JP4645075B2 - Curing type adhesive material - Google Patents

Description

  The present invention relates to a curable adhesive material and an adhesion method using the material.

A curable adhesive has been proposed that combines the easy workability of an adhesive with the same high bonding strength and coating strength as an adhesive. For example, a pressure sensitive adhesive tape using a photopolymerizable composition composed of an acrylate monomer and an epoxy resin is disclosed (Patent Document 1). This material has a problem that the adherend is limited because heat is used in the cationic polymerization process that develops adhesive strength. In order to solve this problem, proposals have been made on materials that utilize light as energy applied in the cationic polymerization process. For example, a pressure-sensitive adhesive containing a radical photopolymerizer, a cationic polymerization component, and an organometallic complex initiator is disclosed (Patent Document 2). Since then, various materials have been studied for the purpose of improving the initial adhesive properties and adhesive strength. Among these materials, the acid generator is considered to be one of the materials that play the most important role in the cationic polymerization process that develops adhesive force. Typical acid generators used for conventionally known adhesive materials include onium salt compounds such as diazonium salts, sulfonium salts, and iodonium salts. Examples of materials using these onium salt compounds as acid generators include a curable adhesive sheet and a method for joining members (Patent Document 3). Any of these can function as a curable adhesive material, but in recent years, in the field of adhesive materials, the effect of rapid progress to a desired degree of polymerization and materials that exhibit good adhesive strength are universal. It has been demanded.
Japanese Patent Laid-Open No. 2-272076 Publication No. 5-506465 Japanese Patent Laid-Open No. 10-120988

  An object of the present invention is to use an adhesive material that has excellent solubility, thermal stability, and initial adhesive force, and has high workability and adhesive force due to rapid progress of cationic polymerization to a desired polymerization degree, and the material. It is to provide a bonding method.

  In order to solve the above problems, the present inventor has developed a material that solves all the above problems as a result of intensive studies.

  That is, the present invention is a curable adhesive comprising an acid generator (A) represented by the following general formula (1), an adhesive polymer (B) or a precursor thereof, and a cationic polymerizable compound (C). Regarding materials.

General formula (1)

_{(Wherein, R 01, R 02, R} 04 and R ₀₅ each independently represent a hydrogen atom, an alkyl group, an aryl group, an alkenyl group, an acyl group, an alkoxyl group, an aryloxy group, an acyloxy group, an alkoxycarbonyloxy group, Represents a halogen atom or —SR ₃₁ .
R ₀₃ represents —SR ₃₁ .
R ₃₁ represents an alkyl group or an aryl group.
R ₁₁ and R ₁₂ each independently represents a hydrogen atom, an alkyl group, an aryl group, an alkoxyl group or an alkenyl group.
R ₂₁ and R ₂₂ each independently represents an alkyl group, an aryl group or an alkenyl group. However, R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₁₂ , R ₂₂ , R ₂₁ and R ₁₁ may be combined to form a ring.
X ⁻ represents an arbitrary anion. )

The present invention also relates to the above curable adhesive material wherein the anion X ⁻ of the general formula (1) is a borate represented by the following general formula (2).

General formula (2)

(Where Y is a fluorine or chlorine atom,
Z is a phenyl group substituted with two or more groups selected from a fluorine atom, a cyano group, a nitro group, and a trifluoromethyl group,
m represents an integer of 0 to 3, n represents an integer of 1 to 4, and m + n = 4. )

  The present invention also relates to the above curable adhesive material, wherein the adhesive polymer (B) is a polymer obtained by radical polymerization of the precursor by irradiation with energy rays.

  Moreover, this invention relates to the curable adhesive sheet formed by forming the layer containing the said curable adhesive material on a base material.

  The present invention also relates to a method for adhering a base material, wherein the curable adhesive material on the base material is irradiated with an energy ray and cured.

  The present invention also relates to an adhesive bonded by the above bonding method.

  The curable adhesive material of the present invention has a good initial adhesive strength, and can obtain high heat resistance, durability, and adhesive strength after crosslinking and curing with energy rays. Therefore, it can be used as a material excellent in workability that achieves both temporary fixability and adhesive strength when bonding various materials. In addition, since the curable adhesive material of the present invention uses the acid generator (A), cationic polymerization proceeds rapidly to the desired degree of polymerization by irradiation with energy rays, so that high workability and adhesion are achieved. Have power. In addition, even when irradiated with a small amount of energy rays, a very strong acid is efficiently generated. Therefore, workability can be improved by shortening the irradiation time of energy rays, and deterioration of the substrate due to energy ray irradiation can be reduced. Is possible. The curable adhesive material of the present invention can be used for various adhesive applications.

  Hereinafter, embodiments of the present invention will be described in detail.

  The curable adhesive material of the present invention is a material having an adhesive force at room temperature, but is gradually crosslinked and cured by irradiating energy rays, and finally high adhesive force, heat resistance and durability can be obtained. Material. Therefore, it is a material that can achieve both the temporary fixing property by the initial adhesive force and the final adhesive force.

[Acid generator (A)]
First, the acid generator (A) of the present invention will be described. The acid generator (A) of the present invention is a material that generates an acid upon irradiation with energy rays, and the acid generated from the acid generator has a function of initiating and promoting crosslinking by cationic polymerization of a cationically polymerizable compound. Yes.

  A feature of the acid generator (A) of the present invention is that it has a specific structure at the cation site, thereby realizing a significant increase in sensitivity to energy rays, particularly light irradiation in the wavelength region of 300 nm to 450 nm. For this reason, the acid generator (A) of the present invention can achieve significantly higher sensitivity and improved characteristics as compared with conventionally known phenacylsulfonium salt-based acid generators if the anion species is the same. In principle, any anionic species can be used.

  The acid generator (A) of the present invention has a structure represented by the general formula (1), and a sulfonium cation can be obtained by introducing a specific substituent, that is, a thio group into the benzene ring of the phenacylsulfonium cation. In addition, suitable light absorption characteristics can be imparted to a wavelength region of 300 nm to 450 nm. In addition, by having this structure, the sulfonium cation of the present invention decomposes very efficiently without using a sensitizer in combination with light irradiation in the wavelength region. It is possible to function as a highly sensitive material that is generated automatically.

General formula (1)

(However, R ₀₁ , R ₀₂ , R ₀₄ and R ₀₅ are each independently a hydrogen atom, alkyl group, aryl group, alkenyl group, acyl group, alkoxyl group, aryloxy group, acyloxy group, alkoxycarbonyloxy group, Represents a halogen atom or —SR ₃₁ .
R ₀₃ represents —SR ₃₁ .
R ₃₁ represents an alkyl group or an aryl group.
R ₁₁ and R ₁₂ each independently represent a hydrogen atom, an alkyl group, an aryl group, an alkoxyl group or an alkenyl group.
R ₂₁ and R ₂₂ each independently represents an alkyl group, an aryl group or an alkenyl group. However, R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₁₂ , R ₂₂ , R ₂₁ and R ₁₁ may be combined to form a ring.
X ⁻ represents an arbitrary anion. )

  One specific example of the acid generator (A) of the present invention is shown as compound (2).

Compound (2)

  As a comparative compound, it was shown as a conventional phenacyl sulfonium-based compound (3).

Compound (3)

  Compound (2), which is one specific example of the acid generator (A) of the present invention, is a relatively transparent material having a molar extinction coefficient of 800 at 365 nm corresponding to one of the emission lines of a mercury lamp, for example. However, when irradiated with light of this wavelength, the compound (3), which is a conventionally known phenacylsulfonium acid generator having the same anion, is far superior to the case where it is used alone or in combination with a sensitizer. It is a material having an innovative function of having high sensitivity as an acid generator and having very high sensitivity while having good transparency.

At present, the details of the reaction mechanism of the acid generation by light irradiation are not clear, but the sulfonium cation part of compound (2) absorbs energy rays, so that a proton is extracted from the cation part through a hydrogen abstraction reaction in the molecule. It is considered that an acid having an anion X ⁻ as a counter anion, that is, H ⁺ X ⁻ is generated. At that time, it is considered that by having a specific cation structure, suitable energy ray absorption characteristics are imparted, and at the same time, decomposition proceeds efficiently due to a substituent effect in an excited state.

  The energy ray source used for generating an acid from the acid generator (A) of the present invention is not particularly limited, but a light source capable of irradiating light in a wavelength region of 300 nm to 450 nm that expresses particularly suitable sensitivity is preferable, and Other energy rays may be emitted simultaneously with the light in the wavelength region. A particularly preferable light source is a light source having a main wavelength of light emission in a wavelength region of 300 nm to 450 nm. Specific examples include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a mercury xenon lamp, a metal halide lamp, a high power metal halide lamp, and a xenon. Examples include, but are not limited to, lamps and pulsed light xenon lamps. Also suitable are lasers having an emission wavelength in the wavelength region of 300 nm to 450 nm, such as Nd-YAG triple wave laser, He-Cd laser, nitrogen laser, Xe-Cl excimer laser, Xe-F excimer laser, and semiconductor excitation solid laser. It can be used as an energy ray source. An electron beam can also be used as a suitable energy beam source. All of the acid generators of the present invention have suitable absorption in the wavelength region of 300 nm to 450 nm, and the absorption characteristics are slightly different depending on the substituents. However, by appropriately selecting the above-mentioned light source, a very high sensitivity can be obtained. It can function as an energy ray acid generator. In addition, these light sources can be appropriately irradiated through optical devices such as filters, mirrors, and lenses.

  Next, the structure of the acid generator (A) of the present invention will be described in detail.

  As shown in the general formula (1), the acid generator (A) of the present invention can introduce various substituents as long as the properties are not impaired. By introducing a substituent, the acid generator (A) of the present invention can be used by appropriately adjusting the absorption characteristics of energy rays such as the maximum absorption wavelength and transmittance, and the solubility in the resin or solvent used together.

The substituents R ₀₁ , R ₀₂ , R ₀₄ and R ₀₅ in the general formula (1) are each independently a hydrogen atom, alkyl group, aryl group, alkenyl group, acyl group, alkoxyl group, aryloxy group, acyloxy group, An alkoxycarbonyloxy group, a halogen atom or a thio group represented by —SR ₃₁ is represented . R ₀₃ represents —SR ₃₁ .

_Examples of the alkyl group in the substituents R ₀₁ , R ₀₂ , R ₀₄ and R ₀₅ in the general formula (1) include linear, branched, monocyclic or condensed polycyclic alkyl groups having 1 to 18 carbon atoms. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, isopentyl Group, sec-butyl group, t-butyl group, sec-pentyl group, t-pentyl group, t-octyl group, neopentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl Group, 4-decylcyclohexyl group and the like can be mentioned, but are not limited thereto.

_Examples of the aryl group in the substituents R ₀₁ , R ₀₂ , R ₀₄ and R ₀₅ in the general formula (1) include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms which may contain a hetero atom. Specific examples include phenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-indenyl group, 9-fluorenyl group, 2-furyl group, 2-thienyl group, 2 -Indolyl group, 3-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-carbazolyl group, 3-carbazolyl group and the like can be mentioned, but are not limited thereto.

_Examples of the alkenyl group in the substituents R ₀₁ , R ₀₂ , R ₀₄ and R ₀₅ in the general formula (1) include linear, branched, monocyclic or condensed polycyclic alkenyl groups having 1 to 18 carbon atoms. They may have a plurality of carbon-carbon double bonds in the structure, and specific examples thereof include vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, Propenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group , Cyclopentenyl group, cyclohexenyl group, 1,3-butadienyl group, cyclohexadienyl group, cyclopentadienyl group, and the like. No.

The acyl group in the substituents R ₀₁ , R ₀₂ , R ₀₄ and R ₀₅ in the general formula (1) is a hydrogen atom or a straight chain, branched chain, monocyclic or condensed polycyclic having 1 to 18 carbon atoms. Examples include a carbonyl group to which an aliphatic group is bonded, or a carbonyl group to which a monocyclic or condensed polycyclic aromatic group having 4 to 18 carbon atoms which may contain a hetero atom is bonded, and these are unsaturated bonds in the structure. Specific examples include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, cyclopentyl Carbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, Yl group, benzoyl group, 1-naphthoyl group, 2-naphthoyl group, cinnamoyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, isonicotinoyl group and the like, but are not limited thereto. .

_Examples of the alkoxyl group in the substituents R ₀₁ , R ₀₂ , R ₀₄ and R ₀₅ in the general formula (1) include linear, branched, monocyclic or condensed polycyclic alkoxyl groups having 1 to 18 carbon atoms. Specific examples include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, dodecyloxy, octadecyloxy, isodecyl Propoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, t-butoxy group, sec-pentyloxy group, t-pentyloxy group, t-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclo Butyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyl Alkoxy group, norbornyl group, Boroniruokishi group, 4-decyl cyclohexyl group, 2-tetrahydrofuranyl group, there may be mentioned 2-tetrahydropyranyloxy group, and the like, but is not limited thereto.

_Examples of the aryloxy group in the substituents R ₀₁ , R ₀₂ , R ₀₄ and R ₀₅ in the general formula (1) include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms which may contain a hetero atom. Specific examples include phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group, 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group Group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group, 3-carbazolyloxy group, 4-carbazolyloxy group, - acridinyl but oxy group, and the like, but is not limited thereto.

The acyloxy group in the substituents R ₀₁ , R ₀₂ , R ₀₄ and R ₀₅ in the general formula (1) is a hydrogen atom or a linear, branched, monocyclic or condensed polycyclic having 1 to 18 carbon atoms. Examples include a carbonyloxy group to which an aliphatic group is bonded, or a carbonyloxy group to which a monocyclic or condensed polycyclic aromatic group having 4 to 18 carbon atoms which may contain a hetero atom is bonded. Specific examples include acetoxy Group, propionyloxy group, butyryloxy group, isobutyryloxy group, valeryloxy group, isovaleryloxy group, pivaloyloxy group, lauroyloxy group, myristoyloxy group, palmitoyloxy group, stearoyloxy group, cyclopentylcarbonyloxy group, cyclohexylcarbonyl Oxy group, acryloyloxy group, methacryloyloxy Group, crotonoyloxy group, isocrotonoyloxy group, oleoyloxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3-furoyloxy group, 2-thenoyloxy group Nicotinoyloxy group, isonicotinoyloxy group, 9-anthroyloxy group, 5-naphthathenoyloxy group, and the like, but are not limited thereto.

Examples of the alkoxycarbonyloxy group in the substituents R ₀₁ , R ₀₂ , R ₀₄ and R ₀₅ in the general formula (1) include carbonic acid ester groups having 1 to 12 carbon atoms, and specific examples thereof include t-butoxycarbonyloxy. Group, t-pentyloxycarbonyloxy group, 1,1-diethylpropyloxycarbonyloxy group, 1-ethyl-2-cyclopentenyloxycarbonyloxy group, 2-tetrahydropyranyloxycarbonyloxy group, 1-ethylcyclopentyloxycarbonyl Although an oxy group etc. can be mentioned, it is not limited to these.

The alkyl group, aryl group, alkenyl group, acyl group, alkoxyl group, aryloxy group, acyloxy group, alkoxycarbonyloxy group in the substituents R ₀₁ , R ₀₂ , R ₀₄ and R ₀₅ in the general formula (1) described above are Further, it may be substituted with other substituents, and examples of such other substituents include hydroxyl group, mercapto group, cyano group, nitro group, halogen atom, alkyl group, aryl group, acyl group, alkoxyl group. , Aryloxy group, acyloxy group, alkylthio group, arylthio group, and the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Yes.

  Examples of the alkyl group include linear, branched, monocyclic or condensed polycyclic alkyl groups having 1 to 18 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, isopentyl, sec-butyl, t-butyl, sec-pentyl, t-pentyl, Examples include t-octyl group, neopentyl group, cyclopropyl group, cyclobutyl, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like.

  Examples of the aryl group include a monocyclic or condensed polycyclic aryl group having 4 to 18 carbon atoms which may contain a hetero atom, and specific examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and 9-anthryl. Group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 9-fluorenyl group, 2-furanyl group, 2-thienyl group, 2-indolyl group Group, 3-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-acridinyl group and the like.

  As the acyl group, a hydrogen atom, a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a carbon atom which may contain a hetero atom is 4 carbon atoms. To 18 monocyclic or condensed polycyclic aromatic bonded carbonyl groups,

  They may have an unsaturated bond in the structure. Specific examples include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group. , Palmitoyl group, stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, benzoyl group, 1-naphthoyl group, 2-naphthoyl group, cinnamoyl group, 3-furoyl Group, 2-thenoyl group, nicotinoyl group, isonicotinoyl group, 9-anthroyl group, 5-naphthathenoyl group and the like.

  Examples of the alkoxyl group include linear, branched, monocyclic or condensed polycyclic alkoxyl groups having 1 to 18 carbon atoms, and specific examples include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy. Group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, t-butoxy group, sec-pentyloxy group, t-pentyloxy group, t-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group , Boronyloxy group, 4-decyl Cyclohexyloxy group, 2-tetrahydrofuranyl group, 2-tetrahydrofuranyl group, etc. can be exemplified.

  Examples of the aryloxy group include monocyclic or condensed polycyclic aryloxy groups having 4 to 18 carbon atoms that may contain a hetero atom, and specific examples include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group. 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9- Fluorenyloxy group, 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyl Examples thereof include an oxy group, a 3-carbazolyloxy group, a 4-carbazolyloxy group, and a 9-acridinyloxy group.

  The acyloxy group is a hydrogen atom or a carbonyloxy group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a carbon number which may contain a hetero atom. Examples include a carbonyloxy group having 4 to 18 monocyclic or condensed polycyclic aromatics bonded thereto, and specific examples include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, and an isovaleryloxy group. Group, pivaloyloxy group, lauroyloxy group, myristoyloxy group, palmitoyloxy group, stearoyloxy group, cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group, acryloyloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, Oreo Ruoxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3-furoyloxy group, 2-thenoyloxy group, nicotinoyloxy group, isonicotinoyloxy group, 9-anth A royloxy group, a 5-naphthacenoyloxy group, etc. can be mentioned.

  Examples of the alkylthio group include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms, and specific examples include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, and a pentylthio group. Hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group and the like.

  Examples of the arylthio group include a monocyclic or condensed polycyclic arylthio group having 4 to 18 carbon atoms which may contain a hetero atom, and specific examples include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a 9-anthrylthio group. Group, 9-phenanthrylthio group, 2-furylthio group, 2-thienylthio group, 2-pyrrolylthio group, 6-indolylthio group, 2-benzofurylthio group, 2-benzothienylthio group, 2-carbazolylthio group, 3 -A carbazolylthio group, a 4-carbazolylthio group, etc. can be mentioned, However, It is not limited to these.

Examples of the halogen atom in the substituents R ₀₁ , R ₀₂ , R ₀₄ and R ₀₅ in the general formula (1) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The substituents in the substituents R ₀₁ , R ₀₂ , R ₀₄ and R ₀₅ in the general formula (1) do not have to be the same, and the above substituents can be used in any combination. However, it is essential that the substituent R ₀₃ is a thio group represented by —SR ₃₁ . Two adjacent substituents selected from R ₀₁ , R ₀₂ , R ₀₄ and R ₀₅ may be bonded to each other via a divalent organic residue to form a cyclic structure. The divalent organic residue here is an alkylene group which may have a substituent having 1 to 4 carbon atoms, an arylene group which may have a substituent, an arylalkylene group, or -C = C-, —O—, —S—, —NH—, —SO ₂ —, —CO—, —COO—, —OCOO—, —CONH—, —SO ₂ —O—, and a combination thereof. An alkylene group which may have a substituent is meant.

Next, the thio group represented by —SR ₃₁ in the substituents R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ and R ₀₅ in the general formula (1) will be described. Thio group denoted by -SR ₃₁ is in a state in which the substituents R ₃₁ via the sulfur atom is bonded to any position of the benzene ring of the phenacyl group, the substituent R ₃₁ is an alkyl group or an aryl Represents a group.

Examples of the alkyl group in the substituent R ₃₁ in the general formula (1) include a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms. Specific examples include a methyl group. , Ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, t- Butyl, sec-pentyl, t-pentyl, t-octyl, neopentyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, norbornyl, boronyl, 4-decylcyclohexyl, etc. However, it is not limited to these.

Examples of the aryl group in the substituent R ₃₁ in the general formula (1) include a monocyclic or condensed polycyclic aryl group having 4 to 18 carbon atoms that may contain a hetero atom. Specific examples include a phenyl group, 1 -Naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 2-furyl group, 2-thienyl group, 2-pyrrolyl group, 6-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 4-quinolinyl group, 4-isoquinolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-acridinyl group, 3-phenothiazinyl group, 2-phenoxathinyl group, 3-phenoxazinyl group, 3 -A thiantenyl group etc. can be mentioned, However, It is not limited to these. These aryl groups may be bonded to a sulfur atom substituted position other than the above, they are also included in the scope of the thio group denoted by -SR ₃₁ of the present invention.

The alkyl group and aryl group represented by R ₃₁ described above may be further substituted with other substituents, such as a hydroxyl group, a mercapto group, a cyano group, a nitro group, Examples thereof include a halogen atom, an alkyl group, an aryl group, an acyl group, an alkoxyl group, an aryloxy group, an acyloxy group, an alkylthio group, and an arylthio group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkyl group include linear, branched, monocyclic or condensed polycyclic alkyl groups having 1 to 18 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, Hexyl, heptyl, octyl, nonyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, isopentyl, sec-butyl, t-butyl, sec-pentyl, t-pentyl, t-octyl group, neopentyl group, cyclopropyl group, cyclobutyl, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group, etc.

  Examples of the aryl group include a monocyclic or condensed polycyclic aryl group having 4 to 18 carbon atoms which may contain a hetero atom, and specific examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and 9-anthryl. Group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 1-acenaphthyl group, 9-fluorenyl group, 2-furanyl group, 2-thienyl group, 2-indolyl group, 3-indolyl group Group, 2-benzofuryl group, 2-benzothienyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-acridinyl group, etc.

  As the acyl group, a hydrogen atom, a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a carbon atom which may contain a hetero atom is 4 carbon atoms. To 18 monocyclic or condensed polycyclic aromatic carbonyl groups, which may have an unsaturated bond in the structure. Specific examples thereof include formyl group, acetyl group, propionyl group, Butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group Benzoyl group, 1-naphthoyl group, 2-naphthoyl group, N'namoiru groups, 3-furoyl, 2-thenoyl group, nicotinoyl group, isonicotinoyl group, 9-Ansuroiru groups, etc. can be mentioned 5-Nafutasenoiru groups,

  Examples of the alkoxyl group include linear, branched, monocyclic or condensed polycyclic alkoxyl groups having 1 to 18 carbon atoms, and specific examples include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy. Group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropoxy group, isobutoxy group, isopentyloxy group, sec-butoxy group, t-butoxy group, sec-pentyloxy group, t-pentyloxy group, t-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group , Boronyloxy group, 4-decyl Cyclohexyloxy group, 2-tetrahydrofuranyl group, 2-tetrahydrofuranyl group, and the like can be given.

  Examples of the aryloxy group include monocyclic or condensed polycyclic aryloxy groups having 4 to 18 carbon atoms that may contain a hetero atom, and specific examples include a phenoxy group, a 1-naphthyloxy group, and a 2-naphthyloxy group. 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9- Fluorenyloxy group, 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyl An oxy group, a 3-carbazolyloxy group, a 4-carbazolyloxy group, a 9-acridinyloxy group, and the like,

  The acyloxy group is a hydrogen atom or a carbonyloxy group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or a carbon number which may contain a hetero atom. Examples include a carbonyloxy group having 4 to 18 monocyclic or condensed polycyclic aromatics bonded thereto, and specific examples include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a valeryloxy group, and an isovaleryloxy group. Group, pivaloyloxy group, lauroyloxy group, myristoyloxy group, palmitoyloxy group, stearoyloxy group, cyclopentylcarbonyloxy group, cyclohexylcarbonyloxy group, acryloyloxy group, methacryloyloxy group, crotonoyloxy group, isocrotonoyloxy group, Oreo Ruoxy group, benzoyloxy group, 1-naphthoyloxy group, 2-naphthoyloxy group, cinnamoyloxy group, 3-furoyloxy group, 2-thenoyloxy group, nicotinoyloxy group, isonicotinoyloxy group, 9-anth And a royloxy group, a 5-naphthacenoyloxy group, etc.

  Examples of the alkylthio group include a linear, branched, monocyclic or condensed polycyclic alkylthio group having 1 to 18 carbon atoms, and specific examples include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, and a pentylthio group. A hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, an octadecylthio group, etc., and the arylthio group includes a monocyclic or condensed polycyclic arylthio group having 4 to 18 carbon atoms that may contain a hetero atom, Specific examples include phenylthio group, 1-naphthylthio group, 2-naphthylthio group, 9-anthrylthio group, 9-phenanthrylthio group, 2-furylthio group, 2-thienylthio group, 2-pyrrolylthio group, 6-indolylthio group. 2-benzofurylthio group, 2-benzothienylthio group, 2-carbazolylthio group Group, 3-Karubazoriruchio group, 4-Karubazoriruchio of the group and the like, but is not limited thereto.

The thio group represented by —SR ₃₁ in the general formula (1) is bonded to the benzene ring of the phenacyl group as at least one of R ₀₁ to R ₀₅ , and the number thereof is any one of 1 to 5. may be, but from the viewpoint of the absorption characteristics of the synthetic difficulty and light, if to no R ₀₁ one or two any of R ₀₅ is a thio group denoted by -SR ₃₁ are preferred, R ₀₁ Most preferably, only one of R ₀₅ is a thio group represented by —SR ₃₁ (where R ₀₃ is a thio group represented by —SR ₃₁ ) . When any one of R ₀₁ to R ₀₅ is a thio group represented by —SR ₃₁ , they do not have to be the same, and the substituent R ₃₁ can be independently selected. .

In the general formula (1), the substitution position of the thio group represented by —SR ₃₁ may be any position of R ₀₁ to R ₀₅ (where R ₀₃ is a thio group represented by —SR ₃₁ ). ) When there are a plurality of thio groups represented by —SR ₃₁ , any combination of substitution positions from R ₀₁ to R ₀₅ is possible. When only one of R ₀₁ to R ₀₅ is a thio group represented by —SR ₃₁ , the substitution position is preferably R ₀₁ , R ₀₃ or R ₀₅ , especially when R ₀₃ is a thio group. The synthesis difficulty is low, and preferable absorption characteristics and acid generation sensitivity can be realized.

In addition, the thio group represented by —SR ₃₁ is bonded to adjacent substituents R ₀₁ to R ₀₅ , R ₁₁ , R ₁₂ , R ₂₁ or R ₂₂ through a divalent organic residue to form a cyclic structure. It may be formed. The divalent organic residue here is an alkylene group which may have a substituent having 1 to 4 carbon atoms, an arylene group which may have a substituent, an arylalkylene group, or -C = C-, —O—, —S—, —NH—, —SO ₂ —, —CO—, —COO—, —OCOO—, —CONH—, —SO ₂ —O—, and a combination thereof. An alkylene group which may have a substituent is meant.

The alkyl group, aryl group, alkoxyl group and alkenyl group in the substituents R ₁₁ and R ₁₂ in the general formula (1), the alkyl group, aryl group and alkenyl group in R ₂₁ and R ₂₂ are the substituents R ₀₁ , R _The same substituents as those exemplified as the alkyl group, aryl group, alkoxyl group and alkenyl group in ₀₂ , R ₀₄ and R ₀₅ can be mentioned.

The substituent R ₂₁ may be bonded to any one of R ₂₂ , R ₁₁ , R ₁₂ , R ₀₁ or R ₀₅ via a divalent organic residue to form a ring structure. The substituent R ₁₁ may be bonded to R ₀₁ or R ₀₅ via a divalent organic residue to form a ring structure. The divalent organic residue here is an alkylene group which may have a substituent having 1 to 4 carbon atoms, an arylene group which may have a substituent, an arylalkylene group, or -C = C-, —O—, —S—, —NH—, —SO ₂ —, —CO—, —COO—, —OCOO—, —CONH—, —SO ₂ —O—, and a combination thereof. An alkylene group which may have a substituent is meant.

Next, the anion X ⁻ in the general formula (1) will be described.

The anion X ⁻ in the general formula (1) is not particularly limited in principle, but a non-nucleophilic anion is preferable. When the anion X ⁻ is a non-nucleophilic anion, a nucleophilic reaction is unlikely to occur in cations coexisting in the molecule or in various materials used together. As a result, the acid generator itself represented by the general formula (1) or It is possible to improve the aging stability of the composition using. The non-nucleophilic anion here refers to an anion having a low ability to cause a nucleophilic reaction. Examples of such anions include BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , BiCl ₅ ⁻ , SnCl ₆ ⁻ , ClO ₄ ⁻ , dithiocarbamate anion, SCN ^{− and the} like.

As the anion X ⁻ in the general formula (1), the borate anion represented by the following general formula (2) can also be synthesized relatively easily, the generated acid is very strong, high solubility and high safety and health. Since it has, it can use especially preferable.

General formula (2)

(Where Y is a fluorine or chlorine atom,
Z is a phenyl group substituted with two or more groups selected from a fluorine atom, a cyano group, a nitro group, and a trifluoromethyl group,
m represents an integer of 0 to 3, n represents an integer of 1 to 4, and m + n = 4. )

  As the substituent Z in the general formula (2), 3,5-difluorophenyl group, 2,4,6-trifluorophenyl group, 2,3,4,6-tetrafluorophenyl group, pentafluorophenyl group, 2 , 4-bis (trifluoromethyl) phenyl group, 3,5-bis (trifluoromethyl) phenyl group, 2,4,6-trifluoro-3,5-bis (trifluoromethyl) phenyl group, 3,5 -Dinitrophenyl group, 2,4,6-trifluoro-3,5-dinitrophenyl group, 2,4-dicyanophenyl group, 4-cyano-3,5-dinitrophenyl group, 4-cyano-2,6- Examples thereof include, but are not limited to, bis (trifluoromethyl) phenyl group.

  Therefore, as the structure of the borate anion represented by the general formula (2), specifically, pentafluorophenyl trifluoroborate, 3,5-bis (trifluoromethyl) phenyl trifluoroborate, bis (pentafluorophenyl) ) Difluoroborate, bis [3,5-bis (trifluoromethyl) phenyl] difluoroborate, tris (pentafluorophenyl) fluoroborate, tris [3,5-bis (trifluoromethyl) phenyl] fluoroborate, tetrakis (penta Fluorophenyl) borate, tetrakis [3,5-bis (trifluoromethyl) phenyl] borate and the like.

  Among these, tetrakis (pentafluorophenyl) borate and tetrakis [3,5-bis (trifluoromethyl) phenyl] borate are particularly preferable as the anion represented by the general formula (2).

An anion in which boron, which is the central element of the anion represented by the general formula (2), is replaced with gallium, that is, a gallate anion can also be used as the anion X ⁻ in the general formula (1). Among such anions, tetrakis (pentafluorophenyl) gallate is a preferred anion.

    The acid generator (A) represented by the general formula (1) of the present invention comprises a combination of the sulfonium cation exemplified above and various anions.

Specific structures are shown below, but the structure of the acid generator of the present invention is not limited thereto.

However, X ⁻ in the above structural formula is BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , SbCl ₆ ⁻ , BiCl ₅ ⁻ , SnCl ₆ ⁻ , ClO ₄ ⁻ , SCN ⁻ and the structures shown below. Any of anions selected from may be used.

  In addition, the curable adhesive material of the present invention includes, if necessary, unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, Benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives and other polymethine dyes, carbazole derivatives, acridine derivatives, Azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, trialis Rumethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, It can contain sensitizers such as annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, and organic ruthenium complexes, thereby improving the sensitivity to energy rays in the crosslinking process by cationic polymerization. Can do.

  Among these sensitizers, anthracene derivatives, benzophenone derivatives, xanthene derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, carbazole derivatives, pyrylium derivatives, thiopyrylium derivatives, and styryl derivatives are particularly preferable. Specific examples of these sensitizers include the following, but the present invention is not limited thereto. Needless to say, the sensitizer should be selected in consideration of the wavelength of the energy ray irradiated in the crosslinking step by cationic polymerization and the desired polymerization sensitivity.

(Specific examples of anthracene derivatives) Anthracene, 1-anthracenecarboxylic acid, 2-anthracenecarboxylic acid, 9-anthracenecarboxylic acid, 9-anthracaldehyde, 9,10-bis (chloromethyl) anthracene, 9,10-bis (phenyl) Ethynyl) anthracene, 9-bromoanthracene, 1-chloro-9,10-bis (phenylethynyl) anthracene, 9-chloromethylanthracene, 9-cyanoanthracene, 9,10-dibromoanthracene, 9,10-dichloroanthracene, 9 , 10-dicyanoanthracene, 9,10-dimethylanthracene, 9,10-dibutylanthracene, 9,10-diphenylanthracene, 9,10-di-p-tolylanthracene, 9,10-bis (p-methoxyphenyl) anthracene , -Hydroxymethylanthracene, 9-hydroxymethylanthracene, 9-methylanthracene, 9-phenylanthracene, 9,10-dimethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenoxyanthracene, 9,10-dimethoxyanthracene 2-sulfonic acid sodium salt, 1,4,9,10-tetrahydroxyanthracene, 2,2,2-trifluoro-1- (9-anthryl) ethanol, 1,8,9-trihydroxyanthracene, 1,8- Dimethoxy-9,10-bis (phenylethynyl) anthracene, 9-vinylanthracene, 9-anthracenemethanol, trimethylsiloxy ether of 9-anthracenemethanol, and the like.

(Specific examples of benzophenone derivatives) Benzophenone, 4,4′-dimethylbenzophenone, 4,4′-di-tert-butyl-benzophenone, 4,4′-dimethoxybenzophenone, 4,4′-dibutoxybenzophenone, 4,4 '-Bis (methylthio) benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-butylbenzophenone, KAYACURE BMS manufactured by Nippon Kayaku Co., Ltd. etc.

(Specific examples of xanthene derivatives and thioxanthone derivatives) xanthene, 3,6-dimethoxyxanthone, 3,6-dimethoxyxanthane, rose bengal, eosin Y, rhodamine B, rhodamine 6G, erythrosine, fluorescein, uranin, 2,4,5 7-tetraiodo-3-hydroxy-6-fluorone, 3-butoxy-5,7-diiodo-6-fluorone, 9-cyano-3-butoxy-5,7-diiodo-6-fluorone, 2-octanoyl-4, 5,7-triiodo-6-fluorone, 9-cyano-2-octanoyl-4,5,7-triiodo-3-hydroxy-6-fluorone, 2-octyl-4,5,7-triiodo-3-hydroxy- 6-Fluorone, 9-cyano-2-octyl-4,5,7-triiodo-3-hydride Carboxymethyl-6-fluorone, thioxanthone, manufactured by Nippon Kayaku Co., Ltd. of Kayacure (KAYACURE) BMS, KAYACURE CPTX, KAYACURE ITX, Kayacure DETX-S, Kayacure like.

(Specific examples of coumarin derivatives and ketocoumarin derivatives) Coumarin, 7-methylcoumarin, 7-methoxycoumarin, 7-dimethylaminocoumarin, 7-diethylaminocoumarin, 5,7-dimethoxycoumarin, 6,7-dimethoxycoumarin, 7-diethylamino -4-methylcoumarin, 7-diethylamino-4-cyanocoumarin, 7-diethylamino-4-trifluoromethylcoumarin, 7-diethylamino-3-acetylcoumarin, 7-diethylamino-3-benzoylcoumarin, 7-diethylamino-3- Ethoxycarbonylcoumarin, 7-diethylamino-3- (2-benzothiazolyl) coumarin, 7-diethylamino-3- (2-benzoxazolyl) coumarin, 7-diethylamino-3- (2-benzimidazolyl) coumarin, 7- Ethylamino-3- (2-benzothiazolyl) coumarin, 3,3′-carbonylbis (coumarin), 3,3′-carbonylbis (7-methylcoumarin), 3,3′-carbonylbis (7-butylcoumarin) 3,3′-carbonylbis (7-tert-butylcoumarin), 3,3′-carbonylbis (7-methoxycoumarin), 3,3′-carbonylbis (7-butoxycoumarin), 3,3′- Carbonyl bis (7-tert-butoxycoumarin), 3,3′-carbonylbis (7-dimethylaminocoumarin), 3,3′-carbonylbis (7-diethylaminocoumarin), 3,3′-carbonylbis (7- Dibutylaminocoumarin), 10,10′-carbonylbis [1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1 , 5H, 11H- [1] benzopyrano [6,7,8-ij] quinolizin-11-one], and further, NKX-1317, NKX-1318, NKX-1767, manufactured by Japan Photosensitivity Laboratories, Inc. NKX-1768, NKX-1320, NKX-1769, NKX-1770, NKX-1771 and the like.

(Specific examples of carbazole derivatives) N-ethyl-3-acetylcarbazole, N-ethyl-3-benzoylcarbazole, N-ethyl-3-O-toluoylcarbazole, N-ethyl-3,6-dibenzoylcarbazole, N -p-tolyl-3-benzoylcarbazole, Np-tolyl-3,6-dibenzoylcarbazole, N-phenyl-3-benzoylcarbazole, N-ethyl-1,3,6-tribenzoylcarbazole, N-butyl -3,6-di-O-toluoylcarbazole, Np-anisyl-1,6-dibenzoylcarbazole, N-benzyl-1,8-diacetyl-3,6-dibenzoylcarbazole, N-methyl-3 -Benzoyl-6-ethylcarbazole, N-vinyl-3-p-methoxybenzoylcarbazole, N-acetyl-3,6-benzoylcarbazole, N-butyl-3-benzoyl-6-t- Chill carbazole, N- ethyl-3,6-di -p- toluoyl carbazole, N- ethyl-1,8-dibenzoyl carbazole.

(Specific examples of pyrylium derivatives) 2,4,6-triphenylpyrylium tetrafluoroborate, 2,4,6-tri (p-tris) pyrylium tetrafluoroborate, 2,4,6-tris (4-butyl Phenyl) pyrylium tetrafluoroborate, 2,4,6-tris (4-tert-butylphenyl) pyrylium tetrafluoroborate, 2,4,6-tris (4-methoxyphenyl) pyrylium tetrafluoroborate, 2, 4,6-tris (4-butoxyphenyl) pyrylium tetrafluoroborate, 2,4,6-tris (4-tert-butoxyphenyl) pyrylium tetrafluoroborate, 2,4,6-tris (4-dimethylamino) Phenyl) pyrylium tetrafluoroborate, 2,4,6-tris (4-diethylamino) Enyl) pyrylium tetrafluoroborate, 4- (4-butylphenyl) -2,6-diphenylpyrylium tetrafluoroborate, 4- (4-tert-butylphenyl-) 2,6-diphenylpyrylium tetrafluoroborate, 4- (4-methoxyphenyl) -2,6-diphenylpyrylium tetrafluoroborate, 4- (4-butoxyphenyl) -2,6-diphenylpyrylium tetrafluoroborate, 4- (4-tert-butoxyphenyl) -2,6-diphenylpyrylium tetrafluoroborate, 4- (4-dimethylaminophenyl) -2,6-diphenylpyrylium tetrafluoroborate, 4- (4-diethylaminophenyl) -2,6-diphenylpyrylium tetra Fluoroborate, 4- (4-butoxif Nyl) -2,6-bis (methoxyphenyl) pyrylium tetrafluoroborate, 4- (4-diethylaminophenyl) -2,6-bis (methoxyphenyl) pyrylium tetrafluoroborate, 2- (4-methoxyphenyl) -4,6-diphenylpyrylium tetrafluoroborate, 2- (4-diethylaminophenyl) -4,6-diphenylpyrylium tetrafluoroborate, 2,4,6-triphenylpyrylium perchlorate, 2,4,6 -Triphenylpyrylium hexafluorophosphate, 2,4,6-triphenylpyrylium tetraphenylborate, 2,4,6-triphenylpyrylium triphenylbutylborate and the like.

(Specific examples of thiopyrylium derivatives) 2,4,6-triphenylthiopyrylium tetrafluoroborate, 2,4,6-tri (p-tris) thiopyrylium tetrafluoroborate, 2,4,6-tris (4 -Butylphenyl) thiopyrylium tetrafluoroborate, 2,4,6-tris (4-tert-butylphenyl) thiopyrylium tetrafluoroborate, 2,4,6-tris (4-methoxyphenyl) thiopyrylium tetra Fluoroborate, 2,4,6-tris (4-butoxyphenyl) thiopyrylium tetrafluoroborate, 2,4,6-tris (4-tert-butoxyphenyl) thiopyrylium tetrafluoroborate, 2,4,6 -Tris (4-dimethylaminophenyl) thiopyrylium tetrafluoroborate, 2 4,6-tris (4-diethylaminophenyl) thiopyrylium tetrafluoroborate, 4- (4-butylphenyl) -2,6-diphenylthiopyrylium tetrafluoroborate, 4- (4-tert-butylphenyl-) 2,6-diphenylthiopyrylium tetrafluoroborate, 4- (4-methoxyphenyl) -2,6-diphenylthiopyrylium tetrafluoroborate, 4- (4-butoxyphenyl) -2,6-diphenylthiopyrylium Tetrafluoroborate, 4- (4-tert-butoxyphenyl) -2,6-diphenylthiopyrylium tetrafluoroborate, 4- (4-dimethylaminophenyl) -2,6-diphenylthiopyrylium tetrafluoroborate, 4 -(4-Diethylaminophenyl) -2,6- Phenylthiopyrylium tetrafluoroborate, 4- (4-butoxyphenyl) -2,6-bis (methoxyphenyl) thiopyrylium tetrafluoroborate, 4- (4-diethylaminophenyl) -2,6-bis (methoxyphenyl) ) Thiopyrylium tetrafluoroborate, 2- (4-methoxyphenyl) -4,6-diphenylthiopyrylium tetrafluoroborate, 2- (4-diethylaminophenyl) -4,6-diphenylthiopyrylium tetrafluoroborate, 2,4,6-triphenylthiopyrylium perchlorate, 2,4,6-triphenylthiopyrylium hexafluorophosphate, 2,4,6-triphenylthiopyrylium tetraphenylborate, 2,4,6- Triphenylthiopyrylium triphenylbuty Ruborate etc.

(Specific examples of styryl derivatives) 2- [2- (4-dimethylamino) phenyl] ethynyl] benzoxazole, 2- [2- (4-dimethylamino) phenyl] ethynyl] benzothiazole, 2- [2- (4 -Dimethylamino) phenyl] ethynyl] -3,3-dimethyl-3H-indole, 2- [2- (4-dimethylamino) phenyl] ethynyl] quinoline, 4- [2- (4-dimethylamino) phenyl] ethynyl ] Quinoline, 2- [2- (4-dimethylamino) phenyl] ethynyl] naphtho [1,2-d] thiazole, and NK-528, NK-97 and NK manufactured by Nippon Photosensitivity Laboratories, Inc. -91, NK-342, NK-1055, NK-557, NK-92, NK-96, NK-375, NK-376, NK-383, NK-526, K-3578, NK-3576, NK-3798, NKX-1595, NK-1473 and the like.

  The acid generator (A) used in the present invention is used alone or in combination of two or more. It is also possible to use an acid generator with heat. When the thermal stability of the base material to be deposited is high, it is possible to advance the crosslinking of the cationic polymerizable compound (C) more rapidly by using these together and heating after light irradiation. .

  The amount of the acid generator (A) used in the present invention is preferably in the range of 0.01 to 20 parts by weight, particularly preferably based on 100 parts by weight of the cationically polymerizable compound (C). 0.5 parts by weight to 10 parts by weight. When the addition amount of the acid generator (A) is less than 0.01 parts by weight, crosslinking by cationic polymerization does not proceed sufficiently, and good adhesive strength may not be obtained. Moreover, when there are more addition amounts of an acid generator (A) than 20 weight part, since there are too many low molecular components in a curable adhesive material, sufficient cohesion force and adhesive strength may not be obtained. .

[Adhesive polymer (B) and its precursor]
Next, the adhesive polymer (B) and its precursor of the present invention will be described. The tacky polymer (B) used in the present invention is blended to impart tackiness at room temperature to the curable adhesive material. The tacky polymer (B) has tackiness at room temperature and is not particularly limited as long as it is compatible with the cationic polymerizable compound (C) described later. The material used as a component can be used. For example, acrylic polymer, polyester, polyurethane, silicone, polyether, polycarbonate, polyvinyl ether, polyvinyl chloride, ethylene-vinyl acetate copolymer, polyvinyl acetate, polyisobutylene and the like can be mentioned. These may be used alone or in combination of two or more as the adhesive polymer (B) of the present invention. Here, the term “compatible” refers to a state where the phases are not completely separated into two phases.

  Moreover, the polymer which copolymerized the monomer which comprises said resin with another monomer is also contained in the category of the adhesive polymer (B) of this invention. The structure of these adhesive polymers (B) is not particularly limited, and includes a homopolymer structure, a block copolymer structure, an alternating copolymer structure, a random copolymer structure, a stereoregular structure, and a hyperbranched structure. You may have a structure, a dendritic structure, a cyclic structure, etc.

  Furthermore, the adhesive polymer (B) of the present invention includes a polymer material that exhibits adhesiveness by adding a tackifying resin such as a liquid resin to a material that does not have adhesiveness alone at room temperature. It is out. For example, even a polyester having a glass transition point Tg of room temperature or higher, xylene resin, alkylphenol resin, rosin ester, rosin derivative such as rosin ester, terpene derivative, organic acid ester, epoxy resin, urethane resin, polyester resin, By adding a liquid resin such as liquid rubber, it can be used as the adhesive polymer (B) of the present invention.

  Among these tacky polymers (B), particularly preferred polymers include acrylic polymers. Acrylic polymers are widely used in the field of pressure-sensitive adhesive materials, and are preferable because the pressure-sensitive adhesive force to the substrate can be appropriately controlled. Acrylic polymers are also preferred because of their excellent compatibility with the cationically polymerizable compound (C) used in the present invention. The structure of the acrylic polymer used in the present invention is not particularly limited. Examples of acrylic polymers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and cyclohexyl (meth) acrylate. , N-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, isomyristyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, glycidyl (meth) acrylate, tetrahydrofurfuryl ( The thing which copolymerized (meth) acrylate can be mentioned. Also, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 5-hydroxy Molecules such as pentyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 3-hydroxy-3-methylbutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate (Meth) acrylates having a hydroxyl group therein are also included in the monomer that forms an acrylic polymer that can be used as the adhesive polymer (B). Among these, an acrylic polymer having a low glass transition point, in particular, an alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms as a main component is preferable because it has high adhesiveness. .

  In addition, if necessary, in order to improve heat resistance and cohesive force at high temperatures, one or more of crosslinkable monomers such as polyfunctional acrylate monomers and polyfunctional vinyl monomers may be copolymerized. It is also possible to obtain an adhesive polymer (B). For example, ethylene glycol di (meth) acrylate, hexanediol (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, polyester acrylate, epoxy acrylate, urethane acrylate Etc.

  A polymer obtained by copolymerizing the above acrylic monomer with another monomer is also included in the acrylic polymer. The other monomer is not particularly limited as long as it has an unsaturated bond copolymerizable with an acrylic monomer, but is preferably one that does not react with the cationically polymerizable compound (C) described later. When the monomer has a functional group that reacts with the cationically polymerizable compound (C) such as carboxylic acid, the adhesive polymer (B) of the present invention and the cationically polymerizable compound (C) are blended. This is because cationic polymerization proceeds and crosslinking starts, and sufficient initial adhesive force cannot be expressed, or the stability may be significantly reduced.

  Examples of the monomer having an unsaturated bond copolymerized with an acrylic monomer and usable as the adhesive polymer (B) of the present invention include styrene, α-methylstyrene, p-chlorostyrene, p-methylstyrene, p-chloromethylstyrene, p-methoxystyrene, indene, N-acryloylmorpholine, N-vinylcaprolactone, N-vinylpiperidine, N-vinylpyrrolidone, p-tert-butoxystyrene, divinylbenzene, vinyl acetate, vinyl butyrate, Examples thereof include vinyl propionate, vinyl caproate, vinyl benzoate, vinyl cinnamate, and (meth) acrylonitrile, but are not limited thereto. Moreover, the silane coupling agent which has an unsaturated bond is also contained in the monomer which has an unsaturated bond which can be copolymerized with an acryl-type monomer and can be used as the adhesive polymer (B) of this invention. These 1 type (s) or 2 or more types are used by copolymerizing with a (meth) acryl monomer. In the case of a copolymer, it is preferable that the acrylic monomer unit in the copolymer is 20% by weight or more.

  When the acrylic polymer obtained by copolymerizing glycidyl (meth) acrylate with the (meth) acrylic monomer described above is used for the adhesive polymer (B) of the present invention, a cationically polymerizable compound (C ) As well as the tacky polymer (B) are preferred because they are involved in the crosslinking reaction and exhibit good adhesive strength. Examples of such an adhesive polymer (B) include a copolymer of glycidyl (meth) acrylate and ethyl (meth) acrylate and / or cyclohexyl (meth) acrylate.

  Among the (meth) acrylic monomers described above, when an acrylic polymer obtained by copolymerizing acrylates having a hydroxyl group in the molecule is used for the adhesive polymer (B) of the present invention, it is determined by cationic polymerization. This is preferable because the crosslinking step proceeds promptly and good adhesive strength can be achieved.

  When the silane coupling agent which has an unsaturated bond is used for the acrylic monomer mentioned above, since the adhesiveness of the curable adhesive material of this invention to a glass base material improves, it is preferable.

  The molecular weight of the adhesive polymer (B) used in the present invention is not particularly limited, but an acrylic polymer preferably has a weight average molecular weight of 200,000 to 5,000,000. If the weight-average molecular weight of the adhesive polymer (B) is less than 200,000, the cohesive force at the time of initial adhesion of the curable adhesive material cannot be sufficiently obtained, and if the weight-average molecular weight is larger than 5 million, the curable type This is not preferable because the viscosity of the adhesive material becomes too high, and the workability when applied to a substrate to be bonded or processed on a sheet is lowered.

  The glass transition temperature Tg of the adhesive polymer (B) used in the present invention is not particularly limited. This is because the curable adhesive material including additives such as a tackifier needs only to be tacky, and cannot be uniquely determined.

  The polymerization method for obtaining the acrylic polymer used as the above-mentioned adhesive polymer (B) is not particularly limited, and any known method can be used. Examples of the polymerization method include radical polymerization and anionic polymerization.

  When the acrylic polymer is obtained by radical polymerization, both thermal polymerization using a known thermal polymerization initiator typified by peroxide and polymerization using energy rays typified by light can be used. In the case of polymerization by energy rays, the precursor of the adhesive polymer (B) used as the raw material of the adhesive polymer (B) described above (for example, (meth) acrylic monomer, styrene monomer, maleic monomer) Etc.) or a monomer having an unsaturated bond copolymerizable therewith and a radical polymerization initiator having sensitivity to energy rays to prepare a composition, and irradiating the composition with energy rays increases the adhesiveness. A molecule (B) can be obtained. This radical polymerization by energy rays can be carried out in a suitable medium such as a solvent, and the cationically polymerizable compound (C) of the present invention can also be used as this medium. That is, it is suitable for a composition in which a precursor of an adhesive polymer (B), a radical polymerization initiator (D) sensitive to energy rays, an acid generator (A), and a cationic polymerizable compound (C) are blended. By irradiating with energy rays, it is also possible to obtain a curable adhesive material comprising the acid generator (A), the adhesive polymer (B) and the cationic polymerizable compound (C) according to the present invention.

  The material that can be used as the radical polymerization initiator (D) that is sensitive to the energy rays used to synthesize the acrylic adhesive polymer (B) can be any material that can sufficiently polymerize the monomers used. There is no particular limitation. For example, α-hydroxy ketones, α-amino ketones, acylphosphine oxides, metallocenes, various onium salts, biimidazoles, oxime esters and the like can be mentioned.

  Specific examples of the radical polymerization initiator (D) include Irgacure 651, Irgacure 184, Darocur 1173, Irgacure 500, Irgacure 1000 described in the Ciba Specialty Chemicals Photopolymerization Initiator General Catalog (issued in 1997). IRGACURE 2959, IRGACURE 907, IRGACURE 369, IRGACURE 1700, IRGACURE 149, IRGACURE 1800, IRGACURE 1850, IRGACURE 819, IRGACURE 784, and IRGACURE 261. Triazine derivatives described in JP-B-59-1281, JP-B-61-9621 and JP-A-60-60104, US Pat. No. 2,848,328, JP-B 36-22062, JP-B 37-13109 Ortho-quinonediazides described in Japanese Patent Publication No. 38-18015 and Japanese Patent Publication No. 45-9610, Japanese Patent Publication No. 55-39162, Japanese Patent Publication No. 59-140203 and Macromolecules, Vol. 10, No. 1307. Various onium compounds, including iodonium compounds described on page (1977, published by the American Chemical Society), azo compounds described in JP-A-59-142205, JP-A-1-54440, European Patent No. 109851, European Patent No. 126712, Journal of Imaging Science, 30th Vol., Page 174 (1986), metal allene complexes, titanocenes described in JP-A-61-151197, JP-A-55-127550, and JP-A-60-202437, 2,4 , 5-triarylimidazole dimer, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,1′-biimidazole, JP-A-59-107344 Examples of the photopolymerization initiator that can be used in combination with the organic halogen compounds described in the publications. Furthermore, JP 05-255347 A, JP 05-255421 A, JP 06-157623 A, JP 2001-206903 A, JP 2001-213909 A, JP 2001-261728 A, and the like. These sulfonium borates can also be used as the radical polymerization initiator (D) of the present invention. Usually, one or more of these exemplified compounds are selected and used.

  The radical polymerization initiator (D) can be used in combination with a sensitizer in order to increase sensitivity to the irradiated energy rays. Examples of the sensitizer that can be used include the same sensitizers that can be used in combination with the acid generator (A) described above.

  The addition amount of the radical polymerization initiator (D) having sensitivity to energy rays is not particularly limited, but is 0.05 to 7% by weight with respect to the total weight of the acrylic monomer and the copolymerized monomer. Is more preferable, and 0.1 to 2% by weight is more preferable. When the content of the radical polymerization initiator (D) is less than 0.05% by weight, the resulting acrylic polymer is not sufficiently polymerized. Conversely, when the content exceeds 5% by weight, the molecular weight of the resulting acrylic polymer is increased. , The cohesive strength and heat resistance become insufficient.

  The energy rays used to obtain the acrylic adhesive polymer (B) are not particularly limited as long as the radical polymerization initiator (D) can absorb and generate radicals. Examples of such energy rays include light such as ultraviolet rays, near ultraviolet rays, visible light, near infrared rays, infrared rays, and electron beams. The definition of each of these energy lines was according to Ryogo Kubo et al. “Iwanami Rikagaku Dictionary 4th Edition” (1987, Iwanami Shoten). Therefore, the curable composition of the present invention includes a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp, an argon ion laser, a helium cadmium laser, and helium. Acrylic adhesive polymer (B) by energy ray irradiation with various light sources such as neon laser, krypton ion laser, various semiconductor lasers, YAG laser, excimer laser, light emitting diode, CRT light source, plasma light source, electron beam irradiator Can be obtained. Among these energy rays, ultraviolet rays and visible light are preferable because they are easy to use in terms of the apparatus.

  Since the process of obtaining the adhesive polymer (B) by radical polymerization is susceptible to inhibition by oxygen, the atmosphere in which radical polymerization is performed is inerted as necessary, or the film is irradiated with light sandwiched between films having low oxygen permeability. Measures can be taken.

  As a step of using a curable adhesive material, there is a step of initiating and promoting the crosslinking of the cationic polymerizable compound (C) by irradiating energy rays to generate an acid from the acid generator (A). The energy beam used for obtaining the adhesive polymer (B) and the energy beam used for cationic polymerization may be substantially the same or different. When the energy rays used in these two steps are substantially different, polymerization in each step can be selectively advanced. For example, a radical polymerization initiator system for obtaining an acrylic adhesive polymer (B) by radical polymerization is set so as to be substantially sensitive to light of 365 nm or more, and a cation produced by the acid generator (A). If the crosslinking step of the polymerizable compound (C) is substantially sensitive to light of 365 nm or less, each step can be independently performed by appropriately switching the light source. Moreover, when the energy beam used for obtaining the adhesive polymer (B) and the energy beam used for cationic polymerization are substantially the same, the energy beam was irradiated to obtain the adhesive polymer (B). At the stage, crosslinking of the cationically polymerizable compound (C) with the acid generator (A) is also started. Since radical polymerization proceeds rapidly and crosslinking by cationic polymerization proceeds relatively slowly, the expression of adhesiveness and crosslinking by cationic polymerization can be initiated by one-step light irradiation. Workability can be improved if the crosslinking rate by cationic polymerization is appropriately controlled by an operation such as setting the addition amount of the acid generator (A) appropriately. However, when crosslinking by cationic polymerization is too fast, attention should be paid because adhesiveness or adhesiveness may be lost immediately after light irradiation, and it may not function as a curable adhesive material.

[Cationically polymerizable compound (C)]
Next, the cationic polymerizable compound (C) will be described. The cationic polymerizable compound (C) functions to crosslink with an acid generated from the acid generator (A) upon irradiation with energy rays, and to increase the adhesive strength. The cationically polymerizable compound (C) includes various monomers having a cationically polymerizable functional group in the molecule, such as a vinyl ether group, an epoxy group, an alicyclic epoxy group, an oxetane group, an episulfide group, an ethyleneimine group, and a hydroxyl group, Oligomers or polymers can be used. Moreover, it is not limited about the polymer which has these functional groups, It is possible to use each polymer, such as an acrylic type, a urethane type, a polyester type, a polyolefin type, a polyether type, a natural rubber, a block copolymer rubber, and a silicone type. it can.

  The cationic polymerizable compound (C) may be used alone or in combination of two or more. As the cationic polymerizable compound (C), a compound having an epoxy group, an oxetane group or a vinyl ether group is preferably used. Since the polymerization of these functional groups is relatively highly reactive and the curing time is short, the bonding process can be shortened.

  An epoxy resin is suitably used as the compound having an epoxy group. Examples of the epoxy resin include bisphenol A type, glycidyl ether type, phenol novolac type, bisphenol F type, cresol novolac type, and glycidyl amine type epoxy resins. These epoxy resins may be liquid at room temperature or solid. Epoxy group-containing oligomers can also be preferably used, and examples thereof include bisphenol A type epoxy oligomers (for example, Epicoat 1001, 1002 manufactured by Yuka Shell Epoxy Co., Ltd.). Furthermore, addition polymers of the above epoxy group-containing monomers and oligomers may be used, and examples thereof include glycidylated polyester, glycidylated polyurethane, and glycidylated acrylic.

  Furthermore, the material which added and modified | denatured other components to these materials is also contained as a cation polymeric compound (C) of this invention. For example, an epoxy resin in which various rubber materials such as NBR, SBR, acrylic rubber, isoprene rubber, butyl rubber and the like are dispersed may be mentioned, and the characteristics such as flexibility and adhesive strength of the curable adhesive material of the present invention are enhanced. be able to. Epoxy resins formed by adding various resins such as acrylic, urethane, urea, polyester, and styrene are also included as the cationically polymerizable compound (C) of the present invention.

  As the cationically polymerizable compound in the present invention, the above epoxy resin and vinyl ether can be used in combination. Examples of vinyl ethers include n-propyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tert-butyl vinyl ether, tert-amyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether, 2-chloroethyl vinyl ether, ethylene Glycolbutyl vinyl ether, triethylene glycol methyl vinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, butane-1,4-diol-divinyl ether, hexane-1,6-diol- Divinyl ether, benzoic acid (4-bi Loxy) butyl, cyclohexane-1,4-dimethanol-divinyl ether, di (4-vinyloxy) butyl isophthalate, di (4-vinyloxy) butyltrimethylolpropane trivinyl ether succinate, di (4-vinyloxy) butyl glutarate 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 6-hydroxyhexyl vinyl ether, cyclohexane-1,4-dimethanol-monovinyl ether, diethylene glycol monovinyl ether, 3-aminopropyl vinyl ether, 2- (N, N-diethylamino) Mention may be made of urethane vinyl ethers such as ethyl vinyl ether and polyester vinyl ether.

  Vinyl ether has high reactivity with the acid generated from the acid generator (A) and is consumed by the polymerization reaction more rapidly than the epoxy resin. Therefore, the crosslinking reaction of the epoxy resin by cationic polymerization can be substantially delayed, and the speed of the crosslinking reaction can be set to a desired one by controlling the addition amount.

  The content of the epoxy group in the epoxy resin used for the cationically polymerizable compound (C) of the present invention is not particularly limited, but is usually 0.0001 to 0.015 mol / g, preferably 0.001 to 0.01 mol / g. It is. When the content of the epoxy group is less than this range, the cross-linked portion is too small and sufficient adhesive force as the curable adhesive material of the present invention cannot be obtained. As will be described later, the curable adhesive material of the present invention generates an acid from the acid generator (A) by irradiation of energy rays, starts crosslinking of the cationic polymerizable compound (C), and then adheres to the adherend. There are also cases where they are pasted together. At that time, when the content of the epoxy group of the cationically polymerizable compound is larger than this range, curing by crosslinking proceeds too much before being bonded to the adherend, and sufficient initial adhesive force may not be expressed. is there.

  When the cationically polymerizable compound (C) is crosslinked, there is an influence of humidity. Therefore, it is desirable to consider that the humidity does not become too high when crosslinking is performed by irradiation with energy rays.

  When the energy ray is irradiated to the curable adhesive material of the present invention, an acid is generated from the acid generator (A) and the cationically polymerizable compound (C) is cross-linked to develop a high adhesive force to the adherend. Is possible. The energy ray can be irradiated either before or after the curable adhesive material is brought into contact with the adherend. Cationic polymerization starts immediately after irradiation with energy rays, but progresses more slowly than radical polymerization, so it gradually progresses after the irradiation with energy rays and the adhesive strength increases, and conversely, it gradually loses adhesive strength. I will do it. Therefore, by appropriately adjusting the polymerization rate of the cationic polymerizable compound (C), it is possible not to lose the initial adhesive force for a certain period of time after irradiation with energy rays. If the adherend is transparent, or if there is no part that is shaded with respect to the energy beam source and it can be irradiated uniformly, the energy beam is brought into contact with the adherend after contacting the curable adhesive material of the present invention. However, if the adherend is opaque or the energy rays cannot be irradiated sufficiently uniformly, the curable adhesive material of the present invention is irradiated with the energy rays in advance to form a cation. It is also possible to use the curable adhesive material of the present invention in contact with an adherend after initiating crosslinking by polymerization. When the adherend has sufficient heat resistance, it is irradiated with energy rays, and the curable adhesive material of the present invention is brought into contact with the adherend at the same time or after contact, and then cured by crosslinking. It is also possible to heat for the purpose of promoting.

  The crosslinking rate by cationic polymerization can be adjusted by adding a vinyl ether material or changing the amount of the acid generator (A) added as described above.

  In order to adjust the crosslinking rate by cationic polymerization, it is also possible to add a compound having Si—O bond such as alkoxysilanes, siloxanes, silanols, etc. to the curable adhesive material of the present invention. Since the compound having a Si-O bond reacts preferentially with the cation growth species generated during the progress of cationic polymerization, it can apparently delay the crosslinking reaction, and the adhesive material of the present invention has an initial adhesive force. The maintenance time can be extended.

  The acid generator (A) absorbs and decomposes the energy rays used to generate an acid from the acid generator (A) of the curable adhesive material of the present invention and to crosslink the cationic polymerizable compound (C). However, it is not particularly limited as long as it can generate an acid and does not damage the adherend. Examples of such energy rays are the same as those described in the description of the photoacid generator (A).

  The curable adhesive material of the present invention can be used after adding crosslinked rubber particles. By adding the crosslinked rubber particles, the stress applied to the curable adhesive material of the present invention can be relieved, and the adhesive force can be improved and the followability to deformation can be improved. Rubber polymers that can be used as crosslinked rubber particles include acrylic rubber, acrylonitrile / butadiene rubber (NBR), random styrene / butadiene rubber (SBR), butyl rubber (IIR), isoprene rubber (IR), butadiene rubber (BR), ethylene / Propylene rubber (EPM), ethylene / propylene / diene rubber (EPDM), urethane rubber, styrene / isoprene / styrene block rubber (SIS), styrene / ethylene / butadiene / styrene block rubber (SEBS), styrene / butadiene block rubber, etc. Examples include synthetic rubber-based polymers. If the average particle size of these crosslinked rubber particles is too large, a uniform curable adhesive material may not be obtained, so the average particle size is preferably 2 μm or less.

  The curable adhesive material of the present invention may contain a tackifying resin. Examples of the tackifier resin include rosin resins, modified rosin resins, terpene resins, aromatic modified terpene resins, terpene phenol resins, C5 or C10 petroleum resins, and the like. A seed | species or 2 or more types can be added to the curable adhesive material of this invention, and adhesiveness and adhesive force can be improved. In particular, when the adherend to which the present invention contacts for adhesion is a polyolefin, the tackiness and adhesiveness can be improved by adding a rosin resin, a modified rosin resin, or a petroleum resin.

  The curable adhesive material of the present invention has hollow inorganic materials such as glass balloons, alumina balloons and ceramic balloons, vinylidene chloride balloons, acrylic balloons and the like in order to improve shearing adhesive strength and the like as necessary. It can be used by adding one or more kinds of organic organic materials, organic spheres such as nylon beads, acrylic beads and silicon beads, fiber base materials such as glass, polyester, rayon, nylon and cellulose. is there.

  The curable adhesive material of the present invention is basically used for producing an adhesive obtained by bonding two substrates (also called adherends). The order in which the curable adhesive material of the present invention contacts the two substrates is not particularly limited. It may be used by directly applying to an adherend to be bonded, or may be applied on a base material, or impregnated into a base material and used as a sheet. The object to which the curable adhesive material of the present invention is applied is not particularly limited, and it can be used by applying to any object such as a planar object, a three-dimensional object, and an uneven object. In the case of coating on a base material, after coating on a peeled substrate, it is transferred to another base material using a roll or laminator, and then the peeled base material is peeled off. It can exist as an adhesive sheet consisting of only one curable adhesive material layer of the present invention. Moreover, you may apply | coat to the single side | surface or both surfaces of the base material used as a support body, and may obtain the sheet | seat of a curable adhesive material. The substrate used for applying the curable adhesive material of the present invention is not particularly limited, and any known material can be used. For example, PET film, polypropylene film, cellophane, synthetic resin film represented by polyimide, various papers, cloth, non-woven fabric, metal foil represented by aluminum foil, resin plate such as acrylic plate, metal plate, wood, foam And circuit board materials such as glass and glass epoxy substrate. Of course, the substrate itself on which the curable adhesive material of the present invention is applied in a sheet form may be an adherend. When the substrate is paper or nonwoven fabric, it can be used as a sheet impregnated with the curable adhesive material of the present invention. Furthermore, after applying the curable adhesive material of the present invention, the substrate can be deformed and bonded so as to be fixed in the deformed shape.

  As described above, the adhesive polymer (B) can be obtained by radical polymerization using energy rays. However, after processing into a sheet as described above, radical polymerization is performed by irradiating energy rays. It is also possible to obtain an adhesive polymer (B). That is, a precursor of an adhesive polymer (B) that is a monomer that is a raw material for the acrylic adhesive polymer (B), a radical polymerization initiator (D) that is sensitive to energy rays, and an acid generator (A) And the composition containing the cationic polymerizable compound (C) are applied in the form of a sheet, and then irradiated with energy rays, and the acid generator (A), the adhesive polymer (B) and the cationic polymerizable compound according to the present invention. It is also possible to obtain a sheet-like curable adhesive material composed of (C).

  The film thickness when the curable adhesive material of the present invention is used in the form of a sheet is not particularly limited, but is preferably about 10 μm to 1000 μm.

  When applying the curable adhesive material of the present invention, any known method can be used. Examples thereof include bar coater, applicator, calendar method, extrusion coating, comma coater, die coater, and lip coater. Further, the curable adhesive material of the present invention may contain a solvent, and after application, it can be formed into a sheet with the solvent removed through an appropriate dryer.

  The curable adhesive material of the present invention includes a thickener such as acrylic rubber, epichlorohydrin rubber, butyl rubber, and isoprene rubber, a thixotropic agent such as colloidal silica and polyvinylpyrrolidone, in order to improve moldability and coatability. One or more fillers such as calcium carbonate, titanium oxide and clay may be contained.

  The curable adhesive material of the present invention may be appropriately crosslinked in a state before light irradiation in order to balance the wettability and cohesive force of the adherend and the curable adhesive material. The method of initial crosslinking is not particularly limited, but generally includes functional groups in a curable adhesive material and molecular crosslinking with polyfunctional oligomers, ionic crosslinking with metal oxides or metal chelates, etc. The method used can be used.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to only the following Example at all.

Examples 1-5 and Comparative Examples 1-6
A 1000 mL separable flask is equipped with a stirrer, a cooler, a thermometer and a nitrogen gas inlet, 18 g of 2-ethylhexyl acrylate, 42 g of N-vinylpyrrolidone and 49 g of ethyl acetate are added, and the mixed solution in the flask is nitrogen gas. For 20 minutes to remove dissolved oxygen and oxygen present in the flask. Next, the mixture was heated up to reflux while stirring while flowing nitrogen gas.

  After reaching reflux, a solution obtained by diluting 0.012 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane with 1 g of ethyl acetate as a thermal polymerization initiator was added to the system. After 1 hour, a solution prepared by diluting 0.018 g of 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane with 0.4 g of ethyl acetate was added. Furthermore, after 2 hours, 3 hours and 4 hours after the start of the polymerization, 0.024 g, 0.045 g and 0.18 g of di (3,5,5-trimethylcyclohexanoyl) peroxide were respectively 0%. A solution diluted with 5 g of ethyl acetate was added.

  7.5 hours after the first polymerization initiator was charged, the reaction was stopped, and an acrylic copolymer having a weight average molecular weight of about 520,000 was obtained as an adhesive polymer (B). Further, the flask was cooled to room temperature, and 18 g of an epoxy resin (manufactured by Yuka Shell Epoxy, trade name: Epicoat 828) as the cationic polymerizable compound (C) and 0.30 g of an acid generator as shown in Table 1 were used. And, if necessary, 0.15 g of anthracene was added as a sensitizer for cationic polymerization and stirred, and then a uniform curable adhesive material was obtained.

  The curable adhesive material is coated on a corona-treated surface of a 100 μm-thick PET film having a corona treatment on one side so that the coating thickness after drying is 200 μm, and then dried at 100 ° C. for 2 minutes. Dried. In this way, a sheet-like curable adhesive material supported by a polyethylene terephthalate film was obtained. The initial adhesive strength and adhesive strength of the curable adhesive materials were evaluated by the following methods.

Initial adhesive strength: In accordance with JIS Z-0237 “Testing method for adhesive tape and adhesive sheet”, the above-mentioned sheet-like adhesive material having a width of 20 mm is pressure-bonded to a hard PVC plate, and after 50 minutes, 50 mm / min is peeled off. The 180-degree angle peel strength was measured at a speed to obtain the initial adhesive strength (N / cm).

Adhesive strength: The surface of the adhesive composition of the sheet-like adhesive material was irradiated with light containing ultraviolet rays having a wavelength of 250 to 400 nm for 60 seconds at a light irradiation intensity of 38 mW / cm ² using an ultrahigh pressure mercury lamp. Next, in accordance with JIS Z-0237, a 20 mm wide light-adhesive adhesive sheet was pressed onto a SUS plate after 10 seconds of light irradiation and allowed to cure at room temperature for 36 hours to produce an adhesive test piece. did. Thereafter, the adhesion test piece was taken out in an atmosphere of 23 ° C.-65% RH, and the 180-degree angle peel strength was measured at a peel rate of 50 mm / min to obtain an adhesive force (N / cm).

  The results are shown in Table 1. From Table 1, it can be seen that the examples of the present invention have sufficient initial adhesive strength, and the adhesive strength is very high compared to the comparative examples. Further, the comparative example has only an adhesive strength of an adhesive level without using a sensitizer, while the examples showed high adhesive strength without using a sensitizer.

Examples 6-10 and Comparative Examples 7-12
35 g of 2-ethylhexyl acrylate, 15 g of vinyl pyrrolidone, 25 g of Epicoat 828 (manufactured by Yuka Shell Epoxy), 0.027 g of Irgacure 819 (manufactured by Ciba) as the photo radical polymerization initiator, and the acid generator shown in Table 2 0.25 g was mixed while purging with nitrogen to obtain a uniform composition.

The composition obtained above is coated on the corona-treated surface of a PET film having a thickness of 100 μm and subjected to a corona treatment on one side so as to have a thickness of 200 μm. Then, it was sandwiched between the films to obtain a sheet-like curable adhesive material. Light from a high-pressure mercury lamp was irradiated from above the transparent PET film of the adhesive material through a filter that blocks light having a wavelength of 370 nm or less, and energy of 1800 mJ / cm ² was applied. The initial adhesive strength of the obtained curable adhesive material was measured by the same method as in the above-described examples. The results are shown in Table 2.

  The same method as in the above-described example except that the transparent PET film subjected to the peeling treatment in the sheet-like curable adhesive material exhibiting initial adhesive strength was removed and the light irradiation time was set to 90 seconds. Then, the adhesive force was measured. The results are shown in Table 2.

  Similar to the results of Table 1, the results of Table 2 show that the examples of the present invention have sufficient initial adhesive strength, and the adhesive strength is very high compared to the comparative examples. Further, the comparative example has only an adhesive strength of an adhesive level without using a sensitizer, while the examples showed high adhesive strength without using a sensitizer.

The curable adhesive material of the present invention has a good initial adhesive strength, and can obtain high heat resistance, durability, and adhesive strength after crosslinking and curing with energy rays. Therefore, it can be used as a material excellent in workability that achieves both temporary fixability and adhesive strength when bonding various materials. In addition, since the curable adhesive material of the present invention uses the acid generator (A), cationic polymerization proceeds rapidly to the desired degree of polymerization by irradiation with energy rays, so that high workability and adhesion are achieved. Have power. In addition, even when irradiated with a small amount of energy rays, a very strong acid is efficiently generated. Therefore, workability can be improved by shortening the irradiation time of energy rays, and deterioration of the substrate due to energy ray irradiation can be reduced. Is possible. The curable adhesive material of the present invention can be used for various adhesive applications.

Claims (6)

A curable adhesive material comprising an acid generator (A) represented by the following general formula (1), an adhesive polymer (B) or a precursor thereof, and a cationically polymerizable compound (C).
General formula (1)

(However, R ₀₁ , R ₀₂ , R ₀₄ and R ₀₅ are each independently a hydrogen atom, alkyl group, aryl group, alkenyl group, acyl group, alkoxyl group, aryloxy group, acyloxy group, alkoxycarbonyloxy group, Represents a halogen atom or —SR ₃₁ .
R ₀₃ represents —SR ₃₁ .
R ₃₁ represents an alkyl group or an aryl group.
R ₁₁ and R ₁₂ each independently represents a hydrogen atom, an alkyl group, an aryl group, an alkoxyl group or an alkenyl group.
R ₂₁ and R ₂₂ each independently represents an alkyl group, an aryl group or an alkenyl group. However, R ₀₁ , R ₀₂ , R ₀₃ , R ₀₄ , R ₀₅ , R ₁₂ , R ₂₂ , R ₂₁ and R ₁₁ may be combined to form a ring.
X ⁻ represents an arbitrary anion. ) It is curable pressure-sensitive adhesive material according to claim 1, wherein the borate is denoted by the following general formula (2) ^- anion X in the general formula (1).
General formula (2)

(Where Y is a fluorine or chlorine atom,
Z is a phenyl group substituted with two or more groups selected from a fluorine atom, a cyano group, a nitro group, and a trifluoromethyl group,
m represents an integer of 0 to 3, n represents an integer of 1 to 4, and m + n = 4. ) The curable adhesive material according to claim 1 or 2, wherein the adhesive polymer (B) is a polymer obtained by radical polymerization of the precursor by irradiation with energy rays. A curable adhesive sheet formed by forming a layer containing the curable adhesive material according to any one of claims 1 to 3 on a substrate. A method for adhering a base material comprising irradiating an energy ray on the curable adhesive material according to any one of claims 1 to 3 on the base material and curing the material. An adhesive bonded by the bonding method according to claim 5 .