CN103597047A - Removable adhesive tape and manufacturing method thereof - Google Patents

Removable adhesive tape and manufacturing method thereof Download PDF

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Publication number
CN103597047A
CN103597047A CN201280029268.7A CN201280029268A CN103597047A CN 103597047 A CN103597047 A CN 103597047A CN 201280029268 A CN201280029268 A CN 201280029268A CN 103597047 A CN103597047 A CN 103597047A
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CN
China
Prior art keywords
methyl
adhesive tape
peeling
bonding
self adhesive
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Pending
Application number
CN201280029268.7A
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Chinese (zh)
Inventor
东昌嗣
诸石裕
藤田茂
井上彻雄
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Nitto Denko Corp
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Nitto Denko Corp
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Publication of CN103597047A publication Critical patent/CN103597047A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • 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
    • C09J7/22—Plastics; Metallised plastics
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
    • C08G2261/12—Copolymers
    • C08G2261/128—Copolymers graft
    • 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
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • 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
    • C09J2451/00—Presence of graft polymer
    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • 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
    • C09J2477/00—Presence of polyamide
    • C09J2477/006—Presence of polyamide in the substrate
    • 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
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate
    • 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
    • C09J2481/00—Presence of sulfur containing polymers
    • C09J2481/006—Presence of sulfur containing polymers in the substrate

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Graft Or Block Polymers (AREA)
  • Laminated Bodies (AREA)

Abstract

Provided is a removable adhesive tape which has with excellent heat resistance and little increase in adhesive force during removal, and which leaves no adhesive residue or contamination on the adhered. This removable adhesive tape is formed from a heat-resistant film substrate and a cured adhesive layer on one surface of said heat-resistant film substrate, wherein the cured adhesive layer is formed by photo-curing an adhesive layer formed from an adhesive composition containing 0.15-4.0 parts by weight of a photo-cationic polymerization initiator per 100 parts by weight of a graft polymer formed by graft polymerization of chains containing cyclic ether group-containing monomers onto a (meth)acrylic polymer.

Description

Peel off again by self adhesive tape and manufacture method thereof
Technical field
The present invention relates to peel off again by self adhesive tape and manufacture method thereof.More specifically, relate to the peeling off again by self adhesive tape and manufacture method thereof of, thermotolerance pollution-free to adherend and releasable excellence.
Background technology
In electronics, used various substrates, wiring substrate, carry out to parts on substrate install, lead frame is made, when scolding tin processing, heat treated, take that to protect electronic unit, circuit be object, uses masking tape.While using in this case, exist as follows and require: while attaching masking tape in operation without float etc. and when peeling off after heating process etc. bonding force rising less, to adherend without cull, pollution.
For such requirement, various schemes have been proposed.A kind of heat-resisting peeling off again with self adhesive tape for example proposed, it is provided with the crosslinked binder layer forming of acrylic polymers on thermotolerance backing rete, described acrylic polymers forms (patent documentation 1) by (methyl) glycidyl acrylate and (methyl) acrylic acid copolymer, and then, disclose a kind of tackiness agent, it is to the acrylic polymers forming containing carboxylic monomer copolymerization is cross-linked and is formed with epoxies linking agent.(patent documentation 2)
Prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2005-53975 communique
Patent documentation 2: Japanese kokai publication hei 5-163468 communique
Summary of the invention
the problem that invention will solve
The object of the present invention is to provide a kind of peeling off again with self adhesive tape, in its various operations after attaching, do not produce the cementability that floats etc. and the rising of the bonding force in heating process less and on adherend without the excellent heat resistance of cull, pollution etc.
for the scheme of dealing with problems
The inventor etc. have carried out repeatedly deep discussion in order to solve aforementioned problems, found that following peeling off again with self adhesive tape, thereby have completed the present invention.
That is, the present invention relates to a kind of peeling off again with self adhesive tape, its be possess heat-resistant film base material and the curing bonding bond layer that arranges on the one side of this heat-resistant film base material peel off again use self adhesive tape,
This solidifies bonding bond layer and forms for the bonding bond layer being formed by bonding adhesive composite is carried out to photocuring, described bonding adhesive composite contains 0.15～4.0 weight part light cationic polymerization starter in 100 weight part graftomer, and described graftomer is that the chain that graft polymerization comprises containing ring-type ether monomer to (methyl) acrylic polymers forms.
Preferably, aforementioned adhesion adhesive composite also contains isocyanates linking agent.
Aforementioned adhesion adhesive composite can also contain 5～100 weight part epoxy resin and/or oxetane resins with respect to the aforementioned graftomer of 100 weight part.
Preferably, this gel fraction that solidifies bonding bond layer is 80～99%.
Above-mentioned (methyl) acrylic polymers, with respect to this (methyl) acrylic polymers total amount, can contain 0.2～10 % by weight hydroxyl monomer as monomeric unit.
Above-mentioned graftomer can be by under the existence of 0.02～5 weight part superoxide, makes that 2～50 weight parts are aforementioned to be obtained containing other monomer-grafted of ring-type ether monomer and 5～50 weight parts is aggregated on 100 weight parts aforementioned (methyl) acrylic polymers.
Above-mentioned smooth cationic polymerization starter can be light acid producing agent.
Preferably, aforementioned light acid producing agent is using vinyl acetic monomer as solvent and while being adjusted into 10% concentration, and sediment-free ground dissolves.
Storage modulus at 23 ℃ of above-mentioned curing bonding bond layer can be 9.0 * 10 4～1.0 * 10 6pa.
The group that above-mentioned heat-resistant film base material can select free polyethylene terephthalate, polyimide, aromatic poly amide, PEN and polyphenylene sulfide to form.
The thickness of above-mentioned bonding bond layer can be 0.5～100 μ m.
The invention still further relates to a kind of manufacture method of peeling off again with self adhesive tape, described peeling off again arranges curing bonding bond layer and forms on the one side of heat-resistant film base material with self adhesive tape,
Described manufacture method comprises following operation:
Bonding adhesive composite be coated on the one side of heat-resistant film base material and form the operation of bonding bond layer, described bonding adhesive composite contains 0.15～4.0 weight part light cationic polymerization starter in 100 weight part graftomer, and described graftomer is that the chain that graft polymerization comprises containing ring-type ether monomer to (methyl) acrylic polymers forms; With
This bonding bond layer is carried out to the operation that rayed makes its photocuring.
the effect of invention
Of the present invention peel off again can be for electronic circuit board with self adhesive tape cover with self adhesive tape, electronic unit temporary fixed with self adhesive tape etc.Excellent heat resistance, have the degree of not floating in various operations etc. cementability, without the cementability in heating process rise, especially owing to thering is acrylic adhesives, can not adhere to be considered to cause low molecular contaminants that the contact of electronic circuit is bad, excellent peeling off again use self adhesive tape.
Embodiment
The curing bonding bond layer that possesses heat-resistant film base material and arrange on the one side of this heat-resistant film base material with self adhesive tape of peeling off again of the present invention.Herein, solidifying bonding bond layer is the bonding bond layer being formed by bonding adhesive composite to be carried out to photocuring form, described bonding adhesive composite contains 0.15～4.0 weight part light cationic polymerization starter in 100 weight part graftomer, and described graftomer is that the chain that graft polymerization comprises containing ring-type ether monomer to (methyl) acrylic polymers forms.
First, the monomeric unit comprising as (methyl) acrylic polymers, can be used arbitrarily (methyl) acrylate, and there is no particular limitation.Preferably, for example, contain (methyl) alkyl acrylates with more than 4 alkyl of carbonatoms more than 50 overall % by weight of (methyl) acrylic polymers herein.
In this manual, during referred to as " (methyl) alkyl acrylate ", refer to (methyl) acrylate of the alkyl with straight chain or side chain.The carbonatoms of aforesaid alkyl is more than 4, is preferably carbonatoms 4～9.It should be noted that, (methyl) acrylate refers to acrylate and/or methacrylic ester, and " (methyl) " of the present invention has same meaning.
Object lesson as (methyl) alkyl acrylate, can list (methyl) n-butyl acrylate, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid n-pentyl ester, (methyl) vinylformic acid isopentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) vinylformic acid isopentyl ester, (methyl) ethyl acrylate, (methyl) vinylformic acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) vinylformic acid ester in the positive ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the positive last of the ten Heavenly stems, (methyl) isodecyl acrylate, (methyl) vinylformic acid dodecyl ester, the different myristin of (methyl) vinylformic acid, (methyl) vinylformic acid n-tridecane base ester, (methyl) vinylformic acid n-tetradecane base ester, (methyl) stearyl acrylate ester, the different stearyl ester of (methyl) vinylformic acid etc.Wherein, example (methyl) n-butyl acrylate, (methyl) ethyl acrylate etc. especially, they can be used alone or in combination.
In the present invention, aforementioned (methyl) alkyl acrylate is more than 50 % by weight with respect to whole monomer components of (methyl) acrylic polymers, more than being preferably 80 % by weight, more preferably more than 90 % by weight.In addition, also all monomer is all (methyl) alkyl acrylate, be preferably below 98 % by weight, and can be also below 97 % by weight.
In (methyl) of the present invention acrylic polymers, be preferably also included in addition the hydroxyl monomer that contains at least one hydroxyl in alkyl.That is, this monomer is to comprise 1 monomer of the hydroxyalkyl of hydroxyl above.Herein, hydroxyl is preferably present in the end of alkyl.The carbonatoms of alkyl is preferably 4～12, and more preferably 4～8, more preferably 4～6.Think by comprising such hydroxyl monomer, the consistency containing between the homopolymer of ring-type ether monomer of taking position, the graftomer of hydrogen during to graft polymerization by force and generating when graft polymerization has desirable influence, contributes to prepare the good graftomer of thermotolerance.
As such monomer, can be not particularly limited to use the material that there is the polymerizability functional group of the unsaturated double-bond that comprises (methyl) acryl and there is hydroxyl.Such as listing (methyl) acrylic acid hydroxy alkyl esters such as (methyl) vinylformic acid-2-hydroxyl ethyl ester, (methyl) 2-hydroxypropyl acrylate, (methyl) vinylformic acid-3-hydroxypropyl acrylate, (methyl) vinylformic acid-4-hydroxy butyl ester, the own ester of (methyl) vinylformic acid-6-hydroxyl, (methyl) vinylformic acid-8-hydroxyl monooctyl ester, (methyl) vinylformic acid-10-hydroxyl ester in the last of the ten Heavenly stems, (methyl) vinylformic acid-12-hydroxyl lauryl; (methyl) vinylformic acid-4-methylol cyclohexyl, 4-hydroxy butyl vinyl ether etc.Among them, preferably use (methyl) acrylic acid hydroxy alkyl ester, particularly preferably (methyl) vinylformic acid-2-hydroxyl ethyl ester and (methyl) vinylformic acid-4-hydroxy butyl ester.
Hydroxyl monomer, with respect to the total amount that forms the monomer component of (methyl) acrylic polymers, more than being preferably 0.02 % by weight, more preferably more than 0.05 % by weight, is preferably below 10 % by weight, more preferably below 3 % by weight.Most preferably be 0.05 % by weight～3 % by weight.
Monomer component as forming aforementioned (methyl) acrylic polymers, except aforementioned monomer, can also be used containing unsaturated carboxylic acid monomer.
As containing unsaturated carboxylic acid monomer, can use ad lib and there is the monomer that (methyl) acryl or vinyl etc. have the functional group of unsaturated double-bond and have carboxyl.Monomer as containing unsaturated carboxylic acid, for example, can list (methyl) vinylformic acid, (methyl) vinylformic acid carboxylic ethyl ester, (methyl) vinylformic acid carboxylic pentyl ester, methylene-succinic acid, toxilic acid, fumaric acid, β-crotonic acid etc.They can be used alone or in combination.Preferably use in these (methyl) vinylformic acid, particularly preferably use vinylformic acid.
Monomer containing unsaturated carboxylic acid is preferably used with the ratio of 0.01～2 % by weight with respect to the total amount that forms the monomer component of (methyl) acrylic polymers, 0.05～2 % by weight more preferably, more preferably 0.05～1.5 % by weight, is particularly preferably 0.1～1 % by weight.
Monomer component as forming aforementioned (methyl) acrylic polymers also can be used singly or in combination other comonomer in the scope of not damaging object of the present invention.As other comonomer, such as can list (methyl) acrylate, (methyl) acryl or the vinyl etc. with the alkyl that comprises carbonatoms less than 4 have the functional group of the polymerizability with unsaturated double-bond and have aromatic ring containing aromatic ring monomer.Object lesson as (methyl) acrylate of the alkyl that comprises carbonatoms less than 4, can list (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate etc., as the object lesson containing aromatic ring monomer, can list (methyl) vinylformic acid phenoxy ethyl, (methyl) benzyl acrylate, phenol ring oxidative ethane modification (methyl) acrylate, (methyl) vinylformic acid-2-naphtho-ethyl ester, (methyl) vinylformic acid-2-(4-methoxyl group-1-naphthyloxy) ethyl ester, (methyl) vinylformic acid phenoxy group propyl ester, (methyl) vinylformic acid phenoxy group binaryglycol ester, (methyl) vinylformic acid polystyrene ester etc.
In addition, as other comonomer, can list maleic anhydride, itaconic anhydride etc. containing anhydride group monomer; Acrylic acid caprolactone affixture; Styrene sulfonic acid, allyl sulphonic acid, 2-(methyl) acrylamide-2-methyl propane sulfonic acid, (methyl) acrylamide propane sulfonic acid, (methyl) vinylformic acid sulphur propyl ester, (methyl) acryloxy naphthene sulfonic acid etc. are containing sulfonic group monomer; The phosphorous acid group monomers such as 2-hydroxyethyl acryl phosphoric acid ester; (methyl) alkoxyalkyl acrylate class monomers such as (methyl) vinylformic acid methoxyl group ethyl ester, (methyl) vinylformic acid ethoxy ethyl ester etc.
In addition, can also use the vinyl monomers such as vinyl acetate, propionate, vinylbenzene, alpha-methyl styrene, N-caprolactam; (methyl) glycidyl acrylate, (methyl) vinylformic acid methyl glycidyl ester, (methyl) vinylformic acid 3,4-epoxycyclohexyl methyl esters etc. are containing epoxy group(ing) monomer; The glycols acrylate monomers such as (methyl) polyalkylene glycol acrylate ester, (methyl) vinylformic acid polypropylene glycol ester, (methyl) vinylformic acid methoxyl group glycol ester, (methyl) vinylformic acid methoxyl group polypropylene glycol ester; The acrylic ester monomers such as (methyl) tetrahydrofurfuryl acrylate, fluoro (methyl) acrylate, organosilicon (methyl) acrylate, vinylformic acid 2-methoxyl group ethyl ester; Amide-containing monomer, emulsion stability, containing imide monomer, N-acryloyl morpholine, vinyl ether monomers etc.
The weight-average molecular weight of (methyl) of the present invention acrylic polymers is preferably more than 600,000, more preferably more than 700,000 and below 2,000,000.It should be noted that, weight-average molecular weight refers to utilizes GPC(gel permeation chromatography) value measuring and calculate by polystyrene conversion.
The manufacture of (methyl) acrylic polymers like this can suitably select the known manufacture method such as solution polymerization, mass polymerization, letex polymerization, various radical polymerizations to carry out.In addition, gained (methyl) acrylic polymers can be that random copolymers can be also segmented copolymer.
It should be noted that, in solution polymerization, as polymer solvent, such as using vinyl acetic monomer, toluene etc.Example as concrete solution polymerization adds polymerization starter under the non-active gas air-flows such as nitrogen, under common 50～70 ℃ of left and right, reaction conditions about 5～30 hours, reacts.
The polymerization starter that radical polymerization is used, chain-transfer agent, emulsifying agent etc. can be not particularly limited suitably to select to use.It should be noted that, the weight-average molecular weight of (methyl) acrylic polymers can be controlled according to the consumption of polymerization starter, chain-transfer agent, reaction conditions, according to their kind, suitably adjusts its consumption.
As polymerization starter, for example, can list 2,2 '-Diisopropyl azodicarboxylate, 2, two (2-amidine propane) dihydrochlorides, 2 of 2 '-azo, two [2-(5-methyl-2-tetrahydroglyoxaline-2-yl) propane] dihydrochlorides, 2 of 2 '-azo, two (the 2-methyl-prop amidine) dithionates, 2 of 2 '-azo, two (the N of 2 '-azo, N '-dimethylene isobutyl amidine), 2, (He Guangchun medicine company manufactures two [N-(2-the propyloic)-2-methyl-prop amidine] hydrates of 2 '-azo, the azo-initiator such as VA-057); The persulphate such as Potassium Persulphate, ammonium persulphate; Peroxy dicarbonate two (2-ethylhexyl) ester, peroxy dicarbonate two (4-tert-butylcyclohexyl) ester, peroxide-butyl carbonate, new peroxide tert-butyl caprate, the tertiary own ester of peroxidation PIVALIC ACID CRUDE (25), tert-Butyl peroxypivalate, dilauroyl peroxide, the positive decoyl of peroxidation two, peroxidation-2 ethyl hexanoic acid-1,1,3,3-tetramethyl-butyl ester, peroxidation two (4-toluyl), dibenzoyl peroxide, peroxidation tert-butyl isobutyrate, 1, the peroxide initiators such as 1-bis-(tertiary hexyl peroxy) hexanaphthene, tertbutyl peroxide, hydrogen peroxide; The combination of the combination of persulphate and sodium bisulfite, superoxide and sodium ascorbate etc. by the combination of superoxide and reductive agent and redox class initiator etc., but be not limited to these.
Aforementioned polymerization starter can be used separately, also can mix two or more uses, with respect to monomer component total amount 100 weight parts, is preferably 0.005～1 weight part left and right, more preferably 0.02～0.5 weight part left and right as overall content.
It should be noted that, for example to use 2,2 '-Diisopropyl azodicarboxylate is manufactured (methyl) acrylic polymers of aforementioned weight-average molecular weight as polymerization starter, the consumption of polymerization starter is with respect to total amount 100 weight parts of monomer component, preferably be made as 0.06～0.3 weight part left and right, be further preferably made as 0.08～0.2 weight part left and right.
As chain-transfer agent, for example, can list lauryl mercaptan, glycidyl mercaptan, mercaptoacetic acid, 2 mercapto ethanol, Thiovanic acid, thioglycollic acid-2-ethyl hexyl ester, 2,3-dimercapto-1-propyl alcohol etc.Chain-transfer agent can be used separately also can mix two or more uses, as overall content, is the monomer component of 100 weight parts with respect to total amount, is below 0.1 weight part left and right.
In addition, as the emulsifying agent using when the letex polymerization, such as listing the nonionic class emulsifying agents such as the anionic species emulsifying agents such as Sodium Lauryl Sulphate BP/USP, Texapon Special, Sodium dodecylbenzene sulfonate, polyoxyethylene alkyl oxide ammonium sulfate, polyoxyethylene alkyl phenyl ether sodium sulfate, polyoxyethylene alkyl oxide, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxy propylidene block polymer etc.These emulsifying agents may be used alone, can also be used in combination two or more.
And then, as reactive emulsifier, as the emulsifying agent that has imported the free-radical polymerised functional groups such as propenyl, allyl group ether, particularly, for example have AQUARON HS-10, HS-20, KH-10, BC-05, BC-10, more than BC-20(, be the first industrial drugmaker and manufacture), ADEKAREASOAP SE10N(ADEKA company manufactures) etc.Reactive emulsifier is introduced in polymer chain after polymerization, so water tolerance improvement, is preferred.The consumption of emulsifying agent is the monomer component of 100 weight parts with respect to total amount, is 0.3～5 weight part, from polymerization stability, mechanical stability, and 0.5～1 weight part more preferably.
The second-order transition temperature (Tg) of (methyl) acrylic polymers is, below 250K, to be preferably below 240K.More than second-order transition temperature is also preferably 200K.Second-order transition temperature below 250K, becomes the bonding bonding composition of the good and inner force of cohesion excellence of thermotolerance if.(methyl) acrylic polymers like this can recently be adjusted by suitably changing the monomer component, the composition that use.In addition, such second-order transition temperature for example can be as the acquisition of getting off: by solution polymerization, use the polymerization starters such as 0.06～0.2 part of Diisopropyl azodicarboxylate, benzoyl peroxide and use the polymer solvents such as vinyl acetic monomer, under stream of nitrogen gas, at 50 ℃～70 ℃, make its reaction 8～30 hours, thereby obtain.Herein, second-order transition temperature (Tg) is calculated and is tried to achieve by following FOX formula.
1/Tg=W1/Tg1+W2/Tg2+W3/Tg3+···
Above-mentioned Tg1, Tg2, Tg3 etc. are for representing the numerical value of second-order transition temperature of the homopolymer 1,2,3 etc. of each copolymer composition with absolute temperature, W1, W2, W3 etc. are the weight fraction of each copolymer composition.It should be noted that, the second-order transition temperature of homopolymer (Tg) is from Polymer Handbook(4thedition, John Wiley & Sons.Inc.) obtain.
Then, by (methyl) acrylic polymers obtaining so directly for graft polymerization or by the solution that adds thinner to dilute and obtain for graft polymerization.
As thinner, be not particularly limited, can list vinyl acetic monomer or toluene etc.
Make to react to carry out graft polymerization with (methyl) acrylic polymers and optionally make to react to carry out graft polymerization containing ring-type ether monomer and other monomer with (methyl) acrylic polymers containing ring-type ether monomer.
Herein, to being not particularly limited containing ring-type ether monomer, be preferably containing epoxy group(ing) monomer or oxygen heterocyclic ring butane group monomer or the two combination.
As containing epoxy group(ing) monomer, can exemplify glycidyl acrylate, glycidyl methacrylate, vinylformic acid-3,4-epoxycyclohexyl methyl esters, methacrylic acid-3,4-epoxycyclohexyl methyl esters or vinylformic acid-4-hydroxy butyl ester glycidyl ether etc., these can be used alone or in combination.
As oxygen heterocyclic ring butane group monomer, can exemplify (methyl) vinylformic acid-3-oxetanyl methyl esters, (methyl) vinylformic acid-3-methyl-3-oxetanyl methyl esters, (methyl) vinylformic acid-3-ethyl-3-oxetanyl methyl esters, (methyl) vinylformic acid-3-butyl-3-oxetanyl methyl esters or (methyl) vinylformic acid-3-hexyl-3-oxetanyl methyl esters, these can be used alone or in combination.
More than being preferably 2 weight parts containing the amount of ring-type ether monomer with respect to 100 weight parts (methyl) acrylic polymers, more preferably more than 3 weight parts.To the upper limit, there is no particular limitation, is preferably below 100 weight parts, more preferably below 50 weight parts, more preferably below 30 weight parts.Containing the amount of ring-type ether monomer, if more than 2 weight parts, the function of the bonding caking agent of conduct of composition shows fully, on the other hand, is 100 weight parts when above, and viscosity reduces and initial adhesion is difficult sometimes.
When graft polymerization, can use other monomer that carries out cografting together with containing ring-type ether monomer.As such monomer, so long as not containing the monomer of ring-type ether, be just not particularly limited, can list (methyl) alkyl acrylate of carbonatoms 1～9 etc.As the object lesson of (methyl) alkyl acrylate, can exemplify (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) n-butyl acrylate, ethyl acrylate etc.In addition, also can use (methyl) cyclohexyl acrylate, such ester ring type (methyl) esters of acrylic acid of (methyl) isobornyl acrylate.These may be used singly or in combin.
If use these other monomers that carries out cografting when grafting, can make bonding caking agent easily solidify, for example when photocuring, can reduce the irradiation dose of light, in addition, when thermofixation, can reduce the amount of thermal curing catalyst.Its reason infers it is the mobility raising due to grafted chain, or because grafted chain, the not grafted chain of by-product life and the consistency of trunk polymkeric substance improve.
Other monomer so is also preferably selected from and main chain (trunk) monomer that composition of (methyl) acrylic polymers is identical.
When compounding, containing the amount of the monomer beyond ring-type ether monomer and weight ratio containing ring-type ether monomer in containing ring-type ether monomer: other monomer, is preferably 90:10～10:90,80:20～20:80 more preferably.When the content of other monomer lacks, reduction is sometimes insufficient for the effect of curing photocuring amount, when content is many, and the worry that has the peel resistance after photocuring to increase.
Grafting polymerizing condition is not particularly limited, can be undertaken by method known in those skilled in the art.When polymerization, preferably use superoxide as polymerization starter.
The amount of such polymerization starter, with respect to 100 weight parts (methyl) acrylic polymers, is 0.02～5 weight part.In the few situation of the amount of this polymerization starter, graft polymerization reaction is too time-consuming, in many situations, generates a large amount of homopolymer containing ring-type ether monomer, therefore not preferred.
If graft polymerization for example utilizes solution polymerization, can carry out as got off: in the solution of (methyl) acrylic copolymer, add the solvent containing ring-type ether monomer and capable of regulating viscosity, carry out after nitrogen replacement, the polymerization starter that adds the such peroxide of 0.02～5 weight part dibenzoyl peroxide, at 50 ℃～80 ℃, heat 4～15 hours, thereby carry out, but be not limited to this.
The state of gained graftomer (size of the branch portion of molecular weight, graftomer etc.) can suitably be selected according to reaction conditions.
Form of the present invention peeling off again with the bonding adhesive composite of self adhesive tape and comprise graftomer and the light cationic polymerization starter obtaining like this.
As light cationic polymerization starter, also can preferably use the cationic of light arbitrarily polymerization starter known in those skilled in the art.More specifically, can use at least one in the group of selecting free allyl group sulfonium hexafluorophosphate, triarylsulfonium salt, sulfonium phosphofluoric acid salt and two (alkyl phenyl) iodine hexafluorophosphate composition.
Such light cationic polymerization starter can be used alone, but also also mix together two or more, as overall content, with respect to the aforementioned graftomer of 100 weight part, is 0.15～4.0 weight part, is preferably 0.2～3.9 weight part.
Light cationic initiator produces muddiness, cannot dissolve completely while being mixed in polymkeric substance when being prepared into vinyl acetic monomer 10% solution, if likely cannot dissolve over a certain amount of, becomes the reason that hinders effect or pollution.Therefore, in order to make, solidify better material, the light cationic initiator that preferably solvability is good in polymers soln.Particularly preferably in the light cationic initiator dissolving in vinyl acetic monomer 10% solution.As such light cationic initiator, such as listing the CPI series of San-Apro Ltd., the TAS series of Sumitomo Seika Co., Ltd etc.The ESACURE1064 that in addition, also can use LAMBERTI company to manufacture.
Form of the present invention peeling off again with the bonding adhesive composite of self adhesive tape and can add as required linking agent.As linking agent; be not particularly limited, can example as the isocyanates linking agent in 1 molecule with the compound of more than 2 isocyanate group (comprise and isocyanate group has been carried out to the isocyanic ester regenerative functional group of temporary protection by end-capping reagent or several polymers etc.).
As isocyanates linking agent, can list the aliphatic isocyanates such as the alicyclic isocyanates such as the aromatic isocyanates such as tolylene diisocyanate, Xylene Diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate etc.
More specifically, such as listing the lower aliphatic polyisocyanates such as butylidene vulcabond, hexamethylene diisocyanate, the alicyclic isocyanate classes such as cyclopentylidene vulcabond, cyclohexylidene vulcabond, isophorone diisocyanate, 2,4 toluene diisocyanate, 4, the aromatic diisocyanate classes such as 4 '-diphenylmethanediisocyanate, Xylene Diisocyanate, polymethylene multi-phenenyl isocyanate, (Nippon Polyurethane Industry Co., Ltd. manufactures TriMethylolPropane(TMP)/tolylene diisocyanate trimer affixture, trade(brand)name CORONATE L), (Nippon Polyurethane Industry Co., Ltd. manufactures TriMethylolPropane(TMP)/hexamethylene diisocyanate trimer affixture, trade(brand)name CORONATE HL), (Nippon Polyurethane Industry Co., Ltd. manufactures the isocyanuric acid ester body of hexamethylene diisocyanate, trade(brand)name CORONATE HX) isocyanate addition product such as, polyethers polyisocyanates, polyester polyisocyanates, and the affixture of they and various polyvalent alcohols, pass through isocyanurate-bond, biuret linkage, allophanic acid ester bonds etc. have carried out multiple functionalized polyisocyanates etc.In the middle of these, because speed of response is used aliphatic isocyanates soon and preferably.
Above-mentioned isocyanates linking agent can be used separately a kind of, also can mix use two or more, as overall content with respect to the aforementioned graftomer of 100 weight part, preferably contain the aforementioned isocyanate compound linking agent of 0.05～5 weight part, more preferably contain 0.1～4 weight part, further preferably contain 0.2～3 weight part.Can consider force of cohesion, stop peeling off etc. and contain with suitable amount in endurance test.
Such isocyanates linking agent, owing to also can contributing to the curing reaction of the ring-type ether in grafted chain in the main chain at bonding adhesive polymer crosslinked, is therefore preferably used.
In addition, as linking agent, can be used in combination organic linking agent, multi-functional metallo-chelate.As organic linking agent, can list epoxies linking agent (referring to the compound in 1 molecule with more than 2 epoxy group(ing)).As epoxies linking agent, can list ethylene glycol diglycidylether, propylene glycol diglycidylether, terephthalic acid diglycidyl ester acrylate, spiral shell ethylene glycol diglycidylether etc.These may be used alone, can also be used in combination two or more.
Multi-functional metallo-chelate refers to the material of polyvalent metal and organic compound covalent bonding or coordination bonding.As polyvalent metal atom, can list Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti etc.As carry out covalent linkage and or the organic compound of coordination bonding in atom, can list Sauerstoffatom etc., as organic compound, can list alkyl ester, alkylol cpd, carboxylic acid cpd, ether compound, ketone compound etc.
In the present invention, as linking agent, all right further Jia Ru oxazoline class linking agent, superoxide.
Zuo Wei oxazoline class linking agent, can be not particularly limited to use the material of Ju You oxazolinyl in molecule.Oxazolinyl can be any one in 2-oxazolinyl, 3-oxazolinyl, 4-oxazolinyl.Zuo Wei oxazoline class linking agent, is preferably that unsaturated monomer and addition polymerization oxazoline carry out copolymerization and the polymkeric substance that obtains is particularly preferably the material that has used 2-pseudoallyl-2-oxazoline in addition polymerization oxazoline.As an example, can list trade(brand)name " EPOCROS WS-500 " that Japanese catalyst (strain) manufactures etc.
As superoxide, thereby so long as make the crosslinked material carrying out of the base polymer of bonding adhesive composite by adding thermogenesis free radical activity kind, just can suitably use, but consider operability, stability, preferably using 1 minute half life temperature is the superoxide of 80 ℃～160 ℃, and more preferably using 1 minute half life temperature is the superoxide of 90 ℃～140 ℃.
As operable superoxide, for example, can list peroxy dicarbonate two (2-ethylhexyl) ester (1 minute half life temperature: 90.6 ℃), peroxy dicarbonate two (4-tert-butylcyclohexyl) ester (1 minute half life temperature: 92.1 ℃), peroxide-butyl carbonate (1 minute half life temperature: 92.4 ℃), new peroxide tert-butyl caprate (1 minute half life temperature: 103.5 ℃), the tertiary own ester of peroxidation PIVALIC ACID CRUDE (25) (1 minute half life temperature: 109.1 ℃), tert-Butyl peroxypivalate (1 minute half life temperature: 110.3 ℃), dilauroyl peroxide (1 minute half life temperature: 116.4 ℃), the positive decoyl of peroxidation two (1 minute half life temperature: 117.4 ℃), peroxidation-2 ethyl hexanoic acid-1,1,3,3-tetramethyl-butyl ester (1 minute half life temperature: 124.3 ℃), peroxidation two (4-toluyl) (1 minute half life temperature: 128.2 ℃), dibenzoyl peroxide (1 minute half life temperature: 130.0 ℃), peroxidation tert-butyl isobutyrate (1 minute half life temperature: 136.1 ℃), 1,1-bis-(tertiary hexyl peroxidation) hexanaphthene (1 minute half life temperature: 149.2 ℃) etc.Wherein, especially from the viewpoint of crosslinking reaction efficiency excellence, preferably use peroxy dicarbonate two (4-tert-butylcyclohexyl) ester (1 minute half life temperature: 92.1 ℃), dilauroyl peroxide (1 minute half life temperature: 116.4 ℃), dibenzoyl peroxide (1 minute half life temperature: 130.0 ℃) etc.
It should be noted that, the transformation period of superoxide means the index of the decomposition rate of superoxide, refers to until the residual quantity of superoxide becomes the time of half.About under at any time for obtaining the decomposition temperature of transformation period, time transformation period under arbitrary temp, be recorded in manufacturers's goods catalogue etc., such as being recorded in " the organo-peroxide goods catalogue the 9th edition (in May, 2003) " etc. of NOF Corp.
Aforementioned superoxide can be used separately a kind of, also can mix in addition use two or more, as overall content, with respect to the aforementioned graftomer of 100 weight part, aforementioned superoxide is 0.01～2 weight part, preferably contains 0.04～1.5 weight part, more preferably contains 0.05～1 weight part.In order to adjust processibility, re-workability, crosslinked stability, separability etc., can within the scope of this, suitably select.
It should be noted that, as the measuring method of peroxide breakdown amount remaining after reaction treatment, for example can be by HPLC(high performance liquid chromatography) measure.
More specifically, for example, can carry out as follows: take out the bonding adhesive composite after about 0.2g reaction treatment at every turn, be immersed in 10ml vinyl acetic monomer, with vibrating machine, at 25 ℃, with 120rpm, carry out 3 hours mechanical shaking extractions, then at room temperature standing 3 days.Then, add 10ml acetonitrile, under 25 ℃, 120rpm, vibrate 30 minutes, by approximately 10 μ l with membrane filter (0.45m), filter the extracting solution injection HPLC obtaining, analyze, as the amount of peroxides after reaction treatment.
By aforementioned linking agent, form bonding bond layer, but when forming bonding bond layer, adjust the overall addition of linking agent and take into full account crosslinking Treatment temperature, the impact of crosslinking Treatment time is necessary.
Form of the present invention peeling off again and use the bonding adhesive composite of self adhesive tape in order further to improve bonding force, thermotolerance, can also contain epoxy resin, oxetane resin.
As epoxy resin, such as can example bisphenol A-type, the epoxy resin such as glycidic amine type such as bifunctional epoxy resin, polyfunctional epoxy resin and glycolylurea type, triglycidyl group isocyanuric acid ester type such as Bisphenol F type, bisphenol S type, brominated bisphenol A type, Hydrogenated Bisphenol A type, bisphenol AF type, biphenyl type, naphthalene type, fluorenes type, phenol phenolic varnish type, cresols phenolic varnish type, trihydroxybenzene methylmethane type, four phenol ethane types.These epoxy resin can be used separately a kind of, or are used in combination two or more.
As these epoxy resin, do not limit, can use commercially available epoxy resin.So commercially available epoxy resin is not limited, for example, comprise: as the Japan Epoxy Resins Co. of bisphenol-type epoxy resin, the jER828 of Ltd., jER806 etc.; As the Japan Epoxy Resins Co. of alicyclic epoxy resin, the YX8000 of Ltd., YX8034 etc.; The EP4000 of Asahi Denka Co., Ltd., EP4005 etc.; DENACOL EX-313, EX-512, the known epoxy resin such as EX-614B, EX-810 as the Nagase ChemteX Corporation of the poly epihydric alcohol ethers of polyvalent alcohol.
As oxetane resin, can use Isosorbide-5-Nitrae-dimethylbenzene dioxy rings such as bis-{ [(3-ethyl-3-oxetanyl) methoxyl group] methyl } benzene butane, 3-ethyl-3-{ [3-ethyl oxygen ring mix butane-3-yl] methoxyl group } methyl of mixing } the known oxetane resin such as the assorted butane of oxygen ring, the assorted butane of 3-ethylhexyl oxygen ring, the assorted butane of 3-ethyl-3-hydroxyl oxygen ring, the assorted butane of 3-ethyl-3-methylol oxygen ring.These oxetane resins can be used separately a kind of, or are used in combination two or more.
As oxetane resin, do not limit, can use commercially available resin.For ARONE OXETANE OXT-121, OXT221, OXT101 and the OXT212 etc. of so commercially available oxetane resin ，Ke example Toagosei Co., Ltd, but be not limited to these.
Such epoxy resin and oxetane resin can or combine both by any one and be used to form of the present invention peeling off again with in the bonding adhesive composite of self adhesive tape.
In the present invention, with respect to the aforementioned graftomer of 100 weight part, in the situation that containing epoxy resin and/or oxetane resin, more than its total amount is preferably 5 weight parts, more preferably more than 10 weight parts, be preferably below 100 weight parts, more preferably below 70 weight parts.If total amount is more than 5 weight parts, can confirm the unusual effect that bonding force improves and thermotolerance improves.When total amount surpasses 100 weight part, sometimes can not be fully curing.
In the present invention, when acrylic polymers grafting is added to epoxy resin containing ring-type ether monomer in the graftomer that obtains, can prepare the composition that strike-through etc. does not occur before solidifying, can make good bonding bond layer.Think that this is because ring-type ether and low-molecular-weight epoxy resin by grafting are compatible, can form firmly bonding bond layer structure.
Form of the present invention peeling off again with in the bonding adhesive composite of self adhesive tape, can other tackifiers of compounding, tenderizer.Tackifiers, with respect to 100 weight part graftomer, is counted 10～100 weight parts, can preferably be used 20～80 weight parts with total amount.
And then, in order to improve the water tolerance on interface, form of the present invention peeling off again with in the bonding adhesive composite of self adhesive tape, with respect to 100 weight part graftomer, also can compounding 0.01～2 weight part silane coupling agent.Preferred compounding 0.02～1 weight part.In the time of too much, the bonding force of liquid crystal cells is increased, releasable is poor, and when very few, water tolerance does not improve, therefore not preferred.
As silane coupling agent, can list 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyldiethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane etc. is containing epoxy silane coupling, 3-TSL 8330, N-2-(amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-triethoxysilyl-N-(1, 3-dimethyl butyrate fork base) propylamine etc. contains amino silicane coupling agent, 3-acryloxy propyl trimethoxy silicane, 3-methacryloxypropyl triethoxyl silanes etc. are containing (methyl) acryl silane coupling agent, 3-isocyanate group propyl-triethoxysilicanes etc. contain isocyanato silanes coupling agent etc.
And then, also can add anti-aging agent or antioxidant.As such anti-aging agent or antioxidant, can use the hindered phenol anti-oxidants Irganox series such as BASF AG, the K-NOX series of the Sort of Co., Ltd. chemistry, the antioxidants such as ADEKA STAB of ADEKA Co., Ltd., they can add separately also can mix multiple interpolation.
Form of the present invention peeling off again with in the bonding adhesive composite of self adhesive tape, the known additive that also can contain other, can add powders such as tinting material, pigment, dyestuff, tensio-active agent, softening agent, tackifiers, surface lubricant, flow agent, tenderizer, antioxidant, anti-aging agent, photostabilizer, UV light absorber, stopper, inorganic or organic filler, metal powder, particulate state, paper tinsel shape thing etc. aptly according to the purposes of using.In addition, in controllable scope, also can adopt the redox system that is added with reductive agent.
Of the present invention peeling off again can be by being coated with aforementioned adhesion adhesive composite on the one side at heat-resistant film base material with the bonding bond layer comprising in self adhesive tape, dryly removes polymer solvent etc. and carry out crosslinking Treatment, then carries out photocuring and form.Or by by moving at the upper binder layer forming of barrier film (stripping film) mode being set on heat-resistant film base material, also can form peeling off again of excellent heat resistance and use self adhesive tape.
As heat-resistant film base material of the present invention, if the temperature in heating process reaches 160 ℃ of left and right, pet film is fully, but more than this, preferably uses the film of polyimide, aromatic poly amide, PEN, polyphenylene sulfide etc.The thickness of such film is preferably used the thickness of 5～100 μ m.For of the present invention, peel off with for self adhesive tape, the states such as band shape of sheet, lengthwise are also all included again.
About forming the method for bonding bond layer, more specifically, such as reaching by following method: aforementioned adhesion adhesive composite is applied on the barrier film etc. that carried out lift-off processing, dry remove polymer solvent etc. and carry out crosslinking Treatment and form bonding bond layer, then to the method for heat-resistant film base material transfer printing; Or from from the beginning of be coated with aforementioned adhesion adhesive composite at heat-resistant film base material, the dry method of removing polymer solvent etc. and forming bonding bond layer.
When coat binding caking agent, can suitably newly add more than one solvents except polymer solvent.
As the isolated body that carried out lift-off processing, preferably use organosilicon release liner.Constituent material as release liner, for example can list polyethylene, polybutene film, polyhutadiene film, poly-methyl pentene film, polyvinyl chloride film, vinyl chloride copolymer film, ethylene-vinyl acetate copolymer film, polybutylene terephthalate film, polyurethane film, polypropylene, polyethylene terephthalate, the plastics films such as polyester film, paper, cloth, the porous materials such as non-woven fabrics, net, foamed sheet, the sheet that tinsel and their layered product etc. are suitable etc., viewpoint from surface smoothness excellence, can use aptly plastics film.Or can enumerate the suitable sheet such as slice, net, foam, tinsel and their layered product etc.
On such liner or on heat-resistant film base material, coating forms the bonding adhesive composite of peeling off again with self adhesive tape of the present invention, it is dried and forms in the operation of bonding bond layer, as making the dry method of bonding caking agent, can be according to object and suitable employing appropriate means.Preferably use the method for above-mentioned coated film heat drying.Heat drying temperature is preferably 40 ℃～200 ℃, more preferably 50 ℃～180 ℃, is particularly preferably 70 ℃～170 ℃.By making Heating temperature in above-mentioned scope, can obtain having the bonding caking agent of excellent adhesion characteristic.
Can adopt aptly reasonable time time of drying.Be preferably 5 second～20 minute above-mentioned time of drying, more preferably 5 second～10 minute, are particularly preferably 10 second～5 minute.
In addition, can form anchor layer on the surface of heat-resistant film base material, or carry out the various easy bonding processing such as corona treatment, Cement Composite Treated by Plasma, then form bonding bond layer.In addition, can carry out easy bonding processing to the surface of bonding bond layer.
As the formation method of bonding bond layer, can make in all sorts of ways.Particularly, such as listing roller coat cloth, roller, lick coating, intaglio plate coating, reversion type coating, roller and brush that cloth, spraying, dip roll coating, excellent painting, scraper for coating, airblade coating, curtain coating, lip are coated with, methods such as extrusion coated method based on mould painting etc.
Thickness to bonding bond layer is not particularly limited, for example, be 0.5～100 μ m left and right.Be preferably 2～50 μ m, more preferably 3～25 μ m, more preferably 3～15 μ m.
In the situation that aforementioned adhesion bond layer exposes, can protect bonding bond layer until in reality with the sheet (isolated body) that carried out lift-off processing.
Constituent material as such protection with isolated body; such as listing the suitable sheet such as the porous materials such as the plastics films such as polyethylene, polypropylene, polyethylene terephthalate, polyester film, paper, cloth, non-woven fabrics, net, foamed sheet, tinsel and their layered product etc.; from the viewpoint of surface smoothness excellence, suitable use plastics film.
As this plastics film; so long as can protect the film of aforementioned adhesion bond layer; just be not particularly limited, such as listing polyethylene film, polypropylene film, polybutene film, polyhutadiene film, poly-methyl pentene film, polyvinyl chloride film, vinyl chloride copolymer film, pet film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film etc.
Coating uses or protects the release liner of use, the thickness of aforementioned isolated body is generally 5～200 μ m, is preferably 5～100 μ m left and right.The antistatic treatment such as that aforementioned isolated body can also utilize is as required silicone based, releasing agent of fluorine class, chain alkyl class or fatty acid acyl amine, ground silica etc. carry out the demoulding and antifouling processing, carry out application type, kneading type, evaporation type.Especially, by the surface of aforementioned isolated body suitably being carried out to the lift-off processing such as organosilicon processing, chain alkyl processing, fluorine processing, can further improve from the separability of aforementioned adhesion bond layer.
Form the bonding adhesive composite of peeling off again with self adhesive tape of the present invention, by irradiating specific light, cause curing.Of the present invention peeling off again with self adhesive tape has the bonding bond layer that carried out photocuring, and the bonding of the bonding or adherend of adherend and member become to more reliable.
To irradiating the light of use, be not particularly limited, be preferably ultraviolet ray, visible ray and electron rays isoreactivity energy-ray.Crosslinking Treatment based on uviolizing can be carried out with suitable ultraviolet light sources such as high voltage mercury lamp, low pressure mercury lamp, excimer laser, metal halide lamps.Now, as ultraviolet irradiation amount, degree of crosslinking that can be as required and selecting aptly, conventionally, for ultraviolet ray, it is desirable at 0.2～10J/cm 2scope in select.Temperature during to irradiation is not particularly limited, but considers the thermotolerance of supporter, is preferably until 140 ℃ of left and right.
It should be noted that, UVA (320-390nm), the UVB (280-320nm) of UV Power Puck, the integration amount of UVC (250-260nm), UVV (395-445nm) that light quantity is manufactured with Electronic Instrumentation and Technology Inc. represent.
By irradiating active energy beam, light cationic initiator decomposes and produces acid, carries out the curing reaction based on ring-type ether.
The gel fraction that solidifies bonding bond layer of the present invention is preferably 80～98%, preferably becomes the extra high bonding bond layer of force of cohesion.Storage modulus at its 23 ℃ is preferably 9.0 * 10 4～1.0 * 10 6pa, has binding property in addition, therefore becomes bonding adhesive composite and the adhesive sheet of excellent heat resistance.
Herein, after photocuring reaction, refer to by carrying out 0.2J/cm 2above rayed and the state reached.
Of the present invention peeling off again with self adhesive tape obtains by such operation, can be used for variously covering, fixing purposes.
Embodiment
Below, by embodiment, illustrate the present invention, but the present invention is not limited to these embodiment.It should be noted that, part and % in each example are weight basis.Room temperature while below the there is no special stipulation condition of placing is all 23 ℃, 65%RH(1 hour or 1 week).
The mensuration > of < weight-average molecular weight
The weight-average molecular weight of (methyl) acrylic polymers obtaining is by GPC(gel permeation chromatography) measure.Sample is used the filtrate obtaining as follows: sample dissolution is made in dimethyl formamide to the solution of 0.1 % by weight, by its standing evening, the filtrate of then filtering gained with the film filter of 0.45 μ m.
Analytical equipment: TOSOH CORPORATION manufactures, HLC-8120GPC
Post: TOSOH CORPORATION manufactures, G7000HXL+GMHXL+GMHXL
Column dimension: each 7.8mm φ * 30cm, adds up to 90cm
Elutriant: tetrahydrofuran (THF) (concentration 0.1 % by weight)
Flow: 0.8ml/min
Detector: differential refractometer (RI)
Column temperature: 40 ℃
Injection rate: 100 μ l
Standard test specimen: polystyrene
The mensuration > of < gel fraction
The bonding caking agent of be dried/crosslinking Treatment (initial weight W 1) is immersed in vinyl acetic monomer solution, at room temperature places after 1 week, take out insoluble composition, measure and make its dried weight (W2), as following, try to achieve.
Gel fraction=(W2/W1) * 100
The measuring method > of < bonding force
By what obtain in embodiment/comparative example, peel off again the sample that cuts into width 20mm, length 100mm with self adhesive tape, with the roller of 2Kg, be attached on non-alkali glass for reciprocal 1 time, under the condition of 23 ℃ of * 50%RH, place after 30 minutes, with 90 ° of peel angle, peeling rate 300mm/ minute, measure peeling adhesion force (N/20mm), using this value as initial bonding force.
The sample of attaching is heated 5 minutes in the baking oven of 260 ℃, under the condition of 23 ℃ of * 50%RH, place after 30 minutes, with 90 ° of peel angle, peeling rate 300mm/ minute, measure peeling adhesion force (N/20mm), using this value bonding force after heating.As the pollutional condition of adherend, if release surface there is cull, pollute for *, if do not observe completely, be zero.
The measuring method > of < dynamic viscoelastic
Device: TA Instruments, the ARES that Inc. manufactures
Deformation pattern: reverse
Measure frequency: fixed frequency 1Hz
Heat-up rate: 5 ℃/min
Measure temperature: near the second-order transition temperature of bonding caking agent until 160 ℃ measure
Shape: parallel plate 8.0mm φ
Sample thickness: 0.5～2mm(installs initial)
Read storage modulus at 23 ℃ (G ')
(embodiment 1)
Using the positive butyl ester of 100 parts by weight of acrylic acid, 3 parts by weight of acrylic acid-4-hydroxy butyl ester, together add in the four-hole boiling flask that possesses agitating vane, thermometer, nitrogen ingress pipe, condenser as 0.1 weight part 2.2 '-Diisopropyl azodicarboxylate and the 200 weight part vinyl acetic monomers of polymerization starter, limit is slowly stirred limit importing nitrogen and is carried out after nitrogen displacement in 1 hour, liquid temperature in maintenance flask is near 60 ℃, carry out 10 hours polyreactions, the acrylic polymers solution of preparation weight-average molecular weight 920,000.The second-order transition temperature of the acrylic polymers obtaining is 231K.
With vinyl acetic monomer dilution gained acrylic polymers solution, making solids component is 25%, prepares diluting soln (I).In possessing the four-hole boiling flask of agitating vane, thermometer, nitrogen ingress pipe, condenser, with respect to 400 weight part diluting solns (I), add 20 parts of vinylformic acid-4-hydroxy butyl ester glycidyl ethers, 20 parts of isobornyl acrylate and 0.2 part of benzoyl peroxide, limit is slowly stirred limit importing nitrogen and is carried out after nitrogen displacement in 1 hour, keep liquid temperature in flask near 65 ℃ 4 hours, then at 70 ℃, carry out 4 hours polyreactions, obtain graftomer solution.
Then, solids component 100 weight parts with respect to the graftomer solution making like this, 1 part of triarylsulfonium salt of compounding (manufacture of San-Apro Ltd. company, " CPI-200K "), 0.4 part of isocyanates linking agent (NCO linking agent, Mitsui Chemicals, Inc.'s manufacture, " Takenate D110N "), 1.0 parts of antiagers (Hinered phenols antiager, Ciba Japan K.K. manufacture, " IRGANOX1010 "), prepare binder solution.
Above-mentioned bonding adhesive solution is coated on the Kapton of 25 μ m, the thickness that makes dried bonding bond layer is 6 μ m, at 120 ℃, make its dry 3 minutes, on bonding plane, attach the pet film (manufacture of resin company of Mitsubishi, MRF38) of the 38 μ m that carried out organosilicon lift-off processing.
Then, with metal halide UV lamp, from PET film side, this tackiness agent aspect is carried out to 1.2J/cm 2rayed, at 50 ℃, slaking is two days, makes of the present invention peeling off again and uses self adhesive tape.
Change amount and the light quantity of isocyanates linking agent and light cationic polymerization initiators, in addition, carry out same operation with embodiment 1, make respectively peeling off again of embodiment 2～10,12 and comparative example 1～4 and use self adhesive tape.Wherein, for embodiment 11, be made as 5 parts by weight of acrylic acid-4-hydroxy butyl ester, the acrylic polymers solution (second-order transition temperature is 235K) of preparation weight-average molecular weight 930,000.And then, in embodiment 11, in order to prepare grafting part, vinylformic acid-4-hydroxy butyl ester glycidyl ether and isobornyl acrylate are made as respectively to 50 parts.
Herein, as light cationic polymerization initiators, embodiment 1～11 is all used the triarylsulfonium salt identical with embodiment (San-Apro Ltd. manufacture, " CPI-200K ") with comparative example 1～4, for embodiment 12, uses the ESACURE1064 of LAMBERTI company.
The sample of gained in above-described embodiment and comparative example has been carried out to the evaluation of gel fraction, storage modulus, initial bonding force, caking power and the pollution of binder layer, evaluation result is shown in table 1.In table 1, each compounding scale shows the weight part with respect to 100 weight part graftomer.
[table 1]
Figure BDA0000437534570000221
In table 1, with the visible cull of comparative example 3 of *.

Claims (12)

1. peel off again with a self adhesive tape, it is characterized in that, its be possess heat-resistant film base material and the curing bonding bond layer that arranges on the one side of this heat-resistant film base material peel off again use self adhesive tape,
This solidifies bonding bond layer and forms for the bonding bond layer being formed by bonding adhesive composite is carried out to photocuring, described bonding adhesive composite contains 0.15～4.0 weight part light cationic polymerization starter in 100 weight part graftomer, and described graftomer is that the chain that graft polymerization comprises containing ring-type ether monomer to (methyl) acrylic polymers forms.
2. according to claim 1 peeling off again with self adhesive tape, is characterized in that, described bonding adhesive composite also contains isocyanates linking agent.
3. according to claim 1 and 2 peeling off again with self adhesive tape, is characterized in that, described bonding adhesive composite also contains any one or both in 5～100 weight part epoxy resin and oxetane resin with respect to graftomer described in 100 weight parts.
4. according to peeling off again with self adhesive tape described in any one in claim 1～3, wherein, this gel fraction that solidifies bonding bond layer is 80～99%.
5. according to peeling off again with self adhesive tape described in any one in claim 1～4, it is characterized in that, described (methyl) acrylic polymers, with respect to this (methyl) acrylic polymers total amount, contains 0.2～10 % by weight hydroxyl monomer as monomeric unit.
6. according to peeling off again with self adhesive tape described in any one in claim 1～5, it is characterized in that, described graftomer is by under the existence at 0.02～5 weight part superoxide, makes described in 2～50 weight parts to be aggregated to described in 100 weight parts and to obtain on (methyl) acrylic polymers containing other monomer-grafted of ring-type ether monomer and 5～50 weight parts.
7. according to peeling off again with self adhesive tape described in any one in claim 1～6, it is characterized in that, described smooth cationic polymerization starter is light acid producing agent.
8. according to claim 7 peeling off again with self adhesive tape, is characterized in that, described light acid producing agent is using vinyl acetic monomer as solvent and while being adjusted into 10% concentration, and sediment-free ground dissolves.
9. according to peeling off again with self adhesive tape described in any one in claim 1～8, it is characterized in that, described storage modulus of solidifying at 23 ℃ of bonding bond layer is 9.0 * 10 4～1.0 * 10 6pa.
10. according to peeling off again with self adhesive tape described in any one in claim 1～9, it is characterized in that the group that described heat-resistant film base material selects free polyethylene terephthalate, polyimide, aromatic poly amide, PEN and polyphenylene sulfide to form.
11. according to peeling off again with self adhesive tape described in any one in claim 1～10, it is characterized in that, described bonding bond layer forms with the thickness setting of 0.5～100 μ m.
12. 1 kinds of manufacture method of peeling off again with self adhesive tape, described peeling off again arranges curing bonding bond layer and forms on the one side of heat-resistant film base material with self adhesive tape,
Described manufacture method comprises following operation:
Bonding adhesive composite be coated on the one side of heat-resistant film base material and form the operation of bonding bond layer, described bonding adhesive composite contains 0.15～4.0 weight part light cationic polymerization starter in 100 weight part graftomer, and described graftomer is that the chain that graft polymerization comprises containing ring-type ether monomer to (methyl) acrylic polymers forms; With
This bonding bond layer is carried out to the operation that rayed makes its photocuring.
CN201280029268.7A 2011-06-14 2012-06-07 Removable adhesive tape and manufacturing method thereof Pending CN103597047A (en)

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