CN108865017B - Adhesive composition and surface protective film - Google Patents

Adhesive composition and surface protective film Download PDF

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CN108865017B
CN108865017B CN201711126884.5A CN201711126884A CN108865017B CN 108865017 B CN108865017 B CN 108865017B CN 201711126884 A CN201711126884 A CN 201711126884A CN 108865017 B CN108865017 B CN 108865017B
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acrylate
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adhesive composition
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CN108865017A (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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    • 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
    • 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
    • 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)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Polarising Elements (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention provides an adhesive composition and a surface protective film, which have excellent adhesive balance, contamination resistance, excellent adhesive performance and excellent antistatic performance without time deterioration under low-speed stripping speed and high-speed stripping speed. An adhesive composition comprising an acrylic polymer which is a copolymer obtained by copolymerizing (A) a (meth) acrylate monomer having an alkyl group and having carbon atoms of C1 to C18, (B) a hydroxyl group-containing copolymerizable monomer, and (C) a carboxyl group-containing copolymerizable monomer and having an acid value of 0.1 to 1.0, wherein 100 parts by weight of the (meth) acrylate monomer having an alkyl group and having carbon atoms of C1 to C18 contains at least 70 parts by weight of 2-ethylhexyl acrylate; the crosslinking agent is (D) an isocyanate compound with more than three functions; the antistatic agent is an ionic compound having an anion with a fluorine atom number of F7 or more and having a melting point of 25 to 50 ℃.

Description

Adhesive composition and surface protective film
Technical Field
The present invention relates to an adhesive composition containing an antistatic agent and a surface protective film. More specifically, the present invention relates to an adhesive composition for a surface protective film used for protecting the surface of a polarizing plate by being attached to the polarizing plate constituting a liquid crystal display, which has excellent adhesive properties and excellent antistatic properties without time-dependent deterioration, and a surface protective film using the same.
Background
Conventionally, in a process of manufacturing an optical member such as a polarizing plate as a member constituting a liquid crystal display, a surface protective film for temporarily protecting a surface of the optical member is attached. Such a surface protective film is used only in a process of manufacturing an optical member, and is peeled and removed from the optical member when the optical member is mounted on a liquid crystal display. Such a surface protective film for protecting the surface of the optical member is used only in the manufacturing process, and is therefore also generally referred to as a process film.
In the surface protective film used in the process of producing the optical member, an adhesive layer is formed on one surface of a polyethylene terephthalate (PET) resin film having optical transparency. Before being bonded to an optical member, a release film subjected to release treatment for protecting the adhesive layer is bonded to the adhesive layer.
In addition, optical members such as polarizing plates are subjected to product inspection accompanied with optical evaluations such as display capability, color tone, contrast, and contamination of foreign substances of the liquid crystal display panel in a state where a surface protective film is bonded thereto. Therefore, as performance required for the surface protective film, it is required that no bubbles or foreign matters and low molecular weight components of the adhesive composition adhere to the adhesive layer, that is, contamination resistance is required.
In addition, when the surface protective film is peeled from an optical member such as a polarizing plate, peeling static electricity generated by static electricity generated when the adhesive layer is peeled from an adherend may have an influence on a failure of an electric control circuit of a liquid crystal display. Therefore, the adhesive layer is required to have excellent antistatic performance.
Further, in recent years, as a protective layer (also referred to as a protective film) of a polarizer of a polarizing plate, in addition to conventional triacetyl cellulose (TAC), use of a material which easily causes peeling static electricity when peeling a surface protective film of a polarizing plate such as acrylic resin such as polymethyl methacrylate (PMMA), polyester resin such as polyethylene terephthalate (PET), cycloolefin polymer, polycarbonate, or the like has been expanded. Therefore, the antistatic performance required for the adhesive layer for the surface protective film of the polarizing plate must be superior to that of the conventional one.
Further, when the surface protective film is finally peeled from an optical member such as a polarizing plate, it is required to be peeled quickly. That is, in order to enable rapid peeling even at high-speed peeling, it is required that the change in the adhesive force due to the peeling speed is small.
As described above, in recent years, from the viewpoint of ease of use in using a surface protective film, as performance required for an adhesive agent layer constituting the surface protective film, there have been required: (1) obtaining the balance of the adhesive force under the low-speed stripping speed and the high-speed stripping speed; (2) has stain resistance; (3) excellent antistatic performance, etc.
However, even if the above-described requirements (1) to (3) as requirements for the adhesive agent layer constituting the surface protective film can be satisfied individually, it is very difficult to satisfy all of the requirements (1) to (3) for the adhesive agent layer of the surface protective film at the same time.
To solve such problems, for example, (1) a balance of adhesive force is obtained at a low peeling speed and a high peeling speed; (2) has stain resistance; and (3) excellent antistatic performance, and the following proposals are known.
With respect to (1) obtaining a balance of adhesive force at a low peeling speed and a high peeling speed, there is a problem that in an acrylic adhesive layer obtained by crosslinking a copolymer of an alkyl (meth) acrylate having an alkyl group having 7 or less carbon atoms and a carboxyl group-containing copolymerizable compound as a main component with a crosslinking agent, the adhesive migrates to the adherend side and the adhesive force to the adherend increases greatly with time in the case of long-time adhesion. In order to avoid these problems, there is known an adhesive agent layer provided by using a copolymer of an alkyl (meth) acrylate having an alkyl group with 8 to 10 carbon atoms and a copolymerizable compound having an alcoholic hydroxyl group, and crosslinking the copolymer with a crosslinking agent (patent document 1).
Further, there has been proposed a pressure-sensitive adhesive layer obtained by blending a small amount of a copolymer of an alkyl (meth) acrylate and a carboxyl group-containing copolymerizable compound in the same copolymer as described above and crosslinking the copolymer with a crosslinking agent. However, when these are used for surface protection of a plastic sheet or the like having a low surface tension and a smooth surface, there are problems that a peeling phenomenon such as floating occurs due to heating at the time of processing or storage, and that removability is poor at the time of peeling at a high speed in the field of manual work.
In order to solve these problems, an adhesive composition has been proposed in which a) 100 parts by weight of an alkyl (meth) acrylate containing an alkyl (meth) acrylate having an alkyl group with 8 to 10 carbon atoms as a main component is added with b) 1 to 15 parts by weight of a carboxyl group-containing copolymerizable compound and c) 3 to 100 parts by weight of a vinyl ester of an aliphatic carboxylic acid having 1 to 5 carbon atoms to form a copolymer of a monomer mixture, and a crosslinking agent having an equivalent weight or more to the carboxyl group of the component b) is blended (patent document 2).
The pressure-sensitive adhesive composition described in patent document 2 does not cause a peeling phenomenon such as lifting during processing or storage, has a small increase in adhesive strength with time and is excellent in removability, and can be remounted with a small force even when stored for a long period of time, particularly even when stored for a long period of time in a high-temperature atmosphere, and at this time, can be remounted with a small force even when peeled at a high speed without generating adhesive residue on an adherend.
Further, regarding (2) having stain resistance, disclosed is an adhesive composition containing: 100 parts by mass of a (meth) acrylic copolymer having a weight average molecular weight of 10 to less than 100 million, the (meth) acrylic copolymer being composed of 0 to less than 0.5 parts by mass of a carboxyl group-containing monomer, 0.6 to 9 parts by mass of a hydroxyl group-containing (meth) acrylic monomer, and 99.4 to 90.5 parts by mass of a (meth) acrylate monomer; and 0.1 to 5 parts by mass of a carbodiimide-based crosslinking agent (patent document 3).
The adhesive composition described in patent document 3 is characterized in that a carbodiimide-based crosslinking agent is used as a crosslinking agent for a (meth) acrylic copolymer having a specific composition. This makes it possible to provide the adhesive layer with a crosslinked structure that can follow shrinkage caused by pressure and temperature during the autoclave treatment. Therefore, the adhesive agent layer formed using the adhesive agent composition can suppress or prevent foaming even under high-temperature and high-pressure conditions (at the time of autoclave treatment), and is excellent in the resistance to staining of an adherend and also excellent in transparency.
Further, with respect to (3) excellent antistatic property, as a method for imparting antistatic property to the surface protective film, a method of kneading an antistatic agent into a base film, and the like are shown. As the antistatic agent, for example, there are disclosed: (a) having quaternary ammonium salts, pyridines
Figure BDA0001468542410000041
Various cationic antistatic agents having cationic groups such as salts and primary to tertiary amino groups; (b) anionic antistatic agents having sulfonate, sulfate, phosphate, phosphonate and other anionic groups; (c) amphoteric antistatic agents such as amino acids and amino sulfates; (d) nonionic antistatic agents such as aminoalcohols, glycerols, and polyethylene glycols; (e) a polymer type antistatic agent obtained by polymerizing the above antistatic agent in a high molecular weight (patent document 4).
In addition, in recent years, it has been proposed to include such an antistatic agent directly in an adhesive layer without including it in a base film or without coating it on the surface of the base film.
Further, an antistatic pressure-sensitive adhesive composition comprising a dispersion of a salt having an anion containing a fluorine group and a sulfonyl group, wherein the salt having an anion containing a fluorine group and a sulfonyl group is dispersed in a state of being dissolved in a polyether ester plasticizer having a polyether group in the main chain thereof is disclosed (patent document 5).
With respect to the adhesive composition described in patent document 5, it is disclosed that a plasticizer formed of the following ester is used as the plasticizer: an ester of a monovalent or divalent carboxylic acid having a saturated or unsaturated acyclic hydrocarbon group and an alcohol having an acyclic hydrocarbon group having 1 to 20 carbon atoms; or an epoxidized ester of an unsaturated group in the unsaturated acyclic hydrocarbon group. Consider that: such a mono-or dicarboxylic acid having a saturated or unsaturated acyclic hydrocarbon group has a carbon number close to that of an acrylic monomer constituting an acrylic copolymer used in the adhesive layer, and therefore, compatibility with the antistatic adhesive composition is improved, and the mono-or dicarboxylic acid can be suitably retained in the plasticizer acrylic antistatic adhesive composition, and therefore bleeding (bleed-out) is suppressed.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 63-225677
Patent document 2: japanese laid-open patent publication No. 11-256111
Patent document 3: japanese patent laid-open publication No. 2011-
Patent document 4: japanese laid-open patent publication No. 11-070629
Patent document 5: japanese laid-open patent publication No. 2014-118469
Disclosure of Invention
Technical problem to be solved by the invention
As described above, in the related art, as performance required for an adhesive layer constituting a surface protective film, it is required to have a balance of adhesive force at a low peeling speed and a high peeling speed, stain resistance, excellent antistatic performance, and the like. However, even if the required performances can be satisfied individually, the required performances all demanded for the adhesive agent layer of the surface protective film cannot be satisfied at the same time.
The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an adhesive composition and a surface protective film which have excellent balance of adhesive force, stain resistance, excellent adhesive performance, and excellent antistatic performance without deterioration with time at a low peeling speed and a high peeling speed.
Means for solving the problems
In an adhesive composition having antistatic properties and a surface protective film using the same, the relationship between the antistatic properties and the stain resistance to an adherend is a Trade-off relationship, and it is extremely difficult to improve the stain resistance while maintaining the antistatic properties.
However, the inventors of the present application have found that an adhesive composition containing: a copolymer obtained by copolymerizing a copolymerizable monomer having a carboxyl group; a polyether-containing silicone compound; an antistatic agent comprising an ionic compound having an anion having a fluorine atom number of F7 or more (for example, nonafluorobutanesulfonate anion) and having a melting point of 25 ℃ or more.
In order to solve the above-mentioned problems, the present invention provides an adhesive composition comprising an antistatic agent and a crosslinking agent, wherein the adhesive composition comprises an acrylic polymer which is a copolymer having an acid value of 0.1 to 1.0 and obtained by copolymerizing: (A) a (meth) acrylate monomer having an alkyl group with a carbon number of C1 to C18, (B) a hydroxyl group-containing copolymerizable monomer, and (C) a carboxyl group-containing copolymerizable monomer; the acrylic polymer contains (A) 2-ethylhexyl acrylate in an amount of 70 parts by weight or more per 100 parts by weight of the (meth) acrylate monomer having an alkyl group with a carbon number of C1 to C18; the glass transition temperature of the acrylic polymer is 0 ℃ or lower; the crosslinking agent is (D) an isocyanate compound with more than three functions; the antistatic agent is an ionic compound which has anions with more than F7 fluorine atoms, is formed by cations and anions and has a melting point of 25-50 ℃; the adhesive composition further contains (E) a crosslinking retarder and a crosslinking catalyst other than a tin compound as (F) a crosslinking catalyst.
The adhesive composition of the present invention is an adhesive composition for a surface protective film to be bonded to a protective layer of a polarizer of a polarizing plate, and preferably: the protective layer of the polarizer is one selected from the group consisting of a TAC-based film, a PMMA-based film, and a PET-based film, and the surface treatment performed on the surface of the protective layer of the polarizer is one selected from the group consisting of an untreated, AG-treated, LR-treated, AR-treated, AG-LR-treated, and AG-AR-treated.
Preferably: the above-mentionedThe anion of the ionic compound contains a radical selected from the group consisting of 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 kind of anion in the group, relative to 100 weight parts of the acrylic polymer, as the essential component, with 0.01-10 weight parts of the ionic compound.
Preferably: the cation of the ionic compound is selected from pyridine
Figure BDA0001468542410000061
Imidazole
Figure BDA0001468542410000062
Phosphonium, sulfonium, or pyrrolidines
Figure BDA0001468542410000063
Guanidine (guanidine)
Figure BDA0001468542410000064
Ammonium, isourea
Figure BDA0001468542410000065
(isouronium), thiourea
Figure BDA0001468542410000066
(thiouronium m), piperidine
Figure BDA0001468542410000067
Pyrazoles
Figure BDA0001468542410000068
(pyrazolium), methyl
Figure BDA0001468542410000069
(methylium), lithium, morpholine
Figure BDA00014685424100000610
(morpholinoium) in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the acrylic polymer, as an essential component.
Preferably: the surface resistivity of the adhesive layer obtained by crosslinking the adhesive composition is 1.0 x 10+12Omega/□ or less, the adhesive layer has a peeling electrostatic pressure in the range of-0.3 to +0.3kV against a low refractive index layer formed by using the composition for forming a low refractive index layer containing a fluorine compound, and the adhesive layer formed by crosslinking the adhesive composition has an adhesive force of 0.04 to 0.2N/25mm at a low peeling speed of 0.3 m/min and an adhesive force of 2.0N/25mm or less at a high peeling speed of 30 m/min against a polarizing plate.
Preferably: the (B) hydroxyl-containing copolymerizable monomer is at least one selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-methylol (meth) acrylamide and N-hydroxyethyl (meth) acrylamide,
the (B) hydroxyl group-containing copolymerizable monomer is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group and having C1 to C18,
the carboxyl group-containing copolymerizable monomer (C) is at least one selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylmaleic acid, carboxypolycaprolactone mono (meth) acrylate, and 2- (meth) acryloyloxyethyltetrahydrophthalic acid,
the (C) carboxyl group-containing copolymerizable monomer is contained in an amount of 0.01 to 0.5 part by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group of C1 to C18.
Preferably: the crosslinking retarder (E) is a compound of keto-enol tautomer, the crosslinking retarder (E) is contained in a proportion of 0.1-300 parts by weight relative to 100 parts by weight of the acrylic polymer, the crosslinking catalyst (F) is at least one metal chelate compound selected from the group consisting of aluminum chelate compounds, titanium chelate compounds and iron chelate compounds, the crosslinking catalyst (F) is contained in a proportion of 0.001-0.5 parts by weight relative to 100 parts by weight of the acrylic polymer, and the weight part ratio of (E)/(F) is 80-1000.
Preferably: the adhesive composition contains a polyether modified siloxane compound having an HLB value of 6-12 and a weight average molecular weight of 10000 or less in a proportion of 0.01-0.5 parts by weight relative to 100 parts by weight of the acrylic polymer.
Preferably: the adhesive composition contains, relative to 100 parts by weight of the acrylic polymer, 0.1 to 5.0 parts by weight of: a copolymer obtained by copolymerizing a (meth) acrylate monomer having an alkyl group and having a carbon number of C1-18 and a mono (meth) acrylate monomer having a polyalkylene glycol chain, and having a weight average molecular weight of more than 10 ten thousand and not more than 30 ten thousand.
Preferably: in the polyalkylene glycol chain-containing mono (meth) acrylate monomer, the average number of repeating units of alkyleneoxy groups (alkylene oxides) constituting the polyalkylene glycol chain is 3 to 14; the diester component in the polyalkylene glycol chain-containing mono (meth) acrylate monomer is 0.2% or less; in 100 parts by weight of the copolymer having a weight average molecular weight of more than 10 ten thousand and not more than 30 ten thousand, at least one selected from the group consisting of polyalkylene glycol mono (meth) acrylate, methoxy polyalkylene glycol (meth) acrylate, and ethoxy polyalkylene glycol (meth) acrylate is contained as the polyalkylene glycol chain-containing mono (meth) acrylate monomer in a proportion of 1 to 50 parts by weight.
The present invention also provides an adhesive film, wherein an adhesive layer obtained by crosslinking the adhesive composition is laminated on one surface of a resin film.
Further, the present invention provides a surface protective film using the adhesive film.
The present invention also provides a surface protective film for a polarizing plate, which uses the adhesive film.
The present invention also provides an optical film with an adhesive layer, wherein the adhesive layer formed from the adhesive composition is laminated on at least one surface of the optical film.
The present invention also provides the adhesive film described above, wherein an antistatic treatment and an antifouling treatment are applied to one surface of the resin film, that is, a surface opposite to the side on which the adhesive layer is formed.
Effects of the invention
The adhesive composition of the present invention has excellent adhesion performance and excellent antistatic performance without deterioration with time, compared with conventional adhesive compositions for surface protective films.
In particular, the surface protective film according to the present invention has excellent adhesion performance and excellent antistatic property against peeling without deterioration with time in the case where the adherend is an adherend having a low refractive index layer formed using a composition for forming a low refractive index layer containing a fluorine compound or a stain-proofing layer containing a fluorine compound laminated on the surface of an optical film, as compared with a surface protective film produced by a conventional technique. That is, the surface protective film according to the present invention has a remarkable effect in simultaneously achieving both antistatic performance and stain resistance.
That is, the adhesive composition and the surface protective film using the same according to the present invention have excellent adhesive performance and excellent antistatic property against peeling without time deterioration, and thus are extremely valuable in industrial applications.
Detailed Description
The present invention will be described below based on preferred embodiments.
The adhesive composition of the present embodiment contains an antistatic agent and a crosslinking agent, and is characterized by containing an acrylic polymer which is a copolymer obtained by copolymerizing the following monomers and having an acid value of 0.1 to 1.0: (A) a (meth) acrylate monomer having an alkyl group with a carbon number of C1 to C18, (B) a hydroxyl group-containing copolymerizable monomer, and (C) a carboxyl group-containing copolymerizable monomer; the acrylic polymer contains (A) 2-ethylhexyl acrylate in an amount of 70 parts by weight or more per 100 parts by weight of the (meth) acrylate monomer having an alkyl group with a carbon number of C1 to C18; the glass transition temperature of the acrylic polymer is 0 ℃ or lower; the crosslinking agent is (D) an isocyanate compound with more than three functions; the antistatic agent is an ionic compound which has anions with more than F7 fluorine atoms, is formed by cations and anions and has a melting point of 25-50 ℃; the adhesive composition further contains (E) a crosslinking retarder and a crosslinking catalyst other than a tin compound as (F) a crosslinking catalyst.
The acrylic polymer used in the adhesive composition of the present embodiment is a main polymer of the adhesive composition, and has a glass transition temperature of 0 ℃ or lower. The acrylic polymer is preferably a copolymer mainly composed of (a) a (meth) acrylate monomer having an alkyl group and having C1 to C18.
Examples of the (meth) acrylate monomer having an alkyl group having from C1 to C18 include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, tetradecyl (meth) acrylate, pentadecyl (meth) acrylate, hexadecyl (meth) acrylate, and mixtures thereof, Heptadecyl (meth) acrylate, octadecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. The alkyl group of the alkyl (meth) acrylate monomer may be any of a linear, branched, and cyclic alkyl group.
The acrylic polymer used in the pressure-sensitive adhesive composition of the present embodiment preferably contains 70 parts by weight or more of 2-ethylhexyl acrylate in 100 parts by weight of the (meth) acrylate monomer (a) having an alkyl group and having C1 to C18.
The acrylic polymer used in the adhesive composition of the present embodiment contains (B) a copolymerizable monomer containing a hydroxyl group. The hydroxyl group-containing copolymerizable monomer (B) is preferably at least one selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide and the like.
The (B) hydroxyl group-containing copolymerizable monomer is preferably contained in an amount of 0.1 to 10 parts by weight, more preferably 1.6 to 8.5 parts by weight, and particularly preferably 2.1 to 7.5 parts by weight, based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group of C1 to C18.
The acrylic polymer used in the adhesive composition of the present embodiment contains (C) a copolymerizable monomer containing a carboxyl group. The carboxyl group-containing copolymerizable monomer (C) is preferably at least one selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylmaleic acid, carboxypolycaprolactone mono (meth) acrylate, 2- (meth) acryloyloxyethyltetrahydrophthalic acid and the like.
The (C) carboxyl group-containing copolymerizable monomer is preferably contained in an amount of 0.01 to 0.5 parts by weight, more preferably 0.01 to 0.45 parts by weight, and particularly preferably 0.01 to 0.4 parts by weight, based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group of C1 to C18.
The method for producing the acrylic polymer contained in the adhesive composition according to the present embodiment is not particularly limited, and an appropriate and known polymerization method such as a solution polymerization method or an emulsion polymerization method can be used. The weight average molecular weight of the copolymer of the acrylic polymer is, for example, 50 to 300 ten thousand. The acid value of the acrylic polymer is preferably 0.1 to 1.0. This can improve contamination resistance. Wherein "acid value" is an index indicating the content of acid, and is expressed in mg of potassium hydroxide required for neutralizing 1g of a carboxyl group-containing polymer.
The adhesive composition according to the present embodiment contains (G) an antistatic agent. The antistatic agent (G) of the present embodiment is an ionic compound having an anion having a fluorine atom number of F7 or more and formed of a cation and an anion. The ionic compound preferably has a melting point of 25 to 50 ℃ and is solid at ordinary temperature (e.g., 25 ℃). The ionic compound is preferably contained as an essential component in a proportion of 0.01 to 10 parts by weight relative to 100 parts by weight of the acrylic polymer.
In addition, there is a need to improve the antistatic properties of the adhesive layer so as to lower the lower limit of the surface resistivity to 1.0X 10+10When the amount of omega/□ is less than or equal to omega/□, the ionic compound is preferably contained in an amount of 0.01 to 15 parts by weight based on 100 parts by weight of the acrylic polymer.
As said is separatedThe anion of the sub-compound is selected from the group consisting of6F5(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 the group consisting of. Wherein n is an integer of 1 or more.
As the cation of the ionic compound, there may be mentioned one selected from the group consisting of pyridine
Figure BDA0001468542410000121
Imidazole
Figure BDA0001468542410000122
Phosphonium, sulfonium, or pyrrolidines
Figure BDA0001468542410000123
Guanidine (guanidine)
Figure BDA0001468542410000124
Ammonium, isourea
Figure BDA0001468542410000125
Thiourea
Figure BDA0001468542410000126
Piperidine derivatives
Figure BDA0001468542410000127
Pyrazoles
Figure BDA0001468542410000128
Methyl radical
Figure BDA0001468542410000129
Lithium, morpholine
Figure BDA00014685424100001210
At least one of the group consisting of.
Specific examples of the antistatic agent (G) include methyltrioctylammonium tris (pentafluorobenzenesulfonyl) methide salt and 3-methyl-1-octylpyridine
Figure BDA00014685424100001211
Nonafluorobutane sulfonate, 1-ethyl-3-methylimidazole
Figure BDA00014685424100001212
Tetrakis (pentafluorophenyl) borate, 1-butyl-1-methylpiperidine
Figure BDA00014685424100001213
Bis (pentafluorobenzenesulfonyl) imide salts, and the like.
The adhesive composition according to the present embodiment further contains (D) a trifunctional or higher isocyanate compound as a crosslinking agent. Examples of the trifunctional or higher-functional isocyanate compound (D) include biuret modified products or isocyanurate modified products of diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, toluene diisocyanate, and xylylene diisocyanate, and adducts with trihydric or higher-polyhydric alcohols such as trimethylolpropane and glycerin. The proportion of the trifunctional or higher isocyanate compound (D) is, for example, 0.01 to 5 parts by weight based on 100 parts by weight of the acrylic polymer.
The adhesive composition according to the present embodiment may contain (E) a crosslinking retarder. Examples of the crosslinking retarder (E) include β -ketoesters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate (oleyl acetoacetate), lauryl acetoacetate, and stearyl acetoacetate, and β -diketones such as acetylacetone, 2, 4-hexanedione, and benzoylacetone. These crosslinking retarders are compounds of keto-enol tautomers, and in an adhesive composition containing a polyisocyanate compound as a crosslinking agent, by blocking (blocking) the isocyanate group of the crosslinking agent, excessive viscosity increase or gelation of the adhesive composition after blending with the crosslinking agent can be suppressed, and the pot life of the adhesive composition can be extended. (E) The crosslinking retarder is preferably a compound of keto-enol tautomer, and particularly preferably at least one selected from the group consisting of acetylacetone and ethyl acetoacetate. The crosslinking retarder is preferably contained in an amount of 0.1 to 300 parts by weight based on 100 parts by weight of the acrylic polymer.
The adhesive composition according to the present embodiment may contain a crosslinking catalyst other than a tin compound as the (F) crosslinking catalyst. When a polyisocyanate compound is used as the crosslinking agent, (F) the crosslinking catalyst may be any one that can function as a catalyst for the reaction (crosslinking reaction) between the copolymer and the crosslinking agent. Examples of the crosslinking catalyst other than the tin compound include amine compounds such as tertiary amines, and organic metal compounds such as metal chelate compounds, organolead compounds, and organozinc compounds.
The metal chelate compound as the crosslinking catalyst (F) is a compound in which 1 or more polydentate ligands L are bonded to the central metal atom M. The metal chelate compound may have 1 or more monodentate ligands X bonded to the metal atom M, or may not have monodentate ligands X. Specific examples of the metal chelate compound include iron (III) tris (2, 4-pentanedionate), iron (III) triacetylacetonate, titanium (III) triacetylacetonate, ruthenium (III) triacetylacetonate, zinc (III) bisacetoacetonate, aluminum (III) triacetylacetonate, zirconium (III) tetraacetonatoacetonate, iron (III) tris (2, 4-hexanedionate), zinc (2, 4-hexanedionate), titanium (2, 4-hexanedionate), aluminum (2, 4-hexanedionate), zirconium (2, 4-hexanedionate), and the like.
The crosslinking catalyst (F) is preferably at least one metal chelate compound selected from the group consisting of aluminum chelate compounds, titanium chelate compounds and iron chelate compounds. The crosslinking catalyst (F) is preferably contained in an amount of 0.001 to 0.5 part by weight based on 100 parts by weight of the acrylic polymer.
Since the (E) crosslinking retarder has an effect of suppressing crosslinking in contrast to the (F) crosslinking catalyst, it is preferable to appropriately set the ratio of the (E) crosslinking retarder to the (F) crosslinking catalyst. In order to prolong the storage life of the adhesive composition and improve the storage stability, the weight ratio of (E)/(F) is preferably 80-1000. Here, the weight part ratio of (E)/(F) is a value calculated as a quotient obtained by dividing the weight part of (E) by the weight part of (F).
The adhesive composition according to the present embodiment may contain (H) a polyether-modified siloxane compound as an optional component. (H) The polyether-modified silicone compound is a silicone compound having a polyether group, except for the general siloxane unit [ -SiR ]1 2-O-]In addition, it contains siloxane units [ -SiR ] having polyether groups1(R2O(R3O)nR4)-O-]. Here, R1Represents one or more alkyl or aryl groups, R2And R3Represents one or more alkylene groups, R4Represents one or two or more kinds of alkyl groups, acyl groups, or the like (terminal groups). The polyether group includes polyoxyethylene [ (C)2H4O)n]Or polyoxypropylene [ (C)3H6O)n]And the like. In the siloxane units having a polyether group, the end of the polyether group may be an OH group (R in the above formula)4＝H)。
(H) The polyether modified siloxane compound is preferably a polyether modified siloxane compound with an HLB value of 6-12. Further, the (H) polyether-modified silicone compound is preferably contained in an amount of 0.01 to 0.5 part by weight, more preferably 0.02 to 0.35 part by weight, and particularly preferably 0.02 to 0.25 part by weight, based on 100 parts by weight of the acrylic polymer. The HLB value is, for example, a hydrophilic-lipophilic balance (hydrophilic-lipophilic ratio) defined in JIS K3211 (term for surfactant) and the like.
The polyether-modified siloxane compound can be obtained, for example, by: an organic compound having an unsaturated bond and a polyoxyalkylene group is grafted to a polyorganosiloxane main chain having a silicon hydride group by a hydrosilylation reaction. Specific examples thereof include dimethylsiloxane-methyl (polyoxyethylene) siloxane copolymer, dimethylsiloxane-methyl (polyoxyethylene) siloxane-methyl (polyoxypropylene) siloxane copolymer, and dimethylsiloxane-methyl (polyoxypropylene) siloxane polymer.
By blending (H) the polyether-modified siloxane compound into the adhesive composition, the adhesive force and reworkability of the adhesive agent layer can be improved. (H) The polyether-modified siloxane compound preferably has a weight average molecular weight of 10000 or less. From the viewpoint of compatibility with acrylic polymers, the polyether-modified silicone compound having a low HLB value and a low molecular weight has good compatibility, but the polyether-modified silicone compound having a low molecular weight has a high HLB value, and even if the compatibility with the polymer is slightly low, excellent antistatic properties can be obtained.
The adhesive composition according to the present embodiment may contain, as an optional component, a copolymer (hereinafter referred to as "copolymer B") having a weight average molecular weight of more than 10 ten thousand and not more than 30 ten thousand as an antistatic auxiliary agent, the copolymer being obtained by copolymerizing (meth) acrylate monomer having an alkyl group having carbon atoms of C1 to 18 with (I) mono (meth) acrylate monomer having a polyalkylene glycol chain. The copolymer B is preferably contained in an amount of 0.1 to 5.0 parts by weight, more preferably 0.1 to 3.5 parts by weight, and particularly preferably 0.1 to 2.5 parts by weight, based on 100 parts by weight of the acrylic polymer.
The polyalkylene glycol chain-containing mono (meth) acrylate monomer (I) may be a compound in which one of a plurality of hydroxyl groups of the polyalkylene glycol is esterified to a (meth) acrylate. The (meth) acrylate group is a polymerizable group and therefore can be copolymerized with the acrylic polymer. It may be other polyalkylene glycol mono (meth) acrylates whose hydroxyl group remains OH, or may be other alkoxy polyalkylene glycol mono (meth) acrylates whose hydroxyl group is converted to an alkyl ether.
The polyalkylene glycol constituting the polyalkylene glycol chain may be any glycol compound having one or two or more alkylene groups, and examples thereof include polyethylene glycol, polypropylene glycol, polybutylene glycol, polyethylene glycol-polypropylene glycol, polyethylene glycol-polybutylene glycol, polypropylene glycol-polybutylene glycol, and polyethylene glycol-polypropylene glycol-polybutylene glycol.
The average number of repeating alkylene oxide groups constituting the polyalkylene glycol chain of the (I) polyalkylene glycol chain-containing mono (meth) acrylate monomer is preferably 3 to 14. The "average number of repeating alkyleneoxy groups" means the average number of repeating alkyleneoxy groups in the "polyalkylene glycol chain" moiety contained in the molecular structure of the (I) polyalkylene glycol chain-containing mono (meth) acrylate monomer. In addition, the diester component in the (I) polyalkylene glycol chain-containing mono (meth) acrylate monomer is preferably 0.2% or less. The "diester component in the monomer" means the content (wt%) of the polyalkylene glycol di (meth) acrylate contained in the polyalkylene glycol chain-containing mono (meth) acrylate monomer (I).
The polyalkylene glycol chain-containing mono (meth) acrylate monomer (I) is preferably at least one selected from the group consisting of polyalkylene glycol mono (meth) acrylate, methoxy polyalkylene glycol (meth) acrylate, and ethoxy polyalkylene glycol (meth) acrylate. The proportion of the polyalkylene glycol chain-containing mono (meth) acrylate monomer (I) in the copolymer B is preferably 1 to 50 parts by weight, more preferably 2 to 35 parts by weight, and particularly preferably 2 to 25 parts by weight, based on 100 parts by weight of the copolymer B.
Examples of the monomer other than the (I) polyalkylene glycol chain-containing mono (meth) acrylate monomer copolymerized into the copolymer B include at least one of a (meth) acrylate monomer having an alkyl group and having C1-18 carbon atoms and a hydroxyl group-containing copolymerizable monomer. Specific examples of these monomers include (meth) acrylic monomers as exemplified in the above (a) and (B). The monomers copolymerized into the copolymer B may also be different from the monomers copolymerized into the acrylic polymer. The copolymer B may not be copolymerized with a copolymerizable monomer having a carboxyl group.
The pressure-sensitive adhesive composition of the present embodiment may contain known additives such as a surfactant, a curing accelerator, a plasticizer, a filler, a curing retarder, a processing aid, an antioxidant, and the like as appropriate. These additives may be used alone or in combination of two or more.
The adhesive composition of the present embodiment is suitable as an adhesive composition for a surface protective film to be attached to a protective layer of a polarizer of a polarizing plate. Here, the protective layer of the polarizer of the polarizing plate may be one selected from the group consisting of a TAC-based film, a PMMA-based film, and a PET-based film. Here, TAC is an abbreviation of triacetyl cellulose, PMMA is an abbreviation of polymethyl methacrylate, and PET is an abbreviation of polyethylene terephthalate.
The surface treatment applied to the surface of the protective layer of the polarizer of the polarizing plate may be one selected from the group consisting of no treatment, AG treatment, LR treatment, AR treatment, AG-LR treatment, and AG-AR treatment. Here, AG means Anti-Glare (Anti Glare), LR means Low Reflection (Low Reflection), and AR means Anti-Reflection (Anti Reflection).
In the adhesive layer obtained by crosslinking the adhesive composition of the present embodiment, the surface resistivity of the adhesive layer is preferably 1.0 × 10+12Omega/□ or less, more preferably 5.0X 10+11Omega/□ or less, particularly preferably 1.0X 10+11Omega/□ or less. When the surface resistivity is high, the performance of releasing static electricity generated when the adhesive layer is peeled from an adherend is poor. Therefore, by sufficiently reducing the surface resistivity, the peeling electrostatic voltage generated by the static electricity generated when the adhesive layer is peeled from the adherend can be reduced, and the influence on the adherend can be suppressed.
In the adhesive layer obtained by crosslinking the adhesive composition of the present embodiment, the peeling electrostatic pressure of the adhesive layer to the low refractive index layer formed using the composition for forming a low refractive index layer containing a fluorine compound is preferably in the range of-0.3 to +0.3 kV. Examples of the fluorine compound used in the composition for forming a low refractive index layer include a fluorine-containing copolymer which is one or two or more polymers selected from fluorinated olefins, fluorinated vinyl ethers, fluorinated alkyl (meth) acrylates, and the like, and a condensate of a silane compound containing a fluorinated alkyl group. The fluorine-containing copolymer may be copolymerized with a non-fluorinated monomer such as an olefin, a vinyl ether, or a (meth) acrylate, in addition to the fluorinated monomer. The low refractive index layer may be combined with a high refractive index layer or the like to constitute an antireflection layer.
The adhesive layer obtained by crosslinking the adhesive composition of the present embodiment preferably has an adhesive force of 0.04 to 0.2N/25mm to a polarizing plate at a low peeling speed of 0.3 m/min, an adhesive force of 2.0N/25mm or less at a high peeling speed of 30 m/min, and an adhesive force of 0.2 to 1.6N/25mm at a high peeling speed of 30 m/min. This provides a performance of reducing a change in adhesive force due to the peeling speed, and allows quick peeling even by high-speed peeling. Further, even when the surface protective film is temporarily peeled off for reattachment, excessive force is not required, and the surface protective film is easily peeled off from the adherend.
The gel fraction of the adhesive layer obtained by crosslinking the adhesive composition of the present embodiment is preferably 95 to 100%, and more preferably 97 to 100%. By such a high gel fraction, the adhesive force is not excessively high at a low peeling speed, elution of unpolymerized monomer or oligomer from the copolymer is reduced, and the reworkability or durability at high temperature and high humidity is improved, whereby contamination of an adherend can be suppressed.
The adhesive film of the present embodiment is obtained by forming an adhesive layer obtained by crosslinking the adhesive composition of the present embodiment on one surface or both surfaces of a resin film. The surface protective film of the present embodiment is a surface protective film in which an adhesive layer obtained by crosslinking the adhesive composition of the present embodiment is formed on one surface of a resin film. The adhesive composition of the present embodiment has excellent antistatic performance, excellent balance of adhesive force at a low peeling speed and a high peeling speed, and contamination resistance. Therefore, the composition can be suitably used for the surface protective film of a polarizing plate.
As a base film of the adhesive layer or a release film (separator) for protecting the adhesive surface, a resin film such as a polyester film or the like can be used.
The antistatic treatment and the antifouling treatment may be performed on one surface of the resin film, that is, the surface opposite to the side on which the adhesive layer is formed. Examples of the antistatic treatment include coating or kneading of an antistatic agent. Examples of the antifouling treatment include treatments with silicone-based or fluorine-based release agents or coating agents, silica fine particles, and the like. The release film may be subjected to a release treatment with a silicone-based, fluorine-based, or long chain alkyl-based release agent on the surface of the adhesive layer to be bonded to the pressure-sensitive adhesive surface.
Further, an optical film with an adhesive layer can be obtained by laminating an adhesive layer obtained by crosslinking the adhesive composition of the present embodiment on at least one surface of an optical film. Examples of the optical film include a polarizing film, a retardation film, an antireflection film, an Anti Glare (Anti Glare) film, an ultraviolet absorbing film, an infrared absorbing film, an optical compensation film, and a brightness enhancement film. Examples of devices to which the optical member is applied include a liquid crystal panel, an organic EL panel, and a touch panel.
In the case of an optical surface protective film or adhesive film such as a surface protective film for a polarizing plate, the base film and the adhesive layer preferably have sufficient transparency.
Examples
The present invention will be specifically described below with reference to examples.
< preparation of acrylic Polymer solution >
[ example 1]
Nitrogen gas was introduced into a reaction apparatus equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introduction tube, and the air in the reaction apparatus was replaced with nitrogen gas. Then, 90 parts by weight of 2-ethylhexyl acrylate, 10 parts by weight of methyl acrylate, 5.5 parts by weight of 8-hydroxyoctyl acrylate, and 0.2 parts by weight of acrylic acid were added to the reaction apparatus, together with a solvent (ethyl acetate). Then, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours, and reacted at 65 ℃ for 6 hours to obtain an acrylic polymer solution used in example 1.
Examples 2 to 6 and comparative examples 1 to 3
Acrylic polymer solutions used in examples 2 to 6 and comparative examples 1 to 3 were obtained in the same manner as the acrylic polymer solution used in example 1, except that the monomer compositions were each as shown in (a) to (C) of table 1.
< preparation of adhesive composition and surface protective film >
[ example 1]
To the acrylic polymer solution of example 1 prepared as described above, 2.0 parts by weight of a crosslinking agent (CORONATE HX), 9 parts by weight of a crosslinking retarder (acetylacetone), 0.1 part by weight of a crosslinking catalyst (titanium triacetylacetonate), 0.9 part by weight of an antistatic agent (methyltrioctylammonium tris (pentafluorobenzenesulfonyl) methide salt), 0.05 part by weight of a polyether-modified silicone compound (HLB ═ 7), and 0.2 part by weight of copolymer B-1 (molecular weight 15 ten thousand) were added and mixed with stirring to obtain the pressure-sensitive adhesive composition of example 1. The adhesive composition was coated on a release film (silicone resin-coated PET film), and then dried at 90 ℃ to remove the solvent, thereby obtaining an adhesive layer having a thickness of 20 μm. Then, the adhesive layer with the release film was transferred onto the surface of the base film (PET film on which one surface was subjected to the antistatic and antifouling treatment) opposite to the surface subjected to the antistatic and antifouling treatment, to obtain the surface protective film of example 1 having a laminated structure of "base film/adhesive layer/release film".
Examples 2 to 6 and comparative examples 1 to 3
Surface protective films of examples 2 to 6 and comparative examples 1 to 3 were obtained in the same manner as the surface protective film of example 1 described above, except that the additive compositions were as described in (D) to (H) and the copolymer B of table 1, respectively.
[ Table 1]
Figure BDA0001468542410000191
In table 1, the weight parts of each component were determined assuming that the total amount of (meth) acrylate monomers having an alkyl group of C1 to C18 was 100 weight parts.
In table 1, in each column of (D), (E), (F), (G), (H), and (copolymer B), the content ratio (parts by weight) of each component is represented by the numerical value in parentheses (), assuming that the acrylic polymer is 100 parts by weight.
In addition, the names of the compounds of the abbreviations used in Table 1 are shown in tables 2 to 3. In Table 2, the names of the compounds having the abbreviations of the monomers other than (I) the polyalkylene glycol chain-containing mono (meth) acrylate monomer among the constituent monomers of the copolymer B shown in Table 3 are also included. Cornate (registered trademark) HX, cornate HL, and cornate L are trade names of TOSOH CORPORATION, and TAKENATE (registered trademark) D-140N is a trade name of Mitsui Chemicals, inc.
[ Table 2]
Figure BDA0001468542410000211
[ Table 3]
Figure BDA0001468542410000221
(G) In the antistatic agent, G-1 to G-4 are all solid ionic compounds having an anion having a fluorine atom number of F7 or more and a melting point of 25 ℃ or higher. G-5 is a solid ionic compound having an anion of F5 in the number of fluorine atoms and having a melting point of 25 ℃ or higher.
(H) In the polyether modified siloxane compound, the weight average molecular weights of H-1 to H-6 are all less than 10000.
(I) In the polyalkylene glycol chain-containing mono (meth) acrylate monomer, the diester component in the monomers I-1 to I-3 is 0.2% or less, and the diester component in the monomer I-4 is 0.8%. In addition, n in the column of group (I) in table 3 is a numerical value representing the average number of repeating units of alkyleneoxy groups.
< test method and evaluation >
The surface protective films of examples 1 to 6 and comparative examples 1 to 3 were aged in an atmosphere of 23 ℃ and 50% RH for 7 days, and then evaluated by the following test methods.
< test method of adhesion >
The release film was peeled off, and the surface protective film with the adhesive layer exposed was bonded to the surface of the polarizing plate via the adhesive layer, and after leaving for 1 day, the surface protective film was subjected to a autoclaving treatment at 50 ℃ and 5 atmospheres for 20 minutes, and after leaving for 12 hours at room temperature, the film was used as a sample for measuring the adhesive force. The obtained measurement sample was peeled in the 180 ° direction at a low speed (0.3 m/min) or a high speed (30 m/min) using a tensile tester, and the peel strength measured was taken as the adhesion.
Here, the protective layer of the polarizer is one selected from the group consisting of triacetyl cellulose (TAC), polymethyl methacrylate (PMMA), and polyethylene terephthalate (PET).
In addition, for an LR polarizing plate and an AG-LR polarizing plate, a low reflection surface treatment is performed on the surface of a protective layer of a polarizer of the polarizing plate using a composition containing a fluorine compound.
< test method of surface resistivity >
After curing the surface protective film, the release film was peeled off to expose the adhesive layer before bonding the surface protective film to the polarizing plate, and the surface resistivity of the adhesive layer was measured using a resistivity meter HIRESTA UP-HT450 (manufactured by Mitsubishi Chemical analytical co.
< test method of Peel Electrostatic Voltage >
The surface protective film with the adhesive layer exposed is bonded to a polarizing plate having a low refractive index layer formed on the surface to be bonded using a composition for forming a low refractive index layer containing a fluorine compound, with the release film removed. When the surface protective film was peeled at 180 ℃ at a stretching speed of 30 m/min, the voltage (electrostatic voltage) generated by charging the adherend was measured using high-precision electrostatic sensors SK-035 and SK-200 (manufactured by KEYENCE CORPOR ATION), and the maximum value of the measured values was defined as the peeling electrostatic voltage.
< test method for contamination resistance >
The Low Reflection (LR) surface-treated polarizing plate was bonded to one surface of a glass plate via an adhesive layer (double-sided adhesive tape) using a bonding machine. Then, a surface protective film was attached to the surface of the polarizing plate using an attaching machine. After storage for 3 days and 30 days in an environment of 23 ℃ and 50% RH, the surface protective film was peeled off, and the state of contamination of the surface of the polarizing plate was visually observed. As criteria for determining contamination resistance, the case where the surface of the polarizing plate was not contaminated was evaluated as "o", the case where there was little contamination was evaluated as "Δ", and the case where there was contamination was evaluated as "x".
Table 4 shows the evaluation results of the surface protective films of examples 1 to 6 and comparative examples 1 to 3. "surface resistivity" is determined by mixing "m.times.10+n"mE + n" (where m is an arbitrary real number and n is a positive integer) is given. The column "protective layer for polarizer of polarizing plate" shows the material and surface treatment of the protective layer for polarizer of polarizing plate used in the adhesion test. "surface treated" Plain means untreated.
[ Table 4]
Figure BDA0001468542410000241
The surface protective films of examples 1 to 6 had an adhesive force of 0.04 to 0.2N/25mm at a low peeling speed of 0.3 m/min and an adhesive force of 2.0N/25mm or less at a high peeling speed of 30 m/min, respectively, to a polarizing plate as an adherend, and were excellent in adhesive performance.
In addition, the surface resistivity of the adhesive layer of the surface protective films of examples 1 to 6 was 1.0X 10+12Omega/□ or less, adhesive layerThe low refractive index layer formed by using the composition for forming a low refractive index layer containing a fluorine compound has a stripping charged voltage in the range of-0.3 to +0.3kV, and is excellent in antistatic performance.
Further, the surface protective films of examples 1 to 6 did not stain the polarizing plate as an adherend and were excellent in stain resistance even after storage for 3 days and 30 days.
That is, the evaluation results of the surface protective films of examples 1 to 6 shown in table 4 prove that the technical problems of the present invention can be solved.
In the surface protective film of comparative example 1, 100 parts by weight of (a) 2EHA in the (meth) acrylate monomer having an alkyl group with a carbon number of C1 to C18 in the acrylic polymer contained in the adhesive composition was used in a smaller amount of 50 parts by weight, and (C) a copolymerizable monomer containing a carboxyl group was not copolymerized. In addition, the antistatic agent contained F5 anion having less fluorine atoms than F7 in the adhesive composition according to the surface protective film of comparative example 1. Therefore, the adhesive layer of the surface protective film of comparative example 1 had a large adhesive force, high peel static pressure, and poor stain resistance.
In addition, in the surface protective film of comparative example 2, the acid value of the acrylic polymer contained in the adhesive composition exceeded 1.0, and the stain resistance was poor.
In addition, in the surface protection film of comparative example 3, the antistatic agent contained in the adhesive composition contained F5 anion having less fluorine atoms than F7, and the stain resistance was poor.
Thus, the surface protective films of comparative examples 1 to 3 failed to solve the technical problems of the present invention.

Claims (15)

1. An adhesive composition comprising an antistatic agent and a crosslinking agent, characterized in that,
the adhesive composition contains an acrylic polymer of a copolymer having an acid value of 0.1 to 1.0, which is obtained by copolymerizing:
(A) a (meth) acrylate monomer having an alkyl group with a carbon number of C1-C18,
(B) A hydroxyl group-containing copolymerizable monomer, and
(C) a carboxyl group-containing copolymerizable monomer;
the acrylic polymer contains (A) 2-ethylhexyl acrylate in an amount of 70 parts by weight or more per 100 parts by weight of the (meth) acrylate monomer having an alkyl group with a carbon number of C1 to C18;
the glass transition temperature of the acrylic polymer is 0 ℃ or lower;
the crosslinking agent is (D) an isocyanate compound with more than three functions;
the antistatic agent is an ionic compound which has anions with more than F7 fluorine atoms, is formed by cations and anions, and has a melting point of 25-50 ℃;
the anion of the ionic compound is selected from the group consisting of 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-And CF3(CF2)3SO3 -At least one member selected from the group consisting of n is an integer of 1 or more;
the adhesive composition further contains (E) a crosslinking retarder and a crosslinking catalyst other than a tin compound as (F) a crosslinking catalyst.
2. The adhesive composition according to claim 1, which is an adhesive composition for a surface protective film to be attached to a protective layer of a polarizer of a polarizing plate,
the protective layer of the polarizer is one selected from the group consisting of a TAC-based film, a PMMA-based film, and a PET-based film, and the surface treatment performed on the surface of the protective layer of the polarizer is one selected from the group consisting of an untreated, AG-treated, LR-treated, AR-treated, AG-LR-treated, and AG-AR-treated.
3. The adhesive composition according to claim 1 or 2, wherein the ionic compound is contained as an essential component in a proportion of 0.01 to 10 parts by weight relative to 100 parts by weight of the acrylic polymer.
4. The adhesive composition according to claim 1 or 2, wherein the cation of the ionic compound is one selected from the group consisting of pyridine, imidazole, phosphonium, sulfonium, pyrrolidine, guanidine, ammonium, isourea, thiourea, piperidine, pyrazole, methyl, lithium, morpholine,
the ionic compound is contained as an essential component in a proportion of 0.01 to 10 parts by weight relative to 100 parts by weight of the acrylic polymer.
5. Adhesive composition according to claim 1 or 2,
the surface resistivity of the adhesive layer obtained by crosslinking the adhesive composition is 1.0 x 10+12Below the value of omega/□, the ratio of omega/□,
the adhesive layer has a peeling electrostatic pressure in the range of-0.3 to +0.3kV against a low refractive index layer formed by using a composition for forming a low refractive index layer containing a fluorine compound,
the adhesive layer obtained by crosslinking the adhesive composition has an adhesive force of 0.04-0.2N/25 mm at a low peeling speed of 0.3 m/min and an adhesive force of 2.0N/25mm or less at a high peeling speed of 30 m/min.
6. Adhesive composition according to claim 1 or 2,
the (B) hydroxyl-containing copolymerizable monomer is at least one selected from the group consisting of 8-hydroxyoctyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-hydroxy (meth) acrylamide, N-methylol (meth) acrylamide and N-hydroxyethyl (meth) acrylamide,
the (B) hydroxyl group-containing copolymerizable monomer is contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group and having C1 to C18,
the carboxyl group-containing copolymerizable monomer (C) is at least one selected from the group consisting of (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, 2- (meth) acryloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxypropylhexahydrophthalic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylmaleic acid, carboxypolycaprolactone mono (meth) acrylate, and 2- (meth) acryloyloxyethyltetrahydrophthalic acid,
the (C) carboxyl group-containing copolymerizable monomer is contained in an amount of 0.01 to 0.5 part by weight based on 100 parts by weight of the (meth) acrylate monomer having an alkyl group of C1 to C18.
7. Adhesive composition according to claim 1 or 2,
the (E) crosslinking delaying agent is a compound of keto-enol tautomer,
the crosslinking retarder (E) is contained in a proportion of 0.1-300 parts by weight relative to 100 parts by weight of the acrylic polymer,
the crosslinking catalyst (F) is at least one metal chelate compound selected from the group consisting of an aluminum chelate compound, a titanium chelate compound and an iron chelate compound,
the crosslinking catalyst (F) is contained in a proportion of 0.001 to 0.5 part by weight relative to 100 parts by weight of the acrylic polymer,
the weight part ratio of the (E)/the (F) is 80-1000.
8. The adhesive composition according to claim 1 or 2, wherein the adhesive composition contains the polyether-modified siloxane compound having an HLB value of 6 to 12 and a weight-average molecular weight of 10000 or less in a proportion of 0.01 to 0.5 parts by weight relative to 100 parts by weight of the acrylic polymer.
9. The adhesive composition according to claim 1 or 2, wherein the adhesive composition contains, relative to 100 parts by weight of the acrylic polymer, 0.1 to 5.0 parts by weight of: a copolymer having a weight average molecular weight of more than 10 ten thousand and not more than 30 ten thousand, which is obtained by copolymerizing a (meth) acrylate monomer having an alkyl group containing C1-18 and a mono (meth) acrylate monomer containing a polyalkylene glycol chain.
10. Adhesive composition according to claim 9,
in the polyalkylene glycol chain-containing mono (meth) acrylate monomer, the average number of repeating units of alkyleneoxy groups constituting the polyalkylene glycol chain is 3 to 14,
the diester component in the polyalkylene glycol chain-containing mono (meth) acrylate monomer is 0.2% or less,
in 100 parts by weight of the copolymer having a weight average molecular weight of more than 10 ten thousand and not more than 30 ten thousand, at least one selected from the group consisting of polyalkylene glycol mono (meth) acrylate, methoxy polyalkylene glycol (meth) acrylate, and ethoxy polyalkylene glycol (meth) acrylate is contained as the polyalkylene glycol chain-containing mono (meth) acrylate monomer in a proportion of 1 to 50 parts by weight.
11. An adhesive film characterized in that an adhesive layer obtained by crosslinking the adhesive composition according to any one of claims 1 to 10 is laminated on one surface of a resin film.
12. A surface protective film using the adhesive film according to claim 11.
13. A surface protective film for a polarizing plate, which uses the adhesive film according to claim 11.
14. An optical film with an adhesive layer, wherein an adhesive layer comprising the adhesive composition according to any one of claims 1 to 10 is laminated on at least one surface of the optical film.
15. The adhesive film according to claim 11, wherein an antistatic treatment and an antifouling treatment are applied to one surface of the resin film, that is, a surface opposite to the side on which the adhesive layer is formed.
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