CN108865017A - Adhesion agent composition and surface protection film - Google Patents

Adhesion agent composition and surface protection film Download PDF

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Publication number
CN108865017A
CN108865017A CN201711126884.5A CN201711126884A CN108865017A CN 108865017 A CN108865017 A CN 108865017A CN 201711126884 A CN201711126884 A CN 201711126884A CN 108865017 A CN108865017 A CN 108865017A
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methyl
weight
parts
agent composition
film
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CN108865017B (en
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长仓毅
大津贺健太郎
吉田弘幸
铃木史惠
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
    • 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
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • 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
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C09J133/066—Copolymers with monomers not covered by C09J133/06 containing -OH groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C09J11/04—Non-macromolecular additives inorganic
    • 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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • 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
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • 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
    • C09J2433/00—Presence of (meth)acrylic polymer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Polarising Elements (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention provides a kind of under the peeling rate of low speed and the peeling rate of high speed, the balancing good of adhesion strength, and has stain resistance, the adhesion agent composition and surface protection film of the excellent antistatic property with excellent adhesive performance and non-deterioration.The adhesion agent composition contains made of making the carboxylic copolymerisable monomer copolymerization of (methyl) acrylate monomer of the carbon atom number C1~C18 of (A) alkyl, the copolymerisable monomer of (B) hydroxyl, (C), the acrylic polymer for the copolymer that acid value is 0.1~1.0, in (methyl) acrylate monomer that the carbon atom number of (A) alkyl of 100 parts by weight is C1~C18, acrylic acid-2-ethyl caproite is contained with ratios more than 70 parts by weight；Crosslinking agent is the isocyanate compound of (D) trifunctional or more；Antistatic agent be F7 or more with number of fluorine atoms anion, ionic compound that fusing point is 25~50 DEG C.

Description

Adhesion agent composition and surface protection film
Technical field
The present invention relates to a kind of adhesion agent composition and surface protection film containing antistatic agent.It more specifically, is one Kind is by being attached on the polarizing film for constituting liquid crystal display, for the surface protection film on the surface of protection polarizing film is used , the adhesion agent composition of excellent antistatic property with excellent adhesive performance and non-deterioration, and used this The surface protection film of adhesion agent composition.
Background technique
Back and forth, in the manufacturing process as optical components such as the polarizing films of component for constituting liquid crystal display, patch With the surface protection film on the surface for temporary protection optical component.Such surface protection film is only used for manufacture optical component Process in, when optical component is installed on liquid crystal display, it is removed to removing from optical component.Due to only manufacturing The surface protection film on the surface in process using such for protecting optical component, therefore it is also generally referred to as process film.
For the surface protection film used in the process of manufacture optical component like this, with optical clear Adhering agent layer is formed on the single side of polyethylene terephthalate (PET) resin film of property.Fit in optical component it Before, the mold release film through demoulding processing for protecting the adhering agent layer is fitted on adhering agent layer.
In addition, the optical components such as polarizing film are received with being fitted with the state of surface protection film with the aobvious of LCD panel Show that ability, tone, contrast, foreign matter such as are mixed at the product examination of optical evaluation.Therefore, as the demand to surface protection film Performance, it is desirable that the low molecular weight compositions of no bubble or foreign matter and adhesion agent composition are attached on adhering agent layer, that is, require tool There is stain resistance.
In addition, adhering when being removed from the optical components such as polarizing film surface protection film with being removed from adherend Generated electrostatic when oxidant layer and the removing electrostatic generated may generate the failure of the electric control circuit of liquid crystal display It influences.It is therefore desirable to which adhering agent layer has excellent antistatic property.
Further, in recent years, as the protective layer (otherwise referred to as protective film) of the polarizer of polarizing film, in addition to previous Other than triacetyl cellulose (TAC), expanding to the acrylic resins such as removing polymethyl methacrylate (PMMA), poly- pair The surface of the polarizing film of the polyester resins such as ethylene terephthalate (PET), cyclic olefin quasi polymer, polycarbonate etc. is protected The utilization of the material of removing electrostatic is easily caused when cuticula.Therefore, the adhering agent layer of the surface protection film of polarizing film is sought The antistatic property asked must be more excellent than previous.
Furthermore, it is desirable that when finally removing surface protection film from the optical components such as polarizing film, can rapidly be removed. That is, in order to even if high speed remove when can rapidly remove, it is desirable that adhesion strength due to peeling rate caused by variation it is small.
Like this, in recent years, from the angle for using difficulty when using surface protection film, as to composition surface The required performance of the adhering agent layer of protective film, it is desirable that：(1) it under the peeling rate of low speed and the peeling rate of high speed, is glued The balance puted forth effort；(2) there is stain resistance；(3) excellent antistatic property etc..
However, allowing to meet respectively as the above-mentioned of the required performance to the adhering agent layer for constituting surface protection film (1) each required performance in~(3), but meet the complete of (1)~(3) sought the adhering agent layer of surface protection film simultaneously The required performance in portion is extremely difficult technical problem.
In order to solve such technical problem, for example, about (1) in the peeling rate of low speed and the peeling rate of high speed Under, obtain the balance of adhesion strength；(2) there is stain resistance；And the antistatic property that (3) are excellent, it is known to following motion.
About (1) under the peeling rate of low speed and the peeling rate of high speed, the balance of adhesion strength is obtained, with carbon Atomicity is that (methyl) alkyl acrylate of 7 alkyl below and the copolymer of carboxylic copolymerizable compound are used as mainly Ingredient in the adhering agent layer for carrying out acrylic compounds made of crosslinking Treatment to it by crosslinking agent, exists in long-time bonding In the case of, sticker transfer adheres to adherend side, or to the bonding force of adherend through when ascending big problem.In order to keep away Exempt from these problems, it is known to which one kind is provided with adhering agent layer person, and it is 8~10 that the adhering agent layer, which is using with carbon atom number, The copolymer of (methyl) alkyl acrylate of alkyl and the copolymerizable compound with alcohol hydroxyl group, it is total to this by crosslinking agent Polymers carries out adhering agent layer (patent document 1) made of crosslinking Treatment.
In addition, also the motion person etc. that is provided with adhering agent layer, the adhering agent layer are into copolymer same as described above A small amount of copolymer for blending (methyl) alkyl acrylate and carboxylic copolymerizable compound, by crosslinking agent to the copolymer Carry out adhering agent layer made of crosslinking Treatment.However, if they to be used for the table of low, plastic plate of smooth surface of surface tension etc. Face protection generates due to then there is heating when processing or when preservation and the peelings such as floats, or there are handworks The problem of releasable difference when in field to remove at a high speed.
In order to solve these problems, propose a kind of adhesion agent composition, wherein to a) with carbon atom number be 8~ (methyl) alkyl acrylate of 10 alkyl is made in 100 parts by weight of (methyl) alkyl acrylate as main component, is added B) carboxylic 1~15 parts by weight of copolymerizable compound and c) carbon atom number be 1~5 aliphatic carboxylic acid vinyl esters 3~ 100 parts by weight, to form the copolymer of monomer mixture, and having been blended thereto relative to the carboxyl of above-mentioned b) ingredient is to work as Crosslinking agent (patent document 2) more than amount.
The adhesion agent composition recorded in patent document 2 is not generated and the peelings such as floats in processing or the when of preservation, In addition, bonding force through when ascending small and releasable it is excellent, even if long-term preservation, even if long especially under high-temperature atmosphere Phase saves, and can also be removed again with lesser power, does not generate residue glue on adherend at this time, and even if carrying out high speed stripping From when can also be removed again with lesser power.
In addition, there is stain resistance about (2), a kind of adhesion agent composition is disclosed, is contained：100 mass parts by 0 Mass parts are more than and less than the carboxyl group-containing monomer of 0.5 mass parts, hydroxyl (methyl) acrylic monomer of 0.6~9 mass parts And 99.4~90.5 mass parts (methyl) acrylate monomer formed, weight average molecular weight be 100,000 more than and less than 1,000,000 (methyl) acrylic copolymer；And 0.1~5 mass parts carbodiimide class crosslinking agent (patent document 3).
The adhesion agent composition recorded in patent document 3, which is characterized in that carbodiimide class crosslinking agent is used as specific group At (methyl) acrylic copolymer crosslinking agent.When can follow thereby, it is possible to provide adhering agent layer by autoclaving The cross-linked structure shunk caused by pressure and temperature.Therefore, the adhering agent layer formed using adhesion agent composition, even if in height Under temperature and condition of high voltage (when autoclaving), also it is able to suppress or prevents to blister, resistance to adherend pollution is excellent, in addition, transparent Property is also excellent.
In addition, the antistatic property excellent about (3), as assigning surface protection film in the method for antistatic property, Show the method etc. that antistatic agent is mediated into base material film.As antistatic agent, such as disclose：(a) there is quaternary ammonium salt, pyrrole PyridineThe various cationic antistatic agents of the cation groups such as salt, primary amino group~tertiary amino；(b) have sulfonate radical, sulfate group, The anionic antistatic agents of the anionic groups such as phosphate-based, phosphonate radical；(c) both sexes such as amino acids, amidosulphuric acid esters are anti- Electrostatic agent；(d) non-ionic antistatic agents such as alkamine, glycerols, polyethylene glycols；(e) by antistatic agent as described above Polymer Antistatic Agent made of molecular weight etc. (patent document 4).
In addition, proposing in recent years, it is contained in such antistatic agent in base material film, or be not coated on substrate On the surface of film, but directly make that it includes in adhering agent layer.
In addition, also disclose a kind of antistatic property adhesion agent composition, by have containing fluorine-based and sulfonyl yin from The salt of son disperses, which is characterized in that and it is above-mentioned to have the salt containing fluorine-based and sulfonyl anion, in being dissolved in main chain Dispersed (patent document 5) in the state of polyethers ester plasticizer containing polyether-based.
About the adhesion agent composition recorded in patent document 5, disclose use the plasticizer that is formed by following esters as Plasticizer：It is 1~20 by the unitary or dicarboxylic acids with saturated or unsaturated non-ring type alkyl and with carbon atom number The ester that the alcohol of non-ring type alkyl is formed；Or the ester that the unsaturated group in the unsaturated non-ring type alkyl is at least partially epoxidized.Recognize For：Such unitary or dicarboxylic acids with saturated or unsaturated non-ring type alkyl, by viscous with being used in composition Carbon atom number similar in the carbon atom number of the acrylic monomers of acrylic copolymer in oxidant layer, with antistatic property sticker group The compatibility for closing object becomes well, can suitably keep in plasticizer acrylic compounds antistatic property adhesion agent composition, because This inhibits exudation (bleed-out).
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Application 63-225677 bulletin
Patent document 2：Japanese Unexamined Patent Publication 11-256111 bulletin
Patent document 3：Japanese Unexamined Patent Publication 2011-122054 bulletin
Patent document 4：Japanese Unexamined Patent Publication 11-070629 bulletin
Patent document 5：Japanese Unexamined Patent Publication 2014-118469 bulletin
Summary of the invention
The technical problem to be solved in the present invention
Like this, in the prior art, as the required performance to the adhering agent layer for constituting surface protection film, it is desirable that low The balance of adhesion strength is obtained under the peeling rate of speed and the peeling rate of high speed, with stain resistance, excellent antistatic property Deng.However, allowing to meet each required performance respectively, it can not meet simultaneously and the adhering agent layer of surface protection film is sought Whole required performances.
The present invention completes in view of the foregoing, and technical problem is to provide a kind of peeling rate and high speed in low speed Peeling rate under, the balancing good of adhesion strength, and have stain resistance, have excellent adhesive performance and non-deterioration Excellent antistatic property adhesion agent composition and surface protection film.
Solve the technological means of technical problem
In the adhesion agent composition with antistatic property and the surface protection film for having used the adhesion agent composition, resist The relationship of antistatic property and the stain resistance to adherend is the relationship of shifting (Trade-off), is maintaining antistatic property It is extremely difficult for improving stain resistance while energy.
However, the inventor of the present application discovered that a kind of adhesion agent composition is able to solve the technical problem, the adhesion Agent composition contains：Copolymer made of being copolymerized the copolymerisable monomer containing carboxyl；Silicone compounds containing polyethers；By having The ion combination that the fusing point for the anion (for example, nine fluorine butane azochlorosulfonate acid anions) that number of fluorine atoms is F7 or more is 25 DEG C or more The antistatic agent that object is formed.
In order to solve the above technical problem, the present invention provides a kind of adhesion agent compositions, contain antistatic agent and crosslinking Agent, which is characterized in that the adhesion agent composition contain be copolymerized following monomers made of, the copolymer of acid value 0.1~1.0 Acrylic polymer：(A) carbon atom number of alkyl is that (methyl) acrylate monomer, (B) of C1~C18 contain hydroxyl The copolymerisable monomer of copolymerisable monomer and (C) containing carboxyl；In the acrylic polymer, described in 100 parts by weight (A) carbon atom number of alkyl is to contain propylene in (methyl) acrylate monomer of C1~C18 with ratios more than 70 parts by weight Acid -2- ethylhexyl；The glass transition temperature of the acrylic polymer is 0 DEG C or less；The crosslinking agent is (D) three official Isocyanate compound more than energy；The antistatic agent be with number of fluorine atoms be F7 or more anion, by cation The ionic compound that the fusing point formed with anion is 25~50 DEG C；The adhesion agent composition further contains (E) crosslinking and prolongs Slow agent and the crosslinking catalyst in addition to tin compound as (F) crosslinking catalyst.
Adhesion agent composition of the invention is the surface protection film on the protective layer for fit in the polarizer of polarizing film Adhesion agent composition, preferably：The protective layer of the polarizer of the polarizing film is selected from by TAC class film, PMMA class film, PET class film One of group of composition, and the surface treatment implemented on the surface of the protective layer in the polarizer of the polarizing film be selected from by One of untreated, AG processing, LR processing, AR processing, AG-LR processing, the group of AG-AR processing composition.
It is preferred that：The anion of the ionic compound contains selected from by C6F5(CF2)nCOO-、C6F5(CF2)nSO3 -、C6F5 (CF2)nO-、C6F5O(CF2)nSO3 -、(C6F5CO)2N-、(C6F5CO)3C-、(C6F5SO2)2N-、(C6F5SO2)3C-、(C6F5OSO2)2N-、(C6F5OSO2)3C-、(C6F5)4B-、CF3(CF2)3SO3 -At least one of group of composition is above to be used as anion, relative to The acrylic polymer of 100 parts by weight contains the ionic compound as must using the ratio of 0.01~10 parts by weight Need ingredient.
It is preferred that：The cation of the ionic compound is selected from by pyridineImidazolesPhosphonium, sulfonium, pyrrolidinesGuanidineAmmonium, isourea(isouronium), thiocarbamide(thiouroniu m), piperidinesPyrazoles(pyrazolium), first Base(methylium), lithium, morpholine(morpholinium) one of the group formed, the institute relative to 100 parts by weight Acrylic polymer is stated, the ionic compound is contained as an essential component with the ratio of 0.01~10 parts by weight.
It is preferred that：The surface resistivity 1.0 × 10 of adhering agent layer made of being crosslinked the adhesion agent composition+12Ω/□ Hereinafter, the low-refraction that the adhering agent layer forms the composition for using the low-index layer formation containing fluorine compounds For the removing electrostatic pressure of layer in the range of -0.3~+0.3kV, adhering agent layer made of being crosslinked the adhesion agent composition is to inclined Shake piece, the adhesion strength when the peeling rate of low speed is 0.3m/ minute be 0.04~0.2N/25mm, it is fast in the removing of high speed Adhesion strength when degree is 30m/ minutes is 2.0N/25mm or less.
It is preferred that：The copolymerisable monomer of (B) containing hydroxyl is selected from by (methyl) acrylic acid -8- hydroxyl monooctyl ester, (first Base) the own ester of acrylic acid -6- hydroxyl, (methyl) acrylic acid -4- hydroxybutyl, (methyl) 2-Hydroxy ethyl acrylate, N- hydroxyl In the compound group that (methyl) acrylamide, N- methylol (methyl) acrylamide, N- ethoxy (methyl) acrylamide form At least one more than,
(methyl) acrylate monomer that carbon atom number relative to (A) alkyl described in 100 parts by weight is C1~C18, Contain the described copolymerisable monomer of (B) containing hydroxyl with the ratio of 0.1~10 parts by weight,
The copolymerisable monomer of (C) containing carboxyl be selected from by (methyl) acrylic acid, carboxyethyl (methyl) acrylate, Carboxylic amyl (methyl) acrylate, 2- (methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2- (methyl) acryloxy Propyl hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyl phthalic acid, 2- (methyl) acryloyl-oxyethyl amber Amber acid, 2- (methyl) acryloyl-oxyethyl maleic acid, carboxy-polycaprolactone list (methyl) acrylate, 2- (methyl) acryloyl It is more than at least one of compound group of oxygroup ethyl tetrahydrophthalic acid composition,
(methyl) acrylate monomer that carbon atom number relative to (A) alkyl described in 100 parts by weight is C1~C18, Contain the described copolymerisable monomer of (C) containing carboxyl with the ratio of 0.01~0.5 parts by weight.
It is preferred that：(E) crosslinking delay agent is the compound of ketone-enol tautomers, the institute relative to 100 parts by weight Acrylic polymer is stated, described (E) crosslinking delay agent, (F) cross-linking catalyst are contained with the ratio of 0.1~300 parts by weight Agent is the gold more than at least one of group being made of aluminium chelate compound, titanium chelate compound, iron chelating compounds Belong to chelate compound to contain relative to the acrylic polymer of 100 parts by weight with the ratio of 0.001~0.5 parts by weight (F) crosslinking catalyst, the weight part ratio of (E)/(F) are 80~1000.
It is preferred that：Relative to the acrylic polymer of 100 parts by weight, the adhesion agent composition is with 0.01~0.5 The ratio of parts by weight contains that HLB value is 6~12 and weight average molecular weight is 10000 polyether modified siloxane compounds below.
It is preferred that：Relative to the acrylic polymer of 100 parts by weight, the adhesion agent composition is with 0.1~5.0 weight The ratio of amount part contains：Make (methyl) acrylate monomer of carbon atom number C1~18 of alkyl and containing polyalkylene glycol chain Made of single (methyl) acrylate monomer copolymerization, weight average molecular weight is more than 100,000 and is 300,000 copolymers below.
It is preferred that：In described list (methyl) acrylate monomer containing polyalkylene glycol chain, polyalkylene glycol chain is constituted Alkylene oxide group (alkylene oxide) average repeat unit number be 3~14；List (the first containing polyalkylene glycol chain Base) diester component in acrylate monomer is 0.2% or less；The weight average molecular weight of 100 parts by weight be more than 100,000 and To be contained with the ratio of 1~50 parts by weight selected from by polyalkylene glycol mono (methyl) acrylic acid in 300,000 copolymers below The group of ester, methoxypolyalkylene glycol (methyl) acrylate, ethyoxyl polyalkylene glycol (methyl) acrylate composition At least one of above list (methyl) acrylate monomer containing polyalkylene glycol chain as described in.
In addition, the present invention provides a kind of adhesive film, which is characterized in that being laminated on the single side of resin film makes above-mentioned adhesion Adhering agent layer made of the crosslinking of agent composition.
In addition, the present invention provides a kind of surface protection film, it uses above-mentioned adhesive films.
In addition, the present invention provides a kind of surface protection film of polarizing film, it uses above-mentioned adhesive films.
In addition, the present invention provides a kind of optical film with adhering agent layer, it is laminated on the face of at least side of optical film There is the adhering agent layer formed by above-mentioned adhesion agent composition.
In addition, the present invention provides a kind of above-mentioned adhesive film, wherein in the single side of the resin film, i.e. with formation It states and is implemented with antistatic treatment and antifouling process on the opposite face in side of adhering agent layer.
Invention effect
Compared with the adhesion agent composition of previous surface protection film, adhesion agent composition of the present invention has excellent The excellent antistripping antistatic property of different adhesive performance and non-deterioration.
Especially compared with the surface protection film made of conventional art, surface protection film of the present invention, in quilt Viscous object is with the stain-proofing layer containing fluorine compounds on the surface for being laminated in optical film or to use the low folding containing fluorine compounds In the case where penetrating the composition of rate layer formation and the adherend of low-index layer that is formed, there is excellent adhesive performance and not The excellent antistripping antistatic property of deterioration.Surface protection film i.e. of the present invention realize at the same time antistatic property with The aspect of stain resistance has significant effect.
That is, adhesion agent composition of the present invention and used the adhesion agent composition surface protection film have it is excellent Adhesive performance and non-deterioration excellent antistripping antistatic property, therefore utility value industrially is very big.
Specific embodiment
Hereinafter, the present invention will be described based on suitable embodiment.
The adhesion agent composition of present embodiment contains antistatic agent and crosslinking agent, which is characterized in that the sticker group Close object contain be copolymerized following monomers made of, the acrylic polymer of the copolymer of acid value 0.1~1.0：(A) alkyl (methyl) acrylate monomer, the copolymerisable monomer of (B) containing hydroxyl and (C) that carbon atom number is C1~C18 contain carboxyl Copolymerisable monomer；In the acrylic polymer, the carbon atom number of (A) alkyl described in 100 parts by weight is C1~C18 (methyl) acrylate monomer in, acrylic acid-2-ethyl caproite is contained with ratios more than 70 parts by weight；The acrylic compounds The glass transition temperature of polymer is 0 DEG C or less；The crosslinking agent is the isocyanate compound of (D) trifunctional or more；Institute Antistatic agent is stated to be the anion for being F7 or more with number of fluorine atoms, by the fusing point that cation is formed with anion be 25~50 DEG C ionic compound；The adhesion agent composition further contains (E) crosslinking delay agent and removing as (F) crosslinking catalyst Crosslinking catalyst other than tin compound.
Acrylic polymer used in the adhesion agent composition of present embodiment is that the host agent of adhesion agent composition is poly- Object is closed, glass transition temperature is 0 DEG C or less.In addition, acrylic polymer is preferably with the carbon atom number of (A) alkyl for C1 (methyl) acrylate monomer of~C18 makees copolymer as main component.
(methyl) acrylate monomer that carbon atom number as (A) alkyl is C1~C18, can enumerate (methyl) propylene Sour methyl esters, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) third The different monooctyl ester of olefin(e) acid, (methyl) acrylic acid-2-ethyl caproite, (methyl) nonyl acrylate, the different nonyl ester of (methyl) acrylic acid, (methyl) Decyl acrylate, (methyl) acrylic acid hendecane base ester, (methyl) dodecylacrylate, (methyl) acrylic acid tridecyl Ester, (methyl) acrylic acid tetradecane base ester, (methyl) acrylic acid pentadecane base ester, (methyl) aliphatic acrylate, (first Base) acrylic acid heptadecane base ester, (methyl) octadecyl acrylate, (methyl) acrylic acid ring pentyl ester, (methyl) acrylic acid ring Own ester etc..The alkyl of (methyl) alkyl acrylate monomer can be straight chain, branch-like, ring-type in any one.
Acrylic polymer used in the adhesion agent composition of present embodiment, preferably in (A) alkane of 100 parts by weight The carbon atom number of base is to contain acrylic acid -2- in (methyl) acrylate monomer of C1~C18 with ratios more than 70 parts by weight Ethylhexyl.
Acrylic polymer used in the adhesion agent composition of present embodiment contains (B) containing the copolymerizable of hydroxyl Monomer.Copolymerisable monomer as (B) containing hydroxyl is preferably selected from by (methyl) acrylic acid -8- hydroxyl monooctyl ester, (methyl) third The own ester of olefin(e) acid -6- hydroxyl, (methyl) acrylic acid -4- hydroxybutyl, (methyl) 2-Hydroxy ethyl acrylate, N- hydroxyl (methyl) In the compound groups of compositions such as acrylamide, N- methylol (methyl) acrylamide, N- ethoxy (methyl) acrylamide extremely Lack more than one.
(methyl) acrylate monomer that carbon atom number relative to (A) alkyl described in 100 parts by weight is C1~C18, It is preferred that containing the copolymerisable monomer of (B) containing hydroxyl with the ratio of 0.1~10 parts by weight, more preferably with 1.6~8.5 parts by weight Ratio contains the copolymerisable monomer of (B) containing hydroxyl, particularly preferably contains (B) with the ratio of 2.1~7.5 parts by weight and contains hydroxyl Copolymerisable monomer.
Acrylic polymer used in the adhesion agent composition of present embodiment contains (C) containing the copolymerizable of carboxyl Monomer.Copolymerisable monomer as (C) containing carboxyl is preferably selected from by (methyl) acrylic acid, carboxyethyl (methyl) acrylic acid Ester, carboxylic amyl (methyl) acrylate, 2- (methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2- (methyl) acryloyl-oxy Base propyl hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyl phthalic acid, 2- (methyl) acryloyl-oxyethyl Succinic acid, 2- (methyl) acryloyl-oxyethyl maleic acid, carboxy-polycaprolactone list (methyl) acrylate, 2- (methyl) propylene It is more than at least one of compound group of the compositions such as trimethylammonium tetrahydrophthalic acid.
(methyl) acrylate monomer that carbon atom number relative to (A) alkyl described in 100 parts by weight is C1~C18, It is preferred that containing the copolymerisable monomer of (C) containing carboxyl with the ratio of 0.01~0.5 parts by weight, more preferably with 0.01~0.45 weight The ratio of part contains the copolymerisable monomer of (C) containing carboxyl, particularly preferably contains (C) with the ratio of 0.01~0.4 parts by weight and contains There is the copolymerisable monomer of carboxyl.
The preparation method of the acrylic polymer contained in adhesion agent composition of the present embodiment is not special It limits, suitable, the well known polymerization such as usable solution polymerization process, emulsion polymerization.The copolymer of acrylic polymer Weight average molecular weight can for example enumerate 50~3,000,000.The acid value of acrylic polymer is preferably 0.1~1.0.As a result, can Enough improve stain resistance.Wherein, " acid value " is an index for indicating the content of acid, to neutralize the polymer institute that 1g contains carboxyl The mg number of the potassium hydroxide needed is indicated.
Adhesion agent composition of the present embodiment contains (G) antistatic agent.(G) antistatic agent of present embodiment is Ionic compound with the anion that number of fluorine atoms is F7 or more, being formed by cation with anion.It is preferred that the ionization The fusing point for closing object is 25~50 DEG C, under room temperature (such as 25 DEG C) is solid.The acrylic polymer relative to 100 parts by weight Object is closed, the ionic compound is preferably contained as an essential component with the ratio of 0.01~10 parts by weight.
In addition, in the antistatic property for needing to improve adhering agent layer, so that the lower limit value of surface resistivity be made to be reduced to 1.0 ×10+10When Ω/ or less, relative to the acrylic polymer of 100 parts by weight, more preferably with 0.01~15 parts by weight Ratio contain the ionic compound.
As the anion of the ionic compound, can enumerate selected from by C6F5(CF2)nCOO-、C6F5(CF2)nSO3 -、 C6F5(CF2)nO-、C6F5O(CF2)nSO3 -、(C6F5CO)2N-、(C6F5CO)3C-、(C6F5SO2)2N-、(C6F5SO2)3C-、 (C6F5OSO2)2N-、(C6F5OSO2)3C-、(C6F5)4B-、CF3(CF2)3SO3 -It is more than at least one of group of composition.Wherein, n For 1 or more integer.
As the cation of the ionic compound, can enumerate selected from by pyridineImidazolesPhosphonium, sulfonium, pyrrolidinesGuanidineAmmonium, isoureaThiocarbamidePiperidinesPyrazolesMethylLithium, morpholineAt least one of group of composition More than.
As the concrete example of (G) antistatic agent, such as methyl trioctylammonium three (phenyl-pentafluoride sulfonyl) methyl can be enumerated Compound salt, 3- methyl-1-octylpyridiniumNine fluorine butane sulfonate, 1- ethyl-3-methylimidazoleFour (pentafluorophenyl group) boric acid Salt, 1- butyl -1- methyl piperidineBis- (phenyl-pentafluoride sulfonyl) inferior amine salts etc..
The isocyanate compound that adhesion agent composition of the present embodiment further contains (D) trifunctional or more is made For crosslinking agent.As isocyanate compound more than (D) trifunctional, such as hexamethylene diisocyanate, different can be enumerated Isophorone diisocyanate, methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), benzene dimethylene diisocyanate etc. two It is more than the biuret modified body or isocyanurate-modified body of isocyanates, with the ternarys such as trimethylolpropane or glycerol more The adduct etc. of first alcohol.As the ratio of isocyanate compound more than (D) trifunctional, such as can enumerate relative to 100 The acrylic polymer of parts by weight is the ratio of 0.01~5 parts by weight.
Adhesion agent composition of the present embodiment can contain (E) crosslinking delay agent.It, can as (E) crosslinking delay agent Enumerate methyl acetoacetate, ethyl acetoacetate, acetoacetate monooctyl ester, acetoacetate oleyl alcohol ester (oleyl Acetoacetate), the 'beta '-ketoesters such as lauryl acetoacetate, acetoacetate stearyl or acetylacetone,2,4-pentanedione, 2,4- acetyl butyryl, The beta-diketons such as benzoyl acetone.These crosslinking delay agents are the compound of ketone-enol tautomers, are esterified with polyisocyanate Object is closed as in the adhesion agent composition of crosslinking agent, by being blocked (block) to isocyanate group possessed by crosslinking agent, The excessive viscosity for being able to suppress the adhesion agent composition after blending crosslinking agent rises or gelation, extends adhesion agent composition Storage period.(E) crosslinking delay agent is preferably the compound of ketone-enol tautomers, particularly preferably selected from by acetylacetone,2,4-pentanedione, It is more than at least one of compound group of ethyl acetoacetate composition.The acrylic relative to 100 parts by weight Object preferably contains (E) crosslinking delay agent with the ratio of 0.1~300 parts by weight.
Adhesion agent composition of the present embodiment can contain the crosslinking catalyst in addition to tin compound and be used as (F) Crosslinking catalyst.When using polyisocyanate compounds as crosslinking agent, (F) as long as crosslinking catalyst to the copolymer with The reaction (cross-linking reaction) of crosslinking agent plays the substance of the effect as catalyst.As the crosslinking in addition to tin compound Catalyst, can enumerate the aminated compounds such as tertiary amine, and metal chelate compound, organo-lead compound, organic zinc compound etc. have Machine metallic compound etc..
As the metal chelate compound of (F) crosslinking catalyst, to be bonded with 1 or more on central metal atom M Multidentate ligand L compound.Metal chelate compound can have 1 or more monodentate being bonded on metallic atom M and match Body X can also not have monodentate ligand X.As the concrete example of metal chelate compound, three (2,4- pentanedione) iron can be enumerated (III), praseodynium iron, praseodynium titanium, praseodynium ruthenium, bis-acetylacetonate zinc, praseodynium aluminium, four acetyl Acetone zirconium, three (2,4- acetyl butyryl) iron (III), bis- (2,4- acetyl butyryl) zinc, three (2,4- acetyl butyryl) titaniums, three (2,4- acetyl butyryls) Aluminium, four (2,4- acetyl butyryl) zirconiums etc..
As (F) crosslinking catalyst, it is preferably selected from by aluminium chelate compound, titanium chelate compound, iron chelating compounds Metal chelate compound more than at least one of group of composition.Relative to the acrylic polymer of 100 parts by weight, It is preferred that containing (F) crosslinking catalyst with the ratio of 0.001~0.5 parts by weight.
Due to (E) crosslinking delay agent and (F) crosslinking catalyst on the contrary, having the effect of inhibiting crosslinking, it is therefore preferable that suitably The ratio of ground setting (E) crosslinking delay agent and (F) crosslinking catalyst.In order to extend the storage period of adhesion agent composition, storage is improved Stability is deposited, the weight part ratio of (E)/(F) is preferably 80~1000.Herein, the weight part ratio of (E)/(F) is with the weight of (E) The value for the quotient that part is calculated divided by the parts by weight of (F).
Adhesion agent composition of the present embodiment can contain (H) polyether modified siloxane compound as it is any at Point.(H) polyether modified siloxane compound be the silicone compounds with polyether-based, in addition to common siloxane unit [- SiR1 2- O-] other than, also containing the siloxane unit [- SiR with polyether-based1(R2O(R3O)nR4)-O-].Herein, R1Indicate one Kind or two or more alkyl or aryls, R2And R3Indicate one or more kinds of alkylidenes, R4Indicate one or more kinds of Alkyl or acyl group etc. (end group).As polyether-based, polyoxyethylene [(C can be enumerated2H4O)n] or polyoxypropylene [(C3H6O)n] etc. polyoxy alkylidenes.In siloxane unit with polyether-based, it is (above-mentioned that the end of polyether-based is also possible to OH base R in general formula4=H).
(H) polyether modified siloxane compound is preferably the polyether modified siloxane compound that HLB value is 6~12.In addition, Relative to the acrylic polymer of 100 parts by weight, preferably comprise 0.01~0.5 parts by weight, further preferably 0.02~ 0.35 parts by weight, particularly preferably (H) polyether modified siloxane compound containing 0.02~0.25 parts by weight.HLB value refers to example The hydrophilic lipophilic balance as specified in JIS K3211 (surfactant term) etc. (hydrophilic-lipophilic ratio).
Polyether modified siloxane compound can for example obtain in the following manner：By hydrosilylation reactions, will have The organic compound of unsaturated bond and polyoxy alkylidene grafts on the polysiloxane main chain with hydrosilyl group.It is specific and Speech, can enumerate dimethylsiloxane methyl (polyoxyethylene) silicone copolymers, dimethylsiloxane methyl (polyoxy Ethylidene) siloxanes methyl (polyoxypropylene) silicone copolymers, dimethylsiloxane methyl (polyoxypropylene) silicon Oxygen alkane polymer etc..
By blending (H) polyether modified siloxane compound into adhesion agent composition, the viscous of adhering agent layer can be improved Put forth effort and operational again.(H) weight average molecular weight of polyether modified siloxane compound is preferably 10000 or less.From with acrylic acid The angle of the compatibility of quasi polymer is set out, although the compatibility for the polyether modified siloxane compound that HLB value is low, molecular weight is low Well, as long as but be the low polyether modified siloxane compound of molecular weight, HLB value is higher, even if compatible with polymer Property is slightly lower, it is also possible to access excellent antistatic property.
Adhesion agent composition of the present embodiment, can also be super containing the weight average molecular weight as antistatic adjuvant It crosses 100,000 or more and is 300,000 copolymers below (hereinafter referred to as " copolymer B) as any ingredient, the copolymer is by alkyl Carbon atom number is (methyl) acrylate monomer and list (methyl) the acrylate list of (I) containing polyalkylene glycol chain of C1~18 Body is copolymerized.Relative to the acrylic polymer of 100 parts by weight, preferably contained with the ratio of 0.1~5.0 parts by weight Copolymer B more preferably contains copolymer B with the ratio of 0.1~3.5 parts by weight, particularly preferably with the ratio of 0.1~2.5 parts by weight Example contains copolymer B.
List (methyl) acrylate monomer as (I) containing polyalkylene glycol chain, as long as polyalkylene glycol institute A hydroxyl in the multiple hydroxyls having is esterified as compound made of (methyl) acrylate.Due to (methyl) third Olefin(e) acid ester group is polymerizable group, therefore can be copolymerized with the acrylic polymer.It can also be other hydroxyls Still it is polyalkylene glycol mono (methyl) acrylate of OH, is also possible to the poly- Asia of alkoxy that other hydroxyls are transformed to alkyl ether Alkyl diol list (methyl) acrylate etc..
As the polyalkylene glycol for constituting polyalkylene glycol chain, as long as having one or more kinds of alkylidenes Diol compound, such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol propylene glycol, poly- can be enumerated Ethylene glycol-polytetramethylene glycol, polypropylene glycol-polytetramethylene glycol, polyethylene glycol propylene glycol-polytetramethylene glycol etc..
For list (methyl) acrylate monomer of (I) containing polyalkylene glycol chain, polyalkylene two is preferably comprised The average repeat unit number of the alkylene oxide group of alcohol chain is 3~14." the average repeat unit number of alkylene oxide group " refers at (I) containing poly- The part of " polyalkylene glycol chain " contained in the molecular structure of list (methyl) acrylate monomer of alkylene glycol chain In, alkylene oxide units carry out duplicate average.In addition, list (methyl) the acrylate list of (I) containing polyalkylene glycol chain Diester component in body is preferably 0.2% or less." diester component in monomer " refers to the list of (I) containing polyalkylene glycol chain The containing ratio (weight %) of polyalkylene glycol two (methyl) acrylate contained in (methyl) acrylate monomer.
List (methyl) acrylate monomer as (I) containing polyalkylene glycol chain, is preferably selected from by polyalkylene two Alcohol list (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate, ethyoxyl polyalkylene glycol (methyl) It is more than at least one of group of acrylate composition.In the copolymer B of 100 parts by weight, in the copolymer B (I) ratio of the list containing polyalkylene glycol chain (methyl) acrylate monomer is preferably the ratio of 1~50 parts by weight, more preferably For the ratio of 2~35 parts by weight, the particularly preferably ratio of 2~25 parts by weight.
As copolymerization be copolymer B, in addition to list (methyl) acrylate monomer of (I) containing polyalkylene glycol chain Monomer, the carbon atom number that can enumerate alkyl is (methyl) acrylate monomer of C1~18 and the copolymerisable monomer containing hydroxyl Deng at least one of more than.As the concrete example of these monomers, it can enumerate and be exemplified respectively in (A) and (B) etc. (methyl) acrylic monomer.The monomer that copolymerization is copolymer B can also be the list of the acrylic polymer with copolymerization Body is different.Copolymer B can not also be copolymerized the copolymerisable monomer containing carboxyl.
It is not limited only to above-mentioned additive, it is living that surface can also be suitably blended in the adhesion agent composition of present embodiment Add well known to property agent, curing accelerator, plasticizer, filler, cure retarder, processing aid, age resister, antioxidant etc. Add agent.These additives can be used alone or simultaneously using two or more.
The adhesion agent composition of present embodiment is suitable as fitting in the surface on the protective layer of the polarizer of polarizing film The adhesion agent composition of protective film.Herein, the protective layer of the polarizer of polarizing film can be enumerated selected from by TAC class film, PMMA One of class film, group of PET class film composition.Herein, TAC is the abbreviation of triacetyl cellulose, and PMMA is polymethylacrylic acid The abbreviation of methyl esters, PET are the abbreviation of polyethylene terephthalate.
In addition, it is implemented on the surface treatment on the surface of the protective layer of the polarizer of polarizing film, it can be for selected from by not One of reason, AG processing, LR processing, AR processing, AG-LR processing, the group of AG-AR processing composition.Herein, AG refers to anti-dazzle (Anti Glare), LR refer to low reflection (Low Reflection), and AR refers to antireflection (Anti Reflection).
For adhering agent layer made of adhesion agent composition for making present embodiment is crosslinked, the surface electricity of adhering agent layer Resistance rate is preferably 1.0 × 10+12Ω/ is hereinafter, more preferably 5.0 × 10+11Ω/ is hereinafter, particularly preferably 1.0 × 10+11 Ω/ or less.If surface resistivity is big, the performance of release generated electrostatic when removing adhering agent layer from adherend Difference.Therefore, it by sufficiently reducing surface resistivity, can reduce with generated when removing adhering agent layer from adherend Electrostatic and the removing electrostatic pressure generated inhibit the influence to adherend.
Adhesion agent composition for making present embodiment is crosslinked into for adhering agent layer, and preferably adhering agent layer is to using The composition of low-index layer formation containing fluorine compounds and the removing electrostatic pressure of low-index layer that is formed -0.3~+ In the range of 0.3kV.As the fluorine compounds of the composition for low-index layer formation, can enumerate as fluorinated olefins The polymer of one or more of class, fluorinated vinyl ethers, (methyl) acrylic acid fluorinated alkyl esters etc. it is fluorine-containing total The condensation products such as polymers, silane compound containing fluorinated alkyl.Fluorinated copolymer can also be copolymerized other than perfluorinated monomer There are olefines, vinyl ethers, (methyl) acrylate etc. without fluorinated monomer.Low-index layer can also be with high refractive index Layer etc. is combined and constitutes anti-reflection layer.
Adhering agent layer made of being crosslinked the adhesion agent composition of present embodiment to polarizing film, removing in low speed speed Adhesion strength when degree is 0.3m/ minutes is preferably 0.04~0.2N/25mm, viscous when the peeling rate of high speed is 30m/ minutes Put forth effort preferably 2.0N/25mm hereinafter, the adhesion strength when the peeling rate of high speed is 30m/ minutes be more preferably 0.2~ 1.6N/25mm.Change small performance caused by adhesion strength is obtained as a result, due to peeling rate, even if being removed by high speed, also can It is enough rapidly to be removed.In addition, even if not needed excessive when temporarily removing surface protection film to attach again yet Power is easy to remove from adherend.
The gel fraction of adhering agent layer made of being crosslinked the adhesion agent composition of present embodiment is preferably 95~ 100%, more preferably 97~100%.By so high gel fraction, under the peeling rate of low speed, adhesion strength will not mistake Greatly, unconverted monomer or oligomer be can reduce from the dissolution in copolymer, improved under operability again or high temperature and high humility Durability inhibits the pollution of adherend.
The adhesive film of present embodiment makes the sticker of present embodiment by being formed in the one or two sides of resin film Adhering agent layer made of composition crosslinking forms.In addition, the surface protection film of present embodiment is the shape on the single side of resin film At surface protection film made of adhering agent layer made of being crosslinked the adhesion agent composition of present embodiment.Present embodiment is glued Agent composition there is excellent antistatic property, under the peeling rate of low speed and the peeling rate of high speed, adhesion strength it is flat It weighs excellent, and there is stain resistance.Therefore, it may be suitably used to the purposes of the surface protection film of polarizing film.
As the base material film of adhering agent layer or the mold release film (isolation film) of protection bonding plane, the resin films such as polyester film can be used Deng.
It can implement antistatic place on the single side of resin film, face i.e. opposite with the side for being formed with the adhering agent layer Reason and antifouling process.As antistatic treatment, coating or kneading of antistatic agent etc. can be enumerated.As antifouling process, can arrange Enumerate the processing based on silicone, the release agent of fluorine class or smears, silicon dioxide microparticle etc..It, can also be for mold release film Implement the release agent using silicone, fluorine class, chain alkyl class on the face for the side being bonded with the bonding plane of adhering agent layer Deng demoulding processing.
In addition, being crosslinked the adhesion agent composition of present embodiment by being laminated at least one face of optical film Adhering agent layer, the optical film with adhering agent layer can be obtained.As optical film, polarizing coating, phase difference film, counnter attack can be enumerated Penetrate film, anti-dazzle (Anti Glare) film, ultraviolet-absorbing film, infrared absorbing film, optical compensation films, brightness raising film etc..Make The equipment being applicable in by optical component, can enumerate liquid crystal display panel, organic EL panel, touch panel etc..
In the case where the surface protection film and adhesive film of the optics of surface protection film for polarizing film etc., preferred base Material film and adhering agent layer have the adequately transparency.
Embodiment
Hereinafter, the present invention is specifically described using embodiment.
The preparation > of < acrylic polymer solution
[embodiment 1]
Nitrogen is imported into the reaction unit with blender, thermometer, reflux cooler and nitrogen ingress pipe, utilizes nitrogen Gas has replaced the air in reaction unit.Then, added into reaction unit 90 parts by weight acrylic acid-2-ethyl caproite, 10 The methyl acrylate of parts by weight, the acrylic acid -8- hydroxyl monooctyl ester of 5.5 parts by weight, 0.2 parts by weight acrylic acid, be added to simultaneously Solvent (ethyl acetate).Then, the azodiisobutyronitrile as 0.1 parts by weight of polymerization initiator was added dropwise using 2 hours, at 65 DEG C Lower reaction 6 hours, has obtained acrylic polymer solution used in embodiment 1.
[embodiment 2~6 and comparative example 1~3]
Other than the composition of monomer is set to documented by (A) such as table 1~(C), with in above-described embodiment 1 The identical mode of the acrylic polymer solution used has obtained acrylic acid used in embodiment 2~6 and comparative example 1~3 Quasi polymer solution.
The preparation > of < adhesion agent composition and surface protection film
[embodiment 1]
To as described above and in the acrylic polymer solution of the embodiment 1 of preparation, the crosslinking agent of 2.0 parts by weight is added Crosslinking catalyst (the praseodynium of the crosslinking delay agents (acetylacetone,2,4-pentanedione) of (CORONATE HX), 9 parts by weight, 0.1 parts by weight Titanium), the antistatic agents (methyl trioctylammonium three (phenyl-pentafluoride sulfonyl) methide salt) of 0.9 parts by weight, 0.05 parts by weight The copolymer B-1 (molecular weight 150,000) of polyether modified siloxane compound (HLB=7), 0.2 parts by weight, is stirred mixing, obtains The adhesion agent composition of embodiment 1 is arrived.The adhesion agent composition is coated on mold release film (PET film being coated with through silicone resin) After upper, solvent is removed by being dried at 90 DEG C, has obtained the adhering agent layer with a thickness of 20 μm.It then, will be with de- The adhering agent layer of mould film be needed on base material film (antistatic and antifouling process PET film has been carried out to the face of side) with carry out On the opposite face in antistatic and antifouling process face, there is the stepped construction of " base material film/adhering agent layer/mold release film " The surface protection film of embodiment 1.
[embodiment 2~6 and comparative example 1~3]
Other than the composition of additive is set to documented by (D) such as table 1~(H) and copolymer B, with it is upper The identical mode of surface protection film for stating embodiment 1, has obtained the surface protection film of embodiment 2~6 and comparative example 1~3.
[table 1]
In table 1, the total amount of (methyl) acrylate monomer that the carbon atom number of (A) alkyl is C1~C18 is set as 100 weights Part is measured, the parts by weight of each ingredient have been found out.
In addition, in table 1, (D), (E), (F), (G), (H), (copolymer B) each column in, acrylic polymer is set For 100 parts by weight, the content ratio (parts by weight) of each ingredient is illustrated with the numerical value in parantheses ().
In addition, the compound name of the dummy suffix notation of each ingredient used in table 1 is shown in table 2~3.Also include in table 2 It is in the element monomers of copolymer B shown in table 3, remove list (methyl) acrylate monomer of (I) containing polyalkylene glycol chain The compound name of the dummy suffix notation of monomer in addition.In addition, CORONATE (registered trademark) HX, CORONATE HL and CORONATE L is the product name of TOSOH CORPORATION, and TAKENATE (registered trademark) D-140N is Mitsui The product name of Chemicals, Inc..
[table 2]
[table 3]
(G) in antistatic agent, G-1~G-4 be F7 or more with number of fluorine atoms anion, fusing point be 25 DEG C with On solid ionic compound.G-5 be F5 with number of fluorine atoms anion, solid that fusing point is 25 DEG C or more from Sub- compound.
(H) in polyether modified siloxane compound, the weight average molecular weight of H-1~H-6 is 10000 or less.
(I) in the list containing polyalkylene glycol chain (methyl) acrylate monomer, the diester group in the monomer of I-1~I-3 It is divided into 0.2% hereinafter, the diester component in the monomer of I-4 is 0.8%.In addition, the n in the column that (I) of table 3 is organized is to indicate alkylene The numerical value of the average repeat unit number of oxygroup.
< test method and evaluation >
The surface protection film of Examples 1 to 6 and comparative example 1~3 is cured 7 days under 23 DEG C, the atmosphere of 50%RH respectively Afterwards, it is evaluated by test method below.
The test method > of < adhesion strength
Mold release film is removed, the surface protection film for exposing adhering agent layer is fitted in the surface of polarizing film via adhering agent layer On, after placing 1 day, autoclaving in 20 minutes is carried out under 50 DEG C, 5 atmospheric pressure, it is small further to placed 12 at room temperature Shi Hou, as the measurement sample of adhesion strength.Using cupping machine, in low velocity (0.3m/ minutes) or at high speed Obtained measurement sample is peeled along 180 ° of directions under (30m/ minutes), using the peel strength of measurement as adhesion strength.
Herein, the protective layer of the polarizer of the polarizing film is selected from by triacetyl cellulose (TAC), polymethylacrylic acid One of methyl esters (PMMA), group of polyethylene terephthalate (PET) composition.
In addition, for LR polarizing film and AG-LR polarizing film, using the composition containing fluorine compounds to the polarizing film Implement low reflecting surface processing in the surface of the protective layer of polarizer.
The test method > of < surface resistivity
After surface protection film is cured, before being fitted in polarizing film, mold release film is peeled, exposes adhering agent layer, Use resistrivity meter HIRESTA UP-HT450 (Mitsubishi Chemical Analytech Co., Ltd. manufacture) measurement The surface resistivity of adhering agent layer.
The test method > of < removing electrostatic pressure
Mold release film is peeled, the surface protection film for exposing adhering agent layer is fitted on polarizing film, the polarizing film is in quilt The low-index layer that there is the composition using the low-index layer formation containing fluorine compounds on viscous face and formed.With 30m/ When the tensile speed of minute carries out 180 ° of removings to surface protection film, high-precision electrostatic transducer SK-035, SK-200 are used (KEYENCE CORPOR ATION manufacture) measures the voltage (electrostatic pressure) of adherend electrification and generation, by the maximum value of measured value As removing electrostatic pressure.
The test method > of < stain resistance
Using make-up machine, by the polarizing film for implementing low reflection (LR) surface treatment via adhering agent layer (double-sided adhesive Adhesive tape) fit on the single side of glass plate.Then, surface protection film is fitted in the surface of the polarizing film using make-up machine On.After keeping during having been carried out in the environment of 23 DEG C, 50%RH 3 days and 30 days, surface protection film is removed, is seen by visual observation The pollutional condition on the surface of polarizing film is examined.It, will be to the no dirt in the surface of the polarizing film as the judgement benchmark of stain resistance It is evaluated as that "○", there are the case where a little pollution to be evaluated as " △ " the case where dye, polluted situation is evaluated as "×".
The evaluation result to the surface protection film in Examples 1 to 6 and comparative example 1~3 is shown in table 4." sheet resistance Rate " passes through " m × 10+n" be denoted as the mode (wherein, m is arbitrary real number value, and n is positive integer) of " mE+n " and carried out table Show." protective layer of the polarizer of polarizing film " column shows the guarantor of the polarizer of the polarizing film used in the test of adhesion strength The material and surface treatment of sheath.The Plain of " surface treatment " means untreated.
[table 4]
The surface protection film of Examples 1 to 6 to the polarizing film as adherend, peeling rate in low speed be 0.3m/ Adhesion strength when minute is 0.04~0.2N/25mm, and the adhesion strength when the peeling rate of high speed is 30m/ minutes is 2.0N/ 25mm is hereinafter, adhesive performance is excellent.
In addition, the surface resistivity of the adhering agent layer of the surface protection film of Examples 1 to 6 is 1.0 × 10+12Ω/ with Under, the stripping for the low-index layer that adhering agent layer forms the composition for using the low-index layer formation containing fluorine compounds From with voltage in the range of -0.3~+0.3kV, antistatic property is excellent.
Further, even if also not having after keeping of the surface protection film of Examples 1 to 6 during having carried out 3 days and 30 days Pollution to the polarizing film as adherend, stain resistance are also excellent.
That is, the evaluation result shown in table 4 about the surface protection film of Examples 1 to 6, it was confirmed that be able to solve the present invention The technical issues of.
For the surface protection film of comparative example 1, in acrylic polymer contained in adhesion agent composition, The ratio for the 2EHA in (methyl) acrylate monomer that the carbon atom number of (A) alkyl of 100 parts by weight is C1~C18 is less 50 parts by weight of amount, and it is not copolymerized the copolymerisable monomer of (C) containing carboxyl.In addition, being related to for the surface protection film of comparative example 1 Adhesion agent composition for, antistatic agent contain number of fluorine atoms be less than F7 F5 anion.Therefore, the surface of comparative example 1 is protected The adhesion strength of the adhering agent layer of cuticula is big, and removing electrostatic pressure is high, and stain resistance is also poor.
In addition, the acid value of the acrylic polymer contained in adhesion agent composition is super in the surface protection film of comparative example 2 1.0 are crossed, low contamination resistance.
In addition, it is small that the antistatic agent contained in adhesion agent composition contains number of fluorine atoms in the surface protection film of comparative example 3 In the F5 anion of F7, low contamination resistance.
Like this, the surface protection film of comparative example 1~3 not can solve technical problem of the invention.

Claims (15)

1. a kind of adhesion agent composition, contains antistatic agent and crosslinking agent, which is characterized in that
The adhesion agent composition contains the acrylic compounds of the copolymer of acid value 0.1~1.0 made of making following monomers copolymerization Polymer：
(A) carbon atom number of alkyl be C1~C18 (methyl) acrylate monomer,
(B) copolymerisable monomer containing hydroxyl and
(C) containing the copolymerisable monomer of carboxyl；
The carbon atom number of the acrylic polymer (A) alkyl described in 100 parts by weight is (methyl) propylene of C1~C18 In acid ester monomer, acrylic acid-2-ethyl caproite is contained with ratios more than 70 parts by weight；
The glass transition temperature of the acrylic polymer is 0 DEG C or less；
The crosslinking agent is the isocyanate compound of (D) trifunctional or more；
The antistatic agent is that the anion for being F7 or more with number of fluorine atoms by cation is with the fusing point that anion is formed 25~50 DEG C of ionic compound；
The adhesion agent composition further contain (E) crosslinking delay agent and as (F) crosslinking catalyst except tin compound with Outer crosslinking catalyst.
2. adhesion agent composition according to claim 1 is the table on the protective layer for fit in the polarizer of polarizing film The adhesion agent composition of surface protective film, which is characterized in that
The protective layer of the polarizer of the polarizing film is one in the group being made of TAC class film, PMMA class film, PET class film Kind, and the surface treatment implemented on the surface of the protective layer in the polarizer of the polarizing film be selected from by untreated, AG processing, One of LR processing, AR processing, AG-LR processing, the group of AG-AR processing composition.
3. adhesion agent composition according to claim 1 or 2, which is characterized in that the anion of the ionic compound contains Have selected from by C6F5(CF2)nCOO-、C6F5(CF2)nSO3 -、C6F5(CF2)nO-、C6F5O(CF2)nSO3 -、(C6F5CO)2N-、 (C6F5CO)3C-、(C6F5SO2)2N-、(C6F5SO2)3C-、(C6F5OSO2)2N-、(C6F5OSO2)3C-、(C6F5)4B-、CF3(CF2)3SO3 -At least one of group of composition is above to be used as anion,
Relative to the acrylic polymer of 100 parts by weight, the ionization is contained with the ratio of 0.01~10 parts by weight Close object as an essential component.
4. adhesion agent composition according to claim 1 or 2, which is characterized in that the cation of the ionic compound is Selected from by pyridineImidazolesPhosphonium, sulfonium, pyrrolidinesGuanidineAmmonium, isoureaThiocarbamidePiperidinesPyrazolesMethylLithium, morpholineOne of group of composition,
Relative to the acrylic polymer of 100 parts by weight, the ionization is contained with the ratio of 0.01~10 parts by weight Close object as an essential component.
5. adhesion agent composition according to claim 1 or 2, which is characterized in that
The surface resistivity 1.0 × 10 of adhering agent layer made of being crosslinked the adhesion agent composition+12Ω/ hereinafter,
The low-refraction that the adhering agent layer forms the composition for using the low-index layer formation containing fluorine compounds Layer removing electrostatic pressure in the range of -0.3~+0.3kV,
Peeling rate 0.3m/ minute in low speed of the adhering agent layer made of being crosslinked the adhesion agent composition to polarizing film When adhesion strength be 0.04~0.2N/25mm, the adhesion strength when the peeling rate of high speed is 30m/ minutes be 2.0N/25mm with Under.
6. adhesion agent composition according to claim 1 or 2, which is characterized in that
The copolymerisable monomer of (B) containing hydroxyl is selected from by (methyl) acrylic acid -8- hydroxyl monooctyl ester, (methyl) acrylic acid - The own ester of 6- hydroxyl, (methyl) acrylic acid -4- hydroxybutyl, (methyl) 2-Hydroxy ethyl acrylate, N- hydroxyl (methyl) acryloyl Amine, N- methylol (methyl) acrylamide, N- ethoxy (methyl) acrylamide composition at least one of compound group with On,
(methyl) acrylate monomer that carbon atom number relative to (A) alkyl described in 100 parts by weight is C1~C18, with 0.1 The ratio of~10 parts by weight contains the described copolymerisable monomer of (B) containing hydroxyl,
The copolymerisable monomer of (C) containing carboxyl is selected from by (methyl) acrylic acid, carboxyethyl (methyl) acrylate, carboxylic penta Base (methyl) acrylate, 2- (methyl) acryloyl-oxyethyl hexahydrophthalic acid, 2- (methyl) acryloxypropyl Hexahydrophthalic acid, 2- (methyl) acryloyl-oxyethyl phthalic acid, 2- (methyl) acryloyl-oxyethyl succinic acid, 2- (methyl) acryloyl-oxyethyl maleic acid, carboxy-polycaprolactone list (methyl) acrylate, 2- (methyl) acryloxy It is more than at least one of compound group of ethyl tetrahydrophthalic acid composition,
(methyl) acrylate monomer that carbon atom number relative to (A) alkyl described in 100 parts by weight is C1~C18, with The ratio of 0.01~0.5 parts by weight contains the described copolymerisable monomer of (C) containing carboxyl.
7. adhesion agent composition according to claim 1 or 2, which is characterized in that
(E) crosslinking delay agent is the compound of ketone-enol tautomers,
Relative to the acrylic polymer of 100 parts by weight, (E) crosslinking is contained with the ratio of 0.1~300 parts by weight Delayed-action activator,
(F) crosslinking catalyst is in the group being made of aluminium chelate compound, titanium chelate compound, iron chelating compounds At least one above metal chelate compound,
Relative to the acrylic polymer of 100 parts by weight, (F) is contained with the ratio of 0.001~0.5 parts by weight and is handed over Join catalyst,
The weight part ratio of (E)/(F) is 80~1000.
8. adhesion agent composition according to claim 1 or 2, which is characterized in that the propylene relative to 100 parts by weight Acids polymers, the adhesion agent composition contain HLB value with the ratio of 0.01~0.5 parts by weight for 6~12 and Weight-average molecular Amount is 10000 polyether modified siloxane compounds below.
9. adhesion agent composition according to claim 1 or 2, which is characterized in that the propylene relative to 100 parts by weight Acids polymers, the adhesion agent composition are contained with the ratio of 0.1~5.0 parts by weight：Make the carbon atom number C1 of alkyl~ Weight made of 18 (methyl) acrylate monomer and list (methyl) acrylate monomer copolymerization containing polyalkylene glycol chain is equal Molecular weight is more than 100,000 and is 300,000 copolymers below.
10. adhesion agent composition according to claim 1 or 2, which is characterized in that
In described list (methyl) acrylate monomer containing polyalkylene glycol chain, the alkylene oxide group of polyalkylene glycol chain is constituted Average repeat unit number be 3~14,
Diester component in described list (methyl) acrylate monomer containing polyalkylene glycol chain be 0.2% hereinafter,
It is more than 100,000 in the weight average molecular weight of 100 parts by weight and is in 300,000 copolymers below, with 1~50 parts by weight Ratio contain selected from by polyalkylene glycol mono (methyl) acrylate, methoxypolyalkylene glycol (methyl) acrylate, More than at least one of group of ethyoxyl polyalkylene glycol (methyl) acrylate composition, contain polyalkylene two as described List (methyl) acrylate monomer of alcohol chain.
11. a kind of adhesive film, which is characterized in that being laminated on the single side of resin film makes any one of claim 1~10 institute Adhering agent layer made of the adhesion agent composition crosslinking stated.
12. a kind of surface protection film, it uses the adhesive films described in claim 11.
13. a kind of surface protection film of polarizing film, it uses the adhesive films described in claim 11.
14. a kind of optical film with adhering agent layer is laminated on the face of at least side of optical film by claim 1~10 Any one of described in adhesion agent composition formed adhering agent layer.
15. adhesive film according to claim 11, wherein the resin film single side, i.e. be formed with the adhesion The side of oxidant layer is implemented with antistatic treatment and antifouling process on opposite face.
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