CN104946173A - Adhesive composition and surface protection film - Google Patents

Adhesive composition and surface protection film Download PDF

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Publication number
CN104946173A
CN104946173A CN201510308984.4A CN201510308984A CN104946173A CN 104946173 A CN104946173 A CN 104946173A CN 201510308984 A CN201510308984 A CN 201510308984A CN 104946173 A CN104946173 A CN 104946173A
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methyl
mentioned
compound
acrylate
binder composition
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CN201510308984.4A
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CN104946173B (en
Inventor
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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Liquid Crystal (AREA)

Abstract

The invention provides an adhesive composition and a surface protection film which are superior in antistatic property, and capable of simultaneously satisfying demands for durability and reworkability, and superior in balance of peeling adhesive force at low-speed peeling and high-speed peeling. The adhesive composition includes: a copolymer containing (A) a (meth)acrylate monomer having a 4-10C alkyl group, (B) a copolymerizable monomer containing a hydroxyl group, (C) a copolymerizable monomer containing a carboxyl group, and (D) a polyalkylene glycol mono(meth)acrylate monomer; (E) a tri- or higher functional isocyanate compound; (F) a crosslinking retarder; (G) a crosslinking catalyst; (H) an antistatic agent; and (I) a polyether-modified siloxane compound.

Description

Binder composition and surface protection film
The divisional application that the application is the applying date is on November 20th, 2012, application number is 201210472704.X, denomination of invention is the application of " binder 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 on the surface of the optics being fitted in the Polarizer, polarizer etc. that form liquid-crystal display, protect the surface protection film binder 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 of the Polarizer, polarizer etc. for forming liquid-crystal display, the temporary transient coating surface protective membrane on the surface of optics.When optics is assembled into liquid-crystal display, surface protection film is peeled off from optics and removes.Only use in manufacturing process to protect the surface protection film of optical component surfaces.Therefore, usually, operation film is also referred to as.
Manufacturing the surface protection film used in the operation of optics, the one side of polyethylene terephthalate (PET) resin molding with optical transparence forms binder layer.In addition, until before fitting in optics, by order to protect the stripping film being stripped process of this binder layer to fit in above binder layer.
And; due to the optics of Polarizer, polarizer etc.; under the state being fitted with surface protection film; carry out the examination and test of products of the optical assessment be mixed into etc. with the display capabilities of LCD panel, colourity, contrast gradient, impurity; therefore; performance for surface protection film necessity is, within the adhesive layer non-cohesive bubble or impurity.
And, in recent years, need the antistatic property preventing the excellence of electrostatic when being peeled off from the optics of Polarizer, polarizer etc. by surface protection film.This is because from adherend release adhesive oxidant layer time, along with produced electrostatic produce stripping time the charged electric control circuit of liquid-crystal display that likely makes break down.
And, when making surface protection film fit in the optics of Polarizer, polarizer etc., due to a variety of causes, there is temporary transient stripper surface protective membrane, then the situation of adhesive surface protective membrane again.At this moment require easily from the stripping (there is doing over again property (リ ワ ー Network) of the optics of adherend) surface protection film.
And during from the optics stripper surface protective membrane of Polarizer, polarizer etc., requirement can be peeled off rapidly.That is, in order to also peel off rapidly by peeling off at a high speed, require that the impact that bounding force is subject to peeling rate is few.
Like this, in recent years, as the requirement performance of the binder layer for formation surface protection film, the performance of following (1) ~ (4) is required.
(1) balance that low speed peels off the bounding force in peeling off with high speed is obtained.
(2) generation of adhesive residue is prevented.
(3) there is excellent antistatic property.
(4) there is performance of doing over again.
But; although the requirement performance individually of these (1) ~ (4) can be met, be very difficult to possess (1) ~ all of (4) required in the binder layer of surface protection film simultaneously and require performance.
Such as, obtain about (1) balance that low speed peels off the bounding force in peeling off with high speed; (2) generation of adhesive residue can be prevented, there will be a known following motion.
With the multipolymer of (methyl) alkyl acrylate with the copolymerizable compound containing carboxyl with the alkyl of carbonatoms below 7 for main component, with the acrylic adhesives that linking agent is made its crosslinking Treatment, if through long-time after laminating, then there is tackiness agent move to adherend side, and to the bounding force of adherend through time the problem that rises.Produce to prevent this problem, known following tackiness agent (pressure sensitive adhesive): described tackiness agent uses that to have carbonatoms be (methyl) alkyl acrylate of the alkyl of 8 ~ 10 and the multipolymer of copolymerizable compound with alcohol hydroxyl group, obtains (patent documentation 1) its crosslinking Treatment with linking agent.
And following tackiness agent etc. is proposed: described tackiness agent, by mixing (methyl) alkyl acrylate and the multipolymer of the copolymerizable compound containing carboxyl on a small quantity in above-mentioned same multipolymer, obtains with the process of linking agent cross-linking.But, when in the surface protection using it for the low ganoid plastic plate of surface tension etc., have due to the possibility adding releasable difference when thermogenesis is floated the peeling that waits or manually peels off stripping at a high speed when adding man-hour or preserve.
In order to address these problems, binder composition is proposed, described binder composition by (a) 100 weight part be in (methyl) alkyl acrylate of main component to have carbonatoms be (methyl) alkyl acrylate of the alkyl of 8 ~ 10, add (b) 1 ~ 15 weight part containing carboxyl copolymerizable compound and, (c) 3 ~ 100 the carbonatoms of weight part be the multipolymer that the vinyl ester of the aliphatic carboxylic acid of 1 ~ 5 obtains monomer mixture, the linking agent that to be mixed into relative to the carboxyl of above-mentioned (b) composition in this multipolymer be more than equivalent obtains (patent documentation 2).
The binder composition recorded in patent documentation 2, the peeling of to float etc. in not producing when adding man-hour or preserving etc., and bounding force through time rise also little, releasable is outstanding, even the long-term preservation under long-term preservation, particularly high-temperature atmosphere, also can peel off with little power again, at this moment, adherend does not produce adhesive residue, and, also can peel off again with little power when carrying out stripping at a high speed.
Further, about (3), there is excellent antistatic property, as the method for giving surface protection film antistatic property, show and mediate method etc. into static inhibitor to base material film.As static inhibitor, such as, disclose (a) and there is quaternary ammonium salt, pyridinium salt, uncle to the various cationic antistatic agents of amino etc. the cation radical of uncle; 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 non-ionic antistatic agent of the both sexes static inhibitor, (d) alkamine, glycerols, polyethylene glycols etc. of (c) amino acids, amidosulphuric acid ester class etc.; E static inhibitor polymer as above quantizes (patent documentations 3) such as the Polymer Antistatic Agents obtained by ().
Further, in recent years, not only propose such static inhibitor is included in base material film or coats base material film surface, also propose directly to make binder layer contain such static inhibitor.
And, about (4), there is performance of doing over again, such as binder composition is proposed, described binder composition is by be 0.0001 ~ 10 weight part for acrylic resin 100 weight part, and in acrylic resin, mix isocyanate ester compound stiffening agent and specific silicate oligomer obtain (patent documentation 4).
In patent documentation 4, with the carbonatoms of alkyl be the alkyl acrylate of about 2 ~ 12, the carbonatoms of the alkyl alkyl methacrylate that is about 4 ~ 12 etc. is for main monomer component, such as, can comprise the monomer containing carboxyl etc., monomer component containing other functional group.Usually, preferably containing more than 50 % by weight above-mentioned principal monomer, and, wish that the content of the monomer component containing functional group is 0.001 ~ 50 % by weight, preferably 0.001 ~ 25 % by weight, more preferably 0.01 ~ 25 % by weight.Even if due in such patent documentation 4 record binder composition at high temperature or hot and humid under, the rheological parameters' change with time of cohesive force and bounding force is also little, and, also show outstanding effect in the bounding force of curved surface, therefore there is doing over again property.
Usually, if binder layer is made flexible proterties, then adhesive residue becomes easy generation, and doing over again property also easily reduces.That is, peel off difficulty when easily becoming laminating mistakenly, again to fit difficulty.Therefore, needing the monomer crosslinked in host of the functional group by having carboxyl etc., binder layer being made certain hardness, makes it have doing over again property.
[prior art document]
[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 11-070629 publication
[patent documentation 4] Japanese Patent Laid-Open 8-199130 publication
Summary of the invention
[inventing the problem that will solve]
In the prior art, as the requirement performance of the binder layer for formation surface protection film, require: obtain low speed and peel off and the balance of the bounding force in high speed stripping, excellent antistatic property and doing over again property.But, although can meet each, each requirement performance, require in the binder layer of surface protection film whole can not be met and require performance.
The present invention has used for reference above-mentioned situation.Problem of the present invention is to provide a kind of binder composition and surface protection film; described binder composition and surface protection film have antistatic property; obtain low speed peel off and peel off at a high speed in the balance of bounding force, and weather resistance and doing over again property, static resistance are also excellent.
[solving the method for problem]
In order to solve above-mentioned problem, the invention provides a kind of binder composition, it is by (methyl) acrylate monomer containing (A) atomic number of alkyl carbon being C4 ~ C10, (B) copolymerisable monomer containing hydroxyl, (C) copolymerisable monomer containing carboxyl, (D) multipolymer of polyalkylene glycol mono (methyl) acrylate monomer is formed, its further containing (E) 3 official can above isocyanate compound, (F) cross-linked inhibitor, (G) crosslinking catalyst, (H) static inhibitor, (I) polyether-modified silicone compounds.
Above-mentioned (B) copolymerisable monomer containing hydroxyl is for being selected from more than at least one in the compound group 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 composition; It is preferably (methyl) acrylate monomer of C4 ~ C10 relative to above-mentioned (A) atomic number of alkyl carbon of 100 weight parts, above-mentioned (B) copolymerisable monomer containing hydroxyl containing 0.1 ~ 5.0 weight part, and, above-mentioned (B), containing in the copolymerisable monomer of 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.
Above-mentioned (C) copolymerisable monomer containing carboxyl is for being selected from more than at least one in the compound group of (methyl) vinylformic acid, propyloic (methyl) acrylate, carboxylic amyl group (methyl) acrylate composition, be preferably (methyl) acrylate monomer of C4 ~ C10 relative to the carbonatoms of above-mentioned (A) alkyl of 100 weight parts, above-mentioned (C) copolymerisable monomer containing carboxyl containing 0.35 ~ 1.0 weight part.
Above-mentioned (D) polyalkylene glycol mono (methyl) acrylate monomer is for being selected from more than at least one in the compound group of polyalkylene glycol mono (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate, oxyethyl group polyalkylene glycol (methyl) acrylate composition; Be preferably (methyl) acrylate monomer of C4 ~ C10 relative to the carbonatoms of above-mentioned (A) alkyl of 100 weight parts, above-mentioned (D) polyalkylene glycol mono (methyl) acrylate monomer containing 1 ~ 20 weight part.
Above-mentioned (E) 3 official can isocyanate compound above be the isocyanuric acid ester body being 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, more than at least one in the compound group of the biuret body composition of isophorone diisocyanate compound, preferably relative to the above-mentioned multipolymer of 100 weight parts, above-mentioned (E) containing 0.5 ~ 5.0 weight part 3 official can above isocyanate compound.
Preferably above-mentioned (H) static inhibitor be relative to the above-mentioned multipolymer amount of 100 weight parts be 0.1 ~ 5.0 weight part, fusing point is the ionic compound of 30 ~ 80 DEG C, or is the quaternary acrylic monomer of 30 ~ 80 DEG C with 0.1 ~ 5.0 % by weight copolymerization, fusing point in above-mentioned multipolymer.
Above-mentioned (I) polyether-modified silicone compounds to be HLB value be 7 ~ 12 polyether-modified silicone compounds, preferably relative to the above-mentioned multipolymer of 100 weight parts, containing the silicone compounds that above-mentioned (I) of 0.01 ~ 0.5 weight part is polyether-modified.
Above-mentioned (F) cross-linked inhibitor is keto-enol tautomerism compound, preferably relative to the above-mentioned multipolymer of 100 weight parts, and above-mentioned (F) cross-linked inhibitor containing 1.0 ~ 5.0 weight parts.
Above-mentioned (G) crosslinking catalyst is organo-tin compound, preferably relative to the above-mentioned multipolymer of 100 weight parts, and above-mentioned (G) crosslinking catalyst containing 0.01 ~ 0.5 weight part.
Preferably, make the bounding force of the binder layer of above-mentioned binder composition cross-links under low speed peeling rate 0.3m/min be 0.05 ~ 0.1N/25mm, the bounding force under high speed peeling rate 30m/min is below 1.0N/25mm.
Preferably, make the surface resistivity of the binder layer of above-mentioned binder composition cross-links 5.0 × 10 + 10Ω/below, release band voltage is ± 0 ~ 1kV.
Further, the invention provides a kind of bonding film, it is the bonding film that the binder layer of above-mentioned binder composition cross-links is formed on the one or both sides of resin molding.
And; the invention provides a kind of surface protection film; it is the surface protection film that the binder layer of above-mentioned binder composition cross-links is formed in the one side of resin molding; with ballpoint pen be fitted in via above-mentioned binder layer on the surface protection film on adherend describe after; peel off from adherend, do not transfer the pollution to adherend.
Above-mentioned surface protection film, its purposes that can be used as Polarizer surface protection film uses.
Preferably on the face contrary with forming above-mentioned binder layer side of above-mentioned resin molding, carry out antistatic and anti-pollution process.
[invention effect]
According to the present invention, indeterminable over-all properties required in the binder layer of surface protection film in the prior art can be met.In addition, antistatic property can also be obtained and prevent all outstanding performance of the performance of adhesive residue.Specifically, the addition of static inhibitor can be reduced while maintaining antistatic property, the performance preventing adhesive residue can be improved further
Embodiment
Below, based on preferred embodiment the present invention being described.
Binder 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) multipolymer of polyalkylene glycol mono (methyl) acrylate monomer is formed, it is characterized in that further containing (E) 3 official can above isocyanate compound, (F) cross-linked inhibitor, (G) crosslinking catalyst, (H) static inhibitor, (I) polyether-modified silicone compounds.
(methyl) acrylate monomer being C4 ~ C10 as (A) atomic number of alkyl carbon can be enumerated: (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 etc.
Can enumerate as (B) copolymerisable monomer containing hydroxyl: (methyl) hydroxyalkyl acrylates class 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 etc., (methyl) acrylic amide etc. containing hydroxyl of N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide etc.
Preferably, more than at least one in the compound group 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 composition is selected from.
Relative to (methyl) acrylate monomer that above-mentioned (A) atomic number of alkyl carbon of 100 weight parts is C4 ~ C10, above-mentioned (B) copolymerisable monomer containing hydroxyl preferably containing 0.1 ~ 5.0 weight part.
And, at (B) containing in the copolymerisable monomer of 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 preferred less than 1 weight part (allowing situation about not containing), preferably 0 ~ 0.9 weight part.
Preferably (C) copolymerisable monomer containing carboxyl is for being selected from more than at least one in the compound group of (methyl) vinylformic acid, propyloic (methyl) acrylate, carboxylic amyl group (methyl) acrylate composition.
Be preferably (methyl) acrylate monomer of C4 ~ C10 relative to the carbonatoms of (A) alkyl of 100 weight parts, (C) copolymerisable monomer containing carboxyl containing 0.35 ~ 1.0 weight part.
As (D) polyalkylene glycol mono (methyl) acrylate monomer, can be in the multiple hydroxyls had at polyalkylene glycol, hydroxyl be as the esterified compound of (methyl) acrylate.Polymerizable group is become, therefore, it is possible to be copolymerized to host polymkeric substance because (methyl) is acrylate-based.Other hydroxyl both can keep OH constant, also can become the alkyl oxide such as methyl ether or ether, or the saturated carboxylic acid ester etc. such as acetic ester.
As the alkylidene group that polyalkylene glycol has, can enumerate ethylidene, propylidene, butylidene etc., this is infinite.Polyalkylene glycol also can be the multipolymer of the polyalkylene glycol of more than two kinds of poly-ethylidene glycol, polytrimethylene glycol, polybutylene glycol etc.As the multipolymer of polyalkylene 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 multipolymer can be segmented copolymer, random copolymers.
As (D) polyalkylene glycol mono (methyl) acrylate monomer, be preferably selected from more than at least one in the compound group of polyalkylene glycol mono (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate, oxyethyl group polyalkylene glycol (methyl) acrylate composition.
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, methoxyl group gathers ethylidene glycol-(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, oxyethyl group gathers ethylidene glycol-(methyl) acrylate, oxyethyl group polytrimethylene glycol-(methyl) acrylate, oxyethyl group polybutylene glycol-(methyl) acrylate, oxyethyl group-poly-ethylidene glycol-polytrimethylene glycol-(methyl) acrylate, oxyethyl group-poly-ethylidene glycol-polybutylene glycol-(methyl) acrylate, oxyethyl group-polytrimethylene glycol-polybutylene glycol-(methyl) acrylate, oxyethyl group-poly-ethylidene glycol-polytrimethylene glycol-polybutylene glycol-(methyl) acrylate etc.
Be preferably (methyl) acrylate monomer of C4 ~ C10 relative to the carbonatoms of above-mentioned (A) alkyl of 100 weight parts, above-mentioned (D) polyalkylene glycol mono (methyl) acrylate monomer containing 1 ~ 20 weight part.
As (E) 3 official can above isocyanate compound, there is in 1 molecule the polyisocyanate compound of more than at least 3 isocyanic ester (NCO) base, can enumerate: hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, 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 polyvalent alcohols (there is in 1 molecule the compound of the OH base of more than at least 3) more than 3 valencys of TriMethylolPropane(TMP) or glycerine etc.
(E) 3 officials can isocyanate compound above be the polyisocyanate compounds of isocyanic ester (NCO) base at least in 1 molecule with more than 3, be preferably selected from the isocyanuric acid ester body of hexamethylene diisocyanate compound especially, 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 multipolymer of 100 weight parts, (E) preferably containing 0.5 ~ 5.0 weight part 3 official can above isocyanate compound.
As (F) cross-linked inhibitor, can enumerate: the 'beta '-ketoester of methyl acetoacetate, methyl aceto acetate, etheric acid monooctyl ester, etheric acid oil base ester, 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, in the binder composition taking polyisocyanate compound as linking agent, closed by the isocyanate group that linking agent is had, after linking agent can be suppressed to mix, the excessive viscosity of binder composition rises or gelation, extends the storage period of binder composition.
(F) cross-linked inhibitor is preferably keto-enol tautomerism compound, is preferably selected from more than at least one in the compound group of methyl ethyl diketone, methyl aceto acetate composition especially.
Relative to the multipolymer of 100 weight parts, (F) cross-linked inhibitor preferably containing 1.0 ~ 5.0 weight parts.
When taking polyisocyanate compound as linking agent, (G) crosslinking catalyst is the material reaction (crosslinking reaction) of above-mentioned multipolymer and linking agent being played to function as catalyzer, can enumerate: the organometallic compound etc. of the aminated compounds, organo-tin compound, organo-lead compound, organic zinc compound etc. of tertiary amine 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: the soap of dialkyl tin oxide, dialkyl tin, the soap etc. of sub-tin.
(G) crosslinking catalyst preferably has machine tin compound, is preferably selected from more than at least one in the compound group of di-n-octyltin oxide, tin dilaurate dioctyl tin composition especially.
Relative to the multipolymer of 100 weight parts, (G) crosslinking catalyst preferably containing 0.01 ~ 0.5 weight part.
(H) under the preferred normal temperature of static inhibitor (such as 30 DEG C) be the material of solid, more particularly, preferably relative to the above-mentioned multipolymer amount of 100 weight parts be 0.1 ~ 5.0 weight part, fusing point is the ionic compound of 30 ~ 80 DEG C, or is the quaternary acrylic monomer of 30 ~ 80 DEG C with 0.1 ~ 5.0 % by weight copolymerization, fusing point in above-mentioned multipolymer.In the present invention, as (H) static inhibitor, in multipolymer, add the ionic compound that (H1) fusing point is 30 ~ 80 DEG C, or be that the quaternary acrylic monomer copolymerization of 30 ~ 80 DEG C is in multipolymer by (H2) fusing point.Because the fusing point of these (H) static inhibitor is low, and there is chain alkyl, therefore infer that the affinity of itself and acrylic copolymer is high.
As the ionic compound that (H1) fusing point is 30 ~ 80 DEG C, for having the ionic compound of positively charged ion and negatively charged ion, following compound can be enumerated: positively charged ion is the cationic nitrogenous of pyridinium cations, glyoxaline cation, pyrimidine positively charged ion, pyrazoles positively charged ion, pyrroles's positively charged ion, ammonium cation etc. or the compound of phosphorus positively charged ion, sulphur positively charged ion etc.; Negatively charged ion is phosphorus hexafluoride acid group (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.By the chain length of alkyl or the selection of substituent position, number etc., the material that fusing point is 30 ~ 80 DEG C can be obtained.Positively charged ion preferred season cationic nitrogenous, can enumerate: 1-alkyl pyridine drone (carbon atom of 2 ~ 6 has substituting group also passable, without replace also can) etc. season pyridinium cations, 1,3-dialkylimidazolium (carbon atom of 2,4,5 has substituting group also passable, without replace also can) etc. the quaternary ammonium cation etc. of season glyoxaline cation, tetraalkyl ammonium etc.
As the quaternary acrylic monomer that (H2) fusing point is 30 ~ 80 DEG C, for having the ionic compound of positively charged ion and negatively charged ion, following compound can be enumerated: positively charged ion is (methyl) acryloxyalkyl trialkyl ammonium (R 3n +-C nh 2n-OCOCQ=CH 2but, Q=H or CH 3, R=alkyl) etc. containing the quaternary ammonium compound of (methyl) acrylic groups (ア Network リ Le base), negatively charged ion is phosphorus hexafluoride acid group (PF 6 -), thiocyanate ion (SCN -), organic sulfonic acid root (RSO 3 -), perchlorate (ClO 4 -), tetrafluoride borate (BF 4 -) etc. the compound of inorganic or organic anion.
As the object lesson of (H) static inhibitor, be not particularly limited, but can enumerate: 1-octylpyridinium phosphorus hexafluoride hydrochlorate, 1-nonylpyridine phosphorus hexafluoride hydrochlorate, 2-methyl isophthalic acid-dococylpyridinium hexafluorophosphate, 1-octylpyridinium dodecylbenzene sulfonate, 1-dococylpyridinium thiocyanate-, 1-dococylpyridinium dodecylbenzene sulfonate, 4-methyl isophthalic acid-octylpyridinium phosphorus hexafluoride hydrochlorate, acrylate methyl esters phosphorus hexafluoride acid methyl salt ((CH 3) 3n +cH 2oCOCH=CH 2pF 6 -) etc.
(I) polyether-modified silicone compounds is the silicone compounds with polyether-based, except the siloxane unit (-SiR of routine 1 2-O-), also there is the siloxane unit (-SiR of band polyether-based 1(R 2o (R 3o) nr 4)-O-).Herein, R 1represent one kind or two or more alkyl or aryl, R 2and R 3represent one kind or two or more alkylidene group, R 4represent one kind or two or more alkyl, acyl group etc. (terminal group).Can enumerate as polyether-based: polyethylene oxide base ((C 2h 4o) n) or polyoxytrimethylene base ((C 3h 6o) n) etc. polyoxyalkylene.
(I) polyether-modified silicone compounds to be HLB value be 7 ~ 12 polyether-modified silicone compounds, relative to the above-mentioned multipolymer of 100 weight parts, the silicone compounds that above-mentioned (I) preferably containing 0.01 ~ 0.5 weight part is polyether-modified.Be more preferably 0.1 ~ 0.5 weight part.
So-called HLB is, such as, in JIS K3211 (tensio-active agent term) etc. the hydrophilic-lipophilic balance (wetting ability and oil loving ratio) of regulation.
Polyether-modified silicone compounds is, such as, for the organopolysiloxane main chain with silylation, the organic compound grafting with unsaturated link(age) and polyoxyalkylene can be obtained by hydrosilylation reactions.Can enumerate particularly: dimethylsiloxane methyl (polyoxyethylene) silicone copolymers, dimethylsiloxane methyl (polyoxyethylene) siloxanes methyl (polyoxytrimethylene) silicone copolymers, dimethylsiloxane methyl (polyoxytrimethylene) silicone copolymers etc.
By silicone compounds polyether-modified to (I) is mixed into binder composition, the bounding force of tackiness agent and performance of doing over again can be improved.
Moreover, as other composition, can suitably mix containing olefin oxide can the known additive of acrylamide monomer, tensio-active agent, hardening accelerator, softening agent, weighting agent, cure inhibitors, processing aid, antiaging agent, antioxidant etc. that replaces of copolymerization (methyl) acrylic monomer, (methyl) acrylamide monomer, dialkyl group.These can separately or two or more merge use.
The multipolymer of the host used in binder composition of the present invention can be copolymerisable monomer containing carboxyl of copolymerisable monomer containing hydroxyl of (methyl) acrylate monomer of C4 ~ C10 and (B) and (C) 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 process of multipolymer, can use the polymerization process that solution polymerization, letex polymerization etc. are suitable.
As (H) static inhibitor, when using the quaternary acrylic monomer of (H2), the quaternary acrylic monomer that the multipolymer of the host used in binder composition of the present invention can be copolymerisable monomer containing carboxyl of copolymerisable monomer containing hydroxyl of (methyl) acrylate monomer of C4 ~ C10 and (B) and (C) and (D) polyalkylene glycol mono (methyl) acrylate monomer and (H2) by polymerization (A) atomic number of alkyl carbon synthesizes.
By mix in above-mentioned multipolymer (E) 3 official can the polyether-modified silicone compounds of above isocyanate compound, (F) cross-linked inhibitor, (G) crosslinking catalyst, (H) static inhibitor, (I), suitably arbitrary additive can prepare binder composition of the present invention further.In addition, when the quaternary acrylic monomer being 30 ~ 80 DEG C by (H2) fusing point is polymerized in the multipolymer of host, all it doesn't matter whether to add (H) static inhibitor further for multipolymer.
Preferably make the bounding force of the binder layer of above-mentioned binder composition cross-links under low speed peeling rate 0.3m/min be 0.05 ~ 0.1N/25mm, the bounding force under high speed peeling rate 30m/min is below 1.0N/25mm.Thereby, it is possible to obtain bounding force along with peeling rate performance with low uncertainty, even through peeling off at a high speed, promptly peeling off and also becoming possibility.Further, in order to again fit, during temporary transient stripper surface protective membrane, not need excessive power, peel off easily from adherend.
Preferably make the surface resistivity of the binder layer of above-mentioned binder composition cross-links 5.0 × 10 + 10Ω/below, release band voltage is ± 0 ~ 1kV.In addition, in the present invention, described " ± 0 ~ 1kV " is meant to 0 ~-1kV and 0 ~+1kV, that is ,-1 ~+1kV.Due to surface resistivity large time bleed off stripping time due to the poor performance of the electrostatic of charged generation, therefore, by making surface resistivity enough little, the release band voltage with generating from the electrostatic that produces during adherend release adhesive oxidant layer can being reduced, suppressing the impact on the electric control circuit of adherend etc.
The gel fraction making the binder layer (crosslinked after tackiness agent) of binder composition cross-links of the present invention preferably 95 ~ 100%.Like this, because gel fraction is high, the bounding force under low speed peeling rate can be made not become excessive, reduce the stripping of unconverted monomer from multipolymer or oligomer, improve doing over again property, hot and humid in weather resistance, suppress the pollution of adherend.
Bonding film of the present invention is that the binder layer of binder composition cross-links of the present invention is formed on the one or both sides of resin molding.In addition, surface protection film of the present invention is the surface protection film formed in the one side of resin molding by the binder layer of crosslinked binder composition cross-links of the present invention.Binder composition of the present invention well balances mixing owing to making each composition of above-mentioned (A) ~ (I); there is antistatic property; the balancing good of bounding force under low speed peeling rate and high speed peeling rate; and weather resistance and doing over again property are (with ballpoint pen after being fitted in via binder layer the surface protection film on adherend is described; peel off from adherend, do not transfer the pollution to adherend), static resistance is also excellent.Therefore, surface protection film of the present invention suitably can use as the purposes of Polarizer surface protection film.
The resin molding etc. of polyester film etc. can be used as the base material film of binder layer, the stripping film (partition) of protection adhesive face.
In base material film, resin molding with formed on contrary face, binder layer side, the antifouling process of releasing agent by silicone, fluorine class or coating-forming agent, silicon dioxide microparticle etc. can be implemented; By the anti-electrostatic process of the coating or kneading etc. of antistatic agent.
In stripping film, at binder layer with on the face of adhesive face adhesive side, implement the demoulding process by the releasing agent of silicone, fluorine class etc.
Embodiment
Below, based on embodiment, illustrate the present invention.
The preparation > of < acrylic copolymer
[embodiment 1]
Nitrogen is imported, by the air nitrogen replacement in reaction unit to being equipped with in the reaction unit of agitator, thermometer, reflux exchanger and nitrogen ingress pipe.Then, in reaction unit, add 2-EHA 100 weight part, vinylformic acid 8-hydroxyl monooctyl ester 0.9 weight part, vinylformic acid 0.5 weight part, poly-ethylidene glycol mono acrylic ester 3 weight part and solvent (ethyl acetate) 60 parts.Then, through instillation in 2 hours as Diisopropyl azodicarboxylate 0.1 weight part of polymerization starter, make it react 6 hours in 65 DEG C, obtaining weight-average molecular weight is the acrylic copolymer solution 1 used in the embodiment 1 of 500,000.
[embodiment 2 ~ 9 and comparative example 1 ~ 9]
Such described in the composition of monomer each (A) according to table 1 ~ (D) sets, in addition, according in the same manner as the acrylic copolymer solution 1 used in above-described embodiment 1, obtain the acrylic copolymer solution used in embodiment 2 ~ 9 and comparative example 1 ~ 9.
The preparation > of < binder composition and surface protection film
[embodiment 1]
According to as mentioned above, for the acrylic copolymer solution 1 (wherein acrylic copolymer is 100 weight parts) of preparation, add 1-octylpyridinium phosphorus hexafluoride hydrochlorate 1.5 weight part, KF-351A (the polyether-modified silicone compounds of HLB=12) 0.1 weight part, methyl ethyl diketone 2.5 weight part and stir after, be uniformly mixed after adding コ ロ ネ ー ト HX (the isocyanuric acid ester body of hexamethylene diisocyanate compound) 1.5 weight parts, tin dilaurate dioctyl tin 0.02 weight part, obtain the binder composition of embodiment 1.After on the stripping film that polyethylene terephthalate (PET) film this binder composition being coated silicone coating is formed, by the drying in 90 DEG C except desolventizing, the thickness obtaining binder layer is the adhesive sheet of 25 μm.
Then; adhesive sheet is transferred to the reverse side through anti-electrostatic and antifouling treated side through polyethylene terephthalate (PET) film of anti-electrostatic and antifouling process in one side, be there is the surface protection film of the embodiment 1 of the laminar structure of " PET film/binder layer/stripping film (PET film of silicone coating) through anti-electrostatic and antifouling process ".
[embodiment 2 ~ 9 and comparative example 1 ~ 9]
Set described in the composition of additive each (E) as table 1 ~ (I), in addition, according 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 ~ 9.
In table 1, the blending ratio bracket of each composition encloses, and represents the numerical value of the weight part of summation required by 100 weight parts organized with (A).Further, the compound title of the abbreviation correspondence of each composition used in indicator gauge 1 in table 2.In addition, コ ロ ネ ー ト (registered trademark) HX and same HL is the trade(brand)name of Japanese Port リ ウ レ タ Application Industrial Co., Ltd, タ ケ ネ ー ト (registered trademark) D-140N is the trade(brand)name of Mitsui Chemicals, Inc, デ ュ ラ ネ ー ト (registered trademark) 24A-100 is the trade(brand)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(brand)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), using the material exposing binder layer as the test sample of gel fraction and surface resistivity.
And then; the surface protection film this being exposed binder layer via binder layer fits in the surface of the Polarizer be pasted onto on liquid crystal cell; place after 1 day; through 50 DEG C, 5 normal atmosphere, 20 minutes autoclave process, place 12 hours further in room temperature, using the test sample of the material through obtaining above as bounding force, release band voltage and weather resistance.
< gel fraction >
After aging end, correctly measure the quality of the test sample before fitting in Polarizer, soak after 24 hours in toluene, by 200 object metal mesh filters.Then, after 1 hour, correctly measure the quality of residue in 100 DEG C of dried screenings, calculate the gel fraction of binder layer (tackiness agent after crosslinked) from following formula.
Gel fraction (%)=insolubles quality (g)/tackiness agent quality (g) × 100
< bounding force >
Using following stripping strength as bounding force: use tension testing machine with low speed (0.3m/min) and at a high speed (30m/min) to peel through the stripping strength that test sample obtained above (material of the surface protection film that the 25mm that fits on Polarizer surface is wide) measures to 180 ° of directions.
< surface resistivity >
After aging, before fitting in Polarizer, peel off stripping film (PET film of silicone coating) exposed adhesive layer, use resistrivity meter Ha イ レ ス タ UP-HT450 (Mitsubishi Chemical ア Na リ テ ッ Network system) to measure the surface resistivity of binder layer.
< release band voltage >
When peeling off with the draw speed 180 ° of 30m/min the test sample obtained as mentioned above, high precision electrostatic transducer SK-035, SK-200 (Co., Ltd. キ ー エ Application ス system) is used to measure the voltage (with voltage) of the charged generation of Polarizer, using the maximum value of measured value as release band voltage.
Doing over again property of < >
After describing on the surface protection film by test sample obtained above with ballpoint pen (load 500g, reciprocal 3 times), observe Polarizer surface from Polarizer stripper surface protective membrane, confirm not transfer the pollution to Polarizer.Evaluation objective benchmark is the average evaluation of not transferring the pollution to Polarizer is "○", confirm that the track described along ballpoint pen is " Δ " to the average evaluation of transferring the pollution at least partially, the average evaluation confirm that the track described along ballpoint pen is transferred the pollution, also having tackiness agent to depart from from adhesive surface is "×".
< weather resistance >
60 DEG C, be placed through test sample obtained above after 250 hours under 90%RH atmosphere, taken out in room temperature, place after 12 hours further, measure bounding force, confirm significantly not increase compared with initial bounding force.Evaluation objective benchmark is the bounding force after test be the average evaluation of less than 1.5 times of initial bounding force is "○", average evaluation more than 1.5 times is "×".
Evaluation result is shown in Table 3.In addition, surface resistivity is passed through " m × 10 + n" be decided to be mode (but m is arbitrary real number, n the is positive integer) mark of " mE+n ".
[table 3]
The bounding force of surface protection film under low speed peeling rate 0.3m/min of embodiment 1 ~ 9 is 0.05 ~ 0.1N/25mm, and the bounding force under high speed peeling rate 30m/min is below 1.0N/25mm.And surface resistivity is 5.0 × 10 + 10Ω/below, release band voltage is ± 0 ~ 1kV.Further, not to the pollution transportation of adherend after describing on surface protection film via binder layer with ballpoint pen, 60 DEG C, the atmosphere of 90%RH weather resistance when placing for lower 250 hours is also outstanding.
That is, the balance of the bounding force in the stripping under low speed and the stripping under high speed is obtained about (1); (2) generation of adhesive residue can be prevented; (3) there is excellent antistatic property; (4) there is performance of doing over again, side by side meet whole requirement performances.
The surface protection film of comparative example 1 may owing to not containing (D) polyalkylene glycol mono (methyl) acrylate monomer, and the bounding force under low speed peeling rate 0.3m/min is low, and doing over again property is also slightly poor.
In the surface protection film of comparative example 2; may because (B) monomer containing hydroxyl is very few, (D) polyalkylene glycol mono (methyl) acrylate monomer is very few, (E) isocyanate compound too much, the HLB value of (I) polyether-modified silicone compounds is too small, under the bounding force therefore under low speed peeling rate 0.3m/min and high speed peeling rate 30m/min bounding force becomes excessive, release band voltage uprises, doing over again property and weather resistance is deteriorated, gel fraction step-down.
In the surface protection film of comparative example 3; may due to (B) monomer containing hydroxyl too much, (C) acidiferous monomer too much, (D) polyalkylene glycol mono (methyl) acrylate monomer too much, the HLB value of (I) polyether-modified silicone compounds is excessive, the bounding force therefore under low speed peeling rate 0.3m/min is low, surface resistivity is high, release band voltage is high, poor durability.
In the surface protection film of comparative example 4; may because (C) monomer containing acid is very few, do not contain (D) polyalkylene glycol mono (methyl) acrylate monomer; therefore the bounding 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; may due to (B) monomer containing hydroxyl too much, (D) polyalkylene glycol mono (methyl) acrylate monomer is very few, (E) isocyanate compound is very few, under the bounding force therefore under low speed peeling rate 0.3m/min and high speed peeling rate 30m/min bounding force becomes excessive, release band voltage uprises, doing over again property and weather resistance is deteriorated, gel fraction step-down.
The surface protection film of comparative example 6 may be because mixing (F) cross-linked inhibitor, (G) crosslinking catalyst too much, therefore too do not shorten storage period, can not carry out coating owing to carrying out crosslinked before coating.
The surface protection film of comparative example 7 may due to containing have at (A) there is in alkyl (methyl) acrylate monomer C1 alkyl MA, (B) monomer containing hydroxyl too much, containing (D) polyalkylene glycol mono (methyl) acrylate monomer, not mixing (G) crosslinking catalyst, the bounding force under the bounding force therefore under low speed peeling rate 0.3m/min and high speed peeling rate 30m/min is excessive, surface resistivity is high, release band voltage is high, doing over again property and poor durability.
In the surface protection film of comparative example 8; may due to (D) polyalkylene glycol mono (methyl) acrylate monomer too much, silicone compounds of not have mixing (I) polyether-modified, the bounding force under the bounding force therefore under low speed peeling rate 0.3m/min and high speed peeling rate 30m/min is excessive, surface resistivity is high, release band voltage is high, doing over again property difference.
In the surface protection film of comparative example 9; may due to not containing (D) polyalkylene glycol mono (methyl) acrylate monomer, (H) static inhibitor the fusing point silicone compounds that (be liquid under normal temperature), (I) are polyether-modified less than 30 DEG C too much, the bounding force therefore under low speed peeling rate 0.3m/min is low, release band voltage is high, doing over again property is slightly poor, poor durability.
Like this, in the surface protection film of comparative example 1 ~ 9, obtain about (1) balance that low speed peels off the bounding force in peeling off with high speed; (2) generation of adhesive residue is prevented; (3) there is excellent antistatic property; (4) there is performance of doing over again, side by side can not meet whole requirement performances.

Claims (16)

1. a binder composition, it is made up of the multipolymer containing (A) atomic number of alkyl carbon being copolymerisable monomer containing carboxyl of copolymerisable monomer containing hydroxyl of (methyl) acrylate monomer of C4 ~ C10 and (B) and (C) and (D) polyalkylene glycol mono (methyl) acrylate monomer, its further containing (E) 3 official can above isocyanate compound, (F) cross-linked inhibitor, (G) crosslinking catalyst, (H) static inhibitor, (I) HLB value be 7 ~ 12 polyether-modified silicone compounds
Above-mentioned (B) copolymerisable monomer containing hydroxyl is 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
Above-mentioned (H) static inhibitor is be the ionic compound of solid at 30 DEG C of temperature of fusing point 30 ~ 80 DEG C.
2. binder composition according to claim 1, wherein,
Relative to (methyl) acrylate monomer that above-mentioned (A) atomic number of alkyl carbon of 100 weight parts is C4 ~ C10, above-mentioned (B) copolymerisable monomer containing hydroxyl containing 0.1 ~ 5.0 weight part, and, above-mentioned (B), containing in the copolymerisable monomer of 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.
3. binder composition according to claim 1 and 2, wherein,
Above-mentioned (C) copolymerisable monomer containing carboxyl is for being selected from more than at least one in the compound group that is made up of (methyl) vinylformic acid, propyloic (methyl) acrylate, carboxylic amyl group (methyl) acrylate;
Relative to (methyl) acrylate monomer that the carbonatoms of above-mentioned (A) alkyl of 100 weight parts is C4 ~ C10, above-mentioned (C) copolymerisable monomer containing carboxyl containing 0.35 ~ 1.0 weight part.
4. binder composition according to claim 1 and 2, wherein,
Above-mentioned (D) polyalkylene glycol mono (methyl) acrylate monomer is for being selected from more than at least one in the compound group that is made up of polyalkylene glycol mono (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate, oxyethyl group polyalkylene glycol (methyl) acrylate;
Relative to (methyl) acrylate monomer that the carbonatoms of above-mentioned (A) alkyl of 100 weight parts is C4 ~ C10, above-mentioned (D) polyalkylene glycol mono (methyl) acrylate monomer containing 1 ~ 20 weight part.
5. binder composition according to claim 1 and 2, wherein,
Above-mentioned (E) 3 official can isocyanate compound above be selected from the isocyanuric acid ester body by 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, more than at least one in the compound group that the biuret body of isophorone diisocyanate compound forms,
Relative to the above-mentioned multipolymer of 100 weight parts, above-mentioned (E) containing 0.5 ~ 5.0 weight part 3 official can above isocyanate compound.
6. binder composition according to claim 1 and 2, wherein,
Above-mentioned (H) static inhibitor is 0.1 ~ 5.0 weight part relative to the amount of the above-mentioned multipolymer of 100 weight parts.
7. binder composition according to claim 1 and 2, wherein,
Relative to the above-mentioned multipolymer of 100 weight parts, above-mentioned (I) HLB value containing 0.01 ~ 0.5 weight part is the polyether-modified silicone compounds of 7 ~ 12.
8. binder composition according to claim 1 and 2, wherein,
Above-mentioned (F) cross-linked inhibitor is keto-enol tautomerism compound, relative to the above-mentioned multipolymer of 100 weight parts, and above-mentioned (F) cross-linked inhibitor containing 1.0 ~ 5.0 weight parts.
9. binder composition according to claim 1 and 2, wherein,
Above-mentioned (G) crosslinking catalyst is organo-tin compound, relative to the above-mentioned multipolymer of 100 weight parts, and above-mentioned (G) crosslinking catalyst containing 0.01 ~ 0.5 weight part.
10. binder composition according to claim 1 and 2, wherein,
Make the bounding force of the binder layer of above-mentioned binder composition cross-links under low speed peeling rate 0.3m/min be 0.05 ~ 0.1N/25mm, the bounding force under high speed peeling rate 30m/min is below 1.0N/25mm.
11. binder compositions according to claim 1 and 2, wherein,
Make the surface resistivity of the binder layer of above-mentioned binder composition cross-links 5.0 × 10 + 10Ω/below, release band voltage is ± 0 ~ 1kV.
12. 1 kinds of bonding films, its bonding film formed on the one or both sides of resin molding for making the binder layer of the binder composition cross-links described in claim 1 or 2.
13. 1 kinds of surface protection films; its surface protection film formed in the one side of resin molding for making the binder layer of the binder composition cross-links described in claim 1 or 2; with ballpoint pen be fitted in via above-mentioned binder layer on the surface protection film on adherend describe after; peel off from adherend, do not transfer the pollution to adherend.
14. surface protection films according to claim 13, its purposes as Polarizer surface protection film uses.
15. surface protection films according to claim 13, wherein, on the face contrary with forming above-mentioned binder layer side of above-mentioned resin molding, carry out antistatic and anti-pollution process.
16. surface protection films according to claim 14, wherein, on the face contrary with forming above-mentioned binder layer side of above-mentioned resin molding, carry out antistatic and anti-pollution process.
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