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 PDFInfo
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives 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
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives 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
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives 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
- C09J133/24—Homopolymers or copolymers of amides or imides
- C09J133/26—Homopolymers or copolymers of acrylamide or methacrylamide
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/31—Applications of adhesives in processes or use of adhesives in the form of films or foils as a masking tape for painting
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- 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
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.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014165780 | 2014-08-18 | ||
| JP2014-165780 | 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
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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)
| 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 |
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|---|---|---|---|---|
| KR102422205B1 (en) * | 2016-02-25 | 2022-07-18 | 가부시키가이샤 데라오카 세이사쿠쇼 | 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 |
| WO2018181550A1 (en) * | 2017-03-29 | 2018-10-04 | 住化積水フィルム株式会社 | Plating process conveyance tape base material, and plating process conveyance 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 |
| CN111902510B (en) | 2018-03-21 | 2022-07-15 | 3M创新有限公司 | 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 |
| JP7301053B2 (en) * | 2018-08-08 | 2023-06-30 | リンテック株式会社 | Terminal protection tape and method for manufacturing semiconductor device with electromagnetic wave shielding film |
| JPWO2021075188A1 (en) * | 2019-10-15 | 2021-04-22 |
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- 2015-08-17 KR KR1020177007505A patent/KR20170043619A/en unknown
- 2015-08-17 JP JP2015540945A patent/JP6996834B2/en active Active
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| JP2008280375A (en) * | 2007-05-08 | 2008-11-20 | Soken Chem & Eng Co Ltd | Pressure-sensitive adhesive composition for surface-protective film |
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| 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 |
| JPWO2016027787A1 (en) | 2017-06-01 |
| TW201612277A (en) | 2016-04-01 |
| KR20170043619A (en) | 2017-04-21 |
| TWI668284B (en) | 2019-08-11 |
| JP6996834B2 (en) | 2022-01-17 |
| WO2016027787A1 (en) | 2016-02-25 |
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