CN106574161A - Adhesive composition, adhesive obtained by crosslinking same, adhesive for masking films, adhesive for heat-resistant adhesive films, heat-resistant adhesive film for masking, and method for using heat-resistant adhesive film for masking - Google Patents

Adhesive composition, adhesive obtained by crosslinking same, adhesive for masking films, adhesive for heat-resistant adhesive films, heat-resistant adhesive film for masking, and method for using heat-resistant adhesive film for masking Download PDF

Info

Publication number
CN106574161A
CN106574161A CN201580044360.4A CN201580044360A CN106574161A CN 106574161 A CN106574161 A CN 106574161A CN 201580044360 A CN201580044360 A CN 201580044360A CN 106574161 A CN106574161 A CN 106574161A
Authority
CN
China
Prior art keywords
adhesive
monomer
methyl
heat
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201580044360.4A
Other languages
Chinese (zh)
Other versions
CN106574161B (en
Inventor
竹田俊之
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Kasei Corp
Original Assignee
Nippon Synthetic Chemical Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Synthetic Chemical Industry Co Ltd filed Critical Nippon Synthetic Chemical Industry Co Ltd
Publication of CN106574161A publication Critical patent/CN106574161A/en
Application granted granted Critical
Publication of CN106574161B publication Critical patent/CN106574161B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • C09J133/14Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09J133/24Homopolymers or copolymers of amides or imides
    • C09J133/26Homopolymers or copolymers of acrylamide or methacrylamide
    • 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
    • C09J7/20Adhesives in the form of films or foils characterised by their carriers
    • 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
    • C09J2203/00Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/31Applications of adhesives in processes or use of adhesives in the form of films or foils as a masking tape for painting

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)

Abstract

Provided is an adhesive composition which is capable of maintaining an adequate adhesive force even under high temperature conditions, and which is not susceptible to the occurrence of contamination if separated from an object to be bonded after use under high temperature conditions. This adhesive composition is able to be used for a heat-resistant adhesive film for masking, which can be separated with a small force, and the like. An adhesive composition which contains an acrylic resin (A) that has a structural unit derived from a polyoxyethylene structure-containing monomer (a1) and a structural unit derived from a (meth)acrylic acid alkyl ester monomer (a2), and which is characterized in that: the content of the structural unit derived from a polyoxyethylene structure-containing monomer (a1) is 10-45% by weight; and an antistatic agent is not contained.

Description

Adhesive composition, make its crosslinking adhesive, shielding film adhesive, Heat-resistant adhesive film adhesive, masking Heat-resistant adhesive film and its using method
Technical field
The present invention relates to adhesive composition, make its be crosslinked adhesive, shielding film adhesive, Heat-resistant adhesive Film adhesive, masking Heat-resistant adhesive film and its using method, specifically, are related to:Under the high temperature conditions after use Being not likely to produce when peeling off from adherend in pollution and the masking Heat-resistant adhesive film that can be peeled off with little power etc. to use Adhesive composition;The adhesive for being crosslinked it;Shielding film adhesive comprising the adhesive;Comprising the bonding The Heat-resistant adhesive film adhesive of agent;Have the masking of the adhesive phase comprising the adhesive thin with Heat-resistant adhesive on film Film;With, the masking using method of Heat-resistant adhesive film.
Background technology
Flexible printed wiring (FPC) substrate is used for the information terminal electronic equipment such as mobile phone, in recent years, due to being based on The precise treatment of the circuit of high performance, the miniaturization of electronic equipment, therefore the filming of the plywood comprising FPC substrates is little Typeization is advanced.As a result, the intensity decreases of plywood and it is easily damaged, therefore, in order to prevent its damaged, manufacturing process In, it is necessary to protected with protective film.However, due to being exposed to high temperature, therefore the adhesive phase of protective film in manufacturing process Plywood is bonded to, sometimes plywood is damaged when protective film is peeled off or produces by pollution caused by cull institute.In addition, Sometimes under the high temperature conditions bonding force reduces and produces and float, therefore, also existing cannot play as the sufficient of protective film The problem of protective capability.
In addition, in manufacture as the member of formation of the touch panel used in the portable data assistances such as smart mobile phone In the operation of ito transparent electrode layer, including the operation of following annealing:After forming ito transparent electrode layer on plywood, glue Attached protective film, in the state of keeping adhesion protective film constant, is heated under conditions of 150~200 DEG C.The manufacture High temperature is exposed in operation, therefore, the adhesive phase of protective film is bonded to plywood, sometimes when protective film is peeled off Ito transparent electrode layer is damaged or produces by pollution caused by cull institute.In addition, under the high temperature conditions sometimes bonding force is reduced And produce and float, therefore, also there is a problem of that the sufficient protective capability as protective film cannot be played.I.e., in recent years, exist On the basis of not causing adherend pollution after heat-resisting operation, such as in the field of the shielding film of ito transparent electrode layer etc., it is The breakage of film is prevented, also requires to peel off masking Heat-resistant adhesive film with little power when peeling off.
In order to solve these problems, following technology is disclosed.
A kind of adhesive composition is Patent Document 1 discloses, by the hydroxyl third that weight average molecular weight is 450,000~1,500,000 Olefin(e) acid resinoid and isocyanates system crosslinking agent are with the isocyanates base unit weight in isocyanates system crosslinking agent relative to aforementioned containing hydroxyl Amount of hydroxyl groups in base acrylic resin contains for the scope of 0.6~1.6 times (mol ratio), relative to aforementioned hydroxy acryl acid The weight portion of resinoid 100, further includes:With hydroxy acryl acid resinoid and isocyanates system crosslinking agent for it is non-reacted, And formula weight or number-average molecular weight are more than 300 and less than 1500 weight portion of ester compounds 3~20.
The micro- adhesive composition of a kind of heat resistance disclosed in patent document 2, it is characterised in that it is to be laminated to FPC bases The film or piece of material etc. is so that the adhesive composition of the film or the micro- adhesive film/piece of heat resistance of piece reinforcement, the bonding In agent composition, relative to acrylic polymer, compounded with isocyanate resin and metal-chelator.
Prior art literature
Patent document
Patent document 1:Japanese Unexamined Patent Publication 2007-327036 publications
Patent document 2:Japanese Unexamined Patent Publication 2003-261849 publications
The content of the invention
Problems to be solved by the invention
However, in the technology of patent document 1, due to using number-average molecular weight be more than 300 and less than 1500 etc it is low The compound of molecular weight, therefore, the compound is likely to become in itself material the reason for adherend pollutes, in addition, adhesive phase Cause aggregation force to reduce under the high temperature conditions, residual adhesive is also possible on adherend.
In the technology of patent document 2, due to using metal-chelator, therefore, it is dirty that metal ion is likely to become adherend The reason for dye material.In addition, be the crosslinking based on ionic bond based on metalchelated crosslinking, and based on isocyanates, epoxy etc. Covalent bond crosslinking it is different, therefore, bonding easily dissociation, the heat resistance under hot conditions is worse and be possible to produce cull.
Therefore, in the present invention, in this context, it is therefore intended that, there is provided:It is appropriate to be also able to maintain that under the high temperature conditions Bonding force and pollution is not likely to produce when peeling off from adherend after use under the high temperature conditions and (can for example be glued with little power It is less than 1.0N/25mm (to BA plates) with joint efforts) adhesive composition that can use in the masking Heat-resistant adhesive film etc. peeled off.
In addition, the present invention also aims to, there is provided:Make the adhesive of the binder composition cross-links;Comprising this The shielding film adhesive of adhesive;Heat-resistant adhesive film adhesive comprising the adhesive;Have on film and include The masking of the adhesive phase of adhesive Heat-resistant adhesive film;With, the masking using method of Heat-resistant adhesive film.
For solution to problem
However, the present inventor furthers investigate repeatedly, as a result find:By using with specified quantitative from containing polyoxy Asia second The acrylic resin of the construction unit of the monomer of based structures as adhesive composition, such that it is able to solve above-mentioned problem, extremely This completes the present invention.
For example, by using acrylic resin as Heat-resistant adhesive film adhesive composition, the acrylic acid Resinoid be will include specified quantitative as acrylic resin composition monomer the monomer containing polyoxyethylene structure into Obtained from the copolymer composition copolymerization for dividing, such that it is able to solve above-mentioned problem, the present invention is so far completed.
That is, purport of the invention is related to a kind of adhesive composition, it is characterised in that containing acrylic resin (A), institute State acrylic resin (A) and there is the construction unit for being derived from the monomer (a1) containing polyoxyethylene structure and from (methyl) third The construction unit of olefin(e) acid Arrcostab system monomer (a2), from the content of the construction unit of the monomer (a1) containing polyoxyethylene structure For 10~45 weight %, described adhesive composition does not contain antistatic additive.
In addition, the purport of the present invention is related to a kind of adhesive composition, it is characterised in that containing acrylic resin (A), The acrylic resin (A) is by containing the monomer (a1) containing polyoxyethylene structure and (methyl) alkyl acrylate system Obtained from the copolymer composition copolymerization of monomer (a2), the content of the monomer (a1) containing polyoxyethylene structure in copolymer composition is 10~45 weight %.
In addition, the purport of the present invention is further related to, a kind of adhesive, it is characterised in that it is the adhesive combination of the present invention Obtained from thing crosslinking;A kind of shielding film adhesive, it is characterised in that the adhesive comprising the present invention;It is a kind of resistance to hot sticky Close film adhesive, it is characterised in that the adhesive comprising the present invention;Heat-resistant adhesive film is used in one kind masking, and its feature exists In with the adhesive phase of the adhesive comprising the present invention on film;A kind of masking using method of Heat-resistant adhesive film, Characterized in that, the masking Heat-resistant adhesive film of the present invention is adhered to into adherend surface, for more than 100 DEG C heaters Sequence, then by the masking with Heat-resistant adhesive film from adherend sur-face peeling.
It should be noted that " adhesive film " in the present invention is referred to, it is conceptive comprising bonding sheet, adhesive film, bonding Band.
The adhesive composition of the present invention is due to the structure from the monomer containing polyoxyethylene structure containing specified quantitative The acrylic resin of unit, for example, the copolymerization containing the monomer component containing polyoxyethylene structure by specified quantitative is included Acrylic resin obtained from composition copolymerization, therefore, glued using having obtained from the binder composition cross-links of the present invention In the case that the masking of mixture layer is with Heat-resistant adhesive film, adhesive phase is soft and to the adaptability of adherend under normal temperature condition Become good, the minute asperities on adherend surface are followed during stickup, adhesive phase is very close to each otherly with adherend closely sealed.Therefore, Even if under the high temperature conditions adhesive phase generation softening is also all almost very close to each other, therefore contact area will not increase.Profit The effect is used, the masking Heat-resistant adhesive film of adherend is adhered to after high temperature is exposed to, masking Heat-resistant adhesive is peeled off It is not easy to produce the pollution of the adherends such as cull during film, and masking Heat-resistant adhesive film can be peeled off with little power.
The effect of invention
Adhesive composition of the invention and make its crosslinking obtained from adhesive, can manufacture:In hot conditions Pollution and the masking Heat-resistant adhesive film that can be peeled off with little power are not likely to produce when peeling off from adherend after lower use.
Specific embodiment
Hereinafter, the present invention is described in detail, but these are illustrate preferable embodiment one.Need explanation Be, in this specification, (methyl) acrylic acid refer to acrylic or methacrylic acid, (methyl) acryloyl group refer to acryloyl group or Methylacryloyl, (methyl) acrylate refers to acrylate or methacrylate.
The adhesive composition of the present invention is formed containing acrylic resin (A).Acrylic acid used in the present invention Resinoid (A) has the construction unit for being derived from the monomer (a1) containing polyoxyethylene structure and from (methyl) acrylic acid alkyl The construction unit of ester system monomer (a2), for example, it is by containing the monomer (a1) containing polyoxyethylene structure and (methyl) propylene Obtained from the copolymer composition copolymerization of acid alkyl ester system monomer (a2).Acrylic resin (A) further can also have from source The construction unit of self-contained monomer (a3) and the knot from appropriate selection in the construction unit of other co-polymerized monomers (a4) Structure unit.For example, as other copolymer compositions contained in copolymer composition, it is possible to use from containing monomer (a3) and other The appropriate monomer for selecting in co-polymerized monomer (a4).
The monomer (a1) containing polyoxyethylene structure used in the present invention is with the oxygen ethylidene structure of more than 2 Monomer.
The number of repeat unit of the oxygen ethylidene chain of the monomer (a1) containing polyoxyethylene structure is usually more than 2, preferably For 2~20, particularly preferably 2~15, more preferably 2~10.When above-mentioned number of repeat unit is very few, have to being glued The tendency that the adaptability of thing is deteriorated, adherend pollution increase when excessive, after having the tendency of to heat.
As the monomer (a1) containing polyoxyethylene structure, from copolymerizable aspect, preferably containing polyoxyethylene (methyl) acrylic ester monomer of structure, for example, can enumerate:2- butoxy diethylene glycol (methyl) acrylate, methoxyl group Diethylene glycol (methyl) acrylate, methoxy triethylene (methyl) acrylate, ethoxydiglycol (methyl) propylene Acid esters, methoxy poly (ethylene glycol) (methyl) acrylate, octyloxy polyethylene glycol propane diols-mono- (methyl) acrylate, the moon The alkoxyls such as osmanthus acyloxy polyethyleneglycol (methyl) acrylate, stearoyl-oxy polyethyleneglycol (methyl) acrylate gather Ethylene glycol list (methyl) acrylate etc..
They can be used alone or combine two or more and use.
In above-mentioned, as the monomer (a1) containing polyoxyethylene structure, for example, can enumerate:Shown in following formulas (1) (methyl) acrylate containing polyoxyethylene structure.
(in formula, X is ethylidene, and Y is hydrogen atom, alkyl, aryl or aralkyl, R1For hydrogen atom or methyl, n is more than 2 Integer.)
X in above-mentioned formula (1) is ethylidene.
Y in above-mentioned formula (1) is any one of hydrogen atom, alkyl, aryl, aralkyl.Among these, preferably hydrogen Atom, alkyl, aryl, particularly preferably hydrogen atom, alkyl, phenyl, more preferably alkyl.
The preferred carbon number of abovementioned alkyl is shorter, and specifically, carbon number is usually 1~15, is preferably 1~10, particularly preferably For 1~6 alkyl.Specifically, the Y of formula (1) and then preferably methyl, ethyl, propyl group, particularly preferred methyl.
As above-mentioned aryl, the aryl that carbon number 6~20 is usually used, the aryl for preferably using 6~15, specifically, can To enumerate:Phenyl, tolyl, xylyl, xenyl, naphthyl etc., among these, preferred phenyl.
As above-mentioned aralkyl, the aralkyl of carbon number 7~20 is usually used, preferably uses the aralkyl of carbon number 7~15, had For body, benzyl etc. can be enumerated.
It should be noted that abovementioned alkyl, aryl, aralkyl can also have substituent, as substituent, generally can be with Enumerate:The halogen atoms such as fluorine atom, chlorine atom, bromine atoms, atomic iodine, hydroxyl, alkoxyl, amino, sulfanyl, aryl, heteroaryl Deng.
R in above-mentioned formula (1)1For hydrogen atom or methyl.N is more than 2 integer, preferably 2~20, particularly preferably 2~15, more preferably 2~10.
As the preferred monomer (a1) containing polyoxyethylene structure, can enumerate:Methoxy triethylene (methyl) third Olefin(e) acid ester, ethoxydiglycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate.
The content of the monomer (a1) containing polyoxyethylene structure in copolymer composition is usually 10~45 weight %, is preferably 10~40 weight %, particularly preferably 15~35 weight %, more preferably 15~30 weight %.When content is very few, has and add The tendency that bonding force after thermal technology's sequence is uprised, when excessive, there is the pollution increase of the adherend after heating process.
It should be noted that the structure from the monomer (a1) containing polyoxyethylene structure in acrylic resin (A) The content of unit can be utilized1H-NMR is measured and calculates.
(methyl) alkyl acrylate system monomer (a2) used in the present invention is the alkane with aliphatic formula or ester ring type (methyl) acrylate of base ester.The carbon number of the alkyl in Arrcostab is usually 1~20, is preferably 1~12, particularly preferably 1 ~6.When carbon number is excessive, there is the pollution increase of the adherend after heating process.
For example can enumerate:(methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (first Base) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) n-propyl, (methyl) the just own ester of acrylic acid, (first Base) 2-EHA, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) isodecyl acrylate, (methyl) lauryl acrylate, (methyl) acrylic acid hexadecane ester, (methyl) stearyl acrylate ester, the different tristearin of (methyl) acrylic acid Aliphatic (methyl) alkyl acrylate such as ester;The alicyclic rings such as (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate (methyl) acrylate of race etc..
As preferred (methyl) alkyl acrylate system monomer (a2), can enumerate:(methyl) methyl acrylate, (first Base) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) N-propyl, (methyl) the just own ester of acrylic acid.
They can be used alone or combine two or more and use.
The content of (methyl) alkyl acrylate system monomer (a2) in copolymer composition is usually 40~90 weight %, preferably For 45~85 weight %, particularly preferably 50~80 weight %.When content is very few, there is the pollution increase of the adherend after heating process Tendency, when excessive, having the tendency of the bonding force after heating process becomes too high.
It should be noted that the knot from (methyl) alkyl acrylate system monomer (a2) in acrylic resin (A) The content of structure unit can be utilized1H-NMR is measured and calculates.
In addition, in (methyl) alkyl acrylate system monomer (a2), the adherend from after heating process pollutes excellent side Face is set out, and preferably the content of (methyl) alkyl acrylate system monomer (a2-1) with the alkyl that carbon number is 1~6 is 80 weights Amount more than %, it is more than particularly preferably 85 weight %, it is more than more preferably 90 weight %, especially preferably 95 weight % with On.
As above-mentioned containing monomer (a3), if be containing by with aftermentioned crosslinking agent (B) react and can become The monomer of the functional group of crosslinking points, for example, can enumerate:Hydroxyl monomer, carboxyl group-containing monomer, emulsion stability, containing acetyl Acetyl group monomer, monomer containing NCO, containing glycidyl monomer etc..
As hydroxyl monomer, for example, can enumerate:(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 4- hydroxyls Butyl ester, (methyl) acrylic acid 5- hydroxyl pentyl esters, the own ester of (methyl) acrylic acid 6- hydroxyls, (methyl) acrylic acid 8- hydroxyl monooctyl esters etc. third Caprolactone modification monomer, the diethylene glycol (first such as olefin(e) acid hydroxyalkyl acrylate, caprolactone modification (methyl) acrylic acid 2- hydroxy methacrylates Base) oxyalkylene modified monomer and the 2- acryloyl-oxyethyl -2- such as acrylate, polyethylene glycol (methyl) acrylate Hydroxyethyl phthalic acid ester etc. contains primary hydroxy monomers;
(methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (methyl) acrylic acid 3- chlorine 2- hydroxyls The monomers containing secondary hydroxyl such as propyl ester;
The monomers containing tert-hydroxyl such as (methyl) acrylic acid 2,2- dimethyl 2- hydroxy methacrylates.
In above-mentioned hydroxyl monomer, from the reactive excellent aspect with crosslinking agent, particularly preferably (methyl) is used Acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 4- hydroxybutyls.
It should be noted that as the hydroxyl monomer used in the present invention, it is also preferred that using the two (first as impurity Base) acrylate content ratio be less than 0.5% hydroxyl monomer, more preferably less than 0.2%, particularly preferably Less than 0.1% hydroxyl monomer.
As above-mentioned carboxyl group-containing monomer, for example, can enumerate:(methyl) acrylic acid, acrylic acid dimer, butenoic acid, Malaysia Acid, maleic anhydride, fumaric acid, citraconic acid, glutaconate, itaconic acid, acrylamide N- glycolics, cinnamic acid etc., wherein, preferably Use (methyl) acrylic acid.
As above-mentioned emulsion stability, for example, can enumerate:(methyl) tbutylaminoethylacrylate, (methyl) propylene Sour ethylamino ethyl ester, (methyl) acrylate, (methyl) acrylic acid diethylamino ethyl ester etc..
As above-mentioned monomer containing acetoacetyl, for example, can enumerate:2- (acetoacetoxy groups) ethyl (methyl) propylene Acid esters, acetoacetic acid allyl ester etc..
As above-mentioned monomer containing NCO, for example, can enumerate:2- acryloyloxyethyl isocyanates, 2- methyl Acryloyloxyethyl isocyanate, their alkylene oxide addition product etc..
As above-mentioned containing glycidyl monomer, for example, can enumerate:(methyl) glycidyl acrylate, (methyl) third Olefin(e) acid allyl glycidyl etc..
Among these, from can effectively carry out cross-linking reaction aspect, preferably use hydroxyl monomer and/or contain Carboxylic monomer.These (a3) containing monomer can be used alone and can also be applied in combination two or more.
The content containing monomer (a3) in copolymer composition is usually 0.1~30 weight %, is preferably 0.5~20 weight Amount %, particularly preferably 1~15 weight %.When content is very few, crosslinking degree is reduced, the tendency of adherend pollution increase, excessively When, having the tendency of the bonding force after just pasting becomes too high.
It should be noted that the content from the construction unit containing monomer (a3) in acrylic resin (A) Can utilize1H-NMR is measured and calculates.
As other co-polymerized monomers (a4) used sometimes in the present invention, for example, can enumerate:Ethoxyl methyl (first Base) acrylamide, n-butoxy methyl (methyl) acrylamide, (methyl) acryloyl morpholine, dimethyl (methyl) acryloyl Amine, diethyl (methyl) acrylamide, (methyl) acrylamide N- methylols (methyl) acrylamide, N, N- dimethylaminos third Base (methyl) acrylamide etc. (methyl) acrylamide monomer;
(methyl) acrylate, (methyl) acrylic acid N, N- dimethylamino methyl esters, (methyl) acrylic acid N, N- (methyl) the acrylate system such as dimethylamino ethyl ester, (methyl) tbutylaminoethylacrylate monomer;
(methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) acrylate, diethylamino phenyl glycol (methyl) acrylate, (methyl) acrylic acid 2- hydroxyl -3- phenoxy-propyls, styrene, AMS etc. contain 1 virtue The monomer of fragrant ring;
Structure containing biphenylyloxy (methyl) the acrylic ester monomers such as (methyl) acrylic acid biphenylyloxy ethyl ester;
(methyl) acrylic acid 2- methoxy acrylates, (methyl) acrylic acid 2- ethoxy ethyl esters, methoxyl group diethylene glycol (first Base) acrylate, ethoxydiglycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, poly- the third two The monomer containing alkoxyl or oxyalkylene such as alcohol list (methyl) acrylate;
Acrylonitrile, methacrylonitrile, vinyl acetate, propionate, stearic acid vinyl ester, vinyl chloride, inclined two chloroethene Alkene, alkyl vinyl ether, vinyltoluene, vinylpyridine, vinyl pyrrolidone, Dialkyl itaconates, fumaric acid two Arrcostab, allyl alcohol, acryloyl chloride, methyl vinyl ketone, pi-allyl trimethyl ammonium chloride, dimethyl-allyl vinyl ketone Deng.In these co-polymerized monomers, from the aspect for reducing the pollution of the adherend after heating process, preferably (methyl) acrylamide It is monomer.
They can be used alone or combine two or more and use.
The content of other co-polymerized monomers (a4) in copolymer composition is usually 0~40 weight %, is preferably 0.001~30 Weight %, particularly preferably 0.01~25 weight %.When content is excessive, there is adhesion characteristic and be easily reduced.
It should be noted that the construction unit from other co-polymerized monomers (a4) in acrylic resin (A) contains Amount can be utilized1H-NMR is measured and calculates.
Thus, by by containing the above-mentioned monomer (a1) containing polyoxyethylene structure, (methyl) alkyl acrylate system list Body (a2), entering as the polymeric composition of copolymer composition containing monomer (a3), other co-polymerized monomers (a4) as needed Row polymerization, such that it is able to manufacture with the construction unit from the monomer (a1) containing polyoxyethylene structure, from (methyl) third The construction unit of olefin(e) acid Arrcostab system monomer (a2), as needed from containing monomer (a3) construction unit, be derived from The acrylic resin (A) of the construction unit of other co-polymerized monomers (a4).
When acrylic resin (A) is polymerized, for example, can adopt solution free radical polymerization, suspension polymerisation, polymerisation in bulk, breast The known methods such as liquid polymerization.For example, in organic solvent, mix or be added dropwise the above-mentioned monomer containing polyoxyethylene structure (a1), (methyl) alkyl acrylate system monomer (a2), containing monomer (a3) and other co-polymerized monomers (a4) etc. polymerization Property monomer, polymerization initiator (azodiisobutyronitrile, AMBN, benzoyl peroxide etc.), reflux state or 50~ Carry out 2~20 hours being polymerized at 90 DEG C.
The structure list from the monomer (a1) containing polyoxyethylene structure in the acrylic resin (A) obtained in above-mentioned The content of unit is 10~45 weight %, is preferably 10~40 weight %, is particularly preferably 15~35 weight %, is more preferably 15~30 weight %.When content is very few, there is the bonding force after heating process and uprise, when excessive, after having heating process The tendency of adherend pollution increase.
The content of the construction unit from (methyl) alkyl acrylate system monomer (a2) in acrylic resin (A) is led to Often it is 40~90 weight %, is preferably 45~85 weight %, is particularly preferably 50~80 weight %.When content is very few, there is heating The tendency of the adherend pollution increase after operation, when excessive, having the tendency of the bonding force after heating process becomes too high.
The content from the construction unit containing monomer (a3) in acrylic resin (A) is usually 0.1~30 Weight %, preferably 0.5~20 weight %, particularly preferably 1~15 weight %.When content is very few, crosslinking degree is reduced, glued The tendency of thing pollution increase, when excessive, having the tendency of the bonding force after just pasting becomes too high.
The content of the construction unit from other co-polymerized monomers (a4) in acrylic resin (A) is usually 0~40 Weight %, preferably 0.001~30 weight %, particularly preferably 0.01~25 weight %.When content is excessive, there is adhesion characteristic to hold The tendency for easily reducing.
For the weight average molecular weight of acrylic resin (A), usually 100,000~2,500,000, be preferably 200,000~2,200,000, Particularly preferably 400,000~2,000,000.When weight average molecular weight is too low, the heat resistance for having adhesive phase is reduced, adherend pollution increase Tendency, when too high, need Macrodilution solvent, at coating, the aspect of cost, have the tendency of to become unfavorable.
In addition, the decentralization (weight-average molecular weight/number-average molecular weight) of acrylic resin (A) for example be usually less than 20, Preferably less than 15, particularly preferably less than 10, lower limit is usually 1.1.When decentralization is too high, there is the heat resistance drop of adhesive phase Low, the easy tendency for producing foaming etc..
It should be noted that above-mentioned weight average molecular weight is the weight average molecular weight converted based on polystyrene standard molecular weight, By high performance liquid chromatograph (Japanese Waters societies system, " Waters 2695 (main body) " and " Waters 2414 (detector) ") Using post:Shodex GPC KF-806L (exclusion limit molecular weight:2×107, separating ranges:100~2 × 107, theoretical tray Number:10000 grades/root, filler material:Styrene diethylene benzene copoly mer, filler particle diameter:10 μm) 3 series connection and Determine, number-average molecular weight can also utilize same method.In addition, decentralization is asked according to weight average molecular weight and number-average molecular weight Go out.
Polymer derivantization can also can be changed suitably the species of eluent when determining in addition.
Further, the glass transition temperature of acrylic resin (A) is usually -70~0 DEG C, is preferably -65~-5 DEG C, spy It is not preferably -60~-10 DEG C.When glass transition temperature is too high, there is the bonding force after heating process and uprise, vitrifying When transition temperature is too low, there are heat resistance reduction, adherend pollution increase.
Glass transition temperature is calculated according to following Fox formulas.
Tg:The glass transition temperature (K) of copolymer
Tga:The glass transition temperature (K) of the homopolymers of monomer a
Wa:The weight fraction of monomer a
Tgb:The glass transition temperature (K) of the homopolymers of monomer b
Wb:The weight fraction of monomer b
Tgn:The glass transition temperature (K) of the homopolymers of monomer n
Wn:The weight fraction (Wa+Wb++Wn=1) of monomer n
The adhesive composition of the present invention contains aforesaid propylene acid resin (A) as essential component, can combine this Thing directly forms adhesive, or said composition can also be made to contain crosslinking agent (B) makes it be crosslinked and formation adhesive.Make bonding When agent composition is crosslinked, crosslinking agent (B) is further contained preferably in the adhesive composition.
As above-mentioned crosslinking agent (B), for example, can enumerate:Isocyanates system crosslinking agent, epoxy crosslinking agent, aziridine system Crosslinking agent, oxazolines system crosslinking agent, melamine series crosslinking agent, aldehyde system crosslinking agent, amine system crosslinking agent.Among these, from raising Heat-resistant adhesive film sets out with the aspect of the adaptation of base material and the reactive aspect of base polymer, is adapted to use isocyanide Acid esters system crosslinking agent.
As above-mentioned isocyanates system crosslinking agent, for example, can enumerate:2,4 toluene diisocyanate, 2,6- toluene two are different Cyanate, HTDI, 1,3- XDIs, 1,4- XDIs, Double (the isocyanic acids of hexamethylene diisocyanate, diphenyl methane -4,4- diisocyanate, IPDI, 1,3- Root close methyl) hexamethylene, tetramethylxylylene diisocyanate, 1,5- naphthalene diisocyanates, the isocyanide of triphenyl methane three The adduct of polyol compound, these many isocyanides such as acid esters and their polyisocyanate compound and trimethylolpropane Biuret body, isocyanuric acid ester body of ester compound etc..
Among these, from heat resistance aspect, the isocyanuric acid ester body of preferred hexamethylene diisocyanate, 2,4- Adduct, the 2,4- toluene diisocynates of toluene di-isocyanate(TDI) and/or 2,6- toluene di-isocyanate(TDI)s and trimethylolpropane The isocyanuric acid ester body of ester and/or 2,6- toluene di-isocyanate(TDI)s, tetramethylxylylene diisocyanate and trihydroxy methyl The adduct of propane.
As above-mentioned epoxy crosslinking agent, for example, can enumerate:The epoxy resin of bisphenol A/epichlorohydrin type, second two Alcohol diglycidyl ether, polyethyleneglycol diglycidylether, glycerin diglycidyl ether, T 55,1,6- oneself Hexanediol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, d-sorbite polyglycidyl ether, polyglycereol bunching water are sweet Oily ether, pentaerythrite poly epihydric alcohol erythrite, diglycerol polyglycidyl ether, 1,3 '-bis- (N, N- 2-glycidyl amino first Base) hexamethylene, N, N, N ', N '-four glycidyl group-m-xylene diamine etc..
As above-mentioned aziridine system crosslinking agent, for example, can enumerate:- the β of tetramethylol methane-three-aziridinyl propionic ester, - the β of trimethylolpropane-three-aziridinyl propionic ester, N, N '-diphenyl methane -4,4 '-bis- (1- aziridine formamides), N, N '-hexa-methylene -1,6- double (1- aziridine formamides) etc..
As Shang Shu oxazolines system crosslinking agent, for example, can enumerate:Double (the 2- oxazoles of 2,2 '-bis- (2- oxazolines), 1,2- Quinoline -2- bases) ethane, double (2- oxazoline -2- bases) butane of 1,4-, double (2- oxazoline -2- bases) butane of 1,8-, double (the 2- Evil of 1,4- Oxazoline -2- bases) hexamethylene, double (2- oxazoline -2- bases) benzene of 1,2-, double (2- oxazoline -2- bases) benzene of 1,3- etc. includes aliphatic Or aromatic bisoxazoline compounds, 2- vinyl -2- oxazolines, 2- vinyl -4- methyl -2- oxazolines, 2- vinyl - 5- methyl -2- oxazolines, 2- isopropenyl -2- oxazolines, 2- isopropenyl -4- methyl -2- oxazolines, 2- isopropenyl -5- Addition polymerization oxazoline such as ethyl-2-oxazoline etc..
As above-mentioned melamine series crosslinking agent, for example, can enumerate:HMMM, six (ethoxymethyl)s Base melamine, six propoxy methyl melamines, six butoxymethyl melamines, six amoxy methyl melamines, six Hexoxymethyl melamine, melmac etc..
As above-mentioned aldehyde system crosslinking agent, for example, can enumerate:Glyoxal, MDA, butanedial, maleic dialdehyde, glutaraldehyde, Formaldehyde, acetaldehyde, benzaldehyde etc..
As above-mentioned amine system crosslinking agent, for example, can enumerate:Hexamethylene diamine, triethylenediamine, polyethyleneimine, Hexa, diethylenetriamines, trien, IPD, amino resins, polyamide etc..
In addition, these crosslinking agents (B) can be used alone and can also be applied in combination two or more.
The content of above-mentioned crosslinking agent (B) is commonly angled relative to the weight portion of acrylic resin (A) 100, usually 0.1~30 weight Amount part, preferably 0.5~20 weight portion, particularly preferably 1~15 weight portion.When crosslinking agent (B) is very few, there is the aggregation of adhesive Power is reduced, tendency the reason for become cull, and when excessive, the crosslinking of adhesive is excessively carried out, and bonding force is reduced, therefore, have with The tendency for floating is produced between adherend.
In addition, cross-linking reaction can also be carried out by irradiating active energy beam.In the case of above-mentioned, many officials are preferably compounded Energy (methyl) acrylate, as above-mentioned multifunctional (methyl) acrylate, for example, is adapted to, trimethylolpropane tris (first Base) acrylate, ethylene-oxide-modified trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylic acid Ester, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) propylene (methyl) acrylate more than 3 senses such as poly- (methyl) acrylate of acid esters, glycerine polyglycidyl ether.Need explanation It is that the crosslinking irradiated using active energy beam is preferably used with the cross-linking composition using crosslinking agent.
The present invention adhesive composition be characterised by, do not contain antistatic additive.
" antistatic additive is not contained in the present invention " to typically refer to, be entirely free of antistatic additive, but have adhesive to combine yet Thing contains antistatic additive with the degree without antistatic property, specifically, in adhesive composition, antistatic additive Content can be preferably below 0.1 weight %, below particularly preferably 0.05 weight %, more preferably 0.01 weight % Below.
As above-mentioned antistatic additive, for example, can enumerate:The cation of the quaternary ammonium salts such as imidazole salts, tetra-allkylammonium sulfonate Type antistatic additive;Aliphatic sulfonate, fatty alcohol sulfate salt, higher alcohol alkylene oxide addition product sulfuric acid, higher alcohol phosphoric acid The anionic antistatic agents such as ester salt, higher alcohol alcohol alkylene oxide addition product phosphate ester salt;It is double (fluorosulfonyl) acid imide sylvite, double The alkali metal salts such as (three fluorosulfonyls) acid imide lithium salts, lithium chloride, alkali salt, higher alcohol alkylene oxide addition product, poly- alkylene Base diol fatty acid ester etc..
The adhesive composition of the present invention is in the range of the effect for not damaging the present invention and then can also further contain Antioxidant, plasticizer, filler, pigment, diluent, age resistor, ultra-violet absorber, ultra-violet stabilizer, tackifying resin Deng additive, these additives using a kind or can be applied in combination two or more and use.Particularly antioxidant is to keeping viscous The stability of mixture layer is effective.Content during compounding antioxidant is not particularly limited, preferably 0.01~5 weight %. It should be noted that in addition to additive, it is also possible to the manufacture raw material of the constituent containing a small amount of adhesive composition Contained impurity etc. in.
The adhesive composition of the present invention is preferably using acrylic resin (A) as principal component.Herein " as principal component " Refer to, aforesaid propylene acid resin (A) contains more than usual 50 weight % relative to adhesive composition total amount, preferably 60 weights It is more than amount more than %, more preferably 70 weight %.It should be noted that as the upper limit, usually 99.9 weight %.
In addition, the adhesive composition of the present invention is preferably substantially free of acid, thus, it is possible to reduce the adherend of metal etc. Corrosion." it is substantially free of acid " herein specifically to refer to, acid number is preferably below 5mgKOH/g, is particularly preferably Below 1mgKOH/g, more preferably below 0.1mgKOH/g.
The gel fraction of adhesive obtained from the binder composition cross-links of the present invention is usually 40~100%, is preferably 60~100%, particularly preferably 80~100%, more preferably 90~100%, especially preferably 97~100%.
When gel fraction is too low, the aggregation force for having adhesive reduces, produces cull, becomes inclining the reason for adherend pollutes To.
It should be noted that when the gel fraction of adhesive is adjusted to above range, for example, by the kind for adjusting crosslinking agent Ratio of components of hydroxyl in class and amount, adjustment composition etc. can be reached.In addition, the ratio root of above-mentioned crosslinking agent and amount of functional groups According to respective interaction, gel fraction changes, therefore, balance must be obtained respectively.
Above-mentioned gel fraction becomes the target of the degree of cross linking, thus, for example being calculated using following method.That is, as base material High molecular sheet (for example, pet film etc.) on the bonding sheet for being formed with adhesive phase (is not provided with Separator) coated with the SUS wire nettings of 200 mesh, impregnated with 23 DEG C × 24 hours in toluene, will remain in wire netting Undissolved adhesive ingredients weight percent as gel fraction.Wherein, the weight of base material is deducted.
In addition, when adhesive composition does not contain crosslinking agent (B), for by adhesive composition at 180 DEG C and 5 minutes Under conditions of heated after gel fraction, usually 30%~100%, be preferably 40~100%, particularly preferably 50 ~100%, the gel fraction after being heated at 180 DEG C and under conditions of 1 hour is usually 70%~100%, is preferably 80~100%, particularly preferably 90~100%.When gel fraction is too low after heating, there is gathering for the adhesive under overheated condition Collection power is reduced, produces cull, becomes tendency the reason for adherend pollutes.
In the present invention, shielding film adhesive or the bonding of Heat-resistant adhesive film are prepared by above-mentioned adhesive composition Agent, the stacking on the film as base material forms adhesive phase, such that it is able to obtain shielding film, Heat-resistant adhesive film or masking With Heat-resistant adhesive film (below, also sometime collectively referred to as adhesive film).It should be noted that the adhesive for constituting adhesive phase can With directly using above-mentioned adhesive composition, or the adhesive for carrying out being crosslinked using crosslinking agent (B).
The base material of adhesive phase is formed as stacking, for example, can be enumerated:By metal, polyester based resin, polyvinyl fluoride system The individual layer or the film of stepped construction of the formation such as resin, polyimides and its derivative, epoxy resin.In shielding film, heat-resisting Adhesive film or masking on the face of the base material opposite side with adhesive phase, are preferably further arranged with Heat-resistant adhesive film Release film.By shielding film, Heat-resistant adhesive film or masking with Heat-resistant adhesive film for practicality when, can by it is above-mentioned from Type film is peeled off and used.As above-mentioned release film, it is possible to use:Silicon systems release film, olefin-based release film, fluorine system from Type film, chain alkyl system release film, alkyd system release film.
When manufacturing above-mentioned shielding film, Heat-resistant adhesive film or masking Heat-resistant adhesive film, for making containing crosslinking agent (B) method of binder composition cross-links of the invention, can be carried out by the following method:Method (1), is coated with base material After adhesive composition and drying, release film is pasted, carry out maturation process;Method (2), the coating adhesive in release film After composition and drying, base material is pasted, carry out maturation process.Among these, the aspect of base material, workability, stable is never damaged Set out in terms of manufacture, preferably the method for (2).
Herein, having generally given to the maturation process of the adhesive film of heat resistance needs high-temperature to cure for a long time, but In the present invention, by using aminoalkyl (methyl) acrylamide, such that it is able to be terminated at curing with the lower temperature short time Reason.
Above-mentioned maturation process is carried out to obtain the balance of bonding physical property, and used as the condition of curing, temperature is usual For 0~150 DEG C, be preferably 10~100 DEG C, particularly preferably 20~80 DEG C, the time be usually less than 30 days, preferably 14 days with Under, particularly preferably less than 7 days, specifically, for example, can carry out under conditions of 23 DEG C, 3~10 days, 40 DEG C, 1~7 It is carried out under the conditions of waiting.
During coating adhesive composition, preferably will be coated after the adhesive composition solvent dilution, as dilution Concentration, preferably 5~60 weight %, particularly preferably 10~30 weight %.In addition, as above-mentioned solvent, as long as making adhesive Composition dissolving is just not particularly limited, for example, can use:Methyl acetate, ethyl acetate, methyl acetoacetate, acetoacetate The ester series solvents such as ethyl ester;The ketone series solvents such as acetone, MEK, methyl iso-butyl ketone (MIBK);The fragrant family solvent such as toluene, dimethylbenzene; The alcohol series solvents such as methyl alcohol, ethanol, propyl alcohol.Among these, from aspects such as dissolubility, drying property, prices, it is adapted to use acetic acid Ethyl ester, MEK, toluene.
In addition, with regard to the coating of above-mentioned adhesive composition, can be coated with by roller coat, die coating, intaglio plate coating, comma, The conventional method such as serigraphy is carrying out.
The thickness of the adhesive phase in shielding film, Heat-resistant adhesive film or masking Heat-resistant adhesive film is usually 5~ 300 μm, preferably 5~50 μm, particularly preferably 10~30 μm.When the adhesive phase is excessively thin, there is bonding physical property to be difficult to stable Tendency, when blocked up, has adhesive film integrally blocked up, the tendency that usability is deteriorated.
Shielding film, the Heat-resistant adhesive film or masking adhesive phase of Heat-resistant adhesive film is from loss during 1Hz The glass transition temperature (Tg) of elastic modelling quantity be usually less than 0 DEG C, be preferably less than -30 DEG C, be particularly preferably -45 DEG C with Under.From loss elastic modulus Tg it is too high when, have the tendency of adhesive be hardened, heat after bonding force uprise, when too low, have The tendency that heat-resisting contaminative deteriorates.It should be noted that generally, it is -56 DEG C from the lower limit of the Tg of loss elastic modulus.
Shielding film, the Heat-resistant adhesive film or masking adhesive phase of Heat-resistant adhesive film is from loss during 1Hz The glass transition temperature (Tg) of angle tangent (tan δ) is usually less than 0 DEG C, is preferably less than -15 DEG C, particularly preferably -27 DEG C Below.From tan δ Tg it is too high when, have the tendency of adhesive be hardened, heat after bonding force uprise, when too low, there is heat-resisting dirt The tendency that metachromia deteriorates.It should be noted that generally, it is -40 DEG C from the lower limit of the Tg of loss angle tangent.
The bonding force of the adhesive phase of shielding film, Heat-resistant adhesive film or masking Heat-resistant adhesive film can be according to quilt Material of viscous thing etc. and suitably adjust, for example adhere to SUS-BA plates, through the hard situation for applying PET film, glass for processing etc. Under, Initial adhesion is preferably 0.01~1.0N/25mm, particularly preferably 0.05~0.8N/25mm, is more preferably 0.1 ~0.5N/25mm.
In addition, for the bonding force of above-mentioned adhesive phase, it is heat-resisting after bonding force be preferably 0.01~1.0N/25mm, spy You Xuanwei not 0.05~0.9N/25mm, more preferably 0.1~0.8N/25mm.
The masking Heat-resistant adhesive film of the present invention for example can be used as circuit bases such as temporary transient surface protection FPC substrates Plate, the temporary transient surface protection Heat-resistant adhesive film of ito transparent electrode layer are used, or as in manufacturing process in order to temporarily protect The interim fixation Heat-resistant adhesive film held reinforced article and be used for fixation is used.
By viscous object be adherend as masking Heat-resistant adhesive film, can enumerate it is following shown in materials base Material.
The metallic plate or metal forming of aluminium, copper, iron, stainless steel, magnesium, nickel, titanium etc.;
It is polyethylene terephthalate, PEN, polybutylene terephthalate (PBT), poly- to benzene two The polyester based resins such as formic acid glycol ester/polyethylene glycol isophthalate copolymer, acrylate;
Polyethylene, haloflex, chlorine sulfone polyethylene, ethylene propylene rubber, vinyl-vinyl acetate copolymer, second Alkene-ethyl acrylate copolymer, ethylene isobutyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate The polyolefin-based resins such as copolymer, ionomer, polypropylene, polyaromatic polybutene, polymethylpentene;
The polyvinyl fluoride such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene copolymer system resin;
Polystyrene, poly- α-methylstyrene, acrylonitritrile-styrene resin, acrylonitrile-butadiene-styrene (ABS) copolymerization Thing, acrylonitrile-styrene-acrylic ester copolymer;
Polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, butyl polyacrylate etc. poly- (methyl) Alkyl acrylate, copolymer of methyl methacrylatestyrene, methyl methacrylate-α-methylstyrenecopolymer etc. Acrylic resin;
Polyvinyl chloride, plasticising chlorinated polynvinyl chloride (CPVC), ABS modified polyvinyl chlorides, rear chlorinating polyvinyl chloride, polyvinyl chloride-propylene The polyvinyl chloride such as acid resin alloy, VCP, vinyl chloride vinyl acetate copolymer, polyvinylidene chloride gather Compound and its derivative;
Polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral resin, ethylene vinyl alcohol copolymer The polyvinyl acetate such as thing, vinyl-vinyl acetate copolymer, vinylon and its derivative;
Polyvinyl methyl ether, polyvinyl methyl ketone;
Polyformaldehyde, acetal copolymer, PEO, PPOX, chlorinated polyether, phenoxy resin, polyphenylene oxide etc. Polyethers;
Polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene, tetrafluoraoethylene-hexafluoropropylene copolymer, polyvinylidene fluoride, chlorine trifluoro second The fluoride resins such as alkene-vinylidene fluoride copolymer;
Merlon, polycarbonate/ABS alloy;
Nylon, nylon-6, nylon-6,6, nylon-6/6,6 copolymer, nylon-6,10, nylon-6,12, nylon-11, Buddhist nun Imperial -12 grade nylon (polyamide) classes;
BS, butadiene-based plastics;
Polyimides and its derivative, polysulfones, polyphenylene sulfide, high acrylonitrile copolymer;
Organic siliconresin, half inorganic and inorganic polymer;
The phenolic resin such as phenolic resin, phenolic aldehyde-furfural resin, phenol-formaldehyde resin modified and its derivative;
The formaldehyde resins such as furane resins, xylene resin, anline resin, accton-formalin resin;
Unsaturated polyester (UP) and alkyd resin;
Bisphenol-type epoxy resin, epoxy resin composite material, alicyclic ring epoxide resin, epoxy phenolic varnish, biphenyl type epoxy The epoxy resin such as resin, epoxy acrylate;
The polyurethane such as polyurethane, foaming carbamate, urethane acrylate;
Diallyl phthalate resin, triallyl isocyanurate resin, polyallyl sulfone, allyl diglycol carbon The allyl resins such as acid esters, polyallyl ether, polyarylate;
Cellulosic plastic, cellulose ethanoate, cellulose propionate, cellulose acetate butyrate, ethyl cellulose, The cellulose-based resin such as NC Nitroncellulose and nitrocellulose plastics (celluloid).
Particularly, as the material with heat resistance, can enumerate:The metal of aluminium, copper, iron, stainless steel, magnesium, nickel, titanium etc. Plate or metal forming etc.;It is polyethylene terephthalate, PEN, polybutylene terephthalate (PBT), poly- The polyester based resins such as ethylene glycol terephthalate/polyethylene glycol isophthalate copolymer, acrylate;Poly- fluorination second The polyvinyl fluoride such as alkene, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene copolymer system resin;Polyimides spreads out with it It is biological;Bisphenol-type epoxy resin, epoxy resin composite material, alicyclic ring epoxide resin, epoxy phenolic varnish, biphenyl type epoxy tree Epoxy resin such as fat, epoxy acrylate etc..
As the masking purposes of Heat-resistant adhesive film obtained using the adhesive composition of the present invention, can enumerate: Printed base plate, particularly the operation carrier film such as flexible printed board;For preventing the volume of the film with heating process, paper tinsel Song, wrinkle, the protective film of pollution;Printed base plate soft solder plating protective film;The insulation of resistance to thermoconverter etc. and heat-resisting guarantor Shield film;Masking film in the Reflow Soldering operation of electronic circuit board;Various interim fixations, component protection film; The sealing film of through hole;The purposes such as the surface protective film of the touch panel associated components such as ito transparent electrode layer, can be extensive For needing heat-resisting masking purposes, interim fixed-purpose whole.Particularly preferably made using the adhesive composition of the present invention The masking made Heat-resistant adhesive film.
As the use of Heat-resistant adhesive film of the masking of the invention that manufactures using the adhesive composition of the present invention Method, for example, can enumerate:Comprising in the case of heating process in the manufacturing process of adherend, being glued for heating process will be applied The method that thing temporarily carries out surface protection.For example, as the using method of adherend, it is also possible to possess following operation:By this Bright masking Heat-resistant adhesive film adheres to adherend surface, for usual more than 100 DEG C, preferably more than 120 DEG C, it is especially excellent More than 150 DEG C, further preferred more than 170 DEG C of heating process are selected, then from the masking of adherend sur-face peeling with resistance to hot sticky Close film.
The present invention masking with Heat-resistant adhesive film under the high temperature conditions using it is rear, from adherend peel off when on adherend The pollution of cull etc. is not likely to produce, therefore, it can reduce the possibility of the pollution in the manufacturing process of adherend.In addition, this Bright masking Heat-resistant adhesive film under the high temperature conditions stripping after use when can be peeled off with little power, therefore, it can prevent The only breakage on adherend surface, for example, can prevent the breakage of the films such as ito transparent electrode layer.Further, masking of the invention is used Heat-resistant adhesive film is not likely to produce corrosion in the adherend of metal, accordingly it is also possible to reduce producing bad feelings in end article The possibility of condition.
Embodiment
Hereinafter, enumerate embodiment to further illustrate the present invention, but the present invention without departing from its purport just not It is defined in below example.It should be noted that " % " and " part " refers to weight basis in example.In addition, glass transition temperature Degree (Tg) is measured according to the method described above.
The manufacture > of < acrylic resins (A) solution
(Production Example 1:Acrylic resin (A-1))
The middle input ethyl acetate 119 in the reactor for possessing thermometer, mixer, dropping funel and reflux condenser 0.01 part of part, 34.8 parts of acetone and azodiisobutyronitrile (AIBN), warming while stirring after reaching 70 DEG C, was added dropwise with 2 hours Mixed dissolution has ethoxydiglycol acrylate (Kyoeisha Chemical Co., Ltd.'s system, trade name " Light acrylate EC-A ", EO number of repeat unit 2) (a1) 20 parts, (a2) 73.8 parts of butyl acrylate (BA), methyl methacrylate (MMA) (a2) 1 part, (a3) 5 parts of 2-hydroxyethyl methacrylate (HEMA), dimethylaminopropylacryl acid amides (DMAPAA) (a4) 0.2 part and the mixture of 0.026 part of azodiisobutyronitrile (AIBN).Further, in polymerization midway, side adds successively ethyl acetate 2 The polymerization catalyzed liquid side of AIBN0.060 parts is dissolved with aforementioned temperature and make its polymerase 17 hour, Ran Houyong under reflux in part Diluted ethyl acetate, obtains 35% solution of acrylic resin (A-1).
(Production Example 2~20)
With the formula shown in table 1 and Production Example 1 be prepared as acrylic resin (A-2)~(A-12), (A ' -1)~ The solution of (A ' -8).
[table 1]
·ECA:Ethoxydiglycol acrylate (Kyoeisha Chemical Co., Ltd.'s system, trade name " Light Acrylate EC-A ", EO number of repeat unit 2)
·2MTG:Methoxy triethylene acrylate (Osaka Organic Chemical Industry Co., Ltd.'s system, trade name " Viscoat MTG ", EO number of repeat unit 3)
·AME400:Methoxy polyethylene glycol acrylate (Japan Oil Co's system, trade name " BLEMMER AME400 ", EO number of repeat unit 9)
·2MEA:(Osaka organises length of schooling, trade name " 2-MTA ", EO chain repetitives methoxyl group EDIA Number 1)
·BA:Butyl acrylate
·2EHA:2-EHA
·MMA:Methyl methacrylate
·HEMA:2-hydroxyethyl methacrylate
·AAc:Acrylic acid
·DMAPAA:Dimethylaminopropylacryl acid amides
·BMAA:N- (n-butoxy methyl) acrylamide (Kasano Kosan Co., Ltd systems, trade name " AMIDO NBM-2”
< embodiments 1~12, the > of comparative example 1~8
(preparation of adhesive composition)
For acrylic resin (A-1)~(A-11), (A ' -1) that obtain in Production Example 1~11, Production Example 13~19 100 parts of the solid constituent of~(A ' -7), is compounded as described in Table 2 crosslinking agent (the B-1) (isocyanates of TOSOH Co., Ltd It is crosslinking agent, " CORONATE HX "), prepare adhesive composition.
In addition, for 100 parts of the solid constituent of the acrylic resin (A-12), (A ' -8) obtained in Production Example 12,20, As described in Table 2 crosslinking agent (B-2) (the epoxy crosslinking agent of Mitsubishi Gas Chemical Co., Ltd, " TETRAD are compounded like that C "), prepare adhesive composition.
(determining the making with the adhesive film of heat-resisting contamination evaluating for bonding force)
Coat as base material in the way of the adhesive composition of above-mentioned middle preparation is about into 25 μm using dried thickness Kapton (25 μm of thickness) after, make at 100 DEG C its be dried 2 minutes.Afterwards, attach through release in coated side The PET of process, protects coated side, cures 7 days under the atmosphere of 40 DEG C of temperature, obtains adhesive film.
Use gained adhesive film, carries out following evaluations, and its result is summarized in into table 2.
(bonding force:After just pasting)
Under 23 DEG C, the atmosphere of relative humidity 50%, with the reciprocal 2 above-mentioned bondings by 25mm × 100mm of 2kg rubber rollers Film pressurization is pasted on the corrosion resistant plate (SUS304BA plates) as adherend, after placing 30 minutes under same atmosphere, with Peeling rate 300mm/ minutes determine 180 degree peel strength (N/25mm), are evaluated according to following benchmark.
(evaluation)
○:Less than 0.5N/25mm
△:0.5N/25mm is less than 1.0N/25mm
×:1.0N/25mm more than
(bonding force:After heating)
Under 23 DEG C, the atmosphere of relative humidity 50%, with the reciprocal 2 above-mentioned bondings by 25mm × 100mm of 2kg rubber rollers Film pressurization is pasted on the corrosion resistant plate (SUS304BA plates) as adherend, after placing 30 minutes under same atmosphere, Place 1 hour under the conditions of 200 DEG C, recover to 23 DEG C.After further placing 2 hours under 23 DEG C, the atmosphere of relative humidity 50%, 180 degree peel strength (N/25mm) is determined with peeling rate 300mm/ minutes, is evaluated according to following benchmark.
(evaluation)
○:Less than 0.8N/25mm
△:0.8N/25mm is less than 1.0N/25mm
×:1.0N/25mm more than
(heat-resisting contaminative)
Use gained Heat-resistant adhesive film, makes the test film of (cutting out) 25mm × 100mm sizes, and using making, 2kg rollers are past Multiple 2 times method makes the test film be crimped on adherend (SUS304BA plates), places under the temperature and time described in table 2, extensive Again to 23 DEG C.After further placing 2 hours under 23 DEG C, the atmosphere of relative humidity 50%, observe with peeling rate 300mm/ minutes The situation on the adherend surface after 180 degree stripping is carried out, is evaluated according to following benchmark.
(evaluation)
◎:It is fully validated less than pollution.
○:Basic confirmation is less than pollution.
△:Slightly confirm pollution.
×:Clearly confirm pollution.
(making of elastic modulus detection adhesive film)
Then, the adhesive composition obtained in will be above-mentioned coats Jing in the way of dried thickness is about 150 μm After crossing in the PET base material of release process, it is dried at normal temperatures 5 minutes, afterwards, it is dried at 80 DEG C 5 minutes.It Afterwards, attach the PET through release process in coated side, protect coated side, cure 7 days under the atmosphere of 40 DEG C of temperature, obtain Determination of viscoelasticity adhesive film.
Use gained determination of viscoelasticity carries out following evaluations with adhesive film, and its result is summarized in into table 2.
(glass transition temperature of adhesive phase)
Determination of viscoelasticity device (IT measures the DVA-255 of control Co., Ltd. manufacture), in the case where frequency 1Hz is determined, to rise 3 DEG C/min of warm speed, 200 DEG C are warming up to by determination of viscoelasticity adhesive film from -100, simultaneously continuously determine loss elasticity Modulus.Loss elastic modulus is changed into highest temperature as the glass transition temperature from loss elastic modulus.In addition, will Loss angle tangent (tan δ) is changed into highest temperature as the glass transition temperature from loss angle tangent (tan δ).
[table 2]
For the adhesive film of embodiment 1~12, it is known that, the bonding force after just pasting surely not becomes too much, Will not also become too much using rear bonding force at 200 DEG C, under the hot conditions of 1 hour etc, can be with little power from adherend Peel off, pollution is not likely to produce when peeling off from adherend in addition.
On the other hand, for do not contain in the copolymer composition for constituting acrylic resin (A) limit in the present invention containing poly- The monomer (a1) of oxygen ethylidene structure or its poor comparative example 1~6,8, it is known that, although the bonding force after just pasting is not Can be excessive, but become too much using rear bonding force under the high temperature conditions, it is difficult to peeled off from adherend with little power.In addition, right The excessive comparative example 7 of the content of the monomer (a1) containing polyoxyethylene structure of restriction in the present invention, it is known that, although in high temperature Under the conditions of the rear bonding force of use will not also become too much, but pollution is clearly confirmed when peeling off from adherend, adherend is dirty Dye is big.
Industrial applicability
The adhesive composition of the present invention can be suitable for being touched in the circuit substrates such as FPC substrates, ito transparent electrode etc. The masking for being used to be covered, be fixed in included heating process in the manufacturing process of panel associated components is thin with Heat-resistant adhesive Film.

Claims (13)

1. a kind of adhesive composition, it is characterised in that containing acrylic resin (A),
The acrylic resin (A) has the construction unit for being derived from the monomer (a1) containing polyoxyethylene structure and from (first Base) alkyl acrylate system monomer (a2) construction unit,
It is 10~45 weight % from the content of the construction unit of the monomer (a1) containing polyoxyethylene structure,
Described adhesive composition does not contain antistatic additive.
2. a kind of adhesive composition, it is characterised in that containing acrylic resin (A),
The acrylic resin (A) is by containing the monomer (a1) containing polyoxyethylene structure and (methyl) acrylic acid alkyl Obtained from the copolymer composition copolymerization of ester system monomer (a2),
The content of the monomer (a1) containing polyoxyethylene structure in copolymer composition is 10~45 weight %,
Described adhesive composition does not contain antistatic additive.
3. adhesive composition according to claim 1 and 2, it is characterised in that the monomer containing polyoxyethylene structure (a1) it is (methyl) the acrylic ester monomer containing polyoxyethylene structure.
4. the adhesive composition according to any one of claims 1 to 3, it is characterised in that structure containing polyoxyethylene Monomer (a1) oxygen ethylidene chain number of repeat unit be 2~20.
5. the adhesive composition according to any one of claim 2~4, it is characterised in that copolymer composition is included:Containing hydroxyl Base monomer and/or carboxyl group-containing monomer.
6. the adhesive composition according to any one of claim 2~5, it is characterised in that copolymer composition contains (first Base) acrylamide monomer.
7. the adhesive composition according to any one of claim 1~6, it is characterised in that acrylic resin (A) Weight average molecular weight is 100,000~2,500,000.
8. the adhesive composition according to any one of claim 1~7, it is characterised in that also containing crosslinking agent (B).
9. a kind of adhesive, it is characterised in that it is obtained from the binder composition cross-links described in claim 8.
10. a kind of shielding film adhesive, it is characterised in that comprising the adhesive described in claim 9.
11. a kind of Heat-resistant adhesive film adhesives, it is characterised in that comprising the adhesive described in claim 9.
Heat-resistant adhesive film is used in a kind of 12. maskings, it is characterised in that had comprising the bonding described in claim 9 on film The adhesive phase of agent.
13. a kind of masking usings method of Heat-resistant adhesive film, it is characterised in that by the masking described in claim 12 with resistance to Heat bonding film adheres to adherend surface, for more than 100 DEG C heating processes, then by masking Heat-resistant adhesive film From adherend sur-face peeling.
CN201580044360.4A 2014-08-18 2015-08-17 Adhesive composition makes adhesive, shielding film adhesive, Heat-resistant adhesive film adhesive, masking Heat-resistant adhesive film and its application method made of its crosslinking Active CN106574161B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2014-165780 2014-08-18
JP2014165780 2014-08-18
PCT/JP2015/073056 WO2016027787A1 (en) 2014-08-18 2015-08-17 Adhesive composition, adhesive obtained by crosslinking same, adhesive for masking films, adhesive for heat-resistant adhesive films, heat-resistant adhesive film for masking, and method for using heat-resistant adhesive film for masking

Publications (2)

Publication Number Publication Date
CN106574161A true CN106574161A (en) 2017-04-19
CN106574161B CN106574161B (en) 2019-06-14

Family

ID=55350731

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201580044360.4A Active CN106574161B (en) 2014-08-18 2015-08-17 Adhesive composition makes adhesive, shielding film adhesive, Heat-resistant adhesive film adhesive, masking Heat-resistant adhesive film and its application method made of its crosslinking

Country Status (5)

Country Link
JP (1) JP6996834B2 (en)
KR (1) KR20170043619A (en)
CN (1) CN106574161B (en)
TW (1) TWI668284B (en)
WO (1) WO2016027787A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111117513A (en) * 2019-12-31 2020-05-08 浙江福莱新材料股份有限公司 Preparation method of efficient environment-friendly base-paper-free protective adhesive tape
CN111117512A (en) * 2019-12-31 2020-05-08 浙江福莱新材料股份有限公司 Easy-to-peel base-paper-free cold mounting protective film
CN112680142A (en) * 2019-10-17 2021-04-20 Dic株式会社 Adhesive composition, adhesive layer and protective film

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6548347B2 (en) * 2016-02-25 2019-07-24 株式会社寺岡製作所 Adhesive composition and adhesive tape
JP6827670B2 (en) * 2016-09-30 2021-02-10 日本カーバイド工業株式会社 Adhesive composition for optical member protective film and optical member protective film
JP6915291B2 (en) * 2017-02-14 2021-08-04 東洋インキScホールディングス株式会社 Surface protection adhesive and surface protection sheet
JPWO2018181550A1 (en) * 2017-03-29 2020-02-13 住化積水フィルム株式会社 Plating process transport tape base material and plating process transport tape
JP7091610B2 (en) * 2017-05-31 2022-06-28 昭和電工マテリアルズ株式会社 Surface protective film and surface protective film
US11203704B2 (en) 2018-03-21 2021-12-21 3M Innovative Properties Company High temperature resistant masking adhesive composition
JP7077091B2 (en) * 2018-03-23 2022-05-30 リンテック株式会社 Adhesive film
JP7132004B2 (en) * 2018-07-17 2022-09-06 リンテック株式会社 masking sheet
KR102627581B1 (en) * 2018-08-08 2024-01-23 린텍 가부시키가이샤 Method for manufacturing a semiconductor device having a terminal protection tape and an electromagnetic shielding film
WO2021075188A1 (en) * 2019-10-15 2021-04-22 綜研化学株式会社 Adhesive agent composition and adhesive sheet

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH059449A (en) * 1991-06-28 1993-01-19 Toyo Ink Mfg Co Ltd Rereleasable self-adhesive composition
JP2008280375A (en) * 2007-05-08 2008-11-20 Soken Chem & Eng Co Ltd Pressure-sensitive adhesive composition for surface-protective film
JP2011127052A (en) * 2009-12-21 2011-06-30 Ipposha Oil Industries Co Ltd Pressure-sensitive adhesive composition for surface protecting sheet and surface protecting sheet
CN102791817A (en) * 2010-03-18 2012-11-21 积水化学工业株式会社 Pressure-sensitive adhesive composition for optical members and pressure-sensitive adhesive tape for optical members

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101208403B (en) * 2005-06-24 2011-06-29 东洋油墨制造株式会社 Antistatic acrylic pressure-sensitive adhesive
JP4942171B2 (en) * 2006-09-14 2012-05-30 綜研化学株式会社 Adhesive composition and adhesive sheet
WO2010050527A1 (en) * 2008-10-31 2010-05-06 日本合成化学工業株式会社 Adhesive for optical members, optical member having adhesive layer obtained using the same, and adhesive composition for active energy beam-setting and/or thermosetting optical member
KR20120076817A (en) * 2010-12-30 2012-07-10 주식회사 엘지화학 Pressure sensitive adhesive for protective film having anti-static property
JP5934158B2 (en) * 2013-08-28 2016-06-15 藤森工業株式会社 Electrical insulating pressure-sensitive adhesive layer, electrical insulating pressure-sensitive adhesive film, and optical member on which it is bonded

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH059449A (en) * 1991-06-28 1993-01-19 Toyo Ink Mfg Co Ltd Rereleasable self-adhesive composition
JP2008280375A (en) * 2007-05-08 2008-11-20 Soken Chem & Eng Co Ltd Pressure-sensitive adhesive composition for surface-protective film
JP2011127052A (en) * 2009-12-21 2011-06-30 Ipposha Oil Industries Co Ltd Pressure-sensitive adhesive composition for surface protecting sheet and surface protecting sheet
CN102791817A (en) * 2010-03-18 2012-11-21 积水化学工业株式会社 Pressure-sensitive adhesive composition for optical members and pressure-sensitive adhesive tape for optical members

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112680142A (en) * 2019-10-17 2021-04-20 Dic株式会社 Adhesive composition, adhesive layer and protective film
CN111117513A (en) * 2019-12-31 2020-05-08 浙江福莱新材料股份有限公司 Preparation method of efficient environment-friendly base-paper-free protective adhesive tape
CN111117512A (en) * 2019-12-31 2020-05-08 浙江福莱新材料股份有限公司 Easy-to-peel base-paper-free cold mounting protective film

Also Published As

Publication number Publication date
CN106574161B (en) 2019-06-14
JP6996834B2 (en) 2022-01-17
JPWO2016027787A1 (en) 2017-06-01
KR20170043619A (en) 2017-04-21
TWI668284B (en) 2019-08-11
WO2016027787A1 (en) 2016-02-25
TW201612277A (en) 2016-04-01

Similar Documents

Publication Publication Date Title
CN106574161A (en) Adhesive composition, adhesive obtained by crosslinking same, adhesive for masking films, adhesive for heat-resistant adhesive films, heat-resistant adhesive film for masking, and method for using heat-resistant adhesive film for masking
CN107828354B (en) Adhesive for flexible display, adhesive sheet, flexible laminate member, and flexible display
JP5422091B2 (en) Antistatic acrylic adhesive
KR101702694B1 (en) Thermosetting adhesive composition, thermosetting adhesive sheet, method for producing same, and reinforced flexible printed wiring board
CN107325740B (en) Adhesive composition and adhesive sheet
JP2009221324A (en) Pressure-sensitive adhesive for optical member and protection film for optical member using the same
WO2016076356A1 (en) Thermosetting adhesive composition and thermosetting adhesive sheet
KR20130094724A (en) Acrylic resin solution, acrylic adhesive compositon, acrylic adhesive, adhesive sheet, acrylic adhesive for optical member, and optical member with adhesive layer
TWI680171B (en) Adhesive composition and adhesive sheet
JP6279316B2 (en) Method for producing acrylic resin for heat-resistant adhesive film
JP7173254B2 (en) thin adhesive tape
JP2007100041A (en) Pressure-sensitive adhesive and pressure-sensitive adhesive sheet obtained using the same
JP2013032504A (en) Adhesive composition for heat-resistant adhesive film, adhesive for heat-resistant adhesive film produced by crosslinking the same, and use for the adhesive
TWI415918B (en) Adhesive composition for optical film protective sheet and protective film for optical film
JP6309404B2 (en) Adhesive composition and adhesive sheet
JP2014058679A (en) Antistatic acrylic adhesive
CN108699416A (en) Adhesion agent composition and adhesive tape
TWI762468B (en) Adhesive composition and adhesive sheet
JP6701727B2 (en) Adhesive composition, adhesive obtained by crosslinking this, adhesive for masking film, adhesive for heat resistant adhesive film, heat resistant adhesive film for masking
JP2007138015A (en) Adhesive and adhesive sheet using the same
JP2008038103A (en) Heat-resistant pressure-sensitive adhesive composition
TWI815939B (en) Adhesive compositions and adhesive tapes
CN113831870A (en) Adhesive, preparation method thereof and adhesive sheet
JP2023002058A (en) Adhesive composition, adhesive layer, and adhesive film
JP6686830B2 (en) Pressure-sensitive adhesive composition, pressure-sensitive adhesive obtained by crosslinking the same, pressure-sensitive adhesive for masking film, heat-resistant pressure-sensitive adhesive film for masking, and method of using heat-resistant pressure-sensitive adhesive film for masking

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
TA01 Transfer of patent application right
TA01 Transfer of patent application right

Effective date of registration: 20190520

Address after: Tokyo, Japan, Japan

Applicant after: Mitsubishi Kasei Corporation

Address before: Osaka Japan

Applicant before: The Nippon Synthetic Chemical Industry Co., Ltd.

GR01 Patent grant
GR01 Patent grant