CN103242781A - Adhesive composition, adhesive film and surface-protective adhesive film - Google Patents

Adhesive composition, adhesive film and surface-protective adhesive film Download PDF

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Publication number
CN103242781A
CN103242781A CN2013100491371A CN201310049137A CN103242781A CN 103242781 A CN103242781 A CN 103242781A CN 2013100491371 A CN2013100491371 A CN 2013100491371A CN 201310049137 A CN201310049137 A CN 201310049137A CN 103242781 A CN103242781 A CN 103242781A
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China
Prior art keywords
methyl
binder composition
surface protection
film
protection film
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CN2013100491371A
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Chinese (zh)
Inventor
长仓毅
岛口龙介
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Fujimori Kogyo Co Ltd
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Fujimori Kogyo Co Ltd
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Priority to CN201710622246.6A priority Critical patent/CN107216825B/en
Publication of CN103242781A publication Critical patent/CN103242781A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention relates to an adhesive composition, an adhesive film and a surface-protective adhesive film. The invention provides an adhesive composition, an adhesive film and a surface-protective adhesive film using the adhesive composition. The adhesive composition, the adhesive film and the surface-protective adhesive film using the adhesive composition have excellent antistatic property, corrosion resistance, and low pollution. The adhesive composition is acrylic polymer which contains (meth)acrylate monomers with an alkyl carbon number of C1-C14 as main components, and comprises polyether compounds and ionic compounds with a melting point being more than 30 DEG C. The ionic compounds with a melting point being more than 30 DEG C are not alkali metal salts.

Description

Binder composition, bonding film and surface protection film
Technical field
The invention provides a kind of binder composition with antistatic property, and use this binder composition, form the bonding film of the binder layer with antistatic property and surface protection film at least one face of resin molding.Has excellent especially antistatic property according to bonding film of the present invention and surface protection film.Therefore, surface protection film of the present invention can be used in the purpose on the blooming surface of Polarizer that protection uses as building block with the plastic film that is easy to generate static, polarizer, antireflection film etc.
Background technology
All the time, in the manufacturing process of the blooming that constitutes the Polarizer of liquid-crystal display, polarizer, antireflection film etc., at the temporary transient coating surface protective membrane in the surface of blooming.When blooming is assembled into liquid-crystal display, surface protection film is peeled off and removed from blooming.For the surface protection film of protecting the blooming surface only uses, therefore, be also referred to as the operation film in manufacturing process.
The surface protection film that uses in the operation of making blooming forms binder layer in the one side with the polyethylene terephthalate of optical transparence (PET) resin molding.In addition, before fitting in blooming, will fit in for the stripping film of being stripped from processing of protecting this binder layer binder layer above.
And; because the blooming of Polarizer, polarizer, antireflection film etc.; be fitted with under the state of surface protection film; carry out the examination and test of products of the optical assessment that display capabilities, colourity, contrast gradient, impurity with LCD panel sneaks into etc.; therefore; for the surface protection film necessary performance be non-cohesive bubble or impurity in binder layer.
And, in recent years, need be at the antistatic property that surface protection film is prevented the excellence of static when the blooming of Polarizer, polarizer, antireflection film etc. is peeled off.This is because during from adherend release adhesive layer, and the charged electric control circuit of liquid-crystal display that might make when being accompanied by the peeling off of the generation of static electricity that produces breaks down.
And, even require blooming with Polarizer, polarizer, antireflection film etc. to fit in for example binder composition that also do not corrode, that have erosion resistance on the bezel (ベ ゼ Le) etc. of metallic adherend.
And, require not pollute adherend from as the blooming stripper surface protective membrane of the Polarizer of adherend, polarizer, antireflection film etc. the time, namely do not produce adhesive residue.
Like this, in recent years, from being suitable for using the easy-to-use viewpoint of surface protection film, the performance that requires as for the binder layer that constitutes surface protection film requires: (1) has excellent antistatic property; (2) has erosion resistance; (3) prevent the generation etc. of adhesive residue.
Yet; though can satisfy as the independent performance that requires respectively for these (1)～(3) that require performance of the binder layer that constitutes surface protection film, all that are very difficult to satisfy simultaneously desired in the binder layer of surface protection film (1)～(3) require performance.
For example, about having excellent antistatic property, as the method for giving the surface protection film antistatic property, show and mediate into the method for static inhibitor to base material film etc.As static inhibitor, for example disclose (a) and had quaternary ammonium salt, pyridinium salt, uncle to the various cationic antistatic agents of the cation radical of uncle amino etc.; (b) has the anionic antistatic agents of the anion-radicals of sulphonate-base, sulfuric ester alkali, phosphoric acid ester alkali, phosphonic acids alkali etc.; (c) non-ionic antistatic agent of the both sexes static inhibitor of amino acids, amidosulphuric acid ester class etc., (d) alkamine, glycerols, polyethylene glycols etc.; (e) (patent documentations 1) such as polymer static inhibitor that aforesaid static inhibitor polymer quantification is obtained.
And, in recent years, not only propose to be included in such static inhibitor in the base material film or to coat the base material film surface, also propose directly to make binder layer contain such static inhibitor.
And, as static inhibitor use an alkali metal salt in the past, for example, disclose in the patent documentation 2 as the ionic species in (methyl) acrylic polymers, use a kind in the alkaline earth salt of an alkali metal salt that is selected from an alkali metal salt of perchloric acid, the alkaline earth salt of perchloric acid, organic boron complex and organic boron complex.But, contain the binder composition of the static inhibitor that is formed by an alkali metal salt, owing to have metal protection, therefore, be under the situation of metal at adherend, corrode.Therefore, the binder composition that need when having excellent antistatic property, have erosion resistance.
And, about preventing the generation of adhesive residue, for example proposed to mix the stiffening agent of isocyanate ester compound and specific silicate oligopolymer in the acrylic resin with 0.0001 ~ 10 weight part and the binder composition (patent documentation 3) that obtains for acrylic resin 100 weight parts.
In the patent documentation 3, be that the carbonatoms of about 2 ~ 12 alkyl acrylate, alkyl is that alkyl methacrylate of about 4 ~ 12 etc. is the principal monomer composition with the carbonatoms of alkyl, for example, can comprise monomer component monomer of containing carboxyl etc., that contain other functional group.Usually, preferably contain the above above-mentioned principal monomer of 50 weight %, and the content that hope contains the monomer component of functional group is 0.001 ~ 50 weight %, preferred 0.001 ~ 25 weight %, more preferably 0.01 ~ 25 weight %.Even since in the patent documentation 3 binder composition of record at high temperature or hot and humid down, cohesive force and bounding force through the time to change also be little, and, to also showing outstanding effect in the bounding force of curved surface, in addition, the foaming of tackiness agent or peel off does not take place.
Usually, if binder layer is made flexible proterties, then adhesive residue becomes and takes place easily.That is, become easily and peel off difficulty, the difficulty of fitting again when fitting mistakenly.Therefore, need to have functional group monomer crosslinked on host of carboxyl etc., binder layer is made certain rigidity, prevent the generation of adhesive residue.
In addition, about preventing the generation of adhesive residue, known have a following motion.Be that (methyl) alkyl acrylate and the multipolymer of copolymerization that contains carboxyl of the alkyl below 7 is as main component to have carbonatoms, with linking agent it is carried out crosslinking Treatment and obtain the acrylic adhesives layer, after fitting with this binder layer through for a long time, then tackiness agent to the transfer of adherend one side and for the bounding force of adherend through the time rise.In order to address this problem known following tackiness agent (pressure sensitive adhesive): it is that (methyl) alkyl acrylate of 8 ~ 10 alkyl is with the multipolymer with copolymerization compound of alcohol hydroxyl group, obtain (patent documentation 4) with linking agent to its crosslinking Treatment that described tackiness agent has carbonatoms by use.
Following tackiness agent etc. is also proposed: described tackiness agent by mixed with little amount (methyl) alkyl acrylate in above-mentioned same multipolymer with the multipolymer that contains the copolymerization compound of carboxyl, with linking agent its crosslinking Treatment is obtained.But surface tension is low when these tackiness agents are used for, during the surface protection of ganoid plastic plate etc., has owing to add man-hour or add the phenomenon of peeling off that thermogenesis floats etc. when preserving.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese patent laid-open 11-070629 communique
[patent documentation 2] Japanese Patent spy opens the 2006-199873 communique
[patent documentation 3] Japanese patent laid-open 8-199130 communique
[patent documentation 4] Japanese Patent spy opens clear 63-225677 communique
Summary of the invention
[problem that invention will solve]
The binder composition with antistatic property in the past in the purposes that requires excellent antistatic property, uses an alkali metal salt as the static inhibitor that it is contained.But, if use an alkali metal salt, then under adherend is the situation of metal, corrode.In addition, therefore surface protection film in the past can not satisfy the desired performance that requires of the binder layer that uses owing to the contaminative that has for adherend in surface protection film.
The present invention has used for reference above-mentioned situation.Problem of the present invention provides a kind of binder composition, uses its bonding film and surface protection film, and described binder composition has excellent antistatic property, and has erosion resistance, and contaminative is low.
[solving the method for problem]
Binder composition of the present invention will contain fusing point at the ionic compound more than 30 ℃, have erosion resistance, obtain excellent antistatic property as technological thought.In addition, owing to contain (methyl) acrylic monomer with hydroxyl, it is few to access adhesive residue, the binder composition that contaminative is low.Have excellent antistatic property by using such binder composition, can providing, and have erosion resistance, the binder composition that contaminative is low uses its bonding film and surface protection film.
In order to solve aforementioned problems, the invention provides a kind of binder composition, it is that to contain carbonatoms with alkyl be that (methyl) acrylate monomer of C1 ~ C14 is the binder composition of (methyl) acrylic polymers of main component, and described binder composition contains polyether compound and fusing point at the ionic compound more than 30 ℃.
Preferred aforementioned fusing point is not an alkali metal salt at the ionic compound more than 30 ℃.
Preferred aforementioned polyether compound is the compound that contains oxyethylene group.
Preferred aforementioned polyether compound and the copolymerization of aforementioned (methyl) acrylic polymers.
Preferably the acid number of aforementioned (methyl) acrylic polymers is below 1.0.
Preferably aforementioned (methyl) acrylic polymers contains (methyl) acrylic monomer with hydroxyl.
In addition, the invention provides bonding film, it is formed at the one or both sides of resin molding by the crosslinked binder layer that forms of aforementioned adhesion agent composition.
In addition, the invention provides surface protection film, it is formed in the one side of resin molding by the crosslinked binder layer that forms of aforementioned adhesion agent composition, wherein, when described surface protection film is peeled off from adherend, does not have the pollution transportation to adherend.
The aforementioned surfaces protective membrane preferably uses as the purposes of the surface protection film of Polarizer.In addition, preferred, forming the opposite face of side with aforementioned adhesion agent layer and carry out antistatic and anti-pollution processing at the aforementioned resin film.
[effect of invention]
According to the present invention, can provide to have excellent antistatic property and have the low binder composition of erosion resistance, contaminative for adherend and use it and the bonding film and the surface protection film that form.
Embodiment
Below, based on embodiment preferred explanation the present invention.
Binder composition of the present invention is that to contain carbonatoms with alkyl be that (methyl) acrylate monomer of C1 ~ C14 is the binder composition of (methyl) acrylic polymers of main component, and described binder composition contains polyether compound and fusing point at the ionic compound more than 30 ℃.
Carbonatoms as alkyl is (methyl) acrylate monomer of C1 ~ C14, can enumerate: (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid pentyl ester, (methyl) Ethyl acrylate, (methyl) vinylformic acid heptyl ester, (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) vinylformic acid undecyl ester, (methyl) dodecylacrylate, (methyl) tridecyl acrylate, (methyl) vinylformic acid tetradecyl ester, (methyl) vinylformic acid ring pentyl ester, (methyl) cyclohexyl acrylate etc.The alkyl of (methyl) alkyl acrylate monomer can be for straight chain, side chain, ring-type any.To be C1 ~ C14's (methyl) acrylate monomer be preferably 50 ~ 100% with respect to the weight ratio of (methyl) acrylic polymers to the carbonatoms of alkyl.
(methyl) acrylic polymers preferably contains (methyl) acrylic monomer with hydroxyl.As (methyl) acrylic monomer with hydroxyl, can enumerate: (methyl) vinylformic acid hydroxyalkyl acrylate class of (methyl) vinylformic acid 8-hydroxyl monooctyl ester, the own ester of (methyl) vinylformic acid 6-hydroxyl, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxy methacrylate etc.; (methyl) acrylic amide that contains hydroxyl of N-hydroxyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-hydroxyethyl (methyl) acrylamide etc. etc.
(methyl) acrylic polymers can contain the copolymerisable monomer with carboxyl.As the copolymerisable monomer that contains carboxyl, can enumerate: (methyl) vinylformic acid, methylene-succinic acid, Ba Dousuan, toxilic acid, fumaric acid, (methyl) vinylformic acid carboxylic ethyl ester, (methyl) vinylformic acid carboxylic pentyl ester etc.
In addition, (methyl) acrylic polymers also can contain above-mentioned copolyethylene monomer in addition.As other copolyethylene monomer, can enumerate: (methyl) benzyl acrylate, (methyl) vinylformic acid phenoxy ethyl etc. contains (methyl) esters of acrylic acid of aromatic base, and various vinyl monomers such as vinylbenzene, acrylamide, vinyl cyanide, methylvinylether, ethyl vinyl ether, vinyl acetate, ethylene chloride.
But if the undue monomer (hereinafter referred to as acid monomer) that adds the demonstration acidity of the monomer that contains carboxyl etc., then because these acid, probably corrodibility can become big.Therefore, the acid number of (methyl) acrylic polymers is preferably below 1.0.
This paper, " acid number " is one of index of expression acid content, its with in and the mg numerical table of 1g with needed potassium hydroxide of polymkeric substance of acidic component show.
Binder composition of the present invention contains polyether compound.Can enumerate as polyether compound, for the polyether polyol of the polyalkylene glycol of compound with polyoxyalkylene (Port リ ア Le キ レ Application オ キ サ イ De base) etc. with and derivative.As the alkylidene group that polyalkylene glycol and polyoxyalkylene have, can enumerate ethylidene, propylidene, butylidene etc., this is non-limiting.Polyalkylene glycol also can be the multipolymer of the polyalkylene glycol more than 2 kinds of polyoxyethylene glycol, polypropylene glycol, polytetramethylene glycol etc.As the multipolymer of polyalkylene glycol, can enumerate polyethylene glycol-propylene glycol, polyethylene glycol-butyleneglycol, polypropylene glycol-polytetramethylene glycol, polyethylene glycol-propylene glycol-polytetramethylene glycol etc., this multipolymer can be segmented copolymer, random copolymers.
Derivative as polyalkylene glycol can be enumerated, the polyoxyalkylene monoalky lether, the polyoxyalkylene alkyl of polyoxyalkylene dialkyl ether etc., polyoxyalkylene mono-alkenyl ether, the polyoxyalkylene alkenyl ether of polyoxyalkylene two alkenyl ethers etc., polyoxyalkylene list aryl ethers, the polyoxyalkylene aryl ethers of polyoxyalkylene diaryl ether etc., the polyoxyalkylene alkyl phenyl ether, the polyoxyalkylene diols mono fatty acid ester, the polyoxyalkylene diols fatty acid ester of polyoxyalkylene diols di fatty acid ester etc., the polyoxyalkylene sorbitan fatty acid esters, the polyoxyalkylene alkylamine, polyoxyalkylene diamines, polyether-modified silicone compounds etc.
Herein, as the alkyl oxide in the polylalkylene glycol derivatives, can enumerate the lower alkyl ether of methyl ether, ethyl ether etc., the senior alkyl ether of lauryl ether, octadecyl ether etc.As the alkenyl ether in the polylalkylene glycol derivatives, can enumerate vinyl ether, allyl ethers, oleyl ether etc.In addition, as the fatty acid ester in the polylalkylene glycol derivatives, can enumerate the unsaturated fatty acid ester of the polyunsaturated fatty acid ester, (methyl) acrylate, oleic acid ester etc. of acetic ester, stearate etc.
As polyether-modified silicone compounds, can enumerate dimethyl siloxane methyl (polyoxyethylene) silicone copolymers, dimethyl siloxane methyl (polyoxyethylene) siloxanes methyl (polyoxytrimethylene) silicone copolymers, dimethyl siloxane methyl (polyoxytrimethylene) silicone copolymers etc.
Polyether compound preferably contains the compound of oxyethylene group, preferably contains the compound of polyoxyethylene thiazolinyl.
Polyether compound has under the situation of polymerizability functional group, can with the copolymerization of (methyl) acrylic polymers.As polymerizability functional group, the vinyl functional group of preferred (methyl) acryl, vinyl, allyl group etc.As the polyether compound with polymerizability functional group, can enumerate polyalkylene glycol mono (methyl) acrylate, polyalkylene glycol two (methyl) acrylate, alkoxyl group polyalkylene glycol (methyl) acrylate, polyalkylene glycol mono allyl ethers, polyalkylene glycol diallyl ether, alkoxyl group polyalkylene glycol allyl ethers, polyalkylene glycol mono vinyl ether, polyalkylene glycol divinyl ether, alkoxyl group polyalkylene glycol vinyl ether etc.
In order to give binder composition antistatic property of the present invention, preferably it contains static inhibitor.Static inhibitor is solid under normal temperature (for example 30 ℃) preferably, more specifically, is that fusing point is at the ionic compound more than 30 ℃.Such static inhibitor, because lower than an alkali metal salt fusing point, and, owing to have the alkyl of long-chain, infer it and acrylic copolymer has high affinity.
As fusing point at the ionic compound more than 30 ℃, for having the ionic compound of positively charged ion and negatively charged ion, can enumerate following compound: positively charged ion is cationic nitrogenous or phosphorus positively charged ion, the sulphur positively charged ion etc. of pyridinium positively charged ion, glyoxaline cation, pyrimidine positively charged ion, pyrazoles positively charged ion, pyrroles's positively charged ion, ammonium positively charged ion etc., and negatively charged ion is phosphorus hexafluoride acid group (PF 6 -), thiocyanate ion (SCN -), benzene sulfonamide acid group (RC 6H 4SO 3 -), perchlorate (ClO 4 -), tetrafluoride borate (BF 4 -) compound of the inorganic or organic anion that waits.By selecting chain length or substituent position, the number etc. of alkyl, can access fusing point at the material more than 30 ℃.Preferred season of positively charged ion cationic nitrogenous, can enumerate: the 1-alkyl pyridine drone (2 ~ 6 carbon atom has substituting group also passable, also can not have replace) etc. season pyridinium positively charged ion, 1, the quaternary ammonium cation of the season glyoxaline cation of 3-dialkylimidazolium (2,4,5 carbon atom has substituting group also passable, also can not have replace) etc., tetraalkyl ammonium etc. etc.The fusing point of ionic compound is preferably 30 ~ 80 ℃.As the substituting group that positively charged ion can have, can enumerate alkyl, aryl etc.Aforementioned ionic compound is owing to be not an alkali metal salt, and an alkali metal salt that therefore can solve prior art has the problem of metal protection.
The host of using in the binder composition of the present invention (methyl) acrylic polymers can by with the carbonatoms of the alkyl more than a kind or 2 kinds as (methyl) acrylate monomer of C1 ~ C14 as main component, add other monomer as required, make its polymerization and synthesize.The polymerization process of (methyl) acrylic polymers does not limit especially, can use suitable polymerization processs such as solution polymerization, letex polymerization.
Binder composition of the present invention is cross-linked binder polymkeric substance when forming binder layer preferably.As making its method of carrying out crosslinking reaction, binder composition can contain known linking agent, also can make it crosslinked by the photo-crosslinking of ultraviolet ray (UV) etc.As linking agent, can enumerate: the isocyanate compound that 2 functional groups or 3 functional groups are above, the epoxy compounds that 2 functional groups or 3 functional groups are above, the acrylic compound that 2 functional groups or 3 functional groups are above, metal-chelating compounds etc.
In addition, as other composition, the known additive of mixed silanes coupling agent, antioxidant, tensio-active agent, crosslinking accelerator, softening agent, weighting agent, hardening accelerator, sclerosis inhibitor, processing aid, antiaging agent etc. suitably.Can be used singly or two or more kinds in combination these additives.
Make the surface resistivity of the crosslinked binder layer that obtains of aforementioned adhesion agent composition preferably 5.0 * 10 + 10Below Ω/.In addition, the stripping charge of this binder layer is pressed and is preferably ± 0 ~ 1kV.In addition, in the present invention, described " ± 0 ~ 1kV " meaning is 0 ~-1kV and 0 ~+1kV, that is ,-1 ~+1kV.Because surface resistivity bleeds off when big when peeling off because the poor performance of the static of charged generation, therefore, by making surface resistivity enough little, can reduce the stripping charge that the static that produces when following from adherend release adhesive layer generates and press, suppress the influence to the electric control circuit of adherend etc.
Make the gel fraction of the binder layer (tackiness agent after crosslinked) that binder composition cross-links of the present invention obtains be preferably 95 ~ 100%.Like this, because the gel fraction height, the bounding force when low speed is peeled off does not become excessive, reduces from the stripping of unconverted monomer or the oligomer of multipolymer, improves anti fouling performance, the weather resistance in hot and humid, suppresses the pollution of adherend.
Bonding film of the present invention is the bonding film that binder layer that binder composition cross-links of the present invention obtains is formed at the one or both sides of resin molding.In addition, surface protection film of the present invention is the surface protection film that binder layer that binder composition cross-links of the present invention obtains is formed in the one side of resin molding.Binder composition of the present invention is owing to have excellent antistatic property; and has the erosion resistance for adherend; contaminative is low; therefore; surface protection film of the present invention is fitted on the adherend; namely use ballpoint pen via binder layer after surface protection film is described, peel off from adherend, also transferring the pollution to adherend not.Therefore, surface protection film of the present invention can suitably use as the purposes of the surface protection film of Polarizer.
Can use the resin molding of polyester film etc. etc. as the stripping film (partition) of the base material film of binder layer, protection adhesive face.
In base material film, forming on the opposite face of side with binder layer of resin molding, can implement the anti-pollution processing by releasing agent or coating-forming agent, the silicon dioxide microparticle etc. of silicone, fluorine class; The antistatic treatment of the coating by static inhibitor or kneading etc.
In stripping film, on binder layer and the face adhesive face adhesive side, implement the demoulding of the releasing agent etc. by silicone, fluorine class and handle.
Polarizer with the optics of surface protection film etc. with in the situation of surface protection film, base material film and binder layer preferably have enough transparencys.
[embodiment]
Below, specify the present invention by embodiment.
The preparation of＜binder composition＞
[embodiment 1]
In the reaction unit that is equipped with agitator, thermometer, reflux exchanger and nitrogen ingress pipe, import nitrogen, with the air nitrogen replacement in the reaction unit.Then, in reaction unit, add 2-EHA 100 weight parts, vinylformic acid 2-hydroxy methacrylate 3.5 weight parts and solvent (ethyl acetate) 100 weight parts.Then, through Diisopropyl azodicarboxylate 0.1 weight part that splashed into as polymerization starter in 2 hours, make its reaction 8 hours in 65 ℃, obtain acrylic copolymer solution.Adopt the part of acrylic copolymer as the working sample use of following acid number.
For this acrylic copolymer solution, the isocyanuric acid ester body of interpolation 1-octyl group pyridinium phosphorus hexafluoride hydrochlorate 1.5 weight parts, コ ロ ネ ー ト HX(hexamethylene diisocyanate compound) 1.5 weight parts, two lauric acid dioctyl tins, 0.1 weight part, polyoxyethylene glycol (molecular weight 400) 1.0 weight parts, mix, obtain the binder composition of embodiment 1.
[embodiment 2 ~ 4 and comparative example 1 ~ 3]
Each such setting of putting down in writing according to table 1 of the composition of monomer and additive, in addition, according to the binder composition of above-described embodiment 1 similarly, obtain the binder composition of embodiment 2 ~ 4 and comparative example 1 ~ 3.
Herein, (A) material (embodiment 4) of copolymerization among acrylic monomer, (B) carboxylic monomer, (B ') acid monomer, (C) polyether compound, as monomer, before the polymerization of acrylic copolymer solution, add in the reaction unit, (C) material of non-polymerization (embodiment 1 ~ 3), (D) isocyanic ester (NCO) linking agent, (E) crosslinking accelerator, (F) static inhibitor among the polyether compound join in the acrylic copolymer solution after the polymerization as additive.
In the table 1, the blending ratio of each composition encloses with bracket, and expression is the numerical value of the desired weight part of 100 weight parts with the summation of (A) group.And, the compound title of the abbreviation correspondence of each composition that uses in the indicator gauge 1 in the table 2.In addition, コ ロ ネ ー ト (registered trademark) HX and same HL and same L-45 are the trade(brand)names of Japanese Port リ ウ レ タ Application Industrial Co., Ltd, and タ ケ ネ ー ト (registered trademark) D-140N is the trade(brand)name of Mitsui Chemicals, Inc.About the compound title of isocyanic ester (NCO) linking agent of table 2, the meaning of HDI, IPDI, TMP is respectively hexamethylene diisocyanate, isophorone diisocyanate, TriMethylolPropane(TMP).
Table 1
Figure BDA00002830247200091
Figure BDA00002830247200101
Table 2
Figure BDA00002830247200102
The preparation of＜surface protection film＞
The binder composition of embodiment 1 is coated by after on the film formed stripping film of polyethylene terephthalate (PET) of silicone coating, and by in 90 ℃ dry desolventizing, the thickness that obtains binder layer is the adhesive sheet of 25 μ m.Then; adhesive sheet is transferred to one side goes up the reverse side through antistatic and anti-pollution treated side through polyethylene terephthalate (PET) film of antistatic and anti-pollution processing, had the surface protection film of embodiment 1 of the laminar structure of " through the PET of antistatic and anti-pollution processing film/binder layer/stripping film (the PET film of silicone coating) ".
[embodiment 2 ~ 4 and comparative example 1 ~ 3]
Use the binder composition of embodiment 2 ~ 4 and comparative example 1 ~ 3 to replace the binder composition of embodiment 1 respectively, in addition same with the surface protection film of above-described embodiment 1, obtain the surface protection film of embodiment 2 ~ 4 and comparative example 1 ~ 3.
＜test method and evaluation＞
With the surface protection film in embodiment 1 ~ 4 and the comparative example 1 ~ 3 after under 23 ℃, the atmosphere of 50%RH aging 7 days; peel off stripping film (the PET film of silicone coating); after the material that will expose binder layer fits on the aluminium foil; under 60 ℃, the hot and humid atmosphere of 90%RH, placed 48 hours, then with it as corrosive working sample.
And then; via binder layer this surface protection film that exposes binder layer is fitted in the surface that sticks on the Polarizer on the liquid crystal cell; place after 1 day; handle through 50 ℃, 5 normal atmosphere, 20 minutes autoclave; further placed 12 hours in room temperature, will be through the specimen of the above material that obtains as bounding force, stripping charge pressure.
The measuring method of＜acid number 〉
The acid number of acrylic copolymer, with sample dissolution in solvent (material that diethyl ether and ethanol mix 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, be that the potassium hydroxide-ethanol solution of about 0.1mol/l carries out the potential difference titration with concentration, measure in and the amount of the required potassium hydroxide-ethanol solution of sample.Then, try to achieve acid number by following formula.
Acid number=(B * f * 5.611)/S
The amount (ml) of the 0.1mol/l potassium hydroxide-ethanol solution that uses in the B=titration
The factor of f=0.1mol/l potassium hydroxide-ethanol solution
The quality of the solids component of S=sample (g)
The mensuration of＜bounding force＞
With following stripping strength as bounding force: use tension testing machine to peel off the stripping strength of measuring by the above-mentioned specimen that obtains (at the material of the wide surface protection film of Polarizer surface applying 25mm) (N/25mm) with draw speed to 180 ° of directions as 30m/min.
The measuring method that＜stripping charge is pressed＞
When peeling off the specimen that obtains as mentioned above with 180 ° of the draw speeds of 30m/min, use high precision electrostatic transducer SK-035, SK-200 (the キ ー エ of Co., Ltd. Application ス manufacturing) to measure the voltage (with voltage) of the charged generation of Polarizer, press (kV) with the maximum value of measured value as stripping charge.
＜corrosive evaluation method＞
After fitting in sample on the aluminium foil, under the hot and humid condition of 60 ℃ * 90%RH, placed 48 hours.Then, from the aluminium foil peel sample, the Visual Confirmation aluminium foil surface is with following benchmark evaluation.
Zero: aluminium foil surface variable color unconfirmed.
△: confirm a part of variable color of aluminium foil surface.
*: confirm the aluminium foil surface variable color.
The evaluation method of＜contaminative 〉
, after describing by the surface protection film of the above-mentioned specimen that obtains, placed in 70 ℃ * 24 hours with ballpoint pen (load 500g, reciprocal 3 times).From Polarizer stripper surface protective membrane, observe the Polarizer surface, confirm not transfer the pollution to Polarizer, use following benchmark evaluation.
Zero: do not transfer the pollution to Polarizer.
△: confirm to transfer the pollution at least a portion along the track that ballpoint pen is described.
*: confirm to transfer the pollution along the track that ballpoint pen is described, also have tackiness agent to break away from from adhesive surface.
Table 3
Figure BDA00002830247200121
Show test and the result who estimates in the table 3.
In the embodiment 1 ~ 4 of the ionic compound more than 30 ℃ as static inhibitor, form the antistatic property excellence with fusing point, and had also low material of erosion resistance for adherend, contaminative.
In static inhibitor, use in the comparative example 1 of lithium perchlorate, formed that corrodibility is big, also high slightly material of contaminative.
In static inhibitor, use in the high comparative example 2 of the acid number of acrylic polymers of two (fluoroform sulphonyl) imines lithiums, tackiness agent, formed stripping charge press high, antistatic property is poor, also big slightly material of contaminative height, corrodibility.
In static inhibitor, use in the comparative example 3 of trifluoromethanesulfonic acid lithium, formed that corrodibility is big slightly, also high slightly material of contaminative.
Therefore, the surface protection film of comparative example 1 ~ 3 can not satisfy (1) excellent antistatic property simultaneously, (2) erosion resistance, and (3) prevent the generation of adhesive residue.

Claims (15)

1. binder composition, it is that to contain carbonatoms with alkyl be that (methyl) acrylate monomer of C1 ~ C14 is the binder composition of (methyl) acrylic polymers of main component, and described binder composition contains polyether compound and fusing point at the ionic compound more than 30 ℃.
2. binder composition according to claim 1, wherein said fusing point is not an alkali metal salt at the ionic compound more than 30 ℃.
3. binder composition according to claim 1 and 2, wherein said polyether compound is the compound that contains oxyethylene group.
4. binder composition according to claim 1 and 2, wherein said polyether compound and the copolymerization of described (methyl) acrylic polymers.
5. binder composition according to claim 1 and 2 is characterized in that the acid number of described (methyl) acrylic polymers is below 1.0.
6. binder composition according to claim 1 and 2 is characterized in that described (methyl) acrylic polymers contains (methyl) acrylic monomer with hydroxyl.
7. bonding film, it is formed at the one or both sides of resin molding by the binder layer that claim 1 or 2 described binder composition cross-links form.
8. bonding film, it is formed at the one or both sides of resin molding by the binder layer that the described binder composition cross-links of claim 3 forms.
9. bonding film, it is formed at the one or both sides of resin molding by the binder layer that the described binder composition cross-links of claim 4 forms.
10. bonding film, it is formed at the one or both sides of resin molding by the binder layer that the described binder composition cross-links of claim 5 forms.
11. a bonding film, it is formed at the one or both sides of resin molding by the binder layer that the described binder composition cross-links of claim 6 forms.
12. a surface protection film, it is formed in the one side of resin molding by the binder layer that claim 1 or 2 described binder composition cross-links form, and wherein, when described surface protection film is peeled off from adherend, does not have the pollution transportation to adherend.
13. surface protection film according to claim 12, its purposes as the surface protection film of Polarizer is used.
14. surface protection film according to claim 12, its face opposite with described binder layer formation side at described resin molding carries out antistatic and anti-pollution processing.
15. surface protection film according to claim 13, its face opposite with described binder layer formation side at described resin molding carries out antistatic and anti-pollution processing.
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