CN103305158B - Adhesive composition and surface protection film - Google Patents

Adhesive composition and surface protection film Download PDF

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Publication number
CN103305158B
CN103305158B CN201310068785.1A CN201310068785A CN103305158B CN 103305158 B CN103305158 B CN 103305158B CN 201310068785 A CN201310068785 A CN 201310068785A CN 103305158 B CN103305158 B CN 103305158B
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methyl
mentioned
acrylate
surface protection
adhesive phase
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CN103305158A (en
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长仓毅
岛口龙介
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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
    • 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
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • 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
    • 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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Polarising Elements (AREA)
  • Laminated Bodies (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The present invention provides adhesive composition and surface protection film, described adhesive composition and the surface protection film balancing good of bonding force in low speed peeling rate and high speed peeling rate, and durability and performance of doing over again the most excellent.Described adhesive composition is by containing (methyl) acrylate monomer that (A) atomic number of alkyl carbon is C4～C10, (B) copolymerisable monomer containing hydroxyl, (C) copolymerisable monomer containing carboxyl, (D) acrylic polymer of the copolymer of polyalkylene glycol mono (methyl) acrylate monomer is constituted, it contains (E) 3 official further can above isocyanate compound, (F) cross-linked inhibitor, (G) crosslinking catalyst, (H) polyether-modified silicone compounds, the acid number of aforesaid propylene acids polymers is 0.01～8.0.

Description

Adhesive composition and surface protection film
Technical field
The present invention relates to the surface protection film used in the manufacturing process of liquid crystal display.More specifically; the present invention relates to be fitted on the surface of the optics constituting the Polarizer of liquid crystal display, polarizer etc., protect the surface protection film adhesive composition on the surface of the optics of Polarizer, polarizer etc., and use its surface protection film.
Background technology
All the time, in the manufacturing process of the optics for constituting the Polarizer of parts of liquid crystal display, polarizer etc., at the surface of optics temporary transient coating surface protecting film.When optics is assembled into liquid crystal display, surface protection film is peeled off from optics and removes.In order to protect the surface protection film of optical component surfaces only to use in manufacturing process.Therefore, usually, also referred to as operation film.
The surface protection film used in the operation manufacturing optics, forms adhesive phase in the one side of polyethylene terephthalate (PET) resin molding with optical transparence.Additionally, until before fitting in optics, by order to protect the stripping film being stripped process of this adhesive phase to fit in above adhesive phase.
And; optics due to Polarizer, polarizer etc.; when being fitted with surface protection film; carry out the display capabilities with LCD panel, the examination and test of products of colourity, contrast, impurity are mixed into etc. optical assessment; therefore; the performance necessary for surface protection film is, the most non-cohesive bubble or impurity.
And, when the optics making surface protection film fit in Polarizer, polarizer etc., due to a variety of causes, have and temporarily peel off surface protection film, then re-paste the situation of surface protection film.At this moment require easily from the surface protection film of the stripping (there is doing over again property (リ ワ Network)) of the optics of adherend.
And, when the optics of Polarizer, polarizer etc. peels off surface protection film, it is desirable to can peel off rapidly.That is, in order to also be able to peel off rapidly by stripping at a high speed, it is desirable to it is few that bonding force is affected by peeling rate.
So; in recent years; requirement performance as the adhesive phase for constituting surface protection film; easy-to-use point in time using surface protection film; require that (1) obtains the balance of the bonding force during low speed is peeled off and peeled off at a high speed; (2) it is prevented from the generation of adhesive residue, and (3) have performance etc. of doing over again.
But; although disclosure satisfy that the requirement performance individually of these (1)～(3), but it is very difficult to be provided simultaneously with in the adhesive phase of surface protection film the required performance of required (1)～(3).
Such as, obtain low speed about (1) to peel off and the balance of the bonding force in stripping at a high speed；(2) generation of adhesive residue can be prevented, it is known to following motion.
There is (methyl) alkyl acrylate of carbon number alkyl below 7 copolymer with the copolymerizable compound containing carboxyl as main component, the acrylic adhesives its crosslinking Treatment made with cross-linking agent, if through long-time after laminating, then there is binding agent to adherend one side shifting, and to the bonding force of adherend through time the problem that rises.In order to prevent this problem from producing, known following binding agent (contact adhesive): described binding agent uses (methyl) alkyl acrylate and the copolymer of the copolymerizable compound with alcohol hydroxyl group with the alkyl that carbon number is 8～10, with cross-linking agent, its crosslinking Treatment is obtained (patent documentation 1).
And following binding agent etc. is proposed: described binding agent, by mixing the copolymer of (methyl) alkyl acrylate and the copolymerizable compound containing carboxyl in above-mentioned same copolymer on a small quantity, processes by cross-linking agent cross-linking and obtains.But, when in the surface protection using it for the low ganoid plastic plate of surface tension etc., have and float, owing to heating when adding man-hour or preserve produces, the problem that when problem of the peeling waited or manually peel off is peeled off at a high speed, releasable is poor.
In order to solve these problems, adhesive composition is proposed, described adhesive composition is by (methyl) alkyl acrylate as main component of (methyl) alkyl acrylate to have the alkyl that carbon number is 8～10 of (a) 100 weight portion, add (b) 1～15 weight portion the copolymerizable compound containing carboxyl and, c the vinyl esters of the aliphatic carboxylic acid that carbon number is 1～5 of () 3～100 weight portion obtains the copolymer of monomer mixture, it is mixed in this copolymer and obtains (patent documentation 2) relative to the cross-linking agent that carboxyl is more than equivalent of above-mentioned (b) composition.
Adhesive composition described in patent documentation 2, the peeling floated etc. in not producing when adding man-hour or preserving etc., and bonding force through time rise the least, releasable is outstanding, even the long-term preservation under long-term preservation, particularly high-temperature atmosphere, it is also possible to peel off again with little power, at this moment, adherend does not produce adhesive residue, and, it also is able to peel off again with little power when carrying out and peeling off at a high speed.
And, about (3), there is performance of doing over again, adhesive composition is such as proposed, described adhesive composition is by be 0.0001～10 weight portions for acrylic resin 100 weight portion, and the sclerosing agent and the specific silicate oligomer that mix isocyanate ester compound in acrylic resin obtain (patent documentation 3).
In patent documentation 3, with atomic number of alkyl carbon alkyl acrylate, atomic number of alkyl carbon alkyl methacrylate being about 4～12 of being about 2～12 etc. as main monomer component, for instance, it is possible to comprise the monomer etc. containing carboxyl, monomer component containing other functional group.It is generally preferable that containing above-mentioned principal monomers more than 50 weight %, and, it is desirable to the content of the monomer component containing functional group is 0.001～50 weight %, preferably 0.001～25 weight %, more preferably 0.01～25 weight %.Even if the adhesive composition described in such patent documentation 3 at high temperature or hot and humid under, the rheological parameters' change with time of cohesiveness and bonding force is also little, and, to the bonding force of curved surface displays that outstanding effect, therefore there is doing over again property.
Usually, if adhesive phase is made flexible character, then adhesive residue becomes to be susceptible to, and doing over again property is also easily reduced.I.e. it is easy to peel off difficulty when becoming to fit mistakenly, again fit difficulty.Accordingly, it would be desirable to monomer crosslinked in host by the functional group with carboxyl etc., adhesive phase is made certain hardness so that it is there is doing over again property.
[prior art literature]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open No. Sho 63-225677 publication
[patent documentation 2] Japanese Patent Laid-Open 11-256111 publication
[patent documentation 3] Japanese Patent Laid-Open 8-199130 publication
Summary of the invention
[inventing problem to be solved]
In the prior art; requirement performance as the adhesive phase for constituting surface protection film; require: the balance of the bonding force in obtaining low speed stripping and peeling off at a high speed and performance etc. of doing over again; but; although disclosure satisfy that each, each requirement performance, but can not meet the adhesive phase of surface protection film requires whole require performance.
The present invention has used for reference above-mentioned situation.The problem of the present invention is to provide the balancing good of a kind of adhesive composition and surface protection film, described adhesive composition and the surface protection film bonding force in low speed is peeled off and peeled off at a high speed, and durability and performance of doing over again the most excellent.
[method solving problem]
In order to solve above-mentioned problem, the present invention provides a kind of adhesive composition, it is by containing (methyl) acrylate monomer that (A) atomic number of alkyl carbon is C4～C10, (B) copolymerisable monomer containing hydroxyl, (C) copolymerisable monomer containing carboxyl, (D) acrylic polymer of the copolymer of polyalkylene glycol mono (methyl) acrylate monomer is constituted, it contains (E) 3 official further can above isocyanate compound, (F) cross-linked inhibitor, (G) crosslinking catalyst, (H) polyether-modified silicone compounds, the acid number of described acrylic polymer is 0.01-8.0.
Above-mentioned (B) copolymerisable monomer containing hydroxyl is to select more than at least one in the compound group that freely (methyl) acrylic acid 8-hydroxyl monooctyl ester, (methyl) acrylic acid own ester of 6-hydroxyl, (methyl) acrylic acid 4-hydroxybutyl, (methyl) acrylic acid 2-hydroxy methacrylate, N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-ethoxy (methyl) acrylamide form；(methyl) acrylate monomer that above-mentioned (A) atomic number of alkyl carbon is C4～C10 preferably with respect to 100 weight portions, above-mentioned (B) containing the 0.1～5.0 weight portions copolymerisable monomer containing hydroxyl, and, described (B), containing in the copolymerisable monomer of hydroxyl, (methyl) acrylic acid 8-hydroxyl monooctyl ester, (methyl) acrylic acid own ester of 6-hydroxyl, total amount of (methyl) acrylic acid 4-hydroxybutyl are 0～0.9 weight portion.
Above-mentioned (C) copolymerisable monomer containing carboxyl is choosing freely (methyl) acrylic acid, carboxyethyl (methyl) acrylate, carboxylic amyl group (methyl) acrylate, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloxypropyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl phthalic acid, 2-(methyl) acryloyl-oxyethyl succinic acid, 2-(methyl) acryloyl-oxyethyl maleic acid, carboxy-polycaprolactone list (methyl) acrylate, more than at least one in the compound group of 2-(methyl) acryloyl-oxyethyl tetrahydrochysene phthalic acid composition；Preferably with respect to (methyl) acrylate monomer that carbon number is C4～C10 of above-mentioned (A) alkyl of 100 weight portions, the copolymerisable monomer containing carboxyl of above-mentioned (C) containing 0.35～1.0 weight portions.
Above-mentioned (D) polyalkylene glycol mono (methyl) acrylate monomer be at least one in polyalkylene glycol mono (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate, ethyoxyl poly alkylene glycol (methyl) acrylate more than；Preferably with respect to (methyl) acrylate monomer that carbon number is C4～C10 of above-mentioned (A) alkyl of 100 weight portions, above-mentioned (D) polyalkylene glycol mono (methyl) acrylate monomer containing 1～20 weight portions.
Above-mentioned (E) 3 official can isocyanate compound above be the isocyanuric acid ester body selected from hexamethylene diisocyanate compound, the isocyanuric acid ester body of isophorone diisocyanate compound, the adduction object of hexamethylene diisocyanate compound, the adduction object of isophorone diisocyanate compound, the biuret body of hexamethylene diisocyanate compound, isophorone diisocyanate compound biuret body composition compound group at least one more than；Preferably with respect to the above-mentioned copolymer of 100 weight portions, above-mentioned (E) 3 official containing 0.5～5.0 weight portions can above isocyanate compound.
Above-mentioned (H) polyether-modified silicone compounds be HLB value be the polyether-modified silicone compounds of 7～12, preferably with respect to the above-mentioned copolymer of 100 weight portions, containing the silicone compounds that above-mentioned (H) of 0.01～0.5 weight portion is polyether-modified.
Above-mentioned (F) cross-linked inhibitor is keto-enol tautomerism compound, preferably with respect to the above-mentioned copolymer of 100 weight portions, above-mentioned (F) cross-linked inhibitor containing 1.0～5.0 weight portions.
Above-mentioned (G) crosslinking catalyst is organo-tin compound, preferably with respect to the above-mentioned copolymer of 100 weight portions, above-mentioned (G) crosslinking catalyst containing 0.01～0.5 weight portion.
Preferably so that the adhesive phase of above-mentioned binder composition cross-links bonding force under low speed peeling rate 0.3m/min is 0.05～0.1N/25mm, and the bonding force under high speed peeling rate 30m/min is below 1.0N/25mm.
Additionally, the present invention provides a kind of bonding film, it is characterised in that it obtains for forming the adhesive phase making above-mentioned binder composition cross-links on the one or both sides of resin molding.
And; the present invention provides a kind of surface protection film; it is characterized in that its surface protection film obtained for forming adhesive phase in the one side of resin molding; described adhesive phase obtains by making above-mentioned binder composition cross-links; after describing on the surface protection film via described adhesive phase with ball pen, do not transfer the pollution to adherend.
Above-mentioned surface protection film, it can use as the purposes of the surface protection film of Polarizer.
Preferably being formed on the face that side is contrary with described adhesive phase at above-mentioned resin molding, carries out antistatic and anti-pollution process.
[invention effect]
According to the present invention, it is possible to meet the most indeterminable over-all properties required in the adhesive phase of surface protection film.In addition it is possible to obtain the performance preventing adhesive residue of excellence.In particular it is possible to improve the performance preventing adhesive residue further.
Detailed description of the invention
Below, based on the present invention is preferred embodiment described.
The adhesive composition of the present invention is, its host is C4～C10 (methyl) acrylate monomer by containing (A) atomic number of alkyl carbon, (B) copolymerisable monomer containing hydroxyl, (C) copolymerisable monomer containing carboxyl, (D) acrylic polymer of the copolymer of polyalkylene glycol mono (methyl) acrylate monomer is constituted, it contains (E) 3 official further can above isocyanate compound, (F) cross-linked inhibitor, (G) crosslinking catalyst, (H) polyether-modified silicone compounds, the acid number of described acrylic polymer is 0.01-8.0.
Can enumerate as (methyl) acrylate monomer that (A) atomic number of alkyl carbon is C4～C10:
(methyl) butyl acrylate, (methyl) Isobutyl 2-propenoate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 1-Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) acrylic acid nonyl ester, (methyl) acrylic acid different nonyl ester, (methyl) decyl acrylate etc..
Can enumerate as (B) copolymerisable monomer containing hydroxyl: (methyl) hydroxyalkyl acrylates class of (methyl) acrylic acid 8-hydroxyl monooctyl ester, (methyl) acrylic acid own ester of 6-hydroxyl, (methyl) acrylic acid 4-hydroxybutyl, (methyl) acrylic acid 2-hydroxy methacrylate etc., (methyl) acrylic amide etc. containing hydroxyl of N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-ethoxy (methyl) acrylamide etc..
Preferably, more than at least one in the compound group that (methyl) acrylic acid 8-hydroxyl monooctyl ester, (methyl) acrylic acid own ester of 6-hydroxyl, (methyl) acrylic acid 4-hydroxybutyl, (methyl) acrylic acid 2-hydroxy methacrylate, N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-ethoxy (methyl) acrylamide form.
Relative to (methyl) acrylate monomer that above-mentioned (A) atomic number of alkyl carbon is C4～C10 of 100 weight portions, preferably comprise above-mentioned (B) copolymerisable monomer containing hydroxyl of 0.1～5.0 weight portions.
And, in (B) copolymerisable monomer containing hydroxyl, (methyl) acrylic acid 8-hydroxyl monooctyl ester, (methyl) acrylic acid own ester of 6-hydroxyl, total amount of (methyl) acrylic acid 4-hydroxybutyl are preferred less than 1 weight portion (allowing situation about not containing), preferably 0～0.9 weight portion.
Preferably (C) copolymerisable monomer containing carboxyl is for selected from (methyl) acrylic acid, carboxyethyl (methyl) acrylate, carboxylic amyl group (methyl) acrylate, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloxypropyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl phthalic acid, carboxy-polycaprolactone list (methyl) acrylate, more than at least one in the compound group of 2-(methyl) acryloyl-oxyethyl tetrahydrophthalic acid composition.
(methyl) acrylate monomer that carbon number is C4～C10 relative to (A) alkyl of 100 weight portions, preferably comprise (C) copolymerisable monomer containing carboxyl of 0.35～1.0 weight portions, more preferably contain 0.35～0.6 weight portion.
As (D) polyalkylene glycol mono (methyl) acrylate monomer, can be in multiple hydroxyls that poly alkylene glycol has, hydroxyl be as the esterified compound of (methyl) acrylate.Polymerizable group is become, therefore, it is possible to be copolymerized to host polymer owing to (methyl) is acrylate-based.Other hydroxyl both can keep OH constant, it is also possible to becomes the saturated carboxylic acid esters etc. such as the alkyl ether such as methyl ether or ether, or acetas.
The alkylidene having as poly alkylene glycol, can enumerate ethylidene, propylidene, butylidene etc., and this is infinite.Poly alkylene glycol is alternatively the copolymer of the poly alkylene glycol of more than two kinds of poly-ethylidene glycol, polytrimethylene glycol, polybutylene glycol etc..Copolymer as poly alkylene glycol, can enumerate poly-ethylidene glycol-polytrimethylene glycol, poly-ethylidene glycol-polybutylene glycol, polytrimethylene glycol-polybutylene glycol, poly-ethylidene glycol-polytrimethylene glycol-polybutylene glycol etc., this copolymer can be block copolymer, random copolymer.
As (D) polyalkylene glycol mono (methyl) acrylate monomer, it is preferably selected from more than at least one in polyalkylene glycol mono (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate, ethyoxyl poly alkylene glycol (methyl) acrylate.
More specifically, poly-ethylidene glycol-mono-(methyl) acrylate, polytrimethylene glycol-mono-(methyl) acrylate, polybutylene glycol-mono-(methyl) acrylate, poly-ethylidene glycol-polytrimethylene glycol-mono-(methyl) acrylate, poly-ethylidene glycol-polybutylene glycol-mono-(methyl) acrylate, polytrimethylene glycol-polybutylene glycol-mono-(methyl) acrylate, poly-ethylidene glycol-polytrimethylene glycol-polybutylene glycol-mono-(methyl) acrylate can be enumerated；The poly-ethylidene glycol of methoxyl group-(methyl) acrylate, methoxyl group polytrimethylene glycol-(methyl) acrylate, methoxyl group polybutylene glycol-(methyl) acrylate, methoxyl group-poly-ethylidene glycol-polytrimethylene glycol-(methyl) acrylate, methoxyl group-poly-ethylidene glycol-polybutylene glycol-(methyl) acrylate, methoxyl group-polytrimethylene glycol-polybutylene glycol-(methyl) acrylate, methoxyl group-poly-ethylidene glycol-polytrimethylene glycol-polybutylene glycol-(methyl) acrylate；The poly-ethylidene glycol of ethyoxyl-(methyl) acrylate, ethyoxyl polytrimethylene glycol-(methyl) acrylate, ethyoxyl polybutylene glycol-(methyl) acrylate, ethyoxyl-poly-ethylidene glycol-polytrimethylene glycol-(methyl) acrylate, ethyoxyl-poly-ethylidene glycol-polybutylene glycol-(methyl) acrylate, ethyoxyl-polytrimethylene glycol-polybutylene glycol-(methyl) acrylate, ethyoxyl-poly-ethylidene glycol-polytrimethylene glycol-polybutylene glycol-(methyl) acrylate etc..
Preferably with respect to (methyl) acrylate monomer that carbon number is C4～C10 of above-mentioned (A) alkyl of 100 weight portions, above-mentioned (D) polyalkylene glycol mono (methyl) acrylate monomer containing 1～20 weight portions.
Can above isocyanate compound as (E) 3 official, 1 molecule has the polyisocyanate compound of more than at least 3 isocyanates (NCO) bases, can enumerate: hexamethylene diisocyanate, isophorone diisocyanate, methyl diphenylene diisocyanate, toluylene diisocya-nate, the biuret modified body of the diisocyanates (there is in 1 molecule the compound of 2 NCO bases) of xylylene diisocyanate etc. or isocyanurate-modified body, the adduction object (polyalcohol modified body) etc. of polyhydric alcohol (there is in 1 molecule the compound of the OH base of more than at least 3) more than the trivalent of trimethylolpropane or glycerol etc..
(E) 3 officials can isocyanate compound above be the polyisocyanate compound of isocyanates (NCO) base at least in 1 molecule with more than 3, isocyanuric acid ester body selected from hexamethylene diisocyanate compound is particularly preferred, the isocyanuric acid ester body of isophorone diisocyanate compound, the adduction object of hexamethylene diisocyanate compound, the adduction object of isophorone diisocyanate compound, the biuret body of hexamethylene diisocyanate compound, more than at least one in the compound group of the biuret body composition of isophorone diisocyanate compound.Relative to the copolymer of 100 weight portions, (E) 3 official preferably comprising 0.5～5.0 weight portions can above isocyanate compound.
As (F) cross-linked inhibitor, can enumerate: the 'beta '-ketoester of methyl acetoacetate, ethyl acetoacetate, acetoacetic acid monooctyl ester, acetoacetic acid oil base ester, lauryl acetoacetate, acetoacetic acid stearoyl ester etc., acetylacetone,2,4-pentanedione, 2, the beta-diketon of 4-acetyl butyryl, benzoyl acetone etc..These are keto-enol tautomerism compounds, in the adhesive composition with polyisocyanate compound as cross-linking agent, closed by the NCO that cross-linking agent is had, after can suppressing cross-linking agent mixing, the excessive viscosity of adhesive composition rises or gelation, extends the storage period of adhesive composition.
(F) cross-linked inhibitor is preferably keto-enol tautomerism compound, especially preferably more than at least one in the compound group that acetylacetone,2,4-pentanedione, ethyl acetoacetate form.
Relative to the copolymer of 100 weight portions, preferably comprise (F) cross-linked inhibitor of 1.0～5.0 weight portions.
In the case of with polyisocyanate compound as cross-linking agent, (G) crosslinking catalyst be the reaction (cross-linking reaction) for above-mentioned copolymer and cross-linking agent as catalyst the material of function, can enumerate: the organo-metallic compound etc. of the aminated compounds of tertiary amine etc., organo-tin compound, organo-lead compound, organic zinc compound etc..
Can enumerate as tertiary amine: trialkylamine, N, N, N ', N '-tetra, N, N-dialkyl amido alcohol, triethylenediamine, morpholine derivative, bridged piperazine derivatives etc..
As organo-tin compound, can enumerate: dialkyl tin oxide, the soap of dialkyl tin, the soap etc. of stannous.
(G) more than the preferred organo-tin compound of crosslinking catalyst, especially preferably at least one in the compound group that di-n-octyltin oxide, tin dilaurate dioctyl tin form.
Relative to the copolymer of 100 weight portions, preferably comprise (G) crosslinking catalyst of 0.01～0.5 weight portion.
(H) polyether-modified silicone compounds is the silicone compounds with polyether-based, except conventional siloxane unit (-SiR1 2-O-), also there is the siloxane unit (-SiR of band polyether-based1(R2O(R3O)nR4)-O-).Herein, R1Represent one kind or two or more alkyl or aryl, R2And R3Represent one kind or two or more alkylidene, R4Represent (terminal groups) such as one kind or two or more alkyl, acyl groups.Can enumerate as polyether-based: polyethylene oxide base ((C2H4O)n) or polypropylene oxide base ((C3H6O)n) etc. polyoxyalkylene.
The silicone compounds that preferably (H) is polyether-modified be HLB value be the polyether-modified silicone compounds of 7～12.Additionally, relative to the copolymer of 100 weight portions, preferably comprise the silicone compounds that above-mentioned (H) of 0.01～0.5 weight portion is polyether-modified.More preferably 0.1～0.5 weight portion.
The hydrophile-lipophile balance (hydrophilic and oil loving ratio) of the middle regulations such as so-called HLB is, such as JISK3211 (surfactant term).
Polyether-modified silicone compounds is, such as, for having the polysiloxane main chain of silylation, it is possible to make the organic compound grafting with unsaturated bond and polyoxyalkylene obtain by hydrosilylation reactions.Specifically can enumerate: dimethylsiloxane methyl (polyethylene glycol oxide) silicone copolymers, dimethylsiloxane methyl (polyethylene glycol oxide) siloxanes methyl (polypropylene oxide) silicone copolymers, dimethylsiloxane methyl (polypropylene oxide) silicone copolymers etc..
By silicone compounds polyether-modified to (H) is mixed into adhesive composition, it is possible to improve the bonding force of binding agent and performance of doing over again.
Furthermore, composition as other, it is possible to the suitably mixing known additive containing copolymerizable (methyl) acrylic monomer of oxyalkylene, (methyl) acrylamide monomer, the substituted acrylamide monomer of dialkyl group, surfactant, hardening accelerator, plasticizer, filler, cure inhibitors, processing aid, age resister, antioxidant, antistatic additive etc..These can individually or two or more merge use.
As antistatic additive, ionic compound can be enumerated.Further, by enabling ionic acrylic monomer copolymerization to give antistatic property in the copolymer of host.
The copolymer of the host used in the adhesive composition of the present invention can be (methyl) acrylate monomer of C4～C10 and (B) copolymerisable monomer containing hydroxyl and (C) copolymerisable monomer containing carboxyl and the synthesis of (D) polyalkylene glycol mono (methyl) acrylate monomer by polymerization (A) atomic number of alkyl carbon.There is no particular limitation for the polymerization of copolymer, it is possible to use the suitable polymerizations such as polymerisation in solution, emulsion polymerization.
Can the polyether-modified silicone compounds of above isocyanate compound, (F) cross-linked inhibitor, (G) crosslinking catalyst, (H), further the most arbitrary additive by mixing (E) 3 official in above-mentioned copolymer, it is possible to the adhesive composition of the preparation present invention.
Above-mentioned copolymer, preferably acrylic polymer, preferably comprise the acrylic monomer of (methyl) acrylate monomer of 50～100 weight %, (methyl) acrylic acid, (methyl) acrylic amide etc..
It addition, the acid number of acrylic polymer is preferably 0.01～8.0.By this acid number, it is possible to improve contaminative, improve the performance preventing adhesive residue from occurring.
Herein, " acid number " refers to one of index representing acid amount, represents the mg number neutralizing the potassium hydroxide needed for the polymer that 1g contains carboxyl.
Preferably so that the bonding force that the adhesive phase of above-mentioned binder composition cross-links is under low speed peeling rate 0.3m/min is 0.05～0.1N/25mm, the bonding force under high speed peeling rate 30m/min is below 1.0N/25mm.Thereby, it is possible to obtain bonding force along with peeling rate performance with low uncertainty, even through peeling off at a high speed, promptly peeling off and be also possibly realized.Further, in order to again fit, when temporarily peeling off surface protection film, it is not necessary to excessive power, peel off easily from adherend.
Make the gel fraction preferably 95～100% of the adhesive phase (binding agent after crosslinking) of the binder composition cross-links of the present invention.So, high due to gel fraction, it is possible to make the bonding force under low speed peeling rate not become excessive, reduce the unconverted monomer from copolymer or the dissolution of oligomer, improve doing over again property, hot and humid in durability, the pollution of suppression adherend.
The bonding film of the present invention is so that what the adhesive phase of the binder composition cross-links of the present invention was formed on the one or both sides of resin molding.Additionally, the surface protection film that the adhesive phase that the surface protection film of the present invention is the binder composition cross-links by the crosslinking present invention is formed in the one side of resin molding.The adhesive composition of the present invention well balances mixing owing to making each composition of above-mentioned (A)～(H); there is the balancing good of bonding force under low speed peeling rate and high speed peeling rate; and durability and performance of doing over again (after describing on the surface protection film via described adhesive phase with ball pen, not transferring the pollution to adherend) also excellence.Therefore, it is possible to the purposes as the surface protection film of Polarizer is suitably used.
Base material film, the stripping film (partition) of protection adhesive surface as adhesive phase can use the resin molding etc. of polyester film etc..
In base material film, on the face contrary with forming adhesive phase side of resin molding, it is possible to implement by silicone, the releasing agent of fluorine class or the antifouling process of coating agent, silicon dioxide microparticle etc.；Processed by the antistatic of the coating of antistatic agent or kneading etc..
In stripping film, on the face with adhesive surface adhesive side of adhesive phase, implement to be processed by the demoulding of silicone, the releasing agent etc. of fluorine class.
Embodiment
Below, based on embodiment, illustrate the present invention.
The preparation ＞ of ＜ acrylic copolymer
[embodiment 1]
In the reaction unit equipped with agitator, thermometer, reflux condenser and nitrogen ingress pipe, import nitrogen, the air nitrogen in reaction unit is replaced.Then, in reaction unit, 2-EHA 100 weight portion, acrylic acid 8-hydroxyl monooctyl ester 0.9 weight portion, acrylic acid 0.5 weight portion, poly-ethylidene glycol mono acrylic ester 3 weight portion and solvent (ethyl acetate) 60 weight portion are added.Then, instill azodiisobutyronitrile 0.1 weight portion as polymerization initiator through 2 hours, make it react 6 hours in 65 DEG C, obtain the acrylic copolymer solution 1 used in the embodiment 1 that weight average molecular weight is 500,000.Extract a part for acrylic copolymer, as the sample of following acid value measuring.
[embodiment 2～9 and comparative example 1～9]
The composition of monomer each according to (A)～(D) of table 1 described as set, in addition, according in the same manner as the acrylic copolymer solution 1 used in above-described embodiment 1, obtain embodiment 2～9 and comparative example 1～9 in the acrylic copolymer solution that uses.
The preparation ＞ of ＜ adhesive composition and surface protection film
[embodiment 1]
As described above, acrylic copolymer solution 1 (wherein acrylic copolymer is 100 weight portions) for preparation, after adding KF-351A (the polyether-modified silicone compounds of HLB=12) 0.1 weight portion, acetylacetone,2,4-pentanedione 2.5 weight portion and stirring, add stirring mixing after U ロ ネ ト HX (the isocyanuric acid ester body of hexamethylene diisocyanate compound) 1.5 weight portions, tin dilaurate dioctyl tin 0.02 weight portion, obtain the adhesive composition of embodiment 1.After on the stripping film of polyethylene terephthalate (PET) the film composition that this adhesive composition is coated silicone coating, by the dry removing solvent of 90 DEG C, obtaining the bonding sheet that thickness is 25 μm of adhesive phase.
Then; bonding sheet is transferred to one side on through antistatic and antifouling process polyethylene terephthalate (PET) film through antistatic and the reverse side in antifouling process face, be there is the surface protection film of the embodiment 1 of the laminar structure of " through the PET film/adhesive phase/stripping film (PET film of silicone coating) of antistatic and antifouling process ".
[embodiment 2～9 and comparative example 1～9]
The composition of additive each set as described in (E)～(H) of table 1, in addition, according in the same manner as the surface protection film of above-described embodiment 1, the surface protection film obtaining embodiment 2～9 with comparing 1～9.
In table 1, the mixed proportion bracket of each composition encloses, and represents the numerical value that summation is the weight portion required by 100 weight portions organized with (A).Further, table 2 shows the compound name that the abbreviation of each composition used in table 1 is corresponding.Additionally, U ロ ネ ト (registered trade mark) HX and same HL is the trade name of Japan Port リ ウ レ タ Application Industrial Co., Ltd, タ ケ ネ ト (registered trade mark) D-140N is the trade name of Mitsui Chemicals, Inc, デ ュ ラ ネ ト (registered trade mark) 24A-100 is the trade name of Asahi Chemical Industry ケ ミ カ Le ズ Co., Ltd., and KF-351A, KF-352A, KF-353, KF-640 and X-22-6191 are the trade names of KCC of SHIN-ETSU HANTOTAI.
[table 1]
[table 2]
＜ test method and evaluation ＞
By the surface protection film in embodiment 1～9 and comparative example 1～9 in 23 DEG C, under the atmosphere of 50%RH after aging 7 days, peel off stripping film (PET film of silicone coating), to expose the material test sample as gel fraction of adhesive phase.
And then; via adhesive phase, this surface protection film exposing adhesive phase is fitted in the surface of the Polarizer being pasted onto on liquid crystal cell; after placing 1 day; through 50 DEG C, 5 atmospheric pressure, the autoclaves of 20 minutes process, place further 12 hours in room temperature, using through material derived above as bonding force and the test sample of durability.
<acid number>
The acid number of acrylic polymer, sample is dissolved in solvent (material that diethyl ether and ethanol are mixed to get with volume ratio 2:1), use potential difference automatic titration device (capital of a country electronics industry system, AT-610), use 0.1 above-mentioned potential difference titration appratus, carry out potential difference titration with the potassium hydroxide-ethanol solution of concentration about 0.1mol/l, measure for the amount neutralizing the potassium hydroxide-ethanol solution needed for sample.Then, acid number is tried to achieve by following formula.
Acid number=(B × f × 5.611)/S
The amount (ml) of the 0.1mol/l potassium hydroxide-ethanol solution used in B=titration
The factor of f=0.1mol/l potassium hydroxide-ethanol solution
The quality (g) of the solid constituent of S=sample
＜ gel fraction ＞
After aging end, correctly measure the quality of the test sample before fitting in Polarizer, after soaking 24 hours in toluene, by the metal mesh filter of 200 mesh.Then, after 100 DEG C of dried screenings 1 hour, correctly measure the quality of residue, calculate the gel fraction of adhesive phase (binding agent after crosslinking) from following formula.
Gel fraction (%)=insoluble matter quality (g)/binding agent quality (g) × 100
＜ bonding force ＞
Using following peel strength as bonding force: use tensile testing machine to peel through, with the peeling rate (0.3m/min) of low speed and peeling rate (30m/min) at a high speed, the peel strength that test sample obtained above (material of surface protection film wide for 25mm of fitting on Polarizer surface) measures to 180 ° of directions.
＜ doing over again property ＞
After describing on the surface protection film by test sample obtained above with ball pen (load 500g, reciprocal 3 times), peel off surface protection film from Polarizer and observe Polarizer surface, confirm not transfer the pollution to Polarizer.Evaluation objective benchmark is that situation about not transferring the pollution to Polarizer is evaluated as "○", confirm that the track described along ball pen is evaluated as " Δ " to situation about transferring the pollution at least partially, confirm that the situation transferred the pollution along the track of ball pen description, also have binding agent to depart from from adhesive surface is evaluated as "×".
＜ durability ＞
60 DEG C, be placed through test sample obtained above 250 hours under 90%RH atmosphere after, be drawn off in room temperature, after placing 12 hours further, measure bonding force, confirm the most significantly to increase compared with initial bonding force.Evaluation objective benchmark be the bonding force after test be that the situation of less than 1.5 times of initial bonding force is evaluated as "○", situation more than 1.5 times is evaluated as "×".
Evaluation result is shown in Table 3.
[table 3]
The surface protection film of embodiment 1～9 bonding force under low speed peeling rate 0.3m/min is 0.05～0.1N/25mm; bonding force under high speed peeling rate 30m/min is below 1.0N/25mm; after describing on the surface protection film via described adhesive phase with ball pen; do not transfer the pollution to adherend, 60 DEG C, the atmosphere of 90%RH durability when placing for lower 250 hours be also outstanding.
That is, about the balance of the bonding force in (1) acquirement low speed peeling rate and high speed peeling rate；(2) generation of adhesive residue it is prevented from；(3) there is performance of doing over again, simultaneously meet whole requirement performances.
The surface protection film of comparative example 1 is likely to be due to without (D) polyalkylene glycol mono (methyl) acrylate monomer, and the bonding force under low speed peeling rate 0.3m/min is low, and doing over again property is the poorest.
In the surface protection film of comparative example 2; the HLB value being likely to be due to the silicone compounds that (B) monomer containing hydroxyl is very few, (D) polyalkylene glycol mono (methyl) acrylate monomer is very few, (E) isocyanate compound too much, (H) is polyether-modified is too small, and therefore the bonding force under low speed peeling rate 0.3m/min and the bonding force under high speed peeling rate 30m/min become excessive, doing over again property and durability is deteriorated, gel fraction step-down.
In the surface protection film of comparative example 3; the HLB value being likely to be due to the silicone compounds that (B) monomer containing hydroxyl is too much, (C) acidiferous monomer is too much, (D) polyalkylene glycol mono (methyl) acrylate monomer is too much, (I) is polyether-modified is excessive; therefore the acid number of acrylic polymer is high, and the bonding force under low speed peeling rate 0.3m/min is low, doing over again property and poor durability.
In the surface protection film of comparative example 4; it is likely to be due to (C) monomer containing acid very few, without (D) polyalkylene glycol mono (methyl) acrylate monomer; therefore the bonding force under low speed peeling rate 0.3m/min is low, doing over again property and poor durability.
In the surface protection film of comparative example 5; be likely to be due to (B) monomer containing hydroxyl too much, (C) monomer containing acid too much, (D) polyalkylene glycol mono (methyl) acrylate monomer is very few, (E) isocyanate compound is very few; therefore the acid number of acrylic polymer is high, and the bonding force under low speed peeling rate 0.3m/min and the bonding force under high speed peeling rate 30m/min become excessive, doing over again property and durability is deteriorated, gel fraction step-down.
The surface protection film of comparative example 6 is likely due to not mix (F) cross-linked inhibitor, therefore excessively shortens storage period, carries out crosslinking before coating and is unable to be coated.
The surface protection film of comparative example 7 be likely due to containing have at (A) in (methyl) acrylate monomer of alkyl have the MA of C1 alkyl, (B) monomer containing hydroxyl too much, without (D) polyalkylene glycol mono (methyl) acrylate monomer, not mixing (G) crosslinking catalyst, the therefore bonding force under low speed peeling rate 0.3m/min and the bonding force under high speed peeling rate 30m/min is excessive, doing over again property and poor durability.
In the surface protection film of comparative example 8; be likely to be due to (D) polyalkylene glycol mono (methyl) acrylate monomer too much, there is no a polyether-modified silicone compounds of mixing (H), the therefore bonding force under low speed peeling rate 0.3m/min and the bonding force under high speed peeling rate 30m/min is excessive, doing over again property is the poorest.
In the surface protection film of comparative example 9; being likely to be due to the silicone compounds without (D) polyalkylene glycol mono (methyl) acrylate monomer, (H) are polyether-modified too much, therefore the bonding force under low speed peeling rate 0.3m/min is low, doing over again property is the poorest, poor durability.
So, in the surface protection film of comparative example 1～9, about the balance of the bonding force in (1) acquirement low speed peeling rate and high speed peeling rate；(2) generation of adhesive residue is prevented；(3) do over again performance, it is impossible to simultaneously meet whole requirement performances.

Claims (19)

1. an adhesive composition, it is by containing (methyl) acrylate monomer that (A) atomic number of alkyl carbon is C4～C10, (B) copolymerisable monomer containing hydroxyl, (C) copolymerisable monomer containing carboxyl, (D) acrylic polymer of the copolymer of polyalkylene glycol mono (methyl) acrylate monomer is constituted, it contains (E) 3 official further can above isocyanate compound, (F) as the keto-enol tautomerism compound of cross-linked inhibitor, (G) crosslinking catalyst, (H) HLB value is the polyether-modified silicone compounds of 7～12, the acid number of aforesaid propylene acids polymers is 0.01～8.0,
(methyl) acrylate monomer that carbon number is C4～C10 relative to above-mentioned (A) alkyl of 100 weight portions, above-mentioned (B) containing the 0.1～5.0 weight portions copolymerisable monomer containing hydroxyl, above-mentioned (C) containing the 0.35～1.0 weight portions copolymerisable monomer containing carboxyl, above-mentioned (D) polyalkylene glycol mono (methyl) acrylate monomer containing 1～20 weight portions
Relative to the above-mentioned copolymer of 100 weight portions, above-mentioned (E) 3 official containing 0.5～5.0 weight portions can above isocyanate compound,
Above-mentioned (B) copolymerisable monomer containing hydroxyl is to select more than at least one in the compound group that freely (methyl) acrylic acid 8-hydroxyl monooctyl ester, (methyl) acrylic acid own ester of 6-hydroxyl, (methyl) acrylic acid 4-hydroxybutyl, (methyl) acrylic acid 2-hydroxy methacrylate, N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-ethoxy (methyl) acrylamide form
Above-mentioned (C) copolymerisable monomer containing carboxyl is choosing free 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloxypropyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl phthalic acid, 2-(methyl) acryloyl-oxyethyl succinic acid, 2-(methyl) acryloyl-oxyethyl maleic acid, carboxy-polycaprolactone list (methyl) acrylate, more than at least one in the compound group of 2-(methyl) acryloyl-oxyethyl tetrahydrochysene phthalic acid composition.
Adhesive composition the most according to claim 1, wherein, above-mentioned (B), containing in the copolymerisable monomer of hydroxyl, (methyl) acrylic acid 8-hydroxyl monooctyl ester, (methyl) acrylic acid own ester of 6-hydroxyl, total amount of (methyl) acrylic acid 4-hydroxybutyl are 0～0.9 weight portion.
Adhesive composition the most according to claim 1 and 2, wherein, above-mentioned (D) polyalkylene glycol mono (methyl) acrylate monomer is more than at least one in poly-ethylidene glycol-mono-(methyl) acrylate, polytrimethylene glycol-mono-(methyl) acrylate, polybutylene glycol-mono-(methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate, ethyoxyl poly alkylene glycol (methyl) acrylate.
Adhesive composition the most according to claim 1 and 2, wherein, above-mentioned (E) 3 official can isocyanate compound above be more than at least one in the compound group selecting the isocyanuric acid ester body of free hexamethylene diisocyanate compound, the isocyanuric acid ester body of isophorone diisocyanate compound, the adduction object of hexamethylene diisocyanate compound, the adduction object of isophorone diisocyanate compound, the biuret body of hexamethylene diisocyanate compound, the biuret body of isophorone diisocyanate compound to form.
Adhesive composition the most according to claim 1 and 2, wherein, relative to the above-mentioned copolymer of 100 weight portions, the polyether-modified silicone compounds that above-mentioned (H) HLB value is 7～12 containing 0.01～0.5 weight portion.
Adhesive composition the most according to claim 1 and 2, wherein, relative to the above-mentioned copolymer of 100 weight portions, above-mentioned (F) containing 1.0～5.0 weight portions is as the keto-enol tautomerism compound of cross-linked inhibitor.
Adhesive composition the most according to claim 1 and 2, the most above-mentioned (G) crosslinking catalyst is organo-tin compound；
Relative to the above-mentioned copolymer of 100 weight portions, above-mentioned (G) crosslinking catalyst containing 0.01～0.5 weight portion.
Adhesive composition the most according to claim 1 and 2, wherein making the adhesive phase of the above-mentioned binder composition cross-links bonding force under low speed peeling rate 0.3m/min is 0.05～0.1N/25mm, and the bonding force under high speed peeling rate 30m/min is below 1.0N/25mm.
9. a bonding film, it is characterised in that form the adhesive phase making binder composition cross-links according to claim 1 and 2 on the one or both sides of resin molding.
10. a bonding film, it is characterised in that form the adhesive phase making binder composition cross-links according to claim 3 on the one or both sides of resin molding.
11. 1 kinds of bonding films, it is characterised in that form the adhesive phase making binder composition cross-links according to claim 4 on the one or both sides of resin molding.
12. 1 kinds of bonding films, its feature exists, and forms the adhesive phase making binder composition cross-links according to claim 5 on the one or both sides of resin molding.
13. 1 kinds of bonding films, it is characterised in that form the adhesive phase making binder composition cross-links according to claim 6 on the one or both sides of resin molding.
14. 1 kinds of bonding films, it is characterised in that form the adhesive phase making binder composition cross-links according to claim 7 on the one or both sides of resin molding.
15. 1 kinds of bonding films, it is characterised in that form the adhesive phase making binder composition cross-links according to claim 8 on the one or both sides of resin molding.
16. 1 kinds of surface protection films; its surface protection film obtained for forming adhesive phase in the one side of resin molding; described adhesive phase obtains by making binder composition cross-links according to claim 1 and 2; describe on the surface protection film via described adhesive phase with ball pen, do not transfer the pollution to adherend.
17. surface protection films according to claim 16, it uses as the purposes of the surface protection film of Polarizer.
18. surface protection films according to claim 16, it carries out antistatic and anti-pollution process in being formed with described adhesive phase of described resin molding on face that side is contrary.
19. surface protection films according to claim 17, it carries out antistatic and anti-pollution process in being formed with described adhesive phase of described resin molding on face that side is contrary.
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