TW201420709A - Adhesive composition and use thereof, laminated body and peeling method - Google Patents

Abstract

An adhesive composition is provided. The adhesive composition includes a condensation polymer, and a reactive compound reacting with a functional group of the condensation polymer to form a crosslink or a graft and/or a polymerizable compound having a high molecular weight to produce a mixture with the condensation polymer.

Description

Adhesive composition, laminate, and peeling method

The present invention relates to an adhesive composition, a laminate, and a peeling method.

Adhesives are widely used for adhering the fixed adhesive, but there are cases where the adhered adhesive must be peeled off. For example, Patent Document 1 discloses an adhesive sheet which is capable of reducing the peeling force of the release sheet against the adhesive layer by the expansion of the expandable fine particles or the release of the gas of the expandable fine particles. And peeling off.

[Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open Publication No. 2007-254580

Regarding the adhesive sheet of Patent Document 1, there is a limitation in the expansion temperature or the foaming temperature of the expandable fine particles or the expandable fine particles, and it is in the range of 200 ° C to 270 ° C. Unusable situation.

Accordingly, it is an object of the present invention to provide an adhesive composition which can adhere to a bonded body at room temperature and which has sufficient adhesion at 200 ° C to 270 ° C and can be easily used as needed. Stripping. Further, an object of the present invention is to provide a laminate and a peeling method using the adhesive composition.

The present invention provides an adhesive composition comprising: a condensed polymer and a reactive compound which reacts with a functional group of a condensed polymer to form a crosslinked or grafted compound, and/or a high molecular weight polymerized with the above condensation The material forms a polymerizable compound of the mixture.

The adhesive composition can be adhered to the adherend at room temperature and maintains its adhesion at 200 ° C to 270 ° C. Further, the adhesiveness is sufficiently lowered to be peelable based on the formation of cross-linking or grafting or high molecular weight. Here, the formation of the cross-linking or grafting and the high molecular weight are preferably caused by heating or irradiation with active rays. Further, the same compound may function as both a reactive compound and a polymerizable compound. That is, cross-linking or grafting and high molecular weight can also occur simultaneously.

The condensed polymer is preferably polyamine, polyimide or polyamidimide. Further, the functional group in which the reactive compound reacts is at least one main chain functional group selected from the group consisting of a guanamine bond, a ruthenium bond bond, and a valine acid structure, or is selected from a carboxyl group, an amine group, and a carboxylic acid. At least one terminal functional group in the group consisting of a halide structure and a carboxylic anhydride structure is preferred. Here, the terminal includes a side chain in addition to both ends of the molecule.

The condensed polymer preferably has a polyoxyalkylene group. The flexibility and the adhesion are improved by the polyoxyalkylene group. The condensed polymer preferably has a divalent aromatic ring group, and the adhesion at a high temperature is further improved by the presence of a divalent aromatic ring group. Further, the condensed polymer may have a 1,4-piperazinediyl group.

As the reactive compound, an isocyanate compound, a blocked isocyanate compound, an epoxy resin, or a combination of an epoxy resin and the curing agent can be used. By such a reactive compound, the adhesion can be easily lowered at a specific temperature.

The reactive compound may also be a polyfunctional reactive compound. By being polyfunctional, the crosslinked structure can be easily introduced, and it becomes easy to lower the adhesiveness under the desired conditions.

The polymerizable compound preferably comprises an epoxy resin, a cresol resin, a melamine resin, a urea resin, an unsaturated polyester resin, a urethane resin, a cyanate resin, an isocyanate compound, and a closed type. At least one thermosetting compound in a group consisting of isocyanate compounds, and/or a compound which generates at least one of a radical, a cation, and an anion by active light and undergoes self-polymerization or crosslinking reaction, Or a compound which generates a functional group by a reactive light and undergoes a hardening reaction. In the case of applying a thermosetting compound, a curing agent may be used in combination, and in the case of applying a photocurable compound, a photoinitiator or a sensitizer may be used in combination.

In such an adhesive composition, adhesion can be lowered by formation of cross-linking or grafting, and/or high molecular weight.

The adhesive composition can be used as an adhesive at an application temperature in the range of 200 ° C to 270 ° C, and cross-linking or graft formation, and/or high molecular weight can be performed at a temperature exceeding the application temperature. Reduce adhesion.

Further, the adhesive composition can be used as an adhesive at an application temperature in the range of 200 ° C to 270 ° C, and crosslinking or graft formation occurs by irradiation with active light (ultraviolet rays, etc.), and/or The polymer is quantified, whereby the adhesion can be lowered.

The adhesive composition of the present invention can also be used to form a layer of the adhesive composition on the support, and is provided in the form of a laminate having a layer on which the adhesive composition is provided on the support.

Further, the present invention provides a use of a composition comprising a composition comprising a condensed polymer and a reactive group formed by reacting with a functional group of a condensed polymer to form a crosslink or graft. A polymerizable compound which forms a mixture with a condensed polymer, which is a compound and/or a high molecular weight. In this case, the adhesive may be an adhesive which lowers the adhesive force by irradiation with heat and/or active light.

Furthermore, the present invention provides a peeling method in which a bonded body obtained by bonding a bonded body to a layer containing an adhesive composition in the above-described adhesive composition or the laminated body, wherein the adhesive is adhered thereto The agent composition is heated or irradiated with active light to lower the adhesive force, and at least a part of the joined portion is peeled off. Further, in the case of heating or active light irradiation, in the case where the adherend is bonded by the adhesive composition, the adhesive composition may be applied, and the bonded body may be bonded to the layer containing the adhesive composition. Next, the adhesive composition in the layer is made or The layer can be carried out as a whole.

According to the present invention, it is possible to provide an adhesive composition which can adhere to a bonded body at room temperature, has sufficient adhesion at 200 ° C to 270 ° C, and can be easily peeled off as needed. . Further, a laminate using the adhesive composition and a peeling method are provided.

The adhesive composition of the present invention contains a condensed polymer and a reactive compound which reacts with a functional group of the condensed polymer to form a crosslinked or grafted compound, and/or a polymer compounded to form a mixture with the condensed polymer. Polymeric compound. Further, in the present invention, the term "adhesiveness" means that the storage elastic modulus (G') measured at 10 radians/second at a temperature of 20 ° C to 22 ° C is less than 3 × 10 ⁵ Pascal. (Dahlquist benchmark). The adhesive composition of the present invention exhibits sufficient adhesion at 200 ° C to 270 ° C. This sufficient adhesion means, for example, an adhesion force measured in the following 90° peel test of 0.1 N/cm or more.

The first embodiment of the condensed polymer is polyamine. The polyamine has a guanamine group in the main chain, and the terminal of the main chain has an amine group, a carboxyl group, a carboxylic acid halide structure or a carboxylic anhydride structure. The carboxylic acid halide structure may, for example, be a hydrazine halide group such as -COCl or -COBr, and a carboxylic acid anhydride structure means an acid anhydride group formed of a plurality of carboxyl groups. The polyamine is preferably a structural unit represented by the following formula (1-1).

In the above formula (1-1), R ¹ and R ² represent a divalent organic group. R ^{1 is} preferably selected from the group consisting of a chain aliphatic compound, a cyclic aliphatic compound (including an alicyclic compound, a crosslinked cyclic compound, a spirocyclic hydrocarbon), a compound having a benzene ring (including naphthalene, anthracene, and fused tetraphenyl). a divalent organic group obtained by removing two hydrogen atoms from a compound in a group consisting of condensed polycyclic hydrocarbons such as hydrazine and hydrazine and benzene) and a heterocyclic compound.

R ^{2 is} preferably selected from the group consisting of a chain aliphatic compound, a cyclic aliphatic compound (including an alicyclic compound such as a compound having a methylene dicyclohexyl group, a crosslinked cyclic compound, a spirocyclic hydrocarbon), and a benzene ring. Compounds (including condensed polycyclic hydrocarbons such as naphthalene, anthracene, fused tetraphenyl, anthracene, fluorene, and benzene), heterocyclic compounds, polyalkylene oxides (including polyethylene oxide, polypropylene oxide), and polyorganoindenes a divalent organic group obtained by removing two hydrogen atoms from a compound or a halide thereof (fluoride or the like) of a group consisting of oxyalkylene (including polydimethyl siloxane or polymethylphenyl siloxane) . Further, the compound having a benzene ring as described above for the compound providing R ² contains 2,2-bis(4-phenoxyphenyl)propane and 2,2-bis(4-phenoxyphenyl). Bismuth, 2,2-bis(4-phenoxyphenyl)methane, 4,4'-bisphenoxybiphenyl, bis(4-phenoxyphenyl)ether, bis(4-phenoxybenzene) Ketone, 1,3-phenoxybenzene, 1,4-phenoxybenzene, 2,2'-dimethylbiphenyl, 5,5'-dimethyl-2,2'-sulfonyl -biphenyl, diphenyl ether, diphenyl hydrazine, benzophenone, diphenylmethane, and the like.

The second embodiment of the condensed polymer is exemplified by polyimide. The polyimine has an oximine group in the main chain, and the terminal of the main chain has an amine group, a carboxyl group, a carboxylic acid halide structure or a carboxylic anhydride structure. The polyimine is preferably a structural unit represented by the following formula (1-2).

In the above formula (1-2), R ² represents a divalent organic group, and R ³ represents a tetravalent organic group. A preferred group as R ² is the same as in the case of the above formula (1-1). R ^{3 is} preferably selected from the group consisting of a chain aliphatic compound, a cyclic aliphatic compound (including an alicyclic compound, a crosslinked cyclic compound, a spirocyclic hydrocarbon), a compound having a benzene ring (including naphthalene, anthracene, and fused tetraphenyl). a tetravalent organic group obtained by removing four hydrogen atoms from a compound in a group consisting of condensed polycyclic hydrocarbons such as hydrazine and hydrazine and benzene) and a heterocyclic compound.

A third embodiment of the condensed polymer is polyamidoximine. The polyamidoximine has a mercaptoamine group and a quinone imine group in the main chain, and the terminal of the main chain has an amine group, a carboxyl group, a carboxylic acid halide structure or a carboxylic anhydride structure. The polyamidimide preferably has a structural unit represented by the following formula (1-3) or formula (1-4), and a part of the polyamidoximine may have a structure of (1-3). Some have a structure of (1-4).

In the above formula (1-3) and formula (1-4), R ² and R ⁵ represent a divalent organic group, and R ⁴ represents a trivalent organic group. The same as in the formula (1-1) R ² R ² is preferably a group of the above formula (1-1) is the same as the preferred R ⁵ group. R ^{4 is} preferably selected from the group consisting of a chain aliphatic compound, a cyclic aliphatic compound (including an alicyclic compound, a crosslinked cyclic compound, a spirocyclic hydrocarbon), a compound having a benzene ring (including naphthalene, anthracene, and fused tetraphenyl). a trivalent organic group obtained by removing three hydrogen atoms from a compound in a group consisting of condensed polycyclic hydrocarbons such as hydrazine and hydrazine and benzene) and a heterocyclic compound.

The above polyamine, polyimine or polyamidimide preferably has a polyoxyalkylene group. When the condensed polymer contains a polyoxyalkylene group, the glass transition temperature of the adhesive composition is lowered, for example, it becomes easy to adhere at a low temperature such as room temperature, and the adhesiveness is excellent. The polyoxyalkylene group may be a group represented by the following formula (2). In the formula, n represents an integer of 2 or more, and R ⁶ represents an alkanediyl group. Here, the plurality of R ⁶ may be present in the same or different from each other.

In the above formula (2), R ⁶ may be linear or branched, preferably an alkanediyl group having 2 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 3 carbon atoms. Examples of R ⁶ include an ethane-1,2-diyl group, a propane-1,2-diyl group, a propane-1,3-diyl group, and a butane-1,4-diyl group. n is preferably 2 to 70, more preferably 6 to 33.

The polyoxyalkylene diyl group is preferably composed of polyethylene oxide, polypropylene oxide, polybutylene oxide, polyoxytetramethylene ether, polyethylene oxide-polypropylene oxide copolymer, polyethylene. a polyalkylene oxide-derived group such as an alcohol-polyether diol copolymer, a polypropylene glycol-polyether diol copolymer, a polyethylene glycol-polypropylene glycol-polyether diol copolymer, or more preferably a polyoxyethylene group , polyoxypropylene-1,2-diyl.

The method of introducing a polyoxyalkylene diamine into polyamine, polyimine or polyamidimide is simple to use a raw material having a polyoxyalkylene group in at least one raw material (polymerizable monomer).

The polyamine can be obtained, for example, by condensation polymerization of the monomer (A-1) represented by the following formula (A-1) and the monomer (B-1) represented by the following formula (B-1). The carboxyl group of the monomer (A-1) can be converted into a fluorenyl chloride group to form a polydecylamine, which can also be produced by other methods. The monomer (A-1) and the monomer (B-1) may be used alone or in combination of two or more. Further, in the following formulae (A-1) and (B-1), the definitions of R ¹ and R ² are preferably as described above.

HOOC-R ¹ -COOH (A-1)

H ₂ NR ² -NH ₂ (B-1)

The polyimine can be obtained, for example, by condensation polymerization of a monomer (A-2) represented by the following formula (A-2) and a monomer (B-1) to form a poly-proline, and Its dehydration closed loop. An anhydride (monomer (A-2')) represented by the following formula (A-2') may be used instead of the monomer (A-2). Further, the polyimine is not necessarily produced by the method, and may be produced by another method as long as it has the structural unit represented by the above formula (1-2). The monomer (A-2) and the monomer (B-1) may be used alone or in combination of two or more. Further, in the following formula (A-2) and formula (A-2'), the definition of R ³ and preferably are as described above.

The polyamidoximine of the above formula (1-3), for example, can react a monomer (A-3) represented by the following formula (A-3) with a monomer (B-1) to form a diimine. The dicarboxylic acid is obtained by reacting the monomer (C-1) represented by the following formula (C-1) with it. Instead of the monomer (A-3), an anhydride (monomer (A-3')) represented by the following formula (A-3') can also be used. Further, the polyamidoximine of the above formula (1-4) can be obtained, for example, by condensation polymerization of a monomer (A-3) and a monomer (B-1). Instead of the monomer (A-3), a monomer (A-3') can also be used. The polyamidoximine is not necessarily produced by this method, and may be produced by other methods as long as it has a structural unit represented by the above formula (1-3) or formula (1-4). The monomer (A-3), the monomer (A-3'), the monomer (B-1), and the monomer (C-1) may be used alone or in combination of two or more. Further, in the following formula (A-3), formula (A-3'), and formula (C-1), the definitions of R ⁴ and R ⁵ are preferably as described above.

OCN-R ⁵ -NCO (C-1)

The monomer (A-1) (monomer having two carboxyl groups) may, for example, be oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid or hydrazine. Diacid, 1,9-decanedicarboxylic acid, dodecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, octadecanedioic acid, etc. alkyl dicarboxylic acid, phthalic acid, pair An aryl dicarboxylate such as phthalic acid, isophthalic acid, 1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid or 2,6-naphthalene dicarboxylic acid Acid, 4-methylhexahydrophthalic acid, 3-methylhexahydrophthalic acid, 2-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 2-ethyl A dicarboxylic acid having a cyclohexane skeleton such as hexahydrophthalic acid, methylnorbornane-2,3-dicarboxylic acid or methylnorbornane-3,4-dicarboxylic acid. In terms of improvement in heat resistance of the adhesive composition, an aryldicarboxylic acid is preferred.

The monomer (A-2) (monomer having four carboxyl groups) may, for example, be pyromellitic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,4,5-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 3,3',4 , 4'-diphenyl ether tetracarboxylic acid, 3,3',4,4'-biphenyltetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-anthracene Carboxylic acid, 4,4'-sulfonyl diphthalic acid, 1-trifluoromethyl-2,3,5,6-benzenetetracarboxylic acid, 2,2',3,3'-biphenyl Carboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)propane, 2,2-bis(2,3-dicarboxyphenyl)propane, 1,1-bis(2,3-dicarboxybenzene Ethylene, 1,1-bis(3,4-dicarboxyphenyl)ethane, bis(2,3-dicarboxyphenyl)methane, bis(3,4-dicarboxyphenyl)methane, double (3,4-dicarboxyphenyl)anthracene, bis(3,4-dicarboxyphenyl)ether, benzene-1,2,3,4-tetracarboxylic acid, 2,3,2',3-diphenyl Methyl ketone tetracarboxylic acid, 2,3,3',4'-benzophenone tetracarboxylic acid, phenanthrene-1,8,9,10-tetracarboxylic acid, pyrazine-2,3,5,6-tetra Carboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, 3,4,3',4'-biphenyltetracarboxylic acid, 2 ,3,2',3'-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl)dimethylnonane, bis(3,4-dicarboxyphenyl) Methyl phenyl decane, bis(3,4-dicarboxyphenyl)diphenyl decane, 1,4-bis(3,4-dicarboxyphenyldimethyl decyl)benzene, 1,3-double ( 3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldicyclohexane, p-phenylene bis(trimellitic acid ester), ethylidenetetracarboxylic acid, 1,2, 3,4-butane tetracarboxylic acid, decalin-1,4,5,8-tetracarboxylic acid, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene- 1,2,5,6-tetracarboxylic acid, cyclopentane-1,2,3,4-tetra Carboxylic acid, pyrrolidine-2,3,4,5-tetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, bicyclo-(2,2,2)-octyl (7)-ene 2,3,5,6-tetracarboxylic acid, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 2,2-bis(4-(3,4-dicarboxyphenoxy) Phenyl) hexafluoropropane, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide, 4,4'-(4,4'-isopropylidenediphenoxy) - bis(phthalic acid), tetrahydrofuran-2,3,4,5-tetracarboxylic acid, bis(exobicyclo(2,2,1)heptane-2,3-dicarboxylic acid) hydrazine, 1 , 2,4,5-tetracarboxycyclohexane, bicyclo[2.2.2]octane-2,3:5,6-tetracarboxylic acid, 5,5'-endo-(polyoxane-1 , 5-diyl)-bibicyclo[2,2,1]heptane-exo-2,3-dicarboxylic acid, and the like.

The monomer (A-3) (monomer having three carboxyl groups) may, for example, be an aromatic tricarboxylic acid such as trimellitic acid or an alicyclic tricarboxylic acid such as cyclohexane-1,2,4-tricarboxylic acid. Wait.

The monomer (B-1) may, for example, be 2,2-bis[4-(4-aminophenoxy)phenyl]propane or bis[4-(3-aminophenoxy)phenyl]anthracene. Bis[4-(4-aminophenoxy)phenyl]anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, bis[4-(4-amine Phenoxy)phenyl]methane, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4- (4-Aminophenoxy)phenyl]one, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2' - dimethylbiphenyl-4,4'-diamine, 2,2'-bis(trifluoromethyl)biphenyl-4,4'-diamine, 5,5'-dimethyl-2,2 '-sulfonyl-biphenyl-4,4'-diamine, (4,4'-diamino)diphenyl ether, (4,4'-diamino)diphenylanthracene, (4,4 '-Diamino)benzophenone, (3,3'-diamino)benzophenone, (4,4'-diamino)diphenylmethane, (4,4'-diamino An aromatic diamine such as diphenyl ether, (3,3'-diamino)diphenyl ether or N,N'-bis(4-aminophenyl)piperazine, ethylidene diamine, and propyl group Diamines such as alkyl diamines, polyoxyalkylene diamines such as polyethylene oxide diamine and polypropylene oxide diamine, (4,4'-diamino) dicyclohexylmethane, isophorone II Amine, 1,4-diaminopropyl Piperazine, [3,4-bis(1-aminoheptyl)-6-hexyl-5-(1-octenyl)] An aliphatic diamine such as cyclohexene or bisaminomethylnordecene, or a nonoxyalkylene diamine such as polydimethyl siloxane diamine.

The monomer (C-1) may, for example, be diphenylmethane-2,4'-diisocyanate, 3,2'-dimethyldiphenylmethane-2,4'-diisocyanate, 3,3'-di Methyl diphenylmethane-2,4'-diisocyanate, 4,2'-dimethyldiphenylmethane-2,4'-diisocyanate, 4,3'-dimethyldiphenylmethane-2 , 4'-diisocyanate, 5,2'-dimethyldiphenylmethane-2,4'-diisocyanate, 5,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 6 , 2'-dimethyldiphenylmethane-2,4'-diisocyanate or 6,3'-dimethyldiphenylmethane-2,4'-diisocyanate, 3,2'-diethyl Phenylmethane-2,4'-diisocyanate, 3,3'-diethyldiphenylmethane-2,4'-diisocyanate, 4,2'-diethyldiphenylmethane-2,4' -diisocyanate, 4,3'-diethyldiphenylmethane-2,4'-diisocyanate, 5,2'-diethyldiphenylmethane-2,4'-diisocyanate, 5,3' -Diethyldiphenylmethane-2,4'-diisocyanate, 6,2'-diethyldiphenylmethane-2,4'-diisocyanate or 6,3'-diethyldiphenylmethane -2,4'-diisocyanate, 3,2'-dimethoxydiphenylmethane-2,4'-diisocyanate, 3,3'-dimethoxydiphenylmethane-2 , 4'-diisocyanate, 4,2'-dimethoxydiphenylmethane-2,4'-diisocyanate, 4,3'-dimethoxydiphenylmethane-2,4'-diisocyanate , 5,2'-dimethoxydiphenylmethane-2,4'-diisocyanate, 5,3'-dimethoxydiphenylmethane-2,4'-diisocyanate, 6,2'- Dimethoxydiphenylmethane-2,4'-diisocyanate or 6,3'-dimethoxydiphenylmethane-2,4'-diisocyanate, diphenylmethane-4,4'-di Isocyanate, diphenylmethane-3,3'-diisocyanate, diphenylmethane-3,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, benzophenone-4,4'- Diisocyanate, diphenylphosphonium-4,4'-diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, Aromas such as m-xylylene diisocyanate, p-xylylene diisocyanate, naphthalene-2,6-diisocyanate, 4,4'-[2,2bis(4-phenoxyphenyl)propane] diisocyanate A polyisocyanate. Further, the monomer (C-1) can be exemplified by hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane. An aliphatic or alicyclic isocyanate such as diisocyanate, transcyclohexane-1,4-diisocyanate, hydrogenated m-xylylene diisocyanate, or isocyanuric acid diisocyanate. In order to avoid the change over time, the monomer (C-1) may also be a monomer stabilized by a blocking agent, and examples of such a blocking agent include alcohol, phenol, and hydrazine.

As described above, the condensed polymer preferably has a polyoxyalkylene in the structural unit represented by the above formula (1-1), formula (1-2), formula (1-3) or formula (1-4). The dibasic group, more preferably a polyoxyalkylene group present in the structure derived from the monomer (B-1) in the structural unit. That is, monomer (A-1), monomer (A-2), monomer (A-2'), monomer (A-3), monomer (A-3'), and monomer (preferably) At least one of B-1) has the above polyoxyalkylene group, and more preferably at least one of the monomers (B-1) has a polyoxyalkylene group.

Therefore, the condensed polymer preferably has a structural unit obtained by condensation-polymerizing a polymerizable monomer containing a monomer having a polyoxyalkylene group and at least two amine groups (monomer (b-1)).

The content of the monomer (b-1) in the polymerizable monomer is preferably from 5 mol% to 20 mol%, more preferably from 7 mol% to 15 mol%, more preferably from 7 mol% to 15 mol%, based on the total amount of the monomers (B-1). 8 mol% to 10 mol%. The adhesive composition having a structural unit obtained by condensation polymerization of such a polymerizable monomer tends to be more excellent in adhesion to the adherend.

The monomer (b-1) is exemplified by a polyalkylene oxide polyamine. The polyalkylene oxide polyamine is preferably a polyalkylene oxide diamine or a polyalkylene oxide triamine, and such an amine can preferably be JEFFAMINE D-230 (HUNTSMAN, trade name), JEFFAMINE D- Polypropylene oxide diamine such as 400 (HUNTSMAN, trade name), JEFFAMINE D-2000 (HUNTSMAN, trade name), JEFFAMINE D-4000 (HUNTSMAN, trade name), JEFFAMINE ED-600 (HUNTSMAN, trade name), JEFFAMINE ED Polyethylene oxide such as copolymer of polyethylene oxide and polyethylene oxide, such as J-900 (HUNTSMAN, trade name) Polyamine (polyoxypropylene triglyceride triamine) such as ethane diamine, JEFFAMINE T-403 (HUNTSMAN, trade name), JEFFAMINE T-3000 (HUNTSMAN, trade name), JEFFAMINE T-5000 (HUNTSMAN, trade name) )Wait. These may be used alone or in combination of two or more.

Further, the condensed polymer preferably has an alicyclic structure. The adhesive composition having such a structure can suppress water absorption. The alicyclic structure may, for example, be a cyclohexyl group, a dicyclohexyl group, a methylene dicyclohexyl group, an isophorone group or a cyclohexyldimethyl group.

Examples of the carboxylic acid monomer having such an alicyclic structure include 1,4-dicarboxycyclohexane as the monomer (A-1) and cyclohexane-1 as the monomer (A-2'). 2,4,5-tetracarboxylic dianhydride and dicyclohexyl-3,3',4,4'-tetracarboxylic dianhydride, and the monomer (A-3') may, for example, cyclohexane-1,2. 4-tricarboxylic anhydride. Further, as the amine-based monomer having the above alicyclic structure, the monomer (B-1) can be exemplified by bis(4-aminocyclohexyl)methane, isophoronediamine, and 1,3-bis(amino group A). Base) cyclohexane. These may be used alone or in combination of two or more.

Further, the condensed polymer preferably has a methylene dicyclohexyl group in the structural unit, and more preferably a methylene dicyclohexyl group is present in the structure derived from the monomer (B-1) in the structural unit. That is, monomer (A-1), monomer (A-2), monomer (A-2'), monomer (A-3), monomer (A-3'), and monomer (preferably) At least one of B-1) has a methylene dicyclohexyl group, and more preferably at least one of the monomers (B-1) has the above methylene dicyclohexyl group.

In other words, the condensed polymer preferably has a structural unit obtained by condensation-polymerizing a polymerizable monomer containing a monomer having a methylene dicyclohexyl group and at least two amine groups (monomer (b-2)).

The content of the monomer (b-2) in the polymerizable monomer is preferably from 4 mol% to 28.5 mol%, more preferably from 8 mol% to 28.5 mol%, based on the total amount of the monomer (B-1). Preferably, it is 8 mol% to 20 mol%. The water absorption rate of the adhesive composition having a structural unit obtained by condensation polymerization of such a polymerizable monomer is suppressed, and the storage stability is further improved.

As the monomer (b-2), bis(4-aminocyclohexyl)methane can be preferably used.

With respect to the condensed polymer, the structure derived from the monomer (B-1) in the structural unit preferably has a 1,4-piperazinyl group, and more preferably has a piperazine-N,N'-dipropyl group.

That is, the condensed polymer preferably has a polymerizable monomer having a monomer (monomer (b-3)) having a piperazine-N,N'-dipropyl group and at least two amine groups condensed and polymerized. The structural unit obtained.

The content of the monomer (b-3) in the polymerizable monomer is not particularly limited, and the remaining amount after the application of the monomers (b-1) and (b-2) can be used in the maximum amount. according to A condensed polymer having a structural unit obtained by condensation-polymerizing such a polymerizable monomer can obtain an adhesive composition having excellent balance between heat resistance and adhesion.

As the monomer (b-3), 1,4-bis(3-aminopropyl)piperazine can be preferably used.

The condensed polymer can be, for example, condensed and polymerized with the monomer (A-1), the monomer (A-2) or the monomer (A-3) and the polymerizable monomer containing the monomer (B-1). obtain. In addition, monomers (A-1), monomers (A-2), and esters of the monomers (A-3), hydrazine halides, and the like may be used instead of the monomers (A-1) and monomers (A-). 2) and monomer (A-3). Further, the monomer (A-2) and the anhydride of the monomer (A-3) may be used instead of the monomer (A-2) and the monomer (A-3).

The method of the condensation polymerization is not particularly limited. For example, a method in which a polymerizable monomer is dissolved in a solvent and reacted at a reaction temperature of 0 ° C to 200 ° C and a reaction time of about 1 hour to 10 hours may be employed.

The solvent used in the condensation polymerization may, for example, be N-methylpyrrolidone, N-ethylpyrrolidone, N-methylbutylimine, dimethylfuran, toluene, N,N'-dimethyl Ethyl amide, hexamethylene phosphoniumamine, dimethyl hydrazine, and the like. Among them, from the viewpoint of solubility of the resin, N-methylpyrrolidone is preferred.

Further, in the condensation polymerization, an accelerator such as a catalyst may be used for the purpose of promoting the condensation reaction. The amount of the accelerator added is preferably from 0.1 nm to 50 mol equivalents based on 10 mol equivalents of the polymerizable monomer. Examples of the accelerator include inorganic salts such as lithium chloride, calcium chloride, and calcium thiocyanate; tertiary amines such as triethylamine and pyridine; tetramethylammonium chloride, tetraethylammonium bromide, and tetra-n-butyl. A quaternary ammonium salt such as ammonium bromide.

The condensed polymer may be a condensed polymer (modified condensed polymer) obtained by modifying a polymer obtained by condensation polymerization, and the modified condensed polymer may be an olefin-modified polyamine. Alkoxydecane modified polyamine, decane modified polyimine, epoxy modified polyamine, polycarbonate modified polyamine, isocyanate modified polyamine, olefin modified poly Amine, decane modified polyimine, epoxy modified polyimine, polycarbonate modified polyimine, decane modified polyimine, isocyanate modified polyimine, olefin Modified polyamidoximine, alkoxydecane modified polyamidoximine, decane modified polyamidoximine, epoxy modified polyamidoximine, epoxy modified poly Amidoxime, polycarbonate modified polyamidoximine, isocyanate modified polyamidoximine, and the like.

The adhesive composition contains a reactive compound which reacts with the functional group of the condensed polymer described above to form a crosslinked or grafted compound (hereinafter referred to as a "reactive compound"), or a high molecular weight, and the above description The condensed polymer forms a polymerizable compound of a mixture (hereinafter referred to as a "polymerizable compound"), or both a reactive compound and a polymerizable compound (there are two types of a reactive compound and a polymerizable compound) And a case where one compound has a function of both a reactive compound and a polymerizable compound). Further, in the case where the reactive compound forms "crosslinking", the compound may have a plurality of functional groups reactive with the functional group of the condensed polymer. In this case, the plurality of condensed polymers are crosslinked by the reactive compound. On the other hand, in the case where the reactive compound is "grafted", the compound may have a functional group reactive with the functional group of the condensed polymer. In this case, the reactive compound is bonded to the side chain of the condensed polymer. Wait. In addition, The reactive compound and the polymerizable compound are not limited to the low molecular compound, and may be an oligomer or a polymer compound.

The functional group of the condensed polymer which reacts the reactive compound is preferably selected from the group consisting of a guanamine bond (-CONH-), a quinone bond ((-CO) ₂ -N-), and a valine structure (-R ⁰ At least one main chain functional group in the group consisting of (COOH)-CONH-, R ⁰ is a trivalent or higher organic group, or selected from a carboxyl group (-COOH), an amine group (-NH ₂ ), a carboxylic acid At least one terminal functional group in the group consisting of a halide structure (-COOX, X is a halogen atom such as a chlorine atom) and a carboxylic anhydride structure (-CO-O-CO-).

The reactive compound can be, for example, an isocyanate compound, a blocked isocyanate compound, an epoxy resin, or a combination of an epoxy resin and a curing agent for the epoxy resin.

On the other hand, the polymerizable compound may be selected from the group consisting of epoxy resins, cresol resins, melamine resins, urea resins, unsaturated polyester resins, urethane resins, cyanate resins, isocyanate compounds, and blocked isocyanate compounds. a thermosetting compound in a group formed, a compound which generates at least one of a radical, a cation, and an anion by an active ray and undergoes a self-polymerization or crosslinking reaction, or a functional group which is hardened by an active ray and hardens The compound of the reaction. Further, a curing agent for the epoxy resin may be added to the epoxy resin as the polymerizable compound.

The compound (photo-radical polymerizable compound) which generates a radical by the active light and which is self-polymerized may, for example, be a compound having an ethylenically unsaturated bond such as (meth)acrylic acid or (meth)acrylate. Producing anions by active light and Examples of the compound (photo anion polymerizable compound) in which self polymerization occurs include cyanoacrylate and cyanoacrylate. An epoxy compound is exemplified as a compound (photocationic polymerizable compound) which generates a cation by active light and undergoes self-polymerization. Further, the (meth) acrylonitrile group means a methacryl fluorenyl group or an acryl fluorenyl group, and the same is true for other similar compounds.

The compound which generates at least one of a radical, a cation, and an anion by the actinic light and undergoes a crosslinking reaction is exemplified by the presence of a plurality of reactivity among the photoradical polymerizable compound, the photoanion polymerizable compound, and the photocationic polymerizable compound. A functional group of compounds.

A compound which generates a functional group by active light and undergoes a hardening reaction can be exemplified by a light-transfer type resin. The light-transfer type resin has an isocyanate compound or a combination of a urethane resin and a photobase generator, and an amine compound is produced by active light, and an amine group of the amine compound is polymerized and hardened.

The same kind of compound may be mentioned as a reactive compound and a polymerizable compound, and the same compound may exhibit the function of both a reactive compound and a polymeric compound.

The functional group reactive with an amine group, a carboxyl group, and a guanamine bond may, for example, be an epoxy group. The epoxy group and the amine group are bonded, for example, in the form of the following formula (3-1). Further, the epoxy group and the carboxyl group are reacted, for example, in the form of the following formula (3-2), and the epoxy group and the guanamine bond are bonded, for example, by the following formula (3-3) or formula (3-4). Further, in the formula, R ⁷ to R ¹⁰ represent a monovalent organic group.

Examples of the functional group other than the epoxy group which reacts with an amine group, a carboxyl group, and a guanamine bond include an isocyanate group. The isocyanate group and the amine group are bonded by, for example, a reaction of the following formula (4-1). Further, the isocyanate group and the carboxyl group are bonded and bonded, for example, in the following formula (4-2), and the isocyanate group and the guanamine group are bonded and bonded, for example, in the form of the following formula (4-3). Further, in the formula, R ⁸ to R ¹¹ represent a monovalent organic group.

From the viewpoint of efficiently crosslinking, the epoxy resin as the epoxy group-containing compound preferably has two or more epoxy groups. Specific examples can be exemplified: Bisphenol A type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, bisphenol F type epoxy resin, phosphorus containing epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, Aliphatic chain epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A novolac epoxy resin, diglycidyl ether of bisphenol, dihydrate of naphthalenediol A glycerol etherate, a diglycidyl ether of a phenol, a diglycidyl ether of an alcohol, and an alkyl substituent, a halide, a hydride, etc. of these. These epoxy resins may be used alone or in combination of two or more.

The epoxy resin preferably further contains an epoxy hardener. Thereby, the reaction of the epoxy resin is promoted, and the decrease in the adhesion of the adhesive composition becomes remarkable. Examples of the epoxy curing agent include a phenol type epoxy curing agent, a cresol type epoxy curing agent, and an ester type epoxy curing agent. Among them, an ester type epoxy curing agent is preferred because it has excellent properties of reducing the adhesion of the adhesive composition. Further, in the case of using an ester type epoxy hardener, it is considered that the reaction with the epoxy resin occurs in the following manner.

The amount of the epoxy hardener to be added varies depending on the efficiency of curing, and it is preferably 0.1 equivalent to 2.0 functional equivalents per equivalent of the epoxy.

An imidazole may also be added to the hardening accelerator of the epoxy resin. Examples of the imidazoles include imidazole, 2-methylimidazole, 2-undecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-imidazole, 2-phenylimidazole, 2-phenyl- 4-methylimidazole, 1-benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2 -phenylimidazole, 2-phenylimidazoline, naphthoimidazole, pyrazole, triazole, tetrazole, oxazole, pyridine, pyrazine, pyridazine, pyrimidine, benzotriazole, 1-cyanoethyl- 2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenyl Imidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, and the like. The curing accelerator is preferably used in an amount of 0.01 parts by mass to 5.0 parts by mass based on 100 parts by mass of the epoxy resin, from the viewpoint of the curability of the epoxy resin.

The isocyanate compound is preferably a blocked isocyanate compound. The blocked isocyanate compound is a compound which is formed by the reaction of an isocyanate compound and a blocking agent, and is temporarily inerted by a group derived from a blocking agent, and if heated to a specific temperature, the terminal blocking agent is derived. The group undergoes dissociation to form an isocyanate group. Specific examples of the isocyanate compound which can be reacted with the blocking agent include 4,4'-diphenylmethane diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, and naphthalene-1,5-di. Aromatic polyisocyanates such as isocyanate, phthalyl diisocyanate, m-xylylene diisocyanate, 2,4-toluene dimer, hexamethylene diisocyanate, 4,4-methylene bis(cyclohexyl) An aliphatic polyisocyanate such as an isocyanate or an isophorone diisocyanate, or an alicyclic polyisocyanate such as a dicycloheptane triisocyanate.

The blocking agent is preferably a blocking agent having an active hydrogen, and examples thereof include an active methylene group, a diketone, an anthracene, a phenol, an alkanol, and caprolactam. Specifically, methyl ethyl ketone oxime, ε-caprolactam or the like can be used.

The blocked isocyanate compound can be used for the purpose of the invention, and There are no particular restrictions, and may be Sumidule BL-3175, Sumidule BL-4165, Sumidule BL-1100, Sumidule BL-1265, Desmodule TPLS-2957, Desmodule TPLS-2062, Desmodule TPLS-2957, Desmodule TPLS-2078, Desmodule TPLS- 2117, Desmotherm 2170, Desmotherm 2265 (above: Sumitomo Bayer Urethane Co., Ltd., trade name), Coronate 2512, Coronate 2513, Coronate 2520 (above, manufactured by Japan Polyurethane Industry Co., Ltd., trade name), etc. Commercial products.

The polymerizable compound which can be contained in the adhesive composition and which is a mixture with the condensed polymer, as described above, may be a cyanate resin or an isocyanate compound. Specifically, it is preferred to have two or more cyanides in the molecule. An acid group cyanate or an isocyanate having two or more isocyanate groups in the molecule.

The cyanate compound having two or more cyanate groups in the molecule is trimerized as in the following formula (5-1), whereby a triazine ring is formed to carry out polymerization (multimerization). Further, in the formula, R ¹² represents a divalent organic group.

The isocyanate compound having two or more isocyanate groups in the molecule is polymerized by trimerization as in the following formula (5-2). Therefore, an isocyanate is a compound which is bonded to a condensed polymer and is polymerized. Further, in the formula, R ¹¹ represents a divalent organic group.

In the adhesive composition, the amount of the reactive compound or the polymerizable compound added to the condensed polymer is preferably 0.01% by mass to 50% by mass, more preferably 0.1% by mass based on the solid content of the adhesive composition. % to 30% by mass, more preferably 0.5% by mass to 25% by mass, even more preferably 1% by mass to 20% by mass. When it is this range, it is easy to obtain sufficient flatness and adhesiveness, and it can fully reduce adhesiveness.

The adhesive composition may contain a rosin resin, a terpene resin, a coumarone resin, a phenol resin, a styrene resin, an aliphatic petroleum resin, and a fragrance insofar as the purpose of improving the adhesion is not impaired. An adhesion promoter such as a petroleum resin or an aliphatic aromatic copolymer-based petroleum resin.

Further, the adhesive composition may contain an inorganic material such as alloy particles, glass particles or clay particles, or an organic material such as polymer particles. More specifically, alloy particles include tin alloys, lead alloys, indium alloys, zinc alloys, gold alloys, etc., glass Examples of the glass include lead, phosphate, boric acid, vanadate, telluride, and fluoride glass. Examples of the clay include: stevensite, montmorillonite, and kaolinite. ), illite, smectite, chlorite, vermiculite, etc., and polymer particles include polyethylene terephthalate, polyacrylonitrile, and fluororesin ( Polytetrafluoroethylene (PTFE), epoxy resin, nylon, polyimine, polyamidimide, polyethylene naphthalate, and the like. Further, the particles contain eucalyptus oil or fluorine-based oil, and the particles are weakened by heat, and at the same time ooze out in the adhesive composition, and bleed out to the subsequent interface, thereby allowing subsequent The force is further reduced.

Further, the adhesive composition may also contain a foamed material which generates a gas by heat. The foaming material may, for example, be a polymer particle containing a low boiling point compound or an organic material which generates a gas by thermal decomposition. More specific foaming materials are not particularly limited as long as they can achieve the object of the invention, and examples thereof include polyethylene terephthalate and polyacrylonitrile containing a liquid organic substance having a boiling point of 200 ° C to 400 ° C. Polymer particles such as fluororesin (PTFE), epoxy resin, nylon, polyimide, polyamidimide, and polyethylene naphthalate. On the other hand, an organic material which generates a gas by thermal decomposition can be exemplified by an azo compound such as azodicarboxylate, a tetrazole compound such as an aminotetrazole or a bistetrazole, or a sulfonate such as toluenesulfonyl urea. Amidinourea-based compound or the like.

Further, in order to improve thermal efficiency, the adhesive composition may also contain a material that generates heat by electromagnetic waves. The combination of such a material and an electromagnetic wave can be exemplified by the use of infrared rays for particles of an organic polymer, carbon, germanium, a metal oxide, glass, or ceramics. Induction heating (wavelength 0.1mm~1μm), use of microwaves for magnetic, ferromagism, ferromagnetism, antiferromagnetism or superparamagnetism (wavelength 1m~ 1mm) of the induction body is heated.

The adhesive composition preferably contains no hardening catalyst such as an amine, a carboxylic acid, an acid anhydride or a peroxide, and the content of the hardening catalyst in the case of containing a hardening catalyst is preferably relative to the solid content of the adhesive composition. It is 1% by mass or less, more preferably 0.5% by mass or less.

The adhesive composition can also be provided in the form of a film. That is, a film-like adhesive containing the above-described adhesive composition is provided. The film-like adhesive may be a film-like adhesive comprising a layer of a single-layer or multi-layered adhesive composition, or a film-like adhesive layer having a single-layer or multi-layered adhesive composition formed on one or both sides of the support. Agent. An example of a method for producing a film adhesive is shown below.

For example, a film-like adhesive can be produced by applying an adhesive composition varnish containing an adhesive composition onto one side of a support and drying it.

Further, a film-like adhesive having a layer having an adhesive composition on both sides of the support can be produced by applying the adhesive composition varnish to both sides of the support and drying it.

In addition, a layered layer of an adhesive composition formed by applying an adhesive composition varnish to a film such as a release film and drying it is transferred onto a support, thereby forming a film shape. Adhesive.

This method of making using the casting method is easy to obtain. A layer having a flat adhesive composition is preferred.

It is also possible to produce a film-like adhesive comprising a layer of a plurality of adhesive compositions. The film-like adhesive can be produced, for example, by applying a varnish of an adhesive to one surface of a support and drying it to form a layer of an adhesive composition, and then coating another layer having different characteristics on the layer. A varnish of the adhesive and allowed to dry.

Further, the film-like adhesive comprising a layer of the multilayer adhesive composition can also be produced by applying a varnish of a plurality of adhesive compositions having different properties to a film such as a release film and drying it. Thereby, a layer of the adhesive composition is formed, and the layers are sequentially laminated on the support.

Specifically, for example, by using an adhesive composition varnish containing a reactive compound and an adhesive composition varnish containing no reactive compound, a layer having an adhesive composition containing a reactive compound and a non-reactive property can be formed. A layer of the adhesive composition of the two layers of the adhesive composition of the compound. In the case where the film-like adhesive of the layer containing the multilayered adhesive composition is peeled off, the peeling of the interface which the layer of the adhesive composition containing the reactive compound contacts is prioritized. The film-like adhesive in which the layers of the multi-layered adhesive composition having different properties are laminated may be peeled off stepwise under the conditions corresponding to the layers of the respective adhesive compositions.

The thickness of the layer of the adhesive composition is preferably from 0.1 μm to 100 μm, more preferably from 1 μm to 50 μm. The thickness of the layer of the adhesive composition can be appropriately adjusted by the concentration of the adhesive composition in the adhesive composition varnish or the coating amount of the adhesive composition varnish.

The solvent used in the adhesive composition varnish is not particularly limited, and it is sticky. In view of exhibiting good solubility, the glycol composition, the glycol ether solvent, the glycol ester solvent, and the like can be preferably used.

Specific examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, diethylene glycol monomethyl ether, and triethylene glycol. Alcohol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-3-methyl-1-butanol, ethylene glycol monomethyl ether acetate, PMA (propylene glycol monomethyl ether acetate), diethylene Alcohol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and the like. Further, N-methylpyrrolidone, N-ethylpyrrolidone, N-methylbutylimine, N,N'-dimethylacetamide, dimethylformamide, etc. may also be used. . These solvents may be used alone or in combination of two or more.

The support is not particularly limited, and a material having heat resistance to a temperature of 200 ° C or higher is preferably used, and examples thereof include polyester, polyimine, polyamine, polyether oxime, polyphenylene sulfide, and polyether. A support for an organic material such as a ketone, a polyetheretherketone, a triacetylcellulose, a polyetherimine, a polyethylene naphthalate, a polypropylene, an acrylic, a polystyrene, or a polycarbonate. Further, a support containing an inorganic material may be used, and a support containing an inorganic material such as aluminum, magnesium, titanium, chromium, manganese, iron, nickel, zinc, tin, glass, ruthenium wafer, or alloy may be used.

The adhesive composition can be adhered at room temperature, and has sufficient adhesion at 200 ° C to 270 ° C, and the adhesion can be sufficiently lowered as needed to be easily peeled off.

The method of peeling off the adhesive composition may be a method of heating at a temperature exceeding 270 ° C, for example, 275 ° C, lowering the adhesion of the adhesive composition, lifting it up, and peeling off. The heating time can be set as appropriate, for example 30 minutes. Further, even at a temperature of from 200 ° C to 270 ° C, the adhesion of the adhesive composition can be lowered by continuously heating for a long period of time, thereby easily peeling off.

The method of heating the adhesive composition is exemplified by a method of directly contacting a bonded body or a support with a heat source such as a hot plate, and blowing a hot air such as a hot air oven or a dryer to irradiate the microwave ( Microwave), laser (laser) and other methods of electromagnetic waves. Further, the electromagnetic wave can be exemplified by laser light, infrared light, visible light, ultraviolet light, X-ray, or the like.

The preferred adherend for the adhesive composition is preferably a material having heat resistance to a temperature of 200 ° C or higher. The more specific adherend is not particularly limited as long as it can achieve the object of the invention, and examples thereof include polyamine resins such as nylon 6, nylon 66, and nylon 46, polyethylene terephthalate, and polynaphthalene. Polyester resin such as ethylene diformate, polytrimethylene terephthalate, poly(phthalic acid propylene dicarboxylate), polybutylene terephthalate or polybutylene naphthalate, polypropylene, polyethylene, etc. Polyolefin resin, acrylic resin, polyimide resin, polyether oxime resin, polyphenylene sulfide resin, polyether ketone resin, polyether ether ketone resin, triacetyl cellulose resin, polyether oxime resin, Polycarbonate resin, polyarylate resin or a mixed resin thereof, aluminum, magnesium, titanium, chromium, manganese, iron, nickel, zinc, tin, glass, copper, ruthenium wafer and alloy. Among these materials, in terms of high heat resistance, polyester resin, polyamide resin, polyolefin resin, polyimide resin, acrylic resin, aluminum, magnesium, titanium, chromium, manganese are more preferred. , iron, nickel, zinc, tin, glass, copper and tantalum wafers.

[Examples]

Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not Limited to the embodiment.

(Synthesis Example 1)

43.75 parts (mole ratio) of isophthaloyl dichloride, 6.25 parts of terephthaloyl dichloride, and polypropylene glycol diamine (JEFFAMINE (registered trademark) D-2000, manufactured by HUNTSMAN Co., Ltd., The number of repeating units of polypropylene glycol: 33 parts, 5 parts, 45 parts of 1,4-bis(3-aminopropyl)piperazine, and 110 parts of triethylamine, which are condensed in N-methylpyrrolidone polymerization. After completion of the reaction, three times the amount of water was added to the reaction mixture, and the insoluble components were separated and dried to obtain a polyamide resin.

(Example 1)

10.0 g of the polyamidamide resin obtained in Synthesis Example 1, 1.15 g of NC3000H (manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin, and KA1165 as a cresol novolak type epoxy hardener (DIC shares limited) 0.43 g of the varnish of the adhesive composition of Example 1 was dissolved in N,N'-dimethylacetamide so that the solid content was 35% by mass.

(Example 2)

10.0 g of the polyamidamide resin obtained in Synthesis Example 1, 1.15 g of NC3000H (manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin, and HCP-8000-65T (DIC shares as an ester type epoxy hardener) The varnish of the adhesive composition of Example 2 was obtained by dissolving 1.25 g in N,N'-dimethylacetamide in such a manner that the solid content was 35% by mass.

(Example 3)

10.0 g of the polyamidamide resin obtained in Synthesis Example 1, 0.28 g of EPICLON 850S (manufactured by DIC Co., Ltd.) as an epoxy resin, and KA1165 (manufactured by DIC Corporation) as a cresol novolak type epoxy curing agent 0.12 g was dissolved in N,N'-dimethylacetamide so that the solid content thereof was 35% by mass, and the varnish of the adhesive composition of Example 3 was obtained.

(Example 4)

10.0 g of the polyamidamide resin obtained in Synthesis Example 1, 0.28 g of EPICLON 850S (manufactured by DIC Corporation) as an epoxy resin, and HCP-8000-65T (DIC Co., Ltd.) as an ester type epoxy hardener (manufactured) 0.34 g was dissolved in N,N'-dimethylacetamide so that the solid content thereof was 35% by mass, and the varnish of the adhesive composition of Example 4 was obtained.

(Example 5)

10.0 g of the polyamidamide resin obtained in the synthesis example 1 and 0.76 g of NC3000H (manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin were dissolved in N, N'-di as the solid content was 35 mass%. The varnish of the adhesive composition of Example 5 was obtained in methyl acetamide.

(Example 6)

10.0 g of the polyamide resin obtained in Synthesis Example 1 and 1.14 g of NC3000H (manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin were dissolved in N, N'-di as a solid content of 35 mass%. The varnish of the adhesive composition of Example 6 was obtained in methyl acetamide.

(Example 7)

10.0 g of the polyamidamide resin obtained in Synthesis Example 1 and 1.90 g of NC3000H (manufactured by Nippon Kayaku Co., Ltd.) as an epoxy resin were dissolved in N, N'-di as a solid content of 35 mass%. The varnish of the adhesive composition of Example 7 was obtained in methyl acetamide.

(Comparative Example 1)

The polyamine resin obtained in Synthesis Example 1 was dissolved in N,N'-dimethylacetamide so that the solid content thereof was 35% by mass, and a varnish of the adhesive composition of Comparative Example 1 was obtained.

(Comparative Example 2)

10.0 g of the polyamide resin obtained in Synthesis Example 1 and 0.43 g of KA1165 (manufactured by DIC Corporation) as a cresol novolak type epoxy curing agent were dissolved in N so that the solid content was 35% by mass. In the N'-dimethylacetamide, a varnish of the adhesive composition of Comparative Example 2 was obtained.

(Comparative Example 3)

10.0 g of the polyamide resin obtained in Synthesis Example 1 and 1.25 g of EXB-8000-65T (manufactured by DIC Corporation) as an ester epoxy curing agent were dissolved in N so that the solid content was 35% by mass. In the N'-dimethylacetamide, the varnish of the adhesive composition of Comparative Example 3 was obtained.

(Experimental Example 1)

The varnish of the adhesive composition of Example 1 was applied to a polyimide film having a thickness of 50 μm by a layer of a dried adhesive composition of 15 cm square and a thickness of 20 μm using an applicator. Heat at °C for 30 minutes The film-like adhesive of Example 1 was produced by drying. Then, the obtained film-like adhesive was placed on a 10 cm × 10 cm glass plate having a thickness of 70 μm, and passed through a laminator of 0.3 MPa at a rate of 0.8 m/min under a room temperature environment (25 ° C). , by which it sticks. Then, for the measurement of the subsequent adhesion force, a slit having a width of 10 mm was cut out on the adhered film adhesive.

(Experimental Example 2 to Experimental Example 7)

The film-like adhesives of Examples 2 to 7 were produced in the same manner as in Experimental Example 1, except that the varnishes of the adhesive compositions of Examples 2 to 7 were used. Further, the film-like adhesives of Examples 2 to 7 were adhered to the glass plate in the same manner as the film-like adhesive of Example 1, and a slit having a width of 10 mm was cut out.

(Experimental examples 8 to 10)

The film-like adhesives of Comparative Examples 1 to 3 were produced in the same manner as in Experimental Example 1 except that the varnish of the adhesive composition of Comparative Example 1 to Comparative Example 3 was used. Further, the film-like adhesives of Comparative Examples 1 to 3 were adhered to a glass plate in the same manner as the film-like adhesive of Example 1, and a slit having a width of 10 mm was cut out.

The compositions of the film-like adhesives of Examples 1 to 7 and Comparative Examples 1 to 3 are shown in Table 1.

(evaluation of peelability)

The film-like adhesives of Examples 1 to 7 and Comparative Examples 1 to 3 adhered to a glass plate were placed in a hot air drying oven at 200 ° C / 15 min, followed by 250 ° C / 30 min, and then 275 ° C. /30min for heating. The appearance of the film-like adhesive after the adhesion to the glass plate and each of the above-mentioned heating was evaluated. The case where the bulging was not confirmed on the film-like adhesive was evaluated as "A", the case where the ridge was confirmed at the end of the film-like adhesive was evaluated as "B", and the peeling of the film-like adhesive was evaluated as " C". The results are shown in Table 2. Any film adhesive can adhere at room temperature and also exhibit good adhesion at 200 ° C ~ 275 ° C.

Further, the adhesion (adhesion force) and the peeling mode of each of the heated film-like adhesives were evaluated. Specifically, one end of a film-like adhesive cut into a width of 10 mm was peeled off from the glass plate and fixed to a tensile jig of a tensile tester. Pressing the glass plate against the platform, lifting the film-like adhesive and peeling it off from the glass plate 90° peel test. The adhesion of the film-like adhesive was measured by this measurement. Further, the peeling mode was evaluated while measuring the adhesion force. Further, the ratio (%) of the adhesion force after heating at 275 ° C / 30 min with respect to heating at 200 ° C / 15 min was calculated as the adhesion force after the peeling treatment. The results are shown in Table 3. The peeling mode was evaluated as peeling of the film adhesive/glass interface (indicated as "α" in the table), peeling of the interface of the polyimide film/film adhesive (indicated as "β" in the table), and film adhesive Which of the cohesive failures (denoted as "γ" in the table).

As shown in Table 3, it was confirmed that the film-like adhesives of Examples 1 to 7 were heated at 200 ° C / 15 min, then 250 ° C / 30 min, and then 275 ° C / 30 min, thereby allowing the adhesion. It is reduced to 30% or less of the adhesion force after heating to 200 ° C / 15 min.

In Example 2, which uses an ester type epoxy curing agent as an epoxy curing agent, the film-like adhesive of Example 4 has a low adhesive force after heating at 275 ° C / 30 min, and tends to be more easily peeled off.

The film-like adhesives of Examples 1 to 4 and Comparative Example 1 adhered to a glass plate were heated under conditions different from those described above. Specifically, in a hot air drying oven at 200 ° C / 15 min, followed by 260 ° C / 30 min, and then Heating was carried out at 260 ° C / 30 min, followed by 260 ° C / 30 min, and then 275 ° C / 30 min.

The adhesion (adhesion force) and the peeling mode of each of the heated film-like adhesives were evaluated in the same manner as above. The results are shown in Table 4.

Claims (16)

An adhesive composition comprising: a condensed polymer; and a reactive compound which reacts with a functional group of the condensed polymer to form a cross-linking or grafting, and/or a high molecular weight to form a condensed polymer A polymerizable compound of the mixture. The adhesive composition according to claim 1, wherein the formation of the crosslinking or grafting or the above-mentioned high molecular weight is caused by heating or irradiation with active rays. The adhesive composition according to claim 1 or 2, wherein the condensed polymer is polyamine, polyimine or polyamidimide, which reacts with the above reactive compound. The functional group is at least one main chain functional group selected from the group consisting of a guanamine bond, a ruthenium bond bond, and a valine acid structure, or is selected from the group consisting of a carboxyl group, an amine group, a carboxylic acid halide structure, and a carboxylic acid anhydride structure. At least one terminal functional group in the composed group. The adhesive composition according to any one of claims 1 to 3, wherein the condensed polymer has a polyoxyalkylene group. The adhesive composition according to any one of claims 1 to 4, wherein the condensed polymer has a divalent aromatic ring group. The adhesive composition according to any one of claims 1 to 5, wherein the condensed polymer has a 1,4-piperazinediyl group. The adhesive group according to any one of claims 1 to 6 The composition wherein the above reactive compound is an isocyanate compound, a blocked isocyanate compound, an epoxy resin, or a combination of an epoxy resin and a hardener of the above epoxy resin. The adhesive composition according to any one of claims 1 to 7, wherein the reactive compound is a polyfunctional reactive compound. The adhesive composition according to any one of claims 1 to 8, wherein the polymerizable compound comprises: an epoxy resin, a cresol resin, a melamine resin, a urea resin, an unsaturated polyester. At least one thermosetting compound in a group consisting of a resin, a urethane resin, a cyanate resin, an isocyanate compound, and a blocked isocyanate compound; and/or a radical, a cation, and an anion generated by active light A compound which at least one of itself undergoes a self-polymerization or crosslinking reaction, or a compound which generates a functional group by a reactive light and undergoes a hardening reaction. The adhesive composition according to any one of claims 1 to 9, wherein the adhesion is lowered by the formation of the crosslinking or grafting and/or the above-described high molecular weight. The adhesive composition according to any one of claims 1 to 10, wherein the adhesive composition is used as an adhesive at an application temperature in the range of 200 ° C to 270 ° C, and at a temperature exceeding the above application temperature The above-mentioned crosslinking or graft formation and/or the above-described high molecular weight are caused at a temperature to lower the adhesion. The adhesive composition according to any one of claims 1 to 10, wherein the adhesive composition is used as an adhesive at an application temperature in the range of 200 ° C to 270 ° C, and is irradiated with active light. On the other hand, the formation of the above-mentioned cross-linking or grafting and/or the above-mentioned high molecular weight are caused to lower the adhesion. A laminate comprising: a support; and a layer comprising the adhesive composition according to any one of claims 1 to 12, which is disposed on the support. A use of a composition for use as an adhesive, the composition comprising: a condensed polymer; and a reactive compound which reacts with a functional group of the condensed polymer to form a crosslinked or grafted compound, and/or high A polymerizable compound having a molecular weight and a mixture with the above condensed polymer. The use of the composition according to claim 14, wherein the adhesive is an adhesive which reduces adhesion by heating and/or irradiation with active light. A peeling method, which is an adhesive composition according to any one of claims 1 to 12, or an adhesive composition according to the above-mentioned claim 13 a method of peeling a joint formed by bonding a bonded body, wherein the adhesive composition is heated or irradiated with active light to adhere thereto The force is lowered and at least a portion of the joined portion is peeled off.