JP2000044923A - Curable adhesive composition and curable adhesive sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable adhesive composition which exerts a high peel adhesion strength after curing, is stored at an ordinary temperature and has a high shelf stability and a curable adhesive sheet. SOLUTION: A curable adhesive composition contains an adhesive polymer, a photo-cationic polymerizable compound, a compound containing at least one phenol group and a triazine ring or imino group in the molecule and a photo- cationic polymerization initiator, wherein the adhesive polymer is mixed in a proportion of 40 to 90 pts.wt. against 100 pts.wt. the total of the adhesive polymer and the photo-cationic polymerizable compound, and the compound containing at least one phenol group and a triazine ring or imino group in the molecule and the photo-cationic polymerization initiator are mixed at proportions of 0.1 to 10 pts.wt. and 0.01 to 10 pts.wt., respectively, against 100 pts.wt. the total of the adhesive polymer and the photo-cationic polymerizable compound. Furthermore, a curable adhesive sheet comprises these.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable adhesive composition and a curable adhesive sheet which normally exhibit tackiness, that is, pressure-sensitive adhesiveness, and which are cured by irradiating light. Specifically, it shows high peel adhesion after curing,
The present invention also relates to a curable adhesive composition and a curable adhesive sheet having excellent storage stability.

[0002]

2. Description of the Related Art In recent years, various adhesives have been proposed to compensate for the disadvantages of adhesives and pressure-sensitive adhesives. In other words, the adhesive can be easily applied in the same manner as the pressure-sensitive adhesive due to the pressure-sensitive adhesive property at the time of bonding, and is cured by some method after the bonding, and exhibits the same adhesive strength as the adhesive. is there.

JP-A-63-193980 discloses that a composition comprising an acrylic monomer, a photo-radical polymerization initiator and a thermosetting epoxy resin is irradiated with light to polymerize the acrylic monomer. An acrylic pressure-sensitive adhesive obtained by forming an acrylic polymer is disclosed. Here, when used, the acrylic polymer exerts pressure-sensitive adhesiveness, so that it can be applied to an adherend in the same manner as an adhesive. By heating after joining, the thermosetting epoxy resin is cured by heating, and the adhesive strength is increased.

Japanese Patent Publication No. 5-506465 discloses a (meth) acrylate monomer, an epoxy monomer,
An adhesive comprising a photocationic polymerization initiator and a photoradical polymerization initiator is disclosed. Here, by irradiating the adhesive to light, formation of an adhesive acrylic polymer and curing by polymerization of an epoxy monomer progress. In use, since the formed acrylic polymer shows tackiness, it can be easily applied to an adherend in the same manner as a pressure-sensitive adhesive, and curing is progressing by photocationic polymerization of an epoxy monomer. Therefore, it is said that sufficient adhesive strength can be obtained.

Further, JP-A-7-138550 discloses an adhesive comprising a liquid epoxy, crosslinked rubber particles and a latent curing agent. With this adhesive, it can be easily applied to an adherend in the same manner as a conventional adhesive because it has adhesiveness at the time of sticking due to crosslinked rubber particles, and can be cured by heat, light or moisture after sticking. The adhesive strength can be increased by curing by the activation method. It is stated that various curing methods can be adopted depending on the type of the latent curing agent.

JP-A-9-279103 discloses a curable adhesive sheet containing a tacky polymer using an acrylic polymer, a resin having an epoxy group, and a cationic photopolymerization initiator. ing. Here, the pressure-sensitive adhesive property of the adhesive polymer allows the adhesive to be easily attached to an adherend, and achieves high adhesive strength due to the progress of a curing reaction after light irradiation.
Therefore, the simple workability of the adhesive tape and the high adhesive strength of the adhesive are provided.

[0007]

The conventional pressure-sensitive adhesive can be easily applied to the adherend in the same manner as the pressure-sensitive adhesive, and has a curing component in addition to the pressure-sensitive adhesive. Although it can give a strong adhesive cured product as in the case of the agent, various adherence methods have been employed to increase the adhesive strength, and therefore, there have been various restrictions on the adherend.

For example, in the adhesive disclosed in Japanese Patent Publication No. 2-5791, a method for curing an adhesive component is as follows.
Since anaerobic curing is used, there is a disadvantage that the adhesive does not cure sufficiently when used for an adherend such as a breathable cloth or foam.

In the adhesive disclosed in Japanese Patent Application Laid-Open No. 63-193980, since the curing is performed by thermal curing of an epoxy resin, a material having low heat resistance, for example, a vinyl chloride resin, polyethylene or polystyrene. It cannot be used for bonding of electronic materials such as plastics and ICs. Further, since the curing is started by heating, it is necessary to store the adhesive at a low temperature, and there is also a problem that handling during storage and transportation is complicated.

[0010] The adhesive disclosed in Japanese Patent Publication No. 5-506465 is cured by light, so that the adherend to be used for bonding must have a light transmitting property. Did not. In addition, since it contains an acrylic monomer as a compounding component, there is a fear that volatile components at the time of production may cause environmental pollution and adverse effects on the human body.

Further, in the adhesive disclosed in Japanese Patent Application Laid-Open No. Hei 7-138550, an initial adhesiveness and a curing property are obtained by using a liquid state epoxy resin at room temperature, a solid thermoplastic resin at room temperature and crosslinked rubber particles. However, since the liquid epoxy resin is used as a main component, only a temporary adhesive strength can be obtained. For this reason, if the adhered surface is rough or curved, poor adhesion such as peeling or lifting of the end may occur. There is also a problem that the cured product after curing has a high elastic modulus and a low peel strength.

On the other hand, the curable adhesive sheet described in Japanese Patent Application Laid-Open No. 9-279103 has a sufficient adhesive strength before curing as described above, and has a sufficient adhesive strength by being irradiated with light to be cured. Strength develops. However, even with this curable adhesive sheet, the peel strength of the cured sheet may not be sufficient depending on the application. That is, IC card bonding in the electronic field, F
When used in applications such as bonding a reinforcing plate to a PC (flexible printed circuit board), the peel strength was sometimes insufficient. Also, parts and members to be soldered,
Alternatively, when this curable adhesive sheet is used in the production of electric / electronic members that generate heat, the cured product after curing may not have sufficient heat resistance.

An object of the present invention is to provide a photo-curing material which exhibits high pressure-sensitive adhesiveness at room temperature, can be easily attached to an adherend, and cures by irradiation with light, and exhibits sufficient adhesive strength. Curable pressure-sensitive adhesive composition having improved peeling adhesive strength after curing, and can be stored at room temperature, and excellent in storage stability in a pressure-sensitive adhesive and a light-curable pressure-sensitive adhesive sheet. And a curable adhesive sheet.

[0014]

The curable adhesive composition according to the first aspect of the present invention comprises: A: a tacky polymer;
B: a photo-cationic polymerizable compound; C: a compound containing one or more of a phenol group and one or both of a triazine ring and an imino group in a molecule; and D: a photo-cationic polymerization initiator. In a total of 100 parts by weight of the polymer and the cationic photopolymerizable compound, the adhesive polymer is 40 to
90 parts by weight, based on 100 parts by weight of the total of the adhesive polymer and the cationic photopolymerizable compound, one or more phenol groups in the molecule and one or both of a triazine ring and an imino group. The compound containing 0.1
10 to 10 parts by weight, the cationic photopolymerization initiator is 0.01 to
It is characterized by being blended at a ratio of 10 parts by weight.

The curable adhesive composition according to the second aspect of the present invention comprises: A: a tacky polymer; B: a cationic photopolymerizable compound; and C: a molecule containing a nitrogen atom, a sulfur atom or a phosphorus atom. At least one compound C-1 selected from the group consisting of an ester of an acid, an alkylnitro compound, a sulfine and a phosphine, which contains at least one of the following:
A photo-cationic polymerization initiator, wherein the adhesive polymer and the photo-cationic polymerizable compound are mixed in an amount of 40 to 90 parts by weight based on a total of 100 parts by weight of the adhesive polymer and the photo-cationic compound. The compound C-1 is 0.1 to 30 parts by weight and the photocationic polymerization initiator is 0.1 to 30 parts by weight based on 100 parts by weight of the polymerizable compound in total.
It is characterized by being blended in a ratio of from 01 to 10 parts by weight.

The curable adhesive composition according to the third aspect of the present invention comprises: A: a tacky polymer; B: a cationic photopolymerizable compound; and C: a polymer represented by the following structural formula (1). Oxyalkylene alkyl ether carboxylic acid or polyoxyalkylene alkyl ether carboxylate,

[0017]

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(In the structural formula (1), n is an integer of 1 to 30, R 1 and R 2 are each a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, and M is hydrogen or an alkali metal or alkaline earth. D: a photo-cationic polymerization initiator, and the adhesive polymer and the photo-cationic polymerizable compound are combined in an amount of 40 to 90 parts by weight based on a total of 100 parts by weight of the adhesive polymer. The polyoxyalkylene alkyl ether carboxylic acid or polyoxyalkylene alkyl ether carboxylate is 0.01 to 30 parts by weight, and the cationic photopolymerization initiator is 0.01 to It is characterized by being blended at a ratio of 10 parts by weight.

The curable adhesive composition according to the fourth aspect of the present invention comprises: A: a tacky polymer; C: a cationic photopolymerizable compound containing a urethane-modified epoxy resin; and D: cationic photopolymerization initiation. Agent, the adhesive polymer and the cationic photopolymerizable compound in a total of 100 parts by weight of the adhesive polymer is blended in a ratio of 40 to 90 parts by weight,
The urethane-modified epoxy resin is blended at a ratio of 0.5 to 100% by weight in the photo-cationic polymerizable compound, and the photo-cationic polymerization initiator is used for the total of 100 parts by weight of the adhesive polymer and the photo-cationic polymerizable compound. It is characterized by being blended in a ratio of 0.01 to 10 parts by weight.

The curable adhesive composition according to the fifth aspect of the present invention comprises: A: a tacky polymer, B: a cationic photopolymerizable compound, C: a urethane acrylate oligomer, and D: cationic photopolymerization. And an initiator, wherein the adhesive polymer is mixed in a ratio of 40 to 90 parts by weight in a total of 100 parts by weight of the adhesive polymer and the cationic photopolymerizable compound. It is characterized in that the urethane acrylate oligomer is compounded in an amount of 0.1 to 200 parts by weight and the cationic photopolymerization initiator is added in a ratio of 0.01 to 10 parts by weight based on parts by weight.

The curable adhesive composition according to the sixth aspect of the present invention comprises: A: a tacky polymer, B: a cationic photopolymerizable compound, C: a terpene phenol resin, and D: cationic photopolymerization. Including an initiator, the adhesive polymer is blended in a ratio of 40 to 90 parts by weight in a total of 100 parts by weight of the adhesive polymer and the cationic photopolymerizable compound,
10 in total of adhesive polymer and cationic photopolymerizable compound
The terpene phenol resin is 0.01 to 0 parts by weight.
It is characterized in that 60 parts by weight and the cationic photopolymerization initiator are blended in a ratio of 0.01 to 10 parts by weight.

The curable adhesive composition according to the invention according to claim 7 is characterized in that: A: an adhesive polymer comprising a (meth) acrylate copolymer containing phosphoric acid (meth) acrylate as a copolymer component; And B: a cationic photopolymerizable compound;
D: a cationic photopolymerization initiator, wherein the adhesive polymer and the cationic photopolymerizable compound are mixed in an amount of 40 to 90 parts by weight based on a total of 100 parts by weight of the adhesive polymer and the cationic photopolymerizable compound; , And 0.1 to 10 parts by weight based on 100 parts by weight of the total of the adhesive polymer and the cationic photopolymerizable compound.

An eighth aspect of the present invention is a curable pressure-sensitive adhesive sheet formed by using any one of the curable pressure-sensitive adhesive compositions according to the first to sixth aspects of the present invention. Hereinafter, details of the present invention will be described.

(A: adhesive polymer) In the present invention,
The tacky polymers have been used to provide pressure sensitive adhesion. In order to obtain pressure-sensitive adhesiveness, it is necessary that the balance between wettability to an adherend and cohesion is appropriate. Therefore, in order to obtain a cohesive force, in the inventions according to claims 1 to 6, as the adhesive polymer, a general rubber or acrylic-based adhesive which has been widely used as a main component of a pressure-sensitive adhesive has been used. Polymers, silicone-based polymers, polyurethanes, polyesters, polyethers and the like can be used. Further, the adhesive polymer may be a homopolymer or a copolymer.

In the first to sixth aspects of the present invention, it is preferable that an acrylic polymer having an alkyl acrylate having a low glass transition point as a main component can exhibit appropriate pressure-sensitive adhesiveness by itself. It is preferably used.

Preferred acrylic polymers include, for example, homopolymers or copolymers of alkyl (meth) acrylate monomers having an alkyl group having 2 to 14 carbon atoms, and more preferably the above alkyl ( A copolymer of a (meth) acrylate monomer and another vinyl monomer copolymerizable with the alkyl (meth) acrylate monomer can be exemplified.

The above alkyl (meth) acrylate monomers include ethyl acrylate and n-butyl (meth)
Examples thereof include acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, and isomyristyl acrylate.

The vinyl monomer is not particularly limited as long as it is a compound copolymerizable with the alkyl (meth) acrylate monomer. Examples of the vinyl monomer include (meth) acrylic esters other than the alkyl (meth) acrylate, vinyl acetate, styrene, Vinyl chloride, ethylene, propylene, 2
-Hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ε-caprolactone (meth) acrylate, 2-acryloyloxyethyl succinic acid, (meth) acrylonitrile, N-vinylpyrrolidone, isobornyl (meth) acrylate, N -Acryloyl morpholine, benzyl (meth) acrylate,
Glycidyl (meth) acrylate, N-vinylcaprolactone, N-vinylpiperidine, (meth) acrylic acid,
Maleic anhydride, crotonic acid, itaconic acid and the like can be mentioned.

(Adhesive polymer in the invention according to claim 7) In the invention according to claim 7, an alkyl (meth) acrylate as a main component is used as the adhesive polymer, and phosphoric acid (meth) acrylate is co-polymerized with the alkyl (meth) acrylate. A (meth) acrylate copolymer obtained by polymerization is used.

As the above-mentioned alkyl (meth) acrylate, various alkyl (meth) acrylates used for the above-mentioned adhesive polymer can be used. Preferably, an alkyl (meth) acrylate having a glass transition point (Tg) of the homopolymer of 20 ° C. or lower is used.
When the glass transition temperature of the homopolymer of the alkyl (meth) acrylate exceeds 20 ° C., the pressure-sensitive adhesiveness of the copolymer is reduced, and it may be difficult to perform pressure bonding at room temperature.

The phosphoric acid (meth) acrylate is not particularly limited, and examples thereof include those represented by the following structural formulas (2) to (6).

[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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In the above structural formulas (2) to (6), R 1 and R 4 are an alkylene group, an ester group or an ether group, each having 1 to 20 carbon atoms;
Or an alkyl group, an acyl group, an alkoxyl group,
It has 1 to 20 carbon atoms, preferably at least one of R2 and R3 is H.

Specific examples of the above-mentioned phosphoric acid (meth) acrylate include Kyoeisha Chemical Co., trade name: Light Ester P-1M and Light Ester P-2M.

(B: Photocationically Polymerizable Compound) In the present invention, a photocationically polymerizable compound is blended in order to cure the curable adhesive composition by irradiating light. As the photocationically polymerizable compound, various monomers, oligomers or polymers having a photocationically polymerizable functional group in a molecule, for example, a hydroxyl group, a vinyl ether group, an episulfide group, an ethyleneimine group or an epoxy group can be used. . Further, the polymer having these functional groups is not limited, and various polymers such as acrylic, urethane, polyester, polyolefin, polyether, natural rubber, block copolymer rubber, and silicone can be used. it can.

The above cationic photopolymerizable compounds may be used alone or in combination of two or more. As the photocationic polymerizable compound, a compound having an epoxy group is preferably used. Since ring-opening polymerization of an epoxy group has high reactivity and a short curing time, the bonding step can be shortened. Furthermore, since the cohesive force and elastic modulus are high, it is possible to obtain an adhesive cured product having excellent heat resistance and adhesive strength. In addition, adhesion abnormalities such as peeling and displacement can be effectively prevented.

As the compound having an epoxy group,
Epoxy resins are preferably used. Examples of the epoxy resin include bisphenol A type, bisphenol F type, phenol novolak type, cresol novolak type, glycidyl ether type, and glycidylamine type epoxy resins.

An epoxy group-containing oligomer (for example, manufactured by Yuka Shell Epoxy Co., Ltd., trade name: Epicoat 10)
01, Epicoat 1002, etc.) are also preferably used.
Further, an addition polymer of the above-mentioned epoxy group-containing monomer or oligomer may be used, and examples thereof include glycidylated polyester, glycidylated polyurethane, and glycidylated polyacrylate.

Further, other resin components and the like may be blended or added to the cationic photopolymerizable compound to improve flexibility and crack resistance, and to improve adhesion and bending strength. Examples of such a modified product include CTBN (butadiene-acrylonitrile rubber containing a terminal carboxyl group).
Modified epoxy resin; epoxy resin in which various rubbers such as acrylic rubber, NBR, SBR, butyl rubber, or isoprene rubber are dispersed; epoxy resin modified with liquid rubber as described above; acrylic, urethane, urea, polyester, styrene Epoxy resins obtained by adding various resins such as, for example, chelate-modified epoxy resins, and polyol-modified epoxy resins.

The functional equivalent of the cationic photopolymerizable compound is preferably from 150 to 5000 g-resin / mol. If the functional group equivalent is smaller than this,
The reactivity is increased, and the working time until the application to the adherend after irradiation may be restricted. If it is too large, the reaction speed becomes slow, and it may take a long time to cure. However, since the amount of the functional group is determined depending on the desired reaction rate and curing properties, it cannot be determined uniquely.

(Blending ratio of adhesive polymer and cationic photopolymerizable compound) In the present invention, the total amount of the above adhesive polymer and cationic photopolymerizable compound is 100 parts by weight.
It is necessary that the tacky polymer is blended in a ratio of 40 to 90 parts by weight. If it is less than 40 parts by weight, the initial tackiness is low, and if it exceeds 90 parts by weight, the elastic modulus of the cured adhesive is low, and the adhesive strength is low.

(A compound used in the invention according to claim 1 containing at least one phenol group and one or both of a triazine ring and an imino group in the molecule) In the invention described in claim 1, A compound containing one or more phenol groups and one or both of a triazine ring and an imino group is used. A phenol group is an aromatic group represented by -C6H5 (OH), a triazine ring is a six-membered heterocyclic ring containing three nitrogen atoms, and an imino group is a divalent group represented by -NH-. As a compound containing both a phenol group, a triazine ring and an imino group, for example, a commercially available product such as “Irganox 565” manufactured by Ciba-Geigy Corporation may be mentioned.

(Compound C in the invention described in claim 2)
-1) In the invention described in claim 2, the compound C-1
As the acid, an ester of an acid containing at least one nitrogen atom, sulfur atom or phosphorus atom in the molecule, an alkylnitro compound, sulfine, or phosphine is used. Note that R represents an alkyl group.

The acid used for the ester of an acid containing at least one nitrogen atom, sulfur atom or phosphorus atom in the molecule is not particularly limited, but includes, for example, sulfoxylic acid, dithionous acid, Sulfurous acid, thiosulfite, pyrosulfite, sulfuric acid, thiosulfate, pyrosulfuric acid, peroxomonosulfuric acid, dithionic acid, polythionic acid, peroxodisulfuric acid, hypophosphorous acid, phosphorous acid, pyrophosphorous acid, hypophosphoric acid,
Phosphoric acid, pyrophosphoric acid, triphosphoric acid, polymetaphosphoric acid, trimetaphosphoric acid, tetrametaphosphoric acid, peroxomonophosphoric acid, peroxodiphosphoric acid, nitric acid, nitrous acid, hyponitrite and the like can be mentioned.

The ester of the above acid is generally H
n Sm Op, Hn Nm Op or Hn Pm Op (n, m
And p are natural numbers), or may be an organic substance having the structure of these acids in the molecule.

The ester can be obtained by reacting the acid with a hydroxyl group-containing organic substance such as an alcohol. Further, if necessary, a part or all of the acidic group (—OH) of the acid may be replaced with H, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an alicyclic group as long as it has a structure similar to an ester. The structure in which the acid group of these acids is replaced with an aliphatic hydrocarbon group may be a structure in which sulfin R (O) S (O) R, phosphine is used as described above. (R2 PH, RPH
2 or PR3), alkyl nitro compound (RNO2)
And the like.

In the second aspect of the present invention, more preferably, phosphate or phosphine is used as the compound C-1. Phosphoric acid esters are those obtained by esterifying phosphoric acid, phosphorous acid or phosphinic acid, and more preferably phosphoric acid triester, phosphoric acid diester, phosphoric acid monoester, phosphorous acid diester, phosphorous acid monoester. Esters and phosphonic acid esters are used. Modified forms of these various esters can also be suitably used.

The above phosphoric ester, phosphoric diester,
The structures of phosphoric acid monoester, phosphite diester, phosphite monoester, phosphonic acid ester, and phosphine are represented by the following structural formulas (7) to (19).

[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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In the above structural formulas (7) to (19) of the phosphoric ester and phosphine, R 1 to R 4 are
H or an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group or an alicyclic hydrocarbon group, such as an alkyl group and a phenyl group.

If necessary, an arbitrary substituent may be introduced into the above-mentioned aliphatic hydrocarbon group, aromatic hydrocarbon group or alicyclic hydrocarbon group. In this case, the number of carbon atoms of R1 to R4 and the substituent to be introduced may be the same or different.

More preferably, there is at least one acidic group in the phosphate ester molecule, and more preferably, an acidic group in which —OH is directly bonded to the phosphorus atom. Such preferred phosphate esters include, for example, HO (O) P (OC2 H5) (OC
H3). Examples of the phosphate represented by this structure include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri-2-ethylhexyl phosphate, tributoxyethyl phosphate, triphenyl phosphate,
Examples include trigresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, and tri-2-ethylhexyl diphosphate. Further, examples of the phosphoric acid ester having an acidic group include methyl acid phosphate, butyl acid phosphate, dibutyl phosphate, monobutyl phosphate, 2-ethylhexyl acid phosphate, bis-2-ethylhexyl phosphate, isodecyl acid phosphate, and monoisodecyl phosphate. Is mentioned.

(Polyoxyalkylene alkyl ether carboxylic acid or polyoxyalkylene alkyl ether carboxylate used in the invention of claim 3) In the invention of claim 3, the polyoxyalkylene alkyl ether carboxylic acid or polyoxyalkylene alkyl ether carboxylate is used. Alkylene alkyl ether carboxylate is used.

These structures are represented by the above-mentioned structural formula (1), that is, R1O (R2O) nCH2COOM. Here, n is an integer of 1 to 30. When n exceeds 30, the compatibility with other components in the curable adhesive composition according to the second aspect of the present invention decreases, and it becomes difficult to obtain a uniform composition. R1 is a monovalent aliphatic hydrocarbon group having 1 to 30 carbon atoms. Also, if necessary,
Any substituent may be introduced into these substituents. Further, the group represented by R1 may be linear or branched, but when the number of carbon atoms exceeds 30, the compatibility with other components becomes poor and the uniform Obtaining the composition can be difficult.

R 2 is an arbitrary group having 2 to 30 carbon atoms.
It is a valent aliphatic hydrocarbon group, and may have any substituent introduced as necessary. In addition, the above R
2 may be linear or branched. When the carbon number of R2 exceeds 30, the compatibility with other components is reduced, and it may be difficult to prepare a uniform curable adhesive composition.

M may be any of H, an alkali metal and an alkaline earth metal. As a more specific example of the polyoxyalkylene alkyl ether carboxylate, the product represented by the above structural formula, manufactured by Kao Corporation, product number: MX-RLM45 (R1 or R2 is C12 and C1
4, the average value of n = 4.5, M = H), MX-RL
M45 NV (R1 or R2 is a mixture of C12 and C14,
average value of n = 4.5, M = Na), MX-RLM100
(R1 or R2 is a mixture of C12 and C14, average value of n = 10, M = H), MX-RLM100 NV (R1 or R2 is a mixture of C12 and C14, average value of n = 10, M
= Na) and the like.

(Urethane-modified epoxy resin used in the invention according to claim 4) In the invention according to claim 4, a urethane-modified epoxy resin is used, and the urethane-modified epoxy resin is contained in the epoxy resin skeleton. It refers to a resin into which a urethane bond has been introduced. The method for producing the urethane-modified epoxy resin is not particularly limited, and a hydroxyl group of a compound having both an epoxy group and a hydroxyl group in a molecule is reacted with an isocyanate group of a urethane prepolymer to form a urethane bond in the epoxy resin. Examples of the method include introduction.

The urethane prepolymer is OCN-U-
A polymer obtained by reacting a polyisocyanate compound represented by a general formula such as NCO with a polyhydroxy compound represented by a general formula such as HO-R-OH. Here, U and R are each a hydrocarbon chain,
Alternatively, it is a polyether chain, a polyester chain, or the like, but is not necessarily limited to these.

For example, examples of the polyisocyanate compound include compounds having one or more isocyanate groups such as toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and methylene diphenyl diisocyanate.

Examples of the polyhydroxy compound include compounds having two or more hydroxyl groups such as polyether polyol, polyester polyol, castor oil derivative, polytetramethylene glycol, and lactone polyol.

The urethane-modified epoxy resin can be obtained by reacting the urethane prepolymer obtained as described above with a hydroxyl group of a compound having both an epoxy group and a hydroxyl group in the molecule.

For example, a linear urethane-modified epoxy resin is obtained by reacting a hydroxyl group such as glycidol or a resol having an epoxy group with a urethane prepolymer; a branch-type urethane-modified epoxy resin is a bisphenol-type epoxy resin. A resin obtained by reacting a hydroxyl group of a hydroxyacrylate with a urethane prepolymer as an acrylic urethane-modified epoxy resin.

Specific examples of the urethane-modified epoxy resin as described above include, for example, Asahi Denka Co., Ltd., product number: EP
U-6, EPU-15, EPU-16A, EPU-16
B, EPU-17T-6, EPU-4, EPU-75
X, EPU-86, EPU-73, EPU-78, EP
U-11 and the like.

(Urethane acrylate oligomer used in the invention of claim 5) In the invention of claim 5, a urethane acrylate oligomer is used as the photopolymerizable oligomer. More specifically, such urethane acrylate oligomers include, for example, those having the following trade names.

Product name: Art Resin UN, manufactured by Negami Kogyo Co., Ltd.
-1000 PEP, UN-9000 PEP, UN-92
00A, UN-1255, UN-2500, UN-52
00, UN-2111A, UN-3320HA, UN-
3320HC, UN-1101T, UN-1102, U
N-1200TP, UN-6060PTM, SH-38
0G, SH-500, SH-9832 Toagosei Co., Ltd., trade name: Aronix M-1100, Aronix M-1200, Shin Nakamura Chemical Co., trade name: NK ester U-108-
A, NK ester U-4HA, manufactured by Osaka Organic Co., Ltd., trade names: Biscoat 812, Biscoat 813, Biscoat 823, manufactured by Sanyo Kokusaku Pulp Co., Ltd., trade name: USA-10, manufactured by Nippon Synthetic Chemical Company, trade names: XP-4200B, XP-
7000B, XP-2700B, XP-3000B, X
P-2000B, XP-10, manufactured by Sartomer Co., Ltd., trade name: Chemlink 9500, 950
1, 9502, 9503, 9504, 9505 UCB (Daicel UCB), trade name: E
becry1204, 205, 210, 220, 23
0, 254, 264, 265, 270, 284, 129
0 Product name: AH-600, AT-60, manufactured by Kyoeisha Chemical Co., Ltd.
0, UA-306H, AI-600, UA-101T,
UA-1011, UA-306T, UA-306I, U
F-8001, UF-8003, UF-503LN, U
F-1003LC, UF-803TN.

(Terpene phenol resin in the invention according to claim 6) In the invention according to claim 6, the terpene phenol resin is used, and the terpene phenol resin has the following structure.

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Specific examples of the terpene phenol resin include YP-9, manufactured by Yashara Chemical Company.
0, Mighty Ace G125, Mighty Ace G15
0, DLN-140, YS resin PX1205, YS resin PX1150, YS resin PX1000, YS resin PX800, YS resin TO125, YS resin TO
115, YS resin TO105, YS resin TO85,
YS Resin TR105TR, Clearon P125, Clearon P115, Clearon P105, Clearon P8
5, Clearon M115, Clearon M105, Clearon K110, Clearon K100, YS Resin Z11
5, YS resin Z100, YS polystar 2130, Y
S polystar 2115, YS polystar 2100, YS
Polystar U115, YS Polystar T145, YS Polystar T130, YS Polystar T115, YS Polystar T100, YS Polystar T80, YS Polystar T30, YS Polystar S145, Dimalon, Dimer Resin, YS Oil DA, Stalon 2130, Nanolet G1250, YS Oil D, Rubber soft # 20
0, rubber software # 300 and the like.

(Compounding Ratio of Component C) In the invention described in claim 1, the compound containing at least one phenol group and one or both of a triazine ring and an imino group in the molecule is an adhesive polymer and It is blended at a ratio of 0.1 to 10 parts by weight with respect to 100 parts by weight of the total of the cationic photopolymerizable compound. If the amount is less than 0.1 part by weight, the effect of increasing the peel strength and the effect of increasing the storage stability cannot be sufficiently obtained. If the amount exceeds 10 parts by weight, a long curing time is required and the pressure-sensitive adhesive property is impaired. Or the adhesive strength after lamination may not be sufficient. In the invention described in claim 2, the C-1 is 0.1 to 30 parts by weight based on 100 parts by weight of the total of the adhesive polymer and the cationic photopolymerizable compound.
It is blended in a ratio of parts by weight. If the amount is less than 0.1 part by weight, the effect of increasing the peel strength and the effect of increasing the storage stability cannot be sufficiently obtained. If the amount exceeds 30 parts by weight, the pressure-sensitive adhesive property is impaired, or the adhesion after lamination is performed. The strength may not be large enough.

In the invention according to claim 3, the polyoxyalkylene alkyl ether carboxylic acid or the polyoxyalkylene alkyl ether carboxylate is used in an amount of 0.01 to 100 parts by weight of the total of the adhesive polymer and the cationic photopolymerizable compound. It is blended at a ratio of up to 30 parts by weight. When the amount is less than 0.01 part by weight, the peel strength and the storage stability cannot be sufficiently increased, and when the amount exceeds 30 parts by weight, the tackiness decreases, or the strength of the cured adhesive product after curing decreases. Sometimes.

In the invention according to claim 4, the component C is a cationic photopolymerizable compound containing a urethane-modified epoxy resin, and is a main component together with the adhesive polymer. Among them, the urethane-modified epoxy resin is particularly blended at a ratio of 0.5 to 100% by weight in the cationic photopolymerizable compound. If the amount is less than 0.5% by weight, sufficient curing to increase the flexibility after curing cannot be obtained, the adhesive strength after curing will not be sufficient, the peel strength will decrease, and the storage stability will decrease. descend.

In the invention described in claim 5, the urethane acrylate oligomer is used in an amount of 0.1 to 0.1 parts by weight based on 100 parts by weight of the total of the adhesive polymer and the cationic photopolymerizable compound.
It is blended at a ratio of 200 parts by weight. If the amount is less than 0.1 part by weight, the effect of blending the urethane acrylate oligomer, that is, the effect of improving flexibility after curing, the effect of increasing peel adhesion, and the effect of increasing storage stability cannot be sufficiently obtained, and 200 If the amount exceeds the above range, the curing reaction may be insufficient.

In the invention according to claim 6, the terpene phenol resin is blended in an amount of 0.01 to 60 parts by weight based on 100 parts by weight of the total of the adhesive polymer and the cationic photopolymerizable compound. If the amount is less than 0.01 parts by weight, the effect of improving the flexibility after curing and the effect of improving the adhesion to the adherend cannot be sufficiently obtained, the peel strength does not increase, and the storage stability does not increase. When the amount exceeds 60 parts by weight, the adhesive properties are reduced, and the strength of the cured adhesive product after curing is reduced.

(D: Photocationic Polymerization Initiator) In the present invention, the photocationic polymerization initiator is activated by irradiation with light to generate a photocationic polymerization initiator, The polymerization can be initiated with energy.

As the light, microwaves, infrared rays, visible light, ultraviolet rays, X-rays, γ-rays and the like can be used, but generally, the handling is easy and simple, and relatively high energy can be obtained. Ultraviolet rays that can be used are preferably used. More preferably, ultraviolet light having a wavelength of 200 to 400 nm is used.

The ultraviolet rays can be irradiated using an appropriate light source such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and a chemical lamp. The cationic photopolymerization initiator may be either an ionic photoacid generating type or a nonionic photoacid generating type.

The ionic photoacid generating types include onium salts such as aromatic diazonium salts, aromatic halonium salts, and aromatic sulfonium salts, and organic metal salts such as iron-allene complexes, titanocene complexes, and arylsilanol-aluminum complexes. Complexes and the like can be mentioned. More specifically, for example, Optomer SP-150 (manufactured by Asahi Denka), Optmer SP-170 (manufactured by Asahi Denka), UVE
-1014 (manufactured by General Electronics), CD-
Commercially available initiators such as 1012 (manufactured by Sartomer) can be used.

As the nonionic photoacid generating type, nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, sulfonic acid derivative, phenolsulfonic acid ester, diazonaphthoquinone, N-hydroxyimidesulfonate and the like can be used. it can.

The above-mentioned cationic photopolymerization initiators may be used alone or in combination of two or more, and are cured in a plurality of stages using a plurality of photocationic polymerization initiators having different effective active wavelengths. Is also good.

Further, another photopolymerization initiator, for example, a photoradical polymerization initiator or a photoanion polymerization initiator may be used in combination. In this case, the wavelength of light for activating the photo-radical polymerization initiator or the photo-anionic polymerization initiator does not necessarily need to be equal to the wavelength for activating the photo-cationic polymerization initiator.

The cationic photopolymerization initiator is used in the curable adhesive composition according to the present invention in an amount of 0.0001 to 1 with respect to 1 mol of the functional group of the cationic photopolymerizable compound.
It is preferable to mix in a range of 0 mol%. 0.00
When the amount is less than 01 mol%, the cationic photopolymerization does not sufficiently proceed, and the curing rate may be slow.
If the amount is more than mol%, the curing by light irradiation proceeds too quickly, and the working time until sticking to the adherend may be restricted.

(Curable Adhesive Sheet) The curable adhesive sheet according to the eighth aspect of the present invention is obtained by forming the above-mentioned curable adhesive composition according to the present invention into a sheet. Here, the method for forming the curable pressure-sensitive adhesive composition into a sheet is not particularly limited, and it can be performed by processing the curable pressure-sensitive adhesive composition thin by any method.
Preferably, the curable adhesive composition may be applied on a sheet-like support having a surface subjected to a release treatment by various molding methods such as a roll coating method, a gravure coating method, and an extrusion method. When the curable adhesive composition is solid or liquid and has a high viscosity and cannot be applied, the curable adhesive composition is diluted with an appropriate solvent and melted by heating. The method may be applied by lowering the viscosity by using the above method, and then drying.

The curable pressure-sensitive adhesive sheet obtained as described above exhibits pressure-sensitive adhesive properties at room temperature. Therefore, it is preferable to cover and cure the surface of the curable adhesive sheet with a release sheet in order to enhance the handleability.

The support or release sheet used when applying the curable pressure-sensitive adhesive composition to form a sheet includes:
There is no particular limitation, for example, polyethylene terephthalate, polyethylene naphthalate, polyethylene, polypropylene, polycarbonate, nylon, polyarylate, polysulfone, polyether sulfone, polyether ether ketone, polyphenylene sulfide, polystyrene, polyacryl, polyvinyl acetate, triacetyl Examples include cellulose, diacetyl cellulose, cellophane, and the like. The thickness of the support or the release sheet is preferably 1 μm or more, more preferably 10 μm or more.
If the thickness of the release sheet is too thin, the strength is reduced, and the release sheet is easily broken at the time of use.

The thickness of the curable adhesive sheet itself is 1 to 20.
It is preferably about 00 μm, more preferably 1 μm.
0 to 1000 μm. If the thickness of the pressure-sensitive adhesive sheet is less than 1 μm, the adhesiveness may be affected by unevenness of the surface of the adherend, and if the thickness is more than 2000 μm, a long time is required for curing. The pressure-sensitive adhesiveness of the curable pressure-sensitive adhesive sheet at room temperature is preferably 5 or more, more preferably 10 at ball tack at room temperature (25 ° C.).
That is all.

(Other Components) In the curable adhesive composition according to the present invention, in addition to the above-mentioned essential components, known tackifying resins and extenders may be used as long as the object of the present invention is not impaired. You may mix.

For example, in order to increase the tackiness of the curable adhesive composition, a rosin resin, a modified rosin resin, C5
Or a C9 petroleum resin, a tackifier resin such as a cumarone resin may be added, and in the inventions according to claims 1 to 4 and 6, a terpene resin or a terpene phenol resin may be used as the tackifier resin. .

(Method of Using Curable Adhesive Sheet) The method of using the curable adhesive sheet according to the present invention is not particularly limited. For example, when the adhesive is used for bonding a light-transmissive adherend, the curable adhesive sheet and the adherend may be joined and then irradiated with light to be cured.
However, in general, the adherend is often not light transmissive. In such a case, after adhering the curable adhesive sheet to one adherend, the curable adhesive sheet is irradiated with light immediately before joining the other adherend, and then the other is adhered. A curable adhesive sheet is attached to the adherend. In this case, it is preferable to bond the curable adhesive sheet to the other adherend as soon as possible after light irradiation, and more preferably to bond the sheet within 10 minutes.

After bonding, curing by a cationic polymerization reaction proceeds at room temperature, and sufficient adhesive strength and heat resistance of the cured adhesive product are developed in a short time. In this case, the curing reaction may be accelerated by applying heat or heat and humidity, whereby the curing may be performed in a shorter time.

The light used is not particularly limited, and ultraviolet light having a wavelength of 400 nm or less emitted from a mercury lamp, a chemical lamp, a xenon lamp, or the like can be suitably used.

(Function) In the curable pressure-sensitive adhesive composition according to the first to seventh aspects of the present invention, the pressure-sensitive adhesive polymer exhibits pressure-sensitive adhesive properties at room temperature, so that a large pressure is not required. The adherends can be attached to each other. After the light irradiation, the photocationic polymerization initiator is activated to generate cations, whereby the cationically polymerizable compound undergoes cationic polymerization, whereby the curing reaction proceeds. Therefore,
Finally, the adherends are firmly bonded via the curable adhesive.

In addition, according to the first aspect of the present invention, one or more phenol groups in the molecule react with a compound containing one or both of a triazine ring and an imino group, and the flexibility after curing is increased. It is enhanced and the polarity is also enhanced. Therefore, the peel strength is effectively increased.

Further, the compound containing at least one of a phenol group and one or both of a triazine ring and an imino group in the above molecule delays the curing reaction until the adherends are adhered to each other after light irradiation. The working time in the joining operation can be made sufficiently long. Further, at the time of bonding, the workability of the bonding operation can be improved without a decrease in the adhesive strength. In addition, the compound containing one or more of a phenol group and one or both of a triazine ring and an imino group in the molecule maintains wettability with respect to an adherend, so that the adhesive strength after curing is increased. Therefore, the adhesive strength after curing is effectively increased.

Further, the compound containing one or more phenol groups and one or both of a triazine ring and an imino group in the molecule is confined in the matrix of the cured product together with the curing of the adhesive composition. It does not bleed to the adhesive interface and does not lower the peeling force. Therefore, the heat resistance is also improved. In addition, a cation generated by heat or the like during storage is captured by a compound containing at least one phenol group and one or both of a triazine ring and an imino group in the molecule, so that the curing reaction proceeds during storage. And storage stability can be enhanced. In addition, in the invention described in claim 2, a part of the ester, alkylnitro compound, sulfine, or phosphine reacts with the cationically polymerizable compound, so that the flexibility after curing is increased and the polarity is also increased. Therefore, the peel strength is effectively increased.

The curing reaction is delayed by the above-mentioned specific ester, alkylnitro compound, sulfin or phosphine until the adherends are bonded to each other after light irradiation, so that the pot life in the bonding operation is sufficiently long. can do. Further, at the time of bonding, the workability of the bonding operation can be improved without a decrease in the adhesive strength. In addition, the specific ester, alkylnitro compound, sulfine, or phosphine also maintains wettability with respect to an adherend, thereby increasing the adhesive strength after curing. Therefore, the adhesive strength after curing is effectively increased. In addition, after light irradiation, a reaction between the phosphate ester and the cationically polymerizable compound causes microphase separation, thereby enhancing stress relaxation. Accordingly, the adhesive strength is also increased thereby.

Further, the above specific ester, alkylnitro compound, sulfine or phosphine is confined in the matrix of the cured product upon curing,
It does not bleed to the adhesive interface and does not lower the peeling force. Therefore, the heat resistance is also improved. In addition, during storage, cations generated by heat or the like are captured by the above-mentioned specific ester, alkylnitro compound, sulfine or phosphine, so that the progress of the curing reaction during storage can be suppressed, and storage stability is improved. Can be In the invention described in claim 3, since a part of the polyoxyalkylene alkyl ether carboxylic acid or the polyoxyalkylene alkyl ether carboxylate reacts with the cationically polymerizable compound, flexibility and polarity of the cured product after curing are increased. Is enhanced. Therefore, the peel strength is effectively increased.

Further, the above-described polyoxyalkylene alkyl ether carboxylic acid or polyoxyalkylene alkyl ether carboxylate has a —COOH group,
The OM group increases the polarity of the curable adhesive. Therefore, the adhesion to an adherend having a polarity such as a metal can be enhanced, and particularly, the adhesion strength to a metal can be significantly increased. In addition, the appropriately blended polyoxyalkylene alkyl ether carboxylic acid or polyoxyalkylene alkyl ether carboxylate is confined in the matrix of the cured product during curing, and therefore does not easily bleed to the adhesive interface. Therefore, from that point, the peeling force is hardly reduced.

In addition, since the polyoxyalkylene alkyl ether carboxylic acid and the polyoxyalkylene alkyl ether carboxylate capture cations generated by heat or the like during storage, it is possible to suppress the progress of the curing reaction during storage. And storage stability can be enhanced.

According to the fourth aspect of the present invention, since the urethane-modified epoxy resin is blended in the above specific ratio,
It is possible to prevent the curing of the cationically polymerizable compound from progressing too much and the peel strength from decreasing. In addition, the urethane-modified epoxy resin itself has excellent flexibility after curing.
Therefore, the flexibility of the curable adhesive composition after curing is enhanced, and the peel strength is effectively increased by the improvement of the polarity by urethane bonding.

Further, cations generated during storage are captured by urethane bonds, so that the progress of the curing reaction can be prevented, thereby improving the storage stability.
In addition, by blending the urethane-modified epoxy resin, the SP value of the curable adhesive composition is reduced, and the adhesion to the adherend made of plastic is increased. The adhesive strength to the body can be effectively increased.

In the invention described in claim 5, since the urethane-modified acrylate oligomer is blended in the above-described specific ratio, the polarity is increased, and thereby the adhesion to the adherend is enhanced. In addition, an increase in the gel fraction after curing can be suppressed, thereby increasing the peel strength. Accordingly, the adhesive strength and the peel strength after curing can be effectively increased, and in particular, the adhesive strength to a high-polarity plastic such as acryl or polyvinyl chloride can be effectively increased.

In the invention according to claim 6, a part of the terpene phenol resin reacts with the cationically polymerizable compound to increase the flexibility and polarity of the cationically polymerizable compound after curing. Therefore, the peel strength is effectively increased.

In addition, since the OH group of the terpene phenol resin enhances the polarity, the adhesion to a highly polar adherend, for example, a metal, can be enhanced, and especially the adhesion strength to a metal can be increased.

Further, the terpene phenol resin is
As it is cured, it is confined in the matrix of the cured product, so that it is difficult for the adhesive interface to bleed. Therefore, the peeling force is not reduced.

Further, the terpene phenol resin is
Since cations generated during storage are captured, storage stability is also improved. In the invention according to claim 7, a part of the phosphoric acid (meth) acrylate as a copolymer component in the adhesive polymer reacts with the cationically polymerizable compound to increase flexibility and polarity after curing. Therefore, the peel strength is effectively increased.

Further, since the curing reaction is delayed by the phosphorus atom of the phosphoric acid (meth) acrylate, the workability in the laminating operation can be improved. In addition, the wettability to the adherend is increased, and the adhesive strength after curing is increased.

Further, a (meth) acrylate copolymer obtained by copolymerizing the above-mentioned phosphoric acid (meth) acrylate is as follows:
Since cations generated during storage are captured, storage stability is also improved.

Further, by reacting the polymer obtained by copolymerizing the phosphoric acid (meth) acrylate with the cationic photopolymerizable compound, the crosslink density is increased, and the heat resistance of the cured product is effectively increased.

[0119]

The present invention will be described in more detail by way of the following non-limiting examples. In the following examples, the part indicating the blending ratio means part by weight unless otherwise specified.

Example 1 A: 50 parts of polybutyl acrylate (Mw = 800,000) B: Bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., trade name: Epicoat # 828, epoxy equivalent 184 to 194) ) 30 parts, and BEO60E (manufactured by Nippon Rika Co., Ltd., 20 parts of bisphenol ethylene oxide 6 mol adduct diglycidyl ether), C: a compound containing both a phenol group, a triazine ring and an imino group in the molecule (manufactured by Ciba Geigy, "Irganox 565")

[0121]

Embedded image 0.2 parts

Components A, B, and C, 100 parts of methyl ethyl ketone, and an aromatic sulfonium salt-based cationic photopolymerization initiator (trade name: ADEKA OPTOMER SP1 manufactured by Asahi Denka Co., Ltd.)
70) 5 parts together, and at a room temperature of 23 ° C., using a “Homodisper L type” manufactured by Tokushu Kika Kogyo Co., Ltd.
Stir at 0 rpm until uniform. The adhesive composition solution thus obtained was separated from a 50 μm thick release PET.
The film was applied by a roll coater so as to have a final thickness of 50 μm, and dried to obtain a photocurable adhesive sheet. On the surface of the photocurable pressure-sensitive adhesive sheet, a polyethylene-laminated high-quality paper (hereinafter, release paper) whose surface was release-treated with silicone to protect the adhesive surface was laminated.

(Example 2) A: 50 parts of polybutyl acrylate B: 300 parts of a finely dispersed epoxy resin of crosslinked acrylic rubber particles (volume average particle size: 80 nm, manufactured by Nippon Shokubai Co., Ltd., trade name: BPA), and Examples 20 parts of BEO60E used in Example 1 C: 0.2 parts of "Irganox 565" used in Example 1 Photocurable in the same manner as Example 1 except that components A to C were as described above. An adhesive sheet was obtained.

(Example 3) A: 50 parts of polybutyl acrylate B: 50 parts of bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., trade name: Epicoat # 828) C: methyl acid phosphate (manufactured by Daihachi Chemical Co., Ltd.) , Trade name: AP-1) 5 parts The structural formula of methyl acid phosphate is HOP
(O) (OCH3) 2 or (HO) 2 P (O) O
CH3.

The above components were mixed together with 100 parts of methyl ethyl ketone and 5 parts of an aromatic sulfonium salt-based photocationic polymerization initiator (trade name: Adeka Optomer SP170, manufactured by Asahi Denka Co., Ltd.), and the specialized The mixture was stirred with a homodisper L type manufactured by Kogyo Co., Ltd. at a stirring speed of 3000 rpm until the mixture became uniform. The adhesive composition solution thus obtained was applied to a 50 μm-thick release PET film so as to have a final thickness of 50 μm, and dried to obtain a cured adhesive sheet. On the surface of the curable adhesive sheet,
Release paper was laminated to protect the adhesive surface.

(Example 4) A: polybutyl acrylate 50 parts B: crosslinked acrylic rubber particle finely dispersed epoxy resin (volume average particle size: 80 nm, manufactured by Nippon Shokubai Co., Ltd., trade name: BPA) 5
0 parts C: methyl acid phosphate (manufactured by Daihachi Chemical Co., Ltd., trade name: AP-1) 5 parts The same procedure as in Example 3 was carried out except that components A to C were as described above. An adhesive sheet was obtained.

Example 5 A: 50 parts of polybutyl acrylate B: Cross-linked acrylic rubber particle finely dispersed epoxy resin (volume average particle size: 80 nm, manufactured by Nippon Shokubai Co., Ltd., trade name: BPA) 5
0 parts C: butyl nitrate ester (C3 H7) -O-NO2 5 parts A photocurable adhesive sheet was obtained in the same manner as in Example 3 except that the components A to C were as described above. .

(Example 6) A: 50 parts of polybutyl acrylate B: Crosslinked acrylic rubber particle finely dispersed epoxy resin (volume average particle size: 80 nm, manufactured by Nippon Shokubai Co., Ltd., trade name: BPA) 5
0 parts C: 5 parts of sulfuric acid diethyl ester (C2 H5 O) 2 SO2 A curable adhesive sheet was obtained in the same manner as in Example 3 except that the components A to C were as described above.

Comparative Examples 1 and 2 Curable adhesive sheets were obtained in the same manner as in Examples 1 and 2, except that Component C was not used.

(Comparative Example 3) 95 parts of a butyl acrylate monomer and 0.5 part of 2-hydroxyethyl acrylate were polymerized in a separable flask by boiling point polymerization (as a thermal radical polymerization initiator, 100 parts of a butyl acrylate monomer was used). On the other hand, 0.3 parts of Perhexa TMM,
0.5 part of Parloyl 355 was used). The molecular weight of the obtained polymer was Mw = 700,000. To 100 parts by weight of the polymer obtained as described above, 0.5 part of an isocyanate-based cross-linking agent (trade name: Coronate L45, manufactured by Nippon Polyurethane Co., Ltd.) was added, and the mixture was stirred until it became uniform. 50 μm thick release PE
A pressure-sensitive adhesive sheet was prepared by applying the film to a T film so as to have a final thickness of 50 μm and drying the film. Release paper was laminated on the adhesive surface.

(Comparative Examples 4 and 5) Curable adhesive sheets were obtained in the same manner as in Examples 3 and 4, except that Component C was not used.

(Comparative Example 6) Of the formulations of Example 1, the components B and C of Example 1 were blended together with 5 parts of a cationic photopolymerization initiator (Adeka Optomer SP170, manufactured by Asahi Denka Co., Ltd.), and The mixture was stirred at a room temperature of ℃ and manufactured by Tokushu Kika Kogyo Co., Ltd., trade name: Homodisper L type at a stirring speed of 3000 rpm until uniform, and an adhesive composition was obtained. I got a sheet.

(Comparative Example 7) 99.5 parts of a butyl acrylate monomer and 0.2% of 2-hydroxyethyl acrylate.
5 parts using a thermal radical polymerization initiator, by boiling point polymerization,
Polymerized in a separable flask. The molecular weight of the obtained polymer was Mw = 700,000.

To 100 parts by weight of the polymer obtained as described above, 0.5 part of an isocyanate-based crosslinking agent (trade name: Coronate L45, manufactured by Nippon Polyurethane Co., Ltd.) was added.
After stirring until uniform, 50μ with a roll coater
m thickness of release PET film, final thickness is 50μm
Then, an adhesive sheet was prepared by applying such a coating liquid and drying. Release paper was laminated on the adhesive surface.

(Example 8) A: 50 parts of polybutyl acrylate B: 50 parts of bisphenol A type epoxy resin (trade name: Epicoat # 828, manufactured by Yuka Shell Epoxy) C: polyoxyethylene alkyl ether carboxylate (Kao) Co., Ltd., trade name: MX-RLM100) 5 parts A curable adhesive sheet was obtained in the same manner as in Example 3, except that components A to C were as described above.

Example 9 A: 50 parts of polybutyl acrylate B: finely dispersed epoxy resin of crosslinked acrylic rubber particles (volume average particle size: 80 nm, trade name: BPA, manufactured by Nippon Shokubai Co., Ltd.) 5
0 parts C: polyoxyethylene alkyl ether carboxylate (manufactured by Kao Corporation, trade name: MX-RLM100) 5 parts Curing type in the same manner as in Example 3 except that components A to C were as described above. An adhesive sheet was obtained.

(Comparative Examples 8 and 9) An adhesive composition and a curable adhesive sheet were obtained in the same manner as in Examples 7 and 8, except that Component C was not used.

(Comparative Example 10) In the composition of Example 7, the components B and C of Example 5 were replaced with a cationic photopolymerization initiator (trade name: ADEKA OPTMER SP170, manufactured by Asahi Denka Co., Ltd.).
5 parts at a time and at a room temperature of 23 ° C., manufactured by Tokushu Kika Kogyo Co., Ltd., trade name: Homodisper L type, stirring speed 300
The mixture was stirred at 0 rpm until uniform, and an adhesive was obtained. Then, an adhesive sheet was obtained in the same manner as in Example 1.

Example 9 A: 50 parts of polybutyl acrylate B: 50 parts of a bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., trade name: Epicoat # 828) C: urethane-modified epoxy resin (manufactured by Asahi Denka Co., Ltd.) ,Product name:
EPU-17T-6) 10 parts A photocurable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3, except that components A to C were as described above.

(Example 10) A: polybutyl acrylate 50 parts B: crosslinked acrylic rubber particle finely dispersed epoxy resin (volume average particle size: 80 nm, manufactured by Nippon Shokubai Co., Ltd., trade name: BPA) 5
0 parts C: urethane-modified epoxy resin (trade name, manufactured by Asahi Denka Co., Ltd.)
EPU-17T-6) 10 parts A curable adhesive sheet was obtained in the same manner as in Example 3, except that components A to C were as described above.

(Comparative Examples 11 and 12) Except that Component C was not used, an adhesive composition and a curable adhesive sheet were obtained in the same manner as in Examples 9 and 10, respectively.

(Comparative Example 13) Of the composition of Example 9, the components B and C of Example 9 and a cationic photopolymerization initiator (Adeka Optomer SP170, manufactured by Asahi Denka Co., Ltd.)
And 5 parts at a time, at a room temperature of 23 ° C., and a stirring speed of 300 using a homodisper L type manufactured by Tokushu Kika Kogyo Co., Ltd.
After stirring at 0 rpm until the mixture became uniform, an adhesive was obtained, and then an adhesive sheet was obtained in the same manner as in Example 3.

(Example 11) A: 50 parts of polybutyl acrylate B: 50 parts of bisphenol A type epoxy resin (trade name: Epicoat # 828, manufactured by Yuka Shell Epoxy Co., Ltd.) C: Urethane acrylate (phenyl glycidyl ether acrylate and hexa 4 parts of urethane prepolymer of methylene diisocyanate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: AH-600) Curable adhesive in the same manner as in Example 3 except that components A to C were as described above. A wearing sheet was obtained.

(Example 12) A: 50 parts of polybutyl acrylate B: Crosslinked acrylic rubber particle finely dispersed epoxy resin (volume average particle size: 80 nm, manufactured by Nippon Shokubai Co., Ltd., trade name: BPA) 5
0 parts C: urethane acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name:
AH-600) 4 parts A curable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3, except that components A to C were as described above.

(Comparative Examples 14 and 15) Curable adhesive sheets were obtained in the same manner as in Examples 11 and 12, except that Component C was not used.

(Comparative Example 16) Among the formulations of Example 10,
Components B and C of Example 10 and a cationic photopolymerization initiator (trade name: ADEKA OPTOMER SP17 manufactured by Asahi Denka Co., Ltd.)
0) 5 parts at a time and at a room temperature of 23 ° C., using a homodisper L type, manufactured by Tokushu Kika Kogyo Co., Ltd., with stirring speed of 3
After stirring at 000 rpm until uniformity was obtained, an adhesive sheet was obtained in the same manner as in Example 3.

(Example 13) A: 50 parts of polybutyl acrylate B: 50 parts of bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., trade name: Epicoat # 828) C: terpene phenol resin (manufactured by Yasuhara Chemical Co., Ltd.)
(Product name: DLN-140) 10 parts A curable adhesive sheet was obtained in the same manner as in Example 3, except that components A to C were as described above.

(Example 14) A: 50 parts of polybutyl acrylate B: Cross-linked acrylic rubber particle finely dispersed epoxy resin (volume average particle size: 80 nm, manufactured by Nippon Shokubai Co., Ltd., trade name: BPA) 5
0 parts C: Terpene phenol resin (manufactured by Yashara Chemical Co., Ltd.
(Product name: DLN-140) 10 parts A curable adhesive sheet was obtained in the same manner as in Example 3, except that components A to C were as described above.

(Comparative Examples 17 and 18) Curable adhesive sheets were obtained in the same manner as in Examples 13 and 14, except that Component C was not used.

(Comparative Example 19) Among the formulations of Example 13,
Components B and C of Example 13 and a cationic photopolymerization initiator (trade name: ADEKA OPTOMER SP17 manufactured by Asahi Denka Co., Ltd.)
0) 5 parts at a time and at a room temperature of 23 ° C., using a homodisper L type, manufactured by Tokushu Kika Kogyo Co., Ltd., with stirring speed of 3
After stirring at 000 rpm until uniformity was obtained, an adhesive sheet was obtained in the same manner as in Example 3.

(Example 15) [Polymer copolymerized with phosphoric acid acrylate] A chain transfer agent was added to 3 parts of phosphoric acid acrylate (trade name: Light Ester P-1M manufactured by Kyoeisha Chemical Co., Ltd.) and 97 parts of butyl acrylate. Then, copolymerization was carried out in a separable flask using a thermal radical polymerization initiator in 200 parts of ethyl acetate to obtain a polymer obtained by copolymerizing phosphoric acid acrylate.
The weight average molecular weight Mw of the obtained polymer was 700,000.

A: 50 parts of a polymer obtained by copolymerizing phosphoric acid acrylate B: 50 parts of a bisphenol A type epoxy resin (trade name: Epicoat # 828, manufactured by Yuka Shell Epoxy Co.) Components A and B were as described above. A curable pressure-sensitive adhesive sheet was obtained in the same manner as in Example 3, except that Component C was not used.

(Example 16) A: 50 parts of polymer obtained by copolymerizing phosphoric acid acrylate B: Cross-linked acrylic rubber particle finely dispersed epoxy resin (volume average particle diameter: 80 nm, manufactured by Nippon Shokubai Co., trade name: BPA) 5
0 parts A curable adhesive sheet was obtained in the same manner as in Example 1 except that components A and B were as described above, and that component C was not used.

(Comparative Examples 20 and 21) The same procedures as in Example 1 were carried out except that component A was polybutyl acrylate.
In the same manner as in Nos. 5 and 16, a curable adhesive sheet was obtained.

(Evaluation of Examples and Comparative Examples) Regarding the curable pressure-sensitive adhesive sheet obtained as described above, (1) initial adhesive force (180 ° peeling force), and (2) adhesive force after curing (180 ° adhesive force).
(3) Peeling force after curing (T-type peeling force), (4)
Heat resistance and (5) storage stability were each evaluated in the following manner.

(1) Initial adhesive strength (180 ° peeling force): While peeling the release paper of the curable adhesive sheet, a 50 μm polyimide film was pressed at a temperature of 100 ° C. and a pressure of 3 kg /
The laminate was thermally laminated at a speed of 2 m / min.

The laminate was cut to a width of 10 mm, the release PET film laminated on the surface of the curable adhesive sheet in the laminate was peeled off, and ultraviolet light having a wavelength of 365 nm was irradiated with 3 J / cm 2 using an ultra-high pressure mercury lamp. Irradiation was performed.

Next, a stainless plate (SUS30) having a width of 25 mm, a length of 100 mm, and a thickness of 2 mm was prepared.
4, hereinafter referred to as adherend A) by heat lamination at 100 ° C. to produce a sample. The sample was allowed to stand at room temperature for 30 minutes, and the peeling speed was 50 mm /
And peeled 180 °, and the peel strength was measured.

(2) Adhesive force after curing (180 ° peeling force)
After the sample prepared in (1) was further left at room temperature for one day, the 180 ° peel strength was measured in the same manner as in (1). (3) Adhesive force after curing (T-type peeling force) (1) In the method of preparing a sample in the initial adhesive force measurement, the polyimide film and SUS304 were each 100 μm thick.
m, and a sample was prepared in the same manner as in JISZ0237 except that the PET film was changed to a corona-treated PET film and left at room temperature for one day.
The T-type peeling force was measured according to the above.

(4) Heat resistance: A sample prepared in the same manner as the sample whose initial adhesive strength was measured was cured at 23 ° C. and 65% relative humidity for one day, and then cured at 100 ° C. for 30 days.
After drying for 1 minute, the film was exposed to a gear oven at 300 ° C. for 1 hour. Thereafter, the presence or absence of peeling of the bonded end face was visually observed.

(5) Storage stability: Each sheet was placed in a dark place, 40
It was stored for 1 month at the condition of ° C. Thereafter, the initial adhesive force (180 ° peeling force), the adhesive force after curing (180 ° peeling force), the adhesive force after curing (T-type peeling force) and the heat resistance were evaluated in the same manner as described above. The results are shown in Tables 1 to 10 below.

Examples 9 to 12 and Comparative Examples 11 to 1
In the evaluation of 6, as the adherend, not only a stainless steel plate having a width of 25 mm × length 100 mm × thickness 2 mm, but also a soft vinyl chloride resin plate, an acrylic resin plate, a polycarbonate plate, a polystyrene plate, and a width of 50 mm × Length 1
Using a glass epoxy plate of 00 mm x thickness of 300 μm,
Respectively, (1) initial adhesive strength (180 ° peeling force),
(2) Adhesive strength after curing (180 ° peeling force) and (3) Adhesive strength after curing (T-type peeling force) were measured (see Tables 5 and 6).

[0163]

[Table 1]

[0164]

[Table 2]

[0165]

[Table 3]

[0166]

[Table 4]

[0167]

[Table 5]

[0168]

[Table 6]

[0169]

[Table 7]

[0170]

[Table 8]

[0171]

[Table 9]

[0172]

[Table 10]

Example 1 and Comparative Example 1, Example 2 and Comparative Example 2
When Examples 1 and 2 were compared, Examples 1 and 2 showed higher peel adhesion after curing than Comparative Examples 1 and 2. This is because in Examples 1 and 2, the C component (“Irganox 565”) suppressed the cationic polymerization reaction during light irradiation and maintained the adhesion during lamination, thus improving the peel adhesion after curing. it is conceivable that.

When Examples 1 and 2 and Comparative Examples 1 and 2 were compared, the adhesive strength before storage and the adhesive force after storage of Examples 1 and 2 did not change and showed high storage stability. On the other hand, in Comparative Examples 1 and 2, the adhesive strength after storage was low.
This is because the C component captures cations generated during storage, so that the hardening does not occur during storage in Examples 1 and 2, and the wettability to the adherend is maintained when the C component is bonded to the adherend. it is conceivable that.

When Examples 1 and 2 are compared with Comparative Example 3, Examples 1 and 2 show excellent heat resistance.
No decrease in heat resistance due to the addition of the components was observed. This is probably because the C component partially reacted with the photocationically polymerizable compound and was incorporated into the crosslinked structure.

Example 3, Comparative Example 4, and Examples 4 to 6
Comparing with Comparative Example 5, Examples 3 to 6 showed higher adhesive strength after curing than the corresponding Comparative Examples. This is because, in Examples 3 and 4, the phosphoric acid ester is used, and in Examples 5 and 6, the nitric acid ester or the sulfuric acid ester is used, respectively, to suppress the cationic polymerization reaction at the time of light irradiation and maintain the adhesion at the time of bonding. It is considered that the microphase separation occurred due to the improvement of the polarity of the photocurable adhesive composition and the reaction between the ester and the epoxy resin, and the stress relaxation property was enhanced.

In Examples 3 to 6, the adhesive strength after curing was the highest in Example 4 in which a phosphate ester having an acidic group was added. This is considered to be due to the synergistic effect of the effect of improving the polarity by the polar group and the stress relaxation by the acrylic rubber.

Examples 3 to 6 and Comparative Example 6 and Comparative Example 4
In comparison with No. 5, in Examples 3 to 6 and Comparative Example 6, there was no change in the adhesive strength after curing before and after storage, indicating high storage stability. On the other hand, in Comparative Examples 4 and 5, the adhesive strength after storage was reduced. This is because, during storage, the generated cations are captured by the ester, and therefore, in Examples 3 to 6 and Comparative Example 6, no curing occurs during storage, and wettability to the adherend when laminating to the adherend. Is considered to be maintained.

When Examples 3 to 6 and Comparative Example 7 are compared,
Examples 3 to 6 show excellent heat resistance, and no decrease in heat resistance due to the addition of the ester was observed.
This is presumably because the ester partially reacted with the cationic photopolymerizable compound and was incorporated into the crosslinked structure.

Examples 7 and 8 were compared with Comparative Examples 8 and 9,
The adhesive strength after curing was high. This is because in Examples 7 and 8,
Part of the polyoxyalkylene alkyl ether carboxylate reacts with the epoxy to increase flexibility, reduce elastic modulus, increase stress relaxation, and enhance adhesion to metal by improving polarity by the carboxyl group. It is thought that the nature was raised.

In Examples 7 and 8 and Comparative Example 10, the adhesive strength after curing did not decrease even after storage, whereas in Comparative Examples 8 and 9, the adhesive strength after curing decreased after storage. did. This is probably because the polyoxyalkylene alkyl ether carboxylate captures cations generated during storage and suppresses the progress of the curing reaction during storage. Therefore, even after storage, it is considered that high adhesion after curing is exhibited even after storage because adhesion to the adherend is maintained when it is bonded to the adherend.

Further, Examples 7 and 8 maintain the same heat resistance as Comparative Examples 8 to 10. This is probably because the polyoxyalkylene alkyl ether carboxylate reacted with the epoxy and was incorporated into the crosslinked structure.

Examples 9 and 10 showed higher adhesive strength after curing than Comparative Examples 11 and 12. Examples 9 and 10 show that in Examples 9 and 10, the stress relaxation was enhanced by the flexibility improvement by the urethane-modified epoxy, the adhesion to the adherend was enhanced by the improvement in the polarity, and the cation was added to the urethane bonding portion. This is considered to be due to the fact that the curing reaction progresses excessively during the light irradiation to reduce the adhesion due to being trapped, and the adhesion to the adherend is increased.

Although not shown in the table, Examples 9 and 1
0, initial adhesive strength after storage, adhesive strength after curing (180 °
(Peeling force and T-type peeling force) did not change from before storage.
On the other hand, in Comparative Examples 11 and 12, a decrease in adhesive strength of 10 to 20% was observed. This is considered to be because in Examples 9 and 10, cations were trapped in the urethane binding portion, thereby suppressing the progress of the curing reaction during storage.

In Examples 11 and 12, Comparative Examples 14 and 15
As compared with, the adhesive strength after curing was higher. Examples 11 and 12 show that in Examples 11 and 12, the stress relaxation was enhanced by the flexibility improvement by the urethane-modified epoxy, the adhesion to the adherend was enhanced by the improvement in the polarity, and further, the cation was added to the urethane bonding portion. Is trapped,
This is considered to be due to the fact that the curing reaction progressed excessively during light irradiation and the decrease in adhesion was suppressed, and the adhesion to the adherend was enhanced.

Although not shown in the table, Example 11,
In No. 12, the initial adhesive strength after storage and the adhesive strength after curing (180
° peel force and T-type peel force) did not change from before storage. On the other hand, in Comparative Examples 14 and 15, 10 to 20%
A decrease in the adhesive strength was observed. This is similar to Example 11, 1
In No. 2, it is considered that the cation is trapped in the urethane binding portion, thereby suppressing the progress of the curing reaction during storage.

In Examples 13 and 15, Comparative Examples 17 and 18
After the curing, the adhesive strength was increased. This is the first embodiment
In Nos. 3 and 15, a part of the terpene phenol resin reacts with the epoxy to increase the flexibility, reduce the elastic modulus and increase the stress relaxation property, and increase the polarity by the hydroxyl group to the metal, It is considered that the adhesion was improved.

In Examples 13 and 14, Comparative Example 1 was used.
6, 19 and Comparative Example 7, the same heat resistance was maintained. This is probably because the terpene phenol resin is taken into the crosslinked structure by reacting with the epoxy.

When Examples 15 and 16 were compared with Comparative Examples 20 and 21, in Examples 15 and 16, the adhesive strength after curing was effectively increased. This is due to the phosphoric acid acrylate
The cation reaction at the time of light irradiation is suppressed, the adhesion at the time of lamination is maintained, the polarity of the photocurable adhesive and the microphase separation occur due to the reaction between the phosphoric acid acrylate and the epoxy resin, It is considered that the stress relaxation was enhanced.

In particular, Example 16 in which phosphoric acid acrylate having an acidic group and acrylic rubber were added exhibited the highest peel strength. This is considered to be due to a synergistic effect of the effect of improving the polarity by the polar group and the stress relaxation by the acrylic rubber.

Further, Examples 15 and 16 and Comparative Examples 20 and 2
In comparison with No. 1, in Examples 15 and 16, the adhesive strength after curing after storage was not changed from that before storage, indicating high storage stability. On the other hand, in Comparative Examples 20 and 21, the adhesive strength after curing after storage was reduced. This is because in Examples 15 and 16, the (meth) acrylate copolymer containing phosphoric acid acrylate as a copolymer component captures cations generated during storage, so that the curing reaction during storage is suppressed and It is considered that the wettability to the adherend at the time of laminating the body is maintained.

Further, Examples 15 and 16 showed superior heat resistance as compared with Comparative Example 7, and therefore, no decrease in heat resistance due to copolymerization of phosphoric acid acrylate was observed. This is presumably because the phosphoric acid acrylate moiety partially reacted with the cationic photopolymerizable compound and was incorporated into the crosslinked structure.

[0193]

According to the curable pressure-sensitive adhesive composition according to the first to seventh aspects of the present invention, since the pressure-sensitive adhesive polymer exhibits pressure-sensitive adhesive properties, the bonding operation can be performed without requiring a large pressure. obtain. In addition, the irradiation with light causes the cationic polymerization reaction to proceed and cure. Therefore, the adherends can be finally firmly bonded to each other.

In the first aspect of the present invention, the specific phenol group-containing compound is contained in the specific ratio. In the second aspect of the present invention, the specific compound C-1 is contained in the specific compound C-1. Claim 3 is contained in a specific ratio.
In the invention described in the above, since the polyoxyalkylene alkyl ether carboxylic acid or the polyoxyalkylene alkyl ether carboxylate is blended in the specific ratio, the urethane-modified epoxy resin according to the invention described in claim 4, In the invention according to claim 5, since the urethane acrylate oligomer is blended at the specific ratio, and in the invention according to claim 6, the terpene phenol resin is mixed at a specific ratio. Because it is blended in a specific ratio,
Some of these react with the cationically polymerizable compound to increase the flexibility and the polarity of the cured adhesive product.
Accordingly, the peel strength of the cured adhesive to the adherend can be effectively increased.

In addition, since these added components capture cations generated by heat or the like during storage, the progress of the curing reaction during storage can be suppressed, and thus storage stability can be enhanced.

Furthermore, the above-mentioned components added in each of the first to sixth aspects of the present invention are confined in the matrix of the cured product together with the curing, so that they do not easily bleed to the adhesive interface. Therefore, it is difficult for the bleeding of these components to lower the peeling force.

In the invention according to claim 7, since the (meth) acrylate copolymer containing phosphoric acid (meth) acrylate as a copolymer component is used as the adhesive polymer, the phosphoric acid (meth) Part of the acrylate reacts with the cationically polymerizable compound, thereby increasing the flexibility and polarity of the cured adhesive product, thereby effectively increasing the peel strength to the adherend.

The (meth) acrylate copolymer obtained by copolymerizing phosphoric acid (meth) acrylate captures cations generated during storage, so that the progress of the curing reaction during storage can be suppressed. And therefore storage stability can be increased.

The crosslink density is increased by the reaction between the (meth) acrylate-based copolymer obtained by copolymerizing the above-mentioned phosphoric acid (meth) acrylate and the cationic photopolymerizable compound. Is effectively increased.

The curable adhesive sheet according to the eighth aspect of the present invention is constituted by using the curable adhesive composition according to the first to seventh aspects of the present invention. It can be easily attached to the adherend, and the curing reaction can be advanced by irradiation of light, so that the adherends can be firmly joined to each other. Moreover, since the curable adhesive sheet has excellent storage stability, even when stored for a long time,
Its performance can be exhibited stably. In addition, since the sheet is formed in a sheet shape, a complicated operation for applying the adhesive can be omitted, and the adhesive can be easily applied to a portion where the application of the adhesive is difficult or a very small adhesive portion.

Claims (8)

[Claims] 1. A: an adhesive polymer; B: a cationic photopolymerizable compound; C: a compound containing at least one phenol group and one or both of a triazine ring and an imino group in a molecule; A photo-cationic polymerization initiator, wherein the adhesive polymer and the photo-cationic polymerizable compound are mixed in a ratio of 40 to 90 parts by weight based on a total of 100 parts by weight of the adhesive polymer and the photo-cationic polymerizable compound. 0.1 to 10 parts by weight of a compound containing one or more of a phenol group and one or both of a triazine ring and an imino group in the molecule for the total of 100 parts by weight of the polymerizable compound, Curable adhesive composition characterized in that is blended in a proportion of 0.01 to 10 parts by weight. 2. A: an adhesive polymer; B: a cationic photopolymerizable compound; C: an ester of an acid containing at least one nitrogen atom, sulfur atom or phosphorus atom in the molecule, an alkylnitro compound, sulfine and And at least one compound C-1 selected from the group consisting of phosphines; and D: a photocationic polymerization initiator. In a total of 100 parts by weight of the adhesive polymer and the photocationic polymerizable compound, the adhesive polymer is 40 The compound C-1 is contained in an amount of 0.1 to 30 parts by weight based on 100 parts by weight of the total of the adhesive polymer and the cationic photopolymerizable compound.
A curable adhesive composition, wherein the photo cationic polymerization initiator is added in an amount of 0.01 to 10 parts by weight. 3. A: an adhesive polymer; B: a cationic photopolymerizable compound; C: a polyoxyalkylene alkyl ether carboxylic acid or a polyoxyalkylene alkyl ether carboxylate represented by the following structural formula (1): Formula 1 (In the structural formula (1), n is an integer of 1 to 30, R1,
R2 is a monovalent or divalent hydrocarbon group having 1 to 30 carbon atoms, M is hydrogen or an alkali metal or an alkaline earth metal) D: a cationic photopolymerization initiator; The adhesive polymer is blended in a ratio of 40 to 90 parts by weight based on a total of 100 parts by weight of the cationic photopolymerizable compound, and the total of the adhesive polymer and the cationic photopolymerizable compound is 10 parts by weight.
With respect to 0 parts by weight, 0.01 to 30 parts by weight of the polyoxyalkylene alkyl ether carboxylic acid or the polyoxyalkylene alkyl ether carboxylate, and 0.01 to 10 parts by weight of the cationic photopolymerization initiator. A curable adhesive composition comprising: 4. An adhesive polymer, C: a photo-cationic polymerizable compound containing a urethane-modified epoxy resin, and D: a photo-cationic polymerization initiator, wherein the total of the adhesive polymer and the photo-cationic polymerizable compound is 10.
The adhesive polymer is blended at a ratio of 40 to 90 parts by weight in 0 part by weight, and the urethane-modified epoxy resin is blended at a ratio of 0.5 to 100% by weight in the cationic photopolymerizable compound. A curable adhesive composition comprising a cationic polymerization initiator in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the total of the adhesive polymer and the cationic photopolymerizable compound. 5. A composition comprising: A: an adhesive polymer; B: a cationic photopolymerizable compound; C: a urethane acrylate oligomer; and D: a cationic photopolymerization initiator, and the total of the adhesive polymer and the cationic photopolymerizable compound. 10
0 parts by weight of the adhesive polymer is blended in a ratio of 40 to 90 parts by weight, and the total of the adhesive polymer and the cationic photopolymerizable compound is 10
The urethane acrylate oligomer is 0.1 to 200 parts by weight, and the cationic photopolymerization initiator is 0.0
A curable adhesive composition which is blended in an amount of 1 to 10 parts by weight. 6. A composition comprising: A: an adhesive polymer; B: a cationic photopolymerizable compound; C: a terpene phenolic resin; and D: an cationic photopolymerization initiator, and the total of the adhesive polymer and the cationic photopolymerizable compound. 10
0 parts by weight of the adhesive polymer is blended in a ratio of 40 to 90 parts by weight, and the total of the adhesive polymer and the cationic photopolymerizable compound is 10
The terpene phenol resin is 0.01 to 0 parts by weight.
A curable adhesive composition comprising 60 parts by weight of a cationic photopolymerization initiator in an amount of 0.01 to 10 parts by weight. 7. A: an adhesive polymer comprising a (meth) acrylate copolymer containing phosphoric acid (meth) acrylate as a copolymer component; B: a cationic photopolymerizable compound; D: a cationic photopolymerization initiator Wherein the adhesive polymer and the cationic photopolymerizable compound are blended in an amount of 40 to 90 parts by weight based on a total of 100 parts by weight of the adhesive polymer and the cationic photopolymerizable compound. 0.1 to 10 with respect to a total of 100 parts by weight of the polymerizable compound
A curable adhesive composition characterized in that it is blended in a proportion by weight. 8. A curable pressure-sensitive adhesive sheet comprising the curable pressure-sensitive adhesive composition according to claim 1.