CN103476894A

CN103476894A - Adhesive, adhesive material using same, and method for using said adhesive and material

Info

Publication number: CN103476894A
Application number: CN2012800181699A
Authority: CN
Inventors: 福山雄大; 增田克之; 品田咏逸; 大越将司; 山本和德; 山口正利; 大山泰; 柳田裕贵; 片寄光雄
Original assignee: Hitachi Chemical Co Ltd
Current assignee: Showa Denko Materials Co Ltd
Priority date: 2011-04-12
Filing date: 2012-04-12
Publication date: 2013-12-25
Anticipated expiration: 2032-04-12
Also published as: WO2012141266A1; TWI535811B; TW201245373A; WO2012141267A1; CN103476895B; WO2012140740A1; KR101564156B1; CN103476894B; CN103459544A; TW201245372A; KR20130143663A; KR20130143664A; TW201247824A; KR101592662B1; KR101642174B1; CN103476895A; KR20130143665A; WO2012141271A1; CN103459544B

Abstract

An adhesive that satisfies at least one of the belowmentioned conditions (1 and/or 2) and contains a condensation resin that has a structural unit obtained by condensation-polymerizing polymerizable monomers including the following: a monomer (A) that has at least two carboxyl groups; and a monomer (B) that has at least two amino groups. One condition (1) is that at least one of the following is a liquid at 25 DEG C: the first (A) of the aforementioned monomers, an anhydride thereof, and the other (B) of the aforementioned monomers. The other condition (2) is that the condensation resin contains a polyoxyalkane diyl group.

Description

Tackiness agent and use its sticky material and their using method

Technical field

The present invention relates under hot environment also can maintain adhesive tackiness agent and use its sticky material and their using method.

Background technology

All the time, as tackiness agent, what mostly use is the acrylic acid series tackiness agent.In addition, as stable on heating tackiness agent, for example in patent documentation 1, put down in writing the silicone-based tackiness agent.

The prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2009-256542 communique

Summary of the invention

The problem that invention will solve

Yet there are the following problems for the acrylic acid series tackiness agent: under hot environment, (for example, more than 200 ℃) can not maintain tackiness, produce bubbling, strip off.

In addition, there are the following problems for the silicone-based tackiness agent: price object high, that paste limited (for example, low to the tackiness of the plastic materials such as polyester film, polyimide film).

Therefore, the object of the present invention is to provide under hot environment and also can maintain adhesive novel tackiness agent and using method thereof.In addition, the object of the present invention is to provide sticky material and the using method thereof of having used this tackiness agent.

For solving the method for problem

One aspect of the present invention relates to a kind of tackiness agent, it contains the condensation resin with following structural unit, and described structural unit obtains by the polymerizable monomer polycondensation that makes to comprise the monomer (A) with at least 2 carboxyls and the monomer (B) with at least 2 amino.

And above-mentioned tackiness agent meets at least one in following (1) and (2).

(1) at least one that select in the group that acid anhydrides and the above-mentioned monomer (B) of above-mentioned monomer (A), above-mentioned monomer (A) forms at 25 ℃ for aqueous.

(2) above-mentioned condensation resin has polyoxy alkane two bases.

According to above-mentioned tackiness agent, under hot environment, (for example, more than 200 ℃) also maintain high adhesion, the generation of fully suppress bubbling, stripping off.In addition, above-mentioned tackiness agent shows high adhesion for adherends such as plastic materials.Therefore and then above-mentioned tackiness agent is also maintaining high adhesion from adherend is peeled off, can repeatedly carry out with the stickup of adherend and peel off.

Above-mentioned tackiness agent preferably meets above-mentioned (1) and (2) simultaneously.According to such tackiness agent, tackiness further improves.In addition, such tackiness agent can by for example 0～50 ℃ press and easily stick on adherend.

In above-mentioned tackiness agent, above-mentioned condensation resin preferably comprises at least one that select in the group be comprised of polyamide-imide resin, polyimide resin and polyamide resin.

In above-mentioned tackiness agent, above-mentioned condensation resin is preferably polyamide resin.

In above-mentioned tackiness agent, the said structure unit in preferred above-mentioned condensation resin has above-mentioned polyoxy alkane two bases.That is, polyoxy alkane two bases in above-mentioned (2) preferably are contained in the said structure unit.

In above-mentioned tackiness agent, the structure optimization that is derived from above-mentioned monomer (B) in the said structure unit has above-mentioned polyoxy alkane two bases.That is, polyoxy alkane two bases in above-mentioned (2) preferably are contained in the structure that is derived from above-mentioned monomer (B) in the said structure unit.

In above-mentioned tackiness agent, the ratio that the total amount that above-mentioned polymerizable monomer preferably be take with respect to above-mentioned monomer (A) and above-mentioned monomer (B) is 2.5～10mol% comprises the monomer (b-1) with polyoxy alkane two bases and at least 2 amino.

Other side of the present invention relates to a kind of tackiness agent, the condensation resin in its group that contains the above free polyamide resin of choosing of 50 quality %, polyamide-imide resin and polyimide resin composition, and above-mentioned condensation resin has polyoxy alkane two bases.

In above-mentioned tackiness agent, above-mentioned condensation resin can comprise two amine units with polyoxy alkane two bases.

In above-mentioned tackiness agent, above-mentioned condensation resin can further have the fragrant cyclic group of divalence, also can comprise the dicarboxylic acid units of the fragrant cyclic group with divalence.

In above-mentioned tackiness agent, above-mentioned condensation resin can further have Isosorbide-5-Nitrae-piperazine two bases, also can comprise two amine units with Isosorbide-5-Nitrae-piperazine two bases.

In above-mentioned tackiness agent, more than the content of above-mentioned condensation resin is preferably 50 quality %.In addition, above-mentioned tackiness agent also can be comprised of above-mentioned condensation resin.Such tackiness agent, because thermotolerance is more excellent, therefore can be more suitable for using as the thermotolerance tackiness agent.

Above-mentioned tackiness agent for example can as stick on adherend and be heated to more than 200 ℃ after the thermotolerance tackiness agent peeled off from this adherend.That is, above-mentioned tackiness agent can be suitable for having in the technique of the operation that is exposed to the high temperature more than 200 ℃.

Other side of the present invention relates to the application of a kind of condensation resin as tackiness agent, described condensation resin has following structural unit, meet at least one in following (1) and (2), described structural unit obtains by the polymerizable monomer polycondensation that makes to comprise the monomer (A) with at least 2 carboxyls and the monomer (B) with at least 2 amino.

(2) above-mentioned condensation resin has polyoxy alkane two bases.

Other side of the present invention relates to the application of a kind of condensation resin in the manufacture of tackiness agent, described condensation resin has following structural unit, meet at least one in following (1) and (2), described structural unit obtains by the polymerizable monomer polycondensation that makes to comprise the monomer (A) with at least 2 carboxyls and the monomer (B) with at least 2 amino.

(2) above-mentioned condensation resin has polyoxy alkane two bases.

Other side of the present invention relates to the application as tackiness agent of condensation resin with polyoxy alkane two bases, the group that described condensation resin selects free polyamide resin, polyamide-imide resin and polyimide resin to form.

Other side of the present invention relates to the application of condensation resin in the manufacture of tackiness agent with polyoxy alkane two bases, the group that described condensation resin selects free polyamide resin, polyamide-imide resin and polyimide resin to form.

The present invention also provides a kind of sticky material, and it possesses supporter and is arranged at the adhesive coating that contains above-mentioned tackiness agent on this supporter.

The present invention also provides a kind of using method of tackiness agent, and it possesses: paste operation, be situated between by the adhesive coating that contains above-mentioned tackiness agent, the second adherend is pasted on to the first adherend; Heating process, become under the condition more than 200 ℃ in the temperature of above-mentioned adhesive coating, heats above-mentioned the first adherend and above-mentioned the second adherend; And stripping process, peel off above-mentioned adhesive coating and above-mentioned the second adherend from above-mentioned the first adherend that has experienced above-mentioned heating process.

In the using method of above-mentioned tackiness agent, in above-mentioned stickup operation, preferably at 0～50 ℃, paste above-mentioned the first adherend and above-mentioned the second adherend.

In the using method of above-mentioned tackiness agent, in above-mentioned stripping process, preferably at 0～50 ℃, from above-mentioned the first adherend, peel off above-mentioned adhesive coating and above-mentioned the second adherend.

In the using method of above-mentioned tackiness agent, the above-mentioned adhesive coating be stripped from above-mentioned stripping process can be recycled in above-mentioned stickup operation.

The present invention also provides a kind of using method of sticky material, and it possesses: paste operation, according to above-mentioned adhesive coating, be configured in the mode near above-mentioned adherend side, above-mentioned sticky material is pasted on to adherend; Heating process, become under the condition more than 200 ℃ in the temperature of above-mentioned sticky material, heats above-mentioned adherend; And stripping process, peel off above-mentioned sticky material from the above-mentioned adherend that has experienced above-mentioned heating process.

In the using method of above-mentioned sticky material, in above-mentioned stickup operation, preferably at 0～50 ℃, above-mentioned sticky material is pasted on to above-mentioned adherend.

In the using method of above-mentioned sticky material, in above-mentioned stripping process, preferably at 0～50 ℃, from above-mentioned adherend, peel off above-mentioned sticky material.

In the using method of above-mentioned sticky material, the above-mentioned sticky material be stripped from above-mentioned stripping process can be recycled in above-mentioned stickup operation.

The effect of invention

According to the present invention, can provide under hot environment and also can maintain adhesive novel tackiness agent and using method thereof.In addition, according to the present invention, can provide sticky material and the using method thereof of having used this tackiness agent.

The accompanying drawing explanation

Fig. 1 means the constructed profile of a preferred embodiment of tackiness agent of the present invention.

Fig. 2 means and utilizes that differential scanning type calorimeter is that measure, the thermally equilibrated figure of polyamide resin between-50～200 ℃ embodiment 1.

Fig. 3 means and utilizes that differential scanning type calorimeter is that measure, the thermally equilibrated figure of polyamide resin between-50～200 ℃ embodiment 2.

Fig. 4 means and utilizes that differential scanning type calorimeter is that measure, the thermally equilibrated figure of polyamide resin between-50～200 ℃ comparative example 1.

Embodiment

Below, to preferred embodiment describing of tackiness agent of the present invention and sticky material.

(tackiness agent)

The tackiness agent of present embodiment contains the condensation resin with following structural unit, and described structural unit obtains by the polymerizable monomer polycondensation that makes to comprise the monomer (A) with at least 2 carboxyls and the monomer (B) with at least 2 amino.

And the tackiness agent of present embodiment meets at least one in following (1) and (2).

(1) at least one that select in the group that acid anhydrides and the monomer (B) of monomer (A), monomer (A) forms at 25 ℃ for aqueous.

(2) condensation resin has polyoxy alkane two bases.

According to such tackiness agent, even for example remain under the hot environment more than 200 ℃, also maintain high adhesion, the generation of fully suppress bubbling, stripping off.

Here, above-mentioned condensation resin also nonessentially makes above-mentioned polymerizable monomer polycondensation and manufactures, as long as have the structural unit that can be formed by the polycondensation of above-mentioned polymerizable monomer.

; above-mentioned in order to meet (1); and nonessentially make above-mentioned condensation resin for using 25 ℃ to manufacture for aqueous monomer (or acid anhydrides is aqueous monomer at 25 ℃), as long as have can be by comprising 25 ℃ of structural units that form for the polycondensation of the polymerizable monomer of aqueous monomer (or acid anhydrides is aqueous monomer at 25 ℃) for above-mentioned condensation resin.

Said structure unit in above-mentioned condensation resin can be make a kind of monomer (A) and monomer (B) polycondensation and structural unit, can be also make various of monomer (A) and monomer (B) polycondensation and structural unit.In situation for the latter, above-mentioned in order to meet (1), as long as select free various of monomer (A), they acid anhydrides, and the group that forms of various of monomer (B) at least one at 25 ℃ for aqueous.

Monomer (A) and the monomer (B) that can form the said structure unit can be confirmed by following method.That is, can be that generate during the said structure unit by hydrolysis, compound that have at least 2 carboxyls and compound with at least 2 amino be made as respectively monomer (A) and monomer (B).

For example, the structural unit shown in following formula (1-1) can be referred to as to make the monomer polycondensation shown in the monomer shown in following formula (A-1) and following formula (B-1) and structural unit.Here, in formula, R1 and R2 mean the organic group of divalence.

[changing 1]

[changing 2]

[changing 3]

At this, meet above-mentioned (1) in order to make the structural unit shown in formula (1-1), at least one in the monomer shown in the monomer shown in a solemnity (A-1) and formula (B-1) is aqueous getting final product at 25 ℃.

In addition, for example, the structural unit shown in following formula (1-2) can be referred to as to make the monomer polycondensation shown in the monomer shown in following formula (A-2) and above-mentioned formula (B-1) and structural unit.Here, in formula, R ³the organic group that means trivalent.

[changing 4]

[changing 5]

At this, in order to make the structural unit shown in formula (1-2) meet above-mentioned (1), as long as at least one that select in the group is comprised of the acid anhydrides shown in the monomer shown in the monomer shown in formula (A-2), formula (B-1) and following formula (A-2 ') is aqueous at 25 ℃.

[changing 6]

And then, for example, the structural unit shown in following formula (1-3) can be referred to as to make the monomer polycondensation shown in the monomer shown in following formula (A-3) and above-mentioned formula (B-1) and structural unit.Here, in formula, R ⁴the organic group that means tetravalence.

[changing 7]

[changing 8]

At this, in order to make the structural unit shown in formula (1-3) meet above-mentioned (1), as long as at least one that select in the group is comprised of the acid anhydrides shown in the monomer shown in the monomer shown in formula (A-3), formula (B-1) and following formula (A-3 ') is aqueous at 25 ℃.

[changing 9]

As monomer (A), monomer (monomer shown in formula (A-3)) that can enumerate the monomer (monomer shown in formula (A-1)) with 2 carboxyls, the monomer (monomer shown in formula (A-2)) with 3 carboxyls, there are 4 carboxyls etc.

As the monomer with 2 carboxyls, can enumerate for example oxalic acid, propanedioic acid, succsinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, 1,9-nonane diacid, dodecanedioic acid, tetradecane diacid, pentadecane diacid, the alkylene dicarboxylic acids such as octadecane diacid, phthalic acid, terephthalic acid, m-phthalic acid, Isosorbide-5-Nitrae-naphthalene dicarboxylic acids, 1,5-naphthalene dicarboxylic acids, 2,6-naphthalene dicarboxylic acids, acenaphthene-5, the 6-dicarboxylic acid, pyridine-2,3-dicarboxylic acid, pyridine-2, the 6-dicarboxylic acid, the 1H-imidazole-4,5-dicarboxylic acid, 1H-pyrroles-2, the 4-dicarboxylic acid, furans-2, the 5-dicarboxylic acid, the aromatic dicarboxylic acids such as 2,5-ThiophenedicarboxyliAcid Acid, 1,3-cyclohexane dicarboxylic acid, Isosorbide-5-Nitrae-cyclohexane dicarboxylic acid, the 4-methylhexahydrophthaacid acid, the 3-methylhexahydrophthaacid acid, 3-ethyl hexahydrophthalic acid, 4-ethyl hexahydrophthalic acid, methyl norcamphane-2,3-dicarboxylic acid etc. has the dicarboxylic acid of hexanaphthene skeleton, 3-methyl isophthalic acid, 2,3,6-tetrahydrophthalic acid, the 4-methyl isophthalic acid, 2,3,6-tetrahydrophthalic acid, methyl-3, methylene radical-1,2,3 in 6-, 6-tetrahydrophthalic acid etc. has the dicarboxylic acid of tetrahydrobenzene skeleton etc.

That is, as the R in formula (1-1) ¹, can enumerate the alicyclic radical of alkane two bases, divalence, the fragrant cyclic group of divalence etc.

As alkane two bases, alkane two bases that preferably carbonatoms is 1～30, alkane two bases that more preferably carbonatoms is 1～20.Alkane two bases can be also the side chain shape for the straight chain shape, are preferably the straight chain shape.

As the concrete example of alkane two bases, can enumerate methylene radical, ethylidene, glyceryl, Ding Erji, penta 2 bases, dihexyl, heptan two base, Xin Erji, the ninth of the ten Heavenly Stems two base, the last of the ten Heavenly stems two base, undecane two bases, dodecane two bases, tridecane two bases, n-Hexadecane two bases etc.

The alicyclic radical of divalence is the group had without the saturated or undersaturated carbocyclic ring structure of aromatic series.The carbonatoms of the alicyclic radical of divalence is preferably 3～20, and more preferably 4～12.In addition, the alicyclic radical of divalence preferably has cyclohexane ring.

As the alicyclic radical of divalence, can enumerate 1,3-hexanaphthene, two bases, 1,4-hexanaphthene two bases, 4-alkyl cyclohexane-1,2-bis-bases, 3-alkyl cyclohexane-1,2-bis-bases, 4,5-dialkyl cyclic hexane-1,2-bis-bases, 3,4-dialkyl cyclic hexane-1,2-bis-bases, norcamphane two bases, 5-alkyl norcamphane-2,3-bis-bases, 3-alkyl-4-tetrahydrobenzene-1,2-bis-bases, 4-alkyl-4-tetrahydrobenzene-1,2-bis-bases, 4-methyl-3, methylene radical in 6--4-tetrahydrobenzene-1,2-bis-bases etc.

At this, the alkyl of carbocyclic ring structure that is incorporated into the alicyclic radical of divalence is preferably the alkyl of carbonatoms 1～10, the more preferably alkyl of carbonatoms 1～5.

The fragrant cyclic group of divalence is the group with ring structure that aromatic series is arranged.As the fragrant cyclic group of divalence, the fragrant cyclic group of the divalence of preferred carbonatoms 6～20, the more preferably fragrant cyclic group of the divalence of carbonatoms 6～10.

As the fragrant cyclic group of divalence, can enumerate for example benzene two bases, naphthalene two bases, biphenyl two bases, acenaphthene-5,6-bis-bases, pyridine-2,3-bis-bases, pyridine-2,6-bis-bases, 1H-imidazoles-4,5-bis-bases, 1H-pyrroles-2,4-bis-bases, furans-2,5-bis-bases, thiophene-2,5-bis-bases.In addition, as benzene two bases, can enumerate 1,2-benzene, two bases, 1,3-benzene two bases, Isosorbide-5-Nitrae-benzene two bases.In addition, as naphthalene two bases, can enumerate 1,2-naphthalene, two bases 1,3-naphthalene two bases, Isosorbide-5-Nitrae-naphthalene two bases, 1,5-naphthalene two bases, 1,6-naphthalene two bases, 1,7-naphthalene two bases, 1,8-naphthalene two bases, 2,3-naphthalene two bases, 2,6-naphthalene two bases, 2,7-naphthalene two bases etc.In addition, as biphenyl two bases, can enumerate biphenyl-4,4 '-bis-bases.

As the monomer with 3 carboxyls, can enumerate such as the aromatic tricarboxylic acids such as trimellitic acid, hexanaphthene-1,2 the ester ring type tricarboxylic acid such as 4-tricarboxylic acid etc.

That is, as the R in formula (1-2) ³, can enumerate the alicyclic radical of trivalent, the fragrant cyclic group of trivalent etc.

As the alicyclic radical of trivalent, preferred hexanaphthene three bases, more preferably hexanaphthene-1,2,4-tri-bases.

As the fragrant cyclic group of trivalent, can enumerate for example benzene three bases, naphthalene three bases, preferred benzene-1,2,4-tri-bases.

As the monomer with 4 carboxyls, can enumerate for example pyromellitic acid, benzene-1,2,3, the 4-tetracarboxylic acid, 1,2,5,6-naphthalene tetracarboxylic acid, 2,3,6,7-naphthalene tetracarboxylic acid, 1,2,4,5-naphthalene tetracarboxylic acid, Isosorbide-5-Nitrae, 5,8-naphthalene tetracarboxylic acid, 2,3,6,7-anthracene tetracarboxylic acid, phenanthrene-1,8,9, the 10-tetracarboxylic acid, 3,4,9,10-perylene tetracarboxylic acid, 3,3 ', 4,4 '-biphenyltetracarboxyacid acid, 2,2 ', 3,3 '-biphenyltetracarboxyacid acid, 2,3,3 ', 4 '-biphenyltetracarboxyacid acid, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid, 2,3,2 ', 3 '-benzophenone tetracarboxylic acid, 2,3,3 ', 4 '-benzophenone tetracarboxylic acid, 3,3 ', 4,4 '-xenyl ether tetracarboxylic acid, two (3,4-dicarboxyl phenyl) ether, two (3,4-dicarboxyl phenyl) sulfone, 1-trifluoromethyl-2,3,5, the 6-benzene tertacarbonic acid, two (2,3-dicarboxyl phenyl) methane, two (3,4-dicarboxyl phenyl) methane, two (2, the 3-dicarboxyl phenyl) ethane of 1,1-, two (3, the 4-dicarboxyl phenyl) ethane of 1,1-, two (3, the 4-dicarboxyl phenyl) propane of 2,2-, two (2, the 3-dicarboxyl phenyl) propane of 2,2-, 4,4 '-(4,4 '-isopropylidene, two phenoxy groups)-bis-(phthalic acids), to penylene two (trimellitate), two (3,4-dicarboxyl phenyl) dimethylsilane, two (3,4-dicarboxyl phenyl) aminomethyl phenyl silane, two (3,4-dicarboxyl phenyl) diphenyl silane, two (3, the 4-dicarboxyl phenyl)-1,1,3 of 1,3-, the 3-tetramethyl disiloxane, Isosorbide-5-Nitrae-bis-(3,4-dicarboxyl phenyl dimetylsilyl) benzene, two (3, the 4-dicarboxyl phenyl) HFC-236fa of 2,2-, two (4-(3, the 4-di carboxyl phenyloxy) phenyl of 2,2-) HFC-236fa, 4,4 '-bis-(3,4-di carboxyl phenyloxy) diphenylsulfide, 2,3,5,6-pyridine tetracarboxylic acid, tetramethyleneimine-2,3,4, the 5-tetracarboxylic acid, pyrazine-2,3,5, the 6-tetracarboxylic acid, thiophene-2,3,4, the 5-tetracarboxylic acid, tetrahydrofuran (THF)-2,3,4, the 5-tetracarboxylic acid, the ethylidene tetracarboxylic acid, 1,2,3,4-BTCA, 1,1,2,2-ethane tetracarboxylic acid, 1,1,2,3-propane tetracarboxylic acid, 1,1,6,6-hexane tetracarboxylic acid, 1,2,4,5-hexanaphthene tetracarboxylic acid, 1,2,3,4-pentamethylene tetracarboxylic acid, 1,2,3,4-tetramethylene tetracarboxylic acid, naphthane-Isosorbide-5-Nitrae, 5,8-tetracarboxylic acid, 4,8-dimethyl-1,2,3,5,6,7-hexahydro naphthalene-1,2,5,6-tetracarboxylic acid, pentamethylene-1,2,3, the 4-tetracarboxylic acid, 1,2,3,4-tetramethylene tetracarboxylic acid, dicyclo-［ 2.2.2 ］ suffering-7-alkene-2,3,5, the 6-tetracarboxylic acid, two (outer-dicyclo ［ 2.2.1 ］ heptane-2,3-dicarboxylic acid) sulfone, 1,2,4,5-tetracarboxylic hexanaphthene, dicyclo ［ 2.2.2 ］ octane-2,3,5, the 6-tetracarboxylic acid, 5,5 '-(1,1,3,3,5,5-hexam ethylcyclotrisiloxane-1,5-bis-bases) two (dicyclo ［ 2.2.1 ］ heptane-2,3-dicarboxylic acid) etc.

That is,, as the R4 in formula (1-3), can enumerate the alicyclic radical of alkane four bases, tetravalence, the fragrant cyclic group of tetravalence or the heterocyclic radical of tetravalence.In other words, as R ⁴, can enumerate the group obtained by alkane, ester ring type compound, aromatics or 4 hydrogen atoms of hetero ring type compound removal.

The carbonatoms of alkane four bases is preferably 2～10, and more preferably 2～6.As alkane four bases, can enumerate for example ethane-1,1,2,2-tetra-bases, propane-1,1,2,3-tetra-bases, butane-1,2,3,4-tetra-bases, hexane-1,1,6,6-tetra-bases, ethylidene four bases.

As the alicyclic radical of tetravalence, the group that preferably carbonatoms is 4～50, the group that more preferably carbonatoms is 6～30.In addition, the alicyclic radical of tetravalence preferably has cyclohexane ring.

As the alicyclic radical of tetravalence, can enumerate for example from hexanaphthene, pentamethylene, tetramethylene, bis cyclohexane, naphthane, dicyclo ［ 2,2,2 ］ octane, dicyclo ［ 2,2,1 ］ heptane, dimethyl hexahydro naphthalene, dicyclo ［ 2,2,2 ］ suffering-7-alkene, 5,5 '-(1,1,3,3,5,5-hexam ethylcyclotrisiloxane-1,5-bis-bases) two (dicyclo ［ 2.2.1 ］ heptane) or two (dicyclo ［ 2,2,1 ］ heptane) sulfone remove 4 hydrogen atoms and group.

Fragrant cyclic group as tetravalence, can enumerate for example from benzene, naphthalene, anthracene, luxuriant and rich with fragrance, perylene, biphenyl, benzophenone, xenyl ether, sulfobenzide, trifluoromethylbenzene, ditan, 1, the 1-diphenylethane, 2, the 2-diphenyl propane, 2, two (4-Phenoxyphenyl) propane of 2-, two phenol benzoates, the phenylbenzene dimethylsilane, trityl group silane, tetraphenyl silane, 1, 3-phenylbenzene-1, 1, 3, the 3-tetramethyl disiloxane, two (phenylbenzene dimetylsilyl) benzene, 2, 2-phenylbenzene HFC-236fa, 2, two (4-Phenoxyphenyl) HFC-236fa of 2-or diphenylsulfide remove 4 hydrogen atoms and group.

As the heterocyclic radical of tetravalence, can enumerate the group for example obtained from pyridine, pyrazine, thiophene, tetramethyleneimine or 4 hydrogen atoms of tetrahydrofuran (THF) removal.

Conduct in these monomers (A) and acid anhydrides thereof is aqueous compound at 25 ℃, can enumerate 3-methylhexahydrophthaacid acid acid anhydrides, 4-methylhexahydrophthaacid acid acid anhydrides, 3-ethyl hexahydrophthalic acid acid anhydrides, 4-ethyl hexahydrophthalic acid acid anhydrides, the 3-methyl isophthalic acid, 2, 3, 6-tetrahydrophthalic acid acid anhydrides, the 4-methyl isophthalic acid, 2, 3, 6-tetrahydrophthalic acid acid anhydrides, methyl-3, methylene radical-1 in 6-, 2, 3, 6-tetrahydrophthalic acid acid anhydrides, 5, 5 '-outer-(1, 1, 3, 3, 5, 5-hexam ethylcyclotrisiloxane-1, 5-bis-bases) two (dicyclo ［ 2.2.1 ］ heptane-outer-2, the 3-dicarboxylic acid) dicarboxylic anhydride etc.

At this, R1 in above-mentioned formula (1-1) is for example 4-alkyl cyclohexane-1, 2-bis-bases, 3-alkyl cyclohexane-1, 2-bis-bases, 3-alkyl-4-tetrahydrobenzene-1, 2-bis-bases, 4-alkyl-4-tetrahydrobenzene-1, 2-bis-bases, 4-methyl-3, methylene radical in 6--4-tetrahydrobenzene-1, (be preferably 4-methylcyclohexane-1 during 2-bis-base, 2-bis-bases, 3-methylcyclohexane-1, 2-bis-bases, 3-methyl-4-tetrahydrobenzene-1, 2-bis-bases, 4-methyl-4-tetrahydrobenzene-1, 2-bis-bases, 4-methyl-3, methylene radical in 6--4-tetrahydrobenzene-1, during 2-bis-base), the tackiness agent of present embodiment meets above-mentioned (1).

In addition, the R4 in above-mentioned formula (1-3) is during for for example 5,5 '-outer-(1,1,3,3,5,5-hexam ethylcyclotrisiloxane-1,5-bis-bases) two (dicyclo ［ 2.2.1 ］ heptane-outer-2,3-bis-bases), and the tackiness agent of present embodiment meets above-mentioned (1).

In addition, as monomer (B), preferably there is the monomer of 2 amino, as such monomer, for example can enumerate 2,2-two ［ 4-(4-amino-benzene oxygen) phenyl ］ propane, two the 4-(3-amino-benzene oxygen) and phenyl ］ sulfone, two the 4-(4-amino-benzene oxygen) and phenyl ］ sulfone, 2,2-pair the 4-(4-amino-benzene oxygen) and phenyl ］ HFC-236fa, two the 4-(4-amino-benzene oxygen) and phenyl ］ methane, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, two the 4-(4-amino-benzene oxygen) and phenyl ］ ether, two the 4-(4-amino-benzene oxygen) and phenyl ］ ketone, two (4-amino-benzene oxygen) benzene of 1,3-, Isosorbide-5-Nitrae-bis-(4-amino-benzene oxygen) benzene, 2,2 '-dimethyl diphenyl base-4,4 '-diamines, 2,2 '-bis-(trifluoromethyl) xenyl-4,4 '-diamines, 2,6,2 ', 6 '-tetramethyl biphenyl base-4,4 '-diamines, 5,5 '-dimethyl-2,2 '-alkylsulfonyl-xenyl-4,4 '-diamines, (4,4 '-diamino) diphenyl ether, (4,4 '-diamino) sulfobenzide, (4,4 '-diamino) benzophenone, (3,3 '-diamino) benzophenone, (4,4 '-diamino) ditan, (4,4 '-diamino) diphenyl ether, the aromatic diamines such as (3,3 '-diamino) diphenyl ether, the Alkylenediamine such as quadrol, propylene diamine, the polyoxy alkylidene such as polyethyleneoxide diamine, polypropyleneoxide diamine diamines, 1,3-cyclohexane diamine, 1,4-cyclohexane diamine, (4,4 '-diamino) dicyclohexyl methyl hydride, isophorone diamine, 1, the siloxane diamines such as aliphatie diamine, PDMS such as the two aminopropyl piperazines of 4-, ［ two (the amino heptyl of the 1-)-6-hexyl-5-(1-octenyl of 3,4-) ］ tetrahydrobenzene, two amino methyl norcamphanes etc.

That is the R in, reaching (1-3) as formula (1-1), (1-2) ², can enumerate heterocyclic radical, polysiloxane two bases of fragrant cyclic group, the divalence of alicyclic radical, the divalence of alkane two bases, polyoxy alkane two bases, divalence etc.

As alkane two bases in R2, alkane two bases of preferred carbonatoms 1～30, more preferably alkane two bases of carbonatoms 1～20.Alkane two bases can be also the side chain shape for the straight chain shape, are preferably the straight chain shape.

As R ²in alkane two bases, can enumerate methylene radical, ethylidene, glyceryl, Ding Erji, penta 2 bases, dihexyl, heptan two base, Xin Erji, the ninth of the ten Heavenly Stems two base, the last of the ten Heavenly stems two base, undecane two bases, dodecane two bases, tridecane two bases, n-Hexadecane two bases etc.

As the alicyclic radical of the divalence in R2, the alicyclic radical of preferred carbonatoms 3～10, more preferably 4～8 alicyclic radical.In addition, the alicyclic radical of divalence preferably has cyclohexane ring.

As R ²in the alicyclic radical of divalence, can enumerate hexanaphthene two bases, alkyl cyclohexane-1,4-bis-bases, dialkyl cyclic hexane-1,4-bis-bases, norcamphane two bases, alkyl norcamphane-2,3-bis-bases, dicyclohexyl methyl hydride two bases, dicyclohexyl glyceryl, isophorone base, dimethylene cyclohexyl, dimethylene norcamphane base etc.

Here, be combined in R ²in the alkyl of carbocyclic ring structure of alicyclic radical of divalence be preferably the alkyl of carbonatoms 1～10, the more preferably alkyl of carbonatoms 1～5.

As R ²in the fragrant cyclic group of divalence, can enumerate for example benzene two bases (1,2-benzene, two bases, 1,3-benzene, two bases, Isosorbide-5-Nitrae-benzene two bases), naphthalene two bases (1,2-naphthalene, two bases 1,3-naphthalene two bases, Isosorbide-5-Nitrae-naphthalene two bases, 1,5-naphthalene, two bases, 1,6-naphthalene, two bases, 1,7-naphthalene, two bases, 1,8-naphthalene, two bases, 2,3-naphthalene, two bases, 2,6-naphthalene, two bases, 2,7-naphthalene, two bases etc.), 4,4 '-biphenyl, two bases, 3,3 '-biphenyl, two bases, 4,4 '-(2,2 '-diphenyl propane) two bases, 3,3 '-(2,2 '-diphenyl propane) two bases, 4,4 '-(sulfobenzide) two bases, 3,3 '-(sulfobenzide) two bases, 4,4 '-(3,3-phenylbenzene HFC-236fa) two bases, 3,3 '-(3,3-phenylbenzene HFC-236fa) two bases, 4,4 '-(diphenyl ether) two bases, 3,3 '-(diphenyl ether) two bases, 4,4 '-(diphenylketone) two bases, 3,3 '-(diphenylketone) two bases, 4,4 '-(2,2 '-dimethyl diphenyl) two bases, 4,4 '-(2,2 '-bis-(trifluoromethyl) biphenyl) two bases, 4,4 '-(2,6,2 ', 6 '-tetramethyl biphenyl) two bases.

As the heterocyclic radical of the divalence in R2, for example can enumerate (Isosorbide-5-Nitrae-dipropyl piperazine) two bases.

As polysiloxane two bases in R2, can enumerate such as polydimethylsiloxane two bases etc.

25 ℃ of conducts in these monomers (B) are aqueous monomer, can enumerate quadrol, propylene diamine, isophorone diamine, 1, the two aminopropyl piperazines of 4-, ［ two (the amino heptyl of the 1-)-6-hexyl-5-(1-octenyl of 3,4-) ］ tetrahydrobenzene, oxyalkylene diamines, two amino methyl norcamphane, alkyl diamine, polyoxy alkylidene diamines, siloxane diamine etc.

At this, the R in formula (1-1), (1-2) reach (1-3) ²during for alkane two bases for example, (Isosorbide-5-Nitrae-dipropyl piperazine) two bases, dimethylene norcamphane base or isophorone base, the tackiness agent of present embodiment meets above-mentioned (1).

Condensation resin preferably has polyoxy alkane two bases.Condensation resin with such group, Tg reduces, and has good tackiness under low temperature.

At this, as polyoxy alkane two bases, can enumerate the group shown in following formula (2).Here, in formula, n means the integer more than 2, R ⁵mean alkane two bases.A plurality of R that exist ⁵can be same to each other or different to each other.

[changing 10]

R ⁵in alkane two bases can be also the side chain shape for the straight chain shape.As R ⁵in alkane two bases, preferably alkane two bases of carbonatoms 2～4, more preferably alkane two bases of carbonatoms 2～3.As alkane two bases in R5, can enumerate for example ethylidene, 1,2-glyceryl, 1,3-glyceryl, Isosorbide-5-Nitrae-Ding Erji etc.

N in formula (2) is preferably 2～70, and more preferably 6～33.

As polyoxy alkane two bases, preferably by derivative groups of polyoxyalkylene such as polyoxyethylene, polyoxypropylene, polyoxy butylene, polyoxygenated tetramethylene, poloxalkol, polyoxyethylene glycol polytetramethylene glycol multipolymer, polypropylene glycol polytetramethylene glycol multipolymer, polyoxyethylene glycol polypropylene glycol polytetramethylene glycol multipolymers, more preferably polyoxyethylene groups, polyoxy-1, the 2-glyceryl.

Be not particularly limited for the method that imports above-mentioned polyoxy alkane two bases to condensation resin, can enumerate such as by condensation resin modifications such as polyamide resin, polyimide resin, polyamide-imide resins and import the method for above-mentioned polyoxy alkane two bases.

In addition, condensation resin preferably has above-mentioned polyoxy alkane two bases in the said structure unit, more preferably in the structure that is derived from monomer (B) in the said structure unit, has above-mentioned polyoxy alkane two bases.That is, at least one in preferred monomers (A) and monomer (B) has above-mentioned polyoxy alkane two bases, and more preferably at least one in monomer (B) has above-mentioned polyoxy alkane two bases.

The condensation resin more preferably structure that is derived from monomer (B) in the said structure unit has polyoxy alkane two bases.

That is, as condensation resin, preferably have following structural unit, described structural unit obtains by the polymerizable monomer polycondensation that makes to comprise the monomer (b-1) with polyoxy alkane two bases and at least 2 amino.

The content of the monomer in polymerizable monomer (b-1) is preferably 0.5～20mol% with respect to the total amount of monomer (A) and monomer (B), more preferably 1～10mol%, more preferably 2～8mol%.Utilization has the condensation resin of the structural unit that makes such polymerizable monomer polycondensation and obtain, and can obtain the tackiness agent more excellent with the adaptation of adherend.

As monomer (b-1), can enumerate the polyoxy alkylidene diamines, can suitably use such as JEFFAMINE D-230(HUNTSMAN, trade(brand)name), JEFFAMINE D-400(HUNTSMAN, trade(brand)name), JEFFAMINE D-2000(HUNTSMAN, trade(brand)name), JEFFAMINE D-4000(HUNTSMAN, trade(brand)name) etc. polypropyleneoxide diamine; JEFFAMINE ED-600(HUNTSMAN, trade(brand)name), JEFFAMINE ED-900(HUNTSMAN, trade(brand)name) etc. polyoxypropylene and polyoxyethylated multipolymer diamines; JEFFAMINE EDR-148(HUNTSMAN, trade(brand)name),

JEFFAMINE EDR-176(HUNTSMAN, trade(brand)name) etc. polyethyleneoxide diamine; JEFFAMINET-403(HUNTSMAN, trade(brand)name), JEFFAMINE T-3000(HUNTSMAN, trade(brand)name) and JEFFAMINE T-5000(HUNTSMAN, trade(brand)name) etc. triamine.These can use separately, and also two or more kinds may be used.

By 25 ℃ for aqueous or 25 ℃ of acid anhydrides be aqueous monomer (A) be made as monomer (a-1), while by 25 ℃, for aqueous monomer (B), being made as monomer (b-2), the total content of the monomer in polymerizable monomer (a-1) and monomer (b-2) is preferably 15～60mol% with respect to the total amount of monomer (A) and monomer (B), more preferably 20～50mol%, more preferably 25～45mol%.

As the preferably combination of polymerizable monomer, preferably: the R that monomer (A) comprises formula (A-1) ¹for the compound of the fragrant cyclic group of divalence, the R of formula (A-2) ³for the compound of the fragrant cyclic group of trivalent and the R of formula (A-3) ⁴for at least one in the compound of the fragrant cyclic group of tetravalence, monomer (B) comprises monomer (b-1) and monomer (b-2).

In addition, as the preferably combination of polymerizable monomer, also preferably: the R of the aromatic nucleus based compound that monomer (A) comprises divalence, formula (A-2) ³for the compound of the fragrant cyclic group of trivalent and the R of formula (A-3) ⁴for at least one and monomer (a-1) in the compound of the fragrant cyclic group of tetravalence, monomer (B) comprises monomer (b-1).

Condensation resin for example can be obtained by the polycondensation of the polymerizable monomer that comprises monomer (A) and monomer (B).In addition, can also use the acid anhydrides of monomer (A), the carboxylate of monomer (A), the etheride of monomer (A) etc. to replace monomer (A).In addition, polymerizable monomer can also comprise other monomers such as diisocyanate cpd.

More than the content of the monomer in polymerizable monomer (A) and monomer (B) is preferably 30mol% with respect to the total amount of polymerizable monomer, more preferably more than 50mol%, more preferably more than 70mol%.In addition, the content of monomer (A) and monomer (B) can be also 100mol%.

Method to polycondensation is not particularly limited, and for example can adopt following method: above-mentioned polymerizable monomer is dissolved in to solvent, is reacted under about 0～200 ℃ of temperature of reaction, 1～5 hour reaction times.

As the solvent used in polycondensation, can enumerate for example N-Methyl pyrrolidone, N-ethyl pyrrolidone, N methyl succinimide, dimethyl furan, toluene, N, N '-N,N-DIMETHYLACETAMIDE, hexa-methylene phosphamide, methyl-sulphoxide etc.From the deliquescent viewpoint of resin, preferred N-Methyl pyrrolidone in these.

In addition, in polycondensation, for the purpose that promotes condensation reaction, can use the accelerators such as catalyzer.The addition of accelerator is made as 0.1～50mol equivalent with respect to polymerizable monomer 10mol equivalent.As accelerator, can enumerate inorganic salt such as lithium chloride, calcium chloride, calcium thiocyanide; The tertiary amine such as triethylamine, pyridine; The quaternary ammonium salts such as tetramethyl ammonium chloride, tetraethylammonium bromide, four-normal-butyl bromination ammonium.

Condensation resin can also be to polycondensation and polymkeric substance further carry out the resin after modification, can enumerate for example olefin-modified polymeric amide, alkoxysilane-modified polymeric amide, silicone-modified polyimide, the epoxy group(ing) modified polyamide, polycarbonate modified polymeric amide, olefin-modified polyimide, silicone-modified polyimide, the epoxy group(ing) modified polyimide, polycarbonate modified polyimide, silicone-modified polyimide, olefin-modified polyamidoimide, alkoxysilane-modified polyamidoimide, silicone-modified polyamidoimide, the epoxy group(ing) modified polyamide imide, the epoxy group(ing) modified polyamide imide, polycarbonate modified polyamidoimide etc.

Condensation resin in present embodiment can be for example polyamide resin, polyamide-imide resin or the polyimide resin with polyoxy alkane two bases.Such condensation resin at least meets above-mentioned (2).

This condensation resin preferably comprises two amine units with polyoxy alkane two bases.That is, preferably polyoxy alkane two bases are contained in two amine units of condensation resin.

As two amine units with polyoxy alkane two bases, can enumerate for example polyoxy alkylidene two amine units.As polyoxy alkylidene two amine units, can enumerate be derived from above-mentioned as the polyoxy alkylidene diamines and the monomeric unit of illustrative monomer.

This condensation resin and then the fragrant cyclic group that can have divalence, can also comprise the dicarboxylic acid units of the fragrant cyclic group with divalence.The fragrant cyclic group that has divalence by condensation resin, can further suppress the clinging power of tackiness agent under hot environment and change.

As the dicarboxylic acid units of the fragrant cyclic group with divalence, the compound of the fragrant cyclic group that the R1 that can enumerate above-mentioned formula (A-1) is divalence.

Condensation resin can have the fragrant cyclic group of benzene two bases as divalence, can also comprise at least one in the group of selecting free O-phthalic acid unit, m-phthalic acid unit and terephthalic acid units to form.There are benzene two bases by condensation resin, can further suppress the clinging power of tackiness agent under hot environment and change.

In addition, this condensation resin can further have Isosorbide-5-Nitrae-piperazine two bases, can also comprise two amine units with Isosorbide-5-Nitrae-piperazine two bases.Utilize two such amine units, can further suppress the clinging power of tackiness agent under hot environment and change.

As two amine units with Isosorbide-5-Nitrae-piperazine two bases, can enumerate for example Isosorbide-5-Nitrae-bis-(omega-amino-alkyl) piperazine unit.In Isosorbide-5-Nitrae-bis-(omega-amino-alkyl) piperazine unit, the carbonatoms of omega-amino-alkyl is preferably 1～10, and more preferably 2～4.

As Isosorbide-5-Nitrae-bis-(omega-amino-alkyl) piperazine unit, can enumerate Isosorbide-5-Nitrae-bis-(3-aminopropyl) piperazine unit etc.

In condensation resin, there are two amine unit content C of Isosorbide-5-Nitrae-piperazine two bases ₂content C with respect to two amine units with polyoxy alkane two bases ₁ratio C ₂/ C ₁be preferably 2～40 with molar ratio computing, more preferably 4～20.

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

The content of two amine units with polyoxy alkane two bases in condensation resin be take the total amount of monomer (A) unit and monomer (B) unit and is preferably 2.5～10mol% as benchmark, more preferably 3.5～7.5mol%, more preferably 4～6mol%.Utilize such condensation resin, can obtain the tackiness agent more excellent with the adaptation of adherend.

The content of the dicarboxylic acid units of the fragrant cyclic group with divalence in condensation resin be take the total amount of monomer (A) unit and monomer (B) unit and is preferably 20～50mol% as benchmark, more preferably 30～50mol%, more preferably 40～50mol%.

The content of two amine units with Isosorbide-5-Nitrae-piperazine two bases in condensation resin be take the total amount of monomer (A) unit and monomer (B) unit and is preferably 15～60mol% as benchmark, more preferably 20～50mol%, more preferably 25～45mol%.

The weight-average molecular weight of condensation resin is preferably 20000～100000, and more preferably 30000～60000.Here, in this specification sheets, weight-average molecular weight means the weight-average molecular weight with polystyrene conversion of measuring by the GPC method.

The content of the condensation resin in the tackiness agent of present embodiment be take the total amount of tackiness agent more than benchmark is preferably 50 quality %, more preferably more than 70 quality %.The content of condensation resin, in above-mentioned scope, can fully maintain high heat resistance and obtain higher tackiness.In addition, the content of condensation resin can be for below 96 quality %, also can be for below 90 quality %.In addition, the tackiness agent of present embodiment can be comprised of condensation resin (that is, the content of condensation resin is 100 quality %).But the content of condensation resin also can be according to purposes and suitably outside above-mentioned scope.

In addition, the tackiness from making hot environment maintains good viewpoint, and the content of the thermosetting resin of the tackiness agent of present embodiment is preferably below 30 quality %, more preferably below 20 quality %, more preferably not containing thermosetting resin.

In order to improve adaptation, in not damaging the purpose scope of invention, can also add the tackifiers such as Gum Rosin, terpine resin, coumarone resin, resol, styrene resin, aliphatics through-stone oleo-resinous, aromatic series through-stone oleo-resinous, aliphatics aromatic series copolymerization through-stone oleo-resinous etc. in the tackiness agent of present embodiment.

(using method of tackiness agent)

The tackiness agent of present embodiment is owing under hot environment, also can maintaining tackiness, purposes that therefore can following for possessing (1)～(3) operation.

(1) paste operation, be situated between by the adhesive coating that contains tackiness agent, the second adherend is pasted on to the first adherend.

(2) heating process, become under the condition more than 200 ℃ in the temperature of adhesive coating, heats the first adherend and the second adherend.

(3) stripping process, peel off adhesive coating and the second adherend from the first adherend that has experienced heating process.

Paste in operation, can for example on the one side of the first adherend, form adhesive coating, configuration the second adherend on this adhesive coating and face the first adherend opposition side is pasted the second adherend on the first adherend by the first adherend and the second adherend are pushed mutually.

In addition, can also on the one side of the second adherend, form adhesive coating, configuration the first adherend on this adhesive coating and face the second adherend opposition side is pasted the second adherend on the first adherend by the first adherend and the second adherend are pushed mutually.

The tackiness agent varnish that adhesive coating for example can comprise tackiness agent and solvent by preparation, be coated with this tackiness agent varnish and be dried and form.The solvent used in tackiness agent varnish is not particularly limited, and glycol series solvent, glycol ethers series solvent, diol ester series solvent etc. are because tackiness agent shows good solubility preferably.

As solvent, can enumerate for example 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, MMB, ethylene glycol monomethyl ether acetate, PMA(propylene glycol monomethyl ether), Diethylene Glycol single-butyl ether acetic ester and TC acetic ester.Except above-mentioned, can also use N-Methyl pyrrolidone, N-ethyl pyrrolidone, N methyl succinimide, N, N '-N,N-DIMETHYLACETAMIDE and dimethyl formamide.These solvents may be used alone, can also be 2 or more kinds in combination.

Paste the adhesive coating in operation, can be by the one side that tackiness agent varnish is coated on to the first adherend or the second adherend and be dried and be arranged on this one side, also the adhesive coating be formed on the aftermentioned supporter can be transferred on the one side of the first adherend or the second adherend by lamination, thereby be arranged on this one side.

Paste in operation, for example, can the first adherend and the second adherend be pasted at 0～50 ℃.

In heating process, the first adherend and the second adherend are heated.The method of heating and the purpose of heating are not particularly limited, and by this heating, adhesive coating is exposed at the temperature more than 200 ℃.Usually for example, when the tackiness agent (, the acrylic acid series tackiness agent) that thermotolerance is low supplies in such heating process, can't maintain tackiness, bubbling can occur, strip off.But the adhesive coating of the tackiness agent that utilization comprises present embodiment, also can maintain tackiness even experience such heating process, the generation that therefore can fully suppress bubbling, strip off.

In heating process, can also form processing to the first adherend and the second adherend through heating.The adhesive coating of the tackiness agent that comprises present embodiment is due to the tracing ability excellence, even, when the first adherend and the second adherend are out of shape due to the processing that is shaped, bubbling, the generation of stripping off are also fully suppressed.

In stripping process, from the first adherend, peel off adhesive coating and the second adherend.At this, adhesive coating and the second adherend can integrally be peeled off from the first adherend, also can from the first adherend, peel off independently of one another.

In stripping process, for example, can peel off adhesive coating and the second adherend from the first adherend at 0～50 ℃.

Also can maintain tackiness even the adhesive coating be stripped from experiences above-mentioned heating process in stripping process, therefore can recycle in pasting operation.

As the first adherend and the second adherend; be not particularly limited, can enumerate and comprise the adherend that is selected from least one organic materials in polyester, polyimide, polymeric amide, polyethersulfone, polyphenylene sulfide, polyetherketone, polyether-ether-ketone, tri acetyl cellulose, polyetherimide, PEN, polypropylene, acrylic, polystyrene, polycarbonate etc.In addition, can also use the supporter that comprises inorganic materials, can use and comprise the supporter that is selected from least one inorganic materials in for example aluminium, magnesium, titanium, chromium, manganese, iron, nickel, zinc, tin, glass, copper, silicon wafer and alloy.

As the first adherend and the second adherend, can use and have the stable on heating material of the temperature more than 200 ℃, can enumerate polyamide resins such as nylon 6, nylon 66, nylon 46; The vibrin such as polyethylene terephthalate, PEN, poly terephthalic acid trimethylene ester, poly-naphthalic acid trimethylene ester, polybutylene terephthalate, PBN; The polyolefin resin such as polypropylene, polyethylene; Acrylic resin, polyimide resin, polyarylate resin or their hybrid resin, aluminium, magnesium, titanium, chromium, manganese, iron, nickel, zinc, tin, glass, copper, silicon wafer and alloy.In these materials, vibrin, polyamide resin, polyolefin resin, polyimide resin, acrylic resin, aluminium, magnesium, titanium, chromium, manganese, iron, nickel, zinc, tin, glass, copper, silicon wafer are owing to showing high heat resistance preferably.

Utilize above-mentioned using method, for example, by rigidity, the first low adherend conscientiously is fixed on the second adherend when high temperature process, and after processing, the first adherend can injury-freely be stripped from also indeformablely.

(sticky material)

Fig. 1 is the constructed profile of a preferred embodiment of expression tackiness agent of the present invention.Tackiness agent 1 shown in Fig. 1 possesses supporter 10 and is arranged at the adhesive coating that contains tackiness agent 14 on this supporter 10.

As supporter; be not particularly limited, can enumerate and comprise the supporter that is selected from least one organic materials in polyester, polyimide, polymeric amide, polyethersulfone, polyphenylene sulfide, polyetherketone, polyether-ether-ketone, tri acetyl cellulose, polyetherimide, PEN, polypropylene, acrylic, polystyrene, polycarbonate etc.In addition, can also use the supporter that comprises inorganic materials, can use and comprise the material that is selected from least one inorganic materials in for example aluminium, magnesium, titanium, chromium, manganese, iron, nickel, zinc, tin, glass, copper, silicon wafer and alloy.

Sticky material for example can be made as follows: the tackiness agent varnish that will comprise tackiness agent and solvent is coated on supporter and is dried, and forms adhesive coating thus and makes.The making method based on casting method so easily obtains smooth adhesive coating, so preferably.As the solvent for tackiness agent varnish, can illustration and above-mentioned same solvent.

In addition, sticky material can also be made as follows: the tackiness agent varnish that will comprise tackiness agent and solvent is coated on mold release film and is dried, by the adhesive coating lamination that forms thus, be transferred to supporter and make.

The thickness of adhesive coating is preferably 0.1～100 μ m, more preferably 1～50 μ m.The thickness of adhesive coating can suitably be adjusted according to the glue spread of the concentration of the tackiness agent in above-mentioned tackiness agent varnish, tackiness agent varnish.

(using method of sticky material)

The tackiness agent of present embodiment, owing under hot environment, also can maintaining tackiness, therefore can be used in the purposes that possesses following (1)～(3) operation.

(1) paste operation, according to adhesive coating, be configured in the mode near the adherend side, sticky material is pasted on to adherend.

(2) heating process, become under the condition more than 200 ℃ and heat adherend in the temperature of sticky material.

(3) stripping process, peel off sticky material from the adherend that has experienced heating process.

Paste in operation, the mode contacted with adherend by the adhesive coating with sticky material is pressed, and sticky material can be sticked on to adherend.Paste in operation, the first adherend and the second adherend can pasted at temperature arbitrarily, from showing suitable tackiness and the viewpoint of operating efficiency, expectation is for example pasted at 0～50 ℃.

In heating process, adherend is heated, and meanwhile adhesive coating is exposed at the temperature more than 200 ℃.Usually, for example, when the tackiness agent that thermotolerance is low (, the acrylic acid series tackiness agent), in such heating process the time, can't maintain tackiness, bubbling can occur, strip off.But, utilize the sticky material of present embodiment, also can maintain tackiness even experienced such heating process, the generation that therefore can fully suppress bubbling, strip off.

In heating process, also can form processing to the adherend after heating.The adhesive coating of the tackiness agent that contains present embodiment is due to the tracing ability excellence, even, when therefore adherend is out of shape due to the processing that is shaped, bubbling, the generation of stripping off are also fully suppressed.

In stripping process, from adherend, peel off sticky material.In stripping process, for example, can peel off sticky material from adherend at 0～50 ℃.

Also can maintain tackiness even the sticky material be stripped from stripping process experiences above-mentioned heating process, therefore can recycle in pasting operation.

As the adherend in this using method, can illustration and above-mentioned the first adherend and the same adherend of the second adherend.

Utilize above-mentioned using method, for example, by rigidity, low adherend conscientiously is fixed on supporter when high temperature process, and after processing, adherend can injury-freely be stripped from also indeformablely.

More than illustrated preferred embodiment of the present inventionly, but the present invention is not limited by above-mentioned embodiment.

For example, a mode of the present invention relates to the application of condensation resin as tackiness agent, described condensation resin has following structural unit, meet at least one in above-mentioned (1) and (2), described structural unit is by obtaining the polymerizable monomer polycondensation that comprises above-mentioned monomer (A) and above-mentioned monomer (B).

In addition, alternate manner of the present invention relates to the application of condensation resin in the manufacture of tackiness agent, described condensation resin has following structural unit, meet at least one in above-mentioned (1) and (2), described structural unit is by obtaining the polymerizable monomer polycondensation that comprises above-mentioned monomer (A) and above-mentioned monomer (B).

In addition, alternate manner of the present invention relates to the application as tackiness agent of condensation resin with polyoxy alkane two bases, the group that described condensation resin selects free polyamide resin, polyamide-imide resin and polyimide resin to form.

In addition, alternate manner of the present invention relates to the application of condensation resin in the manufacture of tackiness agent with polyoxy alkane two bases, the group that described condensation resin selects free polyamide resin, polyamide-imide resin and polyimide resin to form.

Embodiment

Below, utilize embodiment to be described more specifically the present invention, but the present invention is not limited by embodiment.

(embodiment 1)

In the detachable flask that possesses stirrer, reflux exchanger, thermometer, nitrogen ingress pipe, making m-phthaloyl chloride 50 parts of (mol ratio), polypropyleneoxide diamine (JEFFAMINE(registered trademark) D-2000, HUNTSMAN company system) 5 parts of (mol ratio) and Isosorbide-5-Nitrae-45 parts of bis-(3-aminopropyl) piperazines (mol ratio) carry out polycondensation in the N-Methyl pyrrolidone comprised as the triethylamine 110 parts (mol ratios) of acid neutralizing agent, under ice-cooled.After reaction finishes, add the water of 3 times of amounts in reaction mixture, by insoluble component separating, drying, obtain thus the polyamide resin that weight-average molecular weight is 45000.The polyamide resin of acquisition is dissolved in to N, and N '-N,N-DIMETHYLACETAMIDE, obtain tackiness agent varnish.

Then, it is on 25 μ m, the width polyimide film that is 20cm that the mode of using applicator that the tackiness agent varnish of acquisition is become to 20 μ m according to the thickness of dried adhesive coating is coated on thickness, 130 ℃ of heating 5 minutes, and then 150 ℃ of heating are 30 minutes, carry out drying, make sticky material.

The polyamide resin obtained is measured to Tg by the following method, the sticky material obtained is estimated by the following method tackiness, peeled off residue and thermotolerance.The results are shown in table 1.Here, differential scanning type calorimeter is that measure, the thermally equilibrated figure of polyamide resin between-50～200 ℃ embodiment 1 for expression utilizes for Fig. 2.

(mensuration of Tg)

Get in embodiment 1 the polyamide resin 3mg that obtains to the aluminium dish, use TA Instrument differential scanning type processed calorimeter DSC Q2000, by the Thermal Balance Tg between-50～200 ℃.

(adhesive evaluation)

The sticky material obtained in embodiment 1 is disposed to the 10cm of thickness 70 μ m * 10cm sheet glass, and the laminating machine that the speed of take under the condition of 17～25 ℃ 0.8m/ minute is 0.3MPa by roll-in, pasted thus.By the sticky material pasted 200 ℃ of heating after 10 minutes, the end of the polyimide film of sticky material is peeled off a little and held, use rheometer RE3305R(mountain electricity system) tensile testing machine, be determined under 90 degree, draw speed 300mm/min the power (N/cm) of peeling off the required minimum of polyimide film width 10mm.

(peeling off the evaluation of residue)

Measure the weight of the sticky material obtained in embodiment 1, deduct the weight of the polyimide film of measuring in advance, calculate thus the weight of the adhesive coating of sticky material.Then, similarly sticky material pasted to sheet glass and carry out peeling off of sticky material with adhesive evaluation.The weight of the sticky material that mensuration is peeled off, deduct the weight of the polyimide film of mensuration in advance, calculates thus the weight of the adhesive coating of the sticky material after peeling off.Now, the weight of the adhesive coating after peeling off with respect to the ratio of the weight of the adhesive coating before pasting be situation 90% or more as " A ", 90% the situation of being less than is as " B ", evaluation is peeled off having or not of residue thus.

(stable on heating evaluation)

Similarly sticky material is sticked on to sheet glass with adhesive evaluation.The sheet glass that is pasted with sticky material is heated 1 hour in the clean baking oven of 200 ℃, and the Visual Confirmation sticky material has the sheet glass of having no way of to peel off.Will be without situation about peeling off as " A ", using situation about peeling off as " B ", estimate thus thermotolerance.

(embodiment 2)

Make m-phthaloyl chloride 43.75 parts of (mol ratio), 6.25 parts of p-phthaloyl chlorides, polypropylene glycol diamine (JEFFAMINE(registered trademark) D-2000, HUNTSMAN company system) 5 parts and 1, the two 45 parts of polycondensations in N-Methyl pyrrolidone of (3-aminopropyl) piperazine of 4-, obtain polyamide resin.The polyamide resin of acquisition is dissolved in to N, in N '-N,N-DIMETHYLACETAMIDE, obtains tackiness agent varnish.

Then, use the tackiness agent varnish obtained to make similarly to Example 1 sticky material.In addition, the polyamide resin obtained is measured to Tg by aforesaid method, the sticky material obtained is estimated tackiness, peeled off residue and thermotolerance by aforesaid method.The results are shown in table 1.Here, Fig. 3 means and utilizes that differential scanning type calorimeter is that measure, the thermally equilibrated figure of polyamide resin between-50～200 ℃ embodiment 2.

(comparative example 1)

Make 13 parts of m-phthaloyl chlorides, 3,13 parts of 3-diamino diphenyl sulfones carry out polycondensation in N-Methyl pyrrolidone, obtain polyamide resin.The polyamide resin of acquisition is dissolved in to N, and N '-N,N-DIMETHYLACETAMIDE, obtain tackiness agent varnish.

Then, use the tackiness agent varnish obtained to make similarly to Example 1 sticky material.In addition, the polyamide resin obtained is measured to Tg by aforesaid method, the sticky material obtained is estimated tackiness, peeled off residue and thermotolerance by aforesaid method.The results are shown in table 1.Here, Fig. 4 means and utilizes that differential scanning type calorimeter is that measure, the thermally equilibrated figure of polyamide resin between-50～200 ℃ comparative example 1.

[table 1]

Claims

1. a tackiness agent, it contains the condensation resin with following structural unit, meet at least one in following (1) and (2), described structural unit obtains by the polymerizable monomer polycondensation that makes to comprise the monomer (A) with at least 2 carboxyls and the monomer (B) with at least 2 amino

(1) at least one that select in the group that acid anhydrides and the described monomer (B) of described monomer (A), described monomer (A) forms at 25 ℃ for aqueous,

(2) described condensation resin has polyoxy alkane two bases.

2. tackiness agent according to claim 1, it meets described (1) and (2) simultaneously.

3. tackiness agent according to claim 1 and 2, wherein, described condensation resin comprises at least one that select in the group be comprised of polyamide-imide resin, polyimide resin and polyamide resin.

4. according to the described tackiness agent of any one in claim 1～3, wherein, described condensation resin is polyamide resin.

5. according to the described tackiness agent of any one in claim 1～4, wherein, the described structural unit in described condensation resin has described polyoxy alkane two bases.

6. according to the described tackiness agent of any one in claim 1～5, wherein, the structure that is derived from described monomer (B) in described structural unit has described polyoxy alkane two bases.

7. according to the described tackiness agent of any one in claim 1～6, wherein, the ratio that the total amount that described polymerizable monomer be take with respect to described monomer (A) and described monomer (B) is 2.5～10mol% comprises the monomer (b-1) with polyoxy alkane two bases and at least 2 amino.

8. according to the described tackiness agent of any one in claim 1～7, wherein, the content of described condensation resin is more than 50 quality %.

9. according to the described tackiness agent of any one in claim 1～8, it is the tackiness agent be comprised of described condensation resin.

10. a tackiness agent, the condensation resin in its group that contains the above free polyamide resin of choosing of 50 quality %, polyamide-imide resin and polyimide resin composition,

Described condensation resin has polyoxy alkane two bases.

11. tackiness agent according to claim 10, wherein, described condensation resin comprises two amine units with polyoxy alkane two bases.

12., according to the described tackiness agent of claim 10 or 11, wherein, described condensation resin further has the fragrant cyclic group of divalence.

13. tackiness agent according to claim 12, wherein, the dicarboxylic acid units that described condensation resin comprises the fragrant cyclic group with divalence.

14., according to the described tackiness agent of any one in claim 10～13, wherein, described condensation resin further has Isosorbide-5-Nitrae-piperazine two bases.

15. tackiness agent according to claim 14, wherein, described condensation resin comprises two amine units with Isosorbide-5-Nitrae-piperazine two bases.

16., according to the described tackiness agent of any one in claim 10～15, it is the tackiness agent be comprised of described condensation resin.

17. according to the described tackiness agent of any one in claim 1～16, its as stick on adherend and be heated to more than 200 ℃ after the thermotolerance tackiness agent peeled off from this adherend.

18. a condensation resin is as the application of tackiness agent, described condensation resin has following structural unit, meet at least one in following (1) and (2), described structural unit obtains by the polymerizable monomer polycondensation that makes to comprise the monomer (A) with at least 2 carboxyls and the monomer (B) with at least 2 amino

(2) described condensation resin has polyoxy alkane two bases.

19. the application of condensation resin in the manufacture of tackiness agent, described condensation resin has following structural unit, meet at least one in following (1) and (2), described structural unit obtains by the polymerizable monomer polycondensation that makes to comprise the monomer (A) with at least 2 carboxyls and the monomer (B) with at least 2 amino

(2) described condensation resin has polyoxy alkane two bases.

20. one kind has the application of the condensation resin of polyoxy alkane two bases as tackiness agent, the group that described condensation resin selects free polyamide resin, polyamide-imide resin and polyimide resin to form.

21. the application of condensation resin in the manufacture of tackiness agent with polyoxy alkane two bases, the group that described condensation resin selects free polyamide resin, polyamide-imide resin and polyimide resin to form.

22. a sticky material, it possesses supporter and is arranged at the adhesive coating that contains the described tackiness agent of any one in claim 1～17 on this supporter.

23. the using method of a tackiness agent, it possesses:

Paste operation, the adhesive coating of Jie's described tackiness agent of any one in containing claim 1～17, be pasted on the first adherend by the second adherend;

Heating process, become under the condition more than 200 ℃ in the temperature of described adhesive coating, heats described the first adherend and described the second adherend; With

Stripping process, peel off described adhesive coating and described the second adherend from described the first adherend that has experienced described heating process.

24. using method according to claim 23, wherein, in described stickup operation, paste described the first adherend and described the second adherend at 0～50 ℃.

25., according to the described using method of claim 23 or 24, wherein, in described stripping process, at 0～50 ℃, from described the first adherend, peel off described adhesive coating and described the second adherend.

26., according to the described using method of any one in claim 23～25, wherein, the described adhesive coating that will be stripped from described stripping process recycles in described stickup operation.

27. the using method of a sticky material, it possesses:

Paste operation, according to described adhesive coating, be configured in the mode near described adherend side, the described sticky material of claim 22 is pasted on to adherend;

Heating process, become under the condition more than 200 ℃ in the temperature of described sticky material, heats described adherend; With

Stripping process, peel off described sticky material from the described adherend that has experienced described heating process.

28. using method according to claim 27, wherein, in described stickup operation, be pasted on described adherend at 0～50 ℃ by described sticky material.

29., according to the described using method of claim 27 or 28, wherein, in described stripping process, at 0～50 ℃, from described adherend, peel off described sticky material.

30., according to the described using method of any one in claim 27～28, wherein, the described sticky material that will be stripped from described stripping process recycles in described stickup operation.