JP2743656B2 - Curable pressure-sensitive adhesive composition and sheet or tape using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a tacky property at the time of bonding and can be temporarily bonded to an adherend, and then hardened by heating or light irradiation or by simply bonding together to obtain a strong bond. A curable pressure-sensitive adhesive composition exhibiting power and suitable as a so-called pressure-sensitive adhesive, and a curable pressure-sensitive adhesive sheet or tape (hereinafter referred to as a “sheet”), which is produced by applying or impregnating the composition onto a substrate. Described).

[0002]

2. Description of the Related Art A curable pressure-sensitive adhesive sheet which is tacky at the time of bonding and can be easily temporarily adhered to an adherend, and gradually hardens after being adhered to exhibit a strong adhesive strength is provided with moisture in the air. And a moisture-curing type that cures with the moisture of the adherend (JP-B-47-4401)
No. 7, JP-B-49-5895, JP-A-54-5895.
No. 64536, JP-A-58-171460,
JP-A-59-58071, JP-A-61-1452
No. 68, JP-A-61-148281), a thermosetting type which cures with heat (Japanese Patent Publication No. 50-12264, JP-A-51-6235, JP-A-54-102335).
JP, JP-B-55-8113, JP-B-59-1
4508, JP-A-59-108072, JP-A-60-217283, and JP-A-61-8146.
No. 7), a photo-curing type that cures with light (Japanese Patent Laid-Open No. 56-12 / 1981).
No. 0786, JP-A-57-159864, JP-A-60-69178, and JP-A-61-16257.
No. 4), an anaerobic curing type which cures by blocking air (Japanese Patent Publication No. 58-12918, Japanese Patent Application Laid-Open No.
JP-A-199784, JP-A-59-199785, JP-A-60-6773, JP-A-60-115
No. 68, JP-A-60-13868). However, no matter which curing method is used, the most important thing for adhesives is to design a curable resin that satisfies both the adhesive properties before curing and the adhesive properties after curing.

[0003] Conventionally, as a curable pressure-sensitive adhesive composition,
It is known to add a reactive oligomer or monomer to a non-reactive or reactive adhesive polymer (JP-B-50-28970, JP-B-53-31898).
JP, JP-A-53-118439, JP-B-54
-28877, JP-A-60-69178,
JP-B-61-18591, JP-A-61-8327
No. 3, JP-A-61-83274, JP-A-61-83274
No. -101583, Japanese Patent Publication No. 1-36513,
(See Japanese Patent Publication No. 2-5791). However,
In these compositions, if the amount of reactive oligomers or monomers added is large to obtain sufficient adhesive strength after curing, the adhesive properties before curing, especially the cohesive strength, will decrease, and the time between application and curing will increase. There was a possibility that a shift or peeling could occur.
On the other hand, if the amount of the reactive oligomer or monomer added was reduced to improve the adhesive properties before curing, especially the cohesive strength, the curability was lowered and sufficient adhesive strength was not obtained. Even if the amount of reactive oligomer or monomer added is adjusted so that the balance between the adhesive properties before curing and the adhesive properties after curing is the best, both the adhesive properties before curing and the adhesive properties after curing are incomplete. No adhesive having satisfactory performance was obtained. As described above, no curable pressure-sensitive adhesive composition having sufficiently excellent both the pressure-sensitive adhesive property before curing and the adhesive property after curing has been developed.

Therefore, some of the present inventors have introduced a graft chain having a plurality of unsaturated groups into a polymer (JP-A-1-188508, JP-A-1-1-1).
JP-A-93314, JP-A-1-193315, JP-A-3-50213, JP-A-3-50214, JP-A-3-50215, JP-A-3-66779, JP-A-3-66780, JP-A-3-6678
No. 1, JP-A-3-66782, JP-A-3-6
No. 6783, JP-A-3-66784), and a curable pressure-sensitive adhesive composition which imparts curability to the polymer itself and has excellent adhesive properties before and after curing has been developed. Some problems remain in the synthetic surface and some of the adhesive properties of the hydrophilic resin. Since the synthesis of this resin is a reaction that introduces a graft chain into a polymer having a high molecular weight, the reaction rate is extremely slow. If the reaction is stopped, unreacted raw materials may cause odor problems and degrade performance. There was sex. Also, it was difficult to easily and stably produce a product having both excellent adhesive properties before curing and adhesive properties after curing.

[0005]

Since the synthesis of this resin is a reaction to a polymer, the reaction rate is extremely slow. If the reaction is stopped halfway, the problem of odor due to unreacted raw materials and the performance There was a possibility of deterioration. It has also been difficult to easily and stably produce a product having an excellent balance between adhesive properties and adhesive strength after curing.

The present invention improves the above-mentioned problems of the synthetic surface and the physical properties of the conventional curable pressure-sensitive adhesive composition, and provides a curable composition having sufficiently excellent adhesive properties before curing and adhesive strength after curing. An adhesive composition and a sheet or tape using the same are provided.

[0007]

The curable pressure-sensitive adhesive composition of the present invention comprises a compound (a) having an amino group and a cyclic acid anhydride (b) based on 100 parts by weight of the pressure-sensitive rubber-based polymer (A). ), And a curable polyester oligomer (B) obtained by reacting an epoxide (c) having an unsaturated group.
Is a curable pressure-sensitive adhesive composition containing 5 to 200 parts by weight. Sheets obtained using these compositions are excellent in both adhesive properties before curing and adhesive properties after curing.

The curable pressure-sensitive adhesive composition of the present invention may further comprise (1) a polymerization initiator (C) in addition to the pressure-sensitive rubber-based polymer (A) and the curable polyester oligomer (B). 0.1 to 5 parts by weight, based on 100 parts by weight of the total weight of the polymer (A) and the curable polyester oligomer (B), (2) the polyisocyanate (D), the adhesive acrylic polymer (A) and the curable polyester 0.1 to 5 parts by weight, based on 100 parts by weight of the total weight of the oligomer (B), (3) the tackifier (E), the total weight of the tacky acrylic polymer (A) and the curable polyester oligomer (B) A curable pressure-sensitive adhesive composition comprising one or more compounds selected from (1) to (3) out of 1 to 100 parts by weight, based on 100 parts by weight, is polymerized. Initiator ( When C) is added, curing can be rapidly performed, and when polyisocyanate (D) is added, the holding power is improved by the adhesive properties before curing, and the tackifier (E) When added, the adhesion to the plastic substrate is improved. In particular, in thermal curing, anaerobic curing, UV curing, etc. with a heating temperature of 150 degrees or less,
The reaction does not proceed without the polymerization initiator (C), and is added as an almost essential component to the curable pressure-sensitive adhesive composition of the present invention. By applying or impregnating the substrate with the curable pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet excellent in both pressure-sensitive adhesive properties before curing and adhesive properties after curing can be obtained.

The curable pressure-sensitive adhesive composition of the present invention is similar to the conventional one in that it is a blend of a pressure-sensitive adhesive polymer and a reactive oligomer. However, conventional blend-type adhesives cancel out the properties of both blended and cannot be excellent. On the other hand, when the adhesive rubber-based polymer (A) and the curable polyester oligomer (B) of the present invention are used as a curable adhesive composition, the compatibility between the two is appropriately adjusted and the sea-island shape is obtained. Can be formed. For this reason, the component that develops curability and the component that develops tackiness before curing function independently of each other, providing excellent adhesive properties before curing and excellent after curing without compromising the properties of both. Is characterized by exhibiting the adhesive properties of

When the polyisocyanate (D) is added, a crosslinked structure is formed partially between the functional groups contained in the adhesive rubber-based polymer (A) and the curable polyester oligomer (B), While maintaining the sea-island-like microphase-separated structure, the cohesive force before curing can be significantly improved without impairing the curability. When the tackifier (E) is added, the tackifier (E) is further added to the sea-island-like microphase separation structure formed by the tacky rubber-based polymer (A) and the curable polyester oligomer (B). ) Also causes microphase separation, forming a very complicated microphase separation structure. As a result, the adhesive properties before curing and the adhesive properties after curing obtained by the microphase-separated structure composed of the adhesive rubber-based polymer (A) and the curable polyester oligomer (B) are not impaired. By the effect of the tackifier (E), a curable pressure-sensitive adhesive composition having excellent adhesion to a plastic substrate can be obtained.

The adhesive rubber-based polymer (A) includes adhesive acrylic polymers and natural and synthetic rubbers used as rubber-based resins for adhesives.
This is a so-called elastomer.

For the synthesis of the tacky acrylic polymer, a monomer having various functional groups and a long-chain alkyl (meth) acrylate as a main component can be used. As long-chain alkyl (meth) acrylate, butyl (meth)
Acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth)
There are alkyl (meth) acrylates such as acrylate and octyl (meth) acrylate. In addition, methyl (meth) acrylate, ethyl (meth) acrylate,
There are alkyl (meth) acrylates such as propyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. In addition, monomers generally used for the synthesis of acrylic polymers, such as alkyl (meth) acrylates in which the alkyl group is substituted with an aromatic ring group, a heterocyclic group, a halogen atom, etc., can be used for the synthesis of the adhesive acrylic polymer of the present invention. It can also be used. 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, N-methylol acrylamide, and allyl alcohol And as monomers having a tertiary amino group,
Examples thereof include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylamide. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid and citraconic acid. Amide group,
Examples of the monomer having an N-substituted amide group include acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-butoxymethyl (meth)
Acrylamide, N-tert-butylacrylamide, N-octylacrylamide, diacetoneacrylamide, and the like. Examples of the monomer having a nitrile group include acrylonitrile, methacrylonitrile, crotononitrile, and fumaronitrile.

The reaction is a usual radical polymerization, and there is no restriction on the reaction method. The reaction can be carried out by a known polymerization method such as solution polymerization, bulk polymerization, emulsion polymerization, etc. Solution polymerization is preferred because it can proceed directly to the next operation. As the solvent, any solvent can be used as long as the resin of the present invention can be dissolved, such as methyl ethyl ketone, methyl isobutyl ketone, toluene, cellosolve, ethyl acetate, and butyl acetate. A single solvent or a mixture of a plurality of solvents can be used. Among them, ethyl acetate, which does not easily cause chain transfer during the radical polymerization reaction and has an appropriate boiling point, is preferable. Known polymerization initiators used in the polymerization reaction include organic peroxides such as benzoyl peroxide, acetyl peroxide, methyl ethyl ketone peroxide and lauroyl peroxide, and azo initiators such as azobisisobutyronitrile. Anything can be used, and there is no particular limitation.

The adhesive rubber polymer excluding the adhesive acrylic polymer includes natural and synthetic cis-1,4-polyisoprene rubber, recycled rubber, polyisobutylene, butyl rubber, halogenated butyl rubber, partially vulcanized butyl rubber,
There are styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), silicone rubber, chloroprene rubber, nitrile rubber, butadiene rubber, and the like. Among them, SBS, SIS, SEB
Block copolymers such as S have a very high cohesive force and are suitable for the adhesive rubber-based polymer (A) of the present invention. These polymers include methyl ethyl ketone, methyl isobutyl ketone, toluene, cellosolve,
Used by dissolving in a suitable solvent such as ethyl acetate and butyl acetate.

In the curable polyester oligomer (B), the compound (a) having an amino group includes a primary amino group, a secondary amino group, a tertiary amino group, an amide group, an N-
There are compounds having a substituted amide group, and compounds having a primary amino group include monopropylamine, monobutylamine, hexamethylenediamine, trimethylhexamethylenediamine, polyoxypropylenediamine, 3,3 ′
-Dimethyl-4,4'-diaminodicyclohexylmethane, isophoronediamine, 4,4'-diaminodicyclohexyl, 1,3-bis (aminomethyl) cyclohexane, 4,4'-diaminodiphenylmethane (methylenedianiline), 4,4 '-Diaminodiphenyl ether,
Compounds having a secondary amino group such as xylylenediamine include dimethylamine for compounds having a tertiary amino group such as diisopropylamine, dibutylamine, 2-methylimidazole, diphenylguanidine, diethylthiourea, piperidine, pyrrolidine, and morpholine. Examples include benzylamine, methyl 4-dimethylaminobenzoate, p-dimethylaminoacetophenone, N, N-dimethylcyclohexylamine, dimethylaminomethylphenol, and tris (dimethylaminomethyl) phenol. Compounds having an amide group and an N-substituted amide group include acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) ) Acrylamide, N-propoxymethyl (meth) acrylamide, N-butoxymethyl (meth)
Acrylamide, N-tert-butylacrylamide, N-octylacrylamide, diacetoneacrylamide, and the like.

However, among these, compounds having two amino groups at the same time, compounds having a carboxyl group and an amino group at the same time, or ethanolamine, 1-amino-2-propanol, o-aminophenol, m-aminophenol, p- Compounds having two or more functional groups, such as compounds having both an amino group and a hydroxyl group such as aminophenol, are preferred.

In the curable polyester oligomer (B), the cyclic acid anhydride (b) is an intramolecular anhydride of a polycarboxylic acid, and may be a saturated or unsaturated aliphatic polycarboxylic anhydride, an alicyclic ring. Formula polycarboxylic anhydrides, aromatic polycarboxylic anhydrides, and the like, or those partially substituted with saturated or unsaturated hydrocarbon groups, aromatic ring groups, halogen atoms, heterocyclic groups, etc. is there. Specific examples thereof include succinic anhydride, phthalic anhydride, maleic anhydride, itaconic anhydride, glutaric anhydride, dodecenyl succinic anhydride, chlorendexic anhydride, pyromellitic anhydride, trimellitic anhydride, and cyclopentanetetracarboxylic acid. Acid dianhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetramethylene maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride,
5- (2,5-dioxotetrahydroxyfuryl) -3
-Methyl-3-cyclohexene-1,2-dicarboxylic anhydride, methylnadic anhydride, benzophenonetetracarboxylic anhydride, glycerol tris (anhydrotrimellitate), ethylene glycol bis (anhydrotrimellitate), etc. . Among these, it is preferable to use dicarboxylic anhydride or tricarboxylic anhydride which does not form a crosslinked structure.

In the curable polyester oligomer (B), the epoxide (c) having an unsaturated group includes:
Unsaturated aliphatic epoxides, alicyclic epoxides, aromatic epoxides, etc. having an epoxide structure in the molecule, or partially or saturated hydrocarbon groups,
Some are substituted with an aromatic ring group, a halogen atom, a heterocyclic group and the like. Specific examples thereof include glycidyl (meth) acrylate, glycidyl cinnamate, allyl glycidyl ether, vinylcyclohexene monoepoxide, 1,3-butadiene monoepoxide, and the like. These are saturated or unsaturated hydrocarbon groups and aromatic rings. Group, a halogen atom, a heterocyclic group and the like.

The curable polyester oligomer (B) is obtained by reacting the compound (a) having an amino group, the cyclic acid anhydride (b) and the epoxide (c) having an unsaturated group. The reaction can be performed in the presence or absence of a suitable solvent, but to make the reaction easier to control,
It is common to add 10 to 50 parts of solvent to 100 parts by weight of monomer. If the amount of the solvent added is larger than this, the reaction rate becomes extremely slow, and if it is smaller, the control of the reaction becomes difficult. Protection of ethylenically unsaturated groups using a basic catalyst typified by tertiary amines such as N, N-dimethylbenzylamine, triethylamine, tributylamine, N, N-diethylaniline, N, N-dimethylaniline, etc. Hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, p-
The reaction can be performed in a state where a radical polymerization inhibitor such as benzoquinone is added.

In the reaction, the amino group of the compound (a) having an unsaturated group and the acid anhydride group of the cyclic acid anhydride (b) activated by a basic catalyst react preferentially first, and then The carboxyl group generated by this reaction reacts with the epoxy group of the epoxide (c) activated by the basic catalyst to generate a secondary hydroxyl group. Further, the same reaction as described above can be allowed to proceed sequentially, such that the generated hydroxyl group reacts with the acid anhydride group of the cyclic acid anhydride (b). Details of this reaction are described in JP-A-61-479.
28, and JP-A-61-126128.

In this reaction, the amount of the cyclic acid anhydride (b) and the amount of the epoxide (c) to be reacted are adjusted with respect to the amount of the compound (a) to convert the compound (a) having an unsaturated group into A curable polyester oligomer (B) having a desired length at the terminal can be produced. When the cyclic acid anhydride (b) is a dicarboxylic acid anhydride, the proportion of each compound is 1 to 20 mol of the cyclic acid anhydride (b) and 1 to 20 mol of the epoxide ( c) It is preferable to react the cyclic acid anhydride (b) and the epoxide (c) at a ratio of 1 to 20 moles and at a substantially equal mole ratio. When the cyclic acid anhydride (b) is a tricarboxylic acid anhydride, the ratio of 1 to 10 mol of the cyclic acid anhydride (b) and 1 to 20 mol of the epoxide (c) per 1 mol of the compound (a). Preferably, the epoxide (c) is reacted at a ratio of about 1 to 2 mol with respect to 1 mol of the cyclic acid anhydride (b). Compound (a) 1
When the amount of the cyclic acid anhydride (b) or epoxide (c) to be reacted is less than 1 mol, the resulting curable polyester oligomer (B) has a low molecular weight, and the compound (a) The required characteristics cannot be obtained due to the residual. On the other hand, when the amount of the cyclic acid anhydride (b) or the epoxide (c) exceeds 20 mol, the control of the reaction becomes difficult, or the molecular weight becomes too high, so that the necessary properties cannot be obtained. There is.

By mixing a solution of the adhesive rubber-based polymer (A) obtained by the reaction and dissolution and a solution of the curable polyester oligomer (B), a curable adhesive composition can be obtained. it can. It is sufficient to mix the mixture at room temperature until the mixture becomes apparently uniform. However, in order to further enhance the mutual mixing state, it is necessary to synthesize the adhesive rubber-based polymer (A) and the curable polyester oligomer (B). Heating and stirring at a temperature equal to or lower than the boiling point of the solvent used for dissolution may be performed.

In the present invention, since the epoxide (e) having an ethylenically unsaturated group is used, the curable polyester oligomer (B) has an unsaturated group and can be cured by electron beam curing or a suitable polymerization initiator (C). ) Can be easily solidified by a curing method such as heat curing, anaerobic curing, or light curing in combination with (1).

The polymerization initiator (C) used in the case of thermal curing or anaerobic curing includes dialkyl peroxides such as di-tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, and acetyl peroxide. Diacyl peroxides such as oxide, lauroyl peroxide and benzoyl peroxide; ketone peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide and methylcyclohexanone peroxide;
Peroxy ketals such as 1-bis (tert-butylperoxy) cyclohexane, tert-butyl hydroperoxide, cumene hydroperoxide, 1,
Hydroperoxides such as 1,3,3-tetramethylbutyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, tert-butyl Organic peroxides such as peroxyesters such as peroxyacetate, tert-butylperoxy-2-ethylhexanoate and tert-butylperoxybenzoate;
2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2-cyclopropylpropionitrile), 2,2'-azobis (2,4-
Dimethylvaleronitrile), azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyi There is no particular limitation as long as it is a known one such as an azo compound such as lonitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. The polymerization initiator (C) is usually added in an amount of 0.1 to 100 parts by weight of the curable pressure-sensitive adhesive composition of the present invention.
It is used in a proportion of 1 to 15 parts by weight, preferably 0.5 to 5 parts by weight.

When an organic peroxide having a low radical generation rate is used, N, N-dimethylbenzylamine, triethylamine, tributylamine, N, N
-Diethylaniline, N, N-dimethylaniline, N-
Tertiary amines such as phenyldiethanolamine, N-phenyldiisopropanolamine, dimethyl-p-toluidine, triethanolamine and 4-phenylmorpholine, and lithium, calcium, strontium, barium, cerium, zirconium, vanadium, molybdenum, manganese and iron Laurate, naphthenate, octylate, oleate, octenoate and other fatty acid salts, rosin salt and other resin salts, and acetylacetate for metals such as nickel, cobalt, nickel, copper, zinc, tin and lead One or more metal compounds selected from chelate compounds such as nate complex salts can be used as the accelerator. In particular, in the case of anaerobic curing, it is preferable to use one or both of a tertiary amine and a metal compound as an accelerator together with an organic peroxide. Of these accelerators, tertiary amines are usually 100% organic peroxides.
The metal compound is present in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the organic peroxide.
Used in parts by weight.

As the polymerization initiator (C) used in the case of photocuring, benzoin, benzoin methyl ether, benzoin ethyl ether, methyl o-benzoylbenzoate-p-benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin Acetophenones such as benzoin, dimethylbenzyl ketal, trichloroacetophenone, 2,2-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-4'-isopropyl-
Benzophenones such as propiophenones such as 2-methylpropiophenone, α-acyloxime ester, benzophenone, methylbenzophenone, p-chlorobenzophenone and p-dimethylaminobenzophenone;
In addition to thioxanthones such as 2-chlorothioxanthone, 2-ethylthioxanthone, and 2-isopropylthioxanthone, benzyl, dibenzosuberone, etc., edited by Kato Kiyomi: "UV / EB Curing Handbook-Raw Materials-" (1)
(December 985, published by Kobunshi Kanbunkai), pp. 67-73, or "Handbook of Crosslinking Agents" edited by Fuzo Yamashita and Tosuke Kaneko (October 1981, Taiseisha, pp. 582-593). There is something. These polymerization initiators (C)
It may be used together with an accelerator.

Examples of such an accelerator include 4,4'-bis (diethylamino) benzophenone, ethyl N-dimethylaminobenzoate, dimethylethanolamine, glycine, and the like. Those described on page 73 can be used. When light having a relatively long wavelength such as ultraviolet light or visible light is used as the light, it is preferable to use both the polymerization initiator (C) and the accelerator from the viewpoint of curing efficiency. The polymerization initiator (C)
It is used in a proportion of usually 0.05 to 20 parts, preferably 0.5 to 10 parts, based on 100 parts by weight of the curable pressure-sensitive adhesive composition of the present invention.

The above polymerization initiator (C) and accelerator can be used in the form of microcapsules. When a product such as a curable pressure-sensitive adhesive composition or a sheet made of the curable pressure-sensitive adhesive composition is left for a long time before it is used, it can be kept stable until used by this method. In particular, in the case of anaerobic curing, storage stability can be greatly improved by converting one or more of the polymerization initiator and the accelerator used into micromapsels. The method for microencapsulating the polymerization initiator (C) and the accelerator is not particularly limited, and is disclosed in JP-B-38-19574 and JP-B-42-197574.
446, JP-B-42-771, JP-B-42
-2882, JP-B-42-2883, JP-A-56-115371, JP-A-60-60173.
Polymerization method described in Japanese Patent Publication No. 36-91
No. 68, US Pat. No. 3,427,250, BP123
No. 6498, US Pat. No. 3,787,327, US Pat.
6, US Pat. No. 3,574,133, and the like, in-liquid curing coating method, US Pat. No. 2,800,457, US Pat.
No. P2800045, US Pat. No. 3,531,418, US Pat. No. 3,577,515, BP1117178.
Coacervation method (phase separation method) described in US Pat. No. 3,523,906, US Pat.
No. 04, etc., US Pat.
There is a spray drying method described in JP-A-0750. Among these methods, polyurea which can freely control the thickness of the microcapsule wall, can make the thickness of the microcapsule wall uniform, and can increase the strength of the microcapsule wall is used as the microcapsule wall. Preferably, microcapsulation is performed by an interfacial polymerization method or a complex coacervation method using gelatin and gum arabic as microcapsule walls.

In order to improve the adhesive properties before curing, particularly to increase the holding power, a polyisocyanate (D) is further added to the curable adhesive composition of the present invention to form an adhesive rubber-based polymer (A). Can be partially crosslinked. Such polyisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate,
Diisocyanates such as 5-naphthalene diisocyanate, isophorone diisocyanate, lysine diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, or both terminal isocyanate adducts thereof with glycols or diamines, or these There is a mixture, and if necessary, tri- or higher-functional polyisocyanates such as triphenylmethane triisocyanate and polymethylene polyphenyl isocyanate can be used in combination with diisocyanates. The amount of the polyisocyanate (D) to be added is 0.1 to 100 parts by weight of the curable pressure-sensitive adhesive composition.
1 to 5 parts by weight.

In order to improve the adhesion to the plastic substrate, a tackifier (E) can be further added to the curable pressure-sensitive adhesive composition of the present invention. The tackifier (E)
A tackifier that further imparts tackiness to a tacky resin. In a sea-island-like microphase-separated structure formed from a tacky rubber-based polymer (A) and a curable polyester oligomer (B), a tackifier is used. (E) also causes more complicated microphase separation and can improve the adhesion to various adherends, especially to plastic substrates. As the tackifier (E), natural resins such as rosin-based resins and terpene-based resins and derivatives thereof, and synthetic resins such as petroleum resins can be used. Rosin resins include gum rosin, tall oil rosin, wood rosin and other natural rosins, hydrogenated rosins,
There are modified rosins such as polymerized rosin and maleated rosin, and rosin esters such as rosin glycerin ester, hydrogenated rosin glycerin ester, polymerized rosin glycerin ester, rosin pentaerythritol ester, hydrogenated rosin pentaerythritol ester, and polymerized rosin pentaerythritol ester. For terpene resins, α-
Terpene resins such as pinene, β-pinene, limonene,
There are terpene phenol resins such as α-pinene phenol resin and diterpene phenol resin. In addition, aromatic hydrocarbon-modified terpene resins can also be used. On the other hand, synthetic resins that can be used for the tackifier (E) include aliphatic resins,
Examples include alicyclic and aromatic petroleum resins, coumarone indene resins, styrene resins, xylene resins, and rosin-modified phenol resins. The addition amount of the tackifier (E) is 1 to 100 parts by weight based on 100 parts by weight of the curable pressure-sensitive adhesive composition.

In order to adjust the adhesive properties before curing and the adhesive strength after curing, a polyester oligomer synthesized using an epoxide having no ethylenically unsaturated group is used as the curable polyester oligomer having an unsaturated group according to the present invention. (B)
Can be used together. Epoxides having no ethylenically unsaturated group include epichlorohydrin, phenylglycidyl ether, styrene oxide, cyclohexene oxide, and butene oxide.

In order to further increase the adhesive strength after curing, the curable pressure-sensitive adhesive composition of the present invention may further comprise a monomer or oligomer having an ethylenically unsaturated group such as a (meth) acryloyl group. Can be added. By adding a monomer or oligomer having an ethylenically unsaturated group separately from the unsaturated polyester oligomer (A) used in the present invention, the time required for adhesion can be shortened, and the amount of the polymerization initiator (C) can be reduced. can do. Such monomers and oligomers include styrene, alkyl (meth) acrylate, (meth) acrylic acid, polyhydric alcohol poly (meth) acrylate, epoxy poly (meth) acrylate, oligoester poly (meth) acrylate, and polyurethane poly ( (Meth) acrylate, diallyl phthalate, diallyl isophthalate and the like. The amount of these monomers and oligomers used is
It is 60% by weight or less based on the total solid content of the pressure-sensitive adhesive composition of the present invention. If it exceeds 60% by weight, the adhesive properties before curing,
In particular, the cohesive strength becomes remarkably inferior.

The curable pressure-sensitive adhesive composition of the present invention may contain pigments, dyes, inorganic fillers, organic solvents, metal powders such as silver powder, copper powder, nickel powder, etc. Carbon black, graphite, silane coupling agents and the like can be added.

The curable pressure-sensitive adhesive composition of the present invention can be processed into a sheet shape or coated on a highly releasable film such as paper, cloth, plastic film, sheet or tape, etc. The organic solvent is removed by drying if necessary, and cut if necessary to form an adhesive sheet. Also, lining with non-woven fabrics such as rayon and nylon, cloths such as cold gauze, foams such as urethane and acrylic, and using these cloths and foams as a core material, the curable adhesive of the present invention is used. The composition may be used after being applied or impregnated. If the base material, core material, etc. of the sheet used here remain with the curable pressure-sensitive adhesive composition in the bonded area after use, they may be significantly deteriorated by curing treatment such as heating or light irradiation. And does not significantly impede curing.

The pressure-sensitive adhesive sheet thus obtained is 2
After being sandwiched between two adherents of the same or different kind and temporarily bonded by its good adhesiveness, the curable adhesive composition is cured by performing a treatment according to each curing method,
The adherends can be firmly adhered to each other.

When the polymerization initiator (C), the accelerator and the like are microencapsulated, before the temporary adhesion to the adherend,
Alternatively, the microcapsules are broken by applying a force such as pressure from a pressure roll later. Alternatively, it is necessary to destroy the capsule by applying heat or irradiating light such as ultraviolet rays according to the properties of the microcapsule. However, in the case of sustained-release microcapsules, there is no particular need to break them.

In the case of anaerobic curing, after temporarily adhering to the adherend, curing is started immediately by the action of the polymerization initiator (C), and reaches practical strength in about several hours to about one week. In the case of thermosetting, 80-
Heating is performed at 150 ° C. for about 3 to 20 minutes, and contact heating such as hot pressing is performed at 80 to 150 ° C. for about 0.5 seconds to 5 minutes. In the case of photo-curing, at least one of the adherends has a light transmitting property, and can be bonded by irradiating light from the side of the light-transmitting adherend.

In the present invention, the light is a visible ray using a sun or a fluorescent lamp as a radiation source, an ultraviolet ray using a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, a carbon arc lamp, a xenon lamp or the like, or a cobalt 60 ray. In addition to γ-rays as a source or X-rays using an X-ray generator as a source, electron beams using an electron beam accelerator or the like as a source are also included. Among these, in practice, it is preferable to use visible light, ultraviolet light, or an electron beam, in particular, visible light or ultraviolet light having a wavelength of 200 to 800 nm. When ultraviolet light is used as the light, it is preferable to use the polymerization initiator (C) and, if necessary, an accelerator, from the viewpoint of curing efficiency, as described above. Output of radiation source, distance from radiation source, irradiation area, type and amount of resin and polymerization initiator (C) and accelerator used, thickness of curable pressure-sensitive adhesive composition layer, adherend and sheet substrate Usually, the irradiation amount is 0.5 to 50 Mrad in the case of an electron beam, and 20 to 5 in the case of an ultraviolet ray, although it varies depending on the type and thickness.
000mJ / cm ² or so, the time of irradiation is about 0.3 to 30 seconds.

[0039]

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

Preparation of adhesive rubber-based polymer

Polymer 1 93.5 parts butyl acrylate 1.4 parts acrylic acid 5.1 parts 2-hydroxyethyl methacrylate 5.1 parts azobisisobutyronitrile 0.2 parts ethyl acetate 150.0 parts In a nitrogen stream, at 80 ° C. Heated mixture of the above composition 12
To 5 parts, 125 parts of the above mixture of the same composition was added dropwise, and after completion of the addition, the mixture was heated under reflux for 12 hours and cooled to obtain a solution of acrylic polymer 1 (solid content: 40%). Hereinafter, polymers 2 and 3 were obtained in the same manner.

Polymer 2 Butyl acrylate 88.2 parts Vinyl acetate 5.6 parts 2-hydroxyethyl methacrylate 6.2 parts Azobisisobutyronitrile 0.2 parts Ethyl acetate 150.0 parts

Polymer 3 butyl acrylate 92.0 parts acrylamide 2.8 parts 2-hydroxyethyl methacrylate 3.8 parts azobisisobutyronitrile 0.2 parts ethyl acetate 150.0 parts

Polymer 4 CARIFLEX TR-1101 40.0 parts (trade name: rubber-based polymer manufactured by SBS Shell Chemical) Ester gum H 60.0 parts (trade name: hydrogenated rosin ester Arakawa Chemical Co., Ltd.) Toluene 135 0.0 part Methyl ethyl ketone 15.0 parts The above composition was stirred and dissolved at 50 ° C. in a nitrogen atmosphere to obtain a solution of polymer 4 (solid content: 40%). Perform the same operation,
A solution of polymer 5 was obtained.

Polymer 5 Carifrex TR-1107 40.0 parts (trade name: SIS Shell Chemical Co., Ltd., rubber-based polymer) Ester gum H 60.0 parts (trade name: hydrogenated rosin ester, Arakawa Chemical Co., Ltd.) Toluene 135 0.0 parts Methyl ethyl ketone 15.0 parts

Synthesis of curable polyester oligomer

Oligomer 1 Metaxylenediamine 4.5 parts Hexahydrophthalic anhydride 49.2 parts Glycidyl methacrylate 45.4 parts N, N-dimethylbenzylamine 0.9 parts Hydroquinone 0.2 parts Ethyl acetate 25.0 parts The above composition The mixture was mixed and reacted at 80 ° C. for 10 hours in an air atmosphere. After cooling, 125 parts of ethyl acetate was added to the mixture to prepare a solution of a curable polyester oligomer (solid content: 40%).
%). Hereinafter, curable polyester oligomers 2 and 3 were obtained in the same manner.

Oligomer 2 Dibutylamine 4.3 parts Hexahydrophthalic anhydride 49.3 parts Glycidyl methacrylate 45.5 parts N, N-dimethylbenzylamine 0.9 parts Hydroquinone 0.2 parts Ethyl acetate 25.0 parts

Oligomer 3 Dimethylaminoethyl methacrylate 5.2 parts Hexahydrophthalic anhydride 48.9 parts Glycidyl methacrylate 45.0 parts N, N-dimethylbenzylamine 0.9 parts Hydroquinone 0.2 parts Ethyl acetate 25.0 parts

Oligomer 4 Lipoxy SP-1509 100.0 parts (Acrylate oligomer manufactured by Showa Polymer Co., Ltd.) Hydroquinone 0.2 part Ethyl acetate 25.0 parts The above composition was stirred and dissolved in a nitrogen atmosphere at 50 ° C. 4 was obtained (40% solids). By the same operation, a solution of oligomer 5 was obtained.

Oligomer 5 KAYARAD DPCA-30 100.0 parts (trade name: Nippon Kayaku Co., Ltd. acrylate oligomer) Hydroquinone 0.2 parts Ethyl acetate 25.0 parts

[0052]

EXAMPLE 1 60.0 parts of the solution of the polymer 1 and 40.0 parts of the solution of the oligomer 1 were thoroughly mixed, and the resin solution 10
0.4 parts of benzoyl peroxide is uniformly mixed with 0 parts, and silicone-treated polyethylene terephthalate film (hereinafter referred to as “treated PET”)
On top, apply so that the thickness after drying is 30 μm.
After drying at 0 ° C. for 3 minutes, a release paper made of silicon-treated paper was overlaid to obtain an adhesive sheet. Further, to the resin mixture having the above composition, 0.2 parts of tolylene diisocyanate was further added to obtain a pressure-sensitive adhesive sheet, which was then aged at 50 ° C. for 3 days.

With respect to the obtained pressure-sensitive adhesive sheet, the results of measurement of the pressure-sensitive adhesive properties before peeling (peeling adhesion, tack, holding power), the shearing adhesive strength after curing, and the peeling adhesive strength are shown in Table 1.
Curing was performed by heating in an oven at 130 ° C. for 10 minutes. The following method was used for the measurement.

(1) Peel adhesive strength before curing The release paper of the obtained pressure-sensitive adhesive sheet was peeled off, and a thickness of 50
μm untreated polyethylene terephthalate sheet is adhered, cut to a width of 25 mm, and then the treated PET is peeled off.
The resulting adhesive surface was adhered to a stainless steel plate (SUS304) polished with # 280 sandpaper and allowed to stand for 30 minutes.
The 180-degree peel adhesion was measured at 00 mm / min.

(2) Tack before curing An adhesive sheet from which release paper was peeled was set on an inclined surface having an inclination angle of 30 ° so that the adhesive surface was facing upward, and was set at 25 ° C. and a relative humidity of 65 °.
The stainless steel ball was rolled at a running distance of 10 cm and the number of the largest ball that stopped within 10 cm of the adhesive surface was measured. The ball number is
It is indicated by a value 32 times as large as the "ball name" obtained by dividing the diameter of a ball into 32 equal parts according to JIS B1501.

(3) Holding force before curing The release paper of the obtained pressure-sensitive adhesive sheet was peeled off, and a thickness of 50
μm untreated polyethylene terephthalate sheet is adhered, cut to a size of 25 mm in width and 100 mm in length, and then the treated PET is peeled off.
A 5 mm, 25 mm wide part was stuck on a stainless steel plate (SUS304) polished with sandpaper # 280.
The time (sec) until the pressure-sensitive adhesive sheet dropped from the stainless steel plate at 0 ° C. under a load of 1 kg was measured.

(4) Shear adhesive strength after curing The obtained pressure-sensitive adhesive sheet was cut into a length of 10 mm and a width of 10 mm, the release paper was peeled off, and the pressure-sensitive adhesive surface was reduced to a length of 50 mm and a width of 10 m.
m, attached to one end of a 0.5 mm thick aluminum plate,
The treated PET was peeled off, and another aluminum plate having a length of 50 mm, a width of 10 mm, and a thickness of 0.5 mm was attached to the resulting adhesive surface, and the adhesive was cured by a predetermined curing method.
The shear strength was measured at a pulling rate of 5 mm / min at a temperature of 65 ° C. and a relative humidity of 65%.

(5) Peeling adhesive strength after curing The obtained pressure-sensitive adhesive sheet was cut into a width of 25 mm, the release paper was peeled off, and the pressure-sensitive adhesive surface was 100 mm long, 250 mm wide and 10 mm thick.
It is stuck on an aluminum sheet of 0 μm, the treated PET is peeled off, and the resulting adhesive surface is 100 mm long, 25 mm wide,
After sticking another aluminum sheet having a thickness of 100 μm and curing the pressure-sensitive adhesive by a predetermined curing method, T is applied at a tension rate of 300 mm / min at 25 ° C. and a relative humidity of 65%.
The mold peel strength was measured.

Example 2 (Preparation of microencapsulated benzoyl peroxide) One part of polyvinyl alcohol and 100 parts of water were mixed with 30 parts of
C. and stirring with a stirring blade rotating at a speed of 225 rpm, 5 parts of benzoyl peroxide,
A solution prepared by dissolving 5 parts of tolylene diisocyanate in 10 parts of xylene is added and dispersed. After 5 minutes, 1 part of tetraethylene pentamine is added, and then stirring is continued for 2 hours, and tolylene diisocyanate, tetraethylene pentamine,
A dispersion of microcapsules of benzoyl peroxide having walls formed by the reaction between polyvinyl alcohol and water was obtained. Dispersion 1 of the obtained microcapsules
To 22 parts, add 2 parts of glutaraldehyde, stir for 2 hours, then add 2 parts of N- (2-aminoethyl) -γ-aminopropyltrimethoxysilane, and adjust the pH of the dispersion.
Ammonia water was added so that the pH became about 11, and stirring was further continued for 6 hours. Then, the microcapsules were filtered off, washed with ethanol, dried with warm air at 50 ° C., and microencapsulated benzoyl peroxide. I got In the obtained microcapsules, 2 benzoyl peroxides were contained.
0%, average particle size of microcapsules is 40μm
Met.

60.0 parts of the solution of the polymer 1 and 40.0 parts of the solution of the oligomer 1 were thoroughly mixed.
To 0 parts, 10 parts of microencapsulated benzoyl peroxide, 0.1 part of cobalt naphthenate, 0.5 part of dimethyl-p-toluidine and 0.1 part of tolylene diisocyanate were uniformly mixed. In the same manner as in the above, an adhesive sheet was obtained. The adhesive properties before curing were measured in the same manner as in Example 1 while taking care not to break the microcapsules. Also, after bonding the aluminum plate as in Example 1, pressurizing with a pressure roll at 10 kg / cm ² , leaving it at room temperature for one week, and curing it sufficiently, the same conditions as in Example 1 were applied. Was used to measure the shear adhesive strength and the peel adhesive strength. Further, the same measurement was performed two months after the preparation of the pressure-sensitive adhesive sheet. The above measurement results are shown in Table 1.

Example 3 60.0 parts of solution of polymer 1 and solution 4 of oligomer 1
0.0 part was thoroughly mixed, and 0.4 part of 2-hydroxy-2-methylpropiophenone was added to 100 parts of the resin solution.
Parts and 0.1 part of tolylene diisocyanate were uniformly mixed, and a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1. With respect to the obtained pressure-sensitive adhesive sheet, the pressure-sensitive adhesive properties before curing, the shear adhesive strength after curing, and the peel adhesive strength were measured. Measurement of shear adhesive strength after curing is 50 mm long, 10 mm wide, and 188 μm thick
Polyethylene terephthalate plate was used in place of the aluminum plate. The measurement of peel adhesion after curing is 100
A polyethylene terephthalate film having a thickness of 50 mm, a width of 25 mm and a thickness of 50 μm was used in place of the aluminum sheet. Curing was performed by irradiating ultraviolet rays for 15 seconds at a distance of 15 cm under a 2 kW high-pressure mercury lamp. The above measurement results are shown in Table 1.

Example 4 An adhesive sheet was prepared in the same manner as described above except that no photopolymerization initiator such as 2-hydroxy-2-methylpropiophenone was added to the resin solution of Example 3 above. The shear adhesive strength and peel adhesive strength after electron beam curing were measured. For electron beam curing, an electron curtain type electron beam irradiator was used.
5Mra from the side of the polyethylene terephthalate film
It was cured by irradiating the electron beam of d. The above measurement results are shown in Table 1.

Example 5 60.0 parts of solution of polymer 2 and solution 4 of oligomer 1
0.0 part was sufficiently mixed, and 0.4 part of benzoyl peroxide and 0.2 part of tolylene diisocyanate were uniformly mixed with 100 parts of the resin solution in the same manner as in Example 1. A mixture obtained by uniformly mixing 10 parts of microencapsulated benzoyl peroxide, 0.1 part of cobalt naphthenate, 0.5 part of dimethyl-p-toluidine and 0.1 part of tolylene diisocyanate in the same manner as in Example 2, In the same manner as in Example 3, a mixture obtained by uniformly mixing 0.4 part of 2-hydroxy-2-methylpropiophenone and 0.2 part of tolylene diisocyanate was operated as in each example to obtain an adhesive sheet. Was. With respect to the obtained pressure-sensitive adhesive sheets, the pressure-sensitive adhesive properties before curing, the shear adhesive strength after curing, and the peel adhesive strength were measured by the methods described in Examples. Curing was also performed by thermal curing, anaerobic curing, and UV curing, respectively, as described in each example. However, in the anaerobic hardening, the measurement after two months was not performed. The above measurement results are shown in Table 1.

Examples 6 to 8 60.0 parts of solution of polymer 3, solution 4 of oligomer 1
0.0 parts were sufficiently mixed, and otherwise operated in exactly the same manner as in Example 5 to obtain the adhesive properties before curing, and the shear adhesive strength and peel adhesive strength after curing by heat curing, anaerobic curing, and UV curing. Was measured (Example 6). The solution 6 of the polymer 4
The same operation was carried out using 0.0 parts and 40.0 parts of the solution of oligomer 1 (Example 7), and 60.0 parts of the solution of polymer 5 and 40.0 parts of the solution of oligomer 1 (Example 8).
The adhesive properties before curing and the shear adhesive strength and peel adhesive strength after curing by thermal curing, anaerobic curing, and UV curing were measured. The above measurement results are shown in Table 1.

Examples 9 and 10 60.0 parts of solution of polymer 1 and solution 4 of oligomer 2
Using 0.0 part as a resin solution, the adhesive properties before curing and the shear adhesive strength and peel adhesive strength after thermal curing were measured in the same manner as in Example 1 (Example 9). The same operation was performed using the combination of Polymer 1 and Oligomer 3 (Example 10), and the adhesive properties before curing and the shear adhesive strength and peel adhesive strength after heat curing were measured. The above measurement results are shown in Table 1.

Examples 11 to 13 60.0 parts of solution of polymer 1 and 4 of solution of oligomer 1
0.0 part was mixed well, and 100 parts of this solution
Dissolve 8 parts of YS Polystar 2100 (trade name, terpene phenol resin manufactured by Yashara Chemical Co., Ltd.) to make a resin solution. The subsequent operation is completely the same as in the case of thermosetting of Example 5, except that the test plate is changed from a stainless plate to a polypropylene plate. The same operation was performed to measure the shear adhesive strength and the peel adhesive strength after thermosetting (Example 11). The same operation was performed using polymer 2 (Example 12) instead of polymer 1 and polymer 3 (Example 13) instead of polymer 1,
The adhesive properties before curing and the shear adhesive strength and peel adhesive strength after heat curing were measured. The above measurement results are shown in Table 1.

Comparative Examples 1 and 2 60.0 parts of solution of polymer 1 and solution 4 of oligomer 4
0.0 parts were sufficiently mixed, and the other operations were performed in exactly the same manner as in Example 5 to measure the adhesive properties before curing, and the shear adhesive strength and peel adhesive strength after heat curing (Comparative Example 1). . Perform the same operation using oligomer 5 instead of oligomer 4,
The adhesive properties before curing and the shear adhesive strength and peel adhesive strength after heat curing were measured (Comparative Example 2). The above measurement results are shown in Table 1.

Comparative Examples 3 to 5 In Example 11, a resin solution was prepared without adding 8 parts of YS Polystar 2100 (trade name: terpene phenol resin manufactured by Yashara Chemical Co., Ltd.), and the same operation was performed to obtain adhesive properties before curing. And the shear adhesive strength and peel adhesive strength after heat curing were measured (Comparative Example 3). Polymer 2 instead of Polymer 1
(Comparative Example 4) The same operation was performed using Polymer 3 (Comparative Example 5) instead of Polymer 1, and the adhesive properties before curing and the shear adhesive strength and peel adhesive strength after heat curing were measured. The above measurement results are shown in Table 1.

[0069]

[Table 1]

Unit: Peel adhesion before curing g / 25 mm Holding force Second Shear adhesion after curing kg / cm ² Peel adhesion after curing g / 25 mm Curing method H Thermal curing A Anaerobic curing U Ultraviolet curing E Electron beam Curing Test plate Test plate used for measurement S Stainless steel plate P PET plate PP Polypropylene plate G Glass plate TDI Tolylene diisocyanate No additive Additive Additive Example 2 The upper part is immediately after the production of the adhesive sheet. The lower part is two months after the production.

[0071]

As shown in Table 1, the curable pressure-sensitive adhesive composition of the present invention has a peel adhesion before curing of not less than 1400 g / 25 mm width and a tackiness when a stainless steel plate is used as a test plate. 7 or more. The holding power is not less than 1000 seconds even when the polyisocyanate is added, in addition to exhibiting a sufficient holding power when the polyisocyanate is added. This adhesive property is at a level that can be sufficiently used as a normal adhesive, and can be said to be an excellent performance. Further, the shear adhesive strength after curing is 25 kg / c in the case of heat curing and anaerobic curing.
m ² or more, in the case of photocuring 20 kg / cm ² or more, peel adhesion after curing also heat curing in the case of anaerobic curing, 1.5
kg / 25mm width or more, 1kg / 2 even for UV curing
The width is 5 mm or more. Thus, the adhesive properties before curing,
A curable pressure-sensitive adhesive composition having excellent shear adhesive strength and peel adhesive strength after curing can be obtained.

Further, the curable pressure-sensitive adhesive composition of the present invention is easier to react and has a lower odor due to reaction residues, as compared with a conventional curable pressure-sensitive adhesive composition having an unsaturated group introduced into a polymer. In addition to being excellent in point, the original performance as a curable pressure-sensitive adhesive composition, that is, the adhesive properties before curing and the adhesive properties after curing are not inferior to those of the conventional one. Furthermore, by adding an appropriate amount of the polyisocyanate (D), the cohesive force is significantly improved, and by adding the tackifier (E),
The adhesion to the plastic substrate was significantly improved.

As described above, according to the present invention, a curable pressure-sensitive adhesive composition having good adhesive properties at the time of bonding and showing strong adhesive strength after curing, and having an excellent balance between the adhesive properties before curing and the adhesive properties after curing. Things can now be obtained. In addition, since sheets and tapes using this can be temporarily bonded to the adherend, there is no need for mechanical temporary fixing, and after curing, they can reach the same strength as adhesives. It became possible to do.

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Claims (3)

(57) [Claims] 1. An amino group-containing compound (a), a cyclic acid anhydride (b), and an unsaturated group-containing epoxide (c) based on 100 parts by weight of an adhesive rubber-based polymer (A).
A curable pressure-sensitive adhesive composition comprising 5 to 200 parts by weight of a curable polyester oligomer (B) obtained by reacting 2. In addition to the adhesive rubber-based polymer (A) and the curable polyester oligomer (B), (1) a polymerization initiator (C) is added to the adhesive acrylic polymer (A) and the curable polyester oligomer (B). (2) polyisocyanate (D) is added to 100 parts by weight of adhesive acrylic polymer (A) and curable polyester oligomer (B) based on 100 parts by weight of total weight of 0.1 to 5 parts by weight, (3) 1 to 100 parts by weight of tackifier (E) based on 100 parts by weight of total weight of adhesive acrylic polymer (A) and curable polyester oligomer (B) The curable pressure-sensitive adhesive composition according to claim 1, comprising at least one selected from the group consisting of (1) to (3). 3. A pressure-sensitive adhesive sheet or tape produced by applying or impregnating a substrate with the curable pressure-sensitive adhesive composition according to claim 1.