CN108795348B - Adhesive composition and surface protective film - Google Patents

Adhesive composition and surface protective film Download PDF

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CN108795348B
CN108795348B CN201711053007.XA CN201711053007A CN108795348B CN 108795348 B CN108795348 B CN 108795348B CN 201711053007 A CN201711053007 A CN 201711053007A CN 108795348 B CN108795348 B CN 108795348B
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parts
adhesive composition
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CN108795348A (en
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长仓毅
吉田弘幸
大津贺健太郎
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
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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    • 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
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    • 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
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    • 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
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/14—Protective coatings, e.g. hard coatings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0091—Complexes with metal-heteroatom-bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/122—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present only on one side of the carrier, e.g. single-sided adhesive tape
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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    • 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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    • 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
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Polarising Elements (AREA)
  • Surface Treatment Of Optical Elements (AREA)
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Abstract

The invention provides an adhesive composition and a surface protective film which can simultaneously realize excellent antistatic property and stain resistance. The adhesive composition contains an acrylic polymer having a glass transition temperature of 0 ℃ or lower, an antistatic agent and a crosslinking agent, wherein the crosslinking agent is an isocyanate compound having three or more functional groups, the antistatic agent is an ionic compound having a melting point of 25 ℃ or higher and composed of a cation and an anion, and the anion is one selected from the group consisting of a trifluoromethanesulfonate anion, a pentafluoroethanesulfonate anion, a heptafluoropropanesulfonate anion and a nonafluorobutanesulfonate anion, and the antistatic agent 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.

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 having excellent antistatic performance and stain resistance by containing an ionic compound having a specific sulfonate anion such as nonafluorobutane sulfonate as an antistatic agent, and a surface protective film using the same.
Background
Conventionally, in the manufacturing process and the assembling process of precision parts and members such as electronic equipment parts, optical equipment parts, image display panels, and the like, a surface protective film has been attached to the surfaces of the precision parts and members in order to temporarily protect the surfaces of the precision parts and members and prevent the adhesion of particles (particles) and gaseous pollutants from the working environment atmosphere, or the generation of scratches and depressions.
For example, in a surface protective film used in a process of manufacturing an optical member such as a polarizing plate or a retardation plate which is a member constituting a liquid crystal display, an adhesive layer is formed on one surface of a polyethylene terephthalate (PET) resin film having optical transparency, but a release film subjected to a peeling treatment for protecting the adhesive layer is bonded to the adhesive layer before the adhesive layer is bonded to the optical member.
Further, optical members such as a polarizing plate and a retardation plate are subjected to product inspection accompanied with optical evaluation such as display capability, color tone, contrast, and contamination of foreign substances of a liquid crystal display panel in a state where a surface protective film is bonded thereto. Therefore, as a performance required for the surface protective film, it is required that no bubbles or foreign substances adhere to the adhesive layer.
In addition, in recent years, it is considered that when a surface protective film is peeled from an optical member such as a polarizing plate or a retardation plate, peeling static electricity generated by static electricity generated when an 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, excellent antistatic performance is required for the adhesive layer.
As described above, in recent years, as performance required for an adhesive agent layer constituting a surface protective film, excellent antistatic performance, contamination prevention performance, and the like are required from the viewpoint of ease of use in using the surface protective film.
As for excellent antistatic properties, as a method for imparting antistatic properties to a surface protective film, a method of kneading an antistatic agent into a base film, and the like are disclosed, and as the antistatic agent, for example: (a) having quaternary ammonium salts, pyridines
Figure BDA0001453318770000021
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 1).
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 applying it to the surface of the base film (patent document 2).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 11-070629
Patent document 2: japanese patent laid-open publication No. 2000-129235
Disclosure of Invention
Technical problem to be solved by the invention
However, in the case of a surface protective film used for an optical film such as an LR (low reflection) polarizing plate or an AG (anti-glare) -LR polarizing plate, since the surface of the optical film is subjected to an anti-staining treatment or a low reflection surface treatment based on a silicone compound, a fluorine compound, or the like, the peeling static voltage at the time of peeling the surface protective film from the optical film as an adherend becomes high.
Further, the relationship between the antistatic property of an adhesive composition having antistatic property and the stain resistance of a surface protective film using the adhesive composition and the stain resistance to an adherend is a trade-off relationship, and it is difficult to improve the stain resistance while maintaining the antistatic property.
Therefore, in an adhesive composition for a surface protective film used for an optical film such as an LR polarizing plate or an AG-LR polarizing plate, there has been demanded an adhesive composition which can suppress a peeling static voltage at the time of peeling a surface protective film from an optical film to be low and which causes little contamination of an adherend even when an anti-stain treatment or a low reflection surface treatment based on a silicone compound, a fluorine compound or the like is applied to the surface of the optical film.
The present invention has been made in view of the above circumstances, and provides an adhesive composition which can realize both excellent antistatic performance and stain resistance when an adherend is subjected to a surface treatment with a composition containing a fluorine compound, and a surface protective film using the adhesive composition.
Means for solving the problems
The inventors of the present application prepared a novel adhesive composition containing: a copolymer obtained by copolymerizing two or more kinds of alkyl (meth) acrylates in a specific combination while limiting the number of carbon atoms of the alkyl group of the alkyl (meth) acrylate constituting the acrylic polymer of the pressure-sensitive adhesive composition to a specific range; and an antistatic agent comprising an ionic compound having a specific sulfonate anion such as nonafluorobutanesulfonate and having a melting point of 25 ℃ or higher. As a result, the present inventors have found that an adhesive composition having excellent stain resistance and excellent antistatic property against peeling without deterioration with time can be obtained as compared with conventional adhesive compositions for surface protective films, and have completed the present invention.
In particular, it has been clarified that: when the adherend has a fluorine compound-containing antifouling layer laminated on the surface of the optical film or a low refractive index layer formed using a fluorine compound-containing low refractive index forming composition, the surface protection film according to the present invention has excellent stain resistance and excellent antistatic properties without deterioration with time, as compared with the prior art. That is, a surface protective film having an effect of simultaneously realizing antistatic performance and stain resistance can be obtained.
In order to solve the above-mentioned problems, the present invention provides an adhesive composition comprising an acrylic polymer, an antistatic agent and (D) a crosslinking agent,
the acrylic polymer has a glass transition temperature of 0 ℃ or lower,
the crosslinking agent (D) is an isocyanate compound with more than three functions,
the antistatic agent is an ionic compound formed by cations and anions and having a melting point of more than 25 ℃, the anions are one selected from the group consisting of trifluoromethane sulfonate anions, pentafluoroethane sulfonate anions, heptafluoropropane sulfonate anions and nonafluorobutane sulfonate anions,
the antistatic agent is contained in a proportion of 0.01-10 parts by weight relative to 100 parts by weight of the acrylic polymer as an essential component.
Further, it is preferable that: the acrylic polymer is a copolymer obtained by copolymerizing:
(A) at least two or more (meth) acrylate monomers having an alkyl group with carbon atoms of 1-18, wherein the at least two or more (meth) acrylate monomers comprise (a1) at least one (meth) acrylate monomer having an alkyl group with carbon atoms of 1-4 in an amount of 1-50 parts by weight, and comprise (a2) at least one (meth) acrylate monomer having an alkyl group with carbon atoms of 5-18 in an amount of 50-99 parts by weight, and the total amount of (a1) and (a2) is 100 parts by weight;
(B) At least one or more copolymerizable vinyl monomers containing a hydroxyl group and/or a carboxyl group; and
(C) at least one kind of a mono (meth) acrylate monomer having a polyalkylene glycol chain,
wherein (a2) contains at least one selected from the group consisting of isooctyl (meth) acrylate, isononyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate in a proportion of 50 parts by weight or more,
the adhesive composition further contains (E) a crosslinking accelerator for the metal chelate compound and (F) a keto-enol tautomer compound.
The cation is preferably selected from the group consisting of pyridine
Figure BDA0001453318770000041
Imidazole
Figure BDA0001453318770000042
Phosphonium, sulfonium, or pyrrolidines
Figure BDA0001453318770000043
Guanidine (guanidine)
Figure BDA0001453318770000044
Ammonium, isourea
Figure BDA0001453318770000045
(isouronium), thiourea
Figure BDA0001453318770000046
(thiouronium), piperidine
Figure BDA0001453318770000047
Pyrazoles
Figure BDA0001453318770000048
(pyrazolium), methyl
Figure BDA0001453318770000049
(methylium), lithium, morpholine
Figure BDA00014533187700000410
(morpholinoium).
Preferably: the surface resistivity of the adhesive layer obtained by crosslinking the adhesive composition is 1.0 x 10+12Omega/□ or less, and the peeling electrostatic voltage of the adhesive layer is-0.3 to +0.3kV relative to the low refractive index layer formed by using the composition for forming the low refractive index layer containing the fluorine compound.
Preferably: the copolymerizable vinyl monomer containing a hydroxyl group and/or a carboxyl group (B) is at least one or more selected from the group consisting of a copolymerizable monomer containing a hydroxyl group and a copolymerizable monomer containing a carboxyl group,
The copolymerizable monomer containing hydroxyl 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 carboxyl group-containing copolymerizable monomer 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.
Preferably: the average number of repeating units of alkylene oxide (alkylene oxide) constituting the polyalkylene glycol chain in the (C) polyalkylene glycol chain-containing mono (meth) acrylate monomer is 3 to 14,
The diester component in the (C) polyalkylene glycol chain-containing mono (meth) acrylate monomer is 0.2% or less,
at least one or more selected from the group consisting of polyalkylene glycol mono (meth) acrylates, methoxy polyalkylene glycol (meth) acrylates and ethoxy polyalkylene glycol (meth) acrylates is contained as the (C) polyalkylene glycol chain-containing mono (meth) acrylate monomer in a proportion of 1 to 50 parts by weight based on 100 parts by weight in total of at least two or more of the (A) alkyl group (meth) acrylate monomers having C1 to 18 carbon atoms.
Preferably: the crosslinking accelerator (E) is at least one selected from the group consisting of an aluminum chelate compound, a titanium chelate compound and an iron chelate compound,
the crosslinking accelerator (E) is contained in a proportion of 0.001 to 0.5 part by weight and the keto-enol tautomer compound (F) is contained in a proportion of 0.1 to 300 parts by weight with respect to 100 parts by weight of the acrylic polymer, and the weight part ratio of (F)/the (E) is 70 to 1000.
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.
The present invention also 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 above adhesive film.
The present invention also provides an optical film with an adhesive layer, wherein the adhesive layer obtained by crosslinking the adhesive composition is laminated on at least one surface of the optical film.
The present invention also provides an adhesive film, wherein an antistatic treatment and an antifouling treatment are applied to one surface of the resin film, that is, the surface opposite to the side on which the adhesive layer is laminated.
Effects of the invention
The invention provides an adhesive composition and a surface protective film which can simultaneously realize excellent antistatic property and stain resistance.
When an adherend has a fluorine compound-containing antifouling layer or a low refractive index layer formed using a fluorine compound-containing low refractive index layer-forming composition laminated on the surface of an optical film, the pressure-sensitive adhesive composition and the surface protection film using the pressure-sensitive adhesive composition according to the present invention have excellent stain resistance and excellent antistatic properties without deterioration with time, as compared with the prior art.
That is, the adhesive composition and the surface protective film using the same according to the present invention have excellent antistatic properties and contamination resistance, and thus have a great industrial value.
Detailed Description
The present invention will be described below based on preferred embodiments.
The adhesive composition of the present embodiment contains an acrylic polymer having a glass transition temperature of 0 ℃ or lower, an antistatic agent, and (D) a crosslinking agent, wherein the crosslinking agent is a trifunctional or higher isocyanate compound, the antistatic agent is an ionic compound having a melting point of 25 ℃ or higher and formed from a cation and an anion, and the anion is one selected from the group consisting of a trifluoromethanesulfonate anion, a pentafluoroethanesulfonate anion, a heptafluoropropanesulfonate anion, and a nonafluorobutanesulfonate anion; the antistatic agent is contained in a proportion of 0.01-10 parts by weight relative to 100 parts by weight of the acrylic polymer as an essential component.
Further, the antistatic agent is preferably an ionic compound which is solid at a temperature of 25 ℃ and has a melting point of 25 ℃ or higher, and more preferably the antistatic agent has a melting point of 450 ℃ or lower.
The acrylic polymer used in the adhesive composition of the present embodiment 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 carbon atoms of from 1 to 18.
Examples of the (meth) acrylate monomer having an alkyl group having a carbon number of C1 to 18 (a) 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, dodecyl (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.
Further, the proportion of at least one of (meth) acrylate monomers having an alkyl group with a carbon number of C1 to C4 and (a1) is preferably 1 to 50 parts by weight and the proportion of at least one of (meth) acrylate monomers having an alkyl group with a carbon number of C5 to C18 and (a2) is preferably 50 to 99 parts by weight, based on 100 parts by weight in total of the (meth) acrylate monomers having an alkyl group with a carbon number of C1 to C3918. In addition, it is preferable that at least one selected from the group consisting of isooctyl (meth) acrylate, isononyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate is contained in a proportion of 50 parts by weight or more per 100 parts by weight of the total of (a) the (meth) acrylate monomer having an alkyl group with carbon atoms of C1 to 18 and (a2) the (meth) acrylate monomer having an alkyl group with carbon atoms of C5 to C18.
The acrylic polymer used in the pressure-sensitive adhesive composition of the present embodiment may be copolymerized with at least one of the copolymerizable vinyl monomers (B) containing a hydroxyl group and/or a carboxyl group as an optional component. The copolymerizable vinyl monomer having a hydroxyl group and/or a carboxyl group (B) includes at least one selected from the group consisting of a copolymerizable monomer having a hydroxyl group (hydroxyl group-containing monomer) and a copolymerizable monomer having a carboxyl group (carboxyl group-containing monomer). That is, the copolymerization may be carried out by selecting only either one of the hydroxyl group-containing monomer and the carboxyl group-containing monomer, or both the hydroxyl group-containing monomer and the carboxyl group-containing monomer may be copolymerized.
Examples of the hydroxyl group-containing monomer include at least one member 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 proportion of the hydroxyl group-containing monomer contained in the pressure-sensitive adhesive composition of the present embodiment is preferably 0.1 to 20 parts by weight, more preferably 4.1 to 16 parts by weight, and particularly preferably 5.1 to 14 parts by weight, based on 100 parts by weight in total of at least two or more (meth) acrylate monomers having an alkyl group and a carbon number of C1 to 18.
Examples of the carboxyl group-containing monomer include at least one member 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 ratio of the carboxyl group-containing monomer in the adhesive composition according to the present embodiment is preferably 0 to 5.0 parts by weight (it is permissible that the carboxyl group-containing monomer is not copolymerized) per 100 parts by weight in total of at least two or more (meth) acrylate monomers having an alkyl group and a carbon number of C1 to 18, and in the case of copolymerizing the carboxyl group-containing monomer, the ratio is more preferably 0.01 to 5.0 parts by weight, particularly preferably 0.02 to 1.3 parts by weight, and most preferably 0.02 to 0.8 parts by weight.
The acrylic polymer used in the pressure-sensitive adhesive composition of the present embodiment may be copolymerized with (C) a polyalkylene glycol chain-containing mono (meth) acrylate monomer as an optional component. The polyalkylene glycol chain-containing mono (meth) acrylate monomer (C) 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. In the present embodiment, even when the polyalkylene glycol mono (meth) acrylate in which other hydroxyl group is OH is used, the polyalkylene glycol mono (meth) acrylate is not classified as (B) a copolymerizable vinyl monomer containing a hydroxyl group and/or a carboxyl group. (C) The polyalkylene glycol chain-containing mono (meth) acrylate monomer may be other alkoxy polyalkylene glycol mono (meth) acrylate in which a hydroxyl group is converted to an alkyl ether.
The polyalkylene glycol constituting the polyalkylene glycol chain may be a diol compound having one or two or more alkylene groups, and examples thereof include polyethylene glycol, polypropylene glycol, polybutylene glycol, polyethylene-polypropylene glycol, polyethylene-polybutylene glycol, polypropylene glycol-polybutylene glycol, and polyethylene-polypropylene glycol-polybutylene glycol.
In addition, for the (C) polyalkylene glycol chain-containing mono (meth) acrylate monomer, the average number of repeating units of alkylene oxide constituting the polyalkylene glycol chain is preferably 3 to 14. The "average number of repeating units of alkylene oxide" means the average number of repeating units of alkylene oxide in the portion of the "polyalkylene glycol chain" contained in the molecular structure of the (C) polyalkylene glycol chain-containing mono (meth) acrylate monomer. Further, it is preferable that the diester component in the (C) polyalkylene glycol chain-containing mono (meth) acrylate monomer is 0.2% or less. The "diester component in the monomer" means the content (wt%) of the polyalkylene glycol di (meth) acrylate contained in the (C) polyalkylene glycol chain-containing mono (meth) acrylate monomer.
The polyalkylene glycol chain-containing mono (meth) acrylate monomer (C) is preferably at least one selected from the group consisting of polyalkylene glycol mono (meth) acrylate, methoxypolyalkylene glycol (meth) acrylate, and ethoxypolyalkylene glycol (meth) acrylate.
The proportion of the polyalkylene glycol chain-containing mono (meth) acrylate monomer (C) in the adhesive composition according to the present embodiment is preferably 1 to 50 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 2 to 25 parts by weight, based on 100 parts by weight in total of at least two or more (meth) acrylate monomers having an alkyl group and a carbon number of C1 to 18.
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 used in the adhesive composition according to the present embodiment is preferably 100 to 300 ten thousand.
The adhesive composition according to the present embodiment contains (G) an antistatic agent in order to obtain antistatic properties. (G) The antistatic agent is an ionic compound having a melting point of 25 deg.C or higher and formed from a cation and an anion selected from the group consisting of trifluoromethanesulfonate anion (CF)3SO3 -) Pentafluoroethanesulfonate anion (CF)3CF2SO3 -) Heptafluoropropane sulfonate anion (CF)3CF2CF2SO3 -) Nonafluorobutanesulfonate anion (CF)3CF2CF2CF2SO3 -) One of the group consisting of. The adhesive composition according to the present embodiment preferably contains (G) an antistatic agent as an essential component in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the acrylic polymer, and if it is necessary to further improve the antistatic property of the adhesive layer so as to lower the lower limit value of the surface resistivity to 1.0 × 10+10When the amount of the (G) is not more than Ω/□, the antistatic agent is more preferably contained in an amount of 0.01 to 15 parts by weight.
Further, the cation contained in the ionic compound may be selected from the group consisting of pyridine
Figure BDA0001453318770000101
Imidazole
Figure BDA0001453318770000103
Phosphonium, sulfonium, or pyrrolidines
Figure BDA0001453318770000102
Guanidine (guanidine)
Figure BDA0001453318770000104
Ammonium, isourea
Figure BDA0001453318770000105
Thiourea
Figure BDA0001453318770000106
Piperidine derivatives
Figure BDA0001453318770000107
Pyrazoles
Figure BDA0001453318770000108
Methyl radical
Figure BDA0001453318770000109
Lithium, morpholine
Figure BDA00014533187700001010
One of the group consisting of.
Specific examples of the antistatic agent (G) include lithium trifluoromethanesulfonate, lithium nonafluorobutanesulfonate and 1-methyl-3-octylpyridine
Figure BDA00014533187700001011
Trifluoromethanesulfonate, 3-methyl-1-octylpyridine
Figure BDA00014533187700001012
Trifluoromethanesulfonate, 1-methyl-4-octylpyridine
Figure BDA00014533187700001018
Nonafluorobutane sulfonate, 4-methyl-1-octylpyridine
Figure BDA00014533187700001013
Nonafluorobutane sulfonate, dimethyldioctylammonium pentafluoroethane sulfonate, 1-methyl-3-octylpyridine
Figure BDA00014533187700001014
Heptafluoropropane sulfonate, 3-methyl-1-octyl pyridine
Figure BDA00014533187700001019
Heptafluoropropane sulfonate, 1-methyl-3-octyl pyridine
Figure BDA00014533187700001015
Nonafluorobutane sulfonate, 3-methyl-1-octylpyridine
Figure BDA00014533187700001016
Nonafluorobutane sulfonate, 1-octyl-3-methylimidazole
Figure BDA00014533187700001017
Nonafluorobutane sulfonates and the like.
The adhesive composition according to the present embodiment further contains a trifunctional or higher isocyanate compound as the crosslinking agent (D).
Examples of the trifunctional or higher-functional isocyanate compound include biuret modified products or isocyanurate modified products of diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, and xylylene diisocyanate, and adducts with trihydric or higher-polyhydric alcohols such as trimethylolpropane and glycerin.
The proportion of the crosslinking agent (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 further contain (E) a crosslinking accelerator. When a polyisocyanate compound is used as the crosslinking agent, the crosslinking accelerator (E) may be any one that acts as a catalyst on the reaction (crosslinking reaction) between the acrylic polymer and the crosslinking agent, and examples thereof include amine compounds such as tertiary amines, metal chelate compounds, organic tin compounds, organic lead compounds, organic zinc compounds and other organic metal compounds. In the present embodiment, a metal chelate compound is preferred as the crosslinking accelerator.
The metal chelate compound is a compound in which 1 or more polydentate ligands L are bonded to a 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. For example, a metal chelate compound having 1 metal atom M represented by the general formula M (L)m(X)nWhen expressed, m is not less than 1, and n is not less than 0. When m is 2 or more, m L's may be the same ligand or different ligands. When n is 2 or more, n X's may be The same ligand may be different ligands.
Examples of the metal atom M include Fe, Ni, Mn, Cr, V, Ti, Ru, Zn, Al, Zr, and Sn.
Examples of the polydentate ligand L include β -keto esters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate (oleyl acetoacetate), lauryl acetoacetate, and stearyl acetoacetate, β -diketones such as acetylacetone (also called 2, 4-pentanedione), 2, 4-hexanedione, and benzoylacetone. These polydentate ligands L are keto-enol tautomer compounds, and the polydentate ligands L may be enol compounds (e.g., acetylacetonates) obtained by deprotonating enols.
Examples of the monodentate ligand X include a halogen atom such as a chlorine atom and a bromine atom; acyloxy groups such as pentanoyl, hexanoyl, 2-ethylhexanoyl, octanoyl, nonanoyl, decanoyl, dodecanoyl, and octadecanoyl; alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, and butoxy.
Specific examples of the metal chelate compound include iron (III) tris (2, 4-pentanedionate), iron (III) triacetylacetonate, titanium (III) triacetylacetonate, ruthenium (III) triacetylacetonate, zinc bisacetoacetonate, aluminum (III) triacetylacetonate, zirconium (III) tetraacetonatacetonate, 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 accelerator (E) is preferably at least one selected from the group consisting of aluminum chelate compounds, titanium chelate compounds, and iron chelate compounds. The pressure-sensitive adhesive composition according to the present embodiment preferably contains (E) a crosslinking accelerator in an amount of 0.001 to 0.5 parts by weight based on 100 parts by weight of the acrylic polymer.
The adhesive composition according to the present embodiment may also contain (F) a keto-enol tautomer compound. Examples of the keto-enol tautomer compound (F) include β -keto esters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate, and stearyl acetoacetate; beta-diketones such as acetylacetone, 2, 4-hexanedione, and benzoylacetone. In an adhesive composition containing a polyisocyanate compound as a crosslinking agent, these keto-enol tautomer compounds can suppress excessive viscosity increase or gelation of the adhesive composition after blending with the crosslinking agent by blocking the isocyanate group of the crosslinking agent, and can prolong the pot life of the adhesive composition.
The adhesive composition according to the present embodiment preferably contains (F) a keto-enol tautomer compound in a proportion of 0.1 to 300 parts by weight relative to 100 parts by weight of the acrylic polymer.
Further, in contrast to (E) the crosslinking accelerator, (F) the keto-enol tautomer compound has an effect of inhibiting crosslinking, and therefore the ratio of (F) the keto-enol tautomer compound to (E) the crosslinking accelerator is preferably appropriately set. In order to prolong the storage life of the adhesive composition and improve the storage stability, the weight ratio of (F)/(E) is preferably 70 to 1000, more preferably 70 to 700, and particularly preferably 80 to 600. Here, the weight part ratio of (F)/(E) means a quotient calculated by dividing the weight part of (F) by the weight part of (E).
In addition to the above additives, known additives such as an antioxidant, a surfactant, a curing accelerator, a plasticizer, a filler, a curing retarder, a processing aid, and an antioxidant may be appropriately blended in the adhesive composition of the present embodiment. These additives may be used alone or in combination of two or more.
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, and more preferably has a surface resistivity of 5.0X 10+11Omega/□ or less, and particularly preferably has a surface resistivity of 2.0X 10+11Omega/□ or less. When the surface resistivity is high, the performance of releasing static electricity generated by charging when the adhesive layer is peeled from an adherend is poor. Therefore, by sufficiently reducing the surface resistivity of the adhesive layer, the peeling electrostatic voltage generated by the static electricity generated when peeling the adhesive layer from the adherend can be reduced, and the adherend can be inhibited from being damaged Influence.
The adhesive layer obtained by crosslinking the adhesive composition of the present embodiment preferably has a peeling electrostatic pressure in the range of-0.3 to +0.3kV with respect to the low refractive index layer formed using the composition for forming a low refractive index layer containing a fluorine compound. 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 form an antireflection layer.
The adhesive film of the present embodiment is a film in which an adhesive layer obtained by crosslinking the adhesive composition of the present embodiment is laminated on one surface of a base film. The adhesive film of the present embodiment can be suitably used for a surface protective film, a surface protective film for a polarizing plate, and a surface protective film for an optical film. 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.
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 base film may be subjected to an antifouling treatment with a silicone-based or fluorine-based release agent, a coating agent, silica fine particles, or the like, or an antistatic treatment with an antistatic agent such as coating or kneading, on the surface of the resin film opposite to the side on which the adhesive agent layer is formed.
The release film is subjected to a release treatment on the surface of the release film that is bonded to the pressure-sensitive adhesive layer by a silicone-based or fluorine-based release agent.
In the case of an optical surface protective 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 described in detail with reference to examples.
< preparation of acrylic Polymer >
[ example 1]
Nitrogen gas was introduced into a reaction apparatus equipped with a stirrer, a thermometer, a reflux cooler, and a nitrogen gas introduction tube, and the air in the reaction apparatus was replaced with nitrogen gas. Then, 12 parts by weight of methyl acrylate, 88 parts by weight of 2-ethylhexyl acrylate, 12.0 parts by weight of 8-hydroxyoctyl acrylate, 0.1 part by weight of acrylic acid, 20 parts by weight of polypropylene glycol monoacrylate (average number of repeating units of alkylene oxide n is 12) and 100 parts by weight of a solvent (ethyl acetate) were added to the reaction apparatus. Then, 0.1 part by weight of azobisisobutyronitrile as a polymerization initiator was added dropwise over 2 hours, and reacted at 65 ℃ for 8 hours to obtain an acrylic polymer solution of 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 described above, except that the respective monomer compositions were as shown in 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), 1.0 part by weight of an antistatic agent (lithium nonafluorobutane sulfonate), 0.1 part by weight of a crosslinking accelerator (titanium triacetylacetonate), and 9 parts by weight of a keto-enol tautomer compound (acetylacetone) were added and mixed with stirring to obtain an adhesive composition of example 1. The adhesive composition was applied to a release film formed of a polyethylene terephthalate (PET) film coated with a silicone resin, 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 to the surface of the base film made of polyethylene terephthalate (PET) film, which had been subjected to the antistatic and antifouling treatment on the surface thereof, 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 the base film/the adhesive layer/the 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 shown in table 1.
[ Table 1]
Figure BDA0001453318770000161
In table 1, the weight parts of each component are determined by setting the total of (a1) and (a2) of (meth) acrylate monomers having an alkyl group and having C1 to 18 carbon atoms as (a) to 100 weight parts.
In table 1, in each column of (D), (G), (E), and (F), 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 compound names of the abbreviations used in table 1 for the respective components are shown in table 2. (C) In the polyalkylene glycol chain-containing mono (meth) acrylate monomer, the diester component in the monomer is 0.2% or less with respect to C-1 to C-5; for C-6, the diester component in the monomer was 0.8%. G-1 to G-6 are all ionic compounds with melting point of more than 25 ℃ and solid at 25 ℃; g-7 is an ionic compound having a melting point of 15 ℃ and being liquid at 25 ℃.
[ Table 2]
Figure BDA0001453318770000181
Cornate (registered trademark) HX, cornate HL, and cornate L are trade names of TOSOH CORPORATION, and D-127N, TAKENATE (registered trademark) D-140N is a trade name of Mitsui Chemicals, inc. Further, HDI means hexamethylene diisocyanate, IPDI means isophorone diisocyanate, XDI means xylylene diisocyanate, TDI means tolylene diisocyanate, and TMP means trimethylolpropane.
< test method and evaluation >
The surface protective films of examples 1 to 6 and comparative examples 1 to 3 were aged at 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, the surface protective film on which the adhesive layer was exposed was bonded to the surface of a polarizing plate (a polarizing plate using TAC as a protective layer of a polarizer) via the adhesive layer, and the resultant was left to stand for 1 day, then autoclaved at 50 ℃ for 5 atmospheres for 20 minutes, and further left to stand at room temperature for 12 hours to obtain a sample for measuring the adhesive force. The polarizing plate of the adherend is an LR polarizing plate or an AG-LR polarizing plate. The measurement sample obtained above was peeled off in the 180 ° direction at a low speed (0.3 m/min) or a high speed (30 m/min) by a tensile tester, and the peel strength obtained by the measurement was taken as the adhesion.
Here, the surface of the LR polarizing plate and the AG-LR polarizing plate was subjected to low reflection surface treatment with a composition containing a fluorine compound.
< test method of surface resistivity >
After the surface protective film was cured, the release film was peeled off to expose the adhesive layer before the surface protective film was bonded to an adherend, and the surface resistivity of the adhesive layer was measured by a resistivity meter HIRESTA UP-HT450 (manufactured by Mitsubishi Chemical analytical co., Ltd).
< test method of Peel Electrostatic Voltage >
The release film is peeled off, and the surface protective film with the adhesive layer exposed is bonded to an adherend having a low refractive index layer formed on the adherend surface using a composition for forming a low refractive index layer containing a fluorine compound. When the surface protective film was peeled at a tensile speed of 30 m/min at 180 degrees, the voltage (electrostatic voltage) generated by charging the adherend was measured using high-precision electrostatic inductors SK-035 and SK-200 (manufactured by KEYENCE CORPORATION), and the maximum value of the measured values was defined as the peeling electrostatic voltage.
< test method for contamination resistance >
The LR polarizing plate subjected to the low reflection surface treatment or the AG-LR polarizing plate subjected to the low reflection surface treatment (polarizing plate using TAC as a protective layer of a polarizer) 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. Criteria for determining the stain resistance were: the case where no contamination was applied to the surface of the polarizing plate was evaluated as "∘"; the case where there was little contamination was evaluated as "Δ"; the presence of contamination was evaluated as "x".
The evaluation results of the surface protective films of examples 1 to 6 and comparative examples 1 to 3 are shown in Table 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 "surface treatment" indicates the type of the adherend polarizing plate used in the test of adhesive strength.
[ Table 3]
Figure BDA0001453318770000201
The surface protective films of examples 1 to 6 had an adhesive force of 0.03 to 0.05N/25mm (e.g., 0.01 to 0.1N/25mm) at a low peeling speed of 0.3 m/min and an adhesive force of 0.4 to 0.6N/25mm (e.g., 1.0N/25mm or less) at a high peeling speed of 30 m/min, with respect to a polarizing plate as an adherend, and had an appropriate adhesive force and excellent 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, and has excellent antistatic performance in a range of-0.3 to +0.3kV of peeling electrostatic pressure of an adhesive layer relative to a low refractive index layer formed by using the composition for forming a low refractive index layer containing a fluorine compound.
Further, the surface protective films of examples 1 to 6 did not stain the polarizing plate as the adherend even after storage for 3 days or 30 days, and were excellent in stain resistance.
That is, the evaluation results of the surface protective films of examples 1 to 6 shown in table 3 confirm that the technical problems of the present invention can be solved.
The surface protective films of comparative examples 1 to 3 use a liquid ionic compound as the antistatic agent (G), and therefore the adhesive agent layer has high surface resistivity and poor stain resistance.
In addition, the surface protective films of comparative examples 1 to 2 have high peeling electrostatic pressure because the surface resistivity of the adhesive layer is high. The surface protective film of comparative example 3 was not measured for peeling static voltage, but it is presumed that peeling static voltage was high because the surface resistivity of the adhesive agent layer was high.
Further, in the surface protective film of comparative example 2, the glass transition temperature of the acrylic polymer contained in the adhesive composition was more than 0 ℃ (calculated value of +2 ℃). Therefore, the adhesive property is poor and the adhesive force is too large. In the acrylic polymer used in comparative example 2, the proportions of methyl acrylate and acrylic acid were large, and the glass transition temperature of the homopolymer was high (higher than 0 ℃).
As described above, the surface protective films of comparative examples 1 to 3 could not solve the technical problems of the present invention.

Claims (11)

1. An adhesive composition comprising an acrylic polymer, an antistatic agent and (D) a crosslinking agent, characterized in that,
The acrylic polymer is a copolymer obtained by copolymerizing:
100 parts by weight in total of at least two or more (meth) acrylate monomers having an alkyl group and a carbon number of 1 to 18, wherein the (meth) acrylate monomers include 1 to 50 parts by weight of at least one (meth) acrylate monomer having an alkyl group and a carbon number of 1 to C4, and 50 to 99 parts by weight of at least one (meth) acrylate monomer having an alkyl group and a carbon number of C5 to C18;
5.1 to 14 parts by weight in total of at least one of (B) a hydroxyl group-containing copolymerizable vinyl monomer, and/or 0.02 to 0.8 parts by weight in total of at least one of (B) a carboxyl group-containing copolymerizable vinyl monomer;
2 to 25 parts by weight in total of at least one of (C) a polyalkylene glycol chain-containing mono (meth) acrylate monomer,
the average number of repeating units of alkylene oxide constituting the polyalkylene glycol chain of the (C) polyalkylene glycol chain-containing mono (meth) acrylate monomer is 3 to 14, the diester component of the (C) polyalkylene glycol chain-containing mono (meth) acrylate monomer is 0.2% or less,
The acrylic polymer has a glass transition temperature of 0 ℃ or lower,
the crosslinking agent (D) is an isocyanate compound with more than three functions,
the antistatic agent is one or more selected from the group consisting of lithium trifluoromethanesulfonate, lithium nonafluorobutane sulfonate, 1-methyl-3-octylpyridine trifluoromethanesulfonate, 3-methyl-1-octylpyridine trifluoromethanesulfonate, 1-methyl-4-octylpyridine nonafluorobutane sulfonate, 4-methyl-1-octylpyridine nonafluorobutane sulfonate, dimethyl dioctylammonium pentafluoroethane sulfonate, 1-methyl-3-octylpyridine heptafluoropropane sulfonate, 3-methyl-1-octylpyridine heptafluoropropane sulfonate, 1-methyl-3-octylpyridine nonafluorobutane sulfonate, 3-methyl-1-octylpyridine nonafluorobutane sulfonate, and 1-octyl-3-methylimidazolium nonafluorobutane sulfonate,
the antistatic agent is contained in a proportion of 0.01-10 parts by weight relative to 100 parts by weight of the acrylic polymer as an essential component.
2. Adhesive composition according to claim 1,
wherein (a2) contains at least one selected from the group consisting of isooctyl (meth) acrylate, isononyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate in a proportion of 50 parts by weight or more,
The adhesive composition further contains (E) a crosslinking accelerator for the metal chelate compound and (F) a keto-enol tautomer compound.
3. The adhesive composition according to claim 1 or 2, wherein a surface resistivity of an adhesive layer obtained by crosslinking the adhesive composition is 1.0 x 10+12Omega/□ or less, the peeling electrostatic pressure of the adhesive layer relative to the low refractive index layer formed by using the composition for forming the low refractive index layer containing the fluorine compound is in the range of-0.3 to +0.3 kV.
4. Adhesive composition according to claim 1 or 2,
the copolymerizable vinyl monomer containing a hydroxyl group 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 carboxyl group-containing copolymerizable vinyl monomer 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.
5. Adhesive composition according to claim 1 or 2,
the (C) polyalkylene glycol chain-containing mono (meth) acrylate monomer is 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.
6. The adhesive composition according to claim 2, wherein the crosslinking accelerator (E) is at least one or more selected from the group consisting of an aluminum chelate compound, a titanium chelate compound and an iron chelate compound,
the crosslinking accelerator (E) is contained in a proportion of 0.001 to 0.5 part by weight and the keto-enol tautomer compound (F) is contained in a proportion of 0.1 to 300 parts by weight with respect to 100 parts by weight of the acrylic polymer, and the weight part ratio of (F)/the (E) is 70 to 1000.
7. An adhesive film characterized in that an adhesive layer obtained by crosslinking the adhesive composition according to any one of claims 1 to 6 is laminated on one surface of a resin film.
8. A surface protective film using the adhesive film according to claim 7.
9. A surface protective film for a polarizing plate, which uses the adhesive film according to claim 7.
10. An optical film with an adhesive layer, wherein an adhesive layer obtained by crosslinking the adhesive composition according to any one of claims 1 to 6 is laminated on at least one surface of the optical film.
11. The adhesive film according to claim 7, 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 laminated.
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