KR100476798B1 - Thermosetting Pressure Sensitive Adhesive and Adhesive Sheets - Google Patents

Abstract

The present invention, 100 parts by weight (a) of the monomer mixture consisting of 70 to 99% by weight of (meth) acrylic acid alkyl ester having 2 to 14 carbon atoms in the alkyl group and 1 to 30% by weight of monoethylenically unsaturated acid copolymerizable therewith,

0.02 to 5 parts by weight of a polyfunctional (meth) acrylate as a crosslinking agent (b),

0.01 to 4 parts by weight of the photopolymerization base material (c) and

A photopolymerization product of a composition containing 5 to 30 parts by weight of an epoxy resin (d) and substantially free of a curing agent of an epoxy resin, which is a component (d), and is easily adhered to an adherend because it has adhesiveness at room temperature. The present invention relates to a curable pressure-sensitive adhesive and an adhesive sheet using the same, which are capable of temporary adhesion, and which are cured in a short time by heating, thereby exhibiting strong adhesive strength and high heat resistance and further excellent in storage stability.

Description

Thermosetting Pressure Sensitive Adhesive and Its Adhesive Sheets

The present invention relates to a thermosetting pressure-sensitive adhesive having excellent heat resistance, resistant to the use at a high temperature of 100 ° C. or higher, or a soldering process, and an adhesive sheet formed on a substrate to form a sheet or a tape. adhesive sheets).

In order to simplify work, improve safety, and improve hygiene, a method of treating with an adhesive sheet instead of a method of applying and drying a liquid adhesive is often used. As adhesive sheets, the thermosetting type hardened | cured by heat processing is proposed for the adhesive use, such as an electronic component. Although the thermosetting adhesive is excellent in adhesive strength, heat resistance, and the like, it is difficult to have temporary adhesion due to its lack of adhesion at room temperature, and there are many low molecular weight components before curing. In addition, excellent storage stability has a long curing time, and curing in a short time has a problem of insufficient storage stability.

On the other hand, the adhesive sheets (tacky sheets) are tacky at room temperature, can be attached to the target without pre-treatment, it is possible to express the adhesive strength immediately. However, adhesive sheets have a disadvantage that they are generally inferior in adhesive strength and heat resistance as compared to adhesives. Japanese Unexamined Patent Publication (Kokai) No. 5-117593 realizes strong adhesiveness and high heat resistance using a photopolymerizable composition containing acrylic acid alkyl ester as a main component, but does not fall outside the steps of adhesive sheets. . That is, the appearance of adhesive sheets exhibiting high adhesiveness and high heat resistance equivalent to that of the adhesive after bonding, while exhibiting adhesiveness as adhesive sheets at the initial stage of bonding with the adherend is required.

In order to respond to these demands, so-called adhesives having a property of both an adhesive and an adhesive have been proposed. For example, JP-A-2-272076 describes a thermosetting pressure-sensitive adhesive made from a photopolymerizable composition obtained by adding an epoxy resin to an acrylic acid ester monomer. In addition, Japanese Patent Application Laid-Open No. 7-2978 also has a thermosetting type made from a photopolymerizable composition formed by adding an epoxy group-containing alcohol, an ester of an (meth) acrylic acid, and an epoxy resin to an (meth) acrylic acid alkyl ester. Pressure sensitive adhesives are described.

These proposals make the photopolymerizable composition photocurable by ultraviolet irradiation to give a curable adhesive having both adhesive and adhesive properties, but hardening reaction with epoxy groups by adding a curing agent such as imidazole, dicyandiamide, polyamine to the composition. It's about making things happen. In such a case, the above curing reaction proceeds gradually during storage before photopolymerization or after photopolymerization, and there is a fear that the adhesive properties and the like deteriorate. As described above, the thermosetting pressure-sensitive adhesive proposed above has a difficulty in terms of storage stability, and in particular, Japanese Patent Application Laid-Open No. 2-272076 describes acrylic polymers and epoxy resins produced by photopolymerization. The heat resistance is also insufficient because it does not crosslink even after curing.

In view of such a situation, the present invention is tacky at room temperature and can be easily adhered to the adherend, and is cured in a short time by heating, thereby exhibiting strong adhesive strength and high heat resistance, and furthermore, a thermosetting type having excellent storage stability. It is an object to provide a pressure-sensitive adhesive and adhesive sheets such as a sheet form and a tape form.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve this objective, when the monomer which has a carboxyl group etc. in a molecule | numerator is added to the acryl-type monomer which comprises a photopolymerizable composition, and this reacts with an epoxy resin after photopolymerization, an acryl-type polymer and an epoxy resin are bridge | crosslinked. By bonding, high adhesion and high heat resistance are obtained, and the photopolymerized adhesive before reacting with the epoxy resin can be temporarily bonded at room temperature, and can be cured in a short time by reaction with the epoxy resin, and also imidazole, dish Since it does not contain conventional hardening | curing agents, such as an adiamide and a polyamine, it discovered that storage stability becomes excellent and came to complete this invention.

That is, the present invention

100 parts by weight of a monomer mixture (a) consisting of 70 to 99% by weight of (meth) acrylic acid alkyl ester having 2 to 14 carbon atoms in its alkyl group and 1 to 30% by weight of monoethylenically unsaturated acid copolymerizable therewith,

0.02-5 weight of the polyfunctional (meth) acrylate (b) as a crosslinking agent,

0.01 to 4 parts by weight of the photopolymerization initiator (c) and

One side of the thermosetting pressure-sensitive adhesive and the substrate, characterized in that it comprises a photopolymerization product of a composition containing 5 to 30 parts by weight of the epoxy resin (d) and containing almost no curing agent for the epoxy resin as component (d). Or the said thermosetting pressure-sensitive adhesive layer is formed in both surfaces, It is related with adhesive sheets, such as a sheet form and a tape form.

In the present invention, the monomer mixture of component (a) is composed of a (meth) acrylic acid alkyl ester and a monoethylenically unsaturated acid copolymerizable therewith, and usually 30% by weight or less of the (meth) acrylic acid alkyl ester is generally reduced in acryl Various vinyl monomers, such as vinyl acetate, styrene, and acrylonitrile, which are known as monomers for modifying the adhesive can be substituted.

As the (meth) acrylic acid alkyl ester, for example, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth ) Acrylates and the like, among them, at least one (meth) acrylic acid alkyl ester having an average carbon number of 2 to 14 alkyl groups is used. As monoethylenically unsaturated acid copolymerizable with these, (meth) acrylic acid, itaconic acid, 2-acrylamide propanesulfonic acid, etc. are mentioned, for example.

In the monomer mixture of component (a), the use ratio of the (meth) acrylic acid alkyl ester and the monoethylenically unsaturated acid copolymerizable therewith is 70 to 99% by weight of the (meth) acrylic acid alkyl ester, preferably 80 to 95% by weight. %, Monoethylenically unsaturated acid is preferably 1 to 30% by weight, preferably 5 to 20% by weight. When using a vinylic monomer together, the use ratio of the (meth) acrylic-acid alkylester and a vinylic monomer is 70 to 99 weight%, Preferably it is 80 to 95 weight% [However, the use ratio of a vinyl monomer is (meth) To 30% by weight or less relative to the total amount of the acrylic acid alkyl ester and the vinyl monomer], and the use ratio of the monoethylenically unsaturated acid is 1 to 30% by weight, preferably 5 to 20% by weight. Outside the above range, good results on the adhesion properties after the photopolymerization and the epoxy curing reaction are hardly obtained.

In the present invention, the crosslinking agent of component (b) is a polyfunctional (meth) acrylate, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,2- Polyfunctional or higher polyhydric alkyl (meth) acrylate monomers such as ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (meth) acrylate Used.

The amount of the polyfunctional (meth) acrylate slightly varies depending on the number of functional groups and the like, but is 0.02 to 5 parts by weight, preferably 0.2 to 3 parts by weight per 100 parts by weight of the monomer mixture of component (a). By using the polyfunctional (meth) acrylate in such a ratio, due to the crosslinking effect on the acrylic polymer, good cohesive force can be maintained and high heat resistance can be obtained.

As a photoinitiator of the component (c) in this invention, benzoin ethers, such as benzoin methyl ether and benzoin isopropyl ether, substituted benzoin ethers, such as anizo methyl ether, 2, Substituted acetophenones such as 2-diethoxyacetophenone, 2,2-dimethoxy-2-phenoneacetophenone, substituted α-ketols such as 2-methyl-2-hydroxypropiophenone and 2-naphthalene Aromatic sulfonyl chlorides such as sulfonyl chloride and photoactive oximes such as 1-phenone-1,1-propanedione-2- (o-ethoxycarbonyl) oxime.

The use amount of these photoinitiators is 0.01-4 weight part, suitably 0.05-1 weight part per 100 weight part of monomer mixtures of component (a). When the amount is less than 0.01 part by weight, the polymerization rate decreases because it is consumed at a quick time by the light energy. On the other hand, when the amount is more than 4 parts by weight, the polymerization rate increases, but the molecular weight of the polymer is lowered and the cohesion force of the adhesive is likely to be lowered.

In the present invention, the epoxy resin of component (d) is a compound containing two or more epoxy groups in a molecule, and is suitably selected from bisphenol epoxy resins, phenolic epoxy resins, halogenated bisphenol epoxy resins, and the like. These epoxy resins do not have photopolymerizable groups in the molecule.

The use amount of such epoxy resin is 5 to 30 parts by weight, preferably 5 to 20 parts by weight, per 100 parts by weight of the monomer mixture of component (a). If it is less than 5 parts by weight, the crosslinking reaction between the acrylic polymer and the epoxy resin does not proceed sufficiently and the heat resistance becomes insufficient. Moreover, when more than 30 weight part, since hardened | cured material crosslinks excessively, peeling phenomenon will arise in the surface of a to-be-adhered body, and storage stability will also fall.

Although the photopolymerizable composition of this invention contains the monomer mixture of component (a), the polyfunctional (meth) acrylate of component (b), the photoinitiator of component (c), and the epoxy resin of component (d) as essential components, On handling, the monomer mixture of component (a) can be prepolymerized to some degree using the photopolymerization initiator of component (c) (generally, prepolymerization is a coating having, for example, a viscosity range of about 500 to 5000 cps). In the form of syrup). In the case of prepolymerization, gelation may occur when the epoxy resin of component (d) is used. Therefore, the epoxy resin of component (d) is preferably added after prepolymerization.

In such a photopolymerizable composition, in addition to the above four components (a) to (d), conventionally known components such as a tackifier, a polar monomer, a plasticizer, a softener, a filler, a pigment, a dye, an anti-aging agent, and the like as optional components Various additives which have been added can be added within a range that does not prevent photopolymerization by ultraviolet irradiation or the like.

Moreover, general hardening | curing agents, such as imidazole, dicyandiamide, polyamine, which are known as a hardening | curing agent for epoxy resins, cannot be added to such a photopolymerizable composition. However, even if these hardening | curing agents exist, when hardening reaction with an epoxy resin hardly advances and there is no possibility that the storage stability aimed at by this invention may be largely impaired, it will not be restrict | limited. In the present invention, "almost not included" means the same.

In the present invention, the photopolymerizable composition is applied on the adherend or on one side or both sides of the substrate, and then irradiated with ultraviolet rays of about 400 to 1.500 mj / cm 2, so that the components (a) or components (a) and components are Photopolymerization of (b) results in a tackified acrylic pressure sensitive adhesive which is itself a pressure sensitive adhesive. Here, as a base material, besides non-peelable base materials, such as a synthetic resin film, such as a polyester film, and a fiber base material, peelable base materials, such as a release paper, can be used. In the case of a peelable base material, the pressure-sensitive adhesive layer after photopolymerization formed thereon can be transferred onto the above non-peelable base material. The adhesive sheets of the present invention include both those using such a non-peelable substrate as the substrate and those using a peelable substrate.

The acrylic pressure-sensitive adhesive including the photopolymer formed as described above has an adhesive property at room temperature, so that the acrylic pressure-sensitive adhesive can be easily adhered to the adherend, and further, the reaction between the acrylic polymer and the epoxy resin occurs by heat treatment and cures in a short time. It exhibits the excellent performance required as a thermosetting pressure-sensitive adhesive with warning adhesive strength and high heat resistance, particularly withstanding use at a high temperature of 100 ° C. or higher or in a soldering process. The heat treatment is usually carried out at 100 to 200 ° C. for 0.5 to 10 hours, preferably at 130 to 170 ° C. for 1 to 5 hours. In addition, in the state before heat processing, the said reaction hardly advances and storage stability is also excellent.

Example

Next, examples of the present invention will be described in more detail. In addition, a part means a weight part next.

Example 1

Syrup having a viscosity of about 30 poise by adding 90 parts of isononyl acrylate, 10 parts of acrylic acid and 0.05 parts of 2,2-dimethoxy-2-phenylacetophenone to a four-necked flask, and partially photopolymerizing by exposure to ultraviolet light under a nitrogen atmosphere. To obtain. 0.2 parts of trimethylolpropane triacrylate as a crosslinking agent and 15 parts of the trade name "Epikote 828" of Yuka Shell Epoxy Kabushiki Kaisha as a crosslinking agent in 100 parts of the syrup polymerized in this way were uniform. Mixing so as to prepare a photopolymerizable composition.

After apply | coating this photopolymerizable composition on the base material which consists of a polyethylene terephthalate film of 25 micrometers in thickness which carried out the low adhesive peeling process, it is made to photopolymerize by irradiating 900mj / cm <2> ultraviolet-rays. Next, it cut | disconnected to width 20mm and manufactures the adhesive tape whose thickness of a thermosetting pressure-sensitive adhesive layer is 50 micrometers.

Example 2

50 parts of isooctyl acrylate, 35 parts of butyl acrylate, 15 parts of acrylic acid and 0.05 parts of 2,2-dimethoxy-2-phenylacetophenone were charged into a four-necked flask, and partially photopolymerized by exposure to ultraviolet light under a nitrogen atmosphere, A syrup is obtained with a viscosity of about 30 poise. 0.3 parts of 1,6-hexanediol diacrylate as a crosslinking agent and 10 parts of an epoxy resin (trade name "Epicoat 815" of Yucca Shell Epoxy Co., Ltd.) are uniformly mixed to 100 parts of such partially polymerized syrup to form a photopolymerizable composition. Manufacture. Using this photopolymerizable composition, an adhesive tape was produced in the same manner as in Example 1.

Comparative Example 1

Except not using an epoxy resin, a photopolymerizable composition is manufactured like Example 1, and an adhesive tape is manufactured similarly to Example 1 using this.

Comparative Example 2

Instead of 10 parts of acrylic acid, 10 parts of N-vinylpyrrolidone was used, and Asahi Chemical Industry Co., Ltd. trade name "Novacure-HX-" was used as a curing agent for epoxy resins. 3721 ″, except that 3 parts were added, a photopolymerizable composition was produced in the same manner as in Example 1, and an adhesive tape was produced in the same manner as in Example 1 using the same.

Since each of the adhesive tapes of Example 1, Example 2, and Comparative Example 1 and Comparative Example 2 has adhesiveness at room temperature, the adhesive tape can be easily adhered to the adherend. About each of these adhesive tapes, the solvent insoluble component, 90 degree peeling adhesive strength, and soldering heat resistance of the adhesive agent after hardening by heat processing are investigated by the following method. These results are as shown in Table 1. In addition, the value in [] of a solvent insoluble component is shown in Table 1 with reference to the solvent insoluble component before hardening by heat processing.

<Solvent insoluble component>

From the adhesive tape after hardening by the state before hardening or 150 degreeC x 1 hour of heat processing, the quantity which a pressure-sensitive adhesive becomes about 2.0 g is extract | collected, and it weighs precisely. It is filled in a precisely weighed cylindrical filter paper and extracted by Soxhlet extractor (extraction solvent: ethyl acetate, extraction conditions: 24 hours at 80 to 90 ° C). After the extraction treatment, the cylindrical filter paper is taken out and the dry weight of the residue is measured. The ratio of dry weight to weight of the collected sample is taken as the solvent insoluble component (% by weight).

<90 ° peeling adhesive strength>

An adhesive tape having a width of 10 mm and a length of 50 mm is adhered to a polyimide film having a thickness of 25 μm, which is attached to a glass epoxy plate having a thickness of 1 mm. The sample is pressed under a pressurized condition of 150 ° C. × 5 kg / cm 2 × 5 minutes, cured by heat treatment of 150 ° C. × 1 hour, and then left for 30 minutes under atmospheric conditions of a temperature of 23 ° C. and a relative humidity of 65%. Then, a tensile test is performed by pulling the polyimide film in the 90 ° direction at a tensile speed of 50 mm / min from the surface of the glass epoxy plate at 23 ° C. atmospheric conditions. From the obtained chart (strength vs. time), the center value of the strength variation is 90 ° peeling adhesive strength.

<Soldering heat resistance>

A laminated sheet [CCL] (rolled copper foil / adhesive / cafton film: 35 μm / 15 μm / 25 μm) bonded with a glass epoxy plate of 1 mm thickness and copper was used as an adhesive tape to prevent bubbles from entering between the two plates. Bond. The sample cut | disconnected this to the rectangle of length 30mm was crimped | pressurized on pressurization conditions of 150 degreeC * 5 kg / cm <2> * 5 minutes, and it hardened | cured by heat processing of 150 degreeC * 1 hour, and then put a glass epoxy plate up and to 260 degreeC Treat for 30 seconds while floating in the molten solder bath. The sheet bonding state after the treatment was visually observed to determine the foaming of the adhesive and the presence of adhesion abnormalities (floating state, wrinkles, peeling, misalignment), and 0: no change or abnormality. X: It evaluates as a change and abnormality.

From the results of Table 1 above, it was found that the adhesive tapes of Examples 1 and 2 of the present invention had many solvent-insoluble components after curing by heat treatment, and had a high 90 ° peeling adhesive strength, so that the soldering heat resistance was good. . On the other hand, since the adhesive tape of Comparative Example 1 is not a thermosetting type, there are few solvent insoluble components, and both the 90 ° peeling adhesive strength and the soldering heat resistance are inferior, and the adhesive tape of Comparative Example 2 is 90 as the thermosetting type. Good results are obtained with the peel adhesive strength, but the soldering heat resistance is unsatisfactory.

Subsequently, for each of the adhesive tapes of Examples 1, 2, and Comparative Example 2, after storage for 90 days at atmospheric conditions of a temperature of 23 ° C. and a relative humidity of 65% as a storage stability test, peeling 90 ° in the same manner as above. Investigate adhesive strength and soldering heat resistance. As a result, both characteristics of the adhesive tapes of Example 1 and Example 2 of the present invention are almost the same as before storage. On the other hand, the adhesive tape of the comparative example 2 has not only solder heat resistance but 90 degree peeling adhesive strength falls significantly, and cannot actually use it.

As described above, the present invention prepares a specific photopolymerizable composition comprising an epoxy resin and a monoethylenically unsaturated acid, and reacts them after photopolymerization, which is tacky at room temperature so that it can be easily adhered to the adherend, and is also short-term by heating. Thermosetting type pressure-sensitive adhesive with excellent heat resistance and excellent storage stability, which is resistant to use at a high temperature of 100 ° C. or higher, or in a soldering process. Adhesive sheets, such as a form, can be provided.

Claims (16)

100 parts by weight of a monomer mixture (a) consisting of 70 to 99% by weight of (meth) acrylic acid alkyl ester having 2 to 14 carbon atoms in its alkyl group and 1 to 30% by weight of monoethylenically unsaturated acid copolymerizable therewith, 0.02 to 5 parts by weight of a multifunctional (meth) acrylate (b) as a crosslinking agent, 0.01 to 4 parts by weight of the photopolymerization initiator (c) and A thermosetting pressure-sensitive adhesive, comprising: 5 to 30 parts by weight of an epoxy resin (d), and a photopolymerization product of a composition that does not contain a curing agent of an epoxy resin as component (d). The method of claim 1 wherein the (meth) acrylic acid alkyl ester is ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate and isononyl ( Thermosetting pressure-sensitive adhesive, characterized in that at least one selected from the group consisting of meth) acrylate. The thermosetting pressure-sensitive adhesive according to claim 1, wherein the monoethylenically unsaturated acid is at least one selected from the group consisting of (meth) acrylic acid, itaconic acid and 2-acrylamide propanesulfonic acid. The thermosetting pressure-sensitive adhesive according to claim 1, wherein the epoxy resin is at least one selected from the group consisting of bisphenol epoxy resins, phenolic epoxy resins and halogenated bisphenol epoxy resins. 70 to 99% by weight of (meth) acrylic acid alkyl ester and vinyl monomer having an average of 2 to 14 carbon atoms in the alkyl group [However, the amount of the vinyl monomer is 30% by weight based on the total amount of the (meth) acrylic acid alkyl ester and vinyl monomer. % By weight or less] and 100 parts by weight of the monomer mixture (a) consisting of 1 to 30% by weight of a monoethylenically unsaturated acid copolymerizable therewith, 0.02 to 5 parts by weight of a multifunctional (meth) acrylate (b) as a crosslinking agent, 0.01 to 4 parts by weight of the photopolymerization initiator (c) and A thermosetting pressure-sensitive adhesive, comprising: 5 to 30 parts by weight of an epoxy resin (d) and a photopolymerization product of a composition that does not contain a curing agent for an epoxy resin as component (d). The (meth) acrylic acid alkyl ester according to claim 5, wherein the (meth) acrylic acid alkyl ester is ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate and isononyl ( Thermosetting pressure-sensitive adhesive, characterized in that at least one selected from the group consisting of meth) acrylate. 6. The thermosetting pressure sensitive adhesive according to claim 5, wherein the monoethylenically unsaturated acid is at least one selected from the group consisting of (meth) acrylic acid, itaconic acid and 2-acrylamide propanesulfonic acid. 6. The thermosetting pressure sensitive adhesive according to claim 5, wherein the epoxy resin is at least one selected from the group consisting of bisphenol epoxy resins, phenolic epoxy resins and halogenated bisphenol epoxy resins. 100 parts by weight of a monomer mixture (a) consisting of 70 to 99% by weight of (meth) acrylic acid alkyl ester having 2 to 14 carbon atoms in its alkyl group and 1 to 30% by weight of monoethylenically unsaturated acid copolymerizable therewith, 0.02 to 5 parts by weight of a multifunctional (meth) acrylate (b) as a crosslinking agent, 0.01 to 4 parts by weight of the photopolymerization initiator (c) and A thermosetting pressure-sensitive adhesive layer comprising the photopolymerization product of the composition containing 5 to 30 parts by weight of the epoxy resin (d) and not containing the curing agent for the epoxy resin as component (d) is formed on one or both sides of the substrate. Adhesive sheets, characterized in that there is. The method of claim 9, wherein the (meth) acrylic acid alkyl ester is ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate and isononyl ( Adhesive sheet, characterized in that at least one selected from the group consisting of meth) acrylate. The adhesive sheet according to claim 9, wherein the monoethylenically unsaturated acid is at least one selected from the group consisting of (meth) acrylic acid, itaconic acid and 2-acrylamide propanesulfonic acid. The adhesive sheet according to claim 9, wherein the epoxy resin is at least one selected from the group consisting of bisphenol epoxy resins, phenolic epoxy resins and halogenated bisphenol epoxy resins. 70 to 99% by weight of (meth) acrylic acid alkyl ester and vinyl monomer having an average of 2 to 14 carbon atoms in the alkyl group [However, the amount of the vinyl monomer is 30% by weight based on the total amount of the (meth) acrylic acid alkyl ester and vinyl monomer. 100 parts by weight of a monomer mixture (a) consisting of 1 to 30% by weight of a monoethylenically unsaturated acid copolymerizable therewith, 0.02 to 5 parts by weight of a multifunctional (meth) acrylate (b) as a crosslinking agent, 0.01 to 4 parts by weight of the photopolymerization initiator (c) and A thermosetting pressure-sensitive adhesive layer comprising the photopolymerization product of the composition containing 5 to 30 parts by weight of the epoxy resin (d) and not containing the curing agent for the epoxy resin as component (d) is formed on one or both sides of the substrate. Adhesive sheets, characterized in that there is. The method of claim 13, wherein the (meth) acrylic acid alkyl ester is ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate and isononyl ( Adhesive sheet, characterized in that at least one selected from the group consisting of meth) acrylate. The adhesive sheet according to claim 13, wherein the monoethylenically unsaturated acid is at least one selected from the group consisting of (meth) acrylic acid, itaconic acid and 2-acrylamide propanesulfonic acid. The adhesive sheet according to claim 13, wherein the epoxy resin is at least one selected from the group consisting of bisphenol epoxy resins, phenolic epoxy resins and halogenated bisphenol epoxy resins.