JP2500952B2 - Curable adhesive tape or sheet - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has a property as a pressure-sensitive adhesive that exhibits tackiness at the time of bonding and easily adheres to various adherends. The present invention relates to a curable pressure-sensitive adhesive tape or sheet that exhibits adhesive strength.

[0002]

2. Description of the Related Art A curable pressure-sensitive adhesive tape or sheet that has tackiness when bonded and can be easily temporarily adhered to an adherend and gradually hardens after being adhered to has a strong adhesive force Moisture-curing type which is cured by the humidity of the substrate or the moisture of the adherend (Japanese Patent Publication No. 47-44017, Japanese Patent Publication No. 49-5895, Japanese Patent Publication No. 54-64536, Japanese Patent Publication No. 58-17).
No. 1460, No. 59-58071, No. 61-145268, No. 61-14828.
No. 1), a thermosetting type that is cured by heat (Japanese Patent Publication No. 50-12).
No. 464, No. 51-6235, No. 5235
4-102335, JP-B-55-8113, JP-B-59-14508, JP-A-59-10.
8072, JP-A-60-217283, JP-A-61-81467), light-curable photo-curing type (JP-A-56-120786, JP-A-57-15).
9864, JP60-69178A, JP61-162574A, and an anaerobic curing type that cures by blocking air (JP-B-58-12918, JP-A-59-199784). Publication, JP-A-59-
199785, JP 60-6773, JP 60-11568, and JP 60-13868.
Issue gazette).

However, any curable pressure-sensitive adhesive tape or sheet has a serious problem. That is, the moisture-curing type needs to be stored in a dry state until it is used, and requires special equipment for manufacturing. The thermosetting type cannot be applied to heat-sensitive materials, and the photocuring type can only be used with a tape using a transparent film that transmits light. The anaerobic curable type requires a storage state that is always in contact with air, and if the curability is improved, the storage stability is inferior, so it is difficult to balance the curability and the storage ability.

Originally, the most ideal curable pressure-sensitive adhesive tape or sheet is one which is cured and adhered only by being attached without applying any energy. The above-mentioned moisture-curing type and anaerobic-curing type correspond to this, but it is very difficult to express such a function with a normal adhesive tape in terms of storability, and even if it is possible, the balance with curability is insufficient. I can only do something.

In order to solve such a problem, a curable pressure-sensitive adhesive tape of a type in which two tapes are attached at the time of use and the reactive components are contained in different tapes (Japanese Patent Laid-Open No. 58-58).
No. 67777) is proposed. However, the design of the resin structure is very important in order to react easily at room temperature and to exert a strong adhesive strength, and conventional curable pressure-sensitive adhesive resins exhibit satisfactory performance. You cannot do it. The problem with the above-mentioned double-bonding type curable adhesive tape or sheet using a conventional resin is that the adhesive property during bonding and the adhesive property after bonding and curing are poorly balanced, and in most cases the adhesive property is If the adhesive strength was good, the adhesive strength was poor, and if the adhesive strength was high, the initial adhesive properties were poor. Therefore, even if both the preservability and the curability are achieved by adopting a double-bonded tape structure, it is possible to obtain a curable pressure-sensitive adhesive tape having an excellent balance of adhesive properties and adhesive properties without proper resin design. There wasn't.

[0006]

DISCLOSURE OF THE INVENTION The present invention is a conventional two-sided curable adhesive tape produced without considering the structure and molecular weight of the resin, which has a poor balance between adhesive properties and adhesive strength after curing. By providing a resin design that eliminates the above defects and gives due consideration to the balance between the two, it is possible to provide a curable pressure-sensitive adhesive tape that has good preservability and sufficiently excellent adhesive properties before curing and adhesive strength after curing. is there.

[0007]

The present invention is directed to an unsaturated polyester oligomer (A) obtained by reacting a cyclic acid anhydride (a) with an epoxide (b) having an ethylenically unsaturated group, and an adhesive acrylic polymer. A curable resin composition composed of (B) and a pressure-sensitive adhesive (I) containing a polymerization initiator (C) selected from an organic peroxide or an azo compound were coated on a releasable support. Coating a pressure-sensitive adhesive tape or sheet (I) and a pressure-sensitive adhesive (II) obtained by mixing the curable resin composition with a polymerization accelerator (D) of the unsaturated polyester oligomer (A) on a releasable support. A curable pressure-sensitive adhesive tape or sheet comprising the above-mentioned pressure-sensitive adhesive tape or sheet (II), which can be cured by stacking the pressure-sensitive adhesive (I) and the pressure-sensitive adhesive (II).

In the present invention, when the polyester oligomer (A) is obtained, a hydroxyl group or a primary, secondary, or tertiary amino group is used for the purpose of smooth progress of the initial reaction and adjustment of the molecular weight of the polyester oligomer (A) produced. It is necessary to use a compound having a functional group, such as a group, which is the starting point of the reaction. Among these, it is generally preferable to use a compound having a hydroxyl group because of the properties of the raw materials and products and the ease of control during the reaction.

In the present invention, the compound having a hydroxyl group is methanol, ethanol, 1-propanol, 2-
Aliphatic saturated alcohols such as propanol, 1-butanol, 2-butanol, pentanol, hexanol,
Aliphatic unsaturated alcohols such as allyl alcohol, crotyl alcohol, propargyl alcohol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl ( (Meth) acrylate, (meth) acrylate having a hydroxyl group such as N-methylolacrylamide or (meth) acrylamide, alicyclic alcohol such as cyclopentanol or cyclohexanol, aromatic alcohol such as benzyl alcohol or cinnamyl alcohol, full Heterocyclic alcohols such as furyl alcohol and tetrahydrofurfuryl alcohol, ethylene glycol, propylene glycol, 1,4-butylene glycol, butenediol, hexanedio , Cyclohexanediol, bisphenol A, diols such as diethylene glycol,
Triols such as glycerin and trimethylolpropane, phenol, o-cresol, m-cresol, p
-A compound having an alcoholic or phenolic hydroxyl group such as phenols such as cresol may be used.

However, among these, the above-mentioned diol and 2
-Hydroxy-n-butyric acid, 3-hydroxy-n-butyric acid,
Compounds having both a carboxyl group and a hydroxyl group such as p-hydroxybenzoic acid, hydroxypivalic acid, salicylic acid, vanillic acid and 12-hydroxystearic acid, or ethanolamine, 1-amino-2-propanol, o-aminophenol, m- Aminophenol, p
Compounds having two or more functional groups are preferred, such as compounds having an amino group and a hydroxyl group at the same time, such as aminophenol.

In the present invention, the cyclic acid anhydride (a) is an intramolecular anhydride of polyvalent carboxylic acid, and is a saturated or unsaturated aliphatic polyvalent carboxylic acid anhydride or alicyclic polyvalent carboxylic acid anhydride. , Aromatic polycarboxylic acid anhydrides, etc., or some of these substituted with saturated or unsaturated hydrocarbon groups, aromatic ring groups, halogen atoms, heterocyclic groups, etc. Is succinic anhydride, phthalic anhydride, maleic anhydride, itaconic anhydride, glutaric anhydride, dodecenyl succinic anhydride, chlorendecic anhydride, pyromellitic anhydride, trimellitic anhydride, cyclopentanetetracarboxylic dianhydride, Hexahydrophthalic anhydride, Methylhexahydrophthalic anhydride, Tetramethylene maleic anhydride, Tetrahydrophthalic anhydride, Methyltetrahydro None Phthalic acid, endomethylene tetrahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride, 5- (2,5-dioxo-tetrahydroxy-furyl) -3-methyl-3-cyclohexene-1,
2-dicarboxylic acid anhydride, methyl nadic acid anhydride, benzophenone tetracarboxylic acid anhydride, glycerol tris (anhydro trimellitate), ethylene glycol bis (anhydro trimellitate) and the like. Among them, it is preferable to use dicarboxylic acid or tricarboxylic acid anhydride which does not form a crosslinked structure.

In the present invention, as the epoxide (b) having an ethylenically unsaturated group, glycidyl (meth) acrylate, glycidyl cinnamate, allyl glycidyl ether, vinyl cyclohexene monoepoxide,
1,3-Butadiene monoepoxide and the like, which may be substituted with saturated or unsaturated hydrocarbon groups, aromatic ring groups, halogen atoms, heterocyclic groups and the like.

A polyester oligomer (A) having an ethylenically unsaturated group is obtained by reacting the compound having a hydroxyl group with the cyclic acid anhydride (a) and the epoxide (b). The reaction is carried out in the presence or absence of a suitable solvent, N, N-dimethylbenzylamine, triethylamine, tributylamine, N, N-diethylaniline,
Radical polymerization of hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, p-benzoquinone, etc. to protect ethylenically unsaturated groups by using a tertiary amine such as N, N-dimethylaniline as a catalyst as necessary. It can be performed with an inhibitor added.

In the reaction, the hydroxyl group of the compound having a hydroxyl group and the acid anhydride group of the cyclic acid anhydride (a) first react preferentially, and then the carboxyl group generated by this reaction and the epoxy group of the epoxide (b) are reacted. Reacts with groups to form secondary hydroxyl groups. Further, the generated hydroxyl group and cyclic acid anhydride (a)
The reaction with the acid anhydride group of
A reaction similar to the above can proceed.

In this reaction, the amount of the cyclic acid anhydride (a) and the epoxide (b) reacted with the amount of the compound having a hydroxyl group is adjusted so that the compound having a hydroxyl group is terminated. Polyester oligomers (A) of desired length having a number of ethylenically unsaturated groups can be prepared. When the cyclic acid anhydride (a) is a dicarboxylic acid anhydride, the ratio of each compound is 1 to 20 mol of the cyclic acid anhydride (a) to 1 mol of the compound having a hydroxyl group, and the epoxide (b). ) 1
It is preferable that the cyclic acid anhydride (a) and the epoxide (b) are reacted at a ratio of 20 mol, and at a ratio of substantially equimolar. When the cyclic acid anhydride (a) is a tricarboxylic acid, 1 to 10 moles of the cyclic acid anhydride (a) and 1 to 2 moles of the epoxide (b) relative to 1 mole of the compound having a hydroxyl group.
It is preferable to react the epoxide (b) at a ratio of 0 mol, and at a ratio of about 1 to 2 mol with respect to 1 mol of the cyclic acid anhydride (a). When the amount of cyclic acid anhydride (a) or epoxide (b) reacted with 1 mol of a compound having a hydroxyl group is less than 1 mol, the resulting polyester oligomer (A) has a low molecular weight and has a hydroxyl group. Due to residual compounds, the required properties cannot be obtained. On the other hand, when the amount of the cyclic acid anhydride (a) or the epoxide (b) exceeds 20 mol, it becomes difficult to control the reaction or the molecular weight becomes too high, so that the necessary properties tend not to be obtained. There is.

As described above, the polyester oligomer (A) obtained here can use various compounds as a raw material for the compound having a hydroxyl group, the cyclic acid anhydride (a) and the epoxide (b). ， By changing the ratio, it is possible to make a product of any length with a relatively uniform molecular weight. It is also possible to use a mixture of two or more kinds of each compound. Therefore, it is possible to prepare oligomers having various characteristics depending on the purpose of use. Therefore, when it is added to a curable pressure-sensitive adhesive, not only the function as a curable component but also the one functioning as a tackifier, the one acting as a filler, and the type of oligomer and its blending ratio are determined according to the application. By varying it is possible to give the composition the necessary properties.

In the present invention, the adhesive acrylic polymer (B) has a functional group such as a hydroxyl group, a tertiary amino group, a carboxyl group, an amide group, an N-substituted amide group and a nitrile group, and is generally an adhesive agent. It is used as an acrylic resin for automobiles. Further, even if the polymer alone has poor adhesiveness, a polymer showing good adhesive properties by adding the polyester oligomer (A) or other resin can be used as the polymer (B) of the present invention. The acrylic polymer having these functional groups includes one or several kinds of monomers having a hydroxyl group, a tertiary amino group, a carboxyl group, an amide group, an N-substituted amide group, a nitrile group, an alkyl (meth) acrylate, Examples thereof include copolymers with monomers such as vinyl acetate, vinyl propionate, vinyl ether and styrene.

Examples of the monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and N-methylolacrylamide. , Allyl alcohol and the like, and examples of the monomer having a tertiary amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide and the like. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and citraconic acid. Examples of the monomer having an amide group or an N-substituted amide group include acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide,
Examples include N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-tert-butylacrylamide, N-octylacrylamide, diacetone acrylamide. Examples of the monomer having a nitrile group include acrylonitrile, methacrylonitrile, crotononitrile, and fumaronitrile. Further, as the alkyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate,
There are alkyl (meth) acrylates such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and octyl (meth) acrylate. In addition, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, etc., and alkyl (meth) acrylates in which the alkyl group is substituted with an aromatic ring group, heterocyclic group, halogen atom, etc. The monomers used in the synthesis of acrylic polymers can also be used in the synthesis of the polymers of the invention.

The reaction is an ordinary radical polymerization, and there is no limitation on the reaction method, and it can be carried out by a known polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization, etc., but it is easy to control the reaction. Solution polymerization is preferred because it can be directly transferred to the next operation. As the solvent, any solvent such as methyl ethyl ketone, methyl isobutyl ketone, toluene, cellosolve, ethyl acetate, and butyl acetate may be used as long as the resin of the present invention can be dissolved. A single solvent or a mixture of a plurality of solvents may be used. Known polymerization initiators used in the polymerization reaction include organic peroxides such as benzoyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide, lauroyl peroxide, and azo initiators such as azobisisobutyronitrile. Anything can be used, and there is no particular limitation.

A curable adhesive resin can be obtained by mixing the unsaturated polyester oligomer (A) obtained by each reaction with the adhesive acrylic polymer (B). It is sufficient that the mixture is stirred at room temperature until the mixture is apparently uniform. However, in order to further enhance the mutual mixing state, the mixture may be heated and stirred at a temperature lower than the boiling point of the solvent.

In the present invention, since the epoxide (b) having an ethylenically unsaturated group is used, the polyester oligomer (A) has an unsaturated group, and the polymerization initiator (C) or the polymerization accelerator (D) is used. When used together, polymerization can be initiated by simply leaving it at room temperature, and solidification can be easily achieved.

As the polymerization initiator (C), di-tert
Dialkyl peroxides such as butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, diacetyl peroxides such as acetyl peroxide, lauroyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, 3 , 3, 5
-Ketone peroxides such as trimethylcyclohexanone peroxide and methylcyclohexanone peroxide, peroxyketals such as 1,1-bis (tert-butylperoxy) cyclohexane, ter
t-butyl hydroperoxide, cumene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, p-menthane hydroperoxide,
Diisopropylbenzene hydroperoxide, 2,5
-Hydroperoxides such as dimethylhexane-2,5-dihydroperoxide, tert-butylperoxyacetate, tert-butylperoxy-2-
There is no particular limitation as long as it is a known one such as organic peroxides such as peroxyesters such as ethylhexanoate and tert-butylperoxybenzoate, azo compounds such as azobisisobutyronitrile and azobisvaleronitrile. Absent. The polymerization initiator (C) is used in an amount of usually 0.1 to 15 parts by weight, preferably 0.5 to 5 parts by weight, based on 100 parts by weight of the pressure-sensitive adhesive composition of the present invention.

Examples of the polymerization accelerator (D) include N, N-dimethylbenzylamine, triethylamine, tributylamine, N, N-diethylaniline, N, N-dimethylaniline, N-phenyldiethanolamine and N-phenyldiisopropanolamine. , Tertiary amines such as dimethyl-p-toluidine, triethanolamine and 4-phenylmorpholine, lithium, calcium, strontium, barium, cerium, zirconium, vanadium, molybdenum, manganese, iron, cobalt, nickel,
Metals such as copper, zinc, tin and lead Laurates, naphthenates, octylates, oleates, octenoates and other fatty acid salts, resin salts such as rosin salts, chelates such as acetylacetonate complex salts One or more metal compounds selected from compounds and the like can be used as the promoter. In particular, in the case of anaerobic curing, either a tertiary amine or a metal compound is used as a promoter,
Alternatively, it is preferable to use both of them together with an organic peroxide. Of these accelerators, the tertiary amine is usually 1 to 100 parts by weight based on 100 parts by weight of the organic peroxide, and the metal compound is based on 100 parts by weight of the organic peroxide.
It is used in a ratio of 0.01 to 10 parts by weight.

In the present invention, in order to improve the adhesive property before curing, and particularly to increase the cohesive force, polyisocyanate (E) is further added to partially crosslink the adhesive acrylic polymer (B). Such polyisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, 1,5-naphthalene diisocyanate,
There are diisocyanates such as isophorone diisocyanate, lysine diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, etc., or both ends isocyanate adducts of these with glycols or diamines, or a mixture thereof, and necessary Depending on the requirements, trifunctional or higher functional polyisocyanates such as triphenylmethane triisocyanate and polymethylene polyphenyl isocyanate can also be used as a mixture with diisocyanates.

In order to adjust the adhesive property before curing and the adhesive force after curing, a polyester oligomer synthesized by using an epoxide having no ethylenically unsaturated group or an ethylenically unsaturated group used in the present invention is used. An oligomer synthesized by using both the epoxide (b) and the epoxide having no unsaturated group can be used as the polyester oligomer (A) of the present invention. However, when an oligomer having no ethylenically unsaturated group is used, it must be used in combination with an oligomer having an unsaturated group. Examples of epoxides having no ethylenically unsaturated group include epichlorohydrin, phenylglycidyl ether, styrene oxide, cyclohexene oxide, and butene oxide.

In order to further strengthen the adhesive strength after curing, the curable pressure-sensitive adhesive composition of the present invention further comprises a (meth) acryloyl group other than the unsaturated polyester oligomer (A) used in the present invention. A monomer or oligomer having an ethylenically unsaturated group can be added. Examples of such monomers or oligomers include styrene, alkyl (meth) acrylate, (meth) acrylic acid, polyhydric alcohol poly (meth) acrylate, epoxy poly (meth) acrylate, oligoester poly (meth) acrylate, polyurethane poly ( (Meth) acrylate, diallyl phthalate, diallyl isophthalate and the like.
The amount of these monomers and oligomers used is 60% by weight or less based on the total solid content of the curable pressure-sensitive adhesive composition of the present invention. If it exceeds 60% by weight, the adhesive property before curing, especially the cohesive strength, becomes extremely poor.

The curable pressure-sensitive adhesive composition of the present invention contains pigments, dyes, inorganic fillers, organic solvents, silver powder, copper powder, nickel powder, and other metal powders, if necessary, as long as its performance is not impaired. Carbon black, graphite, tackifiers such as xylene resin and rosin resin, and silane coupling agents can be added.

The curable pressure-sensitive adhesive composition of the present invention is a film or sheet having a high releasability such as silicon-treated paper or cloth, a metal foil, a plastic film, etc., as in the usual production method of pressure-sensitive adhesive tapes and sheets. Alternatively, it is coated on a tape or the like, dried to remove the organic solvent if necessary, and cut if necessary to form a double-sided adhesive sheet or tape. In addition, for reinforcement and impact mitigation, it can be lined with non-woven fabric such as rayon and nylon, cloth such as gauze, foam such as urethane and acrylic.

This curable pressure-sensitive adhesive tape sheet is prepared by laminating the tapes (I) and (II) in advance just before use.
It is used in the same manner as a normal adhesive tape, or the tapes of (I) and (II) are attached to the adherends respectively, and the adherends are later adhered to each other. Immediately after the release paper is peeled off, the adhesive surface is easily adhered because the adhesive is made of a resin having a low glass transition point. Then, the low-molecular-weight polymerization initiator and the polymerization accelerator contained in the pressure-sensitive adhesive layer diffuse with the passage of time and act on the reactive resin to promote the reaction, thereby curing the pressure-sensitive adhesive. In any case, the reaction starts from the time when the tapes of (I) and (II) are attached, and gradually solidifies to reach a large adhesive strength.

The curable resin composition of the pressure-sensitive adhesive applied to (I) and (II) comprises the unsaturated polyester oligomer (A) and the pressure-sensitive acrylic polymer (B),
It is not always necessary that (I) and (II) have exactly the same composition. Depending on the purpose of use, the unsaturated polyester oligomer (A) and the tacky acrylic polymer (B) may have different mixing ratios or different monomer compositions. Further, polyisocyanate (E) is added to (I) (I
It is possible to mix only one of the adhesives in I).

[0031]

EXAMPLES The present invention will be described below with reference to examples. In the examples, “part” means “part by weight” and “%” means “% by weight”.

Synthesis of polyester oligomer

Oligomer 1 Ethylene glycol 3.4 parts Hexahydrophthalic anhydride 50.3 parts Glycidyl methacrylate 46.3 parts N, N-Dimethylbenzylamine 0.9 parts Hydroquinone 0.2 parts Ethyl acetate 25.0 parts

Oligomer 2 ethylene glycol 2.5 parts succinic anhydride 40.3 parts glycidyl methacrylate 57.2 parts N, N-dimethylbenzylamine 1.1 parts hydroquinone 0.2 parts ethyl acetate 25.0 parts

The above compositions were mixed and reacted in an air atmosphere at 80 ° C. for 10 hours, and after cooling, ethyl acetate 1 was added.
Twenty-five parts were added to obtain two kinds of polyester oligomer solutions (solid content: 40%).

Synthesis of acrylic polymer

Polymer 1 Butyl acrylate 93.5 parts Acrylic acid 1.4 parts 2-Hydroxyethyl methacrylate 5.1 parts Azobisisobutyronitrile 0.2 parts Ethyl acetate 150.0 parts

Polymer 2 Butyl acrylate 92.0 parts Acrylamide 2.8 parts 2-Hydroxyethyl methacrylate 5.2 parts Azobisisobutyronitrile 0.2 parts Ethyl acetate 150.0 parts

To 125 parts of the mixture of each composition heated to 80 ° C., 125 parts of the mixture of the same composition was dropped, and after completion of the dropping, heated and refluxed for 12 hours, cooled, and a solution of two kinds of acrylic polymer. (Solid content 40%) was obtained.

[0040]

Example 1 45.8 parts of a solution of an oligomer 1 and 54.2 parts of a solution of a polymer 1 were thoroughly mixed to obtain 10 parts of this resin solution.
0.4 part of benzoyl peroxide was evenly mixed with 0 part of the mixture, and the mixture was applied onto a silicone-treated polyethylene terephthalate film so that the thickness after drying was 30 μm, and dried at 60 ° C. for 3 minutes. Adhesive sheet (I)
I got On the other hand, a pressure-sensitive adhesive sheet (II) was obtained in the same manner as in the above pressure-sensitive adhesive except that 0.4 part of benzoyl peroxide was replaced with 0.4 part of diethanolaniline.

Table 1 shows the measurement results of the adhesive properties (peeling adhesive strength, tack, holding power) before curing and the shear adhesive strength after curing of the obtained adhesive sheet. Curing is (I) (I
This was done by sticking together the adhesive sheet I) and leaving it for a while. The measurement was performed as follows.

(1) Peeling adhesive strength before curing A polyethylene terephthalate sheet having a thickness of 50 μm was adhered to the adhesive surface of the obtained adhesive sheet, cut into a width of 25 mm, and then the polyethylene terephthalate film was peeled off to form. Adhesive surface is adhered to a # 280 sandpaper-polished stainless steel plate (SUS304), left for 30 minutes, and then peeled at 180 degrees at a peeling speed of 300 mm / min under conditions of 25 ° C and 65% relative humidity. Was measured.

(2) Tack before curing The obtained adhesive sheet was set on a slope having an inclination angle of 30 degrees, and the running distance was 10c under conditions of 25 ° C and relative humidity of 65%.
Roll a stainless steel ball at m and sticky surface 1
The number of the highest ball that stopped within 0 cm was measured. The number of the ball is represented by 32 times as many as 31 kinds of "name of ball" from 1/16 to 1.

(3) Holding power before curing A polyethylene terephthalate sheet having a thickness of 50 μm is attached to the adhesive surface of the obtained adhesive sheet, cut into a size of width 25 mm and length 100 mm, and then a polyethylene terephthalate film. The 25 mm wide and 25 mm wide part of the resulting adhesive surface was affixed to a stainless steel plate (SUS304) polished with sandpaper # 280, and the adhesive sheet was a stainless steel plate at 40 ° C and a load of 1 kg. The time (seconds) until it fell further was measured.

(4) Shear adhesive strength after curing: 10 mm in length and 10 mm in width at one end of each of two aluminum plates having a length of 50 mm, a width of 10 mm and a thickness of 0.5 mm.
The adhesive surfaces of the adhesive sheets (I) and (II) cut to each other were adhered, the polyethylene terephthalate film was peeled off, and the resulting adhesive surfaces of (I) and (II) were adhered to each other for 24 hours. Then, the shear strength was measured at a pulling rate of 5 mm / min under the conditions of 25 ° C. and relative humidity of 65%.

[0046]

Example 2 To the pressure-sensitive adhesive composition used for the pressure-sensitive adhesive tapes (I) and (II) of Example 1, 0.2 part of tolylene diisocyanate was further added to obtain pressure-sensitive adhesive sheets (I) and (II) in the same manner.
It was aged at 50 ° C for 3 days. With respect to the obtained pressure-sensitive adhesive sheet, the adhesive property before curing and the shear adhesive strength after curing were measured in the same manner as in Example 1. The results are shown in Table 1.

[0047]

Example 3 22.9 parts of the solution of the oligomer 2 and 77.1 parts of the solution of the polymer 2 were thoroughly mixed, and the resin solution 10
0.4 part of benzoyl peroxide and 0.2 part of tolylene diisocyanate were uniformly mixed with 0 part of the mixture to obtain a pressure-sensitive adhesive sheet (I) in the same manner as in Example 1.
Aged for days. On the other hand, a pressure sensitive adhesive sheet (II) was prepared in the same manner as in the above pressure sensitive adhesive except that 0.4 part of benzoyl peroxide was replaced with 0.4 part of diethanolaniline. With respect to the obtained pressure-sensitive adhesive sheet, the adhesive property before curing and the shear adhesive strength after curing were measured in the same manner as in Example 1. The results are shown in Table 1.

[0048]

Example 4 45.8 parts of a solution of oligomer 1 and 54.2 parts of a solution of polymer 1 were thoroughly mixed to obtain 10 parts of this resin solution.
Cumene hydroxyperoxide 0.4 against 0 parts
Parts, and 0.2 parts of tolylene diisocyanate are evenly mixed, and coated on a polyethylene-treated polyethylene terephthalate film so that the thickness after drying is 30 μm, and dried at 60 ° C. for 3 minutes to give an adhesive sheet. (I) was obtained and aged at 50 ° C. for 3 days. On the other hand, a pressure sensitive adhesive sheet (II) was obtained in the same manner as in the above except that 0.4 part of cumene hydroxyperoxide of the pressure sensitive adhesive was replaced with 0.4 part of diethanolaniline and 0.05 part of cobalt naphthenate.

[0049]

Example 5 In the adhesive sheet (I) of Example 4, 0.4 parts of cumene hydroxyperoxide was replaced with 0.4 part of lauryl peroxide, and the adhesive sheet (II) was prepared by removing diethanol from 0.05 part of cobalt naphthenate. Adhesive sheet (II) was operated in the same manner except that only 0.04 part of aniline was used.
I got

[0050]

[Table 1]

[0051]

As shown in Table 1, the curable pressure-sensitive adhesive tape (or sheet) of the present invention has a peel adhesion before curing of 1500 g / 25 mm or more, a tack of 7 or more, and a holding power of polyisocyanate. Even without it, it is 1000 seconds or more. Furthermore, the shear adhesive strength after curing is 30 Kg / cm ² or more, and the adhesive properties before curing and the adhesive strength after curing are excellent. In addition, the curable pressure-sensitive adhesive tape (or sheet) of the present invention is stored as two pressure-sensitive adhesive tapes until use, and components that cause a curing reaction do not work until the two pressure-sensitive adhesive tapes are bonded together. The storage stability, which was a problem with the adhesive tape, was significantly improved. Furthermore, by adding an appropriate amount of polyisocyanate, the cohesive force is improved, and the holding force is kept even after 24 hours without deteriorating the peeling adhesive force before tacking, tack, and shear adhesive force after curing. can do.

Thus, according to the present invention, when joining,
It has high adhesiveness, can be temporarily adhered to an adherend, does not require mechanical temporary fixing, shows a strong adhesive force after curing, and has an excellent balance between adhesive properties before curing and adhesive force after curing. Moreover, a curable pressure-sensitive adhesive tape (or sheet) having excellent storability has come to be obtained.

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Claims (2)

(57) [Claims] 1. A curing comprising an unsaturated polyester oligomer (A) obtained by reacting a cyclic acid anhydride (a) with an epoxide (b) having an ethylenically unsaturated group and an adhesive acrylic polymer (B). and sex resin composition, organic
A pressure-sensitive adhesive tape or sheet (I) obtained by coating a pressure-sensitive adhesive (I) containing a polymerization initiator (C) selected from organic peroxides or azo compounds on a releasable support, and the above curable resin composition. The above unsaturated polyester oligomer
Adhesive (II) prepared by blending (A) polymerization accelerator (D )
Comprising a pressure-sensitive adhesive tape or sheet (II) coated on a releasable support, the pressure-sensitive adhesive (I) and the pressure-sensitive adhesive (II)
A curable pressure-sensitive adhesive tape or sheet, which can be cured by stacking layers. 2. Adhesive (I) and / or adhesive
The curable resin composition of (II) further comprises polyisocyanate
Curing according to claim 1, characterized in that it contains (E).
Adhesive tape or sheet.