CN104449481A - Adhesive composition and surface protection film - Google Patents

Adhesive composition and surface protection film Download PDF

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Publication number
CN104449481A
CN104449481A CN201410397590.6A CN201410397590A CN104449481A CN 104449481 A CN104449481 A CN 104449481A CN 201410397590 A CN201410397590 A CN 201410397590A CN 104449481 A CN104449481 A CN 104449481A
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China
Prior art keywords
methyl
compound
acrylate
monomer
adhesive composition
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CN201410397590.6A
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CN104449481B (en
Inventor
长仓毅
岛口龙介
长谷川良
远藤佳子
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Fujimori Kogyo Co Ltd
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Fujimori Kogyo Co Ltd
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Priority claimed from JP2013195990A external-priority patent/JP6113036B2/en
Priority claimed from JP2013195827A external-priority patent/JP5972845B2/en
Application filed by Fujimori Kogyo Co Ltd filed Critical Fujimori Kogyo Co Ltd
Publication of CN104449481A publication Critical patent/CN104449481A/en
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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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • 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

Abstract

The invention provides an adhesive composition having excellent anti-static performance, excellent balance in adhesive property at both low stripping speed and high stripping speed, and excellent durability and re-processability, and a surface protection film. The adhesive composition includes an acrylic polymer including at least one copolymer from (A) (meth) acrylate monomers having alkyl groups with the carbon atom number being C4 to C18, (B) copolymerizable monomers containing hydroxyl groups, (C) copolymerizable monomers having carboxyl groups, (D) polyalkylene glycol single (meth) acrylate monomers, and (E) hydroxyl group-free and nitrogen-containing vinyl monomers or a (meth) alkyl acrylate monomers containing alkoxy groups. The adhesive composition further includes (F) an isocyanate composition having more than three functional groups, (G) a cross-linking suppressor, (H) a cross-linking catalyst and (I) an anti-static agent. The acid value of the acrylic polymer is 0.01 to 8.0.

Description

Adhesive composition and surface protection film
Technical field
The present invention relates to a kind of for the surface protection film in the manufacturing process of liquid-crystal display.More specifically; the present invention relates to and a kind ofly form the surface of the optics such as Polarizer, polarizer of liquid-crystal display and the surface protection film adhesive composition on the surface for the protection of the optics such as Polarizer, polarizer by being pasted onto, and use the surface protection film of this adhesive composition.
Background technology
All the time, in the manufacturing process of the optics such as Polarizer, polarizer of the parts as formation liquid-crystal display, the adhesive surface protective membrane in order to the surface of temporary protection optics.This surface protection film only uses in the operation manufacturing optics, when optics is assembled into liquid-crystal display, it is peeled off from optics and removes.Because this surface protection film for the protection of optical component surfaces only uses in manufacturing process, therefore, be usually also referred to as " operation film ".
For so manufacturing the surface protection film used in the operation of optics; the one side of polyethylene terephthalate (PET) resin molding with optical transparence is formed with adhesive layer; and; this adhesive layer is fitted with the stripping film through lift-off processing, to protect this adhesive layer until fit on optics.
In addition; for the optics such as Polarizer, polarizer; owing to carrying out the examination and test of products being mixed into etc. optical assessment with the display capabilities of LCD panel, tone, contrast gradient, impurity under the state of fitting surface protection film; 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 optics such as Polarizer, polarizer during stripper surface protective membrane; along with the stripping electrostatic that the electrostatic occurred when adherend peels off adhesive layer produces; likely can have influence on the fault of the electric control circuit of liquid-crystal display; therefore, require that adhesive layer has excellent antistatic property.
In addition; on the optics such as Polarizer, polarizer during coating surface protective membrane; due to a variety of causes; the situation of adhesive surface protective membrane again again to be there is after temporary transient stripper surface protective membrane, now requires easily to peel off (re-workability) from the optics as adherend.
In addition, time finally from the optics such as Polarizer, polarizer stripper surface protective membrane, requirement can be peeled off rapidly.That is, require cohesive force because of the change of peeling rate little, even if also can peel off rapidly when peeling off at a high speed.
So, in recent years, from maneuverable viewpoint during use surface protection film, require that the adhesive layer forming surface protection film has following performance: (1), under low peeling rate and high peeling rate, obtains the balance of cohesive force; (2) generation of glue residue is prevented; (3) excellent antistatic property; And (4) reprocessing (ReWork) performance etc.
But; namely allow to meet the performance requriements to the adhesive layer forming surface protection film respectively; namely; namely allow to meet the indivedual performance requriementss in above-mentioned (1) ~ (4) respectively; but the over-all properties requirement of (1) that the adhesive layer of the surface protection film that meets the demands has ~ (4) is very difficult problem simultaneously.
Such as, under low peeling rate and high peeling rate, obtain about (1) generation that the balance of cohesive force and (2) prevent glue residue, there will be a known suggestion as described below.
At (methyl) alkyl acrylate of the alkyl to have carbonatoms less than 7 and the multipolymer of carboxylic copolymerizable compound as main component, and in the acrylic adhesive layer with linking agent, crosslinking Treatment being carried out to it and make, when through bonding for a long time, there is binding agent move to adherend side and be attached to adherend, and to the bonding force of adherend through time ascending large problem.
In order to avoid this problem, there will be a known a kind of technical scheme being provided with following adhesive layer, described adhesive layer is the multipolymer using (methyl) alkyl acrylate with the alkyl of carbonatoms 8 ~ 10 and the copolymerization compound with alcoholic extract hydroxyl group, and with linking agent, it is carried out to the adhesive layer (patent documentation 1) of crosslinking Treatment.
In addition, also proposed a kind of technical scheme being provided with following adhesive layer, described adhesive layer is by multipolymer same as described above, coordinate the multipolymer of a small amount of (methyl) alkyl acrylate and carboxylic copolymerizable compound, and with linking agent, it is carried out to the adhesive layer of crosslinking Treatment.
But; when using it for surface tension and be low and in the surface protection of ganoid plastic plate etc., there is the problem of releasable difference when the problem, the high speed in field hand-manipulated that produce the peelings such as separation because of heating when adding man-hour or preserve are peeled off.
In order to address these problems, propose a kind of adhesive composition, described adhesive composition is: at (a) to have (methyl) alkyl acrylate of the alkyl of carbonatoms 8 ~ 10 as in (methyl) alkyl acrylate 100 weight part of main component, add (b) 1 ~ 15 carboxylic copolymerizable compound of weight part, and (c) 3 ~ 100 weight part carbonatoms 1 ~ 5 aliphatic carboxylic acid vinyl ester and obtain the multipolymer of monomer mixture, and in this multipolymer, coordinate the adhesive composition (patent documentation 2) of the linking agent of more than the equivalent of the carboxyl of above-mentioned (b) composition.
In the adhesive composition that patent documentation 2 is recorded, the peeling of separation etc. can not be produced when adding man-hour or preserving, and, bonding force through time ascending little, thus releasable is excellent, preserves even long-term, particularly preserve for a long time in high temperature environments, also can peel off again with little strength, now not remaining binder in adherend, even and if when carrying out also to peel off with little strength when peeling off at a high speed again.
In addition, the antistatic property excellent for (3), as the method for giving static resistance for effects on surface protective membrane, proposes the method etc. being mixed into static inhibitor in base material film.As static inhibitor, such as, disclose (a) quaternary ammonium salt, pyridinium salt, there are the various cationic antistatic agents of the cation radicals such as primary ~ uncle is amino; B () has the anionic antistatic agents of the anion-radicals of sulphonate-base, sulfuric ester alkali, phosphoric acid ester alkali, phosphonic acids alkali etc.; The both sexes static inhibitor of (c) amino acids, amidosulphuric acid ester class etc.; The non-ionic antistatic agent of (d) alkamine, glycerols, polyethylene glycols etc.; E () makes static inhibitor as above carry out polymer to quantize (patent documentations 3) such as the Polymer Antistatic Agents obtained.
In addition, propose in recent years and static inhibitor so is directly contained in adhesive layer, instead of be contained in base material film or coat the scheme on base material film surface.
In addition, about (4) re-workability, such as, propose a kind of adhesive composition, described adhesive composition is: relative to 100 parts by weight propylene acid resins, coordinates the solidifying agent of isocyanate ester compound of 0.0001 ~ 10 weight part and specific silicate oligomer and obtains (patent documentation 4).
In patent documentation 4, record: using the carbonatoms of alkyl be the alkyl acrylate of about 2 ~ 12, the carbonatoms of alkyl be the alkyl methacrylate of about 4 ~ 12 etc. as main monomer component, can containing the monomer component containing other functional group such as such as carboxylic monomer.Typically, preferably contain the above-mentioned principal monomer of more than 50 % by weight, and the content of wishing the monomer component containing functional group is 0.001 ~ 50 % by weight, is preferably 0.001 ~ 25 % by weight, is more preferably 0.01 ~ 25 % by weight.The adhesive composition that this patent documentation 4 is recorded, though at high temperature or hot and humid under, the rheological parameters' change with time of its cohesive force and bonding force is also little, and also demonstrates excellent effect to the bonding force of curved surface, therefore has re-workability.
Usually, if adhesive layer is soft proterties, then easily produces glue residue, re-workability also easily reduces.That is, after mistake laminating, peel off difficulty, and be difficult to again paste.From this viewpoint, in order to make it have re-workability, need by there is the functional groups such as carboxyl monomer crosslinked in host to make adhesive layer have certain hardness.
Prior art document
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 63-225677 publication
Patent documentation 2: Japanese Unexamined Patent Publication 11-256111 publication
Patent documentation 3: Japanese Unexamined Patent Publication 11-070629 publication
Patent documentation 4: Japanese Unexamined Patent Publication 8-199130 publication
Summary of the invention
The problem that invention will solve
In the prior art, as the performance requriements of the adhesive layer to formation surface protection film, require that it can obtain the balance of cohesive force and have excellent antistatic property and cycling processability etc. under low peeling rate and high peeling rate all the time.But, namely allow to meet properties requirement respectively, also cannot meet as the over-all properties requirement required by the adhesive layer of surface protection film.
The present invention completes in view of the foregoing, and its problem is, provides a kind of balance of the cohesive force under low peeling rate and high peeling rate excellent and the adhesive composition that endurance quality and cycling processability are also excellent and surface protection film.Further, problem of the present invention is also, provides a kind of adhesive composition and the surface protection film also except aforementioned properties with excellent antistatic property.
Solve the method for problem
In order to solve above-mentioned problem, the invention provides a kind of adhesive composition, it is characterized in that, comprising of this adhesive composition: the carbonatoms containing (A) alkyl is (methyl) acrylate monomer of C4 ~ C18, (B) copolymerisable monomer of hydroxyl, (C) carboxylic copolymerisable monomer, (D) acrylic polymers of polyalkylene glycol mono (methyl) acrylate monomer and (E) not hydroxyl and nitrogenous vinyl monomer or the multipolymer containing at least one in (methyl) alkyl acrylate monomer of alkoxyl group,
And, also comprise the isocyanate compound of more than (F) trifunctional, (G) cross-linked inhibitor and (H) crosslinking catalyst,
The acid number of described acrylic polymers is 0.01 ~ 8.0,
The averaged repeating numbers forming the alkylene oxide (alkylene oxide) of polyalkylene glycol chain in described (D) polyalkylene glycol mono (methyl) acrylate monomer is 3 ~ 14.
In addition; in order to solve above-mentioned problem; the invention provides a kind of adhesive composition; wherein; above-mentioned adhesive composition is also containing (I) static inhibitor, and described (I) static inhibitor is 0.1 ~ 5.0 weight part relative to the content of multipolymer described in 100 weight parts and fusing point is the ionic compound of 30 ~ 50 DEG C or the copolymerization amount in described multipolymer is 0.1 ~ 5.0 % by weight and quaternary ionic compound containing acryl.
In addition, preferably the copolymerisable monomer of above-mentioned (B) hydroxyl for being selected from more than at least one in the compound group that is made up of (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxybutyl, (methyl) vinylformic acid 2-hydroxy methacrylate, N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide; Relative to (methyl) acrylate monomer that aforementioned (A) atomic number of alkyl carbon of 100 weight parts is C4 ~ C18, the copolymerisable monomer of aforementioned (B) hydroxyl containing 0.1 ~ 5.0 weight part; And, in the copolymerisable monomer of aforementioned (B) hydroxyl, the total amount of (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxybutyl is 0 ~ 0.9 weight part;
Preferably aforementioned (C) carboxylic copolymerisable monomer is for being selected from by (methyl) vinylformic acid, (methyl) carboxy ethyl acrylate, (methyl) carboxypentyl acrylate, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloxypropyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl phthalic acid, 2-(methyl) acryloyl-oxyethyl succsinic acid, 2-(methyl) acryloyl-oxyethyl toxilic acid, carboxy-polycaprolactone list (methyl) acrylate, more than at least one in the compound group that 2-(methyl) acryloyl-oxyethyl tetrahydrophthalic acid forms, relative to (methyl) acrylate monomer that the carbonatoms of aforementioned (A) alkyl of 100 weight parts is C4 ~ C18, aforementioned (C) the carboxylic copolymerisable monomer containing 0.35 ~ 1.0 weight part.
In addition, preferably aforementioned (D) polyalkylene glycol mono (methyl) acrylate monomer is selected from more than at least one in polyalkylene glycol mono (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate, oxyethyl group polyalkylene glycol (methyl) acrylate; Relative to (methyl) acrylate monomer that the carbonatoms of aforementioned (A) alkyl of 100 weight parts is C4 ~ C18, aforementioned (D) polyalkylene glycol mono (methyl) acrylate monomer containing 1 ~ 50 weight part.
Isocyanate compound more than aforementioned (F) trifunctional, preferably be selected from by the isocyanuric acid ester of 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, the isocyanuric acid ester of tolunediisocyanate compound, the isocyanuric acid ester of xylylene diisocyanate compound, the isocyanuric acid ester of hydrogenated xylylene diisocyanate cpd, the affixture of tolunediisocyanate compound, the affixture of xylylene diisocyanate compound, in the compound group that the affixture of hydrogenated xylylene diisocyanate cpd forms more than at least one.
In addition, relative to (methyl) acrylate monomer that the carbonatoms of aforementioned (A) alkyl of 100 weight parts is C4 ~ C18, preferably aforementioned (E) hydroxyl and nitrogenous vinyl monomer or the content containing (methyl) alkyl acrylate monomer of alkoxyl group are not 1 ~ 20 weight part.
In addition, relative to the described multipolymer of 100 weight parts, preferably containing isocyanate compound more than described (F) trifunctional of 0.5 ~ 5.0 weight part.
In addition, aforementioned (G) cross-linked inhibitor is keto-enol tautomerism compound, relative to the aforementioned copolymer of 100 weight parts, and aforementioned (G) cross-linked inhibitor containing 1.0 ~ 5.0 weight parts.
Aforementioned (H) crosslinking catalyst is organo-tin compound, preferably relative to the aforementioned copolymer of 100 weight parts, and aforementioned (H) crosslinking catalyst containing 0.01 ~ 0.5 weight part.
In addition, the cohesive force of the adhesive layer preferably making foregoing adhesives composition be cross-linked 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, the surface resistivity of the adhesive layer preferably making foregoing adhesives composition be cross-linked is 5.0 × 10 + 10Ω/below, stripping static voltage is ± 0 ~ 0.3kV.
Further, the invention provides a kind of adhesive film, it is characterized in that, the single or double of resin molding forms adhesive layer and forms, described adhesive layer foregoing adhesives composition is cross-linked form.
In addition; the invention provides a kind of surface protection film; it forms adhesive layer at the one side of resin molding to form; described adhesive layer foregoing adhesives composition is 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 in 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 face contrary with the side being formed with adhesive layer of resin molding, implement antistatic and antifouling process.
Invention effect
Based on the present invention, the over-all properties required by adhesive layer of insurmountable effects on surface protective membrane in the prior art can be met, and excellent antistatic property can be obtained, the generation of glue residue phenomenon can be prevented.Specifically, excellent antistatic property can not only be kept, but also the addition of static inhibitor can be reduced, also can improve the performance preventing glue residue.
In addition, by making the averaged repeating numbers forming the alkylene oxide of polyalkylene glycol chain in aforementioned (D) polyalkylene glycol mono (methyl) acrylate monomer be 3 ~ 14, anti-static function can be made to become good and improve stain resistance (re-workability).
Embodiment
Below, based on preferred embodiment the present invention being described.
Adhesive composition of the present invention, it is characterized in that, its host be by the carbonatoms comprising (A) alkyl be (methyl) acrylate monomer of C4 ~ C18, the acrylic polymers of the copolymerisable monomer of (B) hydroxyl, (C) carboxylic copolymerisable monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) not hydroxyl and nitrogenous vinyl monomer or the multipolymer containing at least one in (methyl) alkyl acrylate monomer of alkoxyl group forms
And, also containing isocyanate compound, (G) cross-linked inhibitor and (H) crosslinking catalyst more than (F) trifunctional,
The acid number of described acrylic polymers is 0.01 ~ 8.0;
The averaged repeating numbers forming the alkylene oxide of polyalkylene glycol chain in aforementioned (D) polyalkylene glycol mono (methyl) acrylate monomer is 3 ~ 14.
Adhesive composition of the present invention; it is characterized in that; except aforementioned component; also containing (I) static inhibitor, aforementioned (I) static inhibitor is 0.1 ~ 5.0 weight part relative to the content of 100 weight part aforementioned copolymer and fusing point is the ionic compound of 30 ~ 50 DEG C or the copolymerization amount in described multipolymer is 0.1 ~ 5.0 % by weight and quaternary ionic compound containing acryl.
Carbonatoms as (A) alkyl is (methyl) acrylate monomer of C4 ~ C18, can enumerate: (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) amyl acrylate, (methyl) Ethyl acrylate, (methyl) heptylacrylate, (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, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid tetradecyl ester, (methyl) vinylformic acid pentadecyl ester, (methyl) aliphatic acrylate, (methyl) vinylformic acid heptadecyl ester, (methyl) octadecyl acrylate, (methyl) myristyl ester, the different tetradecyl ester of (methyl) vinylformic acid, (methyl) vinylformic acid cetyl, (methyl) vinylformic acid isocetyl ester, (methyl) stearyl acrylate acyl ester, (methyl) vinylformic acid isooctadecane base ester etc.
As the copolymerisable monomer of (B) hydroxyl, can enumerate: (methyl) hydroxyalkyl acrylates classes such as (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxybutyl, (methyl) vinylformic acid 2-hydroxy methacrylate; (methyl) acrylic amide etc. containing hydroxyl such as N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide.
The copolymerisable monomer of preferred above-mentioned hydroxyl is selected from more than at least one in the compound group that is made up of (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxybutyl, (methyl) vinylformic acid 2-hydroxy methacrylate, N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide.
Relative to (methyl) acrylate monomer that the carbonatoms of (A) alkyl of 100 weight parts is C4 ~ C18, the copolymerisable monomer of aforementioned (B) hydroxyl preferably containing 0.1 ~ 5.0 weight part.
And, in the copolymerisable monomer of (B) hydroxyl, the total amount of (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxybutyl is preferably lower than 1 weight part (also allowing situation about not containing), is more preferably 0 ~ 0.9 weight part.
Preferably (C) carboxylic copolymerisable monomer is selected from by (methyl) vinylformic acid, (methyl) carboxy ethyl acrylate, (methyl) carboxypentyl acrylate, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloxypropyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl phthalic acid, 2-(methyl) acryloyl-oxyethyl succsinic acid, 2-(methyl) acryloyl-oxyethyl toxilic acid, carboxy-polycaprolactone list (methyl) acrylate, more than at least one in the compound group that 2-(methyl) acryloyl-oxyethyl tetrahydrophthalic acid forms.
Relative to (methyl) acrylate monomer that the carbonatoms of (A) alkyl of 100 weight parts is C4 ~ C18, (C) content of carboxylic copolymerisable monomer is preferably 0.35 ~ 1.0 weight part, is more preferably 0.35 ~ 1.0 weight part.
As (D) polyalkylene glycol mono (methyl) acrylate monomer, as long as the esterified compound for (methyl) acrylate of a hydroxyl in multiple hydroxyls of having of polyalkylene glycol.Be polymerizability base because (methyl) is acrylate-based, therefore, it is possible to 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 can become the saturated carboxylic acid esters etc. such as acetic ester.
As the alkylidene group that polyalkylene glycol has, vinyl, propenyl, butenyl etc. can be enumerated, but be not limited to these.Polyalkylene glycol also can be the multipolymer of the two or more polyalkylene glycols 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.
Preferably the averaged repeating numbers of the alkylene oxide of the formation polyalkylene glycol chain of (D) polyalkylene glycol mono (methyl) acrylate monomer is 3 ~ 14.So-called " averaged repeating numbers of alkylene oxide ", refers to the mean number that in " polyalkylene glycol chain " part contained in the molecular structure of (D) polyalkylene glycol mono (methyl) acrylate monomer, alkylene oxide unit repeats.
As (D) polyalkylene glycol mono (methyl) acrylate monomer, be preferably selected from more than at least one in polyalkylene glycol mono (methyl) acrylate, methoxypolyalkylene 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.
Relative to (methyl) acrylate monomer that the carbonatoms of (A) alkyl of 100 weight parts is C4 ~ C18, (D) polyalkylene glycol mono (methyl) acrylate monomer preferably containing 1 ~ 50 weight part.
In (E), as the vinyl monomer that (E-1) is nitrogenous, can enumerate: the vinyl monomer containing amido linkage, the vinyl monomer etc. containing amino vinyl monomer, there is nitrogenous heterocycle structure.More specifically, can enumerate: the ring-type nitrogen vinyl compound with the heterocycle structure of N-vinyl substituted of NVP, NVP, methyl ethylene pyrrolidone, N-vinyl pyridine, N-vinylpiperidone, N-vinyl pyrimidine, N-vinyl piperazine, N-vinylpyrazine, N-vinyl pyrrole, N-vinyl imidazole, N-Yi Xi Ji oxazole, N-polyvinyl morpholinone, N-caprolactam, N-vinyl laurolactam etc., the ring-type nitrogen vinyl compound with the heterocycle structure that N-(methyl) acryl replaces of N-(methyl) acryloyl morpholine, N-(methyl) acryloylpiperazines, the rare acyl group aziridine of N-(methyl) third, N-(methyl) acryl azetidine, N-(methyl) acryl tetramethyleneimine, N-(methyl) acryloylpiperidine, N-(methyl) acryl azepan, N-(methyl) acryl Azacyclooctane etc., N-N-cyclohexylmaleimide, N-phenylmaleimide etc. have the ring-type nitrogen vinyl compound of the heterocycle structure containing nitrogen-atoms and vinyl-based unsaturated link(age) in 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, the dialkyl group such as N-di-isopropyl (methyl) acrylamide, N, N-dibutyl (methyl) acrylamide, N-ethyl-N-methyl (methyl) acrylamide, N-Methyl-N-propyl (methyl) acrylamide, N-methyl-N-isopropyl (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-dimethrlaminobutyl (methyl) acrylate, N, N-diethylamino methyl (methyl) acrylate, N, N-diethylamino ethyl (methyl) acrylate, N-ethyl-N-methylamino ethyl (methyl) acrylate, N-methyl-N-propylamino ethyl (methyl) acrylate, N-methyl-N-isoproylamino ethyl (methyl) acrylate, N, N-Dibutylaminoethyl (methyl) acrylate, dialkyl amido (methyl) acrylate such as t-butylamino ethyl (methyl) acrylate, N, N-dimethylaminopropyl (methyl) acrylamide, N, N-diethyl amino propyl (methyl) acrylamide, N, N-dipropylamino propyl group (methyl) acrylamide, N, the N of N-diisopropylaminoethyl propyl group (methyl) acrylamide, N-ethyl-N-methylamino propyl group (methyl) acrylamide, N-methyl-N-propylamino propyl group (methyl) acrylamide, N-methyl-N-isoproylamino propyl group (methyl) acrylamide etc., N-dialkyl group substituted-amino propyl group (methyl) acrylamide, the N-vinylcarboxylic acid amide type such as N-vinyl formamide, N-vinyl acetamide, N-vinyl-N-methylacetaniide, (methyl) acrylic amides such as N-methoxymethyl (methyl) acrylamide, N-ethoxyethyl group (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, diacetone acrylamide, N, N-methylene-bis (methyl) acrylamide, the unsaturated carboxylic acid nitriles such as (methyl) vinyl cyanide, Deng.
As the vinyl monomer that (E-1) is nitrogenous, preferably not hydroxyl, more preferably not hydroxyl and carboxyl.As this monomer, be preferably illustrative monomer above, such as: the acrylic monomer containing N, N-dialkyl group substituted-amino, N, N-dialkyl group substituted amido; The N-vinyl substituted lactams such as NVP, N-caprolactam, N-vinyl-2-piperidone; N-(methyl) the acryl substituted cyclic amines such as N-(methyl) acryloyl morpholine, N-(methyl) acryl tetramethyleneimine.
In (E), as (E-2) (methyl) alkyl acrylate monomer containing alkoxyl group, can enumerate: (methyl) vinylformic acid 2-methoxy acrylate, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-propoxy ethyl, (methyl) vinylformic acid 2-isopropoxyethyl cyanoacrylate, (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-methoxybutyl, (methyl) vinylformic acid 4-Ethoxybutyl, (methyl) vinylformic acid 4-propoxy-butyl ester, (methyl) vinylformic acid 4-isopropoxy butyl ester, (methyl) vinylformic acid 4-butoxy butyl ester etc.
These contain (methyl) alkyl acrylate monomer of alkoxyl group, the structure that the atom alkoxy with the alkyl in (methyl) alkyl acrylate replaces.
Relative to (methyl) acrylate monomer that the carbonatoms of (A) alkyl of 100 weight parts is C4 ~ C18, preferably the content of (E-1) not hydroxyl and nitrogenous vinyl monomer or (E-2) (methyl) alkyl acrylate monomer containing alkoxyl group is 1 ~ 20 weight part.To (E-1) not hydroxyl and nitrogenous vinyl monomer and (E-2) (methyl) alkyl acrylate monomer containing alkoxyl group, both can one be used respectively also to can be used together two or more.
As isocyanate compound more than (F) trifunctional, as long as be selected from a part more than at least one or two in the polyisocyanate compounds of isocyanic ester (NCO) base at least with more than three.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 diisocyanate (XDI), hydrogenated xylylene vulcabond (H6XDI), dimethyl diphenylene vulcabond (TOID), tolylene diisocyanate (TDI).
As isocyanate compound more than trifunctional, can enumerate: the biuret modified body of diisocyanates (there is the compound of two NCO bases in a part) or isocyanurate-modified body, with the affixture (polyalcohol modified body) etc. of polyvalent alcohol (at least there is the compound of more than three OH bases in a part) more than the trivalents such as TriMethylolPropane(TMP) (TMP) or glycerine.Relative to the aforementioned copolymer of 100 weight parts, preferably containing isocyanate compound more than aforementioned (F) trifunctional of 0.5 ~ 5.0 weight part.
And, as isocyanate compound more than (F) trifunctional used in the present invention, preferably include and be selected from more than at least one of (F-1) first in aliphatic category isocyanate compound group and be selected from more than at least one of (F-2) second in aromatic series kind isocyanate compound group, wherein, described (F-1) first aliphatic category isocyanate compound group be by the isocyanuric acid ester of 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 formed, described (F-2) second aromatic series kind isocyanate compound group be made up of the isocyanuric acid ester of tolunediisocyanate compound, the isocyanuric acid ester of xylylene diisocyanate compound, the isocyanuric acid ester of hydrogenated xylylene diisocyanate cpd, the affixture of tolunediisocyanate compound, the affixture of xylylene diisocyanate compound, the affixture of hydrogenated xylylene diisocyanate cpd.Preferably and by (F-1) first aliphatic category isocyanate compound group and (F-2) the second aromatic series kind isocyanate compound group.In the present invention, as isocyanate compound more than (F) trifunctional, by and with being selected from more than at least one of (F-1) first in aliphatic category isocyanate compound group and being selected from more than at least one of (F-2) second in aromatic series kind isocyanate compound group, the balance of the cohesive force in low speed stripping area and high speed stripping area can be improved further.
In addition, isocyanate compound preferably more than (F) trifunctional comprises and is selected from more than at least one of aforementioned (F-1) first in aliphatic category isocyanate compound group and is selected from more than at least one of aforementioned (F-2) second in aromatic series kind isocyanate compound group, and relative to the aforementioned copolymer of 100 weight parts, the total content being somebody's turn to do the isocyanate compound of more than (F) trifunctional is 0.5 ~ 5.0 weight part.In addition, as being selected from more than at least one of (F-1) first in aliphatic category isocyanate compound group and the mixture ratio being selected from more than at least one of (F-2) second in aromatic series kind isocyanate compound group, calculating with weight ratio and being preferably (F-1): (F-2) is 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, lauryl acetoacetate, etheric acid stearyl ester etc.; The beta-diketon of methyl ethyl diketone, 2,4-hexanediones, benzoyl acetone etc.These are keto-enol tautomerism compounds, using polyisocyanate compounds as in the adhesive composition of linking agent, closed by the isocyanate group that linking agent is had, can suppress to coordinate the excessive rising of adhesive composition viscosity or the phenomenon of gelation after linking agent, the storage period of adhesive composition can be extended.
Preferably (G) cross-linked inhibitor is keto-enol tautomerism compound, is particularly preferably more than at least one in the compound group being selected from and being made up of methyl ethyl diketone, methyl aceto acetate.
Relative to the multipolymer of 100 weight parts, preferably the content of (G) cross-linked inhibitor is 1.0 ~ 5.0 weight parts.
When using polyisocyanate compounds as linking agent, (H) as long as crosslinking catalyst plays the material of function as the reaction (crosslinking reaction) of catalyzer to aforementioned copolymer and linking agent, can enumerate: the organometallic compound etc. such as aminated compounds, organo-tin compound, organo-lead compound, organic zinc compound of tertiary amine etc.
Can enumerate as tertiary amine: trialkylamine, N, N, N', N'-tetra, 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 etc. of sub-tin.
Preferably (H) crosslinking catalyst is organo-tin compound, is particularly preferably more than at least one in the compound group being selected from and being made up of di-n-octyltin oxide, tin dilaurate dioctyl tin.
Relative 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 to be (I-1) fusing point be ionic compound or (I-2) quaternary ionic compound containing acryl of 30 ~ 50 DEG C.
In the present invention; as (I) static inhibitor; the ionic compound being 30 ~ 50 DEG C by (I-1) fusing point makes an addition in multipolymer, or by (I-2) quaternary ionic compound copolymerization containing acryl in multipolymer.Infer because the fusing point of these (I) static inhibitor is low and have chain alkyl, therefore, high with the affinity of acrylic copolymer.
As the ionic compound that (I-1) fusing point is 30 ~ 50 DEG C, it is the ionic compound with positively charged ion and negatively charged ion, can enumerate: positively charged ion is the cationic nitrogenous Huo person phosphonium cation, sulfonium cation etc. of pyridylium, glyoxaline cation, pyrimidine positively charged ion, pyrazoles positively charged ion, pyrroles's positively charged ion, ammonium cation 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.Be preferably solid under normal temperature (such as 30 DEG C), and by selecting the chain length, substituent position, number etc. of alkyl, the compound that fusing point is 30 ~ 50 DEG C can be obtained.Preferred cationic is quaternary nitrogen positively charged ion, can enumerate: the quaternary ammonium cation etc. of the season glyoxaline cation, tetra-allkylammonium etc. of the season pyridylium, 1,3-dialkylimidazolium (carbon atom of 2,4,5 both can have substituting group and also can not have substituting group) etc. of 1-alkyl pyridine (carbon atom of 2 ~ 6 both can have substituting group and also can not have substituting group) etc.
Relative to the multipolymer of 100 weight parts, preferably (I-1) fusing point is the content of the ionic compound of 30 ~ 50 DEG C is 0.1 ~ 5.0 weight part.
As (I-2) the quaternary ionic compound containing acryl, be 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. containing the quaternary ammonium of (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 -), imide root (R containing F f 2n -) etc. the compound of inorganic or organic anion.As the imide root (R containing F f 2n -) R f, perfluoroalkyl group sulfonyl, the fluorosulfonyl of trifyl, five fluorine ethylsulfonyls etc. can be enumerated.As the imide root containing F, two (fluorosulfonyl) imide root ((FSO can be enumerated 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 containing acryl, preferably copolymerization amount is in the copolymer 0.1 ~ 5.0 % by weight.
As the object lesson of (I) static inhibitor, be not particularly limited, but as the object lesson that (I-1) fusing point is the ionic compound of 30 ~ 50 DEG C, 1-octylpyridinium hexafluorophosphate, 1-nonylpyridine hexafluorophosphate, 2-methyl isophthalic acid-dococylpyridinium hexafluorophosphate, 1-octylpyridinium dodecylbenzene sulfonate, 1-dococylpyridinium thiocyanate-, 1-dococylpyridinium dodecylbenzene sulfonate, 4-methyl isophthalic acid-octylpyridinium hexafluorophosphate etc. can be enumerated.In addition, as the object lesson of (I-2) the quaternary ionic compound containing acryl, dimethylaminomethyl (methyl) acrylate phosphofluoric acid methyl salt ((CH can be enumerated 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 dimethylamine methyl esters 3) 3n +cH 2oCOCQ=CH 2(FSO 2) 2n -, wherein, Q=H or CH 3) etc.
Adhesive composition can contain arbitrarily (J) polyether modified siloxane compound.(J) polyether-modified silicone compounds is the silicone compounds with polyether-based, except common siloxane unit (-SiR 1 2-O-) outside, also there is the siloxane unit (-SiR comprising polyether-based 1(R 2o (R 3o) nr 4)-O-).At this, R 1represent one or more alkyl or aryl, R 2and R 3represent one or more alkylidene group, R 4represent (terminal group) such as one or more alkyl, acyl groups.Can enumerate as polyether-based: polyethylene oxide base ((C 2h 4o) n) or polyoxytrimethylene base ((C 3h 6o) n) etc. polyoxyalkylene.
Preferably (J) polyether modified siloxane compound to be HLB value be 7 ~ 12 polyether modified siloxane compound.In addition, relative to the multipolymer of 100 weight parts, preferably the content of (J) polyether modified siloxane compound is 0.01 ~ 0.5 weight part, is more preferably 0.1 ~ 0.5 weight part.
HLB refers to the hydrophilic-lipophilic balance (wetting ability and oil loving ratio) of the regulations such as such as JIS K3211 (tensio-active agent term).
Polyether modified siloxane compound, such as, obtains by following method: by hydrosilylation reactions, makes the organic compound with unsaturated link(age) and polyoxyalkylene be grafted on the main chain of the organopolysiloxane with silylation and obtain.Specifically, can enumerate: dimethyl siloxane-methyl (polyoxyethylene) silicone copolymers, dimethyl siloxane-methyl (polyoxyethylene) siloxane-methyl (polyoxytrimethylene) silicone copolymers, dimethyl siloxane-methyl (polyoxytrimethylene) silicone copolymers etc.
By (J) polyether modified siloxane compound is matched with adhesive composition, cohesive force and the cycling processability of binding agent can be improved.When adhesive composition is not containing (J) polyether modified siloxane compound, cost can be made lower.
And, as other composition, can suitably coordinate containing alkylene oxide (alkylene oxide) can 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 of copolymerization.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, by making, the carbonatoms of (A) alkyl is (methyl) acrylate monomer of C4 ~ C18, the copolymerisable monomer of (B) hydroxyl, (C) carboxylic copolymerisable monomer and (D) polyalkylene glycol mono (methyl) acrylate monomer carry out being polymerized synthesizing.To the polymerization process of multipolymer, there is no particular limitation, can use the polymerization process that solution polymerization, letex polymerization etc. are suitable.
When the quaternary ionic compound using (I-2) containing acryl as (I) static inhibitor; for the host multipolymer of adhesive composition of the present invention, by making, the carbonatoms of (A) alkyl is (methyl) acrylate monomer of C4 ~ C18, the copolymerisable monomer of (B) hydroxyl, (C) carboxylic copolymerisable monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and (I-2) quaternary ionic compound containing acryl carry out being polymerized synthesizing.
Adhesive composition of the present invention, by coordinating the isocyanate compound of more than (F) trifunctional, (G) cross-linked inhibitor, (H) crosslinking catalyst, (I) static inhibitor, also having suitable any additive to prepare in above-mentioned multipolymer.In addition; if when (I-2) quaternary ionic compound containing acryl being polymerized in host multipolymer; both can add (I) static inhibitor further to multipolymer, also can not add (I) static inhibitor.
Preferred aforementioned copolymer is acrylic polymers, preferably contains (methyl) acrylate monomer or the acrylic monomer such as (methyl) vinylformic acid, (methyl) acrylic amide of 50 ~ 100 % by weight.
In addition, the acid number of preferred acrylic polymers is 0.01 ~ 8.0.Thereby, it is possible to improve contaminative and improve the performance preventing glue residue phenomenon from occurring.
At this, " acid number " is one of index representing acid content, be with in and 1g contain carboxyl polymkeric substance required for the mg number of potassium hydroxide represent.
The cohesive force of the adhesive layer preferably making foregoing adhesives composition be cross-linked 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.Thereby, it is possible to obtain cohesive force with the little performance of the change of peeling rate, even also can peel off rapidly when peeling off at a high speed.Further, even if in order to again paste during temporary transient stripper surface protective membrane, also without the need to excessive strength, be easy to peel off from adherend.
The surface resistivity of the adhesive layer preferably making foregoing adhesives composition be cross-linked is 5.0 × 10 + 10Ω/below, stripping 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, then to the poor performance that the electrostatic produced because of charged when peeling off discharges, therefore, by making surface resistivity enough little, the stripping static voltage produced with the electrostatic that occurs when peeling off adhesive layer from adherend can be reduced, the impact on the electric control circuit of adherend etc. can be suppressed.
The gel fraction of the adhesive layer (binding agent after crosslinked) preferably making adhesive composition of the present invention be cross-linked is 95 ~ 100%.Because gel fraction is so high, when low peeling rate, cohesive force can not become excessive, reduce the phenomenon of stripping unconverted monomer or oligomer from multipolymer, thus the weather resistance under re-workability, high temperature/high humidity can be improved, and suppress the pollution of adherend.
Adhesive film of the present invention forms adhesive layer at the single or double of resin molding to form, and described adhesive layer adhesive composition of the present invention is cross-linked form.In addition, surface protection film of the present invention forms adhesive layer at the one side of resin molding to form, and described adhesive layer adhesive composition of the present invention is cross-linked form.In adhesive composition of the present invention; owing to being combined with each composition of above-mentioned (A) ~ (I) with good balance; so have excellent antistatic property; the balance of the cohesive force under low peeling rate and high peeling rate is excellent; and endurance quality and cycling processability (with ballpoint pen after adhesive layer is described on surface protection film, transferring the pollution to adherend) are also excellent.Therefore, can preferably be used as the surface protection film purposes of Polarizer.
As the base material film of adhesive layer, the stripping film (barrier film) of protection adhesive surface, the resin moldings etc. such as polyester film can be used.
For base material film, can on the face contrary with being formed with adhesive layer side of resin molding, implement the antifouling process undertaken by releasing agent or coating-forming agent, the silicon dioxide microparticle etc. of silicone, fluorine class, the antistatic treatment of being undertaken by the coating of static inhibitor or be mixed into etc. can be implemented.
For stripping film, carry out fitting on the face of side at the adhesive surface with adhesive layer, implement the demoulding process undertaken by the releasing agent etc. of silicone, fluorine class.
Embodiment
Below, the present invention is illustrated based on embodiment.
The following describes not containing the adhesive composition of static inhibitor and embodiment 1 ~ 9, the comparative example 1 ~ 4 of surface protection film.
Manufacture (1) > of < acrylic copolymer
[embodiment 1]
Nitrogen is imported in the reaction unit being furnished with agitator, thermometer, reflux exchanger and nitrogen ingress pipe, thus the air with nitrogen replacement in reaction unit.Then, in reaction unit, add the 2-EHA of 100 weight parts, the vinylformic acid 8-hydroxyl monooctyl ester of 0.9 weight part, the vinylformic acid of 0.5 weight part, the polypropylene glycol mono acrylic ester (forming the averaged repeating numbers n=12 of the alkylene oxide of polyalkylene glycol chain) of 10 weight parts, the NVP of 5 weight parts, and add the solvent (vinyl acetic monomer) of 60 weight parts simultaneously.Then, through the Diisopropyl azodicarboxylate as polymerization starter of 2 hours instillation 0.1 weight parts, at 65 DEG C, make it react 6 hours, obtain 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.
[embodiment 2 ~ 9 and comparative example 1 ~ 4]
Except have adjusted the composition of each monomer respectively as described in (A) in table 1 ~ (E) except, operate in the same manner as the above-mentioned acrylic acid copolymer soln 1 for embodiment 1, obtain for the acrylic acid copolymer soln in embodiment 2 ~ 9 and comparative example 1 ~ 4.
Table 1
Manufacture (1) > of < adhesive composition and surface protection film
[embodiment 1]
To the acrylic acid copolymer soln 1 according to the embodiment 1 manufactured as mentioned above, add 2.5 weight part methyl ethyl diketones and after stirring, be uniformly mixed after adding 1.0 weight part Coronate HX (isocyanuric acid ester of コ ロ ネ ー ト HX, hexamethylene diisocyanate compound), 0.2 weight part Coronate L (affixture of コ ロ ネ ー ト L, tolunediisocyanate compound and TriMethylolPropane(TMP)), 0.02 weight part tin dilaurate dioctyl tin, obtain the adhesive composition of embodiment 1.This adhesive composition is coated on the stripping film be made up of the polyethylene terephthalate scribbling silicone resin (PET) film, then at 90 DEG C, carries out drying and remove solvent, obtain the bonding sheet that adhesive layer thickness is 25 μm.
Then; prepare polyethylene terephthalate (PET) film face implementing antistatic treatment and antifouling process; and bonding sheet is transferred to this polyethylene terephthalate (PET) film with implement on the opposing face in face of antistatic treatment and antifouling process, obtain the surface protection film of the embodiment 1 of the stacked formation with " PET film/adhesive layer/stripping film (scribbling the PET film of silicone resin) implementing antistatic treatment and antifouling process ".
[embodiment 2 ~ 9 and comparative example 1 ~ 4]
Except have adjusted the composition of each additive respectively as described in (F) ~ (H) of table 2 except, operate in the same manner as the surface protection film of above-described embodiment 1, obtain embodiment 2 ~ 9 and the surface protection film comparing 1 ~ 4.
Table 2
Table 1 and table 2 to represent that the whole table of each components matching ratio is divided into the table of two parts.In table 1 and table 2, the numerical value in bracket all represents that the gross weight organized with (A) is set to 100 weight parts and the numerical value of each Parts by Ingredients obtained.In addition, the compound title corresponding with the abbreviation of each composition used 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 is Nippon Polyurethane Industry Co., Ltd. (NipponPolyurethane Industry Co., Ltd.) trade name, Takenate (タ ケ ネ ー ト, registered trademark) D-140N, D-127N, D-110N, D-120N are the trade names of Mitsui Chemicals, Inc.
Table 3
Table 4
< test method and evaluation >
23 DEG C, under the environment of 50%RH, by aging 7 days of the surface protection film of embodiment 1 ~ 9 and comparative example 1 ~ 4.Then, peel stripping film (scribbling the PET film of silicone resin) off, thus adhesive layer is exposed.And then; by the surface protection film that this adhesive layer exposes; the Polarizer surface of pasting on liquid crystal cell is fitted in by adhesive layer; place and under 50 DEG C, 5 normal atmosphere, carry out pressure kettle process 20 minutes after 1 day; at room temperature place after 12 hours further, it can be used as the sample measuring cohesive force, re-workability and weather resistance.
< acid number >
The acid number of acrylic polymers: by sample dissolution in solvent (diethyl ether and ethanol being carried out the solvent mixed with volume ratio 2:1), by potential difference automatic titration device (AT-610, capital of a country electronic industry Co., Ltd. manufactures), and the potassium hydroxide-ethanol solution adopting concentration to be about 0.1mol/L carries out potential difference titration, determine in and the amount of potassium hydroxide-ethanol solution needed for sample.Then, acid number is obtained according to 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 coefficient of f=0.1mol/L potassium hydroxide-ethanol solution
The quality (g) of the solids component of S=sample
< cohesive force >
Adopt tensile testing machine; with low peeling rate (0.3m/min) and high peeling rate (30m/min); above-mentioned obtained mensuration sample (surface protection film wide for 25mm being fitted in the sample on Polarizer surface) is peeled off to 180 ° of directions; determine stripping strength, and using this stripping strength as cohesive force.
< re-workability >
After carrying out describing (load be 500g, 3 times back and forth) with ballpoint pen on the surface protection film of mensuration sample obtained above, from Polarizer stripper surface protective membrane, observe the surface of Polarizer, be confirmed whether to displaced pollution to Polarizer.Evaluation objective benchmark: be evaluated as "○" when not transferring the pollution to Polarizer; Be evaluated as " △ " when confirming that the track described along ballpoint pen at least displaced pollution to local; "×" is evaluated as when confirming that the track described along ballpoint pen has pollution transportation and also confirms from adhesive surface the disengaging having binding agent.
< weather resistance >
By above-mentioned obtained mensuration sample 60 DEG C, place 250 hours under the environment of 90%RH, then take out and be placed in room temperature and place 12 hours further, then measure cohesive force, confirm whether there is obvious increase compared with initial stage cohesive force.Evaluation objective benchmark: is "○" when the cohesive force after test is the average evaluation of less than 1.5 times of initial stage cohesive force, average evaluation more than 1.5 times is "×".
Evaluation result is shown in Table 5.
Table 5
For the surface protection film of embodiment 1 ~ 9, the cohesive force 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; Further, at use ballpoint pen after adhesive layer is described on surface protection film, do not transfer the pollution to adherend, and 60 DEG C, place 250 hours under the environment of 90%RH after weather resistance be also excellent.
That is, meet performance requriementss whole as follows: (1) obtains the balance of the cohesive force under low peeling rate and high peeling rate simultaneously; (2) generation of glue residue is prevented; And (3) cycling processability.
In addition, by making the averaged repeating numbers forming the alkylene oxide of polyalkylene glycol chain in aforementioned (D) polyalkylene glycol mono (methyl) acrylate monomer be 3 ~ 14, stain resistance (re-workability) can be improved further.
For the surface protection film of comparative example 1; its 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 due to not containing (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) nitrogenous vinyl monomer or containing (methyl) alkyl acrylate monomer of alkoxyl group and the cause of (F) isocyanate compound.
For the surface protection film of comparative example 2; its re-workability and poor durability, this may be form because the monomer of (B) hydroxyl is very few, in (D) polyalkylene glycol mono (methyl) acrylate monomer that the averaged repeating numbers n of the alkylene oxide of polyalkylene glycol chain is excessive, cause containing (E) nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxyl group.
For the surface protection film of comparative example 3; because its storage period is too short, be cross-linked before coating, therefore; cannot be coated with, this may be because of (F) isocyanate compound too much, do not coordinate the cause of (G) cross-linked inhibitor.
For the surface protection film of comparative example 4; even if not containing (H) crosslinking catalyst, its storage period is also too short, and is 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, performance requriementss whole as follows cannot be met: (1) obtains the balance of the cohesive force under low peeling rate and high peeling rate simultaneously; (2) generation of glue residue is prevented; And (3) cycling processability.
The following describes embodiment 11 ~ 19, the comparative example 11 ~ 14 of adhesive composition containing static inhibitor and surface protection film.
[embodiment 11]
Nitrogen is imported in the reaction unit being furnished with agitator, thermometer, reflux exchanger and nitrogen ingress pipe, thus the air with nitrogen replacement in reaction unit.Then, in reaction unit, add the 2-EHA of 100 weight parts, the vinylformic acid 8-hydroxyl monooctyl ester of 0.9 weight part, the vinylformic acid of 0.5 weight part, the polypropylene glycol mono acrylic ester (averaged repeating numbers forming the alkylene oxide of polyalkylene glycol chain is n=12) of 10 weight parts, the NVP of 5 weight parts, and add the solvent (vinyl acetic monomer) of 60 weight parts simultaneously.Then, through the Diisopropyl azodicarboxylate as polymerization starter of 2 hours instillation 0.1 weight parts, at 65 DEG C, make it react 6 hours, obtain weight-average molecular weight be 500,000, for the acrylic acid copolymer soln 1 of embodiment 1.Get a part for acrylic copolymer, use as determination of acid value sample described later.
[embodiment 12 ~ 19 and comparative example 11 ~ 14]
Except have adjusted the composition of each monomer respectively as described in (A) in table 6 ~ (E) and (I-2) except, operate in the same manner as the above-mentioned acrylic acid copolymer soln 1 for embodiment 11, obtain for the acrylic acid copolymer soln in embodiment 12 ~ 19 and comparative example 11 ~ 14.
Table 6
The manufacture 2> of < adhesive composition and surface protection film
[embodiment 11]
To the acrylic acid copolymer soln 1 according to the embodiment 11 manufactured as mentioned above, add 1.5 weight part 1-octylpyridinium hexafluorophosphates, 2.5 weight part methyl ethyl diketones after stirring, be uniformly mixed after adding 1.0 weight part Coronate HX (isocyanuric acid ester of コ ロ ネ ー ト HX, hexamethylene diisocyanate compound), 0.2 weight part Coronate L (affixture of コ ロ ネ ー ト L, tolunediisocyanate compound and TriMethylolPropane(TMP)), 0.02 weight part tin dilaurate dioctyl tin, obtain the adhesive composition of embodiment 1.This adhesive composition is coated on the stripping film be made up of the polyethylene terephthalate scribbling silicone resin (PET) film, then at 90 DEG C, carries out drying and remove solvent, obtain the bonding sheet that adhesive layer thickness is 25 μm.
Then; prepare polyethylene terephthalate (PET) film implementing antistatic treatment and antifouling process on one face; and bonding sheet is transferred on the face contrary with the face implementing antistatic treatment and antifouling process of this polyethylene terephthalate (PET) film, obtain the surface protection film of the embodiment 1 of the stacked formation with " PET film/adhesive layer/stripping film (scribbling the PET film of silicone resin) implementing antistatic treatment and antifouling process ".
[embodiment 12 ~ 19 and comparative example 11 ~ 14]
Except have adjusted the composition of each additive respectively as described in (F) ~ (I-1) of table 6 except, operate in the same manner as the surface protection film of above-described embodiment 11, obtain embodiment 12 ~ 19 and the surface protection film comparing 11 ~ 14.
Table 7
Table 6 and table 7 to represent that the whole table of each components matching ratio is divided into the table of two parts, and the numerical value in bracket all represents that the total weight organized with (A) is set to 100 weight parts and the numerical value of each Parts by Ingredients obtained.In addition, the compound title of the abbreviation correspondence of each composition used in table 6 and table 7 is identical with the compound title shown in table 4 with aforementioned table 3.In addition, Coronate (コ ロ ネ ー ト, registered trademark) HX, Coronate HL and Coronate L is Nippon Polyurethane Industry Co., Ltd. (NipponPolyurethane Industry Co., Ltd.) trade name, Takenate (タ ケ ネ ー ト, registered trademark) D-140N, D-127N, D-110N, D-120N are the trade names of Mitsui Chemicals, Inc.
In addition, in table 6, (I-2) in copolymerization (I) static inhibitor in multipolymer is the quaternary ionic compound containing acryl, the compound title of the abbreviation of each composition is shown in Table 8.
In addition, in table 7, (I-1) in (I) static inhibitor added after the polymerization of multipolymer is fusing point is 30 ~ 50 DEG C of ionic compounds, the compound title of the abbreviation of each composition is shown in Table 8.
Table 8
< test method and evaluation (2) >
23 DEG C, under the environment of 50%RH; by the surface protection film of embodiment 11 ~ 19 and comparative example 11 ~ 14 after aging 7 days; peel stripping film (scribbling the PET film of silicone resin) off, thus adhesive layer is exposed, and as the sample of chart surface resistivity.
And then; by the surface protection film that this adhesive layer exposes; the surface of the Polarizer pasted on liquid crystal cell is fitted in by adhesive layer; place and under 50 DEG C, 5 normal atmosphere, carry out pressure kettle process 20 minutes after 1 day; at room temperature place after 12 hours further, the sample it can be used as and measure cohesive force, peeled off static voltage, re-workability and weather resistance.
< surface resistivity >
After weathering, 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 of Co., Ltd. chemical analysis technology (Mitsubishi Chemical Analytech Co., Ltd.) manufacture), determine the surface resistivity of adhesive layer.
< peels off static voltage >
Adopt high precision electrostatic transducer SK-035, SK-200 (Co., Ltd.'s Keyemce (KeyenceCorporation) manufacture), measure with the draw speed of 30m/min to above-mentioned obtained mensuration sample carry out 180 ° peel off time Polarizer charged and produce voltage (static voltage), and using the maximum value of measured value as stripping static voltage.
In addition; the test method of < acid number >, < cohesive force >, < re-workability >, < weather resistance > is identical with the test method of the embodiment 1 ~ 9 in surface protection film, comparative example 1 ~ 4 with the above-mentioned adhesive composition not containing static inhibitor.
Evaluation result is shown in Table 9.In addition, in surface resistivity, represent " m × 10 by " mE+n " + n" (wherein, m is arbitrary real number, and n is positive integer).
Table 9
For the surface protection film of embodiment 11 ~ 19, the cohesive force 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; Surface resistivity is 5.0 × 10 + 10Ω/below, stripping static voltage is ± 0 ~ 0.3kV; Further, use ballpoint pen across adhesive layer after surface protection film is described, do not transfer the pollution to adherend, and 60 DEG C, place 250 hours under the environment of 90%RH after weather resistance be also excellent.
That is, meet performance requriementss whole as follows: (1) obtains the balance of the cohesive force under low peeling rate and high peeling rate simultaneously; (2) generation of glue residue is prevented; (3) excellent antistatic property; And (4) cycling processability.
In addition, by making the averaged repeating numbers forming the alkylene oxide of polyalkylene glycol chain in aforementioned (D) polyalkylene glycol mono (methyl) acrylate monomer be 3 ~ 14, anti-static function can be made to become good and improve stain resistance (re-workability).
For the surface protection film of comparative example 11; its cohesive force under low peeling rate 0.3m/min and high peeling rate 30m/min is excessive, surface resistivity and stripping static voltage is high, 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 containing (methyl) alkyl acrylate monomer of alkoxyl group and the cause of (F) isocyanate compound.
For the surface protection film of comparative example 12; its surface resistivity and peel off high, the re-workability of static voltage and poor durability, this may be form because the monomer of (B) hydroxyl is very few, in (D) polyalkylene glycol mono (methyl) acrylate monomer that the averaged repeating numbers n of the alkylene oxide of polyalkylene glycol chain is excessive, cause containing (E) nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxyl group.
For the surface protection film of comparative example 13; because its storage period is too short, be cross-linked before coating, therefore; cannot be coated with, this may be because (F) isocyanate compound too much, do not coordinate (G) cross-linked inhibitor.
For the surface protection film of comparative example 14; even if not containing (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 11 ~ 14, performance requriementss whole as follows cannot be met: (1) obtains the balance of the cohesive force under low peeling rate and high peeling rate simultaneously; (2) generation of glue residue is prevented; (3) excellent antistatic property; And (4) cycling processability.

Claims (13)

1. an adhesive composition, comprising:
Containing the acrylic polymers that the carbonatoms of (A) alkyl is (methyl) acrylate monomer of C4 ~ C18, the copolymerisable monomer of (B) hydroxyl, (C) carboxylic copolymerisable monomer, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) not hydroxyl and nitrogenous vinyl monomer or the multipolymer containing at least one in (methyl) alkyl acrylate monomer of alkoxyl group
And, also comprise the isocyanate compound of more than (F) trifunctional, (G) cross-linked inhibitor and (H) crosslinking catalyst,
The acid number of described acrylic polymers is 0.01 ~ 8.0,
The averaged repeating numbers forming the alkylene oxide of polyalkylene glycol chain in described (D) polyalkylene glycol mono (methyl) acrylate monomer is 3 ~ 14.
2. adhesive composition as claimed in claim 1, wherein,
Also containing (I) static inhibitor, described (I) static inhibitor is 0.1 ~ 5.0 weight part relative to the content of multipolymer described in 100 weight parts and fusing point is the ionic compound of 30 ~ 50 DEG C or the copolymerization amount in described multipolymer is 0.1 ~ 5.0 % by weight and quaternary ionic compound containing acryl.
3. adhesive composition as claimed in claim 1 or 2, wherein,
The copolymerisable monomer of described (B) hydroxyl is selected from more than at least one in the compound group that is made up of (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxybutyl, (methyl) vinylformic acid 2-hydroxy methacrylate, N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide
Be (methyl) acrylate monomer of C4 ~ C18 relative to the carbonatoms of (A) alkyl described in 100 weight parts, copolymerisable monomer containing (B) hydroxyl described in 0.1 ~ 5.0 weight part, and, in the copolymerisable monomer of described (B) hydroxyl, the total amount of (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxybutyl is 0 ~ 0.9 weight part
Described (C) carboxylic copolymerisable monomer is selected from by (methyl) vinylformic acid, (methyl) carboxy ethyl acrylate, (methyl) carboxypentyl acrylate, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloxypropyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl phthalic acid, 2-(methyl) acryloyl-oxyethyl succsinic acid, 2-(methyl) acryloyl-oxyethyl toxilic acid, carboxy-polycaprolactone list (methyl) acrylate, more than at least one in the compound group that 2-(methyl) acryloyl-oxyethyl tetrahydrophthalic acid forms,
Be (methyl) acrylate monomer of C4 ~ C18 relative to the carbonatoms of (A) alkyl described in 100 weight parts, containing (C) carboxylic copolymerisable monomer described in 0.35 ~ 1.0 weight part.
4. the adhesive composition according to any one of claims 1 to 3, wherein,
Described (D) polyalkylene glycol mono (methyl) acrylate monomer is selected from more than at least one in polyalkylene glycol mono (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate, oxyethyl group polyalkylene glycol (methyl) acrylate
Be (methyl) acrylate monomer of C4 ~ C18 relative to the carbonatoms of (A) alkyl described in 100 weight parts, containing (D) polyalkylene glycol mono (methyl) acrylate monomer described in 1 ~ 50 weight part.
5. the adhesive composition according to any one of Claims 1 to 4, wherein,
Isocyanate compound more than described (F) trifunctional is selected from 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, the isocyanuric acid ester of tolunediisocyanate compound, the isocyanuric acid ester of xylylene diisocyanate compound, the isocyanuric acid ester of hydrogenated xylylene diisocyanate cpd, the affixture of tolunediisocyanate compound, the affixture of xylylene diisocyanate compound, in the compound group that the affixture of hydrogenated xylylene diisocyanate cpd forms more than at least one.
6. the adhesive composition according to any one of Claims 1 to 5, wherein,
Be (methyl) acrylate monomer of C4 ~ C18 relative to the carbonatoms of (A) alkyl described in 100 weight parts, containing (E) described in 1 ~ 20 weight part not hydroxyl and nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxyl group.
7. the adhesive composition according to any one of claim 1 ~ 6, wherein,
Relative to the described multipolymer of 100 weight parts, containing isocyanate compound more than (F) trifunctional described in 0.5 ~ 5.0 weight part.
8. the adhesive composition according to any one of claim 1 ~ 7, wherein,
Described (G) cross-linked inhibitor is keto-enol tautomerism compound, relative to the described multipolymer of 100 weight parts, containing (G) cross-linked inhibitor described in 1.0 ~ 5.0 weight parts,
Described (H) crosslinking catalyst is organo-tin compound, relative to the described multipolymer of 100 weight parts, containing (H) crosslinking catalyst described in 0.01 ~ 0.5 weight part.
9. the adhesive composition according to any one of claim 1 ~ 8, wherein,
The cohesive force of the adhesive layer that described adhesive composition is cross-linked 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.
10. an adhesive film, it forms adhesive layer at the single or double of resin molding to form, and described adhesive layer the adhesive composition according to any one of claim 1 ~ 9 is cross-linked form.
11. 1 kinds of surface protection films; its one side at resin molding forms adhesive layer and forms; described adhesive layer the adhesive composition according to any one of claim 1 ~ 9 is cross-linked form; wherein; with ballpoint pen after described adhesive layer is described on surface protection film, do not transfer the pollution to adherend.
12. surface protection films as claimed in claim 11, its surface protection film purposes as Polarizer is used.
13. surface protection films as claimed in claim 11, wherein, on the face contrary with the side being formed with described adhesive layer of described resin molding, implement antistatic and antifouling process.
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