JP2922286B2 - Thermosetting pressure-sensitive adhesive composition and thermosetting pressure-sensitive adhesive sheet - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention has an adhesive property at room temperature, and is thermally cured by heating after being attached to an adherend, and firmly adheres. The present invention relates to a thermosetting pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer that maintains a high adhesive strength even at a high temperature as described above, and also relates to such a thermosetting pressure-sensitive adhesive. The present invention relates to a thermosetting pressure-sensitive adhesive sheet having a layer.

More specifically, a resin component having a specific amount of each of an acrylic copolymer having a specific molecular weight obtained by copolymerizing a specific amount of two or more epoxy resins having different epoxy equivalent values and an epoxy group-containing monomer, and an epoxy resin. The present invention relates to a thermosetting pressure-sensitive adhesive composition containing a curing agent and a thermosetting pressure-sensitive adhesive sheet using the composition.

[Conventional technology]

Conventionally, a thermosetting pressure-sensitive adhesive composition capable of forming a pressure-sensitive adhesive layer which has tackiness at room temperature and is thermoset by heating, and a pressure-sensitive adhesive sheet having such a pressure-sensitive adhesive layer Are already known.

For example, JP-A-63-312380 discloses that an epoxy resin, preferably a bisphenol-type epoxy resin having an average molecular weight of about 1,000 or less, contains a monomer which forms a polymer having an adhesive Tg of -50 ° C or less as a main component. Contains a component that forms a polymer having a Tg of 0 ° C. or higher and a functional group such as a carboxyl group, a hydroxyl group, an epoxy group, a methylol group, an alkoxymethyl group, an amino group, an amide group, and an allyl group. A thermosetting pressure-sensitive adhesive in which a copolymer obtained by copolymerizing a reactive monomer (particularly preferably a reactive monomer having a hydroxyl group) is blended in an amount of 30 to 200 parts by weight with respect to 100 parts by weight of an epoxy resin. An agent composition is described. And Example 1 of this proposal
(D) shows 70 parts by weight of Epicoat 828, Epicoat 10013
0 parts by weight, a commercially available acrylic adhesive containing an epoxy group 100
A composition comprising parts by weight, 5 parts by weight of dicyandiamide, and an amine-based curing accelerator is disclosed.

However, the above proposal includes "a reactive monomer containing an epoxy group" in a commercially available acrylic pressure-sensitive adhesive to be used.
No disclosure is made as to the copolymerization amount of In general, the copolymerization amount of the “reactive monomer containing an epoxy group” in a commercially available acrylic pressure-sensitive adhesive is at most 5% by weight.
If the copolymerization amount of the above-mentioned “reactive monomer containing an epoxy group” is 3 as in the case of the hydroxyl group-containing reactive monomer in Example 1 (c).
Mol% [eg, glycidyl methacrylate 3 mol% (about 3.3% by weight) with respect to butyl acrylate], and when the amount is less than the copolymerization amount in the present invention, the compatibility of the adhesive composition and the temperature after heat curing. The results are quite poor in terms of adhesion, especially at high temperatures.

[Problems to be solved by the invention]

The present inventors have solved the above-mentioned problems that the conventional thermosetting pressure-sensitive adhesive composition and the thermosetting pressure-sensitive adhesive sheet had, and improved various stability as the adhesive composition. Excellent thermosetting with high adhesiveness before thermosetting and high adhesive strength after thermosetting, especially, adhesive strength at high temperature such as 100 ° C. or more (hereinafter sometimes referred to as high-temperature adhesive strength) Type pressure-sensitive adhesive composition, and further,
As a result of conducting research to obtain a thermosetting pressure-sensitive adhesive sheet,
60 parts by weight of a bisphenol A type epoxy resin having an epoxy equivalent of about 190 (liquid at ordinary temperature), 20 parts by weight of a bisphenol A type epoxy resin having an epoxy equivalent of about 480 (solid at ordinary temperature), 70% by weight of butyl acrylate and 30% by weight of glycidyl methacrylate. Copolymer (number average molecular weight about 90,000)
A thermosetting pressure-sensitive adhesive composition in which dicyandiamide is blended with a resin mixture consisting of 20% by weight has good resin compatibility,
Excellent blending stability, for example, without separation or sedimentation even when left at room temperature for one week or more,
In addition, a double-sided pressure-sensitive adhesive sheet prepared using this composition and a nonwoven fabric as a core material has excellent adhesiveness and extremely excellent adhesive strength after thermosetting, particularly at high temperatures. And conducted further research to complete the present invention.

[Means for solving the problem]

The present invention provides a resin component comprising the following components (A) to (C) (provided that the total of (A) to (C) is 100% by weight): (A) an epoxy resin having an epoxy equivalent of 150 to 300;
85% by weight, (B) an epoxy resin having an epoxy equivalent exceeding 300 5
(C) 15 to 50% by weight of an epoxy group-containing monomer, and 10 to 50% by weight of an acrylic copolymer having a number average molecular weight of 50,000 or more; And (D) an epoxy resin curing agent, which is intended to provide a thermosetting pressure-sensitive adhesive composition characterized by comprising:
To (C) [where the total of (A) to (C) is 100% by weight], (A) an epoxy resin having an epoxy equivalent of 150 to 300,
85% by weight, (B) an epoxy resin having an epoxy equivalent exceeding 300 5
(C) 15 to 50% by weight of an epoxy group-containing monomer, and 10 to 50% by weight of an acrylic copolymer having a number average molecular weight of 50,000 or more; It is another object of the present invention to provide a thermosetting pressure-sensitive adhesive sheet having a thermosetting pressure-sensitive adhesive layer containing (D) an epoxy resin curing agent.

 Hereinafter, the present invention will be described in detail.

The thermosetting pressure-sensitive adhesive composition and the pressure-sensitive adhesive layer of the thermosetting pressure-sensitive adhesive sheet of the present invention comprise, as a resin component, an epoxy resin and an acrylic copolymer comprising the above (A) and (B). (C).

The types of the epoxy resins (A) and (B) are not particularly limited, and include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisephenol AD type epoxy resin, hydrogenated bisphenol A type A bisphenol type epoxy resin such as an epoxy resin can be exemplified. In addition to these, for example, novolak-type epoxy resins such as phenol novolak-type epoxy resin and cresol novolak-type epoxy resin; for example, glycidyl alkyl ether-based epoxy resins such as polyalkylene polyol (such as neopentyl glycol) and polyglycidyl ether; , Tetraglycidyldiaminodiphenylmethane, triglycidyl-
glycidylamine-based epoxy resins such as p-aminophenol, triglycidyl-m-aminophenol, and tetraglycidyl-m-xylenediamine; for example, glycidyl phthalate, diglycidyl hexahydrophthalate,
Glycidyl ester-based epoxy resins such as diglycidyl tetrahydrophthalate: for example, vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl (3,4
-Epoxycyclohexane) carboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl)
Cycloaliphatic epoxy resins such as adipate; heterocyclic epoxy resins such as triglycidyl isocyanurate and glycidylglycidoxyalkylhydantoin; and the like; further, halides of these epoxy resins; polybases of these epoxy resins Various epoxy resins such as an epoxy group-containing resin obtained by reacting an acid or a polyester polycarboxylic acid; a polyglycidyl ester of a polyester polycarboxylic acid; a polyglycidyl ether of a polyester polyol;
Among these epoxy resins, bisphenol A type epoxy resins and novolak type epoxy resins are preferred from the viewpoint of easy availability and good adhesive properties of the obtained pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet. The use of a type epoxy resin is particularly preferred.

In the present invention, among these epoxy resins, two or more epoxy resins having different epoxy equivalent values, that is, one or more epoxy resin (A) having an epoxy equivalent of 150 to 300 and an epoxy resin having an epoxy equivalent of more than 300 (B) One or more epoxy resins are used. The use of only the epoxy resin (A) is not preferred because the resulting pressure-sensitive adhesive sheet has insufficient tackiness and the initial adhesive strength is insufficient, and the use of the epoxy resin (B) alone is not preferred. And the resulting pressure-sensitive adhesive composition may be separated and settled with time, and the adhesive strength after thermosetting tends to be insufficient. Absent.

As such an epoxy resin (A), it is preferable to use a liquid epoxy resin at normal temperature (about 20 ° C.) from the viewpoint of good compatibility with the acrylic copolymer and good blending stability. As B), from the viewpoint of the tackiness of the obtained pressure-sensitive adhesive sheet, the epoxy equivalent is 400
It is preferable to use an epoxy resin which is a solid at room temperature at a temperature of ~ 1000.

The amount of epoxy resin (A) used is 100% by weight of resin component
40 to 85% by weight, preferably 40 to 75% by weight
It is. If the amount of the epoxy resin (A) used is too small, less than the lower limit, the adhesive strength after heat curing, particularly at high temperatures, tends to be insufficient, which is not preferable. The tackiness tends to be too small, and the initial adhesive strength tends to be insufficient.

The amount of epoxy resin (B) used is 100% by weight of resin component
The amount of the acrylic copolymer (C) is preferably x (% by weight) based on the total amount of the resin components, and the use of the epoxy resin (B) is preferred. It is preferable that the amount y (% by weight) be in the range represented by the following formula.

10 ≦ y ≦ −0.2x + 30 When the amount of the epoxy resin (B) used is too small below the lower limit, the adhesiveness tends to be too small, and the initial adhesive strength tends to be insufficient. If the amount exceeds the upper limit, the compatibility with the acrylic copolymer (C) and the blending stability tend to be impaired, which is not preferable.

The acrylic copolymer (C) that can be used in the present invention is obtained by mixing the monomer (a) having an epoxy group with the total amount of the monomer components constituting the copolymer (C) (hereinafter, referred to as “a”). 15 to 5 per 100% by weight)
It is obtained by copolymerizing 0% by weight, preferably 15 to 35% by weight. If the copolymerization amount of the monomer (a) exceeds the upper limit and is too large, problems such as lack of smooth copolymerization reaction, difficulty in obtaining a homogeneous copolymer, and, in some cases, gelation may occur. However, the adhesive strength of the resulting adhesive composition or adhesive sheet after thermal curing tends to decrease rather, which is not preferable. On the other hand, if the copolymerization amount is too small, less than the lower limit, the compatibility with the epoxy resin and the compounding stability may be reduced, and the adhesive strength after thermosetting, particularly at high temperatures, may be poor. It is not preferable because it tends to be sufficient.

Examples of the monomer (a) include (meth) allylic esters of epoxy group-containing alcohols such as glycidyl methacrylate and glycidyl acrylate; and epoxy group-containing alcohols such as glycidyl allyl ether, glycidyl methacryl ether and glycidyl vinyl ether. (Meth) acrylic alcohols or vinyl ethers of alcohols; and the like. Of these, use of glycidyl methacrylate (hereinafter sometimes abbreviated as GMA) is preferred from the viewpoints of availability and good copolymerization reactivity.

The acrylic copolymer (C) used in the present invention is obtained by copolymerizing the monomer (a) with an acrylic acid or methacrylic acid monomer (b) represented by the following general formula. .

H ₂ C = CR ¹ COOR ² ...... Examples of radicals R ² in the monomer (C), methyl group, ethyl group, n- propyl group, n- butyl group, i- butyl, n- hexyl, n- octyl group, i- octyl Group, 2-ethylhexyl group, i-nonyl group, n-dodecyl group, stearyl group and the like. Specific examples thereof include, for example, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, Acrylic ester monomers such as i-butyl acrylate, t-butyl acrylate, n-hexyl acrylate, n-octyl acrylate, i-octyl acrylate, 2-ethylhexyl acrylate, i-nonyl acrylate and stearyl acrylate; for example, methyl methacrylate , Ethyl acrylate, n
-Butyl methacrylate, i-butyl methacrylate,
t-butyl methacrylate, n-hexyl methacrylate, n-octyl methacrylate, i-octyl methacrylate, 2-ethylhexyl methacrylate, i-nonyl methacrylate, n-dodecyl methacrylate, i
-Methacrylate monomers such as dodecyl methacrylate and stearyl methacrylate; and the like.

The amount of the monomer (b) used is, for example, 50 to 85% by weight, preferably 65 to 85% by weight based on 100% by weight of the total amount of the monomers.
% By weight. By appropriately selecting and using the monomer (b) in the above-mentioned usage amount range, it is possible to achieve a good balance of adhesive strength, tackiness, and the like.

Further, the acrylic copolymer (C) used in the present invention
Is a monomer having at least one functional group in addition to the radically polymerizable unsaturated group together with the monomers (a) and (b), and a monomer other than the monomer (a) Body (c)
Can be contained as a copolymerization component. Examples of such a monomer (c) include monomers having a functional group such as a carboxyl group, a hydroxyl group, an amide group or a substituted amide group, an amino group or a substituted amino group, and a mercapto group. In the present invention, one or more of these monomers can be appropriately selected and used. Specific examples of these monomers include, for example, acrylic acid, methacrylic acid, itaconic acid,
Maleic acid, maleic anhydride, fumaric acid, crotonic acid,
Carboxyl group-containing monomers such as citraconic acid (preferably acrylic acid, methacrylic acid, itaconic acid); for example, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate;
Diethylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, dipropylene glycol mono (methacrylate, polypropylene glycol mono (meth) acrylate, allyl alcohol, methallyl alcohol (preferably 2-hydroxyethyl acrylate, 2-hydroxypropyl Hydroxyl-containing monomers such as acrylate, 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate); for example, acrylamide, methacrylamide, N, N
Amide group or substituted amide group-containing monomers such as -dimethylacrylamide, N-methylacrylamide, Nn-butoxymethylacrylamide (preferably acrylamide, methacrylamide); for example, aminoethyl acrylate, N, N-dimethylamino Ethyl acrylate, N, N-diethylaminoethyl acrylate, N, N
-Dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, (preferably N, N-
Amino- or substituted amino-group-containing monomers such as dimethylaminoethyl methacrylate and N, N-diethylaminoethyl methacrylate); and mercapto-group-containing monomers such as vinyl mercaptan and allyl mercaptan. These monomers (c)
Among them, a carboxy group-containing monomer, an amide group-containing monomer and a substituted amino group-containing monomer can be suitably used.

The amount of the monomer (c) used is 100% by weight of the total amount of the monomers.
In contrast, for example, an amount of about 0 to 15% by weight can be exemplified.

Further, the acrylic copolymer (C) used in the present invention, together with the monomers (a) to (c), (a) to (c) copolymerizable with the monomers (a) to (c) A comonomer (d) other than (c) can be contained as a copolymerization component.

Such comonomer (d) includes, for example, saturated fatty acid vinyl ester monomers such as vinyl formate, vinyl acetate, vinyl propionate and vinyl versatate; for example, dibutyl malate, dibutyl fumarate, dibutyl itaconate , dioctyl malate, dioctyl fumarate, alpha such as dioctyl itaconate, straight-chain or branched alkyl esters of C ₁ -C ₈ of β- unsaturated dicarboxylic acids; for example, styrene, alpha-methyl styrene, vinyl toluene, ethyl Aromatic vinyl monomers such as vinylbenzene; vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; and the like.

The amount of the comonomer (d) to be used is generally 0 to 50% by weight, preferably about 0 to 30% by weight, based on 100% by weight of the total amount of the monomers. Since the use of the comonomer (d) can vary depending on the type of the comonomer, the amount of the comonomer cannot be uniquely determined, but the balance between the adhesive strength and the tackiness and the phase with the epoxy resin are not determined. It can be appropriately selected within a range that does not impair the solubility and the blending stability.

Number average molecular weight of the acrylic copolymer (C) as a main component of the thermosetting pressure-sensitive adhesive composition and the thermosetting pressure-sensitive adhesive sheet of the present invention (hereinafter may be abbreviated as ▲).
Is 50,000 or more, preferably 80,000 to 200,000. If the ▼ of the copolymer (C) is too small, less than the lower limit, the tackiness and initial adhesive strength tend to be insufficient, which is not preferred. In addition, since it is not easy to produce a copolymer in which ▼ exceeds 200,000, it is preferable to adjust ▼ to fall within the above range. The weight average molecular weight of the copolymer (C) (hereinafter sometimes abbreviated as ▲) is generally
100,000 or more, preferably 200,000 or more, particularly preferably 300,000 to
1 million is good. When ▼ is equal to or more than the lower limit, it is preferable because the adhesiveness and initial adhesive strength are excellent. On the other hand, when it is equal to or less than the upper limit, the production can be relatively easily performed. It is better to adjust it. Note that both ▲ ▼ and ▲ ▼ indicate gel permeation chromatography (hereinafter referred to as GP
(Abbreviated as C).

The glass transition point (hereinafter sometimes abbreviated as Tg) of the acrylic copolymer (C) is generally 100 ° C. or lower, preferably 30 ° C. or lower, more preferably 0 ° C. or lower, particularly preferably −5 ° C. or lower. It is below ° C. Temperatures below the upper limit are preferred because the resulting pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet have excellent tackiness and initial adhesion.

In the present invention, the glass transition point (Tg) of the acrylic copolymer (C) is a value measured and determined as follows.

Glass transition point: about 0.05mm thick aluminum foil,
In a cylindrical cell having an inner diameter of about 5 mm and a depth of about 5 mm, about 10 mg of a sample of an organic solvent solution of about 50% by weight of an acrylic copolymer is weighed,
A sample dried at 100 ° C. for 2 hours is used as a measurement sample. SSC-5000 type differential scanning calorimeter (Diffe
(Rental Scanning Calorimeter) at a heating rate of 10 ° C / min from -150 ° C.

The amount of the acrylic copolymer (C) used in the present invention must be 10 to 50% by weight, and preferably 15 to 45% by weight, based on 100% by weight of the resin component. If the amount of the acrylic copolymer (C) used exceeds the upper limit and is too large, the adhesive strength after heat curing tends to be insufficient. Is liable to be too small, and the initial adhesive strength tends to be insufficient.

The method for polymerizing the acrylic copolymer (C) used in the present invention is not particularly limited, and known methods such as solution polymerization and emulsion polymerization can be adopted, but a copolymer mixture obtained by polymerization is used. In producing the thermosetting pressure-sensitive adhesive composition, it is preferable to employ solution polymerization, in which the processing steps are relatively simple and can be performed in a short time.

In the solution polymerization, generally, a predetermined organic solvent, a monomer, a polymerization initiator, and a chain transfer agent used as needed are charged into a polymerization tank, and the mixture is stirred in a nitrogen stream or at the reflux temperature of the organic solvent. The reaction is carried out by heating for several hours. In this case, at least a part of the organic solvent, the monomer, the polymerization initiator and / or the chain transfer agent may be sequentially added.

As the organic solvent for polymerization, for example, benzene,
Aromatic hydrocarbons such as toluene, xylene and aromatic naphtha; aliphatics such as n-hexane, n-heptane, n-octane, i-octane, n-decane, dipentene, petroleum spirit, petroleum naphtha and turpentine oil Or alicyclic hydrocarbons; ethyl acetate, n-butyl acetate,
Esters such as n-amyl acetate, 3-methoxybutyl acetate, methyl benzoate, cellosolve acetate, butyl cellosolve acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, isophorone, cyclohexanone, methyl cyclohexanone; ethylene glycol methyl ether, ethylene glycol Glycol ethers such as ethyl ether and ethylene glycol butyl ether; for example, methyl alcohol, ethyl alcohol, n-propyl alcohol;
i-propyl alcohol, n-butyl alcohol, i-
Alcohols such as butyl alcohol, s-butyl alcohol and t-butyl alcohol; and the like. These organic solvents can be used alone or in combination of two or more.

The thermosetting pressure-sensitive adhesive composition of the present invention is preferably a solvent solution containing a polar organic solvent as a main component capable of dissolving an epoxy resin curing agent and the like described below. Among them, an organic solvent having a boiling point of 50 to 150 ° C., particularly preferably 60 to 100 ° C., which can be easily replaced with a polar organic solvent by volatilizing the organic solvent for polymerization from the obtained copolymer solution, Among them, it is particularly preferable to use an organic solvent such as toluene, n-hexane, ethyl acetate, acetone, methyl ethyl ketone, methyl alcohol, and n-propyl alcohol.

Examples of the polymerization initiator include benzoyl peroxide, lauroyl peroxide, caproyl peroxide, di-i-propylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, t-
Organic peroxides such as butyl peroxybivalate; for example, 2,2'-azobis-i-butyronitrile, 2,2'azobis-2,4 dimethylvaleronitrile, 2,2'-azobis-
An azo compound such as 4-methoxy-2,4-dimethylvaleronitrile; and the like can be used alone or in combination. The polymerization initiator is used in an amount of generally about 0.01 to 1.0 part by weight, preferably about 0.02 to 0.5 part by weight, based on 100 parts by weight of the total amount of the monomers.

Further, as the chain transfer agent, for example, cyanoacetic acid; C ₁ -C ₈ alkyl esters of cyanoacetic acid; C ₁ -C ₈ alkyl esters of bromoacetic acid; bromoacetate anthracene, phenanthrene, fluorene, 9-phenyl Aromatic compounds such as fluorene; p-nitroaniline, nitrobenzene, dinitrobenzene, p-nitrobenzoic acid,
aromatic nitro compounds such as p-nitrophenol and p-nitrotoluene; benzoquinone derivatives such as benzoquinone and 2,3,5,6-tetramethyl-p-benzoquinone; borane derivatives such as tributylborane; carbon tetrabromide; Halogenated hydrocarbons such as carbon tetrachloride, 1,1,2,2-tetrabromoethane, tribromoethylene, trichloroethylene, bromotrichloromethane, tribromomethane, and 3-chloro-1-propene; chloral, fulleraldehyde and the like; alkyl mercaptans C ₁ -C _18;; aldehydes thiophenol, aromatic mercaptans such as toluene mercaptan; C ₁ hydroxamate of -C ₁₂ Le alkyl mercaptan; C ₁ -C ₁₀ alkyl esters of mercaptoacetic acid; mercaptoacetic acid And terpenes such as binene and terpinolene; and the like.

When the above-mentioned chain transfer agent is used, its amount is preferably about 0.005 to 3.0 parts by weight per 100 parts by weight of the total amount of the monomers.

The polymerization temperature is generally in the range of about 30 to 180 ° C, preferably about 60 to 150 ° C.

The copolymer solution suitably used in the present invention thus obtained usually contains the acrylic copolymer in an amount of 20 to 90% by weight.
Contains.

The thermosetting pressure-sensitive adhesive composition of the present invention and the pressure-sensitive adhesive layer of the thermosetting pressure-sensitive adhesive sheet obtained by using the composition are the same as those of the epoxy resin (A) and (B). An epoxy resin curing agent (D) is contained together with the polymer (C).

The epoxy resin curing agent (D) has a reactive group that reacts with an epoxy group or a hydroxyl group in the resin component in the molecule of the curing agent, or generates such a reactive group by heating or the like. Compound (hereinafter sometimes referred to as a crosslinkable curing agent) and a catalyst for the ring-opening polymerization reaction of the epoxy group in the resin component in the curing agent molecule, or crosslinkable curing with the epoxy group or hydroxyl group in the resin component And a compound having a group that acts as a catalyst for the reaction with the agent (hereinafter, may be referred to as a catalytic curing agent).

Examples of the crosslinkable curing agent that causes an addition reaction with an epoxy group in the resin component include, for example, linear or aliphatic primary or secondary amines, alicyclic, aromatic or heterocyclic-containing aliphatics. Primary or secondary amines, aromatic primary or secondary amines, polyamidoamines obtained by reacting a polymer of unsaturated fatty acids such as linoleic acid or linolenic acid with polyamines, mercaptan-based compounds, Polybasic acids such as unsaturated fatty acid polymers and octadecanedicarboxylic acid, active hydrogen compound-based curing agents, and the like can be exemplified.
Examples of the curing agent that causes an addition or condensation reaction with a hydroxyl group in the resin component include a phenol resin (resole type), an amino resin, a polyisocyanate, and a blocked product of a polyisocyanate. Further, an acid anhydride which first undergoes an addition reaction with a hydroxyl group in a resin component and then undergoes an addition reaction with a carboxyl group and an epoxy group, such as an acid anhydride, can also be used.

Further, examples of the catalytic curing agent include aliphatic, alicyclic or aromatic tertiary amines or salts thereof, imidazoles or salts thereof, amine amide curing agents, Lewis acids or Bronsted acid salts, urea derivatives and the like. In addition, a polymer of the above-mentioned unsaturated fatty acid, a polybasic acid such as octadecanedicarboxylic acid, and an acid anhydride also have an action as an epoxy group ring-opening polymerization catalyst.

It is preferable that these various curing agents are previously blended with the epoxy resins (A) and (B) and the acrylic copolymer (C) as described later. In this case, the pot life of the blend is long. It is preferable to use a high-temperature activation type curing agent from the viewpoint of, for example, the hardness. Among such high temperature activated curing agents, those which can be suitably used in the present invention include, as crosslinkable curing agents, primary or secondary of high temperature activated alicyclic, aromatic or heterocyclic-containing aliphatic. Amine imides, high temperature activated aromatic primary or secondary amines, high melting point active hydrogen compound hardeners, acid anhydrides, etc. as catalytic hardeners, amine imide hardeners, high temperature activated tertiary Examples thereof include amine or imidazole curing agents, tertiary amine salt or imidazole salt curing agents, and urea derivative curing agents.

Examples of the high temperature activated alicyclic, aromatic or heterocyclic-containing aliphatic primary or secondary amines include, for example, 4-amines.
Amino-2,2,6,6-tetramethylpiperidine, bis (4
-Amino-3-methylcyclohexyl) methane, 2,4-
Dihydrazino-6-methylamino-s-triazine and the like; and high-temperature activated aromatic primary or secondary amines such as diaminodiphenyl sulfone and diaminodiphenylmethane; and a high melting point active hydrogen compound-based curing agent. As, for example, dicyandiamide; for example,
Adipic hydrazide, 5-t-butylhydantorene-
1,3-di (carboxyethyl) dihydrazide [Amicure VDH (trade name), Ajinomoto Co., Ltd.], octadecane-1,1
8-dicarboxylic dihydrazide [Amicure LDH (trade name), Ajinomoto Co., Ltd.], octadeca-7,11-diene-1,
Organic acid dihydrazide such as 18-dicarboxylic acid dihydrazide [Amicure UDH (trade name), Ajinomoto Co.]; and the like.

Examples of the acid anhydride include maleic anhydride, dodecyl succinic anhydride, polyadipic anhydride, polyazeleic anhydride, polysebacic anhydride, poly (ethylene octadecanic acid) anhydride, and poly (phenylhexadecanine). Acid) aliphatic acid anhydrides such as anhydrides; for example, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylhexamic anhydride, etc. Alicyclic anhydrides; for example, aromatic anhydrides such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitate, and glycerol tris trimellitate; Can be illustrated.

Further, as amine imide-based curing agents, trialkyl hydrazinium fatty acid amides [YPH103, YPH201, YPH208
(Trade name); Yuka Shell Epoxy Co., Ltd.], as a high temperature activated tertiary amine or imidazole-based curing agent,
2,4,6-tris (dimethylaminomethyl) phenol,
2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenyl-4-methylimidazole, and the like, as tertiary amine salt or imidazole salt-based curing agents, Amicure PN-23, MY-24 [(trade name) Ajinomoto Co., Ltd.] as a Lewis acid or Bronsted acid salt-based curing agent, for example, a Lewis acid salt such as boron trifluoride monoethylamine salt; for example, a Bronsted acid aliphatic sulfonium salt [Opton CP- 66, CP-77 (trade name), Asahi Denka Co., Ltd.], and urea derivative-based curing agents such as N, N-dimethylurea, N, N'-dimethylurea, N, N ' -Diethyl urea, N-phenyl urea,
N, N-diphenylurea, N, N, N'-triphenylurea, N,
N, N ', N'-tetraphenylurea, N-acetylurea,
N, N'-diacetyl urea, N-acetyl-N'-methyl urea, N-benzyl urea, N, N-dibenzoyl urea, N
-Benzenesulfonylurea, Np-toluenesulfonylurea, Np-toluenesulfonyl-N'-n-butylurea, Np-toluenesulfonyl-N'-i-butylurea, N, N-dimethyl-N '-(3', 4'-dichlorophenyl) urea, parabanic acid, N, N'dimethylparabanic acid, N, N'-dimethylbarbituric acid, 5,5-dimethylhydantoin, 1,3-dimethyluracil, 1 , 5-dimethyluracil and the like.

Among these curing agents, from the viewpoints of good pot life of the obtained thermosetting pressure-sensitive adhesive composition and good bonding performance of the composition and the thermosetting pressure-sensitive adhesive sheet, high-temperature active type crosslinking is preferred. Dicyandiamide (hereinafter referred to as DICY)
), Diaminodiphenylsulfone, diaminodiphenylmethane and the like are particularly preferred. Also, for example, DICY which is a high temperature active type crosslinkable curing agent
When such a material is used, the above-mentioned tertiary amine salt-based curing agent, urea derivative-based curing agent and the like can be used in combination as a high-temperature-active catalytic curing agent to lower the thermosetting temperature.

Among these epoxy resin curing agents (D), the crosslinkable curing agent is used in the case of the active hydrogen compound-based curing agent and the aromatic amine with respect to one epoxy group in the resin component. The number of active hydrogen is usually 0.2 to 2.0, preferably 0.1.
In the case of an acid anhydride, the number is preferably from 0.2 to 2.0, and more preferably from 0.5 to 1.0. Further, a catalytic curing agent such as an amineimide-based curing agent, a tertiary amine or imidazole salt-based curing agent, a Lewis acid or Bronsted acid salt-based curing agent is preferably used in combination with a crosslinkable curing agent. In general, the amount can be about 40 parts by weight or less based on 100 parts by weight of the crosslinking hardener.

These epoxy resin curing agents (D) may be previously blended with the resin components comprising the epoxy resins (A) and (B) and the acrylic copolymer (C). May be blended with the resin component.

However, in order to avoid complication of the operation at the time of use, it is preferable that the curing agent is previously blended with the components (A), (B) and (C). The method of compounding the curing agent is not particularly limited, but it is preferable to dissolve the curing agent in a soluble organic solvent before compounding, from the viewpoint of ease of compounding and the like.

The organic solvent is preferably one that dissolves both the resin component and the epoxy resin curing agent.As such an organic solvent, a polar organic solvent is generally used, for example, methyl ethyl ketone, methyl cyclohexanone, diacetone. Ketones such as alcohols; for example, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-i-propyl ether,
Ethylene glycol butyl ether, diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), tetraethylene glycol dimethyl ether (tetraglyme)
Glycol ethers such as ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol-i-propyl ether acetate; glycol esters such as dimethyl sulfoxide, dimethyl sulfone, tetramethyl sulfone, dimethyl formamide; Other aprotic polar organic solvents such as dimethylacetamide, hexamethylphosphoric triamide, N-methylpyrrolidone, and acetonitrile;

The thermosetting pressure-sensitive adhesive composition of the present invention may further comprise, if necessary, for example, coumarone-indene resin, terpene
Tackifying resins such as phenolic resins, pt-butylphenol / acetylene resins, phenol / formaldehyde resins, terpene resins, xylene / formaldehyde resins, petroleum hydrocarbon resins, hydrogenated hydrocarbon resins, rosin derivatives, and turpentine resins; For example, other modifying resins such as an ethylene-vinyl acetate copolymer resin, an ethylene-acryl copolymer resin, and an ethylene-vinyl acetate-acryl copolymer resin can be added. The addition amount of these resins is, based on a total of 100 parts by weight of the resin component, a tackifying resin, for example, 0 to 60 parts by weight, particularly 0 to 40 parts by weight; Parts by weight, especially 0 to 20 parts by weight;

In addition to these, the pressure-sensitive adhesive composition of the present invention may be optionally used, for example, a phthalic acid ester such as dioctyl phthalate, a phosphate ester such as tricresyl phosphate, a plasticizer such as polybutene or process oil. Agents;
For example, organic or inorganic coloring agents such as titanium oxide, carbon black, and phthalocyanine blue; inorganic fillers such as clay, talc, calcium carbonate, silica, aluminum hydroxide, and glass powder; Aerosil 300 (trade name), manufactured by Nippon Aerosil Co., Ltd.], activated ultrafine calcium carbonate
Known additives such as a thickener such as CCR (trade name; manufactured by Shiraishi Industry Co., Ltd.); an ultraviolet absorber; a preservative; and the like.

As a method for producing the thermosetting pressure-sensitive adhesive composition of the present invention, for example, the solution of the acrylic copolymer (C) thus obtained in an organic solvent solution for polymerization may be prepared from the above two or more kinds. A predetermined amount of each of the epoxy resins (A) and (B), and various additives that can be added as required, is blended, and the organic solvent for polymerization is removed by a known method such as distillation while heating and mixing. Then, a molten mixture comprising the epoxy resins (A) and (B), the acrylic copolymer (C), and various additives added as necessary, is then added to the epoxy resin curing agent (D). In addition, a method of adding a polar organic solvent capable of dissolving and dispersing the epoxy curing agent (D), further adding an appropriate organic solvent as needed, and uniformly mixing can be suitably employed.

The obtained organic solvent solution of the thermosetting pressure-sensitive adhesive composition of the present invention usually has a solid content of about 30 to 70% by weight and a viscosity (B-type rotational viscometer, 25 ° C., 10 RPM; hereinafter, measurement conditions are the same). And
It is good to be about 100 to 20000 cps, preferably about 300 to 5000 cps.

The thermosetting pressure-sensitive adhesive composition of the present invention can be directly applied to one or both of objects to be directly adhered (hereinafter, sometimes referred to as adherends) such as a knife coater, a roll coater, an air coater, and a spray coater. By applying with a known coating machine, drying and bonding the adherends together and heating and curing, the adherends can be firmly adhered. The drying temperature is a temperature at which curing of the pressure-sensitive adhesive layer does not occur, for example,
The curing temperature is preferably about 50 to 120 ° C, and the curing temperature varies depending on the type of the epoxy resin curing agent (D), but is generally about 100 to 250 ° C.

Examples of the adherend to which the thermosetting pressure-sensitive adhesive composition of the present invention can be suitably used include metal, glass, plastic, wood, paper, slate, rubber, decorative board and the like.

Further, the thermosetting pressure-sensitive adhesive composition of the present invention, the same generally known coating machine as described above, for example, non-woven fabric,
Woven fabrics, knitted fabrics, papers, applied to one or both surfaces of various base materials such as plastic films in appropriate thickness, or impregnated into base materials such as non-woven fabrics, woven fabrics, knitted fabrics and papers in appropriate amounts After drying, the release material is placed on the obtained pressure-sensitive adhesive layer to obtain a thermosetting pressure-sensitive adhesive sheet. Alternatively, a "coreless" double-sided pressure-sensitive adhesive sheet can be obtained by directly applying the pressure-sensitive adhesive composition on a release material, drying the composition, and then placing the release material on the surface. The thickness of the pressure-sensitive adhesive layer is generally about 10 to 300μ,
Preferably, it is about 20 to 200 μ. Drying is preferably performed at the same temperature as above, that is, about 50 to 120 ° C.

The resulting thermosetting pressure-sensitive adhesive sheet can be firmly bonded by pressure bonding to a desired portion of the adherend as described above and then heating and curing. In the case of a thermosetting double-sided pressure-sensitive adhesive sheet, adherends of the same type or different types can be firmly bonded to each other via the double-sided pressure-sensitive adhesive sheet.

The thermosetting pressure-sensitive adhesive composition and the thermosetting pressure-sensitive adhesive sheet of the present invention may be stored at a low temperature of, for example, 10 ° C. or lower, preferably 0 ° C. or lower, but at room temperature (about 25 ° C.) Epoxy resin curing agent (D) so that the composition has a pot life of 1 week or more and does not change its adhesive properties even when stored in the above-mentioned condition, and the adhesive sheet does not change its adhesive properties for 1 month or more.
It is good to select the kind and compounding amount of.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples and Comparative Examples.

Incidentally, the compatibility of the composition of the present invention, pot life test method,
The method for preparing the double-sided pressure-sensitive adhesive sheet for the physical property test of the pressure-sensitive adhesive sheet, and the method for measuring the initial adhesive strength, the adhesive strength, and the storage stability of the pressure-sensitive adhesive sheet are as follows.

(1) Composition Compatibility Test The composition solution was left in a closed state at 25 ° C. for 24 hours, and the uniformity, transparency, and the presence or absence of sediment of the solution were visually observed and evaluated according to the following criteria.

 ○ ‥‥‥ The composition solution is uniform and transparent, with no sediment.

Δ ‥‥‥ The composition solution is uniform, but slightly cloudy or sedimented.

× ‥‥‥ Composition solution separated or opaque, or sedimented.

(2) Composition pot life test (2-1) Appearance The composition solution was allowed to stand in a closed state at 25 ° C for 7 days, and the state was evaluated according to the following criteria.

 ◎ ‥‥‥ Almost no change in appearance and viscosity.

 ○ ‥‥‥ No change in appearance, but slightly increased viscosity.

Δ ‥‥‥ No change in appearance, but large increase in viscosity (fluidity).

× ‥‥‥ Extremely high viscosity increase (no fluidity), or
Gelation.

(2-2) Adhesive property The adhesive property of the pressure-sensitive adhesive sheet was measured according to the following items (3) to (5) using the composition solution that had been left in a closed state at 25 ° C. for 7 days. The evaluation is made according to the following criteria as compared with the case where the composition solution is used.

◎ ‥‥‥ Almost no change in initial adhesive strength and adhesive strength (decrease rate less than 10%).

○ ‥‥‥ Initial adhesive strength, decrease rate of adhesive strength, one is less than 10% and the other is 10 to 30%.

△ ‥‥‥ Initial adhesive strength, rate of decrease in adhesive strength, one is less than 10% and the other 30-50%, or both 10-30%.

× ‥‥‥ Initial adhesive strength, rate of decrease in adhesive strength, 50% or more for one or 30% or more for both.

(3) Method for preparing a double-sided pressure-sensitive adhesive sheet A polyamide fiber-based nonwoven fabric having a thickness of about 100μ is immersed in a composition solution adjusted to a solid content of 50 to 60% by weight and a viscosity of about 500 cps, and spread on a release material. After performing a pressing and smoothing treatment from the surface so that the thickness of the double-sided pressure-sensitive adhesive sheet after drying using a blade is about 250μ, in a hot air circulation type dryer at 80 ° C, 10 minutes, and further 100 2 while heating to ℃
It is dried for 0 minutes, and then a release material is placed on the surface and pressed lightly to adhere.

(4) Measurement of initial adhesive strength Thickness 02mm specified in alloy number A-1050P of JIS H-4000
The surface of the aluminum plate was washed with methanol-impregnated gauze, and the double-sided pressure-sensitive adhesive sheet (from which the release material was peeled) prepared in (3) above was placed so as to cover about half of the surface. Another similarly treated aluminum plate is placed on the sheet, and pressed in accordance with the method of JIS Z-0237 to obtain a bonded test piece. Twenty minutes later, this test piece was cut into a 25 mm width, and one of the aluminum plates (the part without the double-sided pressure-sensitive adhesive sheet) was bent to about 90 °, and JIS Z-0337
The peel strength (kg / 25 mm) is measured under the conditions of 20 ° C., 65% RH, and a peel speed of 300 mm / min according to “90 ° Peeling Method”. The value of the initial adhesive strength is preferably 0.5 kg / 25 mm or more, and particularly preferably 1.0 kg / 25 mm or more.

(5) Measurement of adhesive strength (5-1) Room temperature adhesive strength Before curing the test piece prepared in the previous section (3) under predetermined conditions, and then leaving it at 25 ° C. for 24 hours, the previous (3)
The peel strength (kg / 25mm) is measured in the same manner as in the test method in the section. The adhesive strength is preferably 4 kg / 25 mm or more, more preferably 5 kg / 25 mm or more, and 6 kg / 25 mm.
The above is particularly preferred.

(5-2) High Temperature Adhesive Strength After the test specimen prepared in the previous paragraph (3) was cured by heating under predetermined conditions, it was allowed to stand at 25 ° C. for 24 hours, and then placed in a thermostatic chamber adjusted to a predetermined temperature. After leaving to stand for 10 minutes, the peel strength (kg / 25 mm) is measured in the same manner as in the test method described in the above (3) except that the measurement is performed in the thermostat.

(6) Storage stability of the pressure-sensitive adhesive sheet The double-sided pressure-sensitive adhesive sheet obtained in the above item (3) was subjected to storage at 25 ° C.
After leaving it for 30 days, it is measured according to the method of the above (4) and (5), and compared with the case of the adhesive sheet before leaving,
Evaluate according to the following criteria.

◎ ‥‥‥ Almost no change in initial adhesive strength and adhesive strength (decrease rate less than 10%).

○ ‥‥‥ Initial adhesive strength, decrease rate of adhesive strength, one is less than 10% and the other is 10 to 30%.

△ ‥‥‥ Initial adhesive strength, rate of decrease in adhesive strength, one is less than 10% and the other 30-50%, or both 10-30%.

× ‥‥‥ Initial adhesive strength, rate of decrease in adhesive strength, 50% or more for one or 30% or more for both.

Reference Example 1 An organic solvent for initial addition, 37.5 parts by weight of ethyl acetate (EAc) as a polymerization initiator and azobisisobutyronitrile were placed in a separable flask equipped with a reflux condenser, a thermometer, a stirrer, and a sequential dropping device. 0.025 parts by weight of (AIBN), and then 25% by weight of a monomer mixture composed of 70 parts by weight of butyl acrylate (BA) and 30 parts by weight of glycidyl methacrylate (GMA), and heated to a reflux temperature (about
(80 ° C.) for about 20 minutes. Then, at reflux temperature conditions, 75% by weight of the remaining monomer mixture, 25 parts by weight of EAc and AIB
N0.125 parts by weight of a polymerization initiator solution was successively added dropwise over about 90 minutes, and further about 60 minutes EAC 12.5 parts by weight and AIB
After adding a polymerization initiator solution consisting of 0.25 parts by weight of N, 75 parts by weight of toluene was added to dilute the mixture, and the solid content was about 40% by weight and the viscosity was 20%.
An acrylic copolymer solution of 50 cps was obtained. ▲ ▼ of this copolymer was about 90,000, ▲ ▼ was about 600,000, and Tg was −33 ° C.

Reference Examples 2 to 4 In Reference Example 1, an acrylic copolymer solution was obtained in the same manner as in Reference Example 1, except that the use ratio of BA and GMA was changed, and if necessary, the ratio of the initial addition and the sequential addition of the organic solvent was changed. Was. Table 1 shows the monomer compositions of these acrylic copolymer solutions and the ▲, ▼, and Tg of these copolymers.

Reference Example 5 In the same apparatus as in Reference Example 1, toluene 50 was used as an organic solvent.
Parts by weight, 10% by weight of the same monomer mixture as in Reference Example 1
And 0.025 parts by weight of a polymerization initiator (AIBN), and polymerization was carried out for about 20 minutes under reflux temperature conditions. Then, the remaining amount of the monomer mixture was 90% by weight under reflux temperature conditions, 8.3 parts by weight of toluene and A
The polymerization initiator solution consisting of 0.125 parts by weight of IBN and the polymerization initiator solution consisting of 8.3 parts by weight of toluene and 0.25 parts by weight of AIBN were added successively dropwise over about 90 minutes, and the acrylic copolymer was further added for about 60 minutes. A solution was obtained. The viscosity of this acrylic copolymer solution and the ▲ ▼, ▲
▼ and Tg are shown in Table 1.

Reference Examples 6 and 7 In Reference Example 1, 70 parts by weight of BA and 30 parts by weight of GMA were used instead of 70 parts by weight of ethyl acrylate (EA) and 30 parts by weight of GMA; 80 parts by weight of EA and 20 parts by weight of GMA were used. And an acrylic copolymer solution was obtained in the same manner except that the amount ratio of the sequential addition was changed. Table 1 shows the initial polymerization conditions of this acrylic copolymer solution, and ▲, ▼ and Tg of these copolymers.

Example 1 In a separable flask equipped with a solvent distilling device, a thermometer, a stirrer, and a sequential dropping device, 75 parts by weight of the acrylic copolymer (C) solution obtained in Reference Example 1 (as a copolymer) about
30 parts by weight), Epicoat 828 as epoxy resin (A)
[(Trade name), bisphenol A type epoxy resin (epoxy equivalent: about 190); manufactured by Yuka Shell Epoxy Co.] 50 parts by weight, and Epicoat 1001 as epoxy resin (B)
[(Trade name), bisphenol A type epoxy resin (epoxy equivalent: about 480); manufactured by Yuka Shell Epoxy Co.] Add 20 parts by weight, heat and mix at about 120 ° C, and distill off the solvent used in the polymerization. I let it. Then, the mixture is cooled to about 50 ° C., and then 4.2 parts by weight of dicyandiamide (DICY) is used as an epoxy curing agent (when the number of active hydrogens in DICY is 4, the number of active hydrogens per epoxy group is about 0.54). A solution dissolved in 17 parts by weight of dimethylformamide (DMF) and 70 parts by weight of an organic solvent for adjusting viscosity (DMF / ethylene glycol monomethyl ether = 1: 1) are added, and the mixture is stirred and uniformly mixed to be a thermosetting type. A pressure sensitive adhesive composition was produced. The obtained thermosetting pressure-sensitive adhesive composition had a solid content of about 55% by weight and a viscosity of about 1000 cps. Table 2 shows the measurement results of the compatibility of the composition, basic physical properties such as pot life, and various physical properties of the pressure-sensitive adhesive tape using the same.

Comparative Examples 1-2 In Example 1, instead of using 50 parts by weight of the epoxy resin (A) and 20 parts by weight of the epoxy resin (B), 70 parts by weight of the epoxy resin (A) alone was used. A) A thermosetting pressure-sensitive material was prepared in the same manner except that 30 parts by weight of the epoxy resin (B) and 40 parts by weight of the epoxy resin (B) were used and the amount of DICY and DMF was adjusted according to the change in the number of epoxy groups. An adhesive composition was manufactured. Table 2 shows the composition, basic physical properties of the obtained thermosetting pressure-sensitive adhesive composition, and measurement results of various physical properties of the pressure-sensitive adhesive tape using the same.

Examples 2-3 and Comparative Examples 3-4 In Example 1, the mixing ratio of the epoxy resins (A) and (B) and the acrylic copolymer (C) was changed, and accordingly, the epoxy resin (A) and the epoxy resin were changed. A thermosetting pressure-sensitive adhesive composition was produced in the same manner except that the mixing ratio with the resin (B) was changed and the amounts of DICY and DMF used were changed. Table 2 shows the composition, basic physical properties of the obtained thermosetting pressure-sensitive adhesive composition, and measurement results of various physical properties of the pressure-sensitive adhesive tape using the same.

Example 4 A thermosetting pressure-sensitive material was prepared in the same manner as in Example 1, except that 1.5 parts by weight of 1,1-dimethyl-3- (3 ', 4'-dichlorophenyl) urea (biuron) was additionally used as a curing agent. An adhesive composition was manufactured. Table 2 shows the composition, basic physical properties of the obtained thermosetting pressure-sensitive adhesive composition, and measurement results of various physical properties of the pressure-sensitive adhesive tape using the same.

Examples 5 to 7 and Comparative Examples 5 to 7 In Example 1, instead of using the acrylic copolymer of Reference Example 1, the acrylic copolymer of Reference Examples 2 to 7 was used, and the epoxy group accompanying the copolymer was used. DICY according to the change in the number of
A thermosetting pressure-sensitive adhesive composition was produced in the same manner except that the amount of DMF and the amount of DMF used were adjusted. Table 2 shows the composition, basic physical properties of the obtained thermosetting pressure-sensitive adhesive composition, and measurement results of various physical properties of the pressure-sensitive adhesive tape using the same.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁶ , DB name) C09J 163/00-163/10 C09J 133/04-133/14 C09J 7/02-7/04

Claims (2)

(57) [Claims] 1. A resin component comprising the following components (A) to (C) (provided that the total of (A) to (C) is 100% by weight): (A) an epoxy resin having an epoxy equivalent of 150 to 300; ~
85% by weight, (B) an epoxy resin having an epoxy equivalent exceeding 300 5
(C) 15 to 50% by weight of an epoxy group-containing monomer, and 10 to 50% by weight of an acrylic copolymer having a number average molecular weight of 50,000 or more; And (D) an epoxy resin curing agent, comprising: a thermosetting pressure-sensitive adhesive composition. 2. A resin component comprising the following components (A) to (C) (provided that the total of (A) to (C) is 100% by weight): (A) an epoxy resin having an epoxy equivalent of 150 to 300; ~
85% by weight, (B) an epoxy resin having an epoxy equivalent exceeding 300 5
(C) 15 to 50% by weight of an epoxy group-containing monomer, and 10 to 50% by weight of an acrylic copolymer having a number average molecular weight of 50,000 or more; And a thermosetting pressure-sensitive adhesive layer comprising: (D) an epoxy resin curing agent.