic curable composition 40 mm incision. Then, from the intersection of the two incisions, stick the transparent tape so that the length of the next part is 50 mm, and rub it from top to bottom with an eraser to make the transparent tape adhere to the surface of the coating material. Then, after making the scotch tape close for 2 minutes, hold the end of the scotch tape and stretch the covering material in the vertical direction to peel it off. The results are shown in Tables 3 and 4 below. ○: Peeling of the coating material is not observed. ×: Peeling of the coating material is observed. When no peeling of the covering material is observed, it means that the covering material has a high adhesive force.

[Table 2] Composition 1-1 Composition 1-2 Composition 1-3 Composition 1-4 Composition 1-5 Composition 1-6 Composition 1-7 Composition 1-8 Composition 1-9 Composition 1-10 Composition 1-11 Composition 1-12 Composition 1-13 Composition 1-14 Cationic hardening ingredients E-1 80 70 60 80 80 70 60 70 60 40 60 60 70 60 E-2 20 30 20 30 20 30 20 30 20 10 E-3 30 10 20 10 E-4 20 20 E-5 10 E-6 10 E-7 10 E-8 10 E-9 20 E-10 30 20 E-11 10 E-12 10 10 Acid generator F-1 5 5 5 4.5 6 3 5 2 F-2 5 F-3 6 2.5 F-4 4 2.5 F-5 3 F-6 2 2.5 2.5 2 additive Leveling agent G-1 0.1 0.15 0.15 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 G-2 0.1 Sensitizer G-3 1 1 0.1 1 1 0.5 0.5 0.5 G-4 1 G-5 1 Antioxidants G-6 1 1 0.5 2 G-7 0.5 1 pigment G-8 1 1.5 0.5 1 Solvent H-1 30 30 30 100 50 50 H-2 60 H-3 30 30 30 70 H-4 50 50 H-5 60

[Cationic hardening ingredient] E-1: Alicyclic epoxy compound represented by the following formula (E-1) (Celloxide 20121P, manufactured by Daicel, low molecular weight compound) E-2: Aliphatic epoxy compound (low molecular weight compound) represented by the following formula (E-2) E-3: Aliphatic epoxy compound (EHPE-3150, manufactured by Daicel, 1,2-epoxy-4-(2-oxirane) of 2,2-bis(hydroxymethyl)-1-butanol ) Cyclohexane adducts, high molecular weight compounds) E-4: Aliphatic epoxy compound (low molecular weight compound) represented by the following formula (E-4) E-5: Aromatic epoxy compound (low molecular weight compound) represented by the following formula (E-5) E-6: Aromatic epoxy compound (low molecular weight compound) represented by the following formula (E-6) E-7: Aromatic epoxy compound (low molecular weight compound) represented by the following formula (E-7) E-8: Aliphatic epoxy compound (low molecular weight compound) represented by the following formula (E-8) E-9: An oxetane compound represented by the following formula (E-9) (manufactured by Toagosei, OXT-211, low molecular weight compound) E-10: Alicyclic epoxy compound represented by the following formula (E-10) (manufactured by ARKEMA, limonene dioxide, low molecular weight compound) E-11: Aliphatic epoxy compound (low molecular weight compound) represented by the following formula (E-11) E-12: Aromatic epoxy compound represented by the following formula (E-12) (VG-3101L, manufactured by Printec, low molecular weight compound)

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[Acid Generator] F-1: Aromatic sulfonium salt represented by the following formula (F-1) (triaryl sulfonium salt, photoacid generator) F-2: Aromatic sulfonium salt represented by the following formula (F-2) (triaryl sulfonium salt, photoacid generator) F-3: Aromatic sulfonium salt represented by the following formula (F-3) (triaryl sulfonium salt, photoacid generator) F-4: Aromatic sulfonium salt represented by the following formula (F-4) (triaryl sulfonium salt, photoacid generator) F-5: Aromatic sulfonium salt represented by the following formula (F-5) (thermal acid generator, CPI-100P, manufactured by San-Apro, monoaryl sulfonium salt) F-6: Aromatic sulfonium salt represented by the following formula (F-6) (triaryl sulfonium salt, photoacid generator)

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[additive] G-1: Leveling agent (SH-29 Paint Aditive, manufactured by Toray Dow Corning) G-2: Leveling agent (MEGAFAC F-444, manufactured by DIC) G-3: Benzocarbazole sensitizer represented by the following formula (G-3) G-4: Dibutoxyanthracene sensitizer represented by the following formula (G-4) G-5: Diethoxynaphthalene sensitizer represented by the following formula (G-5) G-6: Compound (antioxidant) represented by the following formula (G-6) G-7: Compound (antioxidant) represented by the following formula (G-7) G-8: Dye (porphyrazine dye)

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[Solvent] H-1: Diacetone alcohol H-2: Propylene glycol monomethyl ether H-3: Propylene glycol monomethyl ether acetate H-4: Methyl ethyl ketone H-5: Dipropylene glycol monomethyl ether acetate

[table 3] Example 2-1 Example 2-2 Example 2-3 Example 2-4 Example 2-5 Example 2-6 Example 2-7 Example 2-8 Example 2-9 Example 2-10 Example 2-11 Example 2-12 Example 2-13 Example 2-14 Hardened Hardened object 1-1 Hardened 1-2 Hardened object 1-3 Hardened object 1-4 Hardened material 1-5 Hardened material 1-6 Hardened objects 1-7 Hardened objects 1-8 Hardened objects 1-9 Hardened object 1-10 Hardened 1-11 Hardened 1-12 Hardened 1-13 Hardened object 1-14 Polymerizable composition Composition 1-1 Composition 1-1 Composition 1-1 Composition 1-1 Composition 1-1 Composition 1-1 Composition 1-1 Composition 1-1 Composition 1-1 Composition 1-1 Composition 1-1 Composition 1-1 Composition 1-1 Composition 1-1 Acid catchability (corrosion test, rate of change) 102% 102% 105% 100% 101% 101% 101% 105% 103% 101% 106% 102% 100% 105% Follow force 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 Example 2-15 Example 2-16 Example 2-17 Example 2-18 Example 2-19 Example 2-20 Example 2-21 Example 2-22 Example 2-23 Example 2-24 Example 2-25 Example 2-26 Example 2-27 Example 2-28 Example 2-29 Hardened Hardened object 1-1 Hardened object 1-1 Hardened object 1-1 Hardened 1-2 Hardened 1-2 Hardened 1-2 Hardened object 1-3 Hardened object 1-3 Hardened object 1-3 Hardened object 1-3 Hardened object 1-3 Hardened object 1-3 Hardened object 1-3 Hardened object 1-1 Hardened object 1-1 Polymerizable composition Composition 1-2 Composition 1-3 Composition 1-4 Composition 1-5 Composition 1-6 Composition 1-7 Composition 1-8 Composition 1-9 Composition 1-10 Composition 1-11 Composition 1-12 Composition 1-13 Composition 1-14 Composition 1-15 Composition 1-16 Acid catchability (corrosion test, rate of change) 102% 108% 105% 106% 103% 104% 106% 107% 108% 104% 102% 100% 105% 111% 109% Follow force 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇

[Table 4] Comparative example 2-1 Comparative example 2-2 Comparative example 2-3 Comparative example 2-4 Comparative example 2-5 Hardened Hardened object 1-1 Hardened 1-2 Hardened object 1-3 Hardened object 1-1 Hardened object 1-1 Polymerizable composition no no no Comparative composition 1-1 Comparison composition 1-2 Acid catchability (corrosion test, rate of change) 120% 113% 115% 120% 118% Follow force - - - X X

[Reference Comparative Example 2-1] The polymerizable composition prepared in Example 1-6 was coated on a substrate (indium tin oxide coated glass slide, manufactured by Sigma-Aldrich) to obtain a substrate with a coating film . As the base material, a length of 10 cm and a width of 3 cm are used. The coating system adopts bar coating method. The coating length of the polymerizable composition 1-6 was set to 5 cm, and the coating width was set to 3 cm, and the coating was applied so that the coating film was located in the center of the substrate. Adjust the coating thickness of the polymerizable composition 1-6 so that the film thickness after curing is 3 to 5 μm. For the substrate with the coating film, use UV-LED to ^{irradiate 365 nm ultraviolet rays at 3000 mJ/cm 2 to} polymerize the polymerizable composition to obtain a polymer. The cationic curable composition 1-2 was coated on the obtained polymer by a bar coating method to form a coating film, and the coating film was dried at 90°C for 1 minute. A UV-LED was used to irradiate the dried coating film with ultraviolet rays of 365 nm ^{at 3000 mJ/cm 2, but the cationic curable composition 1-2 did not harden.}

[Reference Comparative Example 2-2] 10 parts by mass of the polymerizable composition 1-1 prepared in Example 1-1 and 90 parts by mass of the cationic curable composition 1-1 were mixed to obtain a mixed composition . The mixed composition was applied to a substrate (indium tin oxide coated glass slide, manufactured by Sigma-Aldrich) to obtain a substrate with a coating film. As the base material, a length of 10 cm and a width of 3 cm are used. The coating system adopts bar coating method. The coating length of the mixed composition is set to 5 cm, and the coating width is set to 3 cm, and the coating is applied with the coating film in the center of the substrate. A UV-LED was used to irradiate the coated substrate with 365 nm ultraviolet rays ^{at 3000 mJ/cm 2, but the mixed composition did not harden.}

Tables 3 and 4 show that the covering structure of Examples 2-1 to 2-29, that is, the covering material having the polymer containing the polymerizable composition of Examples 1-1 to 1-16, and the covering material without the covering structure Compared with the covered structures of Comparative Examples 2-1 to 2-3, the rate of change is smaller. In addition, the covering structure of Examples 2-1 to 2-29, that is, the covering material having the polymer containing the polymerizable composition of Examples 1-1 to 1-16, and Comparative Examples 2-4 and 2-5 That is, compared with the coating material with the polymer containing the comparative polymerizable composition of Comparative Examples 1-1 and 1-2, the rate of change is smaller and the adhesive force of the polymer is stronger. From the above results, it was confirmed that the polymer of the polymerizable composition of the present invention can form a coating material having excellent acid component capturing properties and high adhesiveness.

[Example 3-1 and Comparative Examples 3-1 to 3-2] 1. Preparation of polymerizable composition (Example 3-1 and Comparative Examples 3-1 to 3-2) The components described in Table 5 below were mixed at the ratio described in the table to prepare a polymerizable composition. The symbols in Table 5 indicate the following components. In addition, the A1-1 and D-2 in the table indicate the same contents as the ingredients described in Table 1. In addition, the numerical values indicating the ratio in the table refer to parts by mass.

A2-4: Butyl acrylate A2-5: Hydroxyethyl acrylate B-3: Thermal radical polymerization initiator (2,2'-azobisisobutyronitrile) E-1: Methyl ethyl ketone

2. Formation of covering material The polymerizable compositions of the examples and comparative examples were added to a flask equipped with a cooling tube and a stirrer. While stirring slowly, the temperature of the solution was raised to 80°C. After maintaining the temperature for 4 hours, the temperature was raised to 100°C and kept at the same temperature. Polymerization is carried out at a temperature of 1 hour to obtain a cured product (copolymer, solid content 10%). Furthermore, in Comparative Example 3-2, after the cured product was formed, the imidazole compound D-2 was added to the cured product solution. In addition, the weight average molecular weight (Mw) of the copolymer obtained in Example 3 was 300,000. In addition, the weight average molecular weight (Mw) of the copolymer obtained in Comparative Example 3-1 and Comparative Example 3-2 was 300,000.

Use an applicator to coat the obtained copolymer solution on a PET (polyethylene terephthalate) film (manufactured by Toyobo Co., Ltd.: A4300, thickness: 100 μmm) to form a coating film, which will be used as a solvent The methyl ethyl ketone is dried and removed, thereby forming a coating material. Furthermore, the top view shape of the covering material is a 3 cm×5 cm rectangular shape.

3. Formation of covering structure As the laminated base material (slide/ITO/member containing acid component), a cured product (member containing acid component) is formed on the base material laminated with ITO with the cationic curable composition 1-1, and The above-mentioned coating materials formed by Example 3-1 and Comparative Examples 3-1 to 3-2 were pressure-bonded in a state heated to 80°C, and they were laminated on a laminated base material. Other than that, the same was used as in the examples Obtain the covered structure in the same way as 2-1.

4. Evaluation The corrosion test and the adhesion test described in the above-mentioned [Corrosion Test] and [Adhesion Test] were performed on the coating structure formed from the coating materials obtained in the Examples and Comparative Examples. The results are shown in Table 5 below.

[table 5] Example 3-1 Comparative example 3-1 Comparative example 3-2 1st polymerizable compound A1-1 30 2nd polymerizable compound A2-4 70 70 70 A2-5 30 30 Imidazole compounds D-2 3 Initiator B-3 4 4 4 Solvent E-1 900 900 900 Evaluation Acid catchability (corrosion test, rate of change) 114% 120% 117% Follow force 〇 X X

Table 5 shows that the covered structure obtained from the polymerizable composition of Example 3-1 has a smaller rate of change than the covered structure obtained from the polymerizable composition of Comparative Examples 3-1 to 3-2 , And the adhesion of the covering material is stronger. From this result, it was confirmed that the polymer of the polymerizable composition of the present invention can be used as a coating material having excellent acid component capturing properties and high adhesiveness. [Industrial availability]

The present invention has the following effect: it is possible to provide a polymerizable composition capable of forming a coating material having excellent acid component capturing properties and high adhesiveness.

Claims (12)

A polymerizable composition comprising a first polymerizable compound having an amide group and an ethylenically unsaturated group, and Used to coat components containing acid. The polymerizable composition of claim 1, wherein the first polymerizable compound contains selected from: An acrylamide compound with a structure in which an amide group and an ethylenically unsaturated group are directly bonded, A urethane compound having a urethane bond and an ethylenically unsaturated group, and Isocyanuric acid ring-containing compound with isocyanuric acid ring and ethylenically unsaturated group At least one compound in the group consisting of. The polymerizable composition according to claim 2, wherein the first polymerizable compound contains an acrylamide compound. The polymerizable composition of claim 2, wherein the acrylamide compound is a compound represented by formula (A1),

In the formula, n represents an integer of 1 or 2; when n is an integer of ¹ , R 1 and R ² each independently represent a hydrogen atom, the group represented by the following formula (a), and the number of carbon atoms is 1 to 30 A monovalent hydrocarbon group, a monovalent heterocyclic group having 2 to 30 carbon atoms, or one or more methylene groups in the hydrocarbon group or the heterocyclic group is substituted with two selected from the following group (I) In the case where two or more methylene groups are substituted with divalent groups selected from the following group (I), the divalent groups are not adjacent to each other, and R ¹ and R ² may be Bonded to each other to form a heterocyclic ring, R ³ represents a hydrogen atom or a methyl group; when n is an integer of 2, R ¹ represents a direct bond, a divalent hydrocarbon group with 1 to 30 carbon atoms, and 2 to 30 carbon atoms The divalent heterocyclic group, or one or more methylene groups in the hydrocarbon group or the heterocyclic group is substituted with a divalent group selected from the following group (I), wherein in 2 When more than one methylene group is substituted with a divalent group selected from the following group (I), the divalent group is not adjacent, and R ² represents a hydrogen atom, a monovalent hydrocarbon group having 1 to 30 carbon atoms, A monovalent heterocyclic group containing 2 to 30 carbon atoms, or one or more methylene groups in the hydrocarbon group or the heterocyclic group containing are substituted with a divalent group selected from the following group (I) In the case where two or more methylene groups are substituted with a divalent group selected from the following group (I), the divalent group is not adjacent, and R ² may be bonded to an adjacent nitrogen atom. A heterocyclic ring containing 2 nitrogen atoms is formed, R ³ represents a hydrogen atom or a methyl group, and the 2 R ² and R ³ may be the same or different;

In the formula, R ⁴ represents a hydrogen atom or a monovalent hydrocarbon group with 1 to 30 carbon atoms, R ⁵ represents a hydrogen atom or a methyl group, and X represents a direct bond, a divalent hydrocarbon group with 1 to 30 carbon atoms, and 2 carbon atoms. ~30 divalent heterocyclic group, or one or more methylene groups in the hydrocarbon group or the heterocyclic group is substituted with a divalent group selected from the following group (I), wherein, When two or more methylene groups are substituted with a divalent group selected from the following group (I), the divalent group is not adjacent, and there are plural in the compound represented by the general formula (A1) In the case of the base represented by the above general formula (a), there are a plurality of R ⁴ , R ⁵ and X which may be the same or different, respectively, * represents a bonding bond; Group (I): -O-, -S -, -NR ⁶ -, -NR ⁶ -(C=O)-O-, -CO-, -(C=O)-O-, -O-(C=O)-, -O-(C= O)-O-R ⁶ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 30 carbon atoms. The polymerizable composition according to claim 4, wherein the compound represented by the above formula (A1) is selected from the group consisting of the following compound A1-1, compound A1-2, compound A1-3, compound A1-4 and compound A1-5 The compound in the group of composition, compound A1-1: the compound in formula (A1) where n is 1 and R ¹ and R ² are bonded to each other to form a heterocyclic ring. Compound A1-2: the compound in formula (A1) where n is 1 And R ¹ and R ² are each independently a hydrogen atom, or an alkyl group having 1 to 30 carbon atoms that may have a substituent, or one or more methylene groups in the alkyl group are substituted to be selected from the group (I Compound A1-3: In the formula (A1), n is 1, R ¹ is a hydrogen atom, and R ² is an unsaturated group with 2 to 30 carbon atoms that may have a substituent Compound A1-4 in which one or more methylene groups in the hydrocarbon group with a double bond or the hydrocarbon group with an unsaturated double bond is substituted with a divalent group selected from the above group (I): Formula ( A1) The compound in which n is 1 and R ¹ and R ² are each independently the above group (a) Compound A1-5: In formula (A1), n is 2, and R ¹ is a divalent compound with 1 to 30 carbon atoms A hydrocarbyl group, a divalent heterocyclic group containing 2 to 30 carbon atoms, or one or more methylene groups in the hydrocarbyl group or the heterocyclic group-containing group is substituted with a divalent group selected from the above group (I) And R ² is a hydrogen atom, a monovalent hydrocarbon group having 1 to 30 carbon atoms, or a monovalent heterocyclic group containing 2 to 30 carbon atoms, or one or more of the hydrocarbon group or the heterocyclic group containing A compound in which a methylene group is substituted with a divalent group selected from the group (I). The polymerizable composition of claim 2, wherein the content of the first polymerizable compound in 100 parts by mass of the solid content of the polymerizable composition is 10 parts by mass or more, The content of the acrylamide compound is 40 parts by mass or more in 100 parts by mass of the first polymerizable compound. The polymerizable composition of claim 1, which further comprises a second polymerizable compound having an ethylenically unsaturated group in addition to the first polymerizable compound, The content of the first polymerizable compound is 20 parts by mass or more in the total of 100 parts by mass of the first polymerizable compound and the second polymerizable compound. The polymerizable composition according to any one of claims 1 to 6, wherein the above-mentioned member comprises a cured product of a cationic curable composition, The above-mentioned cation curable composition contains an acid generator and a cation curable component. A method for manufacturing a covering structure, which has a step of covering a member containing an acid component with a covering material, The coating material includes a polymer having a structural unit derived from a first polymerizable compound having an amide group and an ethylenically unsaturated group. The method for manufacturing a covering structure of claim 8, wherein the step of forming the covering material includes: The step of applying a polymerizable composition containing the first polymerizable compound to the above-mentioned member; and The step of polymerizing the first polymerizable compound in the polymerizable composition. A covering structure having a member containing an acid component and a covering material covering the member, The coating material includes a polymer having a structural unit derived from a first polymerizable compound having an amide group and an ethylenically unsaturated group. A coating material comprising a polymer having a structural unit derived from a first polymerizable compound having an amide group and an ethylenically unsaturated group, the coating material being used for coating a member containing an acid component.