CN105219313A - Binder composition and surface protection film - Google Patents

Binder composition and surface protection film Download PDF

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Publication number
CN105219313A
CN105219313A CN201510671721.XA CN201510671721A CN105219313A CN 105219313 A CN105219313 A CN 105219313A CN 201510671721 A CN201510671721 A CN 201510671721A CN 105219313 A CN105219313 A CN 105219313A
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methyl
mentioned
acrylate
binder composition
monomer
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CN105219313B (en
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长仓毅
岛口龙介
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Fujimori Kogyo Co Ltd
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Fujimori Kogyo Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
    • G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
    • G02B5/3041—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks
    • G02B5/305—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid comprising multiple thin layers, e.g. multilayer stacks including organic materials, e.g. polymeric layers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components

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

Abstract

The invention provides a kind of binder composition and surface protection film, the balancing good of described binder composition bounding force in low speed is peeled off and peeled off at a high speed, and weather resistance and doing over again property are also excellent.The invention provides a kind of binder composition, described binder composition is (methyl) acrylate monomer of C4 ~ C10 by the carbonatoms containing (A) alkyl, (B) copolymerisable monomer containing hydroxyl, (C) copolymerisable monomer containing carboxyl, (D) polyalkylene glycol mono (methyl) acrylate monomer, (E) the acrylic polymers of the multipolymer of the nitrogenous vinyl monomer of hydroxyl or (methyl) alkyl acrylate monomer containing alkoxyl group is not formed, its further containing (F) 3 official can above isocyanate compound, (G) cross-linked inhibitor, (H) crosslinking catalyst, (I) polyether-modified silicone compounds, the acid number of aforesaid propylene acids polymers is 0.01 ~ 8.0.

Description

Binder composition and surface protection film
The divisional application that the application is the applying date is on April 3rd, 2013, application number is 201310114472.5, application people is Tengsen Industrial Co., Ltd, denomination of invention is the application for a patent for invention 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. of the parts 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.In order to protect the surface protection film of optical component surfaces only to use in manufacturing process, therefore, be also referred to as operation film.
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, the performance for surface protection film necessity is, within the adhesive layer non-cohesive bubble or impurity.
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; require that (1) obtains the balance of the bounding force in low speed peeling rate and high speed peeling rate; (2) generation of adhesive residue can be prevented, and (3) has performance of doing over again.
But; although the requirement performance individually of these (1) ~ (3) can be met, be very difficult to possess (1) ~ all of (3) 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) prevent the generation of adhesive residue, 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 problem adding releasable difference when thermogenesis is floated the problem of the peeling waited 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.
And, about (3), 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 3).
In patent documentation 3, 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 3 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 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 and doing over again property etc.; 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 makes in view of the foregoing.Problem of the present invention is to provide a kind of binder composition and surface protection film, the balancing good of described binder composition and the bounding force of surface protection film in low speed is peeled off and peeled off at a high speed, and weather resistance and doing over again property 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 (methyl) acrylate monomer of C4 ~ C10 by the carbonatoms containing (A) alkyl, (B) copolymerisable monomer containing hydroxyl, (C) copolymerisable monomer containing carboxyl, (D) polyalkylene glycol mono (methyl) acrylate monomer, (E) the acrylic polymers of the nitrogenous vinyl monomer of hydroxyl or the multipolymer containing at least one in (methyl) alkyl acrylate monomer of alkoxyl group is not formed, its further containing (F) 3 official can above isocyanate compound, (G) cross-linked inhibitor, (H) crosslinking catalyst, (I) polyether-modified silicone compounds, the acid number of aforesaid propylene acids polymers is 0.01 ~ 8.0.
Preferably 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; Relative to (methyl) acrylate monomer that the carbonatoms of above-mentioned (A) alkyl 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, (methyl) vinylformic acid own ester of 6-hydroxyl and (methyl) vinylformic acid 4-hydroxybutyl is 0 ~ 0.9 weight part.
Preferably above-mentioned (C) copolymerisable monomer containing carboxyl is for being selected from by (methyl) vinylformic acid, propyloic (methyl) acrylate, carboxylic amyl group (methyl) acrylate, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloxypropyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl phthalic acid, 2-(methyl) acryloyl-oxyethyl succsinic acid, 2-(methyl) acryloyl-oxyethyl toxilic acid, carboxy-polycaprolactone list (methyl) acrylate, more than at least one in the compound group of 2-(methyl) acryloyl-oxyethyl tetrahydrophthalic acid composition, 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.
Preferably above-mentioned (D) polyalkylene glycol mono (methyl) acrylate monomer is for being 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 above-mentioned (A) alkyl of 100 weight parts is C4 ~ C10, containing 1 ~ 20 weight part above-mentioned (D) polyalkylene glycol mono (methyl) acrylate monomer.
Be preferably (methyl) acrylate monomer of C4 ~ C10 relative to the carbonatoms of above-mentioned (A) alkyl of 100 weight parts, containing 1 ~ 20 weight part above-mentioned (E) the not nitrogenous vinyl monomer of hydroxyl or (methyl) alkyl acrylate monomer containing alkoxyl group.
Preferably above-mentioned (F) 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 of the biuret body composition of isophorone diisocyanate compound, relative to the above-mentioned multipolymer of 100 weight parts, above-mentioned (F) containing 0.4 ~ 5.0 weight part 3 official can above isocyanate compound.
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 (G) cross-linked inhibitor is keto-enol tautomerism compound, preferably relative to the above-mentioned multipolymer of 100 weight parts, and above-mentioned (G) cross-linked inhibitor containing 1.0 ~ 5.0 weight parts.
Above-mentioned (H) crosslinking catalyst is organo-tin compound, preferably relative to the above-mentioned multipolymer of 100 weight parts, and above-mentioned (H) 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.
In addition, the invention provides a kind of bonding film, it makes the binder layer of above-mentioned binder composition cross-links and the bonding film obtained for being formed with on one or two sides of resin molding.
In addition; the invention provides a kind of surface protection film; it is characterized in that it for forming binder layer and the surface protection film obtained in the one side of resin molding; described binder layer obtains by making above-mentioned binder composition cross-links; after describing on surface protection film via described binder layer with ballpoint pen, do not transfer the pollution to adherend.
Above-mentioned surface protection film, it can use as the purposes of the surface protection film of Polarizer.
Preferably carry out antistatic and anti-pollution process being formed on contrary face, side with above-mentioned binder layer of above-mentioned resin molding.
[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, the excellent performance preventing adhesive residue can also be obtained.Specifically, 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, its host is by (methyl) acrylate monomer being C4 ~ C10 containing the carbonatoms of (A) alkyl, (B) copolymerisable monomer containing hydroxyl, (C) copolymerisable monomer containing carboxyl, (D) polyalkylene glycol mono (methyl) acrylate monomer, (E) the acrylic polymers of the nitrogenous vinyl monomer of hydroxyl or the multipolymer containing at least one in (methyl) alkyl acrylate monomer of alkoxyl group is not formed, its further containing (F) 3 official can above isocyanate compound, (G) cross-linked inhibitor, (H) crosslinking catalyst, (I) polyether-modified silicone compounds, the acid number of aforesaid propylene acids polymers is 0.01 ~ 8.0.
Carbonatoms as (A) alkyl is that (methyl) acrylate monomer of C4 ~ C10 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 the carbonatoms of above-mentioned (A) alkyl 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, (methyl) vinylformic acid own ester of 6-hydroxyl and (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 (methyl) vinylformic acid, propyloic (methyl) acrylate, carboxylic amyl group (methyl) acrylate, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloxypropyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl phthalic acid, 2-(methyl) acryloyl-oxyethyl succsinic acid, 2-(methyl) acryloyl-oxyethyl toxilic acid, carboxy-polycaprolactone list (methyl) acrylate, more than at least one in the compound group of 2-(methyl) acryloyl-oxyethyl tetrahydrochysene phthalic acid composition.
Relative to (methyl) acrylate monomer that the carbonatoms of (A) alkyl of 100 weight parts is C4 ~ C10, preferably containing 0.35 ~ 1.0 weight part, (C) copolymerisable monomer containing carboxyl more preferably containing 0.35 ~ 0.6 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 polyalkylene glycol mono (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate, oxyethyl group polyalkylene glycol (methyl) acrylate.
More specifically, poly-ethylidene glycol-mono-(methyl) acrylate, polytrimethylene glycol-mono-(methyl) acrylate, polybutylene glycol-mono-(methyl) acrylate, poly-ethylidene glycol-polytrimethylene glycol-mono-(methyl) acrylate, poly-ethylidene glycol-polybutylene glycol-mono-(methyl) acrylate, polytrimethylene glycol-polybutylene glycol-mono-(methyl) acrylate, poly-ethylidene glycol-polytrimethylene glycol-polybutylene glycol-mono-(methyl) acrylate can be enumerated, 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.
(E) in, as the vinyl monomer that (E-1) is nitrogenous, the vinyl monomer containing amido linkage can be enumerated, containing amino vinyl monomer, the vinyl monomer etc. with nitrogenous heterocycle structure.More specifically, 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. can be enumerated, N-(methyl) acryloyl morpholine, N-(methyl) acryloylpiperazines, N-(methyl) acryl ethylenimine, N-(methyl) acryl azetidine, N-(methyl) acryl tetramethyleneimine, N-(methyl) acryloylpiperidine, N-(methyl) acryl azepine (N-(メ タ) ア Network リ ロ イ Le ア ゼ パ Application), the ring-type nitrogen vinyl compound with the heterocycle structure that N-(methyl) acryl replaces of N-(methyl) acryl azocine etc., N-N-cyclohexylmaleimide, N-phenylmaleimide etc., the ring-type nitrogen vinyl compound with the heterocycle structure in ring with nitrogen-atoms and vinyl unsaturated link(age), (methyl) acrylamide replaced without replacement or monoalkyl of (methyl) acrylamide, N-methyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, the N-tertiary butyl (methyl) acrylamide etc., N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N, N-dipropyl acrylamide, N, (methyl) acrylamide of the dialkyl group replacement of 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 etc., (methyl) vinylformic acid N, N-dimethylaminomethyl ester, (methyl) vinylformic acid N, N-dimethyl aminoethyl ester, (methyl) vinylformic acid N, N-dimethylaminopropyl ester, (methyl) vinylformic acid N, N-dimethylamino isopropyl esters, (methyl) vinylformic acid N, N-dimethrlaminobutyl ester, (methyl) vinylformic acid N, N-diethylamino methyl ester, (methyl) vinylformic acid N, N-diethylamino ethyl ester, (methyl) vinylformic acid N-ethyl-N-methylamino ethyl ester, (methyl) vinylformic acid N-methyl-N-propylamino ethyl ester, (methyl) vinylformic acid N-methyl-N-isoproylamino ethyl ester, (methyl) vinylformic acid N, N-Dibutylaminoethyl ester, (methyl) propenoic acid dialkyl amino ester of (methyl) vinylformic acid t-butylamino ethyl ester etc., 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., aminopropyl (methyl) acrylamide that N-dialkyl group replaces, the N-vinylcarboxylic acid amide type of N-vinyl formamide, N-vinyl acetamide, N-vinyl-N-methylacetaniide etc., (methyl) acrylic amide of N-methoxymethyl (methyl) acrylamide, N-ethoxyethyl group (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, diacetone-acryloamide(DAA), N, N-methylene-bis (methyl) acrylamide etc., the unsaturated carboxylic acid nitrile etc. of (methyl) vinyl cyanide etc.
As the vinyl monomer that (E-1) is nitrogenous, be preferably the material not containing hydroxyl, more preferably do not contain the material of hydroxyl and carboxyl.As the monomer that such monomer is as implied above, preference is as, the acrylic monomer of amide group that the amino replaced containing N, N-dialkyl group or N, N-dialkyl group replace; The lactams of the N-vinyl substituted of NVP, N-caprolactam, N-vinyl-2-piperidone etc.; The cyclic amine of N-(methyl) the acryl replacement of N-(methyl) acryloyl morpholine or N-(methyl) acryloyl tetramethyleneimine etc.
(E) in, as (E-2) (methyl) alkyl acrylate monomer containing alkoxyl group, (methyl) vinylformic acid 2-methoxy ethyl ester can be enumerated, (methyl) vinylformic acid 2-ethoxyethyl group ester, (methyl) vinylformic acid 2-Among ester, (methyl) vinylformic acid 2-isopropoxy ethyl ester, (methyl) vinylformic acid 2-butoxy ethyl ester, (methyl) vinylformic acid 2-methoxy-propyl ester, (methyl) vinylformic acid 2-ethoxycarbonyl propyl ester, (methyl) vinylformic acid 2-propoxypropyl ester, (methyl) vinylformic acid 2-isopropoxide propyl ester, (methyl) vinylformic acid 2-butoxypropyl ester, (methyl) vinylformic acid 3-methoxy-propyl ester, (methyl) vinylformic acid 3-ethoxycarbonyl propyl ester, (methyl) vinylformic acid 3-propoxypropyl ester, (methyl) vinylformic acid 3-isopropoxide propyl ester, (methyl) vinylformic acid 3-butoxypropyl ester, (methyl) vinylformic acid 4-methoxy butyl acrylate, (methyl) vinylformic acid 4-ethoxybutyl ester, (methyl) vinylformic acid 4-propyloxybutyl ester, (methyl) vinylformic acid 4-isopropoxy butyl ester, (methyl) vinylformic acid 4-butoxybutyl ester etc.
These (methyl) alkyl acrylate monomers containing alkoxyl group have the structure that the alkyl atom alkoxy in (methyl) alkyl acrylate replaces.
Be preferably (methyl) acrylate monomer of C4 ~ C10 relative to the carbonatoms of (A) alkyl of 100 weight parts, (E-1) containing 1 ~ 20 weight part be the nitrogenous vinyl monomer of hydroxyl or (E-2) (methyl) alkyl acrylate monomer containing alkoxyl group not.Can use respectively (E-1) not in the nitrogenous vinyl monomer of hydroxyl, (E-2) (methyl) alkyl acrylate monomer containing alkoxyl group a kind or two or more merge and use.
As (F) 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.
(F) 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, (F) preferably containing 0.4 ~ 5.0 weight part 3 official can above isocyanate compound.
As (G) 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.
(G) 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, (G) cross-linked inhibitor preferably containing 1.0 ~ 5.0 weight parts.
When taking polyisocyanate compound as linking agent, (H) 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.
(H) 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, (H) crosslinking catalyst preferably containing 0.01 ~ 0.5 weight part.
(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 is preferably the polyether-modified silicone compounds that HLB value is 7 ~ 12.Further, relative to the multipolymer of 100 weight parts, the silicone compounds that (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 JISK3211 (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, static inhibitor etc. that replaces of copolymerization (methyl) acrylic monomer, (methyl) acrylamide monomer, dialkyl group.These can separately or two or more merge use.
As static inhibitor, ionic compound can be enumerated.Further, by enabling ionic acrylic monomer copolymerization give antistatic property in the multipolymer of host.
The multipolymer of the host used in binder composition of the present invention can by being polymerized copolymerisable monomer containing carboxyl of copolymerisable monomer containing hydroxyl of (methyl) acrylate monomer and (B) that the carbonatoms of (A) alkyl is C4 ~ C10 and (C) and the synthesis of (D) polyalkylene glycol mono (methyl) acrylate monomer.There is no particular limitation for the polymerization process of multipolymer, can use the polymerization process that solution polymerization, letex polymerization etc. are suitable.
By mix in above-mentioned multipolymer (F) 3 official can the polyether-modified silicone compounds of above isocyanate compound, (G) cross-linked inhibitor, (H) crosslinking catalyst, (I), suitably arbitrary additive can prepare binder composition of the present invention further.
Above-mentioned multipolymer, is preferably acrylic polymers, preferably contains the acrylic monomer of (methyl) acrylate monomer, (methyl) vinylformic acid, (methyl) acrylic amide etc. of 50 ~ 100 % by weight.
In addition, the acid number of acrylic polymers is preferably 0.01 ~ 8.0.By this acid number, contaminative can be improved, improve the performance preventing adhesive residue from occurring.
Herein, " acid number " refers to one of index representing sour amount, contains the mg number of the potassium hydroxide needed for polymkeric substance of carboxyl in representing with 1g.
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.
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 during low speed can be made to peel off does not become excessive, reduces 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 one or two sides of resin molding.In addition, surface protection film of the present invention is the surface protection film that the binder layer of binder composition cross-links of the present invention is formed in the one side of resin molding.Binder composition of the present invention well balances mixing owing to making each composition of above-mentioned (A) ~ (I); there is the balancing good of bounding force under low speed is peeled off and peeled off at a high speed; and weather resistance and doing over again property (after describing on surface protection film via binder layer with ballpoint pen, transferring the pollution to adherend) also excellence.Therefore, it is possible to suitably 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, NVP 5 weight part and solvent (ethyl acetate) 60 weight part.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.Extract a part for acrylic copolymer, be used as the sample of determination of acid value below.
[embodiment 2 ~ 9 and comparative example 1 ~ 9]
Such described in the composition of monomer each (A) according to table 1 ~ (E) 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.
[table 1]
The preparation > of < binder composition and surface protection film
[embodiment 1]
For the acrylic copolymer solution 1 of the embodiment 1 of preparation as mentioned above, add KF-351A (the polyether-modified silicone compounds of HLB=12) 0.2 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 (F) as table 2 ~ (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.
[table 2]
The table of the entirety of the blending ratio of each composition of display is divided into two tables by table 1 and table 2, and the numerical value of the weight part of the summation organized with arbitrary (A) required by 100 weight parts encloses with bracket and represents.Further, the compound title of the abbreviation of each composition used in table 1 and table 2 is shown in table 3 and table 4.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, 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 3]
[table 4]
< test method and evaluation >
By the surface protection film in embodiment 1 ~ 9 and comparative example 1 ~ 9 in 23 DEG C, under the atmosphere of 50%RH after aging 7 days, peel off stripping film (PET film of silicone coating), to expose the test sample of material as gel fraction of binder layer.
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 and weather resistance.
< acid number >
The acid number of acrylic polymers, by sample dissolution in solvent (material that diethyl ether and ethanol are mixed to get with volume ratio 2:1), use potential difference automatic titration device (capital of a country electronic industry system, AT-610), use 0.1 above-mentioned potential difference titration apparatus, carry out potential difference titration with the potassium hydroxide-ethanol solution that concentration is about 0.1mol/l, measure in order in and the amount of potassium hydroxide-ethanol solution needed for sample.Then, acid number is tried to achieve by following formula.
Acid number=(B × f × 5.611)/S
The amount (ml) of the 0.1mol/l potassium hydroxide-ethanol solution used in B=titration
The factor of f=0.1mol/l potassium hydroxide-ethanol solution
The quality (g) of the solids component of S=sample
< 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 peels 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 under the peeling rate (0.3m/min) and peeling rate (30m/min) at a high speed of low speed to 180 ° of directions.
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 5.
[table 5]
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; bounding force under high speed peeling rate 30m/min is below 1.0N/25mm; 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 low speed peeling rate and high speed peeling rate is obtained about (1); (2) generation of adhesive residue is prevented; (3) to do over again performance, 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) the acrylate monomer vinyl monomer nitrogenous with (E) or (methyl) alkyl acrylate monomer containing alkoxyl group; bounding force under low speed peeling rate 0.3m/min is low, and doing over again property is also slightly poor.
The surface protection film of comparative example 2, may be very few due to (B) monomer containing hydroxyl, (D) polyalkylene glycol mono (methyl) acrylate monomer is very few, do not contain (E) nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxyl group, (F) isocyanate compound is too much, (I) HLB value of polyether-modified silicone compounds is too small, therefore the bounding force under the bounding force under low speed peeling rate 0.3m/min and high speed peeling rate 30m/min becomes excessive, doing over again property and weather resistance are deteriorated, gel fraction step-down.
The surface protection film of comparative example 3, may be too much due to (B) monomer containing hydroxyl, (C) acidiferous monomer is too much, (D) polyalkylene glycol mono (methyl) acrylate monomer is too much, (E) nitrogenous vinyl monomer or too much containing (methyl) alkyl acrylate monomer of alkoxyl group, (I) HLB value of polyether-modified silicone compounds is excessive, therefore the acid number of acrylic polymers is high, bounding force under bounding force under low speed peeling rate 0.3m/min and high speed peeling rate 30m/min becomes excessive, doing over again property and poor durability.
The surface protection film of comparative example 4; may because (C) monomer containing acid is very few, containing the nitrogenous vinyl monomer of (D) polyalkylene glycol mono (methyl) acrylate monomer, (E) or (methyl) alkyl acrylate monomer containing alkoxyl group very few; therefore the bounding force under low speed peeling rate 0.3m/min is low, doing over again property and poor durability.
The surface protection film of comparative example 5, may be too much due to (B) monomer containing hydroxyl, (C) monomer containing acid is too much, (D) polyalkylene glycol mono (methyl) acrylate monomer is very few, do not contain (E) nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxyl group, (F) isocyanate compound is very few, therefore the acid number of acrylic polymers uprises, bounding force under bounding force under low speed peeling rate 0.3m/min and high speed peeling rate 30m/min becomes excessive, doing over again property and weather resistance are deteriorated, gel fraction step-down.
The surface protection film of comparative example 6 may be owing to not mixing (G) cross-linked inhibitor, therefore too shortening storage period, can not be coated with owing to carrying out crosslinked before coating.
The surface protection film of comparative example 7, may owing to having in alkyl (methyl) acrylate monomer containing the MA with C1 alkyl at (A), (B) monomer containing hydroxyl is too much, do not contain (D) polyalkylene glycol mono (methyl) the acrylate monomer vinyl monomer nitrogenous with (E) or (methyl) alkyl acrylate monomer containing alkoxyl group, not mixing (H) crosslinking catalyst, therefore the bounding force under the bounding force under low speed peeling rate 0.3m/min and high speed peeling rate 30m/min is excessive, doing over again property and poor durability.
The surface protection film of comparative example 8; may due to (D) polyalkylene glycol mono (methyl) acrylate monomer too much, containing (E) nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxyl group, 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, doing over again property is slightly poor.
The surface protection film of comparative example 9; may due to not too much containing the silicone compounds that (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) nitrogenous vinyl monomer or (methyl) alkyl acrylate monomer containing alkoxyl group, (I) are polyether-modified, the bounding force therefore under low speed peeling rate 0.3m/min is low, doing over again property is slightly poor, poor durability.
Like this, in the surface protection film of comparative example 1 ~ 9, the balance that (1) obtains the bounding force in low speed peeling rate and high speed peeling rate can not be met simultaneously; (2) generation of adhesive residue is prevented; (3) there is whole requirement performance of performance of doing over again.

Claims (11)

1. a binder composition, it is the binder composition containing acrylic polymers and linking agent, wherein,
Described acrylic polymers by by the carbonatoms of (A) alkyl 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 (E) not hydroxyl nitrogenous vinyl monomer or form containing the multipolymer that at least one in (methyl) alkyl acrylate monomer of alkoxyl group carries out copolymerization
The acid number of aforesaid propylene acids polymers is 0.01 ~ 8.0,
Be in (methyl) acrylate monomer of C4 ~ C10 at the carbonatoms of above-mentioned (A) alkyl of 100 weight parts, containing (methyl) ethyl acrylates more than 50 weight parts or (methyl) Isooctyl acrylate monomer
And, containing (F) 3 official can the polyether-modified silicone compounds of above isocyanate compound, (G) cross-linked inhibitor, (H) crosslinking catalyst, (I).
2. binder composition according to claim 1, wherein,
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;
Relative to (methyl) acrylate monomer that the carbonatoms of above-mentioned (A) alkyl 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, (methyl) vinylformic acid own ester of 6-hydroxyl and (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 by (methyl) vinylformic acid, propyloic (methyl) acrylate, carboxylic amyl group (methyl) acrylate, 2-(methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2-(methyl) acryloxypropyl hexahydrophthalic acid, 2-(methyl) acryloyl-oxyethyl phthalic acid, 2-(methyl) acryloyl-oxyethyl succsinic acid, 2-(methyl) acryloyl-oxyethyl toxilic acid, carboxy-polycaprolactone list (methyl) acrylate, more than at least one in the compound group of 2-(methyl) acryloyl-oxyethyl tetrahydrophthalic acid composition,
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 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, containing 1 ~ 20 weight part above-mentioned (D) polyalkylene glycol mono (methyl) acrylate monomer.
5. binder composition according to claim 1 and 2, wherein, relative to (methyl) acrylate monomer that the carbonatoms of above-mentioned (A) alkyl of 100 weight parts is C4 ~ C10, containing 1 ~ 20 weight part above-mentioned (E) the not nitrogenous vinyl monomer of hydroxyl or (methyl) alkyl acrylate monomer containing alkoxyl group.
6. binder composition according to claim 1 and 2, wherein,
Above-mentioned (F) 3 official can isocyanate compound above be selected from more than at least one in the compound group that is made up of the biuret body of the adduction object of the adduction object of the isocyanuric acid ester body of the isocyanuric acid ester body of hexamethylene diisocyanate compound, isophorone diisocyanate compound, hexamethylene diisocyanate compound, isophorone diisocyanate compound, hexamethylene diisocyanate compound, the biuret body of isophorone diisocyanate compound;
Relative to the above-mentioned multipolymer of 100 weight parts, above-mentioned (F) containing 0.4 ~ 5.0 weight part 3 official can above isocyanate compound.
7. binder composition according to claim 1 and 2, wherein,
Above-mentioned (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, containing the silicone compounds that above-mentioned (I) of 0.01 ~ 0.5 weight part is polyether-modified.
8. binder composition according to claim 1 and 2, wherein,
Above-mentioned (G) cross-linked inhibitor is keto-enol tautomerism compound;
Relative to the above-mentioned multipolymer of 100 weight parts, above-mentioned (G) cross-linked inhibitor containing 1.0 ~ 5.0 weight parts;
Above-mentioned (H) crosslinking catalyst is organo-tin compound;
Relative to the above-mentioned multipolymer of 100 weight parts, above-mentioned (H) crosslinking catalyst containing 0.01 ~ 0.5 weight part.
9. a bonding film, it is the bonding film being formed with the binder layer making binder composition cross-links according to claim 1 and 2 on one or two sides of resin molding.
10. a surface protection film, it is the surface protection film being formed with the binder layer making binder composition cross-links according to claim 1 and 2 in the one side of resin molding.
11. surface protection films according to claim 10, its purposes as the surface protection film of Polarizer uses.
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