CN105440988A - Adhesive composition and surface protective film - Google Patents

Adhesive composition and surface protective film Download PDF

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Publication number
CN105440988A
CN105440988A CN201510429028.1A CN201510429028A CN105440988A CN 105440988 A CN105440988 A CN 105440988A CN 201510429028 A CN201510429028 A CN 201510429028A CN 105440988 A CN105440988 A CN 105440988A
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China
Prior art keywords
methyl
compound
monomer
binder composition
acrylate
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CN201510429028.1A
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CN105440988B (en
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长仓毅
长谷川良
吉田弘幸
菱沼昌世
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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
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2433/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2433/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2433/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2433/14—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer

Abstract

The present invention provides a good anti-static function and an excellent balance of the adhesive force in the low stripping speed and the high stripping speed, and long service lift and good durability and processability adhesive composition and a surface protective film. The adhesive composition comprises, by weight, 50-95 parts acrylate monomer having carbon number of C4 to C18 of alkyl, 0.1 to 10 parts monomer containing hydroxyl, 0.1 to 1.0 monomer containing carboxyl, 8 to 50 parts acrylate monomer containing poly alkylene glycol, 0.1 to 20 parts vinyl monomer containing nitrogen, and isocyanate compound containing more than bifunctional molecules, crosslinking catalysts, keto-enol tautomer compound and antistatic agent, without siloxane compound.

Description

Binder composition and surface protection film
Technical field
The present invention relates to the surface protection film of the manufacturing process for liquid-crystal display.More specifically; relate to and form the optical component surfaces such as polaroid, polarizer of liquid-crystal display by fitting in, thus in order to the binder composition of the surface protection film of protecting the optical component surfaces such as polaroid, polarizer to use and the surface protection film that uses this binder composition and obtain.
Background technology
All the time, in the manufacturing process of the optics such as polaroid, polarizer of the parts as formation liquid-crystal display, be fitted with the surface protection film for temporary protection optical component surfaces.Such surface protection film only uses in the operation manufacturing optics, peels off removing when optics is assembled in liquid-crystal display from optics.Because such surface protection film for the protection of optical component surfaces only uses in manufacturing process, so be usually also referred to as operation film.
For the surface protection film used in the operation of manufacture optics like this; binder layer is formed at the one side of polyethylene terephthalate (PET) resin molding with optical transparence; and before fitting in optics, the stripping film laminating of lift-off processing over the binder layer by the carrying out for the protection of this binder layer.
In addition; the optics such as polaroid, polarizer is under the state of coating surface protective membrane; owing to carrying out along with the display capabilities of LCD panel, tone, contrast gradient, foreign matter such as to be mixed at the examination of product of optical assessment; so as the requirement performance for surface protection film, require non-cohesive bubble and foreign matter within the adhesive layer.
In addition; in recent years; from the optics such as polaroid, polarizer during stripper surface protective membrane; worry that the fault of stripping charge on the electric control circuit of liquid-crystal display occurred along with the electrostatic produced when being peeled off from binder layer by adherend brings impact, excellent antistatic property is required to binder layer.
In addition, when the optical member adhering such as polaroid, polarizer surface protection film, due to a variety of causes, once stripper surface protective membrane, meeting adhesive surface protective membrane again, now, requires easily to peel off (re-workability) from the optics of adherend.
In addition, finally from the optics such as polaroid, polarizer during stripper surface protective membrane, requirement can be peeled off rapidly.Even if also can peel off rapidly like that as so-called by peeling off at a high speed, require that bounding force is with low uncertainty because peeling rate change.
Thus; in recent years; as the requirement performance of the binder layer for formation surface protection film; consider from the ease of use angle when using surface protection film; require that (1) keeps the balance of bounding force under low peeling rate and high peeling rate; (2) paste is prevented residual, the antistatic property that (3) are excellent and (4) re-workability etc.
But; even if meet for the respective requirement performance in above-mentioned (1) ~ (4) of the requirement performance of the binder layer forming surface protection film, whole requirement performance that simultaneously will meet (1) required by binder layer ~ (4) of surface protection film is very difficult problem.
Such as, under low peeling rate and high peeling rate, keep the balance of bounding force for (1), and (2) prevent to stick with paste residual, known following motion.
And have carbonatoms be (methyl) alkyl acrylate of the alkyl of less than 7 with the multipolymer of copolymerizable compound containing carboxyl for principal constituent, it is carried out in the binder layer of the acrylic acid series of crosslinking Treatment with linking agent, when existing bonding for a long time, tackiness agent shifts to adherend side, in addition, relative to adherend bonding force through time ascending large problem.In order to avoid this situation, knownly be set using that to have carbonatoms be (methyl) alkyl acrylate of the alkyl of 8 ~ 10 and the multipolymer of copolymerizable compound with alcohol hydroxyl group, it carried out the binder layer (patent documentation 1) of crosslinking Treatment with linking agent.
In addition, propose the multipolymer being arranged on and coordinating (methyl) alkyl acrylate and the copolymerizable compound containing carboxyl in multipolymer similar to the above on a small quantity, it is carried out the binder layer etc. of crosslinking Treatment with linking agent.But; during the surface protections such as the plastic plate of these surface smoothings for surface tension is low, also exist because adding man-hour, heating when preserving and produce the problem of the problem of the peelings such as floating and/or the releasable difference when the stripping at high speeds in region hand-manipulated.
In order to address these problems, propose a kind of binder composition, to so that a) to have carbonatoms be (methyl) alkyl acrylate of the alkyl of 8 ~ 10 be add in (methyl) alkyl acrylate 100 weight part of principal constituent copolymerizable compound 1 ~ 15 weight part b) containing carboxyl and c) carbonatoms be the multipolymer that vinyl ester 3 ~ 100 weight part of the aliphatic carboxylic acid of 1 ~ 5 makes monomer mixture, coordinating relative to above-mentioned b in the multipolymer of this monomer mixture) carboxyl of composition is that the linking agent of more than equivalent obtains (patent documentation 2).
In the binder composition recorded in patent documentation 2, add man-hour, preserve time etc. can not produce the peelings such as floating, in addition, bonding force through time ascending little and releasable is excellent, even if preserve for a long time, carrying out in addition peeling off at a high speed even if particularly long-term preservation also can be peeled off by little power again under high-temperature atmosphere, on adherend, now do not produce paste residual, even if can peel off by little power more yet.
In addition, for the antistatic property that (3) are excellent, as the method for giving antistatic property for effects on surface protective membrane, disclose the method etc. being mixed into static inhibitor in base material film.As static inhibitor, such as disclose (a) and there is quaternary ammonium salt, pyridinium salt, primary amino ~ uncle's amino waits the various cationic static inhibitor of cationic groups, b () has sulphonate-base, sulfuric ester alkali, phosphoric acid ester alkali, the anionic property static inhibitor of the anionic property groups such as phosphonic acids alkali, (c) amino acid system, the both sexes static inhibitor such as amidosulphuric acid ester system, (d) amino alcohol system, glycerol system, the nonionic static inhibitor such as polyoxyethylene glycol system, e Polymer Antistatic Agent that () makes static inhibitor polymer as described above quantize and obtain etc. (patent documentation 3).
In addition, in recent years, propose containing such static inhibitor in base material film, or do not coated the surface of base material film, but directly within the adhesive layer containing such static inhibitor.
In addition, for (4) re-workability, propose such as in acrylic resin, relative to acrylic resin 100 weight part, the binder composition (patent documentation 4) obtained with the solidifying agent of 0.0001 ~ 10 weight part cooperation isocyanic ester based compound and specific silicon ester oligopolymer.
In patent documentation 4, with the carbonatoms of alkyl be the alkyl acrylate of 2 ~ 12 degree, the carbonatoms of alkyl be the alkyl methacrylate of 4 ~ 12 degree etc. for main monomer component, such as can comprise the monomer component containing other functional groups such as the monomer containing carboxyl.Typically, preferably containing more than 50 % by weight above-mentioned principal monomer, in addition, the content of the monomer component containing functional group is 0.001 ~ 50 % by weight, is preferably 0.001 ~ 25 % by weight, more preferably 0.01 ~ 25 % by weight.Even if the binder composition recorded in such patent documentation 4 at high temperature or hot and humid under, the rheological parameters' change with time of cohesive force and bonding force is also little, and demonstrates for the also excellent effect of the bonding force of curved surface, so have re-workability.
Usually, if make the binder layer that binder layer becomes flexible, then easily occur to stick with paste to remain, re-workability easily reduces.That is, be difficult to when mistake is fitted peel off, again fit and easily become difficulty.Therefore, it is necessary in order to have re-workability for thinking that the monomer making to have the functional groups such as carboxyl and host are cross-linked and make binder layer be certain hardness.
Prior art document
Patent documentation
Patent documentation 1: Japanese Laid-Open Patent Publication 63-225677 publication
Patent documentation 2: Japanese Unexamined Patent Publication 11-256111 publication
Patent documentation 3: Japanese Unexamined Patent Publication 11-070629 publication
Patent documentation 4: Japanese Unexamined Patent Publication 8-199130 publication
Summary of the invention
Technical problem
In the prior art; as the requirement performance of the binder layer to formation surface protection film; the balance of bounding force is kept under low peeling rate and high peeling rate; require excellent antistatic property and re-workability etc.; but namely allow to meet respective requirement performance respectively, also cannot meet the whole requirement performance required by binder layer of surface protection film.
The present invention completes in view of the foregoing; problem is that providing a kind of possesses excellent antistatic property; the balancing good of bounding force under low peeling rate and high peeling rate, in addition, working life long, weather resistance and the also excellent binder composition of re-workability and surface protection film.
Technical scheme
In order to solve above-mentioned problem, the invention provides a kind of binder composition, it is characterized in that, containing the acrylic acid polymer be made up of the multipolymer of co-polymerized monomer, above-mentioned co-polymerized monomer contains (A) alkyl of 50 ~ 95 weight parts carbonatoms relative to 100 weight parts of the sour based polymer of aforesaid propylene is (methyl) acrylate monomer of C4 ~ C18, 0.1 ~ 10 weight part as can (B) of set of monomers of copolymerization containing hydroxyl can the monomer of copolymerization, (C) of 0.1 ~ 1.0 weight part can the monomer of copolymerization containing carboxyl, (D) polyalkylene glycol mono (methyl) acrylate monomer of 8 ~ 50 weight parts, (E) vinyl monomer containing nitrogen not containing hydroxyl of 0.1 ~ 20 weight part or at least one contained in alkyl (methyl) acrylate monomer of alkoxyl group, in addition, above-mentioned binder composition is not containing silicone compounds, containing (F) two isocyanate compound more than sense, (G) crosslinking catalyst, (H) keto-enol tautomerism body compound, (I) fusing point as static inhibitor is the ionic compound of 25 ~ 50 DEG C and/or the ionic compound containing acryl.
Above-mentioned (F) two isocyanate compound more than sense of 0.1 ~ 10 weight part is preferably contained relative to 100 weight parts of aforesaid propylene acid based polymer, above-mentioned (G) crosslinking catalyst of 0.001 ~ 0.5 weight part, above-mentioned (H) keto-enol tautomerism body compound of 0.1 ~ 300 weight part, in addition, the fusing point contained in above-mentioned binder composition of above-mentioned (I) static inhibitor be the ionic compound of 25 ~ 50 DEG C and the ionic compound containing acryl of copolymerization in above-mentioned multipolymer add up to 0.01 ~ 5.0 weight part, the averaged repeating numbers of the alkylene oxide of the formation polyalkylene glycol chain of above-mentioned (D) polyalkylene glycol mono (methyl) acrylate monomer is 3 ~ 14, two ester moieties in monomer are less than 0.3%, moisture containing ratio is less than 0.1% and solvability in water is turbidity value under 20% aqueous solution state is less than 2%.
Preferably above-mentioned (G) crosslinking catalyst is the crosslinking catalyst of metallo-chelate, and the crosslinking catalyst of above-mentioned (G) metallo-chelate is 70 ~ 1000 relative to weight ratio (H)/(G) of above-mentioned (H) keto-enol tautomerism body compound.
Preferably above-mentioned (B) can the monomer of copolymerization be selected from more than at least one in (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-hydroxyl ethyl ester, N-hydroxyl (methyl) acrylamide, N-hydroxymethyl (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide containing hydroxyl.
Preferably above-mentioned (C) can the monomer of copolymerization be selected from (methyl) vinylformic acid containing carboxyl, (methyl) carboxyethyl acrylates, (methyl) vinylformic acid carboxyl pentyl ester, 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 2-(methyl) acryloyl-oxyethyl tetrahydrophthalic acid.
Preferably above-mentioned (D) polyalkylene glycol mono (methyl) acrylate monomer is selected from more than at least one in polyalkylene glycol mono (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate, oxyethyl group polyalkylene glycol (methyl) acrylate.
Preferred above-mentioned binder composition gel fraction is after cross-linking 95 ~ 100%.
Preferably in the more than sense isocyanate compound of above-mentioned (F) two, as two functional isocyanate compounds, it is non-ring type aliphatic isocyanates compound, it is the compound making diisocyanate cpd and diol compound react and generate, as diisocyanate cpd, being aliphatic diisocyanate, is be selected from tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, one in lysinediisocyanate, as diol compound, comprises and is selected from 2-methyl isophthalic acid, ammediol, 2，2-dimethyl-1，3-propanediol, 2-methyl-2-propyl-1,3-PD, 2-ethyl-2-butyl-1,3-PD, 3-methyl isophthalic acid, 5-pentanediol, 2，2-dimethyl-1，3-propanediol monohydroxy pivalate, polyoxyethylene glycol, one in polypropylene glycol, as trifunctional isocyanates compound, comprises the isocyanuric acid ester body of hexamethylene diisocyanate compound, the isocyanuric acid ester body of isophorone diisocyanate compound, the adducts of hexamethylene diisocyanate compound, the adducts of isophorone diisocyanate compound, the biuret body of hexamethylene diisocyanate compound, the biuret body of isophorone diisocyanate compound, the isocyanuric acid ester body of tolunediisocyanate compound, the isocyanuric acid ester body of xylylene diisocyanate compound, the isocyanuric acid ester body of hydrogenation of benzene dimethylene diisocyanate compound, the adducts of tolunediisocyanate compound, the adducts of xylylene diisocyanate compound, the adducts of hydrogenation of benzene dimethylene diisocyanate compound.
The bounding force under low peeling rate 0.3m/min preferably making the binder layer of above-mentioned binder composition cross-links is 0.04 ~ 0.2N/25mm, and the bounding force under high peeling rate 30m/min is below 2.0N/25mm.
The surface resistivity of the binder layer of above-mentioned binder composition cross-links is preferably made to be 9.0 × 10 + 11Ω/below, release band voltage is ± 0 ~ 0.5kV.
In addition, the invention provides a kind of bonding film, it is characterized in that, is make the binder layer of crosslinked above-mentioned binder composition be formed at the one or two sides of resin molding.
In addition; the invention provides a kind of surface protection film, it is characterized in that, is make the binder layer of crosslinked above-mentioned binder composition be formed at the one side of resin molding; via after on above-mentioned binder layer ballpoint pen scratch-off surface protective membrane, stain does not transfer to adherend.
Above-mentioned surface protection film can use as the purposes of the surface protection film of polaroid.
Preferably contrary in the side defining above-mentioned binder layer with above-mentioned resin molding one side implements anti-charged and antifouling process.
Beneficial effect
According to the present invention, the over-all properties required by the binder layer utilizing the insurmountable surface protection film of prior art can be met, and the antistatic property that can obtain excellence prevents the residual performance of paste with excellent.Specifically, excellent antistatic property can be maintained, and the addition of static inhibitor can be reduced, also can improve further and prevent to stick with paste residual performance.
Embodiment
Below, based on preferred embodiment the present invention being described.
Binder composition of the present invention contains the acrylic acid polymer of the multipolymer comprising co-polymerized monomer, it is characterized in that, above-mentioned co-polymerized monomer is relative to 100 weight parts of the sour based polymer of aforesaid propylene, the carbonatoms of (A) alkyl containing 50 ~ 95 weight parts is (methyl) acrylate monomer of C4 ~ C18, 0.1 ~ 10 weight part as can (B) of set of monomers of copolymerization containing hydroxyl can the monomer of copolymerization, (C) of 0.1 ~ 1.0 weight part can the monomer of copolymerization containing carboxyl, (D) polyalkylene glycol mono (methyl) acrylate monomer of 8 ~ 50 weight parts, (E) nitrogenous vinyl monomer not containing hydroxyl of 0.1 ~ 20 weight part or at least one contained in alkyl (methyl) acrylate monomer of alkoxyl group, in addition, above-mentioned binder composition is not containing silicone compounds, containing (F) two isocyanate compound more than sense, (G) crosslinking catalyst, (H) keto-enol tautomerism body compound, (I) fusing point as static inhibitor is the ionic compound of 25 ~ 50 DEG C and/or the ionic compound containing acryl.
Preferably relative to 100 weight parts of aforesaid propylene acid based polymer, above-mentioned (F) containing 0.1 ~ 10 weight part two isocyanate compound more than sense, above-mentioned (G) crosslinking catalyst of 0.001 ~ 0.5 weight part and above-mentioned (H) keto-enol tautomerism body compound of 0.1 ~ 300 weight part, in addition, the fusing point contained in above-mentioned binder composition of above-mentioned (I) static inhibitor be 25 ~ 50 DEG C ionic compound and in above-mentioned multipolymer the ionic compound containing acryl of copolymerization add up to 0.01 ~ 5.0 weight part, the averaged repeating numbers of the alkylene oxide of the formation polyalkylene glycol chain of above-mentioned (D) polyalkylene glycol mono (methyl) acrylate monomer is 3 ~ 14, two ester moieties in monomer are less than 0.3%, moisture containing ratio is less than 0.1% and solvability in water is turbidity value under 20% aqueous solution state is less than 2%.
Carbonatoms as (A) alkyl is (methyl) acrylate monomer of C4 ~ C18, can enumerate (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) amyl acrylate, (methyl) Ethyl acrylate, (methyl) heptylacrylate, (methyl) Octyl acrylate, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) vinylformic acid ester in the ninth of the ten Heavenly Stems, (methyl) vinylformic acid ester in the different ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid tetradecyl ester, (methyl) vinylformic acid pentadecyl ester, (methyl) aliphatic acrylate, (methyl) vinylformic acid heptadecyl ester, (methyl) octadecyl acrylate, (methyl) myristyl ester, the different myristin of (methyl) vinylformic acid, (methyl) vinylformic acid cetyl, the different cetyl of (methyl) vinylformic acid, (methyl) stearyl acrylate ester, the different stearyl ester of (methyl) vinylformic acid etc.
Preferred above-mentioned co-polymerized monomer is relative to 100 weight parts of acrylic acid polymer, and the carbonatoms containing (A) alkyl with the ratio of 50 ~ 95 weight parts is (methyl) acrylate monomer of C4 ~ C18.
As (B) containing hydroxyl can the monomer of copolymerization, (methyl) hydroxyalkyl acrylates class, N-hydroxyl (methyl) acrylamide, N-hydroxymethyl (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamides etc. such as (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxybutyl, (methyl) vinylformic acid 2-hydroxyl ethyl ester (methyl) acrylic amide etc. containing hydroxyl can be enumerated.
Preferably be selected from more than at least one in (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-hydroxyl ethyl ester, N-hydroxyl (methyl) acrylamide, N-hydroxymethyl (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide.
Preferred above-mentioned co-polymerized monomer relative to 100 weight parts of acrylic acid polymer, with the ratio of 0.1 ~ 10 weight part contain (B) containing hydroxyl can the monomer of copolymerization.
Preferably (C) can the monomer of copolymerization be selected from (methyl) vinylformic acid containing carboxyl, (methyl) carboxyethyl acrylates, (methyl) vinylformic acid carboxyl pentyl ester, hexahydrophthalic acid 2-(methyl) acryloyloxyethyl ester, hexahydrophthalic acid 2-(methyl) acryloxy propyl ester, phthalic acid 2-(methyl) acryloyloxyethyl ester, succsinic acid 2-(methyl) acryloyloxyethyl ester, toxilic acid 2-(methyl) acryloyloxyethyl ester, carboxy-polycaprolactone list (methyl) acrylate, more than at least one in tetrahydrophthalic acid 2-(methyl) acryloyloxyethyl ester.
Preferred above-mentioned co-polymerized monomer relative to 100 weight parts of acrylic acid polymer, with the ratio of 0.1 ~ 1.0 weight part contain (C) containing carboxyl can the monomer of copolymerization.
As (D) polyalkylene glycol mono (methyl) acrylate monomer, as long as a hydroxyl in multiple hydroxyls of having of polyalkylene glycol is with the compound of the form esterification of (methyl) acrylate.Polymerizable group because (methyl) is acrylate-based, thus can with the copolymerization of host polymkeric substance.Other hydroxyls can remain OH, also can be the saturated carboxylic acid such as the alkyl oxide such as methyl ether, ether and/or acetic ester ester etc.
As the alkylidene group that polyalkylene glycol has, vinyl, propenyl, butenyl etc. can be enumerated, but be not limited to these.Polyalkylene glycol can be the multipolymer of the two or more polyalkylene glycol such as polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol.As the multipolymer of polyalkylene glycol, can enumerate polyethylene glycol-propylene glycol, polyethylene glycol-butyleneglycol, polypropylene glycol-polytetramethylene glycol, polyethylene glycol-propylene glycol-polytetramethylene glycol etc., this multipolymer can be segmented copolymer, random copolymers.
Preferably the averaged repeating numbers of the alkylene oxide of the formation polyalkylene glycol chain of (D) polyalkylene glycol mono (methyl) acrylate monomer is 3 ~ 14." averaged repeating numbers of alkylene oxide " refers to the mean number that alkylene oxide unit repeats in the part of " polyalkylene glycol chain " contained by the molecular structure of (D) polyalkylene glycol mono (methyl) acrylate monomer.
As (D) polyalkylene glycol mono (methyl) acrylate monomer, two ester moieties in preferred monomers are less than 0.3%, and moisture containing ratio is less than 0.1% and solvability in water is turbidity value under 20% aqueous solution state is less than 2%.
" two ester moieties in monomer " refer to the containing ratio (% by weight) of polyalkylene glycol two (methyl) acrylate contained in (D) polyalkylene glycol mono (methyl) acrylate monomer.
" moisture containing ratio " refers to the containing ratio (% by weight) of moisture contained in (D) polyalkylene glycol mono (methyl) acrylate monomer.
" turbidity value under 20% aqueous solution state " is the turbidity value (%) of this aqueous solution under the state of instigating (D) polyalkylene glycol mono (methyl) acrylate monomer to be the aqueous solution of 20 % by weight.In other words, (D) polyalkylene glycol mono (methyl) acrylate monomer not only has water-soluble (solvability in water) that become 20% aqueous solution, and needs turbidity value (%) low (gonorrhoea is few) under 20% aqueous solution.
Should illustrate, in this manual, the turbidity value of 20% aqueous solution is add this aqueous solution in the quartz cell of 10mm, the value recorded by turbidometer at optical path length.This index as the hydrophilic degree of (D) polyalkylene glycol mono (methyl) acrylate monomer, even in order to select high density also the monomer that can obtain without the wetting ability of the solution of gonorrhoea is high import.
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, polyoxyethylene glycol-mono-(methyl) acrylate, polypropylene glycol-mono-(methyl) acrylate, polytetramethylene glycol-mono-(methyl) acrylate, polyethylene glycol-propylene glycol-mono-(methyl) acrylate, polyethylene glycol-butyleneglycol-mono-(methyl) acrylate, polypropylene glycol-polytetramethylene glycol-mono-(methyl) acrylate, polyethylene glycol-propylene glycol-polytetramethylene glycol-mono-(methyl) acrylate can be enumerated; Methoxy poly (ethylene glycol)-(methyl) acrylate, methoxyl group polypropylene glycol-(methyl) acrylate, methoxyl group polytetramethylene glycol-(methyl) acrylate, methoxypolyethylene glycol-polypropylene glycol-(methyl) acrylate, methoxypolyethylene glycol-polytetramethylene glycol-(methyl) acrylate, methoxyl group-polypropylene glycol-polytetramethylene glycol-(methyl) acrylate, methoxypolyethylene glycol-polypropylene glycol-polytetramethylene glycol-(methyl) acrylate; Oxyethyl group polyoxyethylene glycol-(methyl) acrylate, oxyethyl group polypropylene glycol-(methyl) acrylate, oxyethyl group polytetramethylene glycol-(methyl) acrylate, oxyethyl group-polyethylene glycol-propylene glycol-(methyl) acrylate, oxyethyl group-polyethylene glycol-butyleneglycol-(methyl) acrylate, oxyethyl group-polypropylene glycol-polytetramethylene glycol-(methyl) acrylate, oxyethyl group-polyethylene glycol-propylene glycol-polytetramethylene glycol-(methyl) acrylate etc.
Preferred above-mentioned co-polymerized monomer, relative to 100 weight parts of acrylic acid polymer, contains (D) polyalkylene glycol mono (methyl) acrylate monomer with the ratio of 8 ~ 50 weight parts.
As the vinyl monomer that (E-1) in (E) is nitrogenous, the vinyl monomer containing amido linkage, the vinyl monomer containing amino, the vinyl monomer etc. with hetero ring type structure containing nitrogen can be enumerated.More specifically, the ring-type nitrogen vinyl compound with hetero ring type structure of the N-vinyl substituted such as 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 can be enumerated, the ring-type nitrogen vinyl compound with hetero ring type structure that N-(methyl) acryls such as N-(methyl) acryloyl morpholine, N-(methyl) acryloylpiperazines, N-(methyl) acryloylaziridine, N-(methyl) acryl azetidine, N-(methyl) acryl tetramethyleneimine, N-(methyl) acryloylpiperidine, N-(methyl) acryl azepan, N-(methyl) acryl Azacyclooctane replace, N-N-cyclohexylmaleimide, N-phenylmaleimide etc. have the ring-type nitrogen vinyl compound with hetero ring type structure of nitrogen-atoms and ethene system unsaturated link(age) in ring, (methyl) acrylamide, N-methyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, the N-tertiary butyl (methyl) acrylamide etc. are without (methyl) acrylamide replaced or monoalkyl replaces, N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N, N-dipropyl acrylamide, N, the dialkyl group such as N-di-isopropyl (methyl) acrylamide, N, N-dibutyl (methyl) acrylamide, N-ethyl-N-methyl (methyl) acrylamide, N-Methyl-N-propyl (methyl) acrylamide, N-methyl-N-isopropyl (methyl) acrylamide replace (methyl) acrylamide, N, N-dimethylamino methyl (methyl) acrylate, N, N-dimethylaminoethyl (methyl) acrylate, N, N-dimethylamino-propyl (methyl) acrylate, N, N-dimethylamino sec.-propyl (methyl) acrylate, N, N-dimethylaminobutyl (methyl) acrylate, N, N-Diethylaminomethyl (methyl) acrylate, N, N-diethylamino ethyl (methyl) acrylate, N-ethyl-N-methylamino ethyl (methyl) acrylate, N-methyl-N-propylamino ethyl (methyl) acrylate, N-methyl-N-isoproylamino ethyl (methyl) acrylate, N, N-Dibutylaminoethyl (methyl) acrylate, dialkyl amido (methyl) acrylate such as t-butylamino ethyl (methyl) acrylate, N, N-dimethylamino-propyl (methyl) acrylamide, N, N-diethylin propyl group (methyl) acrylamide, N, N-dipropylamino propyl group (methyl) acrylamide, N, N, N-dialkyl group substituted-amino propyl group (methyl) acrylamides such as 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, the N-vinylcarboxylic acid amide type such as N-vinyl formamide, N-vinyl acetamide, N-vinyl-N-methylacetaniide, (methyl) acrylic amides such as N-methoxymethyl (methyl) acrylamide, N-ethoxyethyl group (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, diacetone acrylamide, N, N-methylene-bis (methyl) acrylamide, the unsaturated carboxylic acid nitriles etc. such as (methyl) vinyl cyanide.
As the vinyl monomer that (E-1) is nitrogenous, the monomer preferably not containing hydroxyl, does not more preferably contain the monomer of hydroxyl and carboxyl.As such monomer, preferably above illustrative monomer, such as, the acrylic monomer containing N, N-dialkyl group substituted-amino and/or N, N-dialkyl group substituted amido; The N-vinyl substituted lactams such as NVP, N-caprolactam, N-vinyl-2-piperidone; N-(methyl) the acryl substituted cyclic amines such as N-(methyl) acryloyl morpholine, N-(methyl) acryl tetramethyleneimine.
As (E-2) alkyl containing alkoxyl group (methyl) acrylate monomer in (E), (methyl) vinylformic acid 2-methoxy acrylate can be enumerated, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-propoxy ethyl, (methyl) vinylformic acid 2-isopropoxyethyl cyanoacrylate, (methyl) vinylformic acid 2-butoxyethyl, (methyl) vinylformic acid 2-methoxyl group propyl ester, (methyl) vinylformic acid 2-oxyethyl group propyl ester, (methyl) vinylformic acid 2-propoxy-propyl ester, (methyl) vinylformic acid 2-isopropoxy propyl ester, (methyl) vinylformic acid 2-butoxy propyl ester, (methyl) vinylformic acid 3-methoxyl group propyl ester, (methyl) vinylformic acid 3-oxyethyl group propyl ester, (methyl) vinylformic acid 3-propoxy-propyl ester, (methyl) vinylformic acid 3-isopropoxy propyl ester, (methyl) vinylformic acid 3-butoxy propyl ester, (methyl) vinylformic acid 4-methoxybutyl, (methyl) vinylformic acid 4-Ethoxybutyl, (methyl) vinylformic acid 4-propoxy-butyl ester, (methyl) vinylformic acid 4-isopropoxy butyl ester, (methyl) vinylformic acid 4-butoxy butyl ester etc.
These (methyl) acrylate monomers containing alkoxyl group have the structure of the atom that instead of the alkyl in alkyl (methyl) acrylate with alkoxyl group.
Preferred above-mentioned co-polymerized monomer, relative to 100 weight parts of acrylic acid polymer, contains (E) nitrogenous vinyl monomer not containing hydroxyl or at least one contained in alkyl (methyl) acrylate monomer of alkoxyl group with the ratio of 0.1 ~ 20 weight part.Also can distinguish and the nitrogenous vinyl monomer using (E-1) of a kind or two or more not containing hydroxyl and (E-2) alkyl containing alkoxyl group (methyl) acrylate monomer.
As (F) two isocyanate compound more than sense, as long as be selected from least a kind or two or more in the polyisocyanate compounds at least in 1 molecule with more than 2 isocyanic ester (NCO) bases.Having the classification such as fatty family isocyanic ester, fragrant family isocyanic ester, non-ring type system isocyanic ester, ester ring type system isocyanic ester in polyisocyanate compounds, can be any one.
As isocyanate compound more than trifunctional, the adducts (polyalcohol modified body) etc. of the polyvalent alcohol (at least there is the compound of more than 3 OH bases in 1 molecule) of more than 3 valencys such as the biuret modified body of two functional isocyanate compounds (there is the compound of 2 NCO bases in 1 molecule), isocyanurate-modified body, trihydroxy methyl propane (TMP) and glycerol can be enumerated.As (F) two isocyanate compound more than sense, can only use trifunctional isocyanates compound, or only can use two functional isocyanate compounds.In addition, also can be used together trifunctional isocyanates compound and two functional isocyanate compounds.
As trifunctional isocyanates compound, be preferably selected from the isocyanuric acid ester body of hexamethylene diisocyanate compound, the isocyanuric acid ester body of isophorone diisocyanate compound, the adducts of hexamethylene diisocyanate compound, the adducts of isophorone diisocyanate compound, the biuret body of hexamethylene diisocyanate compound, the biuret body of isophorone diisocyanate compound, the isocyanuric acid ester body of tolunediisocyanate compound, the isocyanuric acid ester body of xylylene diisocyanate compound, the isocyanuric acid ester body of hydrogenation of benzene dimethylene diisocyanate compound, the adducts of tolunediisocyanate compound, the adducts of xylylene diisocyanate compound, more than at least one in the adducts of hydrogenation of benzene dimethylene diisocyanate compound.
As two functional isocyanate compounds, being preferably non-ring type aliphatic isocyanates compound, is the compound making diisocyanate cpd and diol compound react and generate.Such as, with general formula " O=C=N-X-N=C=O " (wherein, X is divalent group) represent diisocyanate cpd, use general formula " HO-Y-OH " (wherein, Y is divalent group) when representing diol compound, as the compound making diisocyanate cpd and diol compound react and generate, such as, the compound represented by following general formula Z can be enumerated.
(general formula Z)
O＝C＝N-X-(NH-CO-O-Y-O-CO-NH-X) n-N＝C＝O
At this, n is the integer of more than 0.When n is 0, general formula Z represents " O=C=N-X-N=C=O ".As two senses non-ring type aliphatic isocyanates compound, in general formula Z, can be the compound (relative to diol compound unreacted diisocyanate cpd) of 0 containing n, preferably containing n be that the compound of the integer of more than 1 is as essential component.Two senses non-ring type aliphatic isocyanates compound can be the mixture be made up of multiple compound that the n in general formula Z is different.
The diisocyanate cpd represented by general formula " O=C=N-X-N=C=O " is aliphatic diisocyanate.Preferred X is non-ring type and aliphatic divalent group.As above-mentioned aliphatic diisocyanate, preferably include one or two or more kinds that be selected from tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysinediisocyanate.
The diol compound represented by general formula " HO-Y-OH " is aliphatic diol.Preferred Y is non-ring type and aliphatic divalent group.As above-mentioned diol compound, preferably include and be selected from 2-methyl isophthalic acid, ammediol, 2,2-dimethyl-1,3-propylene glycol, 2-methyl-2-propyl-1,3-PD, 2-ethyl-2-butyl-1, ammediol, 3-methyl isophthalic acid, one or two or more kinds in 5-pentanediol, 2，2-dimethyl-1，3-propanediol monohydroxy pivalate, polyoxyethylene glycol, polypropylene glycol.
Preferably relative to 100 weight parts of acrylic acid polymer, contain (F) two isocyanate compound more than sense with the ratio of 0.1 ~ 10 weight part.
For (G) crosslinking catalyst, when taking polyisocyanate compounds as linking agent, as long as the material that the reaction (crosslinking reaction) of above-mentioned multipolymer and linking agent plays a role as catalyzer, the organometallic compounds etc. such as the amine compounds such as tertiary amine, metallo-chelate, organo-tin compound, organo-lead compound, organic zinc compound can be enumerated.
As tertiary amine, trialkylamine, N, N, N can be enumerated ', N '-tetra, N, N-dialkyl amido alcohol, Triethylene Diamine, morpholine derivative, bridged piperazine derivatives etc.
As metallo-chelate, it is the compound of bonding more than 1 polydentate ligand L in central metal atom M.Metallo-chelate can have the unidentate ligand X also can not with more than 1 that is bonded to atoms metal M.Such as, with M (L) m(X) nwhen representing that atoms metal M is the general formula of the metallo-chelate of 1, m>=1, n>=0.When M is more than 2, the L of m can be identical part, also can be different parts.When n is more than 2, the X of n can be identical part, also can be different parts.
As atoms metal M, Fe, Ni, Mn, Cr, V, Ti, Ru, Zn, Al, Zr, Sn etc. can be enumerated.
As polydentate ligand L; the 'beta '-ketoesters such as methyl acetoacetate, methyl aceto acetate, etheric acid monooctyl ester, etheric acid grease, lauryl acetoacetate, etheric acid stearyl ester, methyl ethyl diketone (another name 2 can be enumerated; 4-pentane diketone), the beta-diketon such as 2,4-hexanedione, benzoylacetone.These are keto-enol tautomerism body compound, in polydentate ligand L, can take off the enolate after proton (such as methyl ethyl diketone) for enol.
As unidentate ligand X; the halogen atoms such as chlorine atom, bromine atoms can be enumerated; the acyloxy such as pentanoyl, caproyl, 2-ethyl hexyl acyl group, capryloyl, nonanoyl, decanoyl, lauroyl, octadecanoyl, the alkoxyl groups etc. such as methoxyl group, oxyethyl group, positive propoxy, isopropoxy, butoxy.
As the concrete example of metallo-chelate, three (2 can be enumerated, 4-pentane two ketone acid) iron (III), praseodynium iron, praseodynium titanium, praseodynium ruthenium, bis-acetylacetonate zinc, praseodynium aluminium, four methyl ethyl diketone zirconiums, three (2, the acid of 4-hexanedione) iron (III), two (2, the acid of 4-hexanedione) zinc, three (2, the acid of 4-hexanedione) titanium, three (2, the acid of 4-hexanedione) aluminium, four (acid of 2,4-hexanedione) zirconium etc.
As organo-tin compound, dialkyl tin oxide, the soap of dialkyl tin, the soap etc. of monovalence tin can be enumerated.
(G) crosslinking catalyst is preferably metallo-chelate or organo-tin compound.As metallo-chelate, preferred aluminum chelate, titanium chelate, iron chelate, tin inner complex etc.As organotin, be preferably selected from more than at least one in dioctyltin oxide, dioctyl tin dilaurate.
Preferably relative to 100 weight parts of acrylic acid polymer, contain (G) crosslinking catalyst with the ratio of 0.001 ~ 0.5 weight part.
As (H) keto-enol tautomerism body compound; the beta-diketons such as the 'beta '-ketoesters such as methyl acetoacetate, methyl aceto acetate, etheric acid monooctyl ester, etheric acid grease, lauryl acetoacetate, etheric acid stearyl ester, methyl ethyl diketone, 2,4-hexanedione, benzoylacetone can be enumerated.(H) keto-enol tautomerism body compound is in the binder composition taking polyisocyanate compounds as linking agent, by the isocyanate group that block cosslinking agent has, thus the excessive viscosity of the binder composition after coordinating linking agent can be suppressed to rise or gelation, the working life of binder composition can be extended.
As (H) keto-enol tautomerism body compound, be particularly preferably more than at least one be selected from methyl ethyl diketone, methyl aceto acetate.
Preferably relative to 100 weight parts of acrylic acid polymer, contain (H) keto-enol tautomerism body compound with the ratio of 0.1 ~ 300 weight part.
Crosslinked effect is suppressed, so preferably suitably set the ratio of (H) keto-enol tautomerism body Compound Phase for (G) crosslinking catalyst because (H) keto-enol tautomerism body compound and (G) crosslinking catalyst have on the contrary.In order to extend the working life of binder composition, improve package stability, preferably (G) crosslinking catalyst is 70 ~ 1000 relative to weight ratio (H)/(G) of (H) keto-enol tautomerism body compound.
Preferably (I) static inhibitor to be (I-1) fusing point be ionic compound and/or (I-2) ionic compound containing acryl of 25 ~ 50 DEG C.
In the present invention; as (I) static inhibitor; the ionic compound being 25 ~ 50 DEG C by (I-1) fusing point adds in multipolymer, and/or makes (I-2) ionic compound containing acryl carry out copolymerization in the copolymer.These (I) static inhibitor are low due to fusing point, and have the alkyl of long-chain, so infer with the affinity of acrylic copolymer high.
As (I) static inhibitor, static inhibitor contained in binder composition and the static inhibitor of copolymerization in above-mentioned multipolymer can be enumerated.Preferably relative to 100 weight parts of acrylic acid polymer, contain (I) static inhibitor with the ratio adding up to 0.01 ~ 5.0 weight part that (I-1) fusing point contained in binder composition is the ionic compound of 25 ~ 50 DEG C and (I-2) ionic compound containing acryl of copolymerization in the copolymer.
As the ionic compound that (I-1) fusing point is 25 ~ 50 DEG C, be the ionic compound with positively charged ion and negatively charged ion, can enumerate cationic nitrogenous Huo person phosphonium cation, sulfonium cation etc., the negatively charged ion such as positively charged ion is pyridylium, glyoxaline cation, pyrimidine positively charged ion, pyrazoles positively charged ion, tetramethyleneimine positively charged ion, ammonium cation is hexafluorophosphate (PF 6 -), thiocyanate-(SCN -), alkylbenzene sulfonate (RC 6h 4sO 3 -), perchlorate (ClO 4 -), a tetrafluoro borate (BF 4 -), the compound of the inorganic or organic anion such as two (fluorosulfonyl) inferior amine salt (FSI), two (trifyl) inferior amine salt (TFSI), fluoroform sulphonate (TF).Being preferably solid under normal temperature (such as 25 DEG C), by selecting the chain length, substituent position, number etc. of alkyl, the ionic compound that fusing point is 25 ~ 50 DEG C can being obtained.Positively charged ion is preferably containing quaternary nitrogen positively charged ion, the season such as 1-alkyl pyridine (carbon atom of 2 ~ 6 can have substituting group also can without replacement) pyridylium, 1 can be enumerated, 3-dialkylimidazolium (2, the carbon atom of 4,5 can have substituting group also can without replacement) etc. season glyoxaline cation, the quaternary ammonium cation etc. such as tetra-allkylammonium.
Preferably relative to 100 weight parts of acrylic acid polymer, contain with the ratio of 0.01 ~ 5.0 weight part the ionic compound that (I-1) fusing point is 25 ~ 50 DEG C.
As (I-2) ionic compound containing acryl, be the ionic compound with positively charged ion and negatively charged ion, can enumerate positively charged ion is (methyl) acryloxyalkyl trialkyl ammonium (R 3n +-C nh 2n-OCOCQ=CH 2, wherein, Q=H or CH 3, R=alkyl) etc. be hexafluorophosphate (PF containing the positively charged ion of (methyl) acryl, negatively charged ion 6 -), thiocyanate-(SCN -), organic sulfonate (RSO 3 -), perchlorate (ClO 4 -), a tetrafluoro borate (BF 4 -), inferior amine salt (R containing F f 2n -) etc. the compound of inorganic or organic anion.As the inferior amine salt (R containing F f 2n -) R f, perfluoroalkyl group sulfonyl or the fluorosulfonyl such as trifyl, pentafluoride ethane alkylsulfonyl can be enumerated.As the inferior amine salt containing F, two (fluorosulfonyl) inferior amine salt ((FSO can be enumerated 2) 2N -), two (trifyl) inferior amine salt ((CF 3sO 2) 2N -), two (pentafluoride ethane alkylsulfonyl) inferior amine salt ((C 2f 5sO 2) 2n-) etc. two sulphonyl imine salt.
Preferably (I-2) ionic compound containing acryl is relative to 100 weight parts of acrylic acid polymer, carries out copolymerization with the ratio of 0.01 ~ 5.0 weight part.
As the concrete example of (I) static inhibitor, be not particularly limited, as the concrete example that (I-1) fusing point is the ionic compound of 25 ~ 50 DEG C, 1-octylpyridinium hexafluorophosphate, 1-nonylpyridine hexafluorophosphate, 2-methyl isophthalic acid-dococylpyridinium hexafluorophosphate, 1-octylpyridinium dodecylbenzene sulfonate, 1-dococylpyridinium thiocyanate-, 1-dococylpyridinium dodecylbenzene sulfonate, 4-methyl isophthalic acid-octylpyridinium hexafluorophosphate etc. can be enumerated.In addition, as the concrete example of (I-2) ionic compound containing acryl, dimethylamino methyl (methyl) acrylate phosphofluoric acid methyl salt ((CH can be enumerated 3) 3n +cH 2oCOCQ=CH 2pF 6 -, wherein, Q=H or CH 3), two (trifyl) imide methyl salt ((CH of dimethylaminoethyl (methyl) acrylate 3) 3n +(CH 2) 2oCOCQ=CH 2(CF 3sO 2) 2n -, wherein, Q=H or CH 3), two (fluorosulfonyl) imide methyl salt ((CH of dimethylamino methyl methyl acrylate 3) 3n +cH 2oCOCQ=CH 2(FSO 2) 2n -, wherein, Q=H or CH 3) etc.
In addition, as other compositions, can suitably coordinate containing alkylene oxide can the known additive such as (methyl) Acrylic Acid Monomer, (methyl) acrylamide monomer, dialkyl group substituted acrylamide monomer, tensio-active agent, curing catalyst, softening agent, weighting agent, cure retarder, processing aid, protective agent, antioxidant of copolymerization.These can be used alone or and with two or more.
But preferred binder composition of the present invention is not containing silicone compounds.At this, silicone compounds refers to the compound with siloxane structure, comprises the modification bodies such as polyether modified siloxane compound.In the present invention, by (D) polyalkylene glycol mono (methyl) acrylate monomer of specified amount is matched with tackiness agent, thus even if not containing silicone compounds, wetting ability also improves, therefore, it is possible to form the binder layer of excellent antistatic property.
The multipolymer of the host that can use in binder composition of the present invention can synthesize by making following monomer polymerization, (methyl) acrylate monomer of described monomer to be the carbonatoms of (A) alkyl be C4 ~ C18, (B) containing hydroxyl can the monomer of copolymerization, (C) containing carboxyl can the monomer of copolymerization, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) vinyl monomer containing nitrogen containing hydroxyl or alkyl (methyl) acrylate monomer containing alkoxyl group.The polymerization process of multipolymer is not particularly limited, and can use the polymerization process that solution polymerization, emulsion polymerization etc. are suitable.
When using (I-2) ionic compound containing acryl as (I) static inhibitor, the multipolymer of the host that can use in binder composition of the present invention can by making (I-2) ionic compound containing acryl and following monomer polymerization and synthesizing, (methyl) acrylate monomer of described monomer to be the carbonatoms of (A) alkyl be C4 ~ C18, (B) containing hydroxyl can the monomer of copolymerization, (C) containing carboxyl can the monomer of copolymerization, (D) polyalkylene glycol mono (methyl) acrylate monomer and (E) vinyl monomer containing nitrogen not containing hydroxyl or alkyl (methyl) acrylate monomer containing alkoxyl group.
Binder composition of the present invention can also by not containing silicone compounds, isocyanate compound, (G) crosslinking catalyst and (H) keto-enol tautomerism body compound in above-mentioned multipolymer more than cooperation (F) two sense, and suitably coordinate arbitrary additive to prepare further.Should illustrate, when being polymerized (I-2) ionic compound containing acryl in the multipolymer of host, the ionic compound that (I-1) fusing point is 25 ~ 50 DEG C can being added relative to multipolymer further, also can not add.
When manufacturing the multipolymer of host, in order to reduce moisture being mixed into binder composition, the solution polymerization etc. preferably employing anhydrous organic solvent carries out polyreaction in anhydrous conditions.Wetting ability particularly due to (D) polyalkylene glycol mono (methyl) acrylate monomer is high, so preferably use the compound that moisture containing ratio is low.
For each monomer used in the manufacture of the multipolymer of host, in order to avoid the viscosity of binder composition rises, preferably do one's utmost to reduce the amount that can play the monomer of multi-functional (more than two functionalities) of function as linking agent.Particularly due to two (methyl) acrylate that two ester moieties of the correspondence of (D) polyalkylene glycol mono (methyl) acrylate monomer are two functional monomers, so preferably use the compound that two ester moieties are few.
Preferred above-mentioned multipolymer is acrylic acid polymer, preferably relative to 100 weight parts of aforesaid propylene acid based polymer, contain the acrylic monomers such as (methyl) acrylate monomer, (methyl) vinylformic acid, (methyl) acrylic amide with the ratio of 50 ~ 100 weight parts.
In addition, the acid number of preferred acrylic acid polymer is 0.01 ~ 8.0.Thereby, it is possible to improve stain, improve and prevent to stick with paste residual performance.
At this, " acid number " is one of index of the content representing acid, represents with the mg number of the potassium hydroxide required for the polymkeric substance 1g in order to neutralize containing carboxyl.
The bounding force under low peeling rate 0.3m/min preferably making the binder layer of above-mentioned binder composition cross-links is 0.04 ~ 0.2N/25mm, and the bounding force under high peeling rate 30m/min is below 2.0N/25mm.Thus, bounding force can be obtained and change little performance because of peeling rate, even if peel off at a high speed, also can peel off rapidly.In addition, owing to again bonding, even if so once at stripper surface protective membrane also without the need to excessive power, easily peel off from adherend.
The surface resistivity of the binder layer of above-mentioned binder composition cross-links is preferably made to be 9.0 × 10 + 11Ω/below, release band voltage is ± 0 ~ 0.5kV.Should illustrate, in the present invention, " ± 0 ~ 0.5kV " refers to 0 ~-0.5kV and 0 ~+0.5kV, that is ,-0.5 ~+0.5kV.If surface resistivity is large, then make the poor performance of the eliminostatic of generation because of charged when peeling off.Therefore, by making surface resistivity enough little, thus the release band voltage along with the electrostatic produced when peeling off adherend from binder layer produces can being reduced, can suppress to impact the electric control circuit etc. of adherend.
The gel fraction preferably making the binder layer of binder composition cross-links of the present invention (tackiness agent after crosslinked) is 95 ~ 100%.Like this, high by gel fraction, thus under low peeling rate, bounding force can not become excessive, reduces, can improve the weather resistance under re-workability, high-temperature high-humidity, suppress the stain of adherend from the unconverted monomer of multipolymer or the stripping of oligopolymer.
Bonding film of the present invention makes the binder layer of crosslinked binder composition of the present invention be formed at the one or two sides of resin molding.In addition, surface protection film of the present invention is the surface protection film making the binder layer of crosslinked binder composition of the present invention be formed at the one side of resin molding.For binder composition of the present invention; because balance coordinates each composition of above-mentioned (A) ~ (I) well; so possess excellent antistatic property; under low peeling rate and high peeling rate; the balancing good of bounding force; in addition, weather resistance and re-workability (swipe after on surface protection film via binder layer ballpoint pen, stain does not transfer to adherend) also excellence.Therefore, it is possible to be used as the purposes of the surface protection film of polaroid aptly.
As the base material film of binder layer, the stripping film (separatory membrane) of protection adhesive face, the resin moldings etc. such as polyester film can be used.
Can at base material film, the face contrary in the side defining binder layer with resin molding implement to utilize silicon-type, the releasing agent, coating agent, silicon dioxide microparticle etc. of fluorine system carry out antifouling process, utilize the coating of static inhibitor, the anti-on-line treatment carried out such as to be mixed into.
At stripping film, utilize silicon-type in the face of the side be combined with adhesive face of binder layer, the releasing agent etc. of fluorine system implements demoulding process.
Embodiment
Below, embodiment is utilized to illustrate the present invention.
The manufacture > of < acrylic copolymer
[embodiment 1]
Nitrogen is imported, with the air in nitrogen replacement reaction unit in the reaction unit possessing stirrer, thermometer, reflux exchanger and nitrogen ingress pipe.Thereafter, 2-EHA 100 weight part, vinylformic acid 8-hydroxyl monooctyl ester 3.0 weight part, vinylformic acid 0.2 weight part, polypropylene glycol mono acrylic ester (the averaged repeating numbers n=12 of the alkylene oxide of formation polyalkylene glycol chain is added in reaction unit, two ester moieties in monomer are 0.1%, solvability in water is the turbidity value in 20% aqueous solution state is 0.8%, moisture containing ratio is 0.05%) 10 weight parts, NVP 5 weight part, and 60 parts by weight solvent (ethyl acetate).Thereafter, dripped Diisopropyl azodicarboxylate 0.1 weight part as polymerization starter with 2 hours, react 6 hours at 65 DEG C, acrylic acid copolymer soln that obtain weight-average molecular weight 500,000, that use in embodiment 1.Take a part for acrylic copolymer, as the mensuration sample of acid number described later.
[embodiment 2 ~ 9 and comparative example 1 ~ 4]
Be respectively except (A) ~ (E) of table 1 and the record like that of (I-2) except making the composition of monomer, carry out in the same manner as the acrylic acid copolymer soln used in the above embodiments 1, obtain the acrylic acid copolymer soln used in embodiment 2 ~ 9 and comparative example 1 ~ 4.
The manufacture > of < binder composition and surface protection film
[embodiment 1]
In the acrylic acid copolymer soln of the embodiment 1 manufactured as mentioned above, add 1-octylpyridinium hexafluorophosphate 1.0 weight part, after methyl ethyl diketone 8.5 weight part stirs, add CoronetHX (the isocyanuric acid ester body of hexamethylene diisocyanate compound) 2.5 weight parts, praseodynium titanium 0.1 weight part carries out being uniformly mixed and obtain the binder composition of embodiment 1.By be coated with this binder composition on the stripping film be made up of polyethylene terephthalate (PET) film being coated with silicone resin after, carry out drying and except desolventizing, the thickness obtaining binder layer is the adhesive sheet of 25 μm at 90 DEG C.
Thereafter; in the face of side; make that adhesive sheet is needed on polyethylene terephthalate (PET) film after anti-charged and antifouling process, contrary with the face after anti-charged and antifouling process face, be there is the surface protection film of the embodiment 1 of the stacked formation of " PET film/binder layer/stripping film (being coated with the PET film of silicone resin) after anti-charged and antifouling process ".
[embodiment 2 ~ 9 and comparative example 1 ~ 4]
Except make the composition of additive respectively as the record of (F) ~ (J) of table 2 except, carry out in the same manner as the surface protection film of the above embodiments 1, obtain the surface protection film of embodiment 2 ~ 9 and comparative example 1 ~ 4.
In table 1 and table 2, for the proportioning of each composition, bracket with bracket and represent the total (A) the organized numerical value as the weight part calculated by 100 weight parts.In Table 1, (I-2) of the copolymerization in the copolymer in (I) static inhibitor ionic compound containing acryl is documented in different hurdles from (I) static inhibitor added after polymerisation.
In addition, the compound name of the abbreviation of each composition used in table 1 and table 2 is represented in table 3 and table 4.Should illustrate, Coronet (registered trademark) HX, this HL and this L are the trade(brand)names of Nippon Polyurethane Industry Co., Ltd., and Takenate (registered trademark) D-140N, D-127N, D-110N, D-120N are the trade(brand)names of Mitsui Chemicals, Inc.For (D) group of table 3, the numerical value of " n " is the averaged repeating numbers of the alkylene oxide forming polyalkylene glycol chain.The numerical value of " diester " is two ester moieties (%) in monomer.The numerical value of " moisture " is moisture containing ratio (%).The numerical value of " turbidity " is the turbidity value (%) under 20% aqueous solution state.In addition, the value of (H)/(G) is shown in table 5.
Table 1
Table 2
Table 3
Table 4
Table 5
(H)/(G)
Embodiment 1 85
Embodiment 2 120
Embodiment 3 100
Embodiment 4 83.3
Embodiment 5 333.3
Embodiment 6 500
Embodiment 7 200
Embodiment 8 187.5
Embodiment 9 375
Comparative example 1 -
Comparative example 2 60
Comparative example 3 3.3
Comparative example 4 -
The synthesis > of < bis-functional isocyanate compound
Two functional isocyanate compounds of synthesis example 1 ~ 3 synthesize as follows.As shown in table 6 and table 7, with mol ratio: the ratio mixing vulcabond of NCO/OH=16 and diol compound, 120 DEG C of reactions 3 hours, thereafter, use thin film evaporation unit under reduced pressure to remove unreacted vulcabond, obtain target two functional isocyanate compound.
Table 6
Synthesis example 1F-1 Synthesis example 2F-2 Synthesis example 3F-3
Diisocyanate cpd HDI HDI HDI
Diol compound L-1 L-2 L-3
Table 7
< test method and evaluation >
By the surface protection film in embodiment 1 ~ 9 and comparative example 1 ~ 4 23 DEG C, under the atmosphere of 50%RH after aging 7 days; peel off stripping film (being coated with the PET film of silicone resin); binder layer is exposed, it can be used as the mensuration sample of gel fraction and surface resistivity.
In addition; the surface protection film exposing this binder layer is made to fit in the surface of the polaroid posting liquid crystal cells via binder layer; place after 1 day; autoclave process in 20 minutes is carried out under 50 DEG C, 5 normal atmosphere; place 12 hours further in room temperature, it can be used as the mensuration sample of bounding force, release band voltage, re-workability and weather resistance.
< gel fraction >
After aging end, Accurate Determining fits in the quality of the mensuration sample before polaroid, floods after 24 hours, filter with 200 object wire cloths in toluene.Thereafter, by filtrate 100 DEG C of dryings after 1 hour, the quality of Accurate Determining residue, calculates the gel fraction of binder layer (tackiness agent after crosslinked) according to following formula.
Gel fraction (%)=insoluble part mass (g)/tackiness agent quality (g) × 100
< bounding force >
Use tensile testing machine; by mensuration sample obtained above (surface protection film of 25mm width being fitted in the surface of polaroid and the sample obtained) in 180 ° of directions; peel off under low peeling rate (0.3m/min) and high peeling rate (30m/min), using the stripping strength that records as bounding force (N/25mm).
< surface resistivity >
After weathering, before fitting in polaroid, peel stripping film (being coated with the PET film of silicone resin) and expose binder layer, using resistrivity meter HIRESTAUP-HT450 (MitsubishiChemicalAnalytech system) to measure the surface resistivity (Ω/) of binder layer.
< release band voltage >
When mensuration sample obtained above being peeled off 180 ° with the draw speed of 30m/min, use high precision electrostatic transducer SK-035, SK-200 (Co., Ltd. keyence system) measure polaroid charged and produce voltage (with voltage), using the maximum value of measured value as release band voltage (kV).
< re-workability >
After on the surface protection film of ballpoint pen (load 500g comes and goes 3 times) mensuration sample obtained above of swiping, after polaroid stripper surface protective membrane, observe the surface of polaroid, confirm that stain does not transfer to the situation of polaroid.For evaluation objective benchmark, average evaluation stain not being transferred to polaroid is "○", along the stain average evaluation transferred at least partially is " △ " with ballpoint pen scraping track by confirming, will confirms along the stain transfer with ballpoint pen scraping track, confirm that the average evaluation that tackiness agent also departs from from adhesive surface is "×".
< weather resistance >
By mensuration sample obtained above 60 DEG C, place 250 hours under the atmosphere of 90%RH after, at room temperature take out, place after 12 hours further, measure bounding force and also compare with the bounding force at initial stage, confirm situation about significantly increasing.For evaluation objective benchmark, the average evaluation being less than 1.5 times of initial bond power by the bounding force after test is "○", is "×" by the average evaluation more than 1.5 times.
Evaluation result is represented in table 8.Should illustrate, surface resistivity is with by " m × 10 + n" be designated as mode (wherein, m is arbitrary real number value, and n the is positive integer) record of " mE+n ".
Table 8
The bounding force of surface protection film under low peeling rate 0.3m/min of embodiment 1 ~ 9 is 0.04 ~ 0.2N/25mm, and the bounding force under high peeling rate 30m/min is below 2.0N/25mm, and surface resistivity is 9.0 × 10 + 11Ω/below, release band voltage is ± 0 ~ 0.5kV, is not transferring to adherend via stain after on binder layer ballpoint pen scraping rear surface protective membrane, 60 DEG C, to place 250 little weather resistance constantly under the atmosphere of 90%RH also excellent.
Namely, meet (1) under the peeling rate of low speed and peeling rate at a high speed, keep the balance of bounding force, it is residual that (2) prevent paste simultaneously, (3) excellent antistatic property, and whole requirement performance of (4) re-workability.
Because the surface protection film of comparative example 1 is containing (F) two more than sense isocyanate compound, (G) crosslinking catalyst, (H) keto-enol tautomerism body compound, thus gel fraction be 0%, little, the surface resistivity of bounding force under low peeling rate 0.3m/min and high peeling rate 30m/min and release band voltage is high, re-workability and poor durability.
Because two ester moieties of (D) polyalkylene glycol mono (methyl) acrylate monomer of the surface protection film of comparative example 2 are many, moisture containing ratio is high, solvability in water is low, containing (J) silicone compounds, so the bounding force under low peeling rate 0.3m/min and high peeling rate 30m/min is excessive, surface resistivity and release band voltage is high, poor durability.
Because two ester moieties of (D) polyalkylene glycol mono (methyl) acrylate monomer of the surface protection film of comparative example 3 are many, moisture containing ratio is high, solvability in water is low; so working life is too short; owing to having carried out gelation, so cannot be coated with before coating.
Because the averaged repeating numbers of the alkylene oxide of the polyalkylene glycol chain of formation (D) polyalkylene glycol mono (methyl) acrylate monomer of the surface protection film of comparative example 4 is large, two ester moieties are many, moisture containing ratio is high, solvability in water is low, not containing (G) crosslinking catalyst and (H) keto-enol tautomerism body compound, so polymerizability is poor, cannot be coated with because viscosity is bad.
Accordingly; in the surface protection film of comparative example 1 ~ 4; (1) cannot be met under low peeling rate and high peeling rate simultaneously; keep the balance of bounding force; (2) paste is prevented residual, whole requirement performance of the antistatic property that (3) are excellent and (4) re-workability.

Claims (14)

1. a binder composition, it is characterized in that, containing the acrylic acid polymer of multipolymer comprising co-polymerized monomer, described co-polymerized monomer is relative to 100 weight parts of described acrylic acid polymer, the carbonatoms of (A) alkyl containing 50 ~ 95 weight parts is (methyl) acrylate monomer of C4 ~ C18, 0.1 ~ 10 weight part as can (B) of set of monomers of copolymerization containing hydroxyl can the monomer of copolymerization, (C) of 0.1 ~ 1.0 weight part can the monomer of copolymerization containing carboxyl, (D) polyalkylene glycol mono (methyl) acrylate monomer of 8 ~ 50 weight parts, (E) vinyl monomer containing nitrogen not containing hydroxyl of 0.1 ~ 20 weight part or at least one contained in alkyl (methyl) acrylate monomer of alkoxyl group,
In addition; described binder composition, not containing silicone compounds, is the ionic compound of 25 ~ 50 DEG C and/or the ionic compound containing acryl containing (F) two isocyanate compound more than sense, (G) crosslinking catalyst, (H) keto-enol tautomerism body compound, (I) as the fusing point of static inhibitor.
2. binder composition according to claim 1, is characterized in that, relative to 100 weight parts of described acrylic acid polymer, contains:
Described (F) two isocyanate compound more than sense of 0.1 ~ 10 weight part,
Described (G) crosslinking catalyst of 0.001 ~ 0.5 weight part,
Described (H) keto-enol tautomerism body compound of 0.1 ~ 300 weight part, in addition,
The fusing point contained in described binder composition of described (I) static inhibitor be the ionic compound of 25 ~ 50 DEG C with the ionic compound containing acryl of copolymerization in described multipolymer add up to 0.01 ~ 5.0 weight part,
The averaged repeating numbers of the alkylene oxide of the formation polyalkylene glycol chain of described (D) polyalkylene glycol mono (methyl) acrylate monomer is 3 ~ 14, two ester moieties in monomer are less than 0.3%, and moisture containing ratio is less than 0.1% and solvability in water is turbidity value under 20% aqueous solution state is less than 2%.
3. binder composition according to claim 1 and 2, it is characterized in that, described (G) crosslinking catalyst is the crosslinking catalyst of metallo-chelate, and the crosslinking catalyst of described (G) metallo-chelate is 70 ~ 1000 relative to weight ratio (H)/(G) of described (H) keto-enol tautomerism body compound.
4. the binder composition according to any one of claims 1 to 3, it is characterized in that, described (B) can the monomer of copolymerization be to be selected from (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-hydroxyl ethyl ester, N-hydroxyl (methyl) acrylamide, N-hydroxymethyl (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide more than at least one containing hydroxyl.
5. the binder composition according to any one of Claims 1 to 4, it is characterized in that, described (C) can the monomer of copolymerization be selected from (methyl) vinylformic acid containing carboxyl, (methyl) carboxyethyl acrylates, (methyl) vinylformic acid carboxyl pentyl ester, 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 2-(methyl) acryloyl-oxyethyl tetrahydrophthalic acid.
6. the binder composition according to any one of Claims 1 to 5, it is characterized in that, described (D) polyalkylene glycol mono (methyl) acrylate monomer is selected from more than at least one in polyalkylene glycol mono (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate, oxyethyl group polyalkylene glycol (methyl) acrylate.
7. the binder composition according to any one of claim 1 ~ 6, is characterized in that, described binder composition gel fraction is after cross-linking 95 ~ 100%.
8. the binder composition of the record according to any one of claim 1 ~ 7, it is characterized in that, in the more than sense isocyanate compound of described (F) two, as two functional isocyanate compounds, being non-ring type aliphatic isocyanates compound, is the compound making diisocyanate cpd and diol compound react and generate, as diisocyanate cpd, be aliphatic diisocyanate, be selected from tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, one in lysinediisocyanate, as diol compound, comprises and is selected from 2-methyl isophthalic acid, ammediol, 2，2-dimethyl-1，3-propanediol, 2-methyl-2-propyl-1,3-PD, 2-ethyl-2-butyl-1,3-PD, 3-methyl isophthalic acid, 5-pentanediol, 2，2-dimethyl-1，3-propanediol monohydroxy pivalate, polyoxyethylene glycol, one in polypropylene glycol, as trifunctional isocyanates compound, comprises the isocyanuric acid ester body of hexamethylene diisocyanate compound, the isocyanuric acid ester body of isophorone diisocyanate compound, the adducts of hexamethylene diisocyanate compound, the adducts of isophorone diisocyanate compound, the biuret body of hexamethylene diisocyanate compound, the biuret body of isophorone diisocyanate compound, the isocyanuric acid ester body of tolunediisocyanate compound, the isocyanuric acid ester body of xylylene diisocyanate compound, the isocyanuric acid ester body of hydrogenation of benzene dimethylene diisocyanate compound, the adducts of tolunediisocyanate compound, the adducts of xylylene diisocyanate compound, the adducts of hydrogenation of benzene dimethylene diisocyanate compound.
9. the binder composition according to any one of claim 1 ~ 8, it is characterized in that, the bounding force under low peeling rate 0.3m/min making the binder layer of described binder composition cross-links is 0.04 ~ 0.2N/25mm, and the bounding force under high peeling rate 30m/min is below 2.0N/25mm.
10. the binder composition according to any one of claim 1 ~ 9, is characterized in that, makes the surface resistivity of the binder layer of described binder composition cross-links be 9.0 × 10 + 11Ω/below, release band voltage is ± 0 ~ 0.5kV.
11. 1 kinds of bonding films, is characterized in that, are to make the binder layer of the binder composition according to any one of crosslinked claim 1 ~ 10 be formed at the one or two sides of resin molding.
12. 1 kinds of surface protection films; it is characterized in that; make the binder layer of the binder composition according to any one of crosslinked claim 1 ~ 10 be formed at the one side of resin molding; via after on described binder layer ballpoint pen scratch-off surface protective membrane, stain does not transfer to adherend.
13. surface protection films according to claim 12, is characterized in that, the purposes as the surface protection film of polaroid uses.
14. surface protection films according to claim 13, is characterized in that, implement anti-charged and antifouling process in the side contrary with the side of the described binder layer being formed with described resin molding.
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