CN103509502A - Adhesive composition and surface-protective film - Google Patents

Adhesive composition and surface-protective film Download PDF

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Publication number
CN103509502A
CN103509502A CN201310227563.XA CN201310227563A CN103509502A CN 103509502 A CN103509502 A CN 103509502A CN 201310227563 A CN201310227563 A CN 201310227563A CN 103509502 A CN103509502 A CN 103509502A
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methyl
compound
acid
monomer
multipolymer
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CN201310227563.XA
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CN103509502B (en
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长仓毅
岛口龙介
长谷川良
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Fujimori Kogyo Co Ltd
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Fujimori Kogyo Co Ltd
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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
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • 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
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners
    • 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
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • 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
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • 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
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • 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
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer

Abstract

The invention provides an adhesive composition with excellent anti-static function, durability and machinability, and the balance of bonding force of the composition under low peeling speed and high peeling speed is excellent. The adhesive composition is formed by crylic acid polymer containing co-polymer; the co-polymer crylic acid polymer comprises (A) (methyl) acrylate monomer containing alkyl and having carbon number C4-C10, (B) co-polymer monomer containing hydroxyl, (C) co-polymer monomer containing carboxylic, (D) poly alkylene diol single (methyl) acrylate monomer and (E) vinyl monomer containing nitrogen without hydroxyl or (methyl) crylic acid alkyl ester monomer having alkoxy, (F) isocyanate compound having tri-sense, (G) cross-linking inhibitor, (H) cross-linking catalyst, (I) antistatic agent, and (J) polyether modified siloxane compound; and the acid value of the crylic acid polymer is 0.01-8.0.

Description

Adhesive composition and surface protection film
Technical field
The present invention relates to a kind of surface protection film of the manufacturing process for liquid-crystal display.More specifically; the present invention relates to the opticses such as a kind of Polarizer that forms liquid-crystal display by sticking on, polarizer surface and for the protection of the surperficial surface protection film adhesive composition of the opticses such as Polarizer, polarizer, and the surface protection film that uses this adhesive composition.
Background technology
All the time, as forming in the manufacturing process of the opticses such as Polarizer, polarizer of the parts of liquid-crystal display, the adhesive surface protective membrane for the surface of temporary protection optics.This surface protection film is only used in the operation of manufacturing optics, when optics is inserted to liquid-crystal display, it is peeled off and is removed from optics.Owing to using in this surface protection film Jin manufacturing process for the protection of optical component surfaces, therefore, be conventionally also known as " operation film ".
For so manufacturing the surface protection film using in the operation of optics; on the one side with the polyethylene terephthalate of optical transparence (PET) resin molding, be formed with adhesive layer; but on adhesive layer, be fitted with the stripping film through lift-off processing, to protect this adhesive layer until fit in optics.
In addition; for opticses such as Polarizer, polarizers; owing to following display capabilities, tone, contrast gradient, the impurity of LCD panel under the state of surface protection film of having fitted, the examination and test of products of optical assessment such as sneak into; so; as the performance requriements of effects on surface protective membrane, require in adhesive layer without bubble, impurity.
In addition; in recent years; from the opticses such as Polarizer, polarizer during stripper surface protective membrane; be accompanied by occur when being peeled off adhesive layer by adherend static produced peels off static; likely can have influence on the fault of the electric control circuit of liquid-crystal display; therefore, require adhesive layer to there is good antistatic property.
In addition; on the opticses such as Polarizer, polarizer during coating surface protective membrane; due to a variety of causes, can there is after temporary transient stripper surface protective membrane again the situation of adhesive surface protective membrane again, now require easily from as being peeled off (re-workability) by the optics of adherend.
In addition, during from optics stripper surface protective membranes such as final Polarizer, polarizers, requirement can be peeled off rapidly.That is, require cohesive force because of the variation of peeling rate little, even if to also can peel off rapidly in the situation that peeling off at a high speed.
So, in recent years, maneuverable viewpoint during from use surface protection film, requires the adhesive layer that forms surface protection film to have following performance: (1), under low peeling rate and high peeling rate, obtains bonding equilibrium of forces; (2) prevent the generation of glue residue; (3) good antistatic property; And (4) reprocessing (ReWork) performance etc.
But; allow to meet respectively to forming the performance requriements of the adhesive layer of surface protection film;; allow to meet respectively the indivedual performance requriementss in above-mentioned (1)～(4); but the over-all properties requirement of (1) that the adhesive layer of the surface protection film that simultaneously meets the demands has～(4) is very difficult problem.
For example, obtain the generation that bonding equilibrium of forces and (2) prevent glue residue about (1) under low peeling rate and high peeling rate, known have a suggestion as described below.
Using there is the alkyl of carbonatoms below 7 (methyl) alkyl acrylate with the multipolymer of the copolymerizable compound that contains carboxyl as main component, and in the acrylic adhesive layer that with linking agent, it is carried out to crosslinking Treatment and make, in the situation that process is long-time bonding, exist binding agent to being attached to by adherend by adherend one side shifting, and to by the bonding force of adherend through time rising property large problem.For fear of this problem, known have a kind of technical scheme that is provided with following adhesive layer, described adhesive layer is use (methyl) alkyl acrylate of the alkyl with carbonatoms 8～10 and have the multipolymer of the copolymerizable compound of alcoholic extract hydroxyl group, and with linking agent, it is carried out to the adhesive layer (patent documentation 1) that crosslinking Treatment forms.
In addition, a kind of technical scheme that is provided with following adhesive layer has also been proposed, described adhesive layer is by multipolymer same as described above, the multipolymer of the copolymerizable compound that coordinates a small amount of (methyl) alkyl acrylate and contain carboxyl, and with linking agent, it is carried out to the adhesive layer that crosslinking Treatment forms.But; in the time of in the surface protection of using it for the low and ganoid plastic plate of surface tension etc., the poor problem of releasable when thering is problem, the high speed in field hand-manipulated that heating when adding man-hour or preserving produces the peelings such as separated and peeling off.
In order to address these problems, a kind of adhesive composition has been proposed, described adhesive composition is: a) usining in (methyl) alkyl acrylate of the alkyl with carbonatoms 8～10 (methyl) alkyl acrylate 100 weight parts as main component, add b) the copolymerizable compound that contains carboxyl of 1～15 weight part, and c) vinyl ester of the aliphatic carboxylic acid of the carbonatoms 1～5 of 3～100 weight parts and obtain the multipolymer of monomer mixture, and coordinate above-mentioned b in this multipolymer) adhesive composition (patent documentation 2) that forms of more than equivalent of the carboxyl of composition linking agent.
In the adhesive composition of recording at patent documentation 2, when adding man-hour or preserving, can not produce separated etc. peeling, and, bonding force through time rising property little, thereby releasable is good, even prolonged preservation, particularly prolonged preservation under hot environment also can be peeled off with little strength again, not residual binding agent on by adherend now, even and if also can peel off with little strength in the situation that carrying out peeling off at a high speed again.
In addition, the antistatic property good for (3), as give the method for static resistance for effects on surface protective membrane, has proposed method of sneaking in base material film by static inhibitor etc.As static inhibitor, such as the various cationic antistatic agents that disclose (a) and have quaternary ammonium salt, pyridine, primary～cation radicals such as tertiary amino; (b) there is the anionic antistatic agents of the anion-radicals of sulfonic acid base, sulfuric ester base, phosphoric acid ester base, phosphonic acids base etc.; (c) non-ionic antistatic agent of the both sexes static inhibitor of amino acids, amidosulphuric acid ester class etc., (d) alkamine, glycerols, polyethylene glycols etc.; (e) make static inhibitor polymer as above quantize (patent documentations 3) such as Polymer Antistatic Agents that obtain.
In addition, proposed in recent years will be so static inhibitor be directly contained in adhesive layer, and be not contained in base material film or coat the scheme on base material film surface.
In addition, about (4) re-workability, for example, a kind of adhesive composition has been proposed, described adhesive composition is: with respect to 100 parts by weight of acrylic acid resinoids, coordinate the solidifying agent of the isocyanate ester compound of 0.0001～10 weight part to obtain (patent documentation 4) with specific silicate oligopolymer.
In patent documentation 4, record: using the carbonatoms of alkyl as the alkyl acrylate of 2～12 left and right, the alkyl methacrylate that the carbonatoms of alkyl is 4～12 left and right etc. as principal monomer composition, can contain the monomer component containing other functional group such as carboxylic monomer etc.Typically, preferably contain above-mentioned principal monomers more than 50 % by weight, and the content of the monomer component of wishing to contain functional group is 0.001～50 % by weight, is preferably 0.001～25 % by weight, more preferably 0.01～25 % by weight.The adhesive composition that this patent documentation 4 is recorded, even at high temperature or under hot and humid, the rheological parameters' change with time of its cohesive force and bonding force is also little, and also demonstrates good effect to the bonding force of curved surface, therefore has re-workability.
Conventionally, if adhesive layer is soft proterties, easily produces glue residue, re-workability and also easily reduce.That is, after mistake laminating, peel off difficulty, and be difficult to again paste.From this viewpoint, in order to make it there is re-workability, need to by there is the functional groups such as carboxyl monomer crosslinked in host so that adhesive layer has certain hardness.
In the prior art, as to forming the performance requriements of the adhesive layer of surface protection film, require it to have all the time and under low peeling rate and high peeling rate, obtain bonding equilibrium of forces, good antistatic property and cycling processability etc.But, allow to meet respectively properties requirement, also cannot meet the desired over-all properties requirement of adhesive layer as surface protection film.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication sho 63-225677 communique
Patent documentation 2: Japanese kokai publication hei 11-256111 communique
Patent documentation 3: Japanese kokai publication hei 11-070629 communique
Patent documentation 4: Japanese kokai publication hei 8-199130 communique
Summary of the invention
The problem that invention will solve
The present invention In view of the foregoing completes; its problem is, also good adhesive composition and surface protection film of the good and endurance quality of a kind of balance with good antistatic property, the cohesive force under low peeling rate and high peeling rate and cycling processability is provided.
Solve the method for problem
In order to solve above-mentioned problem, the invention provides a kind of adhesive composition, it consists of the acrylic polymers that comprises multipolymer, (methyl) acrylate monomer that the carbonatoms that the acrylic polymers of this multipolymer contains (A) alkyl is C4～C10, (B) contain hydroxyl can copolymerization monomer, (C) contain carboxyl can copolymerization monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer, and (E) at least one in hydroxyl and nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer of containing alkoxyl group not, and contain (F) isocyanate compound more than trifunctional, (G) cross-linked inhibitor, (H) crosslinking catalyst, (I) static inhibitor, and (J) polyether modified siloxane compound, the acid number of aforementioned acrylic polymers is 0.01～8.0, more than aforementioned (F) isocyanate compound more than trifunctional comprises at least one being selected from (F-1) first aliphatic category isocyanate compound group and more than being selected from least one in (F-2) second aromatic series kind isocyanate compound group.
In aforementioned (F) isocyanate compound more than trifunctional, preferably aforementioned (F-1) first aliphatic category isocyanate compound group by the isocyanuric acid ester of hexamethylene diisocyanate compound, the affixture of the isocyanuric acid ester of isophorone diisocyanate compound, hexamethylene diisocyanate compound, the biuret of the affixture of isophorone diisocyanate compound, hexamethylene diisocyanate compound, the biuret of isophorone diisocyanate compound form; Preferably aforementioned (F-2) second aromatic series kind isocyanate compound group by the isocyanuric acid ester of tolylene diisocyanate compound, the affixture of the isocyanuric acid ester of xylylene diisocyanate cpd, the isocyanuric acid ester of hydrogenation of benzene dimethyl diisocyanate cpd, the affixture of the affixture of tolylene diisocyanate compound, xylylene diisocyanate cpd, hydrogenation of benzene dimethyl diisocyanate cpd form.
In addition, above-mentioned (B) contain hydroxyl can copolymerization monomer for more than being selected from least one in the compound group being formed by (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxy methacrylate, N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide; (methyl) acrylate monomer that is C4～C10 with respect to aforementioned (A) alkyl carbon atoms number of 100 weight parts, aforementioned (B) that contains 0.1～5.0 weight part contain hydroxyl can copolymerization monomer; And, aforementioned (B) contain hydroxyl can the monomer of copolymerization in, preferably the total amount of (methyl) vinylformic acid 8-hydroxyl monooctyl ester, (methyl) vinylformic acid own ester of 6-hydroxyl and (methyl) vinylformic acid 4-hydroxyl butyl ester is 0～0.9 weight part.
In addition, aforementioned (C) contain carboxyl can copolymerization monomer be to be selected from by (methyl) vinylformic acid, (methyl) vinylformic acid carboxylic ethyl ester, (methyl) vinylformic acid carboxylic pentyl ester, 2-(methyl) acryloxy ethyl hexahydrophthalic acid, 2-(methyl) acryloxy propyl group hexahydrophthalic acid, 2-(methyl) acryloxy ethyl phthalic acid, 2-(methyl) acryloxy ethyl succsinic acid, 2-(methyl) acryloxy ethyl toxilic acid, carboxyl polycaprolactone list (methyl) acrylate, more than at least one in the compound group that 2-(methyl) acryloxy ethyl tetrahydrophthalic acid forms, (methyl) acrylate monomer that is C4～C10 with respect to the carbonatoms of aforementioned (A) alkyl of 100 weight parts, aforementioned (C) that preferably contains 0.35～1.0 weight part contain carboxyl can copolymerization monomer.
In addition, aforementioned (D) polyalkylene glycol mono (methyl) acrylate monomer is more than at least one being selected from polyalkylene glycol mono (methyl) acrylate, methoxyl group polyalkylene glycol (methyl) acrylate, oxyethyl group polyalkylene glycol (methyl) acrylate; (methyl) acrylate monomer that is C4～C10 with respect to the carbonatoms of aforementioned (A) alkyl of 100 weight parts, preferably contains aforementioned (D) polyalkylene glycol mono (methyl) acrylate monomer of 1～20 weight part.
In addition, (methyl) acrylate monomer that is C4～C10 with respect to the carbonatoms of aforementioned (A) alkyl of 100 weight parts, preferably aforementioned (E) not the content of hydroxyl and nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer of containing alkoxyl group be 1～20 weight part.
In addition, more than aforementioned (F) isocyanate compound more than trifunctional comprises at least one being selected from aforementioned (F-1) first aliphatic category isocyanate compound group and more than being selected from least one in aforementioned (F-2) second aromatic series kind isocyanate compound group, and with respect to the aforementioned multipolymer of 100 weight parts, the total content of aforementioned (F) isocyanate compound more than trifunctional is preferably 0.5～5.0 weight part.
In addition, preferably aforementioned (I) static inhibitor is that aforementioned multipolymer with respect to the 100 weight parts ionic compound that contains 30～80 ℃ of 0.1～5.0 weight part and fusing points or the copolymerization amount in aforementioned multipolymer are 0.1～5.0 % by weight and the quaternary ionic compound that contains acryl.
In addition, aforementioned (J) polyether modified siloxane compound is that HLB value is 7～12 polyether modified siloxane compound, preferably with respect to the aforementioned multipolymer of 100 weight parts, and aforementioned (J) polyether modified siloxane compound that contains 0.01～0.5 weight part.
In addition, aforementioned (G) cross-linked inhibitor is keto-enol tautomerism compound, preferably with respect to the aforementioned multipolymer of 100 weight parts, and aforementioned (G) cross-linked inhibitor that contains 1.0～5.0 weight parts.
In addition, aforementioned (H) crosslinking catalyst is organo-tin compound, preferably with respect to the aforementioned multipolymer of 100 weight parts, and aforementioned (H) crosslinking catalyst that contains 0.01～0.5 weight part.
In addition, preferably making the cohesive force of the crosslinked adhesive layer forming of aforementioned adhesive composition under low peeling rate 0.3m/min is 0.05～0.1N/25mm, and the cohesive force under high peeling rate 30m/min is below 1.0N/25mm.
In addition, preferably making the surface resistivity of the crosslinked adhesive layer forming of aforementioned adhesive composition is 5.0 * 10 + 10below Ω/, peeling off static voltage is ± 0～0.3kV.
And, the invention provides a kind of adhesive film, it is characterized in that, at the single or double of resin molding, form adhesive layer and form, described adhesive layer is to make that aforementioned adhesive composition is crosslinked to be formed.
In addition; the invention provides a kind of surface protection film; it is at the one side of resin molding, to form adhesive layer to form; described adhesive layer is aforementioned adhesive composition to be cross-linked form; it is characterized in that; with ballpoint pen, after adhesive layer is described on surface protection film, pollute and be not transferred to by adherend.
In addition, the purposes that surface protection film of the present invention can be used as the surface protection film of Polarizer is used.
In addition, in surface protection film of the present invention, preferably on the contrary face of the side with being formed with adhesive layer of resin molding, implement antistatic and antifouling processing.
Invention effect
Based on the present invention, the desired over-all properties of adhesive layer of insurmountable effects on surface protective membrane in the prior art can be met, and good antistatic property can be obtained, can prevent the generation of glue residue phenomenon.Particularly, not only can keep good antistatic property, but also can reduce the addition of static inhibitor, also can improve the performance that prevents glue residue.
In addition, by and be selected from (F-1) first aliphatic category isocyanate compound group more than one and be selected from more than one in (F-2) second aromatic series kind isocyanate compound group, can improve the balance of the cohesive force in low speed stripping area and high speed stripping area.
Embodiment
Below, based on the present invention is preferred embodiment described.
Adhesive composition of the present invention, it is characterized in that, (methyl) acrylate monomer that its host is is C4～C10 by the carbonatoms that contains (A) alkyl, (B) contain hydroxyl can copolymerization monomer, (C) contain carboxyl can copolymerization monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer, and (E) not the acrylic polymers of the multipolymer of at least one in hydroxyl and nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer of containing alkoxyl group form, also contain (F) isocyanate compound more than trifunctional, (G) cross-linked inhibitor, (H) crosslinking catalyst, (I) static inhibitor, and (J) polyether modified siloxane compound, the acid number of aforementioned acrylic polymers is 0.01～8.0.
(methyl) acrylate monomer that is C4～C10 as the carbonatoms of (A) alkyl, can enumerate: (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate etc.
As (B) contain hydroxyl can copolymerization monomer, can enumerate: (methyl) vinylformic acid hydroxyalkyl acrylate classes such as (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxy methacrylate; (methyl) acrylic amide that N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide etc. contain hydroxyl etc.
Preferably above-mentioned (B) contain hydroxyl can copolymerization monomer be more than at least one being selected from the compound group being formed by (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxy methacrylate, N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide.
(methyl) acrylate monomer that is C4～C10 with respect to the carbonatoms of (A) alkyl of 100 weight parts, aforementioned (B) that preferably contains 0.1～5.0 weight part contain hydroxyl can copolymerization monomer.
And, (B) contain hydroxyl can the monomer of copolymerization in, the total amount of (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl and (methyl) vinylformic acid 4-hydroxyl butyl ester is preferably lower than 1 weight part (also allow situation about not containing), more preferably 0～0.9 weight part.
Preferably (C) contain carboxyl can copolymerization monomer be to be selected from by (methyl) vinylformic acid, (methyl) vinylformic acid carboxylic ethyl ester, (methyl) vinylformic acid carboxylic pentyl ester, 2-(methyl) acryloxy ethyl hexahydrophthalic acid, 2-(methyl) acryloxy propyl group hexahydrophthalic acid, 2-(methyl) acryloxy ethyl phthalic acid, 2-(methyl) acryloxy ethyl succsinic acid, 2-(methyl) acryloxy ethyl toxilic acid, carboxyl polycaprolactone list (methyl) acrylate, more than at least one in the compound group that 2-(methyl) acryloxy ethyl tetrahydrophthalic acid forms.
(methyl) acrylate monomer that is C4～C10 with respect to the carbonatoms of (A) alkyl of 100 weight parts, (C) contain carboxyl can copolymerization the content of monomer be preferably 0.35～1.0 weight part, 0.35～0.6 weight part more preferably.
As (D) polyalkylene glycol mono (methyl) acrylate monomer, so long as a hydroxyl in a plurality of hydroxyls that polyalkylene glycol has esterified be the compound of (methyl) acrylate.Because (methyl) is acrylate-based, be polymerizability base, therefore can carry out copolymerization with host polymkeric substance.Other hydroxyl, both can keep the state of OH, also can become the alkyl oxide of methyl ether, ether etc., or the saturated carboxylic acid ester such as acetic ester etc.
The alkylidene group having as polyalkylene glycol, can enumerate vinyl, propenyl, butenyl etc., but be not limited to these.Polyalkylene glycol can be also the multipolymer of the two or more polyalkylene glycol in polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol etc.As the multipolymer of polyalkylene glycol, can enumerate polyethylene glycol-propylene glycol, polyethylene glycol-butyleneglycol, polypropylene glycol-polytetramethylene glycol, polyethylene glycol-propylene glycol-polytetramethylene glycol etc., this multipolymer can be segmented copolymer, random copolymers.
As (D) polyalkylene glycol mono (methyl) acrylate monomer, more than being preferably at least one being selected from polyalkylene glycol mono (methyl) acrylate, methoxyl group polyalkylene glycol (methyl) acrylate, oxyethyl group polyalkylene glycol (methyl) acrylate.
More specifically, can enumerate: polyoxyethylene glycol-mono-(methyl) acrylate, polypropylene glycol-mono-(methyl) acrylate, polytetramethylene glycol-mono-(methyl) acrylate, polyethylene glycol-propylene glycol-mono-(methyl) acrylate, polyethylene glycol-butyleneglycol-mono-(methyl) acrylate, polypropylene glycol-polytetramethylene glycol-mono-(methyl) acrylate, polyethylene glycol-propylene glycol-polytetramethylene glycol-mono-(methyl) acrylate; Methoxy poly (ethylene glycol)-(methyl) acrylate, methoxyl group polypropylene glycol-(methyl) acrylate, methoxyl group polytetramethylene glycol-(methyl) acrylate, methoxypolyethylene glycol-polypropylene glycol-(methyl) acrylate, methoxypolyethylene glycol-polytetramethylene glycol-(methyl) acrylate, methoxyl group-polypropylene glycol-polytetramethylene glycol-(methyl) acrylate, methoxypolyethylene glycol-polypropylene glycol-polytetramethylene glycol-(methyl) acrylate; Oxyethyl group polyoxyethylene glycol-(methyl) acrylate, oxyethyl group polypropylene glycol-(methyl) acrylate, oxyethyl group polytetramethylene glycol-(methyl) acrylate, oxyethyl group-polyethylene glycol-propylene glycol-(methyl) acrylate, oxyethyl group-polyethylene glycol-butyleneglycol-(methyl) acrylate, oxyethyl group-polypropylene glycol-polytetramethylene glycol-(methyl) acrylate, oxyethyl group-polyethylene glycol-propylene glycol-polytetramethylene glycol-(methyl) acrylate etc.
(methyl) acrylate monomer that is C4～C10 with respect to the carbonatoms of (A) alkyl of 100 weight parts, preferably contains (D) polyalkylene glycol mono (methyl) acrylate monomer of 1～20 weight part.
In (E), as (E-1) nitrogenous vinyl monomer, can enumerate: the vinyl monomer that contains amido linkage, contain amino vinyl monomer, there is the vinyl monomer of nitrogenous heterocycle structure etc.More specifically, can enumerate: the ring-type nitrogen vinyl compound of the heterocycle structure with N-vinyl substituted of NVP, NVP, methyl ethylene pyrrolidone, N-vinyl pyridine, N-vinyl piperidone, N-vinyl pyrimidine, N-vinyl piperazine, N-vinylpyrazine, N-vinyl pyrrole, N-vinyl imidazole, N-Yi Xi Ji oxazole, N-vinyl morpholine, N-caprolactam, N-vinyl laurolactam etc., N-(methyl) acryloyl morpholine, N-(methyl) acryl piperazine, N-(methyl) third rare acyl group aziridine, N-(methyl) acryl azetidine, N-(methyl) acryl tetramethyleneimine, N-(methyl) acryl piperidines, N-(methyl) acryl azepan, N-(methyl) and acryl Azacyclooctane etc. there is N-(methyl) the ring-type nitrogen vinyl compound of the heterocycle structure that replaces of acryl, N-N-cyclohexylmaleimide, N-phenylmaleimide etc. have the ring-type nitrogen vinyl compound that contains the heterocycle structure of nitrogen-atoms and vinyl-based unsaturated link(age) at ring, (methyl) acrylamide that (methyl) acrylamide, N-methyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, the N-tertiary butyl (methyl) acrylamide etc. do not replace or monoalkyl replaces, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N, N-dipropyl acrylamide, N, N-di-isopropyl (methyl) acrylamide, N, the dialkyl group such as N-dibutyl (methyl) acrylamide, N-ethyl-N-methyl (methyl) acrylamide, N-methyl-N-propyl group (methyl) acrylamide, N-methyl-N-isopropyl propyl group (methyl) acrylamide replace (methyl) acrylamide, N, N-dimethylaminomethyl (methyl) acrylate, N, N-dimethyl aminoethyl (methyl) acrylate, N, N-dimethylaminopropyl (methyl) acrylate, N, N-dimethylamino sec.-propyl (methyl) acrylate, N, N-dimethylamino butyl (methyl) acrylate, N, N-diethylamino methyl (methyl) acrylate, N, N-diethylamino ethyl (methyl) acrylate, N-ethyl-N-methylamino ethyl (methyl) acrylate, N-methyl-N-propyl group amino-ethyl (methyl) acrylate, N-methyl-N-isopropyl propyl group amino-ethyl (methyl) acrylate, N, N-dibutylamino ethyl (methyl) acrylate, dialkyl amido (methyl) acrylate such as tertiary butyl amino-ethyl (methyl) acrylate, N, N-dimethylaminopropyl (methyl) acrylamide, N, N-diethylamino propyl group (methyl) acrylamide, N, N-dipropyl aminopropyl (methyl) acrylamide, N, the N of N-diisopropylaminoethyl propyl group (methyl) acrylamide, N-ethyl-N-methylamino propyl group (methyl) acrylamide, N-methyl-N-propyl group aminopropyl (methyl) acrylamide, N-methyl-N-isopropyl propyl group aminopropyl (methyl) acrylamide etc., N-dialkyl group substituted-amino propyl group (methyl) acrylamide, the N-vinyl carboxylic acid amidess such as N-vinyl formamide, N-vinyl acetamide, N-vinyl-N-methylacetamide, N-methoxymethyl (methyl) acrylamide, N-ethoxyethyl group (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, diacetone acrylamide, N, (methyl) acrylic amides such as N-methylene-bis (methyl) acrylamide, the unsaturated carboxylic acid nitriles such as (methyl) vinyl cyanide, Deng.
As (E-1) nitrogenous vinyl monomer, preferred hydroxyl not, more preferably not hydroxyl and carboxyl.As this monomer, be preferably illustrative monomer above, for example: contain N, N-dialkyl group substituted-amino, N, the acrylic monomer of N-dialkyl group substituted amido; The N-vinyl substituted lactan such as NVP, N-caprolactam, N-vinyl-2-piperidone; N-(methyl) acryloyl morpholine, N-(methyl) the N-(methyl such as acryl tetramethyleneimine) acryl substituted cyclic amine.
In (E), (methyl) alkyl acrylate monomer that contains alkoxyl group as (E-2), can enumerate: (methyl) vinylformic acid 2-methoxyl group ethyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-propoxy-ethyl ester, (methyl) vinylformic acid 2-isopropoxy ethyl ester, (methyl) vinylformic acid 2-butoxyethyl, (methyl) vinylformic acid 2-methoxyl group propyl ester, (methyl) vinylformic acid 2-oxyethyl group propyl ester, (methyl) vinylformic acid 2-propoxy-propyl ester, (methyl) vinylformic acid 2-isopropoxy propyl ester, (methyl) vinylformic acid 2-butoxy propyl ester, (methyl) vinylformic acid 3-methoxyl group propyl ester, (methyl) vinylformic acid 3-oxyethyl group propyl ester, (methyl) vinylformic acid 3-propoxy-propyl ester, (methyl) vinylformic acid 3-isopropoxy propyl ester, (methyl) vinylformic acid 3-butoxy propyl ester, (methyl) vinylformic acid 4-methoxyl group butyl ester, (methyl) vinylformic acid 4-oxyethyl group butyl ester, (methyl) vinylformic acid 4-propoxy-butyl ester, (methyl) vinylformic acid 4-isopropoxy butyl ester, (methyl) vinylformic acid 4-butoxy butyl ester etc.
These contain alkoxyl group (methyl) alkyl acrylate monomer, have the structure of the atom alkoxy replacement of the alkyl in (methyl) alkyl acrylate.
(methyl) acrylate monomer that is C4～C10 with respect to the carbonatoms of (A) alkyl of 100 weight parts, preferably (E-1) not the content of hydroxyl and nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer of (E-2) containing alkoxyl group be 1～20 weight part.To (E-1) not hydroxyl and nitrogenous vinyl monomer and (methyl) alkyl acrylate monomer of (E-2) containing alkoxyl group, both can use respectively a kind of also can be used together two or more.
Isocyanate compound as (F) more than trifunctional, so long as at least have the polyisocyanate compounds of more than three isocyanic ester (NCO) bases in a part.Polyisocyanate compounds comprises the classification such as aliphatic category isocyanic ester, aromatic series kind isocyanate, non-ring type kind isocyanate, ester ring type kind isocyanate, and the present invention can be any kind wherein.As the object lesson of polyisocyanate compounds, can enumerate: the aliphatic category isocyanate compounds such as hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), trimethyl hexamethylene diisocyanate (TMDI); The aromatic series kind isocyanate compounds such as diphenylmethanediisocyanate (MDI), xylylene vulcabond (XDI), hydrogenation of benzene dimethyl vulcabond (H6XDI), dimethyl diphenylene vulcabond (TOID), tolylene diisocyanate (TDI).
As isocyanate compound more than trifunctional, can enumerate: biuret modified body or the isocyanurate-modified body of diisocyanates (compound in a part with two NCO bases), the affixture (polyalcohol modified body) of the polyvalent alcohol (compound at least in a part with more than three OH base) with TriMethylolPropane(TMP) (TMP) or glycerine etc. more than trivalent etc.
And, isocyanate compound as (F) that use in the present invention more than trifunctional, more than preferably including at least one being selected from (F-1) first aliphatic category isocyanate compound group and more than being selected from least one in (F-2) second aromatic series kind isocyanate compound group, wherein, described (F-1) first aliphatic category isocyanate compound group is the isocyanuric acid ester by hexamethylene diisocyanate compound, the isocyanuric acid ester of isophorone diisocyanate compound, the affixture of hexamethylene diisocyanate compound, the affixture of isophorone diisocyanate compound, the biuret of hexamethylene diisocyanate compound, the biuret of isophorone diisocyanate compound forms, described (F-2) second aromatic series kind isocyanate compound group by the isocyanuric acid ester of tolylene diisocyanate compound, the affixture of the isocyanuric acid ester of xylylene diisocyanate cpd, the isocyanuric acid ester of hydrogenation of benzene dimethyl diisocyanate cpd, the affixture of the affixture of tolylene diisocyanate compound, xylylene diisocyanate cpd, hydrogenation of benzene dimethyl diisocyanate cpd formed.Preferred also use (F-1) first aliphatic category isocyanate compound group and (F-2) the second aromatic series kind isocyanate compound group.In the present invention, isocyanate compound as (F) more than trifunctional, by more than also using at least one being selected from (F-1) first aliphatic category isocyanate compound group and more than being selected from least one in (F-2) second aromatic series kind isocyanate compound group, can further improve the balance of the cohesive force in low speed stripping area and high speed stripping area.
In addition, more than preferably (F) isocyanate compound more than trifunctional comprises at least one being selected from aforementioned (F-1) first aliphatic category isocyanate compound group and more than being selected from least one in aforementioned (F-2) second aromatic series kind isocyanate compound group, and with respect to the aforementioned multipolymer of 100 weight parts, the total content that is somebody's turn to do (F) isocyanate compound more than trifunctional is 0.5～5.0 weight part.In addition, at least one above at least one above mixture ratio with being selected from (F-2) second aromatic series kind isocyanate compound group as being selected from (F-1) first aliphatic category isocyanate compound group, calculates and is preferably (F-1) with weight ratio: (F-2) in the scope of 10%:90%～90%:10%.
As (G) cross-linked inhibitor, can enumerate: the 'beta '-ketoester of methyl acetoacetate, methyl aceto acetate, etheric acid monooctyl ester, etheric acid grease, etheric acid lauryl, etheric acid stearyl ester etc.; Methyl ethyl diketone, 2, the beta-diketon of 4-hexanedione, benzoyl acetone etc.These are keto-enol tautomerism compounds, usining in the adhesive composition of polyisocyanate compounds as linking agent, by the isocyanate group that linking agent is had, seal, can suppress to coordinate the excess stickiness of adhesive composition after linking agent to rise or the phenomenon of gelation, can extend the storage period of adhesive composition.
Preferably (G) cross-linked inhibitor is keto-enol tautomerism compound, more than being particularly preferably at least one that select in the compound group that free methyl ethyl diketone, methyl aceto acetate form.
With respect to the multipolymer of 100 weight parts, preferably the content of (G) cross-linked inhibitor is 1.0～5.0 weight parts.
Usining polyisocyanate compounds as linking agent in the situation that, (H) crosslinking catalyst so long as catalyzer the material to the reaction of aforementioned multipolymer and linking agent (crosslinking reaction) performance function, can enumerate: the organometallic compounds such as the aminated compounds of tertiary amine etc., organo-tin compound, organo-lead compound, organic zinc compound etc.
As tertiary amine, can enumerate: trialkylamine, N, N, N', N'-tetraalkyl diamines, N, N-dialkyl amido alcohol, triethylene diamine, morpholine derivative, bridged piperazine derivatives etc.
As organo-tin compound, can enumerate: the soap of dialkyl tin oxide, dialkyl tin, the soap of sub-tin etc.
Preferably (H) crosslinking catalyst is organo-tin compound, more than being particularly preferably at least one being selected from the compound group being comprised of di-n-octyltin oxide, two dioctyltin laurate.
With respect to the multipolymer of 100 weight parts, preferably the content of (H) crosslinking catalyst is 0.01～0.5 weight part.
Preferably (I) static inhibitor is that (I-1) fusing point is the ionic compound of 30～80 ℃ or the quaternary ionic compound that (I-2) contains acryl.
In the present invention, as (I) static inhibitor, the ionic compound that is 30～80 ℃ by (I-1) fusing point makes an addition in multipolymer, or the quaternary ionic compound copolymerization that (I-2) contained to acryl is in multipolymer.Supposition is because the fusing point of these (I) static inhibitor is low and have chain alkyl, therefore, high with the affinity of acrylic copolymer.
It as (I-1) fusing point, is the ionic compound of 30～80 ℃, it is the ionic compound with positively charged ion and negatively charged ion, can enumerate: positively charged ion is cationic nitrogenous Huo person phosphonium cation, sulfonium cation of pyridylium, glyoxaline cation, pyrimidine positively charged ion, pyrazoles positively charged ion, pyrroles's positively charged ion, ammonium cation etc. etc., and negatively charged ion is hexafluoro-phosphate radical (PF -6), thiocyanate ion (SCN -), benzene sulfonamide acid group (RC 6h 4sO 3 -), perchlorate (ClO 4-), tetrafluoride borate (BF 4 -) etc. the compound of inorganic or organic anion.For example, under normal temperature (30 ℃), be preferably solid, and be the compound of 30～80 ℃ by selecting the chain length of alkyl, substituent position, number etc., can accessing fusing point.Preferred cationic is quaternary nitrogen positively charged ion, can enumerate: the season pyridylium, 1 of 1-alkyl pyridine (carbon atom of 2～6 both can have substituting group also can not have substituting group) etc., the quaternary ammonium cation of the season glyoxaline cation of 3-dialkylimidazolium (carbon atom of 2,4,5 both can have substituting group also can not have substituting group) etc., tetra-allkylammonium etc. etc.
With respect to the multipolymer of 100 weight parts, preferably (I-1) fusing point is that the content of the ionic compound of 30～80 ℃ is 0.1～5.0 weight part.
The quaternary ionic compound that contains acryl as (I-2), is the ionic compound with positively charged ion and negatively charged ion, can enumerate: positively charged ion is (methyl) acryloxyalkyl trialkyl ammonium (R 3n +-C nh 2n-OCOCQ=CH 2, wherein, Q=H or CH 3, R=alkyl) etc. the quaternary ammonium ion that contains (methyl) acryl; Negatively charged ion is hexafluoro-phosphate radical (PF 6 -), thiocyanate ion (SCN -), organic sulfonic acid root (RSO 3 -), perchlorate (ClO 4 -), tetrafluoride borate (BF 4 -), containing F imide root (R f 2n -) etc. the compound of inorganic or organic anion.As containing F imide root (R f 2n -) R f, can enumerate perfluoroalkyl group sulfonyl, the fluorosulfonyl of trifyl, five fluorine ethylsulfonyls etc.As containing F imide root, can enumerate two (fluorosulfonyl) imide root ((FSO 2) 2n -), two (trifyl) imide root ((CF 3sO 2) 2n -), two (five fluorine ethylsulfonyls) imide root ((C 2f 5sO 2) 2n -) etc. two alkylsulfonyl imide roots.
(I-2) the quaternary ionic compound that contains acryl, preferably the copolymerization amount in multipolymer is 0.1～5.0 % by weight.
Object lesson as (I) static inhibitor, be not particularly limited, but as (I-1) fusing point, be the object lesson of the ionic compound of 30～80 ℃, can enumerate 1-octyl group pyridine hexafluorophosphate, 1-nonyl pyridine hexafluorophosphate, 2-methyl isophthalic acid-dodecyl pyridine hexafluorophosphate, 1-octyl group pyridine dodecylbenzene sulfonate, 1-dodecyl pyridine thiocyanate-, 1-dodecyl pyridine dodecylbenzene sulfonate, 4-methyl isophthalic acid-octyl group pyridine hexafluorophosphate etc.In addition, the object lesson of the quaternary ionic compound that contains acryl as (I-2), can enumerate dimethylaminomethyl (methyl) acrylate phosphofluoric acid methyl salt ((CH 3) 3n +cH 2oCOCQ=CH 2pF 6 -, wherein, Q=H or CH 3), two (trifyl) imide methyl salt ((CH of dimethyl aminoethyl (methyl) acrylate 3) 3n +(CH 2) 2oCOCQ=CH 2(CF 3sO 2) 2n -, wherein, Q=H or CH 3), two (fluorosulfonyl) imide methyl salt ((CH of dimethylaminoethyl acrylate methyl base amino methyl 3) 3n +cH 2oCOCQ=CH 2(FSO 2) 2n -, wherein, Q=H or CH 3) etc.
(J) polyether modified siloxane compound is the silicone compounds with polyether-based, except common siloxane unit (SiR 1 2-O-), outside, also there is the siloxane unit (SiR that comprises polyether-based 1(R 2o(R 3o) nr 4)-O-).At this, R 1the alkyl or aryl that represents one or more; R 2and R 3the alkylidene group that represents one or more; R 4the alkyl, acyl group etc. (terminal group) that represent one or more.As polyether-based, can enumerate: polyoxyethylene thiazolinyl ((C 2h 4o) n), polyoxytrimethylene base ((C 3h 6o) n) etc. polyoxyalkylene.
Preferably (J) polyether modified siloxane compound is that HLB value is 7～12 polyether modified siloxane compound.In addition, with respect to the multipolymer of 100 weight parts, preferably the content of (J) polyether modified siloxane compound is 0.01～0.5 weight part, more preferably 0.1～0.5 weight part.
HLB refers to such as JIS K3211(tensio-active agent term) etc. regulation hydrophilic-lipophilic balance (wetting ability and oil loving ratio).
Polyether modified siloxane compound, for example, can obtain by the following method: by hydrosilylation reactions, make the organic compound with unsaturated link(age) and polyoxyalkylene be grafted on the main chain of the organopolysiloxane with silylation and obtain.Particularly, can enumerate: dimethyl siloxane-methyl (polyoxyethylene) silicone copolymers, dimethyl siloxane-methyl (polyoxyethylene) siloxanes-methyl (polyoxytrimethylene) silicone copolymers, dimethyl siloxane-methyl (polyoxytrimethylene) silicone copolymers etc.
By (J) polyether modified siloxane compound is matched with to adhesive composition, can improve cohesive force and the cycling processability of binding agent.
And, as other composition, can suitably coordinate contain alkylene oxide (alkylene oxide) can copolymerization the known additive such as (methyl) Acrylic Acid Monomer, (methyl) acrylamide monomer, dialkyl group substituted acrylamide monomer, tensio-active agent, curing catalyst, softening agent, weighting agent, curing inhibitors, processing aid, antiaging agent, antioxidant.These both may be used singly or in combination of two or more use.
For the host multipolymer of adhesive composition of the present invention, can by make (methyl) acrylate monomer, (B) that the carbonatoms of (A) alkyl is C4～C10 contain hydroxyl can copolymerization monomer, (C) contain carboxyl can copolymerization monomer and (D) polyalkylene glycol mono (methyl) acrylate monomer carry out polymerization and synthesize.To the polymerization process of multipolymer, there is no particular limitation, can use the suitable polymerization processs such as solution polymerization, letex polymerization.
When as (I) static inhibitor, use (I-2) to contain acryl quaternary ionic compound time; for the host multipolymer of adhesive composition of the present invention, can by make (methyl) acrylate monomer, (B) that the carbonatoms of (A) alkyl is C4～C10 contain hydroxyl can copolymerization monomer, (C) contain carboxyl can copolymerization monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and the quaternary ionic compound that (I-2) contains acryl carry out polymerization and synthesize.
Adhesive composition of the present invention can be by coordinating (F) more than trifunctional isocyanate compound, (G) cross-linked inhibitor, (H) crosslinking catalyst, (I) static inhibitor, (J) polyether modified siloxane compound, also having suitable any additive to prepare in above-mentioned multipolymer.In addition, if in the situation of the quaternary ionic compound polymerization that (I-2) has been contained to acryl in host multipolymer, to multipolymer, both can further add (I) static inhibitor, also can not add (I) static inhibitor.
Preferred aforementioned multipolymer is acrylic polymers, preferably contains the acrylic monomers such as (methyl) acrylate monomer of 50～100 % by weight or (methyl) vinylformic acid, (methyl) acrylic amide.
In addition, preferably the acid number of acrylic polymers is 0.01～8.0.Thus, can improve the performance that contaminative and raising prevent that glue residue phenomenon from occurring.
At this, " acid number " means one of index of acid content, be with in and the mg number of the 1g needed potassium hydroxide of polymkeric substance that contains carboxyl represent.
Preferably making the cohesive force of the crosslinked adhesive layer forming of aforementioned adhesive composition under low peeling rate 0.3m/min is 0.05～0.1N/25mm, and the cohesive force under high peeling rate 30m/min is below 1.0N/25mm.Thus, can obtain cohesive force with the little performance of the variation of peeling rate, even also can peel off rapidly in the situation that peeling off at a high speed.And, even, also without excessive strength, be easy to from being peeled off by adherend during temporary transient stripper surface protective membrane in order again to paste.
Preferably make the surface resistivity of the crosslinked adhesive layer forming of aforementioned adhesive composition 5.0 * 10 + 10below Ω/, peeling off static voltage is ± 0～0.3kV.In addition, in the present invention, the meaning of so-called " ± 0～0.3kV " refers to " 0～-0.3kV " and " 0～+ 0.3kV ", i.e. " 0.3～+ 0.3kV ".If surface resistivity is large, the poor performance discharging because of the charged static producing when peeling off, therefore, by making surface resistivity enough little, can reduce follow occur when being peeled off adhesive layer by adherend static produced peels off static voltage, can suppress by the impact of electric control circuit of adherend etc.
Preferably making the gel fraction of the crosslinked adhesive layer forming of adhesive composition of the present invention (binding agent after crosslinked) is 95～100%.Because gel fraction is so high, the in the situation that of low peeling rate, cohesive force can not become excessive, reduced the phenomenon of from multipolymer stripping unconverted monomer or oligomer, thereby can improve the weather resistance under re-workability, high temperature/high humidity, and suppressed by the pollution of adherend.
Adhesive film of the present invention is at the single or double of resin molding, to form adhesive layer to form, and described adhesive layer is to make that adhesive composition of the present invention is crosslinked to be formed.In addition, surface protection film of the present invention is at the one side of resin molding, to form adhesive layer to form, and described adhesive layer is to make that adhesive composition of the present invention is crosslinked to be formed.In adhesive composition of the present invention; because the balance with good is combined with each composition of above-mentioned (A)～(J); so there is good antistatic property; the balance of the cohesive force under low peeling rate and high peeling rate is good; and endurance quality and cycling processability (with ballpoint pen, after adhesive layer is described on surface protection film, not having to being transferred the pollution by adherend) are also good.Therefore, can preferably as the surface protection film purposes of Polarizer, be used.
As the base material film of adhesive layer, the stripping film (barrier film) of protection adhesive surface, can use the resin moldings such as polyester film etc.
For base material film, can be on the face contrary with being formed with adhesive layer one side of resin molding, the antifouling processing that releasing agent or coating-forming agent, the silicon dioxide microparticle etc. of enforcement by silicone, fluorine class carry out, can implement the coating by static inhibitor or the antistatic treatment of carrying out such as sneak into.
For stripping film, fitting on the face of a side with the adhesive surface of adhesive layer, implement the demoulding that releasing agent by silicone, fluorine class etc. carries out and process.
Embodiment
Below, based on embodiment, illustrate the present invention.
The manufacture of<acrylic copolymer>
[embodiment 1]
To being furnished with in the reaction unit of agitator, thermometer, reflux exchanger and nitrogen ingress pipe, import nitrogen, thus with nitrogen replacement the air in reaction unit.Then, in reaction unit, add 2-EHA, the vinylformic acid 8-hydroxyl monooctyl ester of 0.9 weight part, the vinylformic acid of 0.5 weight part, the NVP of the polyethylene glycol monoacrylate of 3 weight parts, 5 weight parts of 100 weight parts, and added the solvent (ethyl acetate) of 60 weight parts simultaneously.Then, through within 2 hours, splashing into the Diisopropyl azodicarboxylate as polymerization starter of 0.1 weight part, at 65 ℃, make its reaction 6 hours, to have obtained weight-average molecular weight be 500,000, for the acrylic acid copolymer soln 1 of embodiment 1.Get a part for acrylic copolymer, as determination of acid value sample described later, use.
[embodiment 2～9 and comparative example 1～4]
Except (A) as in table 1～(E) with (I-2), adjusted respectively the composition of each monomer, similarly operate with the above-mentioned acrylic acid copolymer soln 1 for embodiment 1, obtained the acrylic acid copolymer soln for embodiment 2～9 and comparative example 1～4.
Table 1
Figure BDA00003323903100181
The manufacture of<adhesive composition and surface protection film>
[embodiment 1]
Acrylic acid copolymer soln 1 to the embodiment 1 according to manufacturing as mentioned above, add 1.5 weight part 1-octyl group pyridine hexafluorophosphates, the polyether modified siloxane compound of 0.2 weight part KF-351A(HLB=12), 2.5 weight part methyl ethyl diketones and stir after, add 1.0 weight part Coronate HX(コ ロ ネ ー ト HX, the isocyanuric acid ester of hexamethylene diisocyanate compound), 0.2 weight part Coronate L(コ ロ ネ ー ト L, the affixture of tolylene diisocyanate compound and TriMethylolPropane(TMP)), after 0.02 weight part two dioctyltin laurate, be uniformly mixed, obtained the adhesive composition of embodiment 1.This adhesive composition is coated on the stripping film consisting of the polyethylene terephthalate that scribbles silicone resin (PET) film, then at 90 ℃, be dried and remove solvent, having obtained adhesive layer thickness is the bonding sheet of 25 μ m.
Then; prepare to implement on a face polyethylene terephthalate (PET) film of antistatic treatment and antifouling processing; and bonding sheet is transferred to this polyethylene terephthalate (PET) film with implement on the opposing face of face of antistatic treatment and antifouling processing, obtained the surface protection film of the embodiment 1 of the stacked formation with " the PET film/adhesive layer/stripping film (scribbling the PET film of silicone resin) that implements antistatic treatment and antifouling processing ".
[embodiment 2～9 and comparative example 1～4]
Except adjusted respectively the composition of each additive as described in (F) of table 2～(J), similarly operate with the surface protection film of above-described embodiment 1, obtained embodiment 2～9 and 1～4 surface protection film relatively.
Table 2
Figure BDA00003323903100191
Table 1 and table 2 are the whole table that represents each components matching ratio to be divided into the table of two parts, and the numerical value in bracket all represents that the total weight with (A) group is made as 100 weight parts and the numerical value of each composition weight part of obtaining.In addition, compound title corresponding to the abbreviation of each composition with using in table 1 and table 2 is shown in table 3 and table 4.In addition, Coronate(コ ロ ネ ー ト, registered trademark) HX, Coronate HL and Coronate L be (the Nippon Polyurethane Industry Co. of Nippon Polyurethane Industry Co., Ltd., Ltd.) trade name, Takenate(タ ケ ネ ー ト, registered trademark) D-140N, D-127N, D-110N, D-120N be the trade name of Mitsui Chemicals, Inc, KF-351A, KF-352A, KF-353, KF-640 and X-22-6191 are the trade names of KCC of SHIN-ETSU HANTOTAI.
In table 1, by (I-1) fusing point adding after quaternary ionic compound in (I) static inhibitor, that (I-2) of copolymerization in multipolymer contains acryl and polymerization, be the ionic compound of 30～80 ℃, be recorded in respectively in different hurdles.
Table 3
Figure BDA00003323903100211
Table 4
Figure BDA00003323903100221
<test method and evaluation>
Under 23 ℃, the environment of 50%RH; by the surface protection film of embodiment 1～9 and comparative example 1～4 after aging 7 days; peel stripping film (scribbling the PET film of silicone resin) off, thereby adhesive layer is exposed, and as the sample of measuring gel fraction and surface resistivity.
And then; the surface protection film that this adhesive layer is exposed; by adhesive layer, fit in the Polarizer surface sticking on liquid crystal cells; place and after 1 day, under 50 ℃, 5 normal atmosphere, carry out pressure kettle and process 20 minutes; further at room temperature place 12 hours, using the surface protection film obtaining thus as measuring cohesive force, peel off the sample of static voltage and weather resistance.
<acid number>
The acid number of acrylic polymers: by sample dissolution in solvent (solvent that diethyl ether and ethanol are mixed with volume ratio 2:1), adopt potential difference automatic titration device (AT-610, capital of a country electronic industry Co., Ltd. manufactures), with the potassium hydroxide-ethanol solution of the about 0.1mol/L of concentration, carry out potential difference titration, measured for and the amount of the required potassium hydroxide-ethanol solution of sample.Then, according to following formula, obtain acid number.
Acid number=(B * f * 5.611)/S
The amount (mL) of the 0.1mol/L potassium hydroxide-ethanol solution using in B=titration
The coefficient of f=0.1mol/L potassium hydroxide-ethanol solution
The quality of the solids component of S=sample (g)
<gel fraction>
Measure exactly after aging end, the quality of the mensuration sample before laminating Polarizer, and in toluene, flood after 24 hours, the wire cloth by 200 sieve meshes filters.Then, at 100 ℃, dry filter thing, after 1 hour, is measured the quality of residue exactly, and according to following formula, calculates the gel fraction of adhesive layer (binding agent after crosslinked).
Gel fraction (%)=insoluble part quality (g)/binding agent quality (g) * 100
<cohesive force>
Adopt tensile testing machine; with low peeling rate (0.3m/min) and high peeling rate (30m/min); to 180 ° of directions, peel off above-mentioned resulting mensuration sample (the wide surface protection film of 25mm is fitted in to the sample that Polarizer surface forms); measured stripping strength, and using this stripping strength as cohesive force.
<surface resistivity>
After aging, before laminating Polarizer, peel stripping film (scribbling the PET film of silicone resin) off and adhesive layer is exposed, adopt resistivity meter HirestaUP-HT450(Ha イ レ ス タ UP-HT450, Mitsubishi Chemical of Co., Ltd. analytical technology (Mitsubishi Chemical Analytech Co., Ltd) manufacture), measured the surface resistivity of adhesive layer.
<peel off static voltage>
Adopt high precision electrostatic transducer SK-035, SK-200(Co., Ltd. Keyemce (Keyence Corporation) to manufacture), measure when above-mentioned resulting mensuration sample is carried out to 180 ° while peeling off with the draw speed of 30m/min, charged and the voltage (static voltage) that produces of Polarizer, using the maximum value of measured value as peeling off static voltage.
<re-workability>
With ballpoint pen, on the surface protection film of mensuration sample obtained above, describe after (load be 500g, 3 times back and forth), from Polarizer stripper surface protective membrane, observe the surface of Polarizer, confirm to Polarizer, not transfer the pollution.Evaluation objective benchmark: when be not evaluated as " zero " when Polarizer is transferred the pollution; When confirming that the track of describing along ballpoint pen is at least evaluated as " △ " when pollution has been shifted in part; When the track of confirming to describe along ballpoint pen has pollution transportation and be evaluated as " * " when adhesive surface also confirms to have the disengaging of binding agent.
<weather resistance>
At 60 ℃, 90%RH environment, transfer to be set up and state resulting mensuration sample after 250 hours, its taking-up is placed under room temperature and is placed further 12 hours, then measure cohesive force, the significantly increase of confirming to compare with initial stage cohesive force not.Evaluation objective benchmark: the cohesive force after test is that the average evaluation below 1.5 times of initial stage cohesive force is that " zero ", the average evaluation over 1.5 times are " * ".
Evaluation result is shown in Table 5.In addition, in surface resistivity, by " mE+n ", represent " m * 10 + n" (wherein, m is real number arbitrarily, and n is positive integer).
Table 5
Figure BDA00003323903100241
Surface protection film for embodiment 1～9, the cohesive force under low peeling rate 0.3m/min is 0.05～0.1N/25mm, the cohesive force under high peeling rate 30m/min is below 1.0N/25mm; Surface resistivity is 5.0 * 10 + 10below Ω/, peeling off static voltage is ± 0～0.3kV; And, use ballpoint pen across adhesive layer after surface protection film is described, not to being transferred the pollution by adherend, and the weather resistance after giving placing for 250 hours under 60 ℃, the environment of 90%RH is also good.
That is, met following whole performance requriements: (1) obtains the balance of the cohesive force under low peeling rate and high speed peeling rate simultaneously; (2) prevent the generation of glue residue; (3) excellent antistatic property; And (4) cycling processability.
In addition, by and be selected from (F-1) first aliphatic category isocyanate compound group more than one and be selected from more than one in (F-2) second aromatic series kind isocyanate compound group, can improve the balance of the cohesive force of low speed stripping area and high speed stripping area.
Surface protection film for comparative example 1; its gel fraction is 0, the cohesive force under low peeling rate 0.3m/min and high peeling rate 30m/min is excessive, re-workability and poor durability, and this may be owing to not comprising (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer that contains alkoxyl group and (F) cause of isocyanate compound.
Surface protection film for comparative example 2; its cohesive force under low peeling rate 0.3m/min and the cohesive force under high peeling rate 30m/min be excessive, peel off that static voltage is high, re-workability and poor durability and gel fraction low, this may be that the monomer that contains hydroxyl due to (B) is very few, (D) polyalkylene glycol mono (methyl) acrylate monomer is very few, (methyl) alkyl acrylate monomer that does not comprise the vinyl monomer that (E) is nitrogenous or contain alkoxyl group, the too small cause of HLB value of (J) polyether modified siloxane compound.
Surface protection film for comparative example 3, its storage period is too short, owing to being cross-linked before coating, therefore, cannot be coated with, and this may be because of (F) isocyanate compound, too much, not coordinate the cause of (G) cross-linked inhibitor.
Surface protection film for comparative example 4, even if do not contain (H) crosslinking catalyst, its storage period is also too short, and owing to being cross-linked before coating, therefore cannot be coated with, this may be because of the too much cause of (F) isocyanate compound.
As mentioned above, in the surface protection film of comparative example 1～4, cannot meet following whole performance requriements: (1) obtains the balance of the cohesive force under low peeling rate and high peeling rate simultaneously; (2) prevent the generation of glue residue; (3) excellent antistatic property; And (4) cycling processability.
Industrial applicibility
Based on binding agent constituent of the present invention, can meet the desired over-all properties of adhesive layer of insurmountable effects on surface protective membrane in the prior art, but also can obtain good antistatic property, prevent the generation of glue residue.In addition, because surface protection film of the present invention has improved the balance of the cohesive force in low speed stripping area and high speed stripping area, therefore, utility value is industrially large.

Claims (24)

1. an adhesive composition, wherein,
This adhesive composition consists of the acrylic polymers that comprises multipolymer, (methyl) acrylate monomer, (B) that the carbonatoms that the acrylic polymers of this multipolymer contains (A) alkyl is C4～C10 contain hydroxyl can copolymerization monomer, (C) contain carboxyl can copolymerization monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) at least one in hydroxyl and nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer of containing alkoxyl group not
And, also contain (F) more than trifunctional isocyanate compound, (G) cross-linked inhibitor, (H) crosslinking catalyst, (I) static inhibitor and (J) polyether modified siloxane compound,
The acid number of described acrylic polymers is 0.01～8.0,
More than described (F) isocyanate compound more than trifunctional comprises at least one being selected from (F-1) first aliphatic category isocyanate compound group and more than being selected from least one in (F-2) second aromatic series kind isocyanate compound group.
2. adhesive composition as claimed in claim 1, wherein,
Described (F-1) first aliphatic category isocyanate compound group in described (F) isocyanate compound more than trifunctional, by the isocyanuric acid ester of hexamethylene diisocyanate compound, the affixture of the isocyanuric acid ester of isophorone diisocyanate compound, hexamethylene diisocyanate compound, the biuret of the affixture of isophorone diisocyanate compound, hexamethylene diisocyanate compound, the biuret of isophorone diisocyanate compound form
Described (F-2) second aromatic series kind isocyanate compound group, by the isocyanuric acid ester of tolylene diisocyanate compound, the affixture of the isocyanuric acid ester of xylylene diisocyanate cpd, the isocyanuric acid ester of hydrogenation of benzene dimethyl diisocyanate cpd, the affixture of the affixture of tolylene diisocyanate compound, xylylene diisocyanate cpd, hydrogenation of benzene dimethyl diisocyanate cpd form.
3. adhesive composition as claimed in claim 1 or 2, wherein,
Described (B) contain hydroxyl can copolymerization monomer, more than at least one being selected from the compound group being formed by (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxy methacrylate, N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide
(methyl) acrylate monomer that is C4～C10 with respect to the carbonatoms of described (A) alkyl of 100 weight parts, described (B) that contains 0.1～5.0 weight part contain hydroxyl can copolymerization monomer,
And, described (B) contain hydroxyl can the monomer of copolymerization in, the total amount of (methyl) vinylformic acid 8-hydroxyl monooctyl ester, (methyl) vinylformic acid own ester of 6-hydroxyl and (methyl) vinylformic acid 4-hydroxyl butyl ester is 0～0.9 weight part.
4. adhesive composition as claimed in claim 1 or 2, wherein,
Described (C) contain carboxyl can copolymerization monomer, to be selected from by (methyl) vinylformic acid, (methyl) vinylformic acid carboxylic ethyl ester, (methyl) vinylformic acid carboxylic pentyl ester, 2-(methyl) acryloxy ethyl hexahydrophthalic acid, 2-(methyl) acryloxy propyl group hexahydrophthalic acid, 2-(methyl) acryloxy ethyl phthalic acid, 2-(methyl) acryloxy ethyl succsinic acid, 2-(methyl) acryloxy ethyl toxilic acid, carboxyl polycaprolactone list (methyl) acrylate, more than at least one in the compound group that 2-(methyl) acryloxy ethyl tetrahydrophthalic acid forms,
(methyl) acrylate monomer that is C4～C10 with respect to the carbonatoms of described (A) alkyl of 100 weight parts, described (C) that contains 0.35～1.0 weight part contain carboxyl can copolymerization monomer.
5. adhesive composition as claimed in claim 3, wherein,
Described (C) contain carboxyl can copolymerization monomer, to be selected from by (methyl) vinylformic acid, (methyl) vinylformic acid carboxylic ethyl ester, (methyl) vinylformic acid carboxylic pentyl ester, 2-(methyl) acryloxy ethyl hexahydrophthalic acid, 2-(methyl) acryloxy propyl group hexahydrophthalic acid, 2-(methyl) acryloxy ethyl phthalic acid, 2-(methyl) acryloxy ethyl succsinic acid, 2-(methyl) acryloxy ethyl toxilic acid, carboxyl polycaprolactone list (methyl) acrylate, more than at least one in the compound group that 2-(methyl) acryloxy ethyl tetrahydrophthalic acid forms,
(methyl) acrylate monomer that is C4～C10 with respect to the carbonatoms of described (A) alkyl of 100 weight parts, described (C) that contains 0.35～1.0 weight part contain carboxyl can copolymerization monomer.
6. adhesive composition as claimed in claim 1 or 2, wherein,
Described (D) polyalkylene glycol mono (methyl) acrylate monomer, more than at least one being selected from polyalkylene glycol mono (methyl) acrylate, methoxyl group polyalkylene glycol (methyl) acrylate, oxyethyl group polyalkylene glycol (methyl) acrylate
(methyl) acrylate monomer that is C4～C10 with respect to the carbonatoms of described (A) alkyl of 100 weight parts, described (D) polyalkylene glycol mono (methyl) acrylate monomer that contains 1～20 weight part.
7. adhesive composition as claimed in claim 1 or 2, is characterized in that,
(methyl) acrylate monomer that is C4～C10 with respect to the carbonatoms of described (A) alkyl of 100 weight parts, described (E) that contains 1～20 weight part be hydroxyl and nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer that contains alkoxyl group not.
8. adhesive composition as claimed in claim 1 or 2, wherein,
More than described (F) isocyanate compound more than trifunctional comprises at least one being selected from described (F-1) first aliphatic category isocyanate compound group and more than being selected from least one in described (F-2) second aromatic series kind isocyanate compound group
With respect to the described multipolymer of 100 weight parts, the total content of described (F) isocyanate compound more than trifunctional is 0.5～5.0 weight part.
9. adhesive composition as claimed in claim 1 or 2, wherein,
Described (I) static inhibitor is that to contain 0.1～5.0 weight part and fusing point be that the ionic compound of 30～80 ℃ or the copolymerization amount in described multipolymer are 0.1～5.0 % by weight and the quaternary ionic compound that contains acryl to the described multipolymer with respect to 100 weight parts.
10. adhesive composition as claimed in claim 3, wherein,
Described (I) static inhibitor is that to contain 0.1～5.0 weight part and fusing point be that the ionic compound of 30～80 ℃ or the copolymerization amount in described multipolymer are 0.1～5.0 % by weight and the quaternary ionic compound that contains acryl to the described multipolymer with respect to 100 weight parts.
11. adhesive compositions as claimed in claim 4, wherein,
Described (I) static inhibitor is that to contain 0.1～5.0 weight part and fusing point be that the ionic compound of 30～80 ℃ or the copolymerization amount in described multipolymer are 0.1～5.0 % by weight and the quaternary ionic compound that contains acryl to the described multipolymer with respect to 100 weight parts.
12. adhesive compositions as claimed in claim 5, wherein,
Described (I) static inhibitor is that to contain 0.1～5.0 weight part and fusing point be that the ionic compound of 30～80 ℃ or the copolymerization amount in described multipolymer are 0.1～5.0 % by weight and the quaternary ionic compound that contains acryl to the described multipolymer with respect to 100 weight parts.
13. adhesive compositions as claimed in claim 6, wherein,
Described (I) static inhibitor is that to contain 0.1～5.0 weight part and fusing point be that the ionic compound of 30～80 ℃ or the copolymerization amount in described multipolymer are 0.1～5.0 % by weight and the quaternary ionic compound that contains acryl to the described multipolymer with respect to 100 weight parts.
14. adhesive compositions as claimed in claim 7, wherein,
Described (I) static inhibitor is that to contain 0.1～5.0 weight part and fusing point be that the ionic compound of 30～80 ℃ or the copolymerization amount in described multipolymer are 0.1～5.0 % by weight and the quaternary ionic compound that contains acryl to the described multipolymer with respect to 100 weight parts.
15. adhesive compositions as claimed in claim 8, wherein,
Described (I) static inhibitor is that to contain 0.1～5.0 weight part and fusing point be that the ionic compound of 30～80 ℃ or the copolymerization amount in described multipolymer are 0.1～5.0 % by weight and the quaternary ionic compound that contains acryl to the described multipolymer with respect to 100 weight parts.
16. adhesive compositions as claimed in claim 1 or 2, wherein,
Described (J) polyether modified siloxane compound is that HLB value is 7～12 polyether modified siloxane compound,
With respect to the described multipolymer of 100 weight parts, described (J) polyether modified siloxane compound that contains 0.01～0.5 weight part.
17. adhesive compositions as claimed in claim 1 or 2, wherein,
Described (G) cross-linked inhibitor is keto-enol tautomerism compound,
With respect to the described multipolymer of 100 weight parts, described (G) cross-linked inhibitor that contains 1.0～5.0 weight parts.
18. adhesive compositions as claimed in claim 1 or 2, wherein,
Described (H) crosslinking catalyst is organo-tin compound,
With respect to the described multipolymer of 100 weight parts, described (H) crosslinking catalyst that contains 0.01～0.5 weight part.
19. adhesive compositions as claimed in claim 1 or 2, wherein,
Making the cohesive force of the crosslinked adhesive layer forming of described adhesive composition under low peeling rate 0.3m/min is 0.05～0.1N/25mm, and the cohesive force under high peeling rate 30m/min is below 1.0N/25mm.
20. adhesive compositions as claimed in claim 1 or 2, wherein,
Making the surface resistivity of the crosslinked adhesive layer forming of described adhesive composition is 5.0 * 10 + 10Ω/ is following, peel off static voltage is ± 0～0.3kV.
21. 1 kinds of adhesive films, is characterized in that,
At the single or double of resin molding, form adhesive layer and form, described adhesive layer is to make in claim 1～20 that the adhesive composition described in any one is crosslinked to be formed.
22. 1 kinds of surface protection films, its one side at resin molding forms adhesive layer and forms, and described adhesive layer is to make in claim 1～20 that the adhesive composition described in any one is crosslinked to be formed, it is characterized in that,
With ballpoint pen, after described adhesive layer is described on surface protection film, do not have to being transferred the pollution by adherend.
23. surface protection films as claimed in claim 22, its surface protection film purposes as Polarizer is used.
24. surface protection films as claimed in claim 22, wherein,
On the contrary face of the side with being formed with described adhesive layer of described resin molding, implement antistatic and antifouling processing.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080200587A1 (en) * 2007-02-16 2008-08-21 3M Innovative Properties Company Pressure-sensitive adhesive containing acicular silica particles crosslinked with polyfunctional aziridines
WO2009008470A1 (en) * 2007-07-11 2009-01-15 Soken Chemical & Engineering Co., Ltd. Pressure-sensitive adhesive composition for polarizing plates and polarizing plate having pressure-sensitive adhesive layer
US20090104450A1 (en) * 2007-10-22 2009-04-23 Nitto Denko Corporation Pressure-sensitive adhesive composition for optical film, pressure-sensitive adhesive layer for optical film, production method thereof, pressure-sensitive adhesive optical film and image display
US20090162577A1 (en) * 2007-12-20 2009-06-25 Nitto Denko Corporation Pressure-sensitive adhesive composition for optical films, pressure-sensitive adhesive optical film and image display
CN102076802A (en) * 2009-04-30 2011-05-25 日东电工株式会社 Adhesive composition for optical film, adhesive layer for optical film, and adhesive optical film, and image display device

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100385720B1 (en) * 1999-04-30 2003-05-27 주식회사 엘지화학 Acrylic pressure-sensitive adhesive composition for optical use having improved rework property and laminates coated therewith
JP4776272B2 (en) * 2004-05-20 2011-09-21 サイデン化学株式会社 Polymer composition for pressure-sensitive adhesive, pressure-sensitive adhesive composition for surface protective film, and surface protective film
TWI340161B (en) * 2005-01-19 2011-04-11 Lg Chemical Ltd Acrylic pressure-sensitive adhesive composition with good re-workability,adhesive sheet,and method of preparing the sheet
JP4149473B2 (en) * 2005-09-21 2008-09-10 サイデン化学株式会社 Polymer composition for pressure-sensitive adhesive, pressure-sensitive adhesive composition for surface protective film, and surface protective film
JP4780766B2 (en) * 2006-03-27 2011-09-28 日東電工株式会社 Optical adhesive, optical film with adhesive, and image display device
JP2008001739A (en) * 2006-06-20 2008-01-10 Bridgestone Corp Adhesive composition for electronic display, adhesive layer for electronic display and adhesive filter for electronic display
JP4942171B2 (en) * 2006-09-14 2012-05-30 綜研化学株式会社 Adhesive composition and adhesive sheet
JP2008248223A (en) * 2007-03-07 2008-10-16 Ipposha Oil Ind Co Ltd Pressure-sensitive adhesive composition for use in surface protecting sheet, and surface protecting sheet using the same
JP2009091406A (en) * 2007-10-04 2009-04-30 Nippon Carbide Ind Co Inc Pressure-sensitive adhesive composition and surface protection film
JP5407204B2 (en) * 2008-07-16 2014-02-05 王子ホールディングス株式会社 Adhesive, double-sided adhesive sheet, optical filter, and display
JP2010037431A (en) * 2008-08-05 2010-02-18 Nippon Shokubai Co Ltd Solvent-based releasable self-adhesive composition and releasable self-adhesive product
KR20100089389A (en) * 2009-02-03 2010-08-12 삼성전자주식회사 Photocurable adhesive composition and photocurable adhesive film made therefrom
JP2010195941A (en) * 2009-02-25 2010-09-09 Sanyo Chem Ind Ltd Antistatic pressure-sensitive adhesive
JP5580069B2 (en) * 2009-02-26 2014-08-27 日東電工株式会社 Adhesive composition for surface protective film and use thereof
JP5623020B2 (en) * 2009-02-27 2014-11-12 日東電工株式会社 Adhesive composition, adhesive layer, and adhesive sheet
KR20120036829A (en) 2009-06-09 2012-04-18 닛폰고세이가가쿠고교 가부시키가이샤 Pressure-sensitive adhesive compositon, pressure-sensitive adhesive, pressure-sensitive adhesive for optical member, and optical member with pressure-sensitive adhesive layer obtained using same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080200587A1 (en) * 2007-02-16 2008-08-21 3M Innovative Properties Company Pressure-sensitive adhesive containing acicular silica particles crosslinked with polyfunctional aziridines
WO2009008470A1 (en) * 2007-07-11 2009-01-15 Soken Chemical & Engineering Co., Ltd. Pressure-sensitive adhesive composition for polarizing plates and polarizing plate having pressure-sensitive adhesive layer
US20090104450A1 (en) * 2007-10-22 2009-04-23 Nitto Denko Corporation Pressure-sensitive adhesive composition for optical film, pressure-sensitive adhesive layer for optical film, production method thereof, pressure-sensitive adhesive optical film and image display
US20090162577A1 (en) * 2007-12-20 2009-06-25 Nitto Denko Corporation Pressure-sensitive adhesive composition for optical films, pressure-sensitive adhesive optical film and image display
CN102076802A (en) * 2009-04-30 2011-05-25 日东电工株式会社 Adhesive composition for optical film, adhesive layer for optical film, and adhesive optical film, and image display device

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