CN108977111A - The manufacturing method of jointing tape, article and article - Google Patents

The manufacturing method of jointing tape, article and article Download PDF

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Publication number
CN108977111A
CN108977111A CN201810464360.5A CN201810464360A CN108977111A CN 108977111 A CN108977111 A CN 108977111A CN 201810464360 A CN201810464360 A CN 201810464360A CN 108977111 A CN108977111 A CN 108977111A
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China
Prior art keywords
adhesive layer
mentioned
adherend
thermal expansivity
jointing tape
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CN201810464360.5A
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Chinese (zh)
Inventor
唐泽久美子
秋山诚二
森野彰规
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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Priority to JP2017110036A priority Critical patent/JP2018203863A/en
Priority to JP2017-110036 priority
Application filed by Dainippon Ink and Chemicals Co Ltd filed Critical Dainippon Ink and Chemicals Co Ltd
Publication of CN108977111A publication Critical patent/CN108977111A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/30Adhesives in the form of films or foils characterised by the adhesive composition
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062Copolymers with monomers not covered by C09J133/06
    • C09J133/066Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02Vinyl aromatic monomers and conjugated dienes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J193/00Adhesives based on natural resins; Adhesives based on derivatives thereof
    • C09J193/04Rosin
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00Adhesives in the form of films or foils
    • C09J7/10Adhesives in the form of films or foils without carriers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/22Expandable microspheres, e.g. Expancel®
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2353/00Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
    • C08J2353/02Characterised by the use of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers of vinyl aromatic monomers and conjugated dienes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2363/00Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2433/00Presence of (meth)acrylic polymer
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2453/00Presence of block copolymer
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2463/00Presence of epoxy resin

Abstract

The present invention provides the manufacturing method of a kind of jointing tape, article and article.The problem to be solved by the present invention is that providing a kind of jointing tape, it can be expanded by heating and heat after expansion also with excellent bonding force, further, the danger that do not ignite placing the jointing tape at high temperature for a long time in substantially closed space.Jointing tape of the invention is jointing tape used in substantially closed space, the jointing tape has thermal expansivity adhesive layer (A), the thermal expansivity adhesive layer (A) is 3~100 mass parts relative to 100 mass parts of total solid content of the adhesive composite (a) containing adhesive composite (a) and thermal expansivity capsule, the content of the thermal expansivity capsule.

Description

The manufacturing method of jointing tape, article and article
Technical field
It can be swollen in the thickness direction thereof by applying the stimulation such as low temperature and the heating of short time the present invention relates to having The jointing tape of swollen composition.
Background technique
One adherend usually can be fixed on the planar section of another adherend, curved face part by jointing tape It is properly used whens dividing equal, such as in the occasions that manufacture with member for automobile, electrical equipment etc. for the various products of representative extensively General use.
On the other hand, it is expected that the use scope of jointing tape gradually expands, for above-mentioned jointing tape, it is desirable that Neng Goushi Occasion preferably for being for example fixed on an adherend in gap possessed by another adherend.Specifically, As the motor for being equipped on hybrid vehicle etc., it is known that usually have in the predetermined position (gap) of core part (rotor core) Embedment has the composition of magnet, and has studied when above-mentioned magnet to be fixed in gap possessed by above-mentioned core part using above-mentioned Jointing tape.
As can be in jointing tape used in such use, it is known that a kind of thermosetting property thermal expansivity jointing tape, it should For jointing tape for example with substrate and the 1st adhesive layer, opposite side of the substrate with the 1st face and in above-mentioned 1st face has the 2nd Face, and there is communication port, the 1st adhesive layer is formed in the 1st face of above-mentioned substrate and includes that thermosetting property thermal expansivity epoxy is viscous Agent is connect, above-mentioned thermosetting property thermal expansivity epoxy adhesive is when heated by the above-mentioned communication port of above-mentioned substrate in above-mentioned substrate The 2nd face on formed the 2nd adhesive layer (for example, referring to patent document 1.).
As above-mentioned thermal expansivity jointing tape, it is known that realized by the addition thermal expansion agent in adhesive layer expansile Jointing tape, especially known addition utilize the volume expansion agent of the vaporization of flammable gas.But using the volume expansion agent In the case where, if long-term at high temperature place, flammable gas can be released from jointing tape, be used in closed space In the case where, when which is detained and generates the ignition sources such as electrostatic spark inside article, it is believed that there is the danger ignited Dangerous problem.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2010-023559 bulletin
Summary of the invention
Subject to be solved by the invention
The problem to be solved by the present invention is to provide a kind of jointing tapes, can be expanded by heating, and heat swollen Also there is excellent bonding force, further, even if placing above-mentioned jointing tape for a long time in substantially closed space after swollen The danger that also do not ignite at high temperature.
The method used for solving the problem
The inventors of the present invention solve the above subject using jointing tape, and above-mentioned jointing tape is substantially closed sky Between used in jointing tape, above-mentioned jointing tape have thermal expansivity adhesive layer (A), above-mentioned thermal expansivity adhesive layer (A) containing adhesive composite (a) and thermal expansivity capsule, the content of above-mentioned thermal expansivity capsule is relative to above-mentioned bonding agent group 100 mass parts of total solid content for closing object (a) are 3~100 mass parts.
The effect of invention
Jointing tape of the invention can be by gap, two or more possessed by adherend as excellent bonding force Adherend between gap be sufficient filling with or be bonded.Further, even if by above-mentioned bonded adhesives belt length in closed space Phase places at high temperature and will not ignite and can safely use in the case where causing flammable gas to be detained.
Detailed description of the invention
Fig. 1 is the concept map for indicating the measuring method of shear bond power.
Symbol description
1 aluminium sheet (C1)
2 aluminium sheets (C2)
3 partitions
4 jointing tapes
Gap between 5 jointing tapes and aluminium sheet (C2)
Specific embodiment
This jointing tape is jointing tape used in substantially closed space, which is characterized in that above-mentioned bonded adhesives Band has thermal expansivity adhesive layer (A), and above-mentioned thermal expansivity adhesive layer (A) contains adhesive composite (a) and thermal expansion Property capsule, the content of above-mentioned thermal expansivity capsule are relative to 100 mass parts of total solid content of above-mentioned adhesive composite (a) 3~100 mass parts.
As jointing tape of the invention, the above-mentioned thermal expansivity adhesive layer (A) by single layer or two layers or more can be enumerated The jointing tape of composition;By (such as the light expansion of above-mentioned thermal expansivity adhesive layer (A) and the dilatancy adhesive layer in addition to it Property adhesive layer, Thermocurable dilatancy adhesive layer) constitute jointing tape;By above-mentioned thermal expansivity adhesive layer (A) and not the jointing tape etc. that expansive adhesive layer (such as aftermentioned adhesive layer (B) etc.) is constituted.
Wherein, as above-mentioned jointing tape, such as from the dilatant by above-mentioned jointing tape by adherend (C1) institute Gap between the gap having or adherend (C1) and adherend (C2) is filled and Nian Jie aspect is set out securely, excellent Choosing uses the jointing tape being made of above-mentioned thermal expansivity adhesive layer (A) and the adhesive layer in addition to it.
As the jointing tape being made of above-mentioned thermal expansivity adhesive layer (A) and the adhesive layer in addition to it, specifically It says, it is preferable to use with the bonding of aftermentioned adhesive layer (B) in at least one side of above-mentioned thermal expansivity adhesive layer (A) on ground Adhesive tape.As above-mentioned jointing tape, above-mentioned thermal expansivity adhesive layer (A1) after maintaining above-mentioned expansion with it is above-mentioned glued Set out in terms of the excellent adaptation of body, preferably by above-mentioned thermal expansivity adhesive layer (A) be pasted in advance before above-mentioned expansion by Convered structure.
Above-mentioned thermal expansivity adhesive layer (A) is, for example, by heating the layer that can be expanded.As above-mentioned thermal expansivity Adhesive layer (A) uses the expansion rate (heat after above-mentioned placement after heating of the thickness direction of thermal expansivity adhesive layer (A) The thickness of thermal expansivity adhesive layer (A) before the thickness of dilatancy adhesive layer (A)/above-mentioned placement) × 100 become 150% Above adhesive layer.Above-mentioned expansion rate is preferably 200% or more, and more preferably 250%~1000%.If it is such viscous Adhesive tape is connect, even if the then such as gap possessed by adherend (C1) or between adherend (C1) and adherend (C2) Gap height (thickness) it is big in the case where, by expanding above-mentioned jointing tape, another adherend can also be fitted It preferably is fixed in above-mentioned gap or is filled in above-mentioned gap with above-mentioned jointing tape.In addition, if it is above-mentioned jointing tape, Even if also another adherend suitably can be then fixed on above-mentioned in the case where the surface of adherend is rough surface Rough surface.
It should be noted that above-mentioned expansion rate refers to: being placed 30 minutes in the environment of by above-mentioned jointing tape at 100 DEG C In the case where, the thermal expansivity adhesive layer (A1) of thermal expansivity adhesive layer (A) expansion formation is made by above-mentioned placement Ratio of the thickness relative to the thickness of the thermal expansivity adhesive layer (A) before above-mentioned placement (before expansion).
The thickness of above-mentioned thermal expansivity adhesive layer (A) before expansion is preferably 10 μm~250 μm of range, more preferably 20 μm~200 μm of range, from obtaining more excellent adhesive strength aspect, further preferably 30 μm~150 μm Range.
On the other hand, the thermal expansivity adhesive layer (A1) formed by the expansion of above-mentioned thermal expansivity adhesive layer (A) Thickness be preferably 15 μm~2500 μm of range, from obtaining more excellent bonding force aspect, preferably 20 μm~ 1500 μm of range.In addition, above-mentioned thermal expansivity adhesive layer (A1) preferably has porous structure.
In addition, as above-mentioned jointing tape, it is preferable to use the thickness of above-mentioned thermal expansivity adhesive layer (A) is relative to above-mentioned The jointing tape that the overall thickness of jointing tape is 10% or more, the jointing tape of 30% or more use is due to being easy another quilt Convered structure is suitably fixed in above-mentioned gap or is filled in above-mentioned gap with above-mentioned jointing tape, therefore more preferably.
Above-mentioned thermal expansivity adhesive layer (A) contains adhesive composite (a).Above-mentioned thermal expansivity adhesive layer (A) can By the way that adhesive composite (a) is coated on such as release liner, the supporter of adhesive tape and is manufactured being dried.
As above-mentioned adhesive composite (a), well known bonding agent composition resin can be used.As above-mentioned bonding agent It constitutes and uses resin, thermoplastic resin, thermosetting resin and their mixture can be used, it can be by epoxy resin, poly- ammonia Ester resin, organic siliconresin, phenolic resin, urea resin, fluororesin, acrylonitrile resin, acrylic resin, polystyrene tree Vinylites such as rouge, butadiene resin etc. are used alone or combine two or more use.
In the case where above-mentioned adhesive composite (a) uses thermoplastic resin, relative to above-mentioned adhesive composite (a) 100 mass parts of total solid content, preferably comprise the thermoplastic composition of 50 mass parts or more, further preferably include 75 mass parts More than, more preferably comprising more than 90 mass parts.
As above-mentioned thermoplastic resin, the resin that can easily expand by heating can be used.As above-mentioned heat Plastic resin is, it is preferable to use the storage modulus G measured by the dynamic viscoelastic spectrum at 1Hz and 23 DEG C23It is 1.0 × 103~5.0 × 107The resin of Pa range, and it is preferable to use the storage modulus G by the dynamic viscoelastic spectrum measurement at 1Hz and 70 DEG C70For 1.0 × 102~1.0 × 107The resin of Pa range, and from obtain even if heating before above-mentioned jointing tape can be prevented from adherend Removing, position are deviateed, and are set out in terms of capable of being expanded into the horizontal jointing tape that can be sufficient filling with above-mentioned gap, particularly preferably Use the storage modulus G by the dynamic viscoelastic spectrum measurement at 1Hz and 120 DEG C120It is 1.0 × 102~1.0 × 106Pa range Resin.
It, can from before heating about the jointing tape of the state before expanding above-mentioned thermal expansivity adhesive layer (A) In terms of enough preventing above-mentioned jointing tape from deviateing from adherend removing, position, and inhibit under normal temperature environment after expanding It sets out, can be used containing the storage modulus G by the dynamic viscoelastic spectrum measurement at 1Hz and 23 DEG C23Preferably 1.0 × 103~ 5.0×107Pa, more preferably 5.0 × 103~1.0 × 107Pa, particularly preferably 5.0 × 103~5.0 × 106The thermoplasticity of Pa The jointing tape of resin.
In addition, as above-mentioned thermoplastic resin, from inhibition adhesive tape in in-plane (flow direction, width direction) Expansion, make its to its thickness direction expansion aspect set out, it is preferable to use have above range in by the dynamic at 1Hz and 23 DEG C The storage modulus G of Viscoelastic Spectral measurement23, and by the dynamic viscoelastic spectrum measurement in the range of 70 DEG C~120 DEG C and under 1Hz Storage modulus is 1.0 × 102Pa~1.0 × 107The resin of Pa range.
As above-mentioned thermoplastic resin, can be used by the storage modulus of the dynamic viscoelastic spectrum measurement at 1Hz and 70 DEG C G70Preferably 1.0 × 102~1.0 × 107Pa, more preferably 5.0 × 102~5.0 × 106Pa, particularly preferably 5.0 × 102~ 1.0×106The resin of Pa.
In addition, can be used as above-mentioned thermoplastic resin by the energy storage of the dynamic viscoelastic spectrum measurement at 1Hz and 70 DEG C Modulus G70Preferably 1.0 × 102~1.0 × 107Pa, more preferably 5.0 × 102~5.0 × 106Pa, particularly preferably 5.0 × 102~1.0 × 106The resin of Pa.
In addition, the storage modulus G that above-mentioned thermoplastic resin is measured by the dynamic viscoelastic spectrum at 1Hz and 120 DEG C120It is preferred that It is 1.0 × 102~1.0 × 106Pa, more preferably 5.0 × 102~5.0 × 106Pa, further preferably 5.0 × 102~2.0 × 105Pa。
The above-mentioned storage modulus G of above-mentioned thermoplastic resin120It is preferred that than above-mentioned storage modulus G70It is small, above-mentioned storage modulus G70 It is preferred that than above-mentioned storage modulus G23It is small.
It should be noted that above-mentioned storage modulus G23、G70And G120Measurement use commercially available test for viscoelastic machine, pass through The measurement of method documented by aftermentioned embodiment.As the test film of said determination, by by thermal expansivity adhesive layer (A) institute The thermoplastic resin (without swelling agent) contained is coated on release liner and is dried etc. and obtains adhesive tape, the adhesive tape that will be obtained Be laminated each other, production thickness 2mm test film come using.
As above-mentioned thermoplastic resin, it is preferable to use for example there is excellent bonding force before inflation, in the swollen of swelling agent Bulge soften at a temperature of beginning, swelling agent made to be easy expansion, after expansion the resin of bonding force that can be excellent in.
As above-mentioned thermoplastic resin, such as the polyurethane series trees such as polyurethane (PU), thermoplastic polyurethane (TPU) can be enumerated Rouge;Polycarbonate (PC);The vinyl chloride-based resins such as polyvinyl chloride (PVC), Chlorovinyl-acetate vinyl copolymer resins;Polypropylene The acrylic acid such as acid, polymethylacrylic acid, polymethyl acrylate, polymethyl methacrylate (PMMA), polyethyl methacrylate It is resin;Polyethylene terephthalate (PET), polypropylene terephthalate, gathers polybutylene terephthalate (PBT) The polyester based resins such as (ethylene naphthalate), polybutylene naphthalate;The polyamide resins such as nylon (registered trademark); Polystyrene (PS), imide-modified polystyrene, acrylonitrile-butadiene-styrene (ABS) (ABS) resin, imide-modified ABS tree The polystyrene such as rouge, styrene-acrylonitrile copolymerization (SAN) resin, acrylonitrile-ethylene-propylene-diene-styrene (AES) resin It is the olefin-based resins such as resin, polyethylene (PE) resin, polypropylene (PP) resin, cyclic olefin resins;Nitrocellulose, acetic acid are fine Tie up the cellulose-based resins such as element;Organic silicon-type resin;The thermoplastic resins such as fluorine resin, styrene series thermoplastic elastomer, alkene Hydrocarbon system thermoplastic elastomer (TPE), vinyl chloride thermoplastic elastomer (TPE), carbamate system thermoplastic elastomer (TPE), ester based thermoplastic elasticity The thermoplastic elastomer (TPE)s such as body, amide based thermoplastic elastomer.
Styrene series thermoplastic elastomer, olefin-based thermoplastic elastomehc are particularly preferably used as thermoplastic resin, in them Property body, vinyl chloride thermoplastic elastomer (TPE), ester based thermoplastic elastomer, carbamate system thermoplastic elastomer (TPE), amide system heat Thermoplastic elastic or acrylic resin etc. particularly preferably use styrene series thermoplastic elastomer or acrylic resin.
As styrene series thermoplastic elastomer, such as the benzene second such as styrene-ethylene-butadiene copolymer (SEB) can be enumerated Alkene system AB type diblock copolymer;Hydride (the styrene-ethylene-of styrene-butadiene-styrene (SBS), SBS Butylene-styrene copolymers (SEBS)), hydride (the benzene second of styrene-isoprene-styrene copolymer (SIS), SIS Alkene-ethylene-propylene, Styrene copolymer (SEPS)), the polystyrenes such as styreneisobutylene-styrol copolymer (SIBS) ABA type triblock copolymer;Four block copolymerization of the polystyrenes ABAB such as s-B-S-butadiene (SBSB) type Object;Five block copolymer of the polystyrenes ABABA such as s-B-S-butadiene-styrene (SBSBS) type;Tool There is the polystyrene segmented copolymer of the AB repetitive unit more than them;By styrene such as SBR styrene butadiene rubbers (SBR) It is hydride obtained by the ethylene double bond hydrogenation of random copolymer;Deng.City also can be used in styrene series thermoplastic elastomer Sell product.
As above-mentioned acrylic resin, can be used for example the monomer polymerization comprising (methyl) alkyl acrylate and Obtained resin.
As above-mentioned (methyl) alkyl acrylate, it is preferable to use (methyl) third of the alkyl with carbon atom number 4~12 Olefin(e) acid ester, in particular, it is preferred that using (methyl) butyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) acrylic acid 2- second Own ester of base etc., is more preferably used alone or in combination butyl acrylate and 2-EHA.
In addition, other than above-mentioned monomer, acrylonitrile, (methyl) acrylic acid, Malaysia can also be used as above-mentioned monomer Acid anhydrides, acrylamide, itaconic acid, styrene, vinyl acetate etc..
In the case where above-mentioned adhesive composite (a) uses thermosetting resin, relative to above-mentioned adhesive composite (a) 100 mass parts of total solid content, preferably comprise the heat curable component of 50 mass parts or more, further preferably include 75 mass parts More than, more preferably comprising more than 90 mass parts.
Wherein, jointing tape aspect excellent obtaining the heat resistance after expansion is, it is preferable to use epoxy resin As above-mentioned thermosetting resin.
As above-mentioned epoxy resin, such as can be by bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol S type ring Oxygen resin, glycolylurea (Hydantoin) type epoxy resin, biphenyl type epoxy resin, alicyclic epoxy resin, triphenyl methane type ring Oxygen resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, naphthol novolac type epoxy resin, Modified (the carboxyl terminal of bicyclopentadiene/phenol epoxy resin, ester ring type amine epoxy resin, aliphatic amine epoxy resin and CTBN Butyronitrile is modified), through halogen modified epoxy resin etc. be used alone or combine two or more use.
Above-mentioned thermal expansivity adhesive layer (A) contains thermal expansivity capsule.As the thermal expansivity capsule, such as can make With by thermal expansivity capsule made of hydrocarbon system solvent microencapsulation.As above-mentioned thermal expansivity capsule, it is preferable to use can be upper The thermal expansivity capsule for generating gas at a temperature of stating before and after the softening point of thermoplastic resin and expanding.Above-mentioned thermal expansivity capsule Expansion start temperature be preferably 50 DEG C~150 DEG C, preferably 60 DEG C~145 DEG C, preferably 70 DEG C~140 DEG C.
As the commercially available product of above-mentioned thermal expansion capsule, for example, can enumerate EXPANCEL (Japanese Fillite Co. Ltd. system), MATSUMOTO MICROSPHERE (Matsumoto Yushi-Seiyaku Co., Ltd.'s system), MICROSPHERE (Kureha Corp.'s system) etc..
As above-mentioned thermal expansivity capsule, from preventing the thermal expansivity adhesive layer caused by the influence due to heat (A) deterioration etc. is set out, and more preferably use makes thermal expansivity capsule made of hydrocarbon system solvent microencapsulation among the above.It is above-mentioned Swelling agent capsule can be used alone or combine two or more use.
Total solid content 100 matter of the content of above-mentioned thermal expansivity capsule relative to above-mentioned thermal expansivity adhesive layer (A) Amount part is preferably 3 mass parts~100 mass parts range, and more preferably 3 mass parts~50 mass parts range is 5 mass parts The range of~30 mass parts is as can sufficiently expand to be filled to gap possessed by adherend, and even if close Above-mentioned jointing tape is placed on for a long time under the environment of the expansion start temperature of thermal expansivity capsule or more in the space closed and is made There are ignition sources to ignite in the case that flammable gas is detained, therefore further preferably.
As above-mentioned adhesive composite (a), consider with excellent bonding force, it is preferable to use thermoplastic before heating expansion Property resin.
As above-mentioned adhesive composite (a), can be used other than above-mentioned resin as needed also containing curing agent, The substance of curing accelerator etc..
As above-mentioned adhesive composite (a), can be used other than above-mentioned resin as needed also using containing solid The substance of agent, curing accelerator etc..
As above-mentioned curing agent, bisphenol-A, Bisphenol F, bisphenol-A D, hydroquinone, resorcinol, methyl can be used for example Resorcinol, xenol, tetramethyl biphenyl phenol, dihydroxy naphthlene, dihydroxy diphenyl ether, phenol resol resins, bisphenol-A phenolic Varnish gum, dicyclopentadiene phenolic resin, terpene phenolic resin, naphthol novolac varnish gum, biphenyl phenolic resin etc. are various Polynary phenol resin;It is obtained by the condensation reaction of the various aldehyde such as various phenol and hydroxy benzaldehyde, crotonaldehyde, glyoxal polynary Phenol resin;And by the various phenolic aldehyde such as mink cell focus or pitch, phenol and the obtained phenol-formaldehyde resin modified of formaldehyde compounds polycondensation Resin;The acid anhydrides such as methyl tetrahydrophthalic anhydride, hexahydrophthalic anhydride, pyromellitic dianhydride, methyl nadic acid;Two Amine such as second triamine, isophorone diamine, diaminodiphenyl-methane, diamino diphenyl sulfone, dicyandiamide etc..
As above-mentioned curing accelerator, such as can be by 2-methylimidazole, 2- methyl -4- ethyl imidazol(e), 2- phenylimidazole Equal imidazoles;The tertiary amines such as 1,8- diazabicylo [5.4.0] endecatylene -7, triethylenediamine, benzyl dimethylamine;Tributylphosphine, three Organic phosphines such as Phenylphosphine etc. are used alone or combine two or more use.
In addition, as jointing tape of the invention, as described above, it is preferred to use the jointing tape with adhesive layer (B).
As the adhesive layer (B) for constituting above-mentioned jointing tape, it can be used and be capable of forming with adherence or cementability The adhesive composite (b) of layer formed.
As above-mentioned adhesive layer (B), the expansion rate of the thickness direction of above-mentioned adhesive layer (B) can be used (after heating Above-mentioned placement after adhesive layer (B) thickness/above-mentioned placement before adhesive layer (B) thickness) × 100 become 120% Adhesive layer below.The expansion rate of above-mentioned adhesive layer (B) is preferably 115% hereinafter, more preferably 110% or less.If It is such jointing tape, even if being then also able to maintain that after above-mentioned thermal expansivity adhesive layer (A) expansion for adherend Excellent bonding force.It should be noted that the expansion rate of above-mentioned adhesive layer (B) refers to: by above-mentioned jointing tape at 100 DEG C In the environment of place 30 minutes in the case where, the thickness of the adhesive layer after above-mentioned placement is relative to above-mentioned viscous before above-mentioned placement Connect the ratio of the thickness of oxidant layer (B).
The thickness of above-mentioned adhesive layer (B) is preferably 1 μm~150 μm of range, be 5 μm~100 μm ranges due to Constitute above-mentioned jointing tape thermal expansivity adhesive layer (A) expansion and fill gap possessed by adherend (C1) or by Gap between convered structure (C1) and adherend (C2), thus when above-mentioned adhesive layer (B) is pasted on adherend (C2) The bonding force that can be excellent in, therefore more preferably.
Preferably expansion rate is low as described above for above-mentioned adhesive layer (B), therefore is preferably substantially free of as can be used in shape At swelling agent illustrated by when above-mentioned thermal expansivity adhesive layer (A).
As above-mentioned bonding agent (B), for example, can properly use containing resins such as thermosetting resin, thermoplastic resins and The content of above-mentioned swelling agent is few or adhesive composite (b) without above-mentioned swelling agent.
As the resin that can be used in above-mentioned adhesive composite (b), known resin is used before can choose.Its In, as above-mentioned resin, from the production efficiency aspect of raising jointing tape of the invention, it is preferable to use for example and as energy It is enough in form the same resin of resin illustrated by the adhesive composite (a) of above-mentioned thermal expansivity adhesive layer (A).
As above-mentioned adhesive composite (b), it can be used and gone back as needed other than above-mentioned adhesive composite (b) Substance containing tackifying resin, crosslinking agent, other additives etc..
As above-mentioned tackifying resin, in order to adjust the strong cementability of adhesive layer (B), rosin series thickening can be used for example Resin, newtrex system tackifying resin, newtrex ester system tackifying resin, rosin phenol system tackifying resin, stabilization rosin ester system Tackifying resin, disproportionated rosin ester system tackifying resin, terpenic series tackifying resin, terpenes phenol system tackifying resin, Petropols system thickening Resin etc..
As above-mentioned crosslinking agent, in order to improve the cohesiveness of adhesive layer (B), well known isocyanates system can be used and hand over Join agent, epoxy crosslinking agent, aziridine system crosslinking agent, multivalent metal salt system crosslinking agent, metallo-chelate system crosslinking agent, ketone-acyl Hydrazine system crosslinking agent,Oxazoline system crosslinking agent, carbodiimides system crosslinking agent, silane system crosslinking agent, glycidyl (alkoxy) Epoxy silane system crosslinking agent etc..
It as above-mentioned additive, can according to need in the range of not interfering desired effects of the invention, using being used for Adjust the alkali (ammonium hydroxide etc.) of pH, acid, foaming agent, plasticizer, softening agent, antioxidant, glass, it is plastic it is fibrous, spherical, The colorants such as pearl, the filler of metallic powder, pigment, dyestuff, pH regulator, epithelium form adjuvant, levelling agent, thickening Additive well known to agent, waterproofing agent, defoaming agent etc..
As above-mentioned adhesive composite (b), from good coating workability etc. is maintained, can be used containing The composition of solvent.As above-mentioned solvent, toluene, dimethylbenzene, ethyl acetate, butyl acetate, acetone, methyl can be used for example Ethyl ketone, hexane etc..It, can be in addition, in the case where using water system adhesive composite as above-mentioned adhesive composite (b) Use water or aqueous solvent based on water as above-mentioned solvent.
Jointing tape of the invention can be used for filling gap possessed by adherend (C1) or adherend (C1) with The use in the space between adherend (C2) is on the way.Furthermore it is possible to for below on the way: in adherend (C1) and glued In the indent and convex situation in surface of body (C2), above-mentioned jointing tape is arranged on adherend (C1), to above-mentioned jointing tape It is heated and makes its expansion, so that landfill is generated due to the concave-convex surface of above-mentioned adherend (C1) and adherend (C2) Gap and bonding.
In addition, being generated and expanding above-mentioned thermal expansivity adhesive layer (A) since jointing tape of the invention is utilized Power make the adhesive layer (A1) or above-mentioned adhesive layer (B) and above-mentioned adherend (C1) and adherend of above-mentioned expansion (C2) it crimps, therefore can be used for for example being unable to being destroyed or deform inside the article of direct weighting, because of direct weighting such Fragile component fixation.
Jointing tape of the invention can for example be manufactured by process below [I], it may be assumed that by above-mentioned adhesive composite (a) it is coated on release liner and is dried, to form thermal expansivity adhesive layer (A).
In jointing tape of the invention, it is made of above-mentioned thermal expansivity adhesive layer (A) and above-mentioned adhesive layer (B) Jointing tape can be manufactured by above-mentioned operation [I] and the process different from above-mentioned operation [I] [II] and process [III], The process [II] is above-mentioned adhesive composite (b) to be coated on release liner and is dried etc. to form adhesive layer (B) process, the process [III] are that above-mentioned adhesive layer (B) is transferred to the one side of above-mentioned thermal expansivity adhesive layer (A) simultaneously By the process of their crimping etc..
It should be noted that above-mentioned thermal expansivity adhesive layer (A) is preferably real during manufacturing above-mentioned jointing tape It is not expanded in matter.
In addition, as jointing tape of the invention, can according to need use above-mentioned thermal expansivity adhesive layer (A) with Jointing tape between adhesive layer (B) with nonwoven layer or resin film layer or layer made of metal (Z).Such bonding Adhesive tape has good rigidity, therefore sticking operation is excellent.
As above-mentioned layer (Z), for example, if be non-woven fabrics, then be used as material, preferably by paper pulp, artificial silk, abaca, Acrylonitrile, nylon, polyester etc. are constituted, and in order to meet the tensile strength of non-woven fabrics, can also be carried out as needed in copy paper process Middle addition polyamide and the 1 process impregnation processing being coated after the drying, are made the 2 of adhesive for viscose glue, thermoplastic resin Process impregnation processing etc..As resin film, can enumerate using polyester film, polyethylene film, polypropylene screen, polychloroethylene film, polyamides The resin film layer of the formation such as the plastic foils such as imines film;As metal layers such as layers made of metal, aluminium, copper.
As above-mentioned layer (Z), it is preferable to use the layer with 1 μm~200 μ m thicks.
Jointing tape with above-mentioned layer (Z) can for example pass through process [I] and the work different from above-mentioned operation [I] Sequence [II], process [IV] and process [V] manufacture, which is by the way that above-mentioned adhesive composite (a) is coated on demoulding It pads and is dried and the process that forms thermal expansivity adhesive layer (A), the process [II] are by by above-mentioned bonding agent group The process that object (b) is coated on release liner and is dried etc. and form adhesive layer (B) is closed, which is by above-mentioned layer (Z) process for being laminated in the one side of above-mentioned thermal expansivity adhesive layer (A), the process [V] are to transfer above-mentioned adhesive layer (B) To the face being made of above-mentioned layer (Z) and the process for crimping them.
The jointing tape of the invention obtained by above method etc. has excellent due to that can be expanded by heating Bonding force, therefore the dilatant that can be mainly suitably used for jointing tape through the invention is had adherend (C1) The occasions that manufacture of article made of gap between some gaps or adherend (C1) and adherend (C2) fills or is Nian Jie In.
As the manufacturing method of above-mentioned article, such as the manufacturing method of article with the following process can be enumerated, it may be assumed that will be upper The thermal expansivity adhesive layer (A) for stating jointing tape is pasted on the process [1] for constituting the position (c1-1) of adherend (C1);It is right The process [2] that above-mentioned thermal expansivity adhesive layer (A) is heated;Make above-mentioned thermal expansivity adhesive layer by above-mentioned heating (A) it expands, to form the process [3] of thermal expansivity adhesive layer (A1);And make the thermal expansion for constituting above-mentioned jointing tape Property adhesive layer (A1) or adhesive layer (B) are pasted on another position (c1-2) for constituting above-mentioned adherend (C1) or another quilt The process [4] of convered structure (C2).
In above-mentioned operation [1], with 0.1N/cm2Above power is crimped on the thermal expansivity adhesive layer (A) of jointing tape The position (c1-1) for constituting adherend (C1), due to the position (c1-1) of above-mentioned jointing tape and composition adherend (C1) Bonding force can be improved, even if heating before be able to suppress jointing tape and adherend (C1) deviation and it is preferred that.
It is crimped in the above-mentioned thermal expansivity adhesive layer (A) for making above-mentioned jointing tape and constitutes above-mentioned adherend (C1) It when position (c1-1), also can according to need using equipment such as press, rollers, they can also be pressed with finger.
The temperature (expansion start temperature) that heating temperature in above-mentioned operation [2] is for example preferably expanded with above-mentioned swelling agent Corresponding temperature, in particular, it is preferred that be 50~150 DEG C, more preferably 60~145 DEG C, be 70~140 DEG C due to keeping when It excellent in stability and does not damage the low adherend of heat resistance and expands above-mentioned jointing tape sufficiently, can be obtained after expansion excellent Different bonding force and it is preferred that.
As above-mentioned heating means, such as it can enumerate and put into article in the heating devices such as baking oven, heating furnace, it is whole to article The method that body is heated;Make above-mentioned thermal expansivity adhesive layer (A) or above-mentioned jointing tape or above-mentioned adherend contact or Close to heat source, thus the method heated to above-mentioned thermal expansivity adhesive layer (A).
As above-mentioned heat source, can be used for example halogen lamp, laser irradiation device, electromagnetic induction heater, hot padding, Hot plate, soldering iron etc..Heating means can be selected according to the size of article.
Jointing tape of the invention expands preferably after above-mentioned heating to its thickness direction, preferably in its flow direction or width Degree direction does not expand substantially.
Above-mentioned thermal expansivity adhesive layer (A) expansion is set to form thermal expansivity adhesive layer by above-mentioned operation [2] (A1) (process [3]).Thermal expansivity adhesive layer (A1) is mainly expanded in the thickness direction of jointing tape by above-mentioned expansion.
In above-mentioned operation [4], made using the power generated and expanding above-mentioned thermal expansivity adhesive layer (A) above-mentioned viscous It connects oxidant layer (A1) or above-mentioned adhesive layer (B) and constitutes another position (c1-2) or another glued of above-mentioned adherend (C1) Body (C2) crimping.Therefore, gap or adherend (C1) possessed by filling adherend (C1) and adherend (C2) it Between gap when, do not need using such as press etc. apply pressure.In addition, making to glue due to the power generated by above-mentioned expansion Connect that adhesive tape is closely sealed with adherend, therefore even if using surface to have indent and convex material (material with rough surface) as quilt In the case where convered structure, also it is not easy to form gap between jointing tape and adherend.
As above-mentioned adherend (C1) and (C2), such as the metals such as glass, aluminium can be enumerated, by acrylic acid, polycarbonate The plastics etc. that equal resins are constituted.As above-mentioned adherend (C1) and (C2), the material being made of same material, shape can be used Material, also can be used the material of unlike material, shape.
As above-mentioned adherend (C1) and (C2), with above-mentioned thermal expansivity adhesive layer (A), above-mentioned adhesive layer (B) The surface of contact may be rough surface.
As the shape of above-mentioned adherend (C1) and above-mentioned adherend (C2), without special provision, such as can enumerate Two-dimensional shapes, 3D shape (curved surface etc.), the shape with concave-convex surface, chimeric shape etc..Or above-mentioned shape Combination.
Jointing tape of the invention can be by integrally applying above-mentioned thermal expansivity adhesive layer (A) or above-mentioned jointing tape It heats and makes its expansion.
As the manufacturing method of above-mentioned article, there is excellent bonding force before heating, can be expanded by heating and It sets out in terms of the bonding force being also excellent in after heating expansion, preferably according to the suitable of above-mentioned operation [1], process [2] and process [3] Sequence carries out.Especially in the case where the surface of adherend (C1) or (C2) are rough surface, from the good bonding force of performance It is effective that aspect, which is set out,.
For example, even if the bonded adhesives before wanting use after process [2] makes its heating expansion in advance brings stickup In the case where indent and convex adherend in surface etc., also it can reduce a possibility that their interface forms minim gap.
Jointing tape of the invention is jointing tape used in substantially closed space, substantially closed space In the state of referring to the air pressure balance inside and outside space, gapless as air exchange does not occur substantially inside and outside the space The space of closing.Therefore, even if by making the case where there are air inflows and the internal or external air pressure in the space rises Under, it is suitable as long as the exchange of air does not occur in the state of air pressure balance inside and outside space substantially inside and outside the space In substantially closed space.Thus, for example in gas leakage test, (air is added in workpiece to be made in workpiece (in detected material) Pressure rise, generate draught head inside and outside workpiece, the test of detection air leakage.It is leaked in workpiece there are hole etc. In the case of, the pressure decline in workpiece, therefore leakage is detected by monitoring the pressure change being applied in workpiece.) in exist When the leakage of air, it can not say it is not substantially closed space accordingly.
When using above-mentioned jointing tape in above-mentioned substantially closed space, the bonding area of above-mentioned jointing tape (cm2) divided by the volume (cm of confined space3) it is resulting value be preferably 0.001~50cm-1, more preferably 0.001~40cm-1, Further preferably 0.002~15cm-1, it is 0.005~15cm-1When, due to that can ensure using jointing tape fixing component Abundant area, therefore sufficient cementability is maintained, and even if jointing tape is placed at high temperature for a long time and makes inflammability gas Body will not ignite in the case where being detained, therefore more preferably.
As above-mentioned article, such as the miniature motor for being equipped on the movable part of automobile can be enumerated.Said motor is usually by outer It fills component (cylindrical member) and its cap-like structure is constituted.As said motor, specifically, can enumerate metal tubular structure The cap-like structure of part and the resin of shape corresponding with above-mentioned cylindrical member is with motor made of the chimeric closed fixation of state. Jointing tape of the invention is formed in the gap between above-mentioned cylindrical member and above-mentioned cap-like structure when can be filled with.Although load Core motor due to the coil of cylinder interior rotation and generate electrostatic spark, but within the above range using above-mentioned jointing tape In the case of, it can be used in the case where not igniting.As purposes, it is not limited to motor.
Embodiment
(modulation example 1)
The modulation > of < adhesive composite (a-1)
By the styrene-butadiene block copolymer of 100 mass parts weight average molecular weight 300,000, (triblock copolymer is embedding with two The mixture of section copolymer.Above-mentioned diblock copolymer is 50 mass % relative to the occupation ratio of the total amount of said mixture. Polystyrene units mass ratio shared in the entirety of above-mentioned styrene-butadiene block copolymer is 30 mass %, is gathered The mass ratio of butadiene unit be 70 mass %), 65 mass parts terpene phenol system tackifying resins (115 DEG C of softening point, molecular weight 1000) substance mixed is dissolved in toluene, to obtain adhesive composite (a-1).
(modulation example 2)