WO2012141266A1 - Adhesive and adhesive material using same, and usage method therefor - Google Patents

Abstract

This adhesive comprises a condensed resin having a structural unit obtained by condensation polymerization of polymerizable monomers, which include a monomer (A) having at least two carboxyl groups and a monomer (B) having at least two amino groups, wherein the adhesive satisfies at least one of (1) and (2), and satisfies (3) below. (1) At least one type selected from the group consisting of the monomer (A), an anhydride of the monomer (A), and the monomer (B) is in liquid form at 25°C. (2) The condensed resin has a polyoxyalkanediyl group. (3) The condensed resin has a cyclohexane ring.

Description

Adhesive, adhesive using the same, and method of using them

The present invention relates to an adhesive that maintains its adhesiveness even in a high-temperature environment, an adhesive material using the same, and a method for using them.

Conventionally, acrylic adhesives are often used as adhesives. Moreover, as a heat resistant adhesive, for example, Patent Document 1 describes a silicone-based adhesive.

JP 2009-256542 A

Incidentally, the acrylic pressure-sensitive adhesive has a problem in that the adhesiveness cannot be maintained under a high-temperature environment (for example, 200 ° C. or more), and floating or peeling occurs.

Also, the silicone-based pressure-sensitive adhesive has a problem that it is expensive and the object to be attached is limited (for example, the adhesiveness to a plastic material such as a polyester film or a polyimide film is low).

Therefore, an object of the present invention is to provide a novel pressure-sensitive adhesive that can maintain the pressure-sensitive adhesive property even in a high-temperature environment, and a method for using the same. Moreover, an object of this invention is to provide the adhesive material using this adhesive, and its usage method.

One aspect of the present invention is a condensation resin having a structural unit obtained by condensation polymerization of a polymerizable monomer containing a monomer (A) having at least two carboxyl groups and a monomer (B) having at least two amino groups. Containing pressure-sensitive adhesive.

The pressure-sensitive adhesive satisfies at least one of the following (1) and (2) and the following (3).
(1) At least one selected from the group consisting of the monomer (A), the anhydride of the monomer (A), and the monomer (B) is liquid at 25 ° C.
(2) The condensation resin has a polyoxyalkanediyl group.
(3) The condensed resin has a cyclohexane ring.

According to the pressure-sensitive adhesive, high adhesiveness is maintained even in a high temperature environment (for example, 200 ° C. or more), and the occurrence of floating and peeling is sufficiently suppressed. Moreover, the said adhesive shows high adhesiveness with respect to adherends, such as a plastic material. Furthermore, since the said adhesive maintains high adhesiveness even after peeling from the adherend, it can be repeatedly applied to and peeled off from the adherend.

It is preferable that the pressure-sensitive adhesive satisfies both the above (1) and (2). According to such an adhesive, the adhesiveness is further improved. Further, such an adhesive can be easily attached to an adherend by pressing at 0 to 50 ° C., for example.

In the pressure-sensitive adhesive, the condensation resin preferably contains at least one selected from the group consisting of polyamideimide resin, polyimide resin and polyamide resin.

In the pressure-sensitive adhesive, the condensation resin is preferably a polyamide resin.

In the pressure-sensitive adhesive, the structural unit in the condensation resin preferably has the polyoxyalkanediyl group. That is, the polyoxyalkanediyl group in (2) is preferably contained in the structural unit.

In the pressure-sensitive adhesive, the structure derived from the monomer (B) in the structural unit preferably has the polyoxyalkanediyl group. That is, it is preferable that the polyoxyalkanediyl group in the above (2) is included in the structure derived from the monomer (B) in the structural unit.

In the pressure-sensitive adhesive, the polymerizable monomer is a monomer having a polyoxyalkanediyl group and at least two amino groups (b-1) in an amount of 2. with respect to the total amount of the monomer (A) and the monomer (B). It is preferably contained at a ratio of 5 to 10 mol%.

Another aspect of the present invention relates to a pressure-sensitive adhesive containing a condensation resin selected from the group consisting of a polyamide resin, a polyamideimide resin and a polyimide resin, wherein the condensation resin has a cyclohexane ring and a polyoxyalkanediyl group. .

In the pressure-sensitive adhesive, the condensation resin may contain a diamine unit having a cyclohexane ring and a diamine unit having a polyoxyalkanediyl group.

In the pressure-sensitive adhesive, the condensed resin may further have a divalent aromatic ring group and may contain a dicarboxylic acid unit having a divalent aromatic ring group.

In the pressure-sensitive adhesive of the present invention, the condensation resin may further have a 1,4-piperazinediyl group and may contain a diamine unit having a 1,4-piperazinediyl group.

In the pressure-sensitive adhesive, the content of the condensation resin is preferably 50% by mass or more. The pressure-sensitive adhesive may be made of the condensation resin. Since such an adhesive is further excellent in heat resistance, it can be used more suitably as a heat resistant adhesive.

The pressure-sensitive adhesive can be used as, for example, a heat-resistant pressure-sensitive adhesive that is affixed to an adherend and is peeled off from the adherend after being heated to 200 ° C. or higher. That is, the pressure-sensitive adhesive can be suitably used for a process having a step of being exposed to a high temperature of 200 ° C. or higher.

Another aspect of the present invention has a structural unit obtained by condensation polymerization of a polymerizable monomer containing a monomer (A) having at least two carboxyl groups and a monomer (B) having at least two amino groups. The present invention relates to the use of a condensation resin satisfying at least one of (1) and (2) and the following (3) as an adhesive.
(1) At least one selected from the group consisting of the monomer (A), the anhydride of the monomer (A), and the monomer (B) is liquid at 25 ° C.
(2) The condensation resin has a polyoxyalkanediyl group.
(3) The condensed resin has a cyclohexane ring.

Another aspect of the present invention has a structural unit obtained by condensation polymerization of a polymerizable monomer containing a monomer (A) having at least two carboxyl groups and a monomer (B) having at least two amino groups. The present invention relates to the use of a condensation resin satisfying at least one of (1) and (2) and the following (3) for the production of an adhesive.
(1) At least one selected from the group consisting of the monomer (A), the anhydride of the monomer (A), and the monomer (B) is liquid at 25 ° C.
(2) The condensation resin has a polyoxyalkanediyl group.
(3) The condensed resin has a cyclohexane ring.

Another aspect of the present invention is a condensation resin selected from the group consisting of a polyamide resin, a polyamideimide resin and a polyimide resin, wherein the condensation resin having a cyclohexane ring and a polyoxyalkanediyl group is used as an adhesive. Use.

Another aspect of the present invention is a condensation resin selected from the group consisting of a polyamide resin, a polyamideimide resin and a polyimide resin, and the production of a pressure-sensitive adhesive of a condensation resin having a cyclohexane ring and a polyoxyalkanediyl group For use, regarding.

The present invention also provides an adhesive material comprising a support and an adhesive layer containing the adhesive provided on the support.

The present invention also includes a step of attaching the second adherend to the first adherend via the adhesive layer containing the adhesive, and a condition that the temperature of the adhesive layer is 200 ° C. or higher. Under the heating step of heating the first adherend and the second adherend, and from the first adherend subjected to the heating step, the adhesive layer and the second adherend And a peeling step for peeling the adhesive.

In the method of using the pressure-sensitive adhesive, the first adherend and the second adherend are preferably stuck at 0 to 50 ° C. in the sticking step.

In the method of using the pressure-sensitive adhesive, it is preferable that the pressure-sensitive adhesive layer and the second adherend are peeled from the first adherend at 0 to 50 ° C. in the peeling step.

In the method of using the pressure-sensitive adhesive, the pressure-sensitive adhesive layer peeled off in the peeling step can be reused in the sticking step.

The present invention also includes an attaching step for attaching the adhesive material to the adherend so that the adhesive layer is disposed on the side close to the adherend, and a condition where the temperature of the adhesive material is 200 ° C. or higher. Thus, there is provided a method for using an adhesive material, comprising: a heating step for heating the adherend and a peeling step for peeling the adhesive material from the adherend that has undergone the heating step.

In the method of using the adhesive material, it is preferable that the adhesive material is applied to the adherend at 0 to 50 ° C. in the attaching step.

In the method of using the pressure-sensitive adhesive material, it is preferable that the pressure-sensitive adhesive material is peeled from the adherend at 0 to 50 ° C. in the peeling step.

In the method of using the pressure-sensitive adhesive material, the pressure-sensitive adhesive material peeled off in the peeling step can be reused in the sticking step.

According to the present invention, a novel pressure-sensitive adhesive capable of maintaining the adhesiveness even in a high temperature environment and a method for using the same are provided. Moreover, according to this invention, the adhesive material using this adhesive and its usage method are provided.

It is a schematic cross section which shows suitable one Embodiment of the adhesive of this invention.

Preferred embodiments of the pressure-sensitive adhesive and pressure-sensitive adhesive material of the present invention will be described below.

(Adhesive)
The pressure-sensitive adhesive according to this embodiment includes a condensation system having a structural unit obtained by condensation polymerization of a polymerizable monomer containing a monomer (A) having at least two carboxyl groups and a monomer (B) having at least two amino groups. Contains a resin.

And the adhesive which concerns on this embodiment satisfy | fills at least one and following (3) among following (1) and (2).
(1) At least one selected from the group consisting of monomer (A), anhydride of monomer (A) and monomer (B) is liquid at 25 ° C.
(2) The condensation resin has a polyoxyalkanediyl group.
(3) The condensed resin has a cyclohexane ring.

According to such a pressure-sensitive adhesive, even when kept in a high temperature environment of, for example, 200 ° C. or higher, high adhesiveness is maintained, and the occurrence of floating and peeling is sufficiently suppressed.

Note that the condensation resin is not necessarily produced by condensation polymerization of the polymerizable monomer, and may have a structural unit that can be formed by condensation polymerization of the polymerizable monomer.

That is, in order to satisfy the above (1), the condensation resin is not necessarily produced using a monomer that is liquid at 25 ° C. (or a monomer that is liquid at 25 ° C. of anhydride) The condensation resin may have a structural unit that can be formed by condensation polymerization of a polymerizable monomer containing a monomer liquid at 25 ° C. (or a monomer whose anhydride is liquid at 25 ° C.).

Even if the structural unit in the condensation resin is a structural unit obtained by condensation polymerization of a kind of monomer (A) and monomer (B), a plurality of monomers (A) and monomer (B) are condensed and polymerized. It may be a structural unit obtained as described above. In the latter case, in order to satisfy the above (1), if at least one selected from the group consisting of a plurality of monomers (A), their anhydrides, and a plurality of monomers (B) is liquid at 25 ° C. Good.

The monomer (A) and monomer (B) that can form the structural unit can be confirmed by the following method. That is, a compound having at least two carboxyl groups and a compound having at least two amino groups, which are produced when the structural unit is hydrolyzed, can be used as the monomer (A) and the monomer (B), respectively.

For example, the structural unit represented by the following formula (1-1) is a structure obtained by condensation polymerization of a monomer represented by the following formula (A-1) and a monomer represented by the following formula (B-1). It can be called a unit. In the formula, R ¹ and R ² represent a divalent organic group.

In order for the structural unit represented by the formula (1-1) to satisfy the above (1), among the monomer represented by the formula (A-1) and the monomer represented by the formula (B-1) It is sufficient that at least one kind is liquid at 25 ° C.

Further, for example, the structural unit represented by the following formula (1-2) is obtained by condensation polymerization of a monomer represented by the following formula (A-2) and a monomer represented by the above formula (B-1). It can be said that it is a structural unit. In the formula, R ³ represents a trivalent organic group.

In order for the structural unit represented by the formula (1-2) to satisfy the above (1), the monomer represented by the formula (A-2), the monomer represented by the formula (B-1), and the following It suffices that at least one selected from the group consisting of anhydrides represented by the formula (A-2 ′) is liquid at 25 ° C.

Further, for example, the structural unit represented by the following formula (1-3) is obtained by condensation polymerization of a monomer represented by the following formula (A-3) and a monomer represented by the above formula (B-1). It can be said that it is a structural unit. In the formula, R ⁴ represents a tetravalent organic group.

In order for the structural unit represented by the formula (1-3) to satisfy the above (1), the monomer represented by the formula (A-3), the monomer represented by the formula (B-1), and It is sufficient that at least one selected from the group consisting of anhydrides represented by the formula (A-3 ′) is liquid at 25 ° C.

As the monomer (A), a monomer having two carboxyl groups (monomer represented by formula (A-1)), a monomer having three carboxyl groups (monomer represented by formula (A-2)), carboxyl And monomers having four groups (monomers represented by the formula (A-3)).

Examples of the monomer having two carboxyl groups include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9-nonanedicarboxylic acid, dodecanedioic acid. Alkylene dicarboxylic acids such as tetradecanedioic acid, pentadecanedioic acid, octadecanedioic acid, phthalic acid, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid Acenaphthylene-5,6-dicarboxylic acid, pyridine-2,3-dicarboxylic acid, pyridine-2,6-dicarboxylic acid, 1H-imidazole-4,5-dicarboxylic acid, 1H-pyrrole-2,4-dicarboxylic acid, Fragrance such as furan-2,5-dicarboxylic acid, thiophene-2,5-dicarboxylic acid Dicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic acid, 3-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid Dicarboxylic acids having a cyclohexane skeleton, such as methylnorbornane-2,3-dicarboxylic acid, 3-methyl-1,2,3,6-tetrahydrophthalic acid, 4-methyl-1,2,3,6-tetrahydrophthalic acid And dicarboxylic acids having a cyclohexene skeleton such as methyl-3,6-endomethylene-1,2,3,6-tetrahydrophthalic acid.

That is, examples of R ¹ in the formula (1-1) include an alkanediyl group, a divalent alicyclic group, and a divalent aromatic ring group.

As the alkanediyl group, an alkanediyl group having 1 to 30 carbon atoms is preferable, and an alkanediyl group having 1 to 20 carbon atoms is more preferable. The alkanediyl group may be linear or branched, and is preferably linear.

Specific examples of alkanediyl groups include methylene, ethylene, propanediyl, butanediyl, pentanediyl, hexanediyl, heptanediyl, octanediyl, nonanediyl, decandiyl, undecandiyl, dodecandiyl, tridecane A candiyl group, a hexadecandiyl group, etc. are mentioned.

The divalent alicyclic group is a group having a saturated or unsaturated carbocyclic structure having no aromaticity. The divalent alicyclic group preferably has 3 to 20 carbon atoms, and more preferably 4 to 12 carbon atoms. The divalent alicyclic group preferably has a cyclohexane ring.

Examples of the divalent alicyclic group include 1,3-cyclohexanediyl group, 1,4-cyclohexanediyl group, 4-alkylcyclohexane-1,2-diyl group, 3-alkylcyclohexane-1,2-diyl group, 4 , 5-dialkylcyclohexane-1,2-diyl group, 3,4-dialkylcyclohexane-1,2-diyl group, norbornanediyl group, 5-alkylnorbornane-2,3-diyl group, 3-alkyl-4-cyclo Hexene-1,2-diyl group, 4-alkyl-4-cyclohexene-1,2-diyl group, 4-methyl-3,6-endomethylene-4-cyclohexene-1,2-diyl group Etc.

Here, the alkyl group bonded to the carbocyclic structure of the divalent alicyclic group is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms.

The divalent aromatic ring group is a group having a ring structure having aromaticity. As the divalent aromatic ring group, a divalent aromatic ring group having 6 to 20 carbon atoms is preferable, and a divalent aromatic ring group having 6 to 10 carbon atoms is more preferable.

Examples of the divalent aromatic ring group include benzenediyl group, naphthalenediyl group, biphenyldiyl group, acenaphthylene-5,6-diyl group, pyridine-2,3-diyl group, pyridine-2,6-diyl group, Examples thereof include 1H-imidazole-4,5-diyl group, 1H-pyrrole-2,4-diyl group, furan-2,5-diyl group, and thiophene-2,5-diyl group. Examples of the benzenediyl group include 1,2-benzenediyl group, 1,3-benzenediyl group, and 1,4-benzenediyl group. The naphthalenediyl group includes 1,2-naphthalenediyl group, 1,3-naphthalenediyl group, 1,4-naphthalenediyl group, 1,5-naphthalenediyl group, 1,6-naphthalenediyl group, 1,7 -Naphthalenediyl group, 1,8-naphthalenediyl group, 2,3-naphthalenediyl group, 2,6-naphthalenediyl group, 2,7-naphthalenediyl group and the like. Examples of the biphenyldiyl group include a biphenyl-4,4'-diyl group.

Examples of the monomer having three carboxyl groups include aromatic tricarboxylic acids such as trimellitic acid, and alicyclic tricarboxylic acids such as cyclohexane-1,2,4-tricarboxylic acid.

That is, R ³ in the formula (1-2) includes a trivalent alicyclic group, a trivalent aromatic ring group, and the like.

The trivalent alicyclic group is preferably a cyclohexanetriyl group, and more preferably a cyclohexane-1,2,4-triyl group.

Examples of the trivalent aromatic ring group include a benzenetriyl group and a naphthalenetriyl group, and a benzene-1,2,4-triyl group is preferable.

Examples of the monomer having four carboxyl groups include pyromellitic acid, benzene-1,2,3,4-tetracarboxylic 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, 2,3,6,7-anthracenetetracarboxylic acid, phenanthrene-1,8 , 9,10-tetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid Acid, 2,3,3 ′, 4′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, 2,3,2 ′, 3′-benzophenone tet Carboxylic acid, 2,3,3 ′, 4′-benzophenone tetracarboxylic acid, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, bis (3 4-dicarboxyphenyl) sulfone, 1-trifluoromethyl-2,3,5,6-benzenetetracarboxylic acid, bis (2,3-dicarboxyphenyl) methane, bis (3,4-dicarboxyphenyl) methane 1,1-bis (2,3-dicarboxyphenyl) ethane, 1,1-bis (3,4-dicarboxyphenyl) ethane, 2,2-bis (3,4-dicarboxyphenyl) propane, , 2-bis (2,3-dicarboxyphenyl) propane, 4,4 '-(4,4'-isopropylidenediphenoxy) -bis (phthalic acid), p-phenylene (Trimellitate), bis (3,4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) methylphenylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 1,3-bis (3,4-dicarboxyphenyl) -1,1,3,3-tetramethyldisiloxane, 1,4-bis (3,4-dicarboxyphenyldimethylsilyl) benzene, 2,2-bis (3,4) -Dicarboxyphenyl) hexafluoropropane, 2,2-bis (4- (3,4-dicarboxyphenoxy) phenyl) hexafluoropropane, 4,4'-bis (3,4-dicarboxyphenoxy) diphenyl sulfide, 2,3,5,6-pyridinetetracarboxylic acid, pyrrolidine-2,3,4,5-tetracarboxylic acid, pyrazine-2 , 3,5,6-tetracarboxylic acid, thiophene-2,3,4,5-tetracarboxylic acid, tetrahydrofuran-2,3,4,5-tetracarboxylic acid, ethylenetetracarboxylic acid, 1,2,3, 4-butanetetracarboxylic acid, 1,1,2,2-ethanetetracarboxylic acid, 1,1,2,3-propanetetracarboxylic acid, 1,1,6,6-hexanetetracarboxylic acid, 1,2, 4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, decahydronaphthalene-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-tetracarboxylic acid 1,2,3,4-cyclobutanetetracarboxylic acid, bicyclo- [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid, bis (exobicyclo [2.2. 1] heptane-2,3-dicarboxylic acid) sulfone, 1,2,4,5-tetracarboxycyclohexane, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid, 5,5 '-(1,1,3,3,5,5-hexamethyltrisiloxane-1,5-diyl) bis (bicyclo [2.2.1] heptane-2,3-dicarboxylic acid) and the like.

That is, R ⁴ in the formula (1-3) includes an alkanetetrayl group, a tetravalent alicyclic group, a tetravalent aromatic ring group, or a tetravalent heterocyclic group. In other words, R ⁴ includes a group in which four hydrogen atoms are removed from an alkane, an alicyclic compound, an aromatic compound, or a heterocyclic compound.

The carbon number of the alkanetetrayl group is preferably 2 to 10, and more preferably 2 to 6. Examples of the alkanetetrayl group include ethane-1,1,2,2-tetrayl group, propane-1,1,2,3-tetrayl group, butane-1,2,3,4-tetrayl group, hexane- Examples thereof include 1,1,6,6-tetrayl group and ethylenetetrayl group.

As the tetravalent alicyclic group, those having 4 to 50 carbon atoms are preferable, and those having 6 to 30 carbon atoms are more preferable. The tetravalent alicyclic group preferably has a cyclohexane ring.

Examples of the tetravalent alicyclic group include cyclohexane, cyclopentane, cyclobutane, bicyclohexane, decahydronaphthalene, bicyclo [2,2,2] octane, bicyclo [2,2,1] heptane, dimethylhexahydronaphthalene, Bicyclo [2,2,2] oct-7-ene, 5,5 '-(1,1,3,3,5,5-hexamethyltrisiloxane-1,5-diyl) bis (bicyclo [2.2 .1] heptane) or bis (bicyclo [2,2,1] heptane) sulfone, a group obtained by removing four hydrogen atoms.

Examples of the tetravalent aromatic ring group include benzene, naphthalene, anthracene, phenanthrene, perylene, biphenyl, benzophenone, biphenyl ether, diphenyl sulfone, trifluoromethylbenzene, diphenylmethane, 1,1-diphenylethane, and 2,2-diphenyl. Propane, 2,2-bis (4-phenoxyphenyl) propane, phenyl bisbenzoate, diphenyldimethylsilane, triphenylmethylsilane, tetraphenylsilane, 1,3-diphenyl-1,1,3,3-tetramethyldi Four hydrogen atoms are removed from siloxane, bis (diphenyldimethylsilyl) benzene, 2,2-diphenylhexafluoropropane, 2,2-bis (4-phenoxyphenyl) hexafluoropropane, or diphenyl sulfide. And the like.

Examples of the tetravalent heterocyclic group include a group formed by removing four hydrogen atoms from pyridine, pyrazine, thiophene, pyrrolidine, or tetrahydrofuran.

Among these monomers (A) and anhydrides thereof, liquid compounds at 25 ° C. include 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, and 3-ethylhexahydrophthalic anhydride. 4-ethylhexahydrophthalic anhydride, 3-methyl-1,2,3,6-tetrahydrophthalic anhydride, 4-methyl-1,2,3,6-tetrahydrophthalic anhydride, methyl- 3,6-endomethylene-1,2,3,6-tetrahydrophthalic anhydride, 5,5′-exo- (1,1,3,3,5,5-hexamethyltrisiloxane-1,5- And diyl) bis (bicyclo [2.2.1] heptane-exo-2,3-dicarboxylic acid) dianhydride.

Here, R ¹ in the above formula (1-1) is, for example, a 4-alkylcyclohexane-1,2-diyl group, a 3-alkylcyclohexane-1,2-diyl group, a 3-alkyl-4-cyclohexene- When it is 1,2-diyl group, 4-alkyl-4-cyclohexene-1,2-diyl group, 4-methyl-3,6-endomethylene-4-cyclohexene-1,2-diyl group (Preferably 4-methylcyclohexane-1,2-diyl group, 3-methylcyclohexane-1,2-diyl group, 3-methyl-4-cyclohexene-1,2-diyl group, 4-methyl-4- A cyclohexene-1,2-diyl group and a 4-methyl-3,6-endomethylene-4-cyclohexene-1,2-diyl group), the pressure-sensitive adhesive according to this embodiment is the above (1 Is satisfied.

In addition, R ⁴ in the above formula (1-3) is, for example, 5,5′-exo- (1,1,3,3,5,5-hexamethyltrisiloxane-1,5-diyl) bis (bicyclo [ 2.2.1] heptane-exo-2,3-diyl group), the pressure-sensitive adhesive according to this embodiment satisfies the above (1).

The monomer (B) is preferably a monomer having two amino groups. Examples of such a monomer include 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, bis [4- (4 -Aminophenoxy) phenyl] methane, 4,4'-bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ketone, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 2,2′-di Tilbiphenyl-4,4′-diamine, 2,2′-bis (trifluoromethyl) biphenyl-4,4′-diamine, 2,6,2 ′, 6′-tetramethylbiphenyl-4,4′-diamine 5,5′-dimethyl-2,2′-sulfonyl-biphenyl-4,4′-diamine, (4,4′-diamino) diphenyl ether, (4,4′-diamino) diphenylsulfone, (4,4 ′ Aromatic diamines such as -diamino) benzophenone, (3,3'-diamino) benzophenone, (4,4'-diamino) diphenylmethane, (4,4'-diamino) diphenyl ether, (3,3'-diamino) diphenyl ether; Alkylene diamines such as ethylene diamine and propylene diamine, polyethylene oxide diamine, polypropylene oxide di Polyalkylene oxide diamines such as min, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, (4,4'-diamino) dicyclohexylmethane, isophoronediamine, 1,4-bisaminopropylpiperazine, [3,4 Bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl)] cyclohexene, aliphatic diamines such as bisaminomethylnorbornane, and siloxane diamines such as polydimethylsiloxane diamine.

That is, as R ² in the formulas (1-1), (1-2) and (1-3), an alkanediyl group, a polyoxyalkanediyl group, a divalent alicyclic group, a divalent aromatic ring group, Examples thereof include a divalent heterocyclic group and a polysiloxane diyl group.

The alkanediyl group for R ² is preferably an alkanediyl group having 1 to 30 carbon atoms, and more preferably an alkanediyl group having 1 to 20 carbon atoms. The alkanediyl group may be linear or branched, and is preferably linear.

Examples of the alkanediyl group in R ² include methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, heptanediyl group, octanediyl group, nonanediyl group, decandiyl group, undecandiyl group, dodecandiyl group, tridecane group. A candiyl group, a hexadecandiyl group, etc. are mentioned.

The divalent alicyclic group for R ² is preferably an alicyclic group having 3 to 10 carbon atoms, and more preferably an alicyclic group having 4 to 8 carbon atoms. The divalent alicyclic group preferably has a cyclohexane ring.

Examples of the divalent alicyclic group in R ² include a cyclohexanediyl group, an alkylcyclohexane-1,4-diyl group, a dialkylcyclohexane-1,4-diyl group, a norbornanediyl group, an alkylnorbornane-2,3-diyl group, Examples include dicyclohexylmethanediyl group, dicyclohexylpropanediyl group, isophoronyl group, bismethylenecyclohexane group, and bismethylenenorbornane group.

Note that the alkyl group bonded to the carbocyclic structure of the divalent alicyclic group in R ² is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. .

Examples of the divalent aromatic ring group in R ² include a benzenediyl group (1,2-benzenediyl group, 1,3-benzenediyl group, 1,4-benzenediyl group), naphthalenediyl group (1,2 -Naphthalenediyl group 1,3-naphthalenediyl group, 1,4-naphthalenediyl group, 1,5-naphthalenediyl group, 1,6-naphthalenediyl group, 1,7-naphthalenediyl group, 1,8-naphthalenediyl group Group, 2,3-naphthalenediyl group, 2,6-naphthalenediyl group, 2,7-naphthalenediyl group, etc.), 4,4′-biphenyldiyl group, 3,3′-biphenyldiyl group, 4,4 ′ -(2,2'-diphenylpropane) diyl group, 3,3 '-(2,2'-diphenylpropane) diyl group, 4,4'-(diphenylsulfone) diyl group, 3,3 '-(diphenylsulfone) ) Diyl group, 4,4 ′-(3,3-diphenylhexafluoropropane) diyl group, 3,3 ′-(3,3-diphenylhexafluoropropane) diyl group, 4,4 ′-(diphenylether) diyl Group, 3,3 ′-(diphenylether) diyl group, 4,4 ′-(diphenylketone) diyl group, 3,3 ′-(diphenylketone) diyl group, 4,4 ′-(2,2′-dimethylbiphenyl) ) Diyl group, 4,4 ′-(2,2′-bis (trifluoromethyl) biphenyl) diyl group, 4,4 ′-(2,6,2 ′, 6′-tetramethylbiphenyl) diyl group It is done.

Examples of the divalent heterocyclic group for R ² include a (1,4-dipropylpiperazine) diyl group.

Examples of the polysiloxane diyl group in R ² include a polydimethylsiloxane diyl group.

Among these monomers (B), those which are liquid at 25 ° C. include ethylenediamine, propylenediamine, isophoronediamine, 1,4-bisaminopropylpiperazine, [3,4-bis (1-aminoheptyl) -6- Hexyl-5- (1-octenyl)] cyclohexene, alkylene oxide diamine, bisaminomethylnorbornane, alkyl diamine, polyalkylene oxide diamine, siloxane diamine and the like.

Here, R ² in the formulas (1-1), (1-2), and (1-3) is, for example, an alkanediyl group, (1,4-dipropylpiperazine) diyl group, bismethylenenorbornane group, or isophoronyl group. The pressure-sensitive adhesive according to this embodiment satisfies the above (1).

The condensation resin preferably has a polyoxyalkanediyl group. The condensed resin having such a group has a low Tg and good adhesiveness at a low temperature.

Here, examples of the polyoxyalkanediyl group include a group represented by the following formula (2). In the formula, n represents an integer of 2 or more, and R ⁵ represents an alkanediyl group. A plurality of R ⁵ may be the same as or different from each other.

The alkanediyl group in R ⁵ may be linear or branched. The alkanediyl group for R ⁵ is preferably an alkanediyl group having 2 to 4 carbon atoms, more preferably an alkanediyl group having 2 to 3 carbon atoms. Examples of the alkanediyl group in R ⁵ include an ethylene group, 1,2-propanediyl group, 1,3-propanediyl group, 1,4-butanediyl group and the like.

N in the formula (2) is preferably 2 to 70, more preferably 6 to 33.

Polyoxyalkanediyl groups include polyethylene oxide, polypropylene oxide, polybutylene oxide, polytetramethylene oxide, polyethylene oxide polypropylene oxide copolymer, polyethylene glycol polytetramethylene glycol copolymer, polypropylene glycol polytetramethylene glycol copolymer A group derived from a polyalkylene oxide such as a polyethylene glycol polypropylene glycol polytetramethylene glycol copolymer is preferred, and a polyoxyethylene group and a polyoxy-1,2-propanediyl group are more preferred.

A method for introducing the polyoxyalkanediyl group into the condensation resin is not particularly limited. For example, a method for introducing the polyoxyalkanediyl group by modifying a condensation resin such as a polyamide resin, a polyimide resin, or a polyamideimide resin. Is mentioned.

The condensed resin preferably has the polyoxyalkanediyl group in the structural unit, and the polyoxyalkanediyl group is present in the structure derived from the monomer (B) in the structural unit. It is more preferable. That is, it is preferable that at least one of the monomer (A) and the monomer (B) has the polyoxyalkanediyl group, and it is more preferable that at least one of the monomers (B) has the polyoxyalkanediyl group.

It is more preferable that the condensed resin has a structure derived from the monomer (B) in the structural unit having a polyoxyalkanediyl group.

That is, the condensation resin preferably has a structural unit obtained by condensation polymerization of a polymerizable monomer containing a monomer (b-1) having a polyoxyalkanediyl group and at least two amino groups.

Examples of the monomer (b-1) include polyalkylene oxide diamines. For example, Jeffamine D-230 (HUNTSMAN, trade name), Jeffamine D-400 (HUNTSMAN, trade name), Jeffamine D-2000 (HUNTSMAN) , Trade name), polypropylene oxide diamines such as Jeffamine D-4000 (HUNTSMAN, trade name); and polypropylene oxides such as Jeffamine ED-600 (HUNTSMAN, trade name) and Jeffamine ED-900 (HUNTSMAN, trade name) Polyethylene oxide copolymer diamines; polyethylene oxide diamines such as Jeffamine EDR-148 (HUNTSMAN, trade name), Jeffamine EDR-176 (HUNTSMAN, trade name); It can be suitably used; Efamin T-403 (HUNTSMAN, trade name), Jeffamine T-3000 (HUNTSMAN, trade name) and Jeffamine T-5000 (HUNTSMAN, trade name) triamine. These may be used alone or in combination of two or more.

The content of the monomer (b-1) in the polymerizable monomer is preferably 0.5 to 20 mol%, preferably 1 to 10 mol%, based on the total amount of the monomer (A) and the monomer (B). More preferably, it is 2 to 8 mol%. According to the condensation resin having a structural unit obtained by condensation polymerization of such a polymerizable monomer, a pressure-sensitive adhesive having further excellent adhesion to an adherend can be obtained.

The condensed resin has a cyclohexane ring. When the condensed resin has a cyclohexane ring, the water absorption rate of the pressure-sensitive adhesive is reduced, and the change in the pressure-sensitive adhesive force of the pressure-sensitive adhesive in a high temperature environment is further suppressed.

The condensed resin preferably has a cyclohexane ring in the structural unit. That is, it is preferable that the cyclohexane ring in the above (3) is contained in a structural unit obtained by condensation polymerization of a polymerizable monomer containing the monomer (A) and the monomer (B). It is preferable to include a monomer having a cyclohexane ring.

The condensed resin preferably has a cyclohexane ring in the structure derived from the monomer (A) or the monomer (B) in the structural unit, and has a cyclohexane ring in the structure derived from the monomer (B). More preferably. That is, at least one of the monomer (A) and the monomer (B) is preferably a monomer having a cyclohexane ring, and at least one of the monomers (B) is more preferably a monomer having a cyclohexane ring.

Examples of the monomer (A) having a cyclohexane ring (hereinafter sometimes referred to as “monomer (a-1)”) include, for example, a divalent alicyclic group in which R ^{1 of the} formula (A-1) has a cyclohexane ring A compound in which R ³ in formula (A-2) is a trivalent alicyclic group having a cyclohexane ring, and R ^{4 in} formula (A-3) is a tetravalent alicyclic group having a cyclohexane ring Compounds.

Specific examples of the monomer (a-1) include 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic acid, 3-methylhexahydrophthalic acid, and 3-ethylhexahydro. Phthalic acid, 4-ethylhexahydrophthalic acid, methylnorbornane-2,3-dicarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3 , 4-cyclopentanetetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, decahydronaphthalene-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-tetracarbonate Boronic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, bicyclo- [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid, bis (exobicyclo [2. 2.1] heptane-2,3-dicarboxylic acid) sulfone, 1,2,4,5-tetracarboxycyclohexane, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid, etc. Can be mentioned.

Examples of the monomer (B) having a cyclohexane ring (hereinafter sometimes referred to as “monomer (b-2)”) include, for example, a divalent alicyclic group in which R ^{2 in the} formula (B-1) has a cyclohexane ring The compound which is is mentioned.

Specific examples of the monomer (b-2) include 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, (4,4′-diamino) dicyclohexylmethane, isophoronediamine, [3,4-bis ( 1-aminoheptyl) -6-hexyl-5- (1-octenyl)] cyclohexene, bisaminomethylnorbornane and the like.

The content of the monomer having a cyclohexane ring in the polymerizable monomer is preferably 0.5 to 40 mol%, preferably 1 to 20 mol%, based on the total amount of the monomer (A) and the monomer (B). More preferably, it is 4 to 16 mol%. According to the condensation resin having a structural unit obtained by condensation polymerization of such a polymerizable monomer, the water absorption is further suppressed, and the change in adhesive force under a high temperature environment can be further suppressed.

When the monomer (A) which is liquid at 25 ° C. or the anhydride is liquid at 25 ° C. is the monomer (a-2) and the monomer (B) which is liquid at 25 ° C. is the monomer (b-3), the polymerizability The total content of the monomer (a-2) and the monomer (b-3) in the monomer is preferably 15 to 60 mol%, and preferably 20 to 50 mol based on the total amount of the monomer (A) and the monomer (B). % Is more preferable, and 25 to 45 mol% is still more preferable.

As a preferred combination of the polymerizable monomers, the monomer (A) is a compound in which R ^{1 in the} formula (A-1) is a divalent aromatic ring group, and R ^{3 in the} formula (A-2) is a trivalent aromatic ring group. And a compound in which R ^{4 in the} formula (A-3) is a tetravalent aromatic ring group, the monomer (B) is the monomer (b-1), the monomer (b-2) and the monomer Preferably, (b-3) is included.

Further, as a preferable combination of the polymerizable monomers, a compound in which the monomer (A) is a divalent aromatic ring group, a compound in which R ^{3 in} the formula (A-2) is a trivalent aromatic ring group, and the formula (A -3) containing at least one of compounds in which R ⁴ is a tetravalent aromatic ring group, and a monomer (a-1), the monomer (B) being a monomer (b-1) and a monomer (b-3) ) Is also preferable.

The condensation resin can be obtained, for example, by condensation polymerization of a polymerizable monomer containing the monomer (A) and the monomer (B). In place of the monomer (A), an anhydride of the monomer (A), an esterified product of the monomer (A), an acid halide of the monomer (A), or the like can be used. Moreover, the polymerizable monomer may contain other monomers such as a diisocyanate compound.

The content of the monomer (A) and the monomer (B) in the polymerizable monomer is preferably 30 mol% or more, more preferably 50 mol% or more, and 70 mol% or more with respect to the total amount of the polymerizable monomers. More preferably. Moreover, 100 mol% may be sufficient as content of a monomer (A) and a monomer (B).

The method of condensation polymerization is not particularly limited. For example, a method of dissolving the polymerizable monomer in a solvent and reacting at a reaction temperature of 0 to 200 ° C. and a reaction time of about 1 to 5 hours can be employed.

Examples of the solvent used for the condensation polymerization include N-methylpyrrolidone, N-ethylpyrrolidone, N-methylsuccinimide, dimethylfuran, toluene, N, N′-dimethylacetamide, hexamethylenephosphoramide, dimethylsulfoxide and the like. Can be mentioned. Of these, N-methylpyrrolidone is preferred from the viewpoint of solubility of the resin.

In the condensation polymerization, an accelerator such as a catalyst can be used for the purpose of promoting the condensation reaction. The addition amount of the accelerator is preferably 0.1 to 50 mol equivalent to 10 mol equivalent of the polymerizable monomer. Examples of the accelerator include inorganic salts such as lithium chloride, calcium chloride, and rhodane calcium; tertiary amines such as triethylamine and pyridine; quaternary ammonium such as tetramethylammonium chloride, tetraethylammonium bromide, and tetra-n-butylammonium bromide. Salt;

The condensation resin may be obtained by further modifying a polymer obtained by condensation polymerization. For example, olefin-modified polyamide, alkoxysilane-modified polyamide, siloxane-modified polyimide, epoxy-modified polyamide, polycarbonate-modified polyamide, olefin-modified polyimide. Siloxane modified polyimide, epoxy modified polyimide, polycarbonate modified polyimide, siloxane modified polyimide, olefin modified polyamideimide, alkoxysilane modified polyamideimide, siloxane modified polyamideimide, epoxy modified polyamideimide, epoxy modified polyamideimide, polycarbonate modified polyamideimide, etc. It is done.

The condensation resin in the present embodiment may be, for example, a polyamide resin, a polyamideimide resin, or a polyimide resin having a cyclohexane ring and a polyoxyalkanediyl group. Such a condensation resin satisfies at least the above (2) and (3).

The condensation resin may contain a diamine unit having a polyoxyalkanediyl group and a diamine unit having a cyclohexane ring. That is, the polyoxyalkanediyl group and the cyclohexane ring may each be included in the diamine unit of the condensed resin.

Examples of the diamine unit having a polyoxyalkanediyl group include a polyalkylene oxide diamine unit. As a polyalkylene oxide diamine unit, the monomer unit derived from the monomer illustrated as said polyalkylene oxide diamine is mentioned.

Examples of the diamine unit having a cyclohexane ring include monomer units derived from the monomer (b-2). Examples of the monomer unit include 1,3-cyclohexanediamine units, 1,4-cyclohexanediamine units, ( 4,4′-diamino) dicyclohexylmethane unit, isophoronediamine unit, [3,4-bis (1-aminoheptyl) -6-hexyl-5- (1-octenyl)] cyclohexene unit, bisaminomethylnorbornane unit, etc. Can be mentioned.

This condensed resin may further have a divalent aromatic ring group and may contain a dicarboxylic acid unit having a divalent aromatic ring group. When the condensed resin has a divalent aromatic ring group, it is possible to further suppress the adhesive force change of the pressure-sensitive adhesive under a high temperature environment.

Examples of the dicarboxylic acid unit having a divalent aromatic ring group include compounds in which R ^{1 in} the above formula (A-1) is a divalent aromatic ring group.

The condensed resin may have a benzenediyl group as a divalent aromatic ring group, and may contain at least one selected from the group consisting of a phthalic acid unit, an isophthalic acid unit, and a terephthalic acid unit. When the condensation resin has a benzenediyl group, it is possible to further suppress the adhesive force change of the pressure-sensitive adhesive under a high temperature environment.

The condensation resin may further have a 1,4-piperazinediyl group and may contain a diamine unit having a 1,4-piperazinediyl group. According to such a diamine unit, the adhesive force change in the high temperature environment of an adhesive is further suppressed.

Examples of the diamine unit having a 1,4-piperazinediyl group include a 1,4-bis (ω-aminoalkyl) piperazine unit. In the 1,4-bis (ω-aminoalkyl) piperazine unit, the ω-aminoalkyl group preferably has 1 to 10 carbon atoms, and more preferably 2 to 4 carbon atoms.

Examples of 1,4-bis (ω-aminoalkyl) piperazine units include 1,4-bis (3-aminopropyl) piperazine units.

In the condensation resin, the ratio C ₂ / C ₁ of the content C ₂ of the diamine unit having a polyoxyalkanediyl group to the content C ₁ of the diamine unit having a cyclohexane ring is 0.1 to 40 in terms of molar ratio. Is preferable, and 0.5 to 8 is more preferable.

The structural unit derived from the monomer (A) in the condensation resin can be referred to as a monomer (A) unit, the structural unit derived from the monomer (B) can be referred to as a monomer (B) unit, It can be said that it is a condensation resin containing a monomer (A) unit and a monomer (B) unit.

The content of the diamine unit having a cyclohexane ring in the condensation resin is preferably 0.1 to 40 mol%, preferably 1 to 20 mol%, based on the total amount of the monomer (A) unit and the monomer (B) unit. More preferably, it is 4 to 16 mol%. According to such a condensation resin, the water absorption rate is further suppressed, and a change in adhesive force under a high temperature environment can be further suppressed.

The content of the diamine unit having a polyoxyalkanediyl group in the condensation resin is preferably 0.5 to 20 mol%, based on the total amount of the monomer (A) unit and the monomer (B) unit, and preferably 1 to 10 mol%. More preferred is 2 to 8 mol%. According to such a condensation resin, a pressure-sensitive adhesive having further excellent adhesion to an adherend can be obtained.

The content of the dicarboxylic acid unit having a divalent aromatic ring group in the condensed resin is preferably 20 to 50 mol%, and preferably 30 to 50 mol%, based on the total amount of the monomer (A) unit and the monomer (B) unit. More preferred is 40 to 50 mol%.

The content of the diamine unit having a 1,4-piperazinediyl group in the condensation resin is preferably 15 to 60 mol%, and preferably 20 to 50 mol%, based on the total amount of the monomer (A) unit and the monomer (B) unit. More preferred is 25 to 45 mol%.

The weight average molecular weight of the condensation resin is preferably 20000 to 100,000, more preferably 30000 to 60000. In addition, in this specification, a weight average molecular weight shows the weight average molecular weight of polystyrene conversion measured by GPC method.

The content of the condensation resin in the pressure-sensitive adhesive according to this embodiment is preferably 50% by mass or more and more preferably 70% by mass or more based on the total amount of the pressure-sensitive adhesive. When the content of the condensation resin is within the above range, higher adhesiveness can be obtained while sufficiently maintaining high heat resistance. The content of the condensation resin may be 96% by mass or less, or 90% by mass or less. Further, the pressure-sensitive adhesive according to this embodiment may be composed of a condensation resin (that is, the content of the condensation resin is 100% by mass). However, the content of the condensation resin can be appropriately out of the above range depending on the application.

Moreover, it is preferable that content of a thermosetting resin is 30 mass% or less, and the adhesive which concerns on this embodiment is 20 mass% or less from a viewpoint of maintaining the adhesiveness in a high temperature environment favorably. It is more preferable that it does not contain a thermosetting resin.

In the pressure-sensitive adhesive according to the present embodiment, rosin resin, terpene resin, coumarone resin, phenol resin, styrene resin, aliphatic petroleum resin, aromatic system are used within the range not impairing the object of the invention in order to enhance adhesion. You may add tackifiers, such as a petroleum resin and an aliphatic aromatic copolymer petroleum resin.

(How to use adhesive)
Since the pressure-sensitive adhesive according to the present embodiment can maintain the pressure-sensitive adhesive property even in a high temperature environment, it can be used for applications including the following steps (1) to (3).
(1) A sticking step of sticking the second adherend to the first adherend via an adhesive layer containing an adhesive.
(2) A heating step of heating the first adherend and the second adherend under conditions where the temperature of the adhesive layer is 200 ° C. or higher.
(3) The peeling process which peels an adhesion layer and a 2nd to-be-adhered body from the 1st to-be-adhered body which passed through the heating process.

In the attaching step, for example, an adhesive layer is formed on one surface of the first adherend, and a second adherend is disposed on the surface of the adhesive layer opposite to the first adherend. The second adherend can be adhered to the first adherend by pressing the first adherend and the second adherend together.

Further, an adhesive layer is formed on one surface of the second adherend, and the first adherend is disposed on the surface of the adhesive layer opposite to the second adherend, The second adherend can be attached to the first adherend by pressing the adherend and the second adherend together.

The adhesive layer can be formed, for example, by preparing an adhesive varnish containing an adhesive and a solvent, applying the adhesive varnish, and drying the adhesive varnish. The solvent used in the adhesive varnish is not particularly limited, but a glycol solvent, a glycol ether solvent, a glycol ester solvent, and the like are preferable because the adhesive exhibits good solubility.

Examples of the solvent include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, and 3-methoxy-3. -Methyl-1-butanol, ethylene glycol monomethyl ether acetate, PMA (propylene glycol monomethyl ether acetate), diethylene glycol monobutyl ether acetate and diethylene glycol monoethyl ether acetate. In addition to the above, N-methylpyrrolidone, N-ethylpyrrolidone, N-methylsuccinimide, N, N′-dimethylacetamide and dimethylformamide can also be used. These solvents may be used alone or in combination of two or more.

The adhesive layer in the attaching step may be provided on the one surface by applying and drying the adhesive varnish on one surface of the first adherend or the second adherend, It may be provided on the one surface by laminating and transferring an adhesive layer formed on a support described later on one surface of the first adherend or the second adherend.

In the attaching step, for example, the first adherend and the second adherend can be attached at 0 to 50 ° C.

In the heating step, the first adherend and the second adherend are heated. Although the heating method and the purpose of heating are not particularly limited, the adhesive layer is exposed to a temperature of 200 ° C. or higher by the heating. Usually, when a pressure-sensitive adhesive having low heat resistance (for example, an acrylic pressure-sensitive adhesive) is subjected to such a heating step, the pressure-sensitive adhesiveness is not maintained, and floating or peeling occurs. However, according to the pressure-sensitive adhesive layer containing the pressure-sensitive adhesive according to the present embodiment, the adhesiveness is maintained even after such a heating step, and thus the occurrence of floating and peeling can be sufficiently suppressed.

In the heating step, the heated first adherend and second adherend may be molded. Since the pressure-sensitive adhesive layer containing the pressure-sensitive adhesive according to the present embodiment is excellent in followability, even when the first adherend and the second adherend are deformed by molding, the occurrence of floating and peeling is sufficiently suppressed. Is done.

In the peeling step, the adhesive layer and the second adherend are peeled from the first adherend. Here, the adhesive layer and the second adherend may be integrally peeled from the first adherend, or may be peeled independently from the first adherend.

In the peeling step, for example, the adhesive layer and the second adherend can be peeled from the first adherend at 0 to 50 ° C.

The pressure-sensitive adhesive layer peeled off in the peeling step can be reused in the sticking step because the adhesiveness is maintained even after the heating step.

The first adherend and the second adherend are not particularly limited, but polyester, polyimide, polyamide, polyethersulfone, polyphenylene sulfide, polyetherketone, polyetheretherketone, triacetylcellulose, polyetherimide And at least one organic material selected from polyethylene naphthalate, polypropylene, acrylic, polystyrene, polycarbonate and the like. A support containing an inorganic material can also be used, for example, at least one inorganic selected from aluminum, magnesium, titanium, chromium, manganese, iron, nickel, zinc, tin, glass, copper, a silicon wafer, and an alloy. A material containing a material can be used.

As the first adherend and the second adherend, a material having heat resistance with respect to a temperature of 200 ° C. or higher may be used. For example, polyamide resin such as nylon 6, nylon 66, nylon 46; polyethylene terephthalate Polyester resins such as polyethylene naphthalate, polytrimethylene terephthalate, polytrimethylene naphthalate, polybutylene terephthalate and polybutylene naphthalate; Polyolefin resins such as polypropylene and polyethylene; Acrylic resin, polyimide resin, polyarylate resin or mixtures thereof Examples include resin, aluminum, magnesium, titanium, chromium, manganese, iron, nickel, zinc, tin, glass, copper, and silicon wafer. Among these materials, polyester resin, polyamide resin, polyolefin resin, polyimide resin, acrylic resin, aluminum, magnesium, titanium, chromium, manganese, iron, nickel, zinc, tin, glass, copper, and silicon wafer have high heat resistance. Is preferable.

According to the above usage method, for example, the first adherend having low rigidity is securely fixed to the second adherend during high-temperature processing, and the first adherend is damaged after processing. It can be peeled without being deformed.

(Adhesive material)
FIG. 1 is a schematic cross-sectional view showing a preferred embodiment of the pressure-sensitive adhesive of the present invention. The pressure-sensitive adhesive 1 shown in FIG. 1 includes a support 10 and a pressure-sensitive adhesive layer 14 containing a pressure-sensitive adhesive provided on the support 10.

The support is not particularly limited, but polyester, polyimide, polyamide, polyethersulfone, polyphenylene sulfide, polyetherketone, polyetheretherketone, triacetylcellulose, polyetherimide, polyethylene naphthalate, polypropylene, acrylic, polystyrene, Examples include those containing at least one organic material selected from polycarbonate and the like. A support containing an inorganic material can also be used, for example, at least one inorganic selected from aluminum, magnesium, titanium, chromium, manganese, iron, nickel, zinc, tin, glass, copper, a silicon wafer, and an alloy. A material containing a material can be used.

The pressure-sensitive adhesive material can be produced, for example, by forming a pressure-sensitive adhesive layer by applying a pressure-sensitive adhesive varnish containing a pressure-sensitive adhesive and a solvent onto a support and drying it. Such a casting method is preferable because a flat adhesive layer can be easily obtained. Examples of the solvent used for the pressure-sensitive adhesive varnish are the same as those described above.

The adhesive material is produced by laminating and transferring an adhesive layer formed by applying an adhesive varnish containing an adhesive and a solvent onto a release film and drying the laminate. You can also.

The thickness of the adhesive layer is preferably from 0.1 to 100 μm, more preferably from 1 to 50 μm. The thickness of the pressure-sensitive adhesive layer can be appropriately adjusted according to the concentration of the pressure-sensitive adhesive in the pressure-sensitive adhesive varnish and the amount of the pressure-sensitive adhesive varnish applied.

(How to use adhesive)
Since the pressure-sensitive adhesive according to the present embodiment can maintain the pressure-sensitive adhesive property even in a high temperature environment, it can be used for applications including the following steps (1) to (3).
(1) A sticking step of sticking the adhesive material to the adherend so that the adhesive layer is disposed on the side close to the adherend.
(2) A heating step of heating the adherend under conditions where the temperature of the adhesive material is 200 ° C. or higher.
(3) The peeling process which peels an adhesive material from the to-be-adhered body which passed through the heating process.

In the sticking step, the pressure-sensitive adhesive material can be stuck to the adherend by pressing the pressure-sensitive adhesive layer so that the pressure-sensitive adhesive layer is in contact with the adherend. In the affixing step, the first adherend and the second adherend can be affixed at an arbitrary temperature, but for example, at 0 to 50 ° C. from the viewpoint of appropriate adhesiveness and work efficiency. It is desirable to stick.

In the heating step, the adherend is heated, and the adhesive layer is exposed to a temperature of 200 ° C. or higher. Usually, when a pressure-sensitive adhesive having low heat resistance (for example, an acrylic pressure-sensitive adhesive) is subjected to such a heating step, the pressure-sensitive adhesiveness is not maintained, and floating or peeling occurs. However, according to the pressure-sensitive adhesive material according to the present embodiment, the adhesiveness is maintained even through such a heating step, and therefore, the occurrence of floating and peeling can be sufficiently suppressed.

In the heating step, the heated adherend may be molded. Since the pressure-sensitive adhesive layer containing the pressure-sensitive adhesive according to the present embodiment is excellent in followability, even when the adherend is deformed by molding, the occurrence of floating or peeling is sufficiently suppressed.

In the peeling process, the adhesive material is peeled off from the adherend. In the peeling step, for example, the adhesive material can be peeled from the adherend at 0 to 50 ° C.

The adhesive material peeled off in the peeling step can be reused in the sticking step because the adhesiveness is maintained even after the heating step.

Examples of adherends in this method of use are the same as the first adherend and the second adherend.

According to the above usage method, for example, an adherend with low rigidity is securely fixed to a support during high-temperature processing, and after processing, the adherend is peeled off without being damaged or deformed. Can do.

The preferred embodiment of the present invention has been described above, but the present invention is not limited to the above embodiment.

For example, one embodiment of the present invention has a structural unit obtained by condensation polymerization of a polymerizable monomer containing the monomer (A) and the monomer (B), and at least one of the above (1) and (2), In addition, the present invention relates to the use of a condensation resin satisfying the above (3) as an adhesive.

Another aspect of the present invention has a structural unit obtained by condensation polymerization of a polymerizable monomer containing the monomer (A) and the monomer (B), and at least one of the above (1) and (2) In addition, the present invention relates to the use of a condensation resin satisfying the above (3) for producing a pressure-sensitive adhesive.

Another aspect of the present invention is a condensation resin selected from the group consisting of a polyamide resin, a polyamideimide resin and a polyimide resin, the pressure-sensitive adhesive of the condensation resin having a cyclohexane ring and a polyoxyalkanediyl group As a use,

Another aspect of the present invention is a condensation resin selected from the group consisting of a polyamide resin, a polyamideimide resin and a polyimide resin, the pressure-sensitive adhesive of the condensation resin having a cyclohexane ring and a polyoxyalkanediyl group Related to the use for the manufacture of.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the examples.

Example 1
In a separable flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet tube, 43.75 parts (molar ratio) of isophthaloyl dichloride, 6.25 parts (molar ratio) of terephthaloyl dichloride, polypropylene oxide diamine (JEFFAMINE ( (Registered trademark) D-2000, manufactured by HUNTSMAN) 5 parts (molar ratio), bis (4-aminocyclohexyl) methane 2.5 parts (molar ratio) and 1,4-bis (3-aminopropyl) piperazine 42.5 Parts (molar ratio) were subjected to condensation polymerization in N-methylpyrrolidone containing 110 parts (molar ratio) of triethylamine as an acid neutralizer under ice cooling. After completion of the reaction, a polyamide resin was obtained by adding 3 times the amount of water to the reaction mixture, separating insoluble components and drying.

Next, the obtained pressure-sensitive adhesive varnish was applied to a polyimide film having a thickness of 25 μm and a width of 20 cm using an applicator so that the thickness of the pressure-sensitive adhesive layer after drying was 20 μm. An adhesive was prepared by heating at 30 ° C. for 30 minutes and drying.

(Example 2)
Except that the condensation polymerization was changed to 5 parts (molar ratio) of bis (4-aminocyclohexyl) methane and 40 parts (molar ratio) of 1,4-bis (3-aminopropyl) piperazine, respectively, Example 1 Similarly, a polyamide resin, an adhesive varnish, and an adhesive material were produced.

(Example 3)
Except that the condensation polymerization was changed to 10 parts (molar ratio) of bis (4-aminocyclohexyl) methane and 35 parts (molar ratio) of 1,4-bis (3-aminopropyl) piperazine, respectively, Example 1 Similarly, a polyamide resin, an adhesive varnish, and an adhesive material were produced.

Example 4
In the condensation polymerization, 5 parts (molar ratio) of bis (4-aminocyclohexyl) methane and 35 parts (molar ratio) of 1,4-bis (3-aminopropyl) piperazine, norbornanediamine (NBDA, manufactured by Mitsui Chemicals Fine) 5 A polyamide resin, a pressure-sensitive adhesive varnish, and a pressure-sensitive adhesive material were produced in the same manner as in Example 1 except that the parts were changed to the respective parts.

(Comparative Example 1)
In a separable flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet tube, 43.75 parts (molar ratio) of isophthaloyl dichloride, 6.25 parts (molar ratio) of terephthaloyl dichloride, polypropylene oxide diamine (JEFFAMINE ( (Registered trademark) D-2000, manufactured by HUNTSMAN Co., Ltd.) 5 parts (molar ratio) and 1,4-bis (3-aminopropyl) piperazine 45 parts (molar ratio) ) -Containing N-methylpyrrolidone under ice cooling. After completion of the reaction, a polyamide resin was obtained by adding 3 times the amount of water to the reaction mixture, separating insoluble components and drying.

(Comparative Example 2)
In a separable flask equipped with a stirrer, reflux condenser, thermometer, and nitrogen inlet tube, 43.75 parts (molar ratio) of isophthaloyl dichloride, 6.25 parts (molar ratio) of terephthaloyl dichloride, polypropylene oxide diamine (JEFFAMINE ( (Registered trademark) D-2000, manufactured by HUNTSMAN Co., Ltd.) 5 parts (molar ratio) and bis (4-aminocyclohexyl) methane 45 parts (molar ratio), N containing 110 parts (molar ratio) triethylamine as an acid neutralizer -Condensation polymerization in methylpyrrolidone under ice-cooling. After completion of the reaction, a polyamide resin was obtained by adding 3 times the amount of water to the reaction mixture, separating insoluble components and drying.

The weight average molecular weight of each polyamide resin obtained in Examples 1 to 4 and Comparative Examples 1 and 2 was determined by the following method. In addition, the pressure-sensitive adhesive materials obtained in Examples 1 to 3 and Comparative Example 4 were evaluated for tackiness, non-peeling, and heat resistance by the following methods. Furthermore, hygroscopicity was evaluated by the following method. The results were as shown in Table 1.

(Evaluation of adhesiveness)
The adhesive material was placed on a 10 cm × 10 cm glass plate having a thickness of 70 μm, and was pasted by passing a laminator with a roll pressure of 0.3 MPa at a speed of 0.8 m / min at 17 to 25 ° C. . Slightly peel off and grip the end of the attached polyimide film of the adhesive material, and pull the polyimide film at a width of 10 mm at 90 degrees and a pulling speed of 300 mm / min using a rheometer RE3305R (manufactured by Yamaden). The minimum force (N / cm) required for peeling was measured.

(Evaluation of remaining peeling)
The weight of the pressure-sensitive adhesive material was measured, and the weight of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive material was calculated by subtracting the weight of the polyimide film measured in advance. Subsequently, the adhesive material was attached to a glass plate and the adhesive material was peeled off in the same manner as the evaluation of adhesiveness. The weight of the peeled adhesive material was measured, and the weight of the pressure-sensitive adhesive layer after peeling was calculated by subtracting the weight of the polyimide film measured in advance. At this time, when the ratio of the weight of the pressure-sensitive adhesive layer after peeling to the weight of the pressure-sensitive adhesive layer before sticking is 90% or more, “A” is indicated, and the case where it is less than 90% is indicated as “B”. The presence or absence of was evaluated.

(Evaluation of heat resistance)
The adhesive material was attached to a glass plate in the same manner as the evaluation of adhesiveness. The glass plate with the adhesive material attached was heated in a clean oven at 200 ° C. for 1 hour, and the presence or absence of peeling of the adhesive material from the glass plate was visually confirmed. The case where there was no peeling was evaluated as “A”, and the case where there was peeling as “B”.

(Hygroscopic evaluation)
About 10 mg of each polyamide resin obtained in Examples 1 to 4 and Comparative Examples 1 and 2 was weighed, and the amount of thermogravimetry was measured with a differential thermothermal gravimetric simultaneous measuring apparatus TAPS3000S (manufactured by Bruker AXS). The measurement was performed at a temperature increase rate of ° C / min. The water absorption was calculated from the thermal weight loss between 50 and 100 ° C.

 

Claims (29)

1. Containing a condensation resin having a structural unit obtained by condensation polymerization of a polymerizable monomer containing a monomer (A) having at least two carboxyl groups and a monomer (B) having at least two amino groups,
   An adhesive that satisfies at least one of the following (1) and (2) and the following (3).
   (1) At least one selected from the group consisting of the monomer (A), the anhydride of the monomer (A), and the monomer (B) is liquid at 25 ° C.
   (2) The condensation resin has a polyoxyalkanediyl group.
   (3) The condensed resin has a cyclohexane ring.
2. The pressure-sensitive adhesive according to claim 1, which satisfies both (1) and (2).
3. The pressure-sensitive adhesive according to claim 1 or 2, wherein the condensation resin contains at least one selected from the group consisting of a polyamideimide resin, a polyimide resin, and a polyamide resin.
4. The pressure-sensitive adhesive according to any one of claims 1 to 3, wherein the condensation resin is a polyamide resin.
5. The pressure-sensitive adhesive according to any one of claims 1 to 3, wherein the structural unit in the condensation resin has the polyoxyalkanediyl group.
6. The pressure-sensitive adhesive according to any one of claims 1 to 4, wherein the structure derived from the monomer (B) in the structural unit has the polyoxyalkanediyl group.
7. The polymerizable monomer is a monomer having a polyoxyalkanediyl group and at least two amino groups (b-1) at a ratio of 2 to 8 mol% based on the total amount of the monomer (A) and the monomer (B). The pressure-sensitive adhesive according to any one of claims 1 to 5, further comprising:
8. Containing a condensation resin selected from the group consisting of polyamide resin, polyamideimide resin and polyimide resin,
   The pressure-sensitive adhesive, wherein the condensed resin has a cyclohexane ring and a polyoxyalkanediyl group.
9. The pressure-sensitive adhesive according to claim 7, wherein the condensed resin includes a diamine unit having a cyclohexane ring and a diamine unit having a polyoxyalkanediyl group.
10. The pressure-sensitive adhesive according to claim 7 or 8, wherein the condensed resin further has a divalent aromatic ring group.
11. The pressure-sensitive adhesive according to claim 9, wherein the condensed resin contains a dicarboxylic acid unit having a divalent aromatic ring group.
12. The pressure-sensitive adhesive according to any one of claims 7 to 10, wherein the condensation resin further has a 1,4-piperazinediyl group.
13. The pressure-sensitive adhesive according to claim 11, wherein the condensation resin contains a diamine unit having a 1,4-piperazinediyl group.
14. The pressure-sensitive adhesive according to any one of claims 1 to 12, which is used as a heat-resistant pressure-sensitive adhesive that is attached to an adherend and heated from 200 ° C or higher and then peeled off from the adherend.
15. The pressure-sensitive adhesive according to any one of claims 1 to 13, wherein the content of the condensation resin is 50% by mass or more.
16. The pressure-sensitive adhesive according to any one of claims 1 to 15, which is a pressure-sensitive adhesive made of the condensation resin.
17. Having a structural unit obtained by condensation polymerization of a polymerizable monomer containing a monomer (A) having at least two carboxyl groups and a monomer (B) having at least two amino groups, and having the following (1) and (2) Use of a condensation resin satisfying at least one of the following (3) as an adhesive.
    (1) At least one selected from the group consisting of the monomer (A), the anhydride of the monomer (A), and the monomer (B) is liquid at 25 ° C.
    (2) The condensation resin has a polyoxyalkanediyl group.
    (3) The condensed resin has a cyclohexane ring.
18. Having a structural unit obtained by condensation polymerization of a polymerizable monomer containing a monomer (A) having at least two carboxyl groups and a monomer (B) having at least two amino groups, and having the following (1) and (2) Use of a condensation resin satisfying at least one of the following (3) for the production of an adhesive.
    (1) At least one selected from the group consisting of the monomer (A), the anhydride of the monomer (A), and the monomer (B) is liquid at 25 ° C.
    (2) The condensation resin has a polyoxyalkanediyl group.
    (3) The condensed resin has a cyclohexane ring.
19. Use of a condensation resin selected from the group consisting of a polyamide resin, a polyamideimide resin and a polyimide resin, having a cyclohexane ring and a polyoxyalkanediyl group, as an adhesive.
20. Use of a condensation resin selected from the group consisting of a polyamide resin, a polyamideimide resin and a polyimide resin, having a cyclohexane ring and a polyoxyalkanediyl group, for the production of an adhesive.
21. An adhesive comprising: a support; and an adhesive layer containing the adhesive according to any one of claims 1 to 16 provided on the support.
22. An attaching step of attaching the second adherend to the first adherend via the adhesive layer containing the adhesive according to any one of claims 1 to 16;
    A heating step of heating the first adherend and the second adherend under conditions where the temperature of the adhesive layer is 200 ° C. or higher;
    A peeling step for peeling the adhesive layer and the second adherend from the first adherend subjected to the heating step;
    A method for using a pressure-sensitive adhesive.
23. The method according to claim 22, wherein, in the attaching step, the first adherend and the second adherend are attached at 0 to 50 ° C.
24. The method according to claim 22 or 23, wherein, in the peeling step, the pressure-sensitive adhesive layer and the second adherend are peeled from the first adherend at 0 to 50 ° C.
25. The method according to any one of claims 22 to 24, wherein the adhesive layer peeled in the peeling step is reused in the sticking step.
26. A sticking step of sticking the adhesive material according to claim 21 to an adherend so that the adhesive layer is disposed on a side close to the adherend;
    A heating step of heating the adherend under conditions where the temperature of the adhesive is 200 ° C. or higher;
    A peeling step of peeling the adhesive material from the adherend that has undergone the heating step;
    A method for using an adhesive material.
27. The method according to claim 26, wherein, in the attaching step, the adhesive material is attached to the adherend at 0 to 50 ° C.
28. 28. The method of use according to claim 26 or 27, wherein in the peeling step, the adhesive material is peeled from the adherend at 0 to 50 ° C.
29. The method according to any one of claims 26 to 28, wherein the adhesive material peeled in the peeling step is reused in the sticking step.

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