WO2019194069A1 - 表面保護フィルム、光学部材、及び、表示装置 - Google Patents
表面保護フィルム、光学部材、及び、表示装置 Download PDFInfo
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- WO2019194069A1 WO2019194069A1 PCT/JP2019/013615 JP2019013615W WO2019194069A1 WO 2019194069 A1 WO2019194069 A1 WO 2019194069A1 JP 2019013615 W JP2019013615 W JP 2019013615W WO 2019194069 A1 WO2019194069 A1 WO 2019194069A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- 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
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/255—Polyesters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- 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
- C09J7/40—Adhesives in the form of films or foils characterised by release liners
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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
- 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
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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
- 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
Definitions
- the present invention relates to a surface protective film, an optical member protected by the surface protective film, and a display device.
- the surface protective film generally has a configuration in which an adhesive layer is provided on a base film (support). Such a surface protective film is bonded to an adherend (protected body) through the pressure-sensitive adhesive layer, and is used for the purpose of protecting the adherend from scratches and dirt during processing and transportation.
- the surface protective film is stored in a state in which a release film (release liner, separator) is bonded for the purpose of protecting the pressure-sensitive adhesive layer until it is bonded to an optical member or display device that is an adherend.
- a release film contains a silicone component as a release agent and is subjected to silicone treatment.
- the surface protective film and the optical member are made of a plastic material, they have high electrical insulation and generate static electricity due to friction and peeling. For this reason, static electricity tends to be generated even when the surface protective film is peeled off from the optical member such as a polarizing plate, and when voltage is applied to the liquid crystal with this static electricity remaining, the alignment of the liquid crystal molecules is lost, There is also a concern that the panel may be lost. Also, the presence of static electricity can be a factor that attracts dust and reduces workability. Under such circumstances, antistatic treatment is applied to the surface protective film. For example, an antistatic function is provided by blending an antistatic component into the base film or pressure-sensitive adhesive layer constituting the surface protective film. (See Patent Document 1).
- PET polyethylene terephthalate
- the surface protection film that has become unnecessary from the adherend eg, an optical member
- the additive precipitates on the PET surface, or the PET oligomer contained in the PET precipitates on the surface of the pressure-sensitive adhesive layer, causing a problem that the adherend that contacts the surface of the pressure-sensitive adhesive layer is contaminated. is doing.
- An object of the present invention is to provide a surface protective film that can prevent contamination of optical members and the like.
- the surface protective film of the present invention comprises a base film made of a resin material, a (meth) acrylic polymer as a base polymer, and an ionic compound as an antistatic component on one side of the base film.
- a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition, a surface of the base film opposite to the surface having the pressure-sensitive adhesive layer, an antistatic layer containing an antistatic component, and the base of the pressure-sensitive adhesive layer.
- a release film is provided on the surface opposite to the surface having the material film, and the release treatment surface of the release film does not contain a silicone component.
- the surface protective film of the present invention preferably further has an antistatic layer containing an antistatic component between the base film and the pressure-sensitive adhesive layer.
- the optical member of the present invention is preferably protected by the surface protective film.
- the display device of the present invention is preferably protected by the surface protective film.
- the surface protective film of the present invention has an antistatic property as a surface protective film by a base film, an antistatic pressure-sensitive adhesive layer, an antistatic layer, and a release film having a release treatment surface that does not contain a silicone component.
- the curling of the surface protective film with the release film is suppressed while maintaining the release film, and further, the release treatment surface of the release film does not contain the silicone component, thereby preventing the contamination by the silicone component.
- a surface protective film capable of preventing contamination of an adherend (for example, an optical member) due to more precipitated components can be obtained and useful.
- the surface protective film disclosed herein is generally in the form of a pressure-sensitive adhesive sheet, pressure-sensitive adhesive tape, pressure-sensitive adhesive label, pressure-sensitive adhesive film, surface protective sheet, and the like, particularly on a touch sensor or glass in a liquid crystal display panel. It is suitable as a surface protective film for protecting the surface of an optical member during processing or transport of an optical member such as a polarizing plate attached to the substrate through an adhesive layer.
- the pressure-sensitive adhesive layer in the surface protective film is typically formed continuously, but is not limited to such a form, and is formed in a regular or random pattern such as a spot or stripe. It may be an adhesive layer.
- the surface protective film disclosed herein may be in the form of a roll or a single sheet.
- the surface protective film 10 includes a base film (for example, a polyester film) 2, an antistatic layer 1 provided on one surface thereof, and a surface opposite to the surface in contact with the antistatic layer of the base film 2.
- a release film 4 is provided on the surface opposite to the surface of the pressure-sensitive adhesive layer 3 that is in contact with the base film 2 of the pressure-sensitive adhesive layer 3.
- the surface protective film 10 peels off the release film 4 that is in contact with the pressure-sensitive adhesive layer 3, and the pressure-sensitive adhesive is applied to an adherend (a touch sensor or a base glass in a liquid crystal display panel (touch panel) as a protection target).
- the surface protective film 10 before use is such that the surface of the pressure-sensitive adhesive layer 3 (sticking surface to the adherend) is at least the release surface (release treatment surface) on the pressure-sensitive adhesive layer 3 side.
- This is a form protected by a release film (separator, release liner) 4.
- the surface of a general release film is often subjected to a silicone treatment for improving peelability.
- the release treatment of the release film in the present invention is not subjected to silicone treatment (no silicone component is used).
- the surface protective film of the present invention comprises a base film made of a resin material, an adhesive layer on one side of the base film, and an antistatic surface on the opposite side of the base film having the adhesive layer.
- a release film is provided on the surface of the pressure-sensitive adhesive layer opposite to the surface having the base film.
- the resin material constituting the base film can be used without any particular limitation. For example, transparency, mechanical strength, thermal stability, moisture shielding property, isotropic property, It is preferable to use a material excellent in properties such as flexibility and dimensional stability.
- the pressure-sensitive adhesive composition can be applied by a roll coater or the like, and can be wound up into a roll shape, which is useful.
- the resin material constituting the base film examples include polyester polymers such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate; cellulose polymers such as diacetyl cellulose and triacetyl cellulose; polycarbonate polymers An acrylic polymer such as polymethyl methacrylate; and the like, a plastic film composed of a resin material having a main resin component (a main component of the resin component, typically a component occupying 50% by weight or more); It can be preferably used as a material film.
- polyester polymers such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate
- cellulose polymers such as diacetyl cellulose and triacetyl cellulose
- An acrylic polymer such as polymethyl methacrylate
- a plastic film composed of a resin material having a main resin component (a main component of the resin component, typically a component
- the resin material examples include styrene polymers such as polystyrene and acrylonitrile-styrene copolymers; olefin polymers such as polyethylene, polypropylene, polyolefins having a cyclic or norbornene structure, and ethylene-propylene copolymers; Examples of the resin material include vinyl chloride polymers; amide polymers such as nylon 6, nylon 6, 6, and aromatic polyamide. Still other examples of the resin material include imide polymers, sulfone polymers, polyether sulfone polymers, polyether ether ketone polymers, polyphenylene sulfide polymers, vinyl alcohol polymers, vinylidene chloride polymers, vinyl butyral polymers. , Arylate polymers, polyoxymethylene polymers, epoxy polymers and the like. A base film made of a blend of two or more of the above-described polymers may be used.
- the base film a plastic film made of a transparent thermoplastic resin material can be preferably used.
- the plastic films it is more preferable to use a polyester film.
- the polyester film refers to a polymer material (polyester resin) having a main skeleton based on an ester bond such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate as a main resin component.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- polybutylene terephthalate polybutylene terephthalate
- Such a polyester film has preferable characteristics as a base film for a surface protective film, such as excellent optical characteristics and dimensional stability.
- various additives such as an antioxidant, an ultraviolet absorber, a plasticizer, a colorant (pigment, dye, etc.) may be blended as necessary.
- a corona discharge treatment, a plasma treatment, an ultraviolet irradiation treatment, an acid treatment, an alkali treatment, or a coating of a primer is applied to one side of the base film (the surface on which the antistatic layer is provided).
- Surface treatment may be performed.
- Such a surface treatment may be, for example, a treatment for enhancing the adhesion between the base film and the antistatic layer.
- a surface treatment in which polar groups such as hydroxyl groups are introduced on the surface of the base film can be preferably employed.
- the surface protective film of the present invention has an antistatic function by having an antistatic layer so as to come into contact with the base film, and further, as the base film, a plastic film subjected to an antistatic treatment is used. It is also possible to use it. Use of the substrate film is preferable because charging of the surface protective film itself when peeled can be suppressed.
- the base film is a plastic film, and by applying an antistatic treatment to the plastic film, the surface protection film itself can be reduced in charge and can have an excellent antistatic ability on the adherend.
- limiting in particular as a method to provide an antistatic function A conventionally well-known method can be used. Examples thereof include a method of applying a conductive resin, a method of depositing or plating a conductive substance, and a method of kneading an antistatic agent.
- the thickness of the substrate film is usually about 5 to 200 ⁇ m, preferably about 10 to 100 ⁇ m.
- the thickness of the base film is within the above range, it is preferable because the workability for bonding to the adherend and the workability for peeling from the adherend are excellent.
- the surface protective film of the present invention includes the base film, the pressure-sensitive adhesive layer, an antistatic layer containing an antistatic component on the surface opposite to the surface having the pressure-sensitive adhesive layer of the base film, and the pressure-sensitive adhesive.
- a release film is provided on the surface opposite to the surface having the base film of the agent layer.
- the antistatic agent composition which comprises an antistatic layer may be the same composition, or may differ.
- the antistatic layer can be formed of an antistatic agent composition containing an antistatic component.
- an antistatic component for example, a conductive polymer is mentioned. It is preferable to use a water-soluble conductive polymer and / or a water-dispersible conductive polymer as the conductive polymer component. By using the conductive polymer, peeling antistatic properties based on the antistatic layer can be satisfied.
- the conductive polymer is “water-soluble” or “water-dispersible”, but is immobilized in the antistatic layer by using a crosslinking agent (for example, a melamine-based or isocyanate-based crosslinking agent) described later. And water resistance can be improved.
- the surface resistance value of the antistatic layer can be kept low, and further, it can contribute to the antistatic properties of the surface protective film, which is preferable. It becomes an aspect.
- the water-soluble conductive polymer is not particularly limited and can be used, and examples thereof include polyaniline sulfonic acid, poly (isothianaphthene diyl-sulfonate) compound, and a quaternary ammonium salt-containing (meth) acrylic acid ester polymer.
- the water-dispersible conductive polymer can be used without any particular limitation, and examples thereof include polythiophenes and polyanilines doped with polyanions. Among them, polyaniline sulfonic acid is preferably used as the water-soluble conductive polymer, and polythiophenes doped with polyanions are preferably used as the water-dispersible conductive polymer.
- the polythiophene has a polymerization degree of preferably 2 to 1000, more preferably 5 to 100. It is preferable for it to be within the above range because of its excellent conductivity.
- the polyanion is a polymer of a structural unit having an anion group and serves as a dopant for the polythiophene.
- the polyanions include polystyrene sulfonic acid, polyvinyl sulfonic acid, polyallyl sulfonic acid, polyacryl sulfonic acid, polymethacryl sulfonic acid, poly (2-acrylamido-2-methylpropane sulfonic acid), polyisoprene sulfonic acid, Polysulfoethyl methacrylate, poly (4-sulfobutyl methacrylate), polymethallyloxybenzene sulfonic acid, polyvinyl carboxylic acid, polystyrene carboxylic acid, polyallyl carboxylic acid, polyacryl carboxylic acid, polymethacryl carboxylic acid, poly (2-acrylamide) -2-methylpropanecarboxylic acid), polyisoprenecarboxylic acid, polyacrylic acid,
- the polyanions preferably have a weight average molecular weight (Mw) of 1,000 to 1,000,000, more preferably 2,000 to 500,000. Within the above range, the doping and dispersibility of polythiophenes are excellent, which is preferable.
- Mw weight average molecular weight
- the antistatic layer for example, poly (3,4-ethylenedioxythiophene) (PEDOT) is used as the polythiophene, and polystyrene sulfonic acid (PSS) is used as a polyanion that can be doped with the polypolythiophene.
- PEDOT and PSS interact with each other and exist at a close distance, whereby PESOT electrons are taken away by PSS, and the antistatic layer can exhibit conductivity, which is a preferable embodiment.
- polystyrene sulfonic acid examples include poly (3,4-ethylenedioxythiophene) / polystyrene sulfonic acid (PEDOT / PSS) trade name “Bytron P” manufactured by BAYER, Shin-Etsu.
- Examples include the trade name “Sepulzida” manufactured by Polymer Co., Ltd. and the trade name “Verazol” manufactured by Soken Chemical Co., Ltd.
- the polyaniline sulfonic acid that can be used as the water-soluble conductive polymer component preferably has a polystyrene-equivalent weight average molecular weight (Mw) of 5 ⁇ 10 5 or less, and more preferably 3 ⁇ 10 5 or less.
- Mw polystyrene-equivalent weight average molecular weight
- the weight average molecular weight of these conductive polymers is usually preferably 1 ⁇ 10 3 or more, and more preferably 5 ⁇ 10 3 or more.
- Examples of commercial products of the polyaniline sulfonic acid include a product name “aquaPASS” manufactured by Mitsubishi Rayon Co., Ltd.
- the antistatic layer disclosed herein includes, for example, one or more other antistatic components (an organic conductive material other than the conductive polymer, an inorganic conductive material, an antistatic material). Agents) and the like.
- the antistatic layer contains substantially no antistatic component other than the conductive polymer, that is, the antistatic component contained in the antistatic layer is substantially free of the conductive polymer.
- An embodiment consisting solely of can be implemented more preferably.
- organic conductive substance examples include cation type antistatic agents having a cationic functional group such as a quaternary ammonium salt, a pyridinium salt, a primary amino group, a secondary amino group, and a tertiary amino group; sulfonates and sulfates Anionic antistatic agents having an anionic functional group such as salts, phosphonates, phosphate esters; amphoteric ionic antistatic agents such as alkylbetaines and derivatives thereof, imidazoline and derivatives thereof, alanine and derivatives thereof; amino alcohols Nonionic antistatic agents such as glycerin and derivatives thereof, glycerin and derivatives thereof, polyethylene glycol and derivatives thereof; polymerization of monomers having the cation type, anion type or zwitterion type ion conductive groups (for example, quaternary ammonium base) Alternatively, an ion conductive polymer obtained by copolymerization; Include; thioph
- the inorganic conductive material examples include tin oxide, antimony oxide, indium oxide, cadmium oxide, titanium oxide, zinc oxide, indium, tin, antimony, gold, silver, copper, aluminum, nickel, chromium, titanium, iron, cobalt, Examples thereof include copper iodide, ITO (indium oxide / tin oxide), and ATO (antimony oxide / tin oxide). Such inorganic conductive materials may be used alone or in combination of two or more.
- the antistatic agent examples include a cationic antistatic agent, an anionic antistatic agent, an amphoteric ion antistatic agent, a nonionic antistatic agent, and a monomer having a cationic, anionic or zwitterionic ion conductive group. And an ion conductive polymer obtained by polymerizing or copolymerizing.
- the antistatic layer can be formed of an antistatic agent composition containing an antistatic component, and preferably contains a polyester resin as a binder.
- the polyester resin is preferably a resin material containing polyester as a main component (typically more than 50% by weight, preferably 75% by weight or more, for example, 90% by weight or more).
- the polyester typically includes polyvalent carboxylic acids (typically dicarboxylic acids) having two or more carboxyl groups in one molecule and derivatives thereof (an anhydride, esterified product, halogenated product of the polyvalent carboxylic acid).
- polyhydric carboxylic acid component selected from, and polyhydric alcohols (typically diols) having two or more hydroxyl groups in one molecule. It is preferable to have a structure in which one or two or more compounds (polyhydric alcohol component) are condensed.
- Examples of compounds that can be employed as the polyvalent carboxylic acid component include oxalic acid, malonic acid, difluoromalonic acid, alkylmalonic acid, succinic acid, tetrafluorosuccinic acid, alkylsuccinic acid, ( ⁇ ) -malic acid, meso -Tartaric acid, itaconic acid, maleic acid, methylmaleic acid, fumaric acid, methylfumaric acid, acetylenedicarboxylic acid, glutaric acid, hexafluoroglutaric acid, methylglutaric acid, glutaconic acid, adipic acid, dithioadipic acid, methyladipic acid, dimethyl Adipic acid, tetramethyladipic acid, methyleneadipic acid, muconic acid, galactaric acid, pimelic acid, suberic acid, perfluorosuberic acid, 3,3,6,6-tetramethylsuberic acid, azelaic acid
- the compound that can be employed as the polyvalent carboxylic acid component include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid and acid anhydrides thereof; adipic acid, sebacic acid, azelaic acid, succinic acid, Aliphatic dicarboxylic acids such as fumaric acid, maleic acid, hymic acid, 1,4-cyclohexanedicarboxylic acid and the acid anhydrides thereof; and lower alkyl esters of the dicarboxylic acids (for example, monoalcohols having 1 to 3 carbon atoms) Ester) and the like.
- aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid and acid anhydrides thereof
- adipic acid, sebacic acid, azelaic acid, succinic acid Aliphatic dicarboxylic acids such as fumaric acid, maleic acid
- examples of compounds that can be employed as the polyhydric alcohol component include ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, and 1,4-butanediol.
- Neopentyl glycol 1,5-pentanediol, 1,6-hexanediol, 3-methylpentanediol, diethylene glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 2-methyl- Diols such as 1,3-propanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, xylylene glycol, hydrogenated bisphenol A, and bisphenol A Is mentioned.
- Other examples include alkylene oxide adducts of these compounds (for example, ethylene oxide adducts, propylene oxide adducts, etc.).
- the molecular weight of the polyester resin is, for example, about 5 ⁇ 10 3 to 1.5 ⁇ 10 5 (preferably 1 ⁇ 10 5) as a weight average molecular weight (Mw) in terms of standard polystyrene measured by gel permeation chromatography (GPC). 4 to about 6 ⁇ 10 4 ).
- the glass transition temperature (Tg) of the polyester resin may be, for example, 0 to 120 ° C. (preferably 10 to 80 ° C.).
- polyester resin a commercially available product name “Vylonal” manufactured by Toyobo Co., Ltd. can be used.
- the antistatic layer is a resin other than a polyester resin (for example, an acrylic resin or an acrylic resin), as long as the performance of the surface protective film disclosed herein (for example, performance such as antistatic properties) is not significantly impaired.
- a polyester resin for example, an acrylic resin or an acrylic resin
- the reason for using the polyester resin as the binder is that additives such as lubricants are blended because the surface free energy is small compared to resins other than the polyester resin (for example, the acrylic resin and polyvinyl alcohol resin).
- a preferred embodiment of the technology disclosed herein is a case where the binder of the antistatic layer is substantially composed only of a polyester resin.
- an antistatic layer in which the proportion of the polyester resin in the binder is 98 to 100% by weight is preferable.
- the proportion of the binder in the whole antistatic layer can be, for example, 50 to 95% by weight, and usually 60 to 90% by weight is appropriate.
- the amount of the conductive polymer used is preferably 10 to 200 parts by weight, more preferably 25 to 150 parts by weight, and still more preferably 40 to 120 parts by weight with respect to 100 parts by weight of the binder. If the amount of the conductive polymer used is too small, the antistatic effect may be reduced. If the amount of the conductive polymer used is too large, the adhesion of the antistatic layer to the base film may be reduced or the transparency may be reduced. May decrease, which is not preferable.
- a method of forming the antistatic layer a method of applying and drying (or curing) a coating material (antistatic agent composition) for forming an antistatic layer on one side or both sides of a base film can be adopted.
- a coating material antistatic agent composition
- the conductive polymer component used for the preparation the water-soluble conductive polymer and / or water-dispersible conductive polymer, and a polyester resin as the binder can be contained, and the conductive polymer is dissolved and dispersed in water.
- Those in the form conductive polymer aqueous solution or conductive polymer dispersion
- conductive polymer aqueous solution or conductive polymer dispersion can be preferably used.
- Such an aqueous conductive polymer solution or aqueous dispersion dissolves a conductive polymer having a hydrophilic functional group (which can be synthesized by a technique such as copolymerizing a monomer having a hydrophilic functional group in the molecule) in water.
- a conductive polymer having a hydrophilic functional group which can be synthesized by a technique such as copolymerizing a monomer having a hydrophilic functional group in the molecule
- -It can be prepared by dispersing.
- hydrophilic functional group examples include sulfo group, amino group, amide group, imino group, hydroxyl group, mercapto group, hydrazino group, carboxyl group, quaternary ammonium group, sulfate ester group (—O—SO 3 H), phosphorus
- An acid ester group for example, —O—PO (OH) 2
- Such hydrophilic functional groups may form a salt.
- a melamine-based, isocyanate-based, epoxy-based or the like crosslinking agent used for crosslinking of general resins can be appropriately selected and used as a crosslinking agent.
- at least a melamine crosslinking agent or an isocyanate crosslinking agent is used.
- the isocyanate-based crosslinking agent it is preferable to use a blocked isocyanate-based crosslinking agent that is stable even in an aqueous solution.
- Specific examples of the blocked isocyanate crosslinking agent include isocyanate crosslinking agents that can be used in the preparation of general pressure-sensitive adhesive layers and antistatic layers (for example, isocyanate compounds (isocyanates used in pressure-sensitive adhesive layers described below)). Cross-linking agents)) with alcohols, phenols, thiophenols, amines, imides, oximes, lactams, active methylene compounds, mercaptans, imines, ureas, diaryl compounds, and bisulfite Those blocked with soda can be used.
- the antistatic agent composition used for forming the antistatic layer contains a surfactant, a leveling agent, a lubricant, etc., thereby suppressing the occurrence of repellency and thickness unevenness during coating.
- a brittle layer is formed in the antistatic layer, and peeling occurs at the interface between the antistatic layer and the pressure-sensitive adhesive layer. It is preferable not to mix.
- other antistatic components may be blended, antioxidants, colorants (pigments, dyes, etc.), fluidity modifiers (thixotropic agents, thickeners, etc.) ), Film-forming aids, surfactants (such as antifoaming agents), and preservatives.
- the antistatic layer is a liquid composition (coating material for forming an antistatic layer, antistatic agent composition) in which the conductive polymer component and the like and additives used as necessary are dissolved in a suitable solvent (water or the like).
- the product can be suitably formed by a technique including applying the product to the base film. For example, a method of applying the coating material on one side of the substrate film and drying it, and performing a curing treatment (heat treatment, ultraviolet treatment, etc.) as necessary can be preferably employed.
- the NV (nonvolatile content) of the coating material can be, for example, 5% by weight or less (typically 0.05 to 5% by weight), and usually 1% by weight or less (typically 0.10 to 5%).
- the NV of the coating material is, for example, 0.05 to 0.50% by weight (for example, 0.10 to 0.40% by weight).
- a more uniform antistatic layer can be formed by using a low NV coating material.
- a solvent capable of stably dissolving (dispersing) the forming component of the antistatic layer is preferable.
- a solvent may be an organic solvent, water, or a mixed solvent thereof.
- the organic solvent include esters such as ethyl acetate; ketones such as methyl ethyl ketone, acetone and cyclohexanone; cyclic ethers such as tetrahydrofuran (THF) and dioxane; aliphatic or alicyclic such as n-hexane and cyclohexane.
- Hydrocarbons aromatic hydrocarbons such as toluene and xylene; aliphatic or alicyclic alcohols such as methanol, ethanol, n-propanol, isopropanol, and cyclohexanol; alkylene glycol monoalkyl ether (for example, ethylene glycol monomethyl ether) , Ethylene glycol monoethyl ether), and glycol ethers such as dialkylene glycol monoalkyl ether;
- the solvent of the coating material is water or a mixed solvent containing water as a main component (for example, a mixed solvent of water and ethanol).
- the thickness of the antistatic layer in the technology disclosed herein is typically 3 to 500 nm, preferably 3 to 100 nm, more preferably 3 to 60 nm. If the thickness of the antistatic layer is too small, it becomes difficult to form the antistatic layer uniformly (for example, the thickness of the antistatic layer varies greatly depending on the location). Unevenness may be likely to occur. On the other hand, if it is too thick, the characteristics (optical characteristics, dimensional stability, etc.) of the base film may be affected.
- the surface protective film disclosed herein has a surface resistance value ( ⁇ / ⁇ ) measured on the surface of the antistatic layer of 1.0 ⁇ 10 10 or less, preferably 1.0 ⁇ 10 4 to 5. 0.0 ⁇ 10 9 , more preferably 1.0 ⁇ 10 5 to 4.0 ⁇ 10 9 , and still more preferably 3.0 ⁇ 10 5 to 3.0 ⁇ 10 9 .
- a surface protective film exhibiting a surface resistance value within the above range can be suitably used as a surface protective film used in the processing or transporting of articles that dislike static electricity such as liquid crystal cells and semiconductor devices. Further, the surface protective film showing the surface resistance value within the above range can be confirmed even when the polarizing plate is mounted above the touch panel sensor and the surface protective film is stuck on the polarizing plate. Can be useful.
- the surface resistance value can be calculated from the surface resistance value measured under an atmosphere of 23 ° C. and 50% RH using a commercially available insulation resistance measuring device (such as a resistivity meter).
- the surface protective film of the present invention contains a base film made of a resin material, a (meth) acrylic polymer as a base polymer, and an ionic compound as an antistatic component on one side of the base film. And an adhesive layer formed from the adhesive composition.
- the (meth) acrylic polymer is a (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms (alkyl (meth) acrylate having an alkyl group having 1 to 14 carbon atoms) as a raw material monomer constituting the (meth) acrylic polymer.
- (meth) acrylic-type monomer 1 type (s) or 2 or more types can be used as a main component.
- the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms it becomes easy to control the adhesive force to the adherend (protected body) to be low, and the light peelability and re-peeling are facilitated.
- a surface protective film having excellent properties can be obtained.
- the (meth) acrylic polymer refers to an acrylic polymer and / or a methacrylic polymer
- the (meth) acrylate refers to acrylate and / or methacrylate.
- the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) ) Acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl ( (Meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (
- the surface protective film of the present invention includes hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl.
- 6 to 14 carbon atoms such as (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-dodecyl (meth) acrylate, n-tridecyl (meth) acrylate, n-tetradecyl (meth) acrylate, etc.
- a (meth) acrylic monomer having an alkyl group is preferred.
- a (meth) acrylic monomer having an alkyl group having 6 to 14 carbon atoms it becomes easy to control the adhesive force to the adherend to be low, and the removability is excellent.
- the pressure-sensitive adhesive composition comprises 60% by weight or more of a (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms with respect to 100% by weight of the total amount of monomer components constituting the (meth) acrylic polymer.
- the content is preferably 70% by weight or more, more preferably 80% by weight or more, and most preferably 90 to 99% by weight. If it is less than 60% by weight, the appropriate wettability of the pressure-sensitive adhesive composition and the cohesive strength of the pressure-sensitive adhesive layer are inferior, which is not preferable.
- the (meth) acrylic polymer contains a (meth) acrylic monomer having a hydroxyl group as a raw material monomer.
- the (meth) acrylic monomer having a hydroxyl group one or more kinds can be used as a main component.
- the (meth) acrylic monomer having a hydroxyl group By using the (meth) acrylic monomer having a hydroxyl group, it is easy to control the crosslinking of the pressure-sensitive adhesive composition, and it is easy to control the balance between the improvement of wettability by flow and the reduction of the adhesive strength in peeling. Become.
- Examples of the (meth) acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and 6-hydroxyhexyl (meth). Acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl acrylate, N-methylol (meth) acrylamide, etc. .
- the glass transition temperature and peeling of the (meth) acrylic polymer should be adjusted so that the Tg is 0 ° C. or lower (usually ⁇ 100 ° C. or higher) because the adhesive performance is easily balanced.
- a polymerizable monomer or the like for adjusting the property can be used as long as the effects of the present invention are not impaired.
- Examples of the (meth) acrylic monomer having a carboxyl group include (meth) acrylic acid, carboxylethyl (meth) acrylate, carboxylpentyl (meth) acrylate, and the like.
- the (meth) acrylic monomer having a carboxyl group is preferably contained in an amount of 5 parts by weight or less, more preferably 100 parts by weight of the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms. Is 2 parts by weight or less, more preferably 0.001 to 1 part by weight, and most preferably 0.01 to 0.1 part by weight. Within the above range, the balance between the wettability of the pressure-sensitive adhesive composition and the cohesive force of the resulting pressure-sensitive adhesive layer can be easily controlled, which is preferable.
- the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms, the (meth) acrylic monomer having a hydroxyl group, and the (meth) having a carboxyl group, which are used in the (meth) acrylic polymer are used in the (meth) acrylic polymer.
- Other polymerizable monomers other than acrylic monomers can be used without particular limitation as long as they do not impair the characteristics of the present invention.
- cohesive strength / heat resistance improving components such as cyano group-containing monomers, vinyl ester monomers, aromatic vinyl monomers, amide group-containing monomers, imide group-containing monomers, amino group-containing monomers, epoxy group-containing monomers, N-acryloylmorpholine
- a component having a functional group functioning as an adhesive strength improvement or a crosslinking base point such as a vinyl ether monomer can be appropriately used.
- These polymerizable monomers may be used alone or in combination of two or more.
- Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
- Examples of the vinyl ester monomer include vinyl acetate, vinyl propionate, and vinyl laurate.
- aromatic vinyl monomer examples include styrene, chlorostyrene, chloromethyl styrene, ⁇ -methyl styrene, and other substituted styrene.
- amide group-containing monomers include acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, and N, N-diethylmethacrylate.
- Examples include amide, N, N′-methylenebisacrylamide, N, N-dimethylaminopropyl acrylamide, N, N-dimethylaminopropyl methacrylamide, and diacetone acrylamide.
- Examples of the imide group-containing monomer include cyclohexylmaleimide, isopropylmaleimide, N-cyclohexylmaleimide, and itaconimide.
- amino group-containing monomer examples include aminoethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and the like.
- epoxy group-containing monomer examples include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and allyl glycidyl ether.
- vinyl ether monomer examples include methyl vinyl ether, ethyl vinyl ether, and isobutyl vinyl ether.
- the (meth) acrylic polymer may further contain an alkylene oxide group-containing reactive monomer as a monomer component.
- the average number of moles of oxyalkylene units added in the alkylene oxide group-containing reactive monomer is preferably 1 to 40 from the viewpoint of compatibility with the ionic compound as the antistatic component, and preferably 3 to 40. More preferably, it is more preferably 4 to 35, and particularly preferably 5 to 30.
- the average added mole number is 1 or more, the effect of reducing the contamination of the adherend (protected body) tends to be obtained efficiently.
- the said average addition mole number is larger than 40, since interaction with an ionic compound is large and there exists a tendency for the viscosity of an adhesive composition to rise and for coating to become difficult, it is unpreferable.
- the terminal of the oxyalkylene chain may be substituted with other functional groups or the like as a hydroxyl group.
- the alkylene oxide group-containing reactive monomer may be used singly or as a mixture of two or more, but the total content is the total monomer component of the (meth) acrylic polymer. It is preferably 20% by weight or less, more preferably 10% by weight or less, still more preferably 5% by weight or less, further preferably 4% by weight or less, and 3% by weight or less. Particularly preferred is 1% by weight or less.
- the content of the alkylene oxide group-containing reactive monomer exceeds 20% by weight, the interaction with the ionic compound is increased, ionic conduction is hindered, and the antistatic property is lowered, which is not preferable.
- Examples of the oxyalkylene unit of the alkylene oxide group-containing reactive monomer include those having an alkylene group having 1 to 6 carbon atoms, such as an oxymethylene group, an oxyethylene group, an oxypropylene group, and an oxybutylene group. It is done.
- the hydrocarbon group of the oxyalkylene chain may be linear or branched.
- the alkylene oxide group-containing reactive monomer is a reactive monomer having an ethylene oxide group.
- a (meth) acrylic polymer having a reactive monomer having an ethylene oxide group as the base polymer, the compatibility between the base polymer and the ionic compound is improved, and bleeding to the adherend is suitably suppressed, and the A soiling pressure-sensitive adhesive composition is obtained.
- alkylene oxide group-containing reactive monomer examples include (meth) acrylic acid alkylene oxide adducts and reactive surfactants having reactive substituents such as acryloyl group, methacryloyl group, and allyl group in the molecule. can give.
- the (meth) acrylic acid alkylene oxide adduct include, for example, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) acrylate, polyethylene glycol-polypropylene glycol (meth) acrylate, polyethylene glycol-polybutylene glycol (meth) ) Acrylate, polypropylene glycol-polybutylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, butoxy polyethylene glycol (meth) acrylate, octoxy polyethylene glycol (meth) acrylate, lauroxy polyethylene Glycol (meth) acrylate, stearoxy polyethylene glycol Lumpur (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, octoxypolyethylene glycol - polyprop
- the reactive surfactant include, for example, an anionic reactive surfactant having a (meth) acryloyl group or an allyl group, a nonionic reactive surfactant, and a cationic reactive surfactant. Can be given.
- other polymerizable monomers other than the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms, the (meth) acrylic monomer having a hydroxyl group, and the (meth) acrylic monomer having a carboxyl group are:
- the content is preferably 0 to 20 parts by weight, more preferably 0 to 10 parts by weight based on 100 parts by weight of the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms. It is preferable to mix within the above range because good removability can be appropriately adjusted.
- the weight average molecular weight (Mw) of the (meth) acrylic polymer is preferably 100,000 to 3,000,000, more preferably 200,000 to 2,000,000, still more preferably 300,000 to 1,000,000.
- Mw weight average molecular weight
- the adhesive force tends to be generated due to the reduced cohesive force of the pressure-sensitive adhesive layer.
- the glass transition temperature (Tg) of the (meth) acrylic polymer is preferably 0 ° C. or lower, more preferably ⁇ 10 ° C. or lower (usually ⁇ 100 ° C. or higher).
- Tg glass transition temperature
- the glass transition temperature of the (meth) acrylic polymer can be adjusted within the above range by appropriately changing the monomer component and composition ratio to be used.
- the obtained (meth) acrylic polymer may be any of a random copolymer, a block copolymer, a graft copolymer, and the like.
- solution polymerization for example, ethyl acetate, toluene or the like is used as a polymerization solvent.
- the reaction is carried out in an inert gas stream such as nitrogen and a polymerization initiator is added, and the reaction is usually performed at about 50 to 70 ° C. under reaction conditions of about 10 minutes to 30 hours.
- a polymerization initiator such as N-(ethylene glycol)
- the reaction is usually performed at about 50 to 70 ° C. under reaction conditions of about 10 minutes to 30 hours.
- by shortening the polymerization time to about 30 minutes to 3 hours it is possible to improve the tackiness of the pressure-sensitive adhesive by suppressing the formation of low molecular weight oligomers produced in the latter stage of the polymerization.
- the polymerization initiator, chain transfer agent, emulsifier and the like used for radical polymerization are not particularly limited and can be appropriately selected and used.
- the weight average molecular weight of a (meth) acrylic-type polymer can be controlled by the usage-amount of a polymerization initiator and a chain transfer agent, and reaction conditions, The usage-amount is suitably adjusted according to these kinds.
- the polymerization initiator is not particularly limited, and examples thereof include a peroxide polymerization initiator and an azo polymerization initiator.
- the peroxide polymerization initiator is not particularly limited, and examples thereof include peroxy carbonate, ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, peroxy ester, and the like.
- benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, 1,1-bis (t-butylperoxy)- 3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclododecane and the like can be mentioned.
- the azo polymerization initiator is not particularly limited.
- organic tellurium compounds can be mentioned as polymerization initiators used for living radical polymerization.
- examples of the organic tellurium compound include (methylterranyl-methyl) benzene, (1-methylterranyl-ethyl) benzene, (2-methylterranyl-propyl) benzene, 1-chloro-4- (methylterranyl-methyl) benzene, 1-hydroxy- 4- (methylterranyl-methyl) benzene, 1-methoxy-4- (methylterranyl-methyl) benzene, 1-amino-4- (methylterranyl-methyl) benzene, 1-nitro-4- (methylterranyl-methyl) benzene, 1- Cyano-4- (methylterranyl-methyl) benzene, 1-methylcarbonyl-4- (methylterranyl-methyl) benzene, 1-phenylcarbonyl-4- (methylterranyl-methyl) benzene, 1-methoxycarbonyl-4- (methylterra
- the methyl terranyl group in these organic tellurium compounds may be an ethyl terranyl group, an n-propyl terranyl group, an isopropyl terranyl group, an n-butyl terranyl group, an isobutyl terranyl group, a t-butyl terranyl group, a phenyl terranyl group, etc. Good.
- the said polymerization initiator can be used individually or in combination of 2 or more types.
- the blending ratio of the polymerization initiator is not particularly limited. For example, it is 0.005 to 5% by weight with respect to the total amount of monomer components (100 parts by weight) constituting the (meth) acrylic polymer. Parts, preferably 0.01 to 3 parts by weight.
- the surface protective film of the present invention has a pressure-sensitive adhesive layer (pressure-sensitive adhesive layer having antistatic properties) formed from a pressure-sensitive adhesive composition containing an ionic compound as an antistatic component.
- the ionic compound include alkali metal salts and / or ionic liquids. By containing these ionic compounds, excellent antistatic properties can be imparted.
- the pressure-sensitive adhesive layer (using the antistatic component) obtained by crosslinking the pressure-sensitive adhesive composition containing the antistatic component as described above is an adherend that is not antistatic when peeled (for example, a polarizing plate) ), And a surface protective film with reduced contamination on the adherend is obtained. For this reason, it becomes very useful as an antistatic surface protective film in a technical field related to optical and electronic components in which charging and contamination are particularly serious problems.
- the alkali metal salt Since the alkali metal salt has high ion dissociation properties, it is preferable in that it exhibits excellent antistatic ability even with a small amount of addition.
- the alkali metal salt include a cation composed of Li + , Na + , K + , Cl ⁇ , Br ⁇ , I ⁇ , AlCl 4 ⁇ , Al 2 Cl 7 ⁇ , BF 4 ⁇ , PF 6 ⁇ , SCN.
- These alkali metal salts may be used alone or in combination of two or more.
- the ionic liquid as an antistatic component (antistatic agent), a pressure-sensitive adhesive layer having a high antistatic effect can be obtained without impairing the adhesive properties.
- the ionic liquid has a low melting point (melting point of 100 ° C. or lower) compared to a normal ionic compound, and thus has a molecular motion. It is easy to obtain an excellent antistatic ability.
- antistatic to the adherend it is considered that excellent peeling antistatic properties on the adherend can be achieved by transferring a very small amount of the ionic liquid to the adherend.
- an ionic liquid having a melting point of room temperature (25 ° C.) or less can be transferred to an adherend more efficiently, excellent antistatic properties can be obtained.
- the ionic liquid since the ionic liquid is in a liquid state at a temperature of 100 ° C. or lower, it can be easily added and dispersed or dissolved in the pressure-sensitive adhesive as compared with a solid salt. Further, since the ionic liquid has no vapor pressure (nonvolatile), it has a characteristic that the antistatic property is continuously obtained without disappearing with time.
- the ionic liquid refers to a molten salt (ionic compound) having a melting point of 100 ° C. or lower and exhibiting a liquid state.
- ionic liquid those composed of an organic cation component represented by the following general formulas (A) to (E) and an anion component are preferably used.
- An ionic liquid having these cations provides a further excellent antistatic ability.
- R a in the formula (A) represents a hydrocarbon group having 4 to 20 carbon atoms, and may be a functional group in which a part of the hydrocarbon group is substituted with a hetero atom
- R b and R c May be the same or different and each represents hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, and a part of the hydrocarbon group may be a functional group substituted with a hetero atom.
- the nitrogen atom contains a double bond, there is no R c .
- R d in the formula (B) represents a hydrocarbon group having 2 to 20 carbon atoms, and may be a functional group in which a part of the hydrocarbon group is substituted with a hetero atom
- R e , R f And R g may be the same or different and each represents hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, and a part of the hydrocarbon group may be a functional group substituted with a hetero atom.
- R h in the formula (C) represents a hydrocarbon group having 2 to 20 carbon atoms, and may be a functional group in which a part of the hydrocarbon group is substituted with a hetero atom
- R i , R j , And R k may be the same or different and each represents hydrogen or a hydrocarbon group having 1 to 16 carbon atoms, and a part of the hydrocarbon group may be a functional group substituted with a hetero atom.
- Z in the formula (D) represents a nitrogen, sulfur, or phosphorus atom
- R 1 , R m , R n , and R o are the same or different and represent a hydrocarbon group having 1 to 20 carbon atoms.
- a functional group in which a part of the hydrocarbon group is substituted with a hetero atom may be used.
- Z is a sulfur atom, there is no Ro .
- R P in the formula (E) represents a hydrocarbon group having 1 to 18 carbon atoms, a part of the hydrocarbon group may be substituted by a functional group with a heteroatom.
- Examples of the cation represented by the formula (A) include a pyridinium cation, a piperidinium cation, a pyrrolidinium cation, a cation having a pyrroline skeleton, a cation having a pyrrole skeleton, and a morpholinium cation.
- Specific examples include, for example, 1-butylpyridinium cation, 1-hexylpyridinium cation, 1-butyl-3-methylpyridinium cation, 1-butyl-3,4-dimethylpyridinium cation, 1-methyl-1-ethylpyrrole Dinium cation, 1-methyl-1-hexylpyrrolidinium cation, 1-ethyl-1-hexylpyrrolidinium cation, pyrrolidinium-2-one cation, 1-propylpiperidinium cation, 1-methyl-1 -Ethylpiperidinium cation, 1-methyl-1-hexylpiperidinium cation, 2-methyl-1-pyrroline cation, 1-ethyl-2-phenylindole cation, 1,2-dimethylindole cation, 1-ethylcarbazole Cation, N-ethyl-N-methylmol Such as O Li cation.
- Examples of the cation represented by the formula (B) include an imidazolium cation, a tetrahydropyrimidinium cation, and a dihydropyrimidinium cation.
- Specific examples include, for example, 1,3-dimethylimidazolium cation, 1-ethyl-3-methylimidazolium cation, 1-hexyl-3-methylimidazolium cation, 1-octyl-3-methylimidazolium cation, 1-decyl-3-methylimidazolium cation, 1-tetradecyl-3-methylimidazolium cation, 1- (2-methoxyethyl) -3-methylimidazolium cation, 1,3-dimethyl-1,4,5, 6-tetrahydropyrimidinium cation, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium cation, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydro Pyrimidinium cation, 1,3-dimethyl-1,4-dihydropyrimidinium cation, 1,3-di Til-1,6-dihydropyrimidinium
- Examples of the cation represented by the formula (C) include a pyrazolium cation and a pyrazolinium cation.
- Specific examples include, for example, 1-methylpyrazolium cation, 3-methylpyrazolium cation, 1-ethyl-2-methylpyrazolinium cation, 1-ethyl-2,3,5-trimethylpyrazolium cation 1-propyl-2,3,5-trimethylpyrazolium cation, 1-butyl-2,3,5-trimethylpyrazolium cation, 1-ethyl-2,3,5-trimethylpyrazolinium cation, 1 -Propyl-2,3,5-trimethylpyrazolinium cation, 1-butyl-2,3,5-trimethylpyrazolinium cation and the like.
- Examples of the cation represented by the formula (D) include a tetraalkylammonium cation, a trialkylsulfonium cation, a tetraalkylphosphonium cation, and a part of the alkyl group is substituted with an alkenyl group, an alkoxyl group, or an epoxy group. And so on.
- Specific examples include, for example, tetramethylammonium cation, tetrabutylammonium cation, tetrapentylammonium cation, tetrahexylammonium cation, triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, N, N-diethyl-N— Methyl-N- (2-methoxyethyl) ammonium cation, glycidyltrimethylammonium cation, trimethylsulfonium cation, triethylsulfonium cation, tributylsulfonium cation, trihexylsulfonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, Tetramethyl
- asymmetric such as triethylmethylammonium cation, tributylethylammonium cation, trimethyldecylammonium cation, diethylmethylsulfonium cation, dibutylethylsulfonium cation, dimethyldecylsulfonium cation, triethylmethylphosphonium cation, tributylethylphosphonium cation, trimethyldecylphosphonium cation, etc.
- Examples of the cation represented by the formula (E) include a sulfonium cation. Further, the formula Specific examples of R P in (E) is a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, An octadecyl group etc. are mentioned.
- the anion component is not particularly limited as long as it satisfies that it becomes an ionic liquid.
- anion component an anion represented by the following formula (F) can also be used.
- an anion component an anion component containing a fluorine atom is particularly preferably used since an ionic liquid having a low melting point can be obtained.
- ionic liquid used in the present invention are appropriately selected from a combination of the cation component and the anion component.
- the said ionic liquid may be used independently, and 2 or more types may be mixed and used for it.
- the content of the ionic compound is preferably 0.01 to 5 parts by weight, more preferably 0.02 to 3 parts by weight, and still more preferably 100 parts by weight of the (meth) acrylic polymer. Is 0.03 to 2 parts by weight, most preferably 0.05 to 1 part by weight. It is excellent in antistatic property when it exists in the said range, and preferable.
- the pressure-sensitive adhesive composition preferably contains an organopolysiloxane having an oxyalkylene chain which is an antistatic aid, and preferably contains an organopolysiloxane having an oxyalkylene side chain. More preferred.
- organopolysiloxane it is presumed that the surface free energy on the surface of the pressure-sensitive adhesive is reduced and light release is realized. Moreover, it is estimated that antistatic property is improved with the ionic compound contained in the said adhesive composition.
- organopolysiloxane a known organopolysiloxane having a polyoxyalkylene main chain can be used as appropriate, and is preferably represented by the following formula.
- R 1 and / or R 2 has an oxyalkylene chain having 1 to 6 carbon atoms, and the alkylene group in the oxyalkylene chain may be linear or branched
- the terminal of may be an alkoxy group or a hydroxyl group, and either R 1 or R 2 may be a hydroxyl group, or may be an alkyl group or an alkoxy group.
- a part of the alkoxy group may be a functional group substituted with a hetero atom.
- N is an integer of 1 to 300.
- organopolysiloxane those having a siloxane-containing site (siloxane site) as the main chain and having an oxyalkylene chain bonded to the end of the main chain are used.
- siloxane site siloxane site
- oxyalkylene chain By using the organosiloxane having the oxyalkylene chain, for example, it is presumed that the compatibility of the (meth) acrylic polymer and the ionic compound is balanced and light release is realized.
- R 1 and / or R 2 in the formula has an oxyalkylene chain containing a hydrocarbon group having 1 to 6 carbon atoms, as the oxyalkylene chain, oxymethylene group, oxyethylene group, oxy Examples thereof include a propylene group and an oxybutylene group, and among them, an oxyethylene group and an oxypropylene group are preferable.
- R 1 and R 2 when both R 1 and R 2 have an oxyalkylene chain, they may be the same or different.
- hydrocarbon group of the oxyalkylene chain may be linear or branched.
- the end of the oxyalkylene chain may be an alkoxy group or a hydroxyl group, but more preferably an alkoxy group.
- N is an integer of 1 to 300, preferably 10 to 200, more preferably 20 to 150.
- n is within the above range, the compatibility with the base polymer is balanced, which is a preferred embodiment.
- you may have reactive substituents, such as a (meth) acryloyl group, an allyl group, and a hydroxyl group, in a molecule
- the organopolysiloxane may be used alone or in combination of two or more.
- organopolysiloxane having an oxyalkylene chain examples include, for example, commercially available products having trade names of X-22-4952, X-22-4272, X-22-6266, KF-6004, KF-889. (Above, manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-201, SF8427 (above, manufactured by Toray Dow Corning), IM22 (produced by Asahi Kasei Wacker), and the like. These compounds may be used alone or in combination of two or more.
- organosiloxane having (bonding) the oxyalkylene chain in the main chain it is also possible to use an organosiloxane having (bonding) the oxyalkylene chain in the side chain.
- Use of an organosiloxane having an alkylene chain is a preferred embodiment because it is easy to achieve both antistatic properties and low contamination.
- an organopolysiloxane having a known polyoxyalkylene side chain can be used as appropriate, and is preferably represented by the following formula.
- R 1 is a monovalent organic group
- R 2 , R 3 and R 4 are alkylene groups
- R 5 is hydrogen or an organic group
- m and n are integers from 0 to 1000, provided that m and n are simultaneously
- a and b are integers from 0 to 100. However, a and b are not 0 at the same time.
- R 1 in the formula is a monovalent group exemplified by an alkyl group such as a methyl group, an ethyl group or a propyl group, an aryl group such as a phenyl group or a tolyl group, or an aralkyl group such as a benzyl group or a phenethyl group. It is an organic group, and each may have a substituent such as a hydroxyl group.
- R 2 , R 3 and R 4 may be an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group or a propylene group.
- R 3 and R 4 are different alkylene groups, and R 2 may be the same as or different from R 3 or R 4 .
- One of R 3 and R 4 is preferably an ethylene group or a propylene group in order to increase the concentration of an ionic compound that can be dissolved in the polyoxyalkylene side chain.
- R 5 may be an alkyl group such as a methyl group, an ethyl group or a propyl group, or a monovalent organic group exemplified by an acyl group such as an acetyl group or a propionyl group, each having a substituent such as a hydroxyl group. It may be. These compounds may be used alone or in combination of two or more. Moreover, you may have reactive substituents, such as a (meth) acryloyl group, an allyl group, and a hydroxyl group, in a molecule
- organosiloxanes having a polyoxyalkylene side chain an organosiloxane having a polyoxyalkylene side chain having a hydroxyl group terminal is presumed to have a good balance of compatibility.
- organosiloxane examples include, for example, commercial names KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF.
- the organosiloxane used in the present invention preferably has an HLB (Hydrophile-Lipophile Balance) value of 1 to 16, more preferably 3 to 14.
- HLB Hydrophile-Lipophile Balance
- the content of the organopolysiloxane is preferably 0.01 to 5 parts by weight, more preferably 0.03 to 3 parts by weight, and still more preferably 100 parts by weight of the (meth) acrylic polymer. Is 0.05 to 1 part by weight, most preferably 0.05 to 0.5 part by weight. It is preferable for it to be in the above-mentioned range since it is easy to achieve both antistatic properties and light releasability (removability).
- the pressure-sensitive adhesive composition may contain a polyoxyalkylene chain-containing compound that is a polyether component that does not contain organopolysiloxane.
- a polyoxyalkylene chain-containing compound that is a polyether component that does not contain organopolysiloxane.
- polyoxyalkylene chain-containing compound not containing the organopolysiloxane examples include, for example, polyoxyalkylene alkylamine, polyoxyalkylene diamine, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene alkylphenyl.
- Nonionic surfactants such as ether, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl allyl ether, polyoxyalkylene alkyl phenyl allyl ether; polyoxyalkylene alkyl ether sulfate ester salt, polyoxyalkylene alkyl ether phosphate ester salt, Polyoxyalkylene alkyl phenyl ether sulfate ester salt, polyoxyalkylene alkyl phenyl ether phosphoric acid
- Anionic surfactants such as stealth salts; other cationic surfactants having polyoxyalkylene chains (polyalkylene oxide chains), amphoteric surfactants, polyether compounds having polyoxyalkylene chains (and derivatives thereof) And acrylic compounds having a polyoxyalkylene chain (and derivatives thereof).
- polyether compound having a polyoxyalkylene chain examples include a block copolymer of polypropylene glycol (PPG) -polyethylene glycol (PEG), a block copolymer of PPG-PEG-PPG, and a block copolymer of PEG-PPG-PEG. Examples thereof include block copolymers.
- the derivative of the polyether compound having a polyoxyalkylene chain include an oxypropylene group-containing compound having a terminal etherification (PPG monoalkyl ether, PEG-PPG monoalkyl ether, etc.), an oxypropylene group having a terminal acetylation Containing compounds (terminal acetylated PPG and the like), and the like.
- the acrylic compound having a polyoxyalkylene chain examples include a (meth) acrylate polymer having an oxyalkylene group.
- the oxyalkylene group has an addition mole number of oxyalkylene units of preferably 1 to 50, more preferably 2 to 30 from the viewpoint of coordination of the ionic compound when an ionic compound is used as the antistatic component. 2 to 20 is more preferable.
- the terminal of the oxyalkylene chain may be a hydroxyl group, or may be substituted with an alkyl group, a phenyl group or the like.
- the (meth) acrylate polymer having an oxyalkylene group is preferably a polymer containing an alkylene oxide (meth) acrylate as a monomer unit (component).
- Specific examples of the (meth) acrylate alkylene oxide examples include methoxy-polyethylene glycol (meth) acrylate type such as methoxy-diethylene glycol (meth) acrylate and methoxy-triethylene glycol (meth) acrylate, ethoxy-diethylene glycol ( Meth) acrylate, ethoxy-polyethylene glycol (meth) acrylate type such as ethoxy-triethylene glycol (meth) acrylate, butoxy-diethylene glycol (meth) acrylate, Butoxy-polyethylene glycol (meth) acrylate type such as toxi-triethylene glycol (meth) acrylate, phenoxy-polyethylene glycol (meth) acrylate
- the monomer unit (component) other monomer units (components) other than the (meth) acrylic acid alkylene oxide can also be used.
- specific examples of other monomer components include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) ) Acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) ) Acrylates, isodecyl (meth) acrylates, n-dodecyl
- the polyoxyalkylene chain-containing compound not containing the organopolysiloxane is a compound having at least a part of a (poly) ethylene oxide chain.
- the compatibility between the base polymer and the antistatic component is improved, bleeding to the adherend is suitably suppressed, and a low-staining adhesive composition is obtained. It is done.
- a PPG-PEG-PPG block copolymer is used, a pressure-sensitive adhesive excellent in low contamination can be obtained.
- the weight of the (poly) ethylene oxide chain in the total polyoxyalkylene chain-containing compound not containing the organopolysiloxane is preferably 5 to 90% by weight, more preferably 5 to 85%. % By weight, more preferably 5 to 80% by weight, most preferably 5 to 75% by weight.
- the molecular weight of the polyoxyalkylene chain-containing compound not containing the organopolysiloxane is suitably a number average molecular weight (Mn) of 50,000 or less, preferably 200 to 30,000, more preferably 200 to 10,000, 200 to 5000 is preferably used.
- Mn number average molecular weight
- Mn means a value in terms of polystyrene obtained by GPC (gel permeation chromatography).
- the content of the polyoxyalkylene chain-containing compound not containing the organopolysiloxane can be, for example, 0.005 to 20 parts by weight, preferably 0, per 100 parts by weight of the (meth) acrylic polymer. 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight, still more preferably 0.05 to 3 parts by weight, and most preferably 0.1 to 0.9 parts by weight. It is preferable for it to be in the above-mentioned range since it is easy to achieve both wettability to the adherend and low contamination.
- the pressure-sensitive adhesive composition preferably contains a crosslinking agent. Moreover, in this invention, it can be set as an adhesive layer using the said adhesive composition.
- a surface protective film (adhesive layer) with more excellent heat resistance can be obtained by appropriately adjusting the structural unit, structural ratio, selection of crosslinking agent and addition ratio of the (meth) acrylic polymer, and crosslinking. be able to.
- an isocyanate compound As the crosslinking agent used in the present invention, an isocyanate compound, an epoxy compound, a melamine resin, an aziridine derivative, a metal chelate compound, or the like may be used.
- an isocyanate compound is a preferred embodiment.
- these compounds may be used independently and may be used in mixture of 2 or more types.
- isocyanate compound examples include aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), and dimer acid diisocyanate, and fats such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate (IPDI).
- aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), and dimer acid diisocyanate
- fats such as cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate (IPDI).
- Aromatic isocyanates such as cyclic isocyanates, 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate (XDI), allophanate bonds, biuret bonds, isocyanurate bonds, uretdione bonds , Urea bond, carbodiimide bond, uretonimine bond, oxadiazinetrione bond Polyisocynate modified products thereof obtained by modifying the.
- Aromatic isocyanates such as cyclic isocyanates, 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate (XDI), allophanate bonds, biuret bonds, isocyanurate bonds, uretdione bonds , Urea bond, carbodiimide bond, uretonimine bond, oxadiazinetrione bond Polyisocyn
- epoxy compound examples include N, N, N ′, N′-tetraglycidyl-m-xylenediamine (trade name: TETRAD-X, manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 1,3-bis (N, N-dioxy). Glycidylaminomethyl) cyclohexane (trade name: TETRAD-C, manufactured by Mitsubishi Gas Chemical Company, Inc.).
- Examples of the melamine resin include hexamethylol melamine.
- Examples of the aziridine derivative include commercial names HDU, TAZM, TAZO (manufactured by Mutual Yakuhin Co., Ltd.) and the like.
- metal chelate compound examples include aluminum, iron, tin, titanium, and nickel as metal components, and acetylene, methyl acetoacetate, and ethyl lactate as chelate components.
- the content of the crosslinking agent used in the present invention is, for example, preferably 0.01 to 10 parts by weight, and preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the (meth) acrylic polymer. It is more preferably contained, more preferably 0.2 to 3 parts by weight, and most preferably 0.5 to 2 parts by weight.
- the content is less than 0.01 parts by weight, the crosslinking formation by the crosslinking agent becomes insufficient, the cohesive force of the resulting pressure-sensitive adhesive layer becomes small, and sufficient heat resistance may not be obtained, It tends to cause glue residue.
- the cohesive force of the polymer is large, the fluidity is lowered, the wettability to the adherend (for example, polarizing plate) becomes insufficient, and the adherend and the pressure-sensitive adhesive. There is a tendency to cause blisters generated between the layer (adhesive composition layer). Furthermore, when the amount of the crosslinking agent is large, the peeling charging property tends to be lowered.
- the pressure-sensitive adhesive composition may further contain a cross-linking catalyst for causing any of the above-described cross-linking reactions to proceed more effectively.
- cross-linking catalysts include tin-based catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, tris (acetylacetonato) iron (tris (acetylacetonato) iron), tris (hexane-2,4-dionato) iron, tris (Heptane-2,4-dionato) iron, tris (heptane-3,5-dionato) iron, tris (5-methylhexane-2,4-dionato) iron, tris (octane-2,4-dionato) iron, Tris (6-methylheptane-2,4-dionato) iron, tris (2,6-dimethylheptane-3,5-dionato) iron, tris (nonane
- tin-based catalysts
- the content (use amount) of the crosslinking catalyst is not particularly limited, but is preferably 0.0001 to 1 part by weight, for example, 0.001 to 0.5 parts per 100 parts by weight of the (meth) acrylic polymer. Part by weight is more preferred. Within the above range, when the pressure-sensitive adhesive layer is formed, the speed of the crosslinking reaction is increased, which is a preferred embodiment.
- the pressure-sensitive adhesive composition may further contain a crosslinking retarder.
- the crosslinking retarder is not particularly limited, and examples thereof include ⁇ -ketoesters such as methyl acetoacetate, ethyl acetoacetate, octyl acetoacetate, oleyl acetoacetate, lauryl acetoacetate, stearyl acetoacetate, acetylacetone, 2,4- Examples thereof include ⁇ -diketones such as hexanedione and benzoylacetone, and isopropyl alcohol. Among them, acetylacetone can be used.
- the crosslinking retarder can be used alone or in combination of two or more.
- the content (amount of use) of the crosslinking retarder is not particularly limited, but is preferably 0.1 to 10 parts by weight, for example, 0.1 to 5 parts by weight with respect to 100 parts by weight of the solvent (when converted). Part is more preferred. Within the above range, the pot life of the pressure-sensitive adhesive (pressure-sensitive adhesive composition) can be extended, which is a preferred embodiment.
- the pressure-sensitive adhesive composition may contain a (meth) acrylic oligomer.
- the weight average molecular weight (Mw) of the (meth) acrylic oligomer is preferably 1000 or more and less than 30000, more preferably 1500 or more and less than 20000, and still more preferably 2000 or more and less than 10,000.
- Mw weight average molecular weight
- the measurement of the weight average molecular weight of a (meth) acrylic-type oligomer can be calculated
- Examples of the monomer constituting the (meth) acrylic oligomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) acrylate.
- Examples of (meth) acrylic oligomers include alkyl (meth) acrylates in which alkyl groups such as isobutyl (meth) acrylate and t-butyl (meth) acrylate have a branched structure; cyclohexyl (meth) acrylate, and isobornyl (meth) Esters of (meth) acrylic acid and alicyclic alcohols such as acrylate and dicyclopentanyl (meth) acrylate; cyclic structures such as aryl (meth) acrylate such as phenyl (meth) acrylate and benzyl (meth) acrylate It is preferable that an acrylic monomer having a relatively bulky structure typified by (meth) acrylate having a monomer content is included as a monomer unit.
- the tackiness of the pressure-sensitive adhesive layer can be further improved.
- those having a ring structure in terms of bulkiness are highly effective, and those having a plurality of rings are more effective.
- ultraviolet rays when employed in the synthesis of a (meth) acrylic oligomer or in the production of a pressure-sensitive adhesive layer, those having a saturated bond are preferred in that they are less likely to cause polymerization inhibition.
- An alkyl (meth) acrylate having a branched structure or an ester with an alicyclic alcohol can be suitably used as a monomer constituting the (meth) acrylic oligomer.
- suitable (meth) acrylic oligomers include, for example, a copolymer of cyclohexyl methacrylate (CHMA) and isobutyl methacrylate (IBMA), and a copolymer of cyclohexyl methacrylate (CHMA) and isobornyl methacrylate (IBXMA).
- CHMA cyclohexyl methacrylate
- IBMA isobutyl methacrylate
- IBXMA isobornyl methacrylate
- the (meth) acrylic oligomer when used, its blending amount is not particularly limited, but is preferably 10 parts by weight or less with respect to 100 parts by weight of the (meth) acrylic polymer, More preferred is 0.1 to 10 parts by weight, still more preferred is 0.5 to 5 parts by weight, and particularly preferred is 1 to 3 parts by weight.
- the blending amount of the (meth) acrylic oligomer exceeds 10 parts by weight, there may be a problem that the elastic modulus is increased and the adhesiveness at low temperature is deteriorated.
- the pressure-sensitive adhesive composition forming the pressure-sensitive adhesive layer of the present invention may further contain a solvent.
- a solvent the solvent used for the above-mentioned solution polymerization method is mentioned, for example.
- the solvent in the pressure-sensitive adhesive composition for forming the pressure-sensitive adhesive layer of the present invention may be the same as or different from the solvent used in the solution polymerization method.
- the solvent in the adhesive composition which forms the adhesive layer of this invention can be used individually or in combination of 2 or more types.
- the pressure-sensitive adhesive composition may contain other known additives as long as the characteristics such as stain resistance can be satisfied.
- powders such as colorants and pigments, surfactants, and the like , Plasticizer, tackifier, low molecular weight polymer, surface lubricant, leveling agent, antioxidant, corrosion inhibitor, light stabilizer, UV absorber, polymerization inhibitor, silane coupling agent, inorganic or organic filling
- An agent, a metal powder, a particle, a foil, and the like can be appropriately added depending on the use.
- the surface protective film of the present invention comprises a base film made of a resin material, a charge on one side of the base film, the pressure-sensitive adhesive layer, and the surface of the base film opposite to the side having the pressure-sensitive adhesive layer.
- a release film is provided on the surface of the pressure-sensitive adhesive layer opposite to the surface having the base material film (antistatic layer / base material). Film / adhesive layer / release film).
- the said adhesive layer is formed by bridge
- the method for forming the pressure-sensitive adhesive layer on the antistatic layer is not particularly limited.
- the antistatic agent composition (solution) is applied to a substrate film, and the polymerization solvent is removed by drying to prevent antistatic. It is possible to form a layer on a base film, and apply and dry the pressure-sensitive adhesive composition on the prepared antistatic layer.
- the antistatic agent composition (solution) is applied to a base film, and a polymerization solvent is dried and removed to form an antistatic layer on the base film. It can also be formed by applying and drying an object on a release film to form an adhesive layer and transferring the adhesive layer onto an antistatic layer.
- a known method used for producing pressure-sensitive adhesive tapes is used as a method for forming the pressure-sensitive adhesive layer when producing the surface protective film of the present invention. Specific examples include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, extrusion coating using a die coater, and the like.
- the thickness of the pressure-sensitive adhesive layer is preferably 3 to 100 ⁇ m, more preferably 5 to 50 ⁇ m, and further preferably 5 to 30 ⁇ m. It is preferable for the thickness of the pressure-sensitive adhesive layer to be in the above-mentioned range since it is easy to obtain an appropriate balance between removability and pressure-sensitive adhesiveness. On the other hand, when it is thicker than the above range, contamination is likely to occur, and when it is thin, the workability of bonding is inferior, which is not preferable.
- the thickness (total thickness) of the surface protective film of the present invention is preferably 10 to 400 ⁇ m, more preferably 12 to 200 ⁇ m, and still more preferably 15 to 100 ⁇ m. Within the above range, it is excellent in adhesive properties (removability, adhesiveness, etc.), workability, and appearance properties, and is a preferred embodiment.
- the said total thickness means the sum total of the thickness containing all layers, such as a base film, an adhesive layer, and an antistatic layer.
- a release film is provided on the surface of the pressure-sensitive adhesive layer opposite to the surface having the base film,
- the release treatment surface of the release film does not contain a silicone component.
- “it does not contain a silicone component” means that it does not contain substantially, and shows that the silicon (Si) element ratio of the mold release process surface of a release film is 0.5 atomic% or less.
- Examples of the “silicone component” include polydimethylsiloxane.
- the element ratio of silicon (Si) based on the measurement by X-ray photoelectron spectroscopy, the element ratio (atomic%) of the silicon atom (Si) of the release treatment surface (release layer surface) of the release film is determined. Calculated.
- the measurement apparatus and measurement conditions are shown below.
- the release film usually has a release layer formed on the base material using the release agent composition.
- the material constituting the substrate include paper and plastic film, and a plastic film is preferably used from the viewpoint of excellent surface smoothness.
- the film is not particularly limited as long as it can protect the pressure-sensitive adhesive layer.
- Examples include a coalesced film, a polyethylene terephthalate (PET) film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.
- PET polyethylene terephthalate
- PET polyethylene terephthalate
- the release treatment surface of the release film is characterized by not containing a silicone component, and the release film as a whole preferably contains no silicone component.
- the release treatment surface of the release film can be subjected to a release treatment with a fluorine-based, long-chain alkyl-based and fatty acid amide-based release agent, silica powder or the like in order to exhibit releasability.
- antifouling treatment antistatic treatment such as coating type, kneading type, vapor deposition type, and other antifouling treatment can be performed as necessary.
- the method for forming the release layer on the substrate is not particularly limited.
- a solution of a release agent composition is applied to the substrate, and the polymerization solvent is dried and removed to form the release layer on the substrate. It is produced by forming. Thereafter, curing may be performed for the purpose of adjusting the component transfer of the release layer.
- the release agent composition when the release agent composition is applied onto the substrate to produce a release layer, contains at least one polymerization solvent other than the polymerization solvent so that it can be uniformly applied onto the substrate. A new solvent may be added.
- a known method used for manufacturing the release layer is used. Specific examples include roll coating, gravure coating, reverse coating, roll brushing, spray coating, air knife coating, extrusion coating using a die coater, and the like.
- the thickness of the release film is usually about 5 to 200 ⁇ m, preferably about 10 to 100 ⁇ m. It is preferable for it to be in the above-mentioned range since it is excellent in workability for bonding to the pressure-sensitive adhesive layer and workability for peeling from the pressure-sensitive adhesive layer.
- the surface protective film disclosed herein may be implemented in a mode including other layers in addition to the base film, the pressure-sensitive adhesive layer, the antistatic layer, and the release film.
- Examples of the arrangement of the “other layer” include a space between the base film and the antistatic layer.
- the optical member of the present invention is preferably protected by the surface protective film. Since the surface protective film has an antistatic pressure-sensitive adhesive layer or antistatic layer, the surface protective film has excellent antistatic properties for peeling, and the release treatment surface of the release film does not contain a silicone component. Excellent curling of the surface protection film itself, so that the surface of the optical member (polarizing plate, etc.) is protected from scratches and contamination without being peeled off during processing, transportation, shipping inspection, etc. Can be useful. In particular, since it can be used for plastic products and the like that are likely to generate static electricity, it is very useful for antistatic applications in the technical fields related to optical and electronic parts where charging is a particularly serious problem.
- the display device of the present invention is preferably protected by the surface protective film. Since the surface protective film has an antistatic pressure-sensitive adhesive layer or antistatic layer, the surface protective film has excellent antistatic properties for peeling, and the release treatment surface of the release film does not contain a silicone component. Excellent in curling of the surface protection film itself, so that it does not peel off during processing, transportation, shipping inspection, etc., and can protect the display device from scratches, contamination, etc. It becomes. In particular, since it can be used for plastic products and the like that are likely to generate static electricity, it is very useful for antistatic applications in the technical fields related to optical and electronic parts where charging is a particularly serious problem.
- Tg glass transition temperature
- Tgn glass transition temperature of the homopolymer of each monomer.
- Formula: 1 / (Tg + 273) ⁇ [Wn / (Tgn + 273)]
- Tg (° C) glass transition temperature of the copolymer
- Wn (-) the weight fraction of each monomer
- Tgn (° C) glass transition temperature of the homopolymer of each monomer
- n is the type of each monomer.
- the weight average molecular weight (Mw) was measured using a GPC apparatus (HLC-8220GPC) manufactured by Tosoh Corporation. The measurement conditions are as follows. Sample concentration: 0.2% by weight (THF solution) Sample injection volume: 10 ⁇ l Eluent: THF Flow rate: 0.6 ml / min Measurement temperature: 40 ° C column: Sample column; TSKguardcolumn SuperHZ-H (1) + TSKgel SuperHZM-H (2) Reference column; TSKgel SuperH-RC (1 piece) Detector: Differential refractometer (RI) The weight average molecular weight was determined in terms of polystyrene.
- the obtained surface protective film with a release film was cut into a width of 10 mm ⁇ length of 50 mm, and a support was obtained using a double-sided tape on the surface of the release film side of the width of 10 mm ⁇ length of 10 mm, which is the upper part of the cut sample.
- the upper part of the acrylic plate to which the surface protective film is not fixed is sandwiched with a chuck, and the part not fixed by the acrylic plate is separated from the surface protective film with the release film fixed to the acrylic plate by the double-sided tape.
- the mold film is cut and peeled from the surface protective film
- the lower part of the surface protective film in a state where the release film is peeled is fixed with a chuck, and pulled in the shearing direction at a pulling speed of 0.06 m / min.
- the maximum shearing force was defined as the shearing force (N / cm 2 ).
- the shear force (N / cm 2 ) is preferably 15 or more, more preferably 15 to 50, still more preferably 20 to 40, and particularly preferably 30 to 50. If the shear force is within the above range, for example, the surface protective film itself can withstand the force in the shearing direction that is generated when the surface protective film tries to curl, and the surface protective film does not slip or shift, and further the surface This is preferable because curling of the adherend to which the protective film is attached can also be suppressed.
- the surface protection film is cut into a size of 50 mm in width and 80 mm in length, and the release film attached to the surface of the adhesive layer of the surface protection film is peeled off, and then the glass plate cut into a width of 70 mm and a length of 100 mm (Matsunami Glass The product was attached to the surface using a hand roller and left at 40 ° C. ⁇ 92% RH for 7 days, and then the surface protective film was peeled off, and contamination of the glass surface was visually confirmed. (Evaluation criteria) If there is no contamination: ⁇ If there is contamination: ⁇
- the obtained surface protective film with a release film was cut into a size of 50 mm in width and 100 mm in length, and a double-sided adhesive tape was used on the antistatic layer side of the cut surface protective film with an acrylic plate (Mitsubishi).
- the product was pressure-bonded to Acrylite L), and the release film was peeled from the surface of the pressure-sensitive adhesive layer of the surface protective film at a peeling angle of 150 ° and a peeling speed of 3 m / min.
- the measurement was performed in an environment of 23 ° C. and 50% RH.
- the “antistatic property” of the surface protective film itself was evaluated based on the “peeling voltage at the time of peeling the release film”.
- the obtained surface protective film with a release film was cut to a size of 50 mm in width and 110 mm in length, and after releasing the release film, the glass plate (made by Matsunami Glass, width 50 mm, length) 100 mm) using a hand roller. This sample was left in an environment of 23 ° C. ⁇ 50% RH for one day, and then set at a predetermined position on a sample fixing table having a height of 20 mm. The edge part of the surface protection film which protruded 10 mm from the said glass plate was fixed to the automatic winder, and it peeled so that it might become a peeling angle of 150 degrees and a peeling speed of 10 m / min.
- the potential (kV) of the adherend (glass) surface generated at this time was measured with a surface potentiometer (KSD-0103, manufactured by Kasuga Denki Co., Ltd.) fixed at a position of 100 mm in height from the center of the glass. .
- the measurement was performed in an environment of 23 ° C. and 50% RH.
- the “antistatic property (peeling antistatic property)” when the surface protective film was peeled from the adherend was evaluated based on “peeling voltage at the time of peeling the surface protective film”.
- the peeling voltage at the time of peeling the release film and the peeling voltage (kV) (absolute value) at the time of peeling the surface protective film are preferably 0.8 kV or less, more preferably 0. 7 kV or less, more preferably 0.6 kV or less.
- kV peeling voltage
- the obtained surface protective film with a release film was cut into a width of 25 mm, the release film was peeled off, and the surface of the pressure-sensitive adhesive layer of the surface protective film was a glass plate (made by Matsunami Glass, blue plate edge polished product, OF1 ) Using a 2 kg roller and left in an environment of 23 ° C. and 50% relative humidity for about 20 minutes to prepare a sample. Subsequently, the surface protective film as the sample was peeled off from the glass plate at an angle of 180 ° at a speed of 0.3 m / min, the peel force of the surface protective film to the glass plate was measured, and the adhesion to glass (N / 25 mm).
- the adhesion to glass (N / 25 mm) is preferably 0.01 to 0.5, more preferably 0.02 to 0.4, and still more preferably 0.05 to 0.35. Particularly preferred is 0.08 to 0.3, and most preferred is 0.09 to 0.2. If the adhesive strength to glass is within the above range, for example, when the surface protective film is applied to the adherend, it does not peel off and has excellent adhesiveness. Is excellent in re-peelability and peel workability, and is a preferred embodiment.
- the (meth) acrylic polymer had a weight average molecular weight (Mw) of 650,000 and a glass transition temperature (Tg) of ⁇ 67.6 ° C.
- the reaction solution was put into a temperature atmosphere of 130 ° C., and toluene, chain transfer agent, and unreacted monomer were removed by drying to obtain a solid (meth) acrylic oligomer.
- the weight average molecular weight (Mw) of the (meth) acrylic oligomer was 5100.
- the (meth) acrylic polymer solution (30% by weight) is diluted to 20% by weight with ethyl acetate, and 500 parts by weight (100 parts by weight of solid content) of this solution has an oxyalkylene chain as an antistatic aid.
- a dispersion containing 25% of a polyester resin as a binder (trade name “Vinaroll MD-1480” manufactured by Toyobo Co., Ltd. (an aqueous dispersion of a saturated copolyester resin) (binder dispersion) was also prepared.
- aqueous dispersion of carnauba wax (wax ester) of 0.5% poly (3,4-dioxythiophene) (PEDOT) as a conductive polymer and polystyrene sulfonate (several An aqueous solution (trade name “Baytron P”, product of HC Stark Co., Ltd.) (conductive polymer aqueous solution) containing 0.8% of average molecular weight (150,000) (PSS) was prepared.
- PES average molecular weight (150,000
- aqueous solution for antistatic layer having an NV (nonvolatile content) of about 0.5% was prepared.
- a transparent polyethylene terephthalate (PET) film (trade name: T100C50, manufactured by Mitsubishi Chemical Corporation) having a thickness of 50 ⁇ m, a width of 30 cm, and a length of 40 cm was prepared.
- the antistatic layer aqueous solution is applied to the PET film with a bar coater, heated to 130 ° C. for 2 minutes and dried, and then the other surface of the base film is similarly coated with the antistatic layer aqueous solution.
- was coated with a bar coater heated to 130 ° C. for 2 minutes and dried to prepare a base film with an antistatic layer (both sides) having an antistatic layer having a thickness of 30 nm on both sides of the base film.
- ⁇ Release film without silicone component> In a reaction vessel equipped with a cooler, 200 parts by weight of xylene (manufactured by Taiyo Chemical Co., Ltd., xylol) and 600 parts by weight of octadecyl isocyanate (manufactured by Ohara Palladium Chemical Co., Ltd., R-NCO) are added and heated with stirring to reflux the xylene. From the beginning, 100 parts by weight of polyvinyl alcohol (manufactured by Kuraray, Kuraray Poval 205) was added in small portions over 2 hours at 10 minute intervals. After the addition of polyvinyl alcohol, the reaction was completed by refluxing for 2 hours. The obtained reaction mixture was cooled to about 80 ° C.
- the thickness of the release layer after drying is 20 nm, and the element ratio (atomic%) of silicon atoms (Si) on the release-treated surface of the release film is below the lower limit of detection as measured by X-ray photoelectron spectroscopy. It was confirmed that the release-treated surface did not contain (substantially) the silicone component.
- Examples 2 to 5 and Comparative Examples 1 to 4 Based on the description in Tables 1 and 2, a pressure-sensitive adhesive layer, a base film (with an antistatic layer), and a release film were prepared. In addition, about the preparation conditions etc., it carried out similarly to Example 1, and produced the surface protective film finally. Moreover, about the base film and release film different from Example 1, the thing as described below was used.
- Example 3 (Preparation of base film with antistatic layer (one side))
- a transparent polyethylene terephthalate (PET) film (trade name: T100C38, manufactured by Mitsubishi Chemical Corporation) having a thickness of 38 ⁇ m, a width of 30 cm, and a length of 40 cm was prepared as a base film.
- the antistatic layer aqueous solution is coated on the PET film with a bar coater, heated to 130 ° C. for 2 minutes and dried to have an antistatic layer having a thickness of 10 nm after drying ( A base film with one side) was produced (see FIG. 1).
- Comparative Example 4 a transparent polyethylene terephthalate (PET) film (manufactured by Mitsubishi Chemical Corporation, trade name: T100C38) having a thickness of 38 ⁇ m, a width of 30 cm, and a length of 40 cm was prepared as a base film.
- PET polyethylene terephthalate
- This PET film was used as a base film without an antistatic layer.
- the mold release agent composition was applied to a PET film having a thickness of 25 ⁇ m as a base material (Diafoil T100-25, manufactured by Mitsubishi Plastics), dried at 130 ° C. for 1 minute, and having a silicone release layer A film was prepared. Note that the thickness of the release layer after drying was 20 nm.
- Table 3 shows the results of various measurements and evaluations described above for the surface protective films according to Examples and Comparative Examples.
- AS-110 used in Example 5 is 1-ethyl-3-methylimidazolium bisfluorosulfonylimide [trade name “ELEXEL AS-” manufactured by Daiichi Kogyo Seiyaku Co., Ltd. 110 ", 100% by weight of active ingredient].
- the surface protective film disclosed herein is optical when manufacturing or transporting optical members such as polarizing plates used as components of liquid crystal display panels, plasma display panels (PDP), organic electroluminescence (EL) displays, and the like. It is suitable as a surface protective film for protecting the member. In particular, it is useful as a surface protective film (optical surface protective film) applied to an optical member such as a polarizing plate mounted on an on-cell or in-cell touch panel.
- optical surface protective film optical surface protective film
- Antistatic layer 1 ' Antistatic layer 2: Substrate film 3: Adhesive layer 4: Release film 10: Surface protective film
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Abstract
Description
ここに開示される表面保護フィルムは、一般に、粘着シート、粘着テープ、粘着ラベル、粘着フィルム、表面保護シート等と称される形態のものであり、特に液晶ディスプレイパネル中のタッチセンサやガラスの上に粘着剤層を介して貼付される偏光板などの光学部材の加工時や搬送時に、光学部材の表面を保護する表面保護フィルムとして好適である。前記表面保護フィルムにおける粘着剤層は、典型的には連続的に形成されるが、かかる形態に限定されるものではなく、例えば点状、ストライプ状等の規則的あるいはランダムなパターンに形成された粘着剤層であってもよい。また、ここに開示される表面保護フィルムは、ロール状であってもよく、枚葉状であってもよい。
本発明の表面保護フィルムは、樹脂材料からなる基材フィルムと、前記基材フィルムの片面に、粘着剤層と、前記基材フィルムの前記粘着剤層を有する面とは反対面に、帯電防止層と、前記粘着剤層の前記基材フィルムを有する面とは反対面に、離型フィルムと、が設けられていることを特徴とする。ここに開示される技術において、基材フィルムを構成する樹脂材料は、特に制限なく使用することができるが、例えば、透明性、機械的強度、熱安定性、水分遮蔽性、等方性、可撓性、寸法安定性等の特性に優れたものを使用することが好ましい。特に、基材フィルムが可撓性を有することにより、ロールコーターなどによって粘着剤組成物を塗布することができ、ロール状に巻き取ることができ、有用である。
本発明の表面保護フィルムは、前記基材フィルムと、前記粘着剤層と、前記基材フィルムの前記粘着剤層を有する面とは反対面に、帯電防止成分を含む帯電防止層と、前記粘着剤層の前記基材フィルムを有する面とは反対面に、離型フィルムと、が設けられていることを特徴とする。また、前記基材フィルムと前記粘着剤層との間に、更に、帯電防止成分を含む帯電防止層を有することが好ましい。前記表面保護フィルムが、帯電防止層を有することにより、表面保護フィルムの剥離帯電防止性や、被着体に貼付後、剥離した際の耐汚染性(低汚染性)に優れ、更に、基材フィルムと粘着剤層との間に帯電防止層を有する場合には、剥離帯電防止性や耐汚染性(低汚染性)がより優れることになり、好ましい態様となる。なお、帯電防止層を基材フィルムの両面に有する場合は、帯電防止層を構成する帯電防止剤組成物は同一組成であっても、異なっていても構わない。
前記帯電防止層は、帯電防止成分を含む帯電防止剤組成物により形成することができる。前記帯電防止成分として、特に限定されないが、例えば、導電性ポリマーが挙げられる。前記導電性ポリマー成分として、水溶性導電性ポリマー及び/又は水分散性導電性ポリマーを使用することが好ましい。前記導電性ポリマーを使用することにより、帯電防止層に基づく剥離帯電防止性を満足することができる。また、前記導電性ポリマーは、「水溶性」又は「水分散性」であるが、後述する架橋剤(例えば、メラミン系やイソシアネート系架橋剤)を使用することにより、帯電防止層中に固定化でき、耐水性を向上できる。前記水溶性導電性ポリマー及び/又は水分散性導電性ポリマーを用いることにより、帯電防止層の表面抵抗値を低く抑えることができ、更に、表面保護フィルムの剥離帯電防止性にも寄与でき、好ましい態様となる。
前記帯電防止層は、帯電防止成分を含む帯電防止剤組成物により形成することができ、更に、ポリエステル樹脂をバインダとして含有することが好ましい。前記ポリエステル樹脂は、ポリエステルを主成分(典型的には50重量%超え、好ましくは75重量%以上、例えば90重量%以上を占める成分)として含む樹脂材料であることが好ましい。前記ポリエステルは、典型的には、1分子中に2個以上のカルボキシル基を有する多価カルボン酸類(典型的にはジカルボン酸類)およびその誘導体(当該多価カルボン酸の無水物、エステル化物、ハロゲン化物等)から選択される1種または2種以上の化合物(多価カルボン酸成分)と、1分子中に2個以上のヒドロキシル基を有する多価アルコール類(典型的にはジオール類)から選択される1種または2種以上の化合物(多価アルコール成分)とが縮合した構造を有することが好ましい。
前記帯電防止層は、架橋剤として、一般的な樹脂の架橋に用いられるメラミン系、イソシアネート系、エポキシ系等の架橋剤を適宜選択して用いることができる。好ましい一態様としては、前記架橋剤の中でも、少なくともメラミン系架橋剤又はイソシアネート系架橋剤を使用することである。前記架橋剤を用いることにより、帯電防止層を形成する際に、水溶性導電性ポリマーや水分散性の導電性ポリマーを帯電防止層中に固定化でき、耐水性や耐溶剤性の向上に優れた効果を実現することができる。
前記帯電防止層は、前記導電性ポリマー成分等および必要に応じて使用される添加剤が適当な溶媒(水など)に溶解した液状組成物(帯電防止層形成用のコーティング材、帯電防止剤組成物)を基材フィルムに付与することを含む手法によって好適に形成され得る。例えば、前記コーティング材を基材フィルムの片面に塗布して乾燥させ、必要に応じて硬化処理(熱処理、紫外線処理など)を行う手法を好ましく採用し得る。前記コーティング材のNV(不揮発分)は、例えば5重量%以下(典型的には0.05~5重量%)とすることができ、通常は1重量%以下(典型的には0.10~1重量%)とすることが適当である。厚みの小さい帯電防止層を形成する場合には、前記コーティング材のNVを例えば0.05~0.50重量%(例えば0.10~0.40重量%)とすることが好ましい。このように低NVのコーティング材を用いることにより、より均一な帯電防止層が形成され得る。
ここに開示される技術における帯電防止層の厚さは、典型的には3~500nmであり、好ましくは3~100nm、より好ましくは3~60nmである。帯電防止層の厚みが小さすぎると、帯電防止層を均一に形成することが困難となり(例えば、帯電防止層の厚みにおいて、場所による厚みのバラツキが大きくなり)、このため、表面保護フィルムの外観にムラが生じやすくなることがあり得る。一方、厚すぎると、基材フィルムの特性(光学特性、寸法安定性等)に影響を及ぼす場合がある。
本発明の表面保護フィルムは、樹脂材料からなる基材フィルムと、前記基材フィルムの片面に、ベースポリマーとしての(メタ)アクリル系ポリマーと、帯電防止成分としてのイオン性化合物と、を含有する粘着剤組成物より形成される粘着剤層と、を有することを特徴とする。
本発明の表面保護フィルムは、帯電防止成分としてのイオン性化合物を含有する粘着剤組成物より形成される粘着剤層(帯電防止性を有する粘着剤層)を有することを特徴とする。前記イオン性化合物としては、アルカリ金属塩、及び/又は、イオン液体が挙げられる。これらのイオン性化合物を含有することにより、優れた帯電防止性を付与することができる。なお、前記のように帯電防止成分を含有する粘着剤組成物を架橋してなる粘着剤層(帯電防止成分を使用)は、剥離した際に帯電防止されていない被着体(例えば、偏光板)への帯電防止が図れ、被着体への汚染が低減された表面保護フィルムとなる。このため、帯電や汚染が特に深刻な問題となる光学・電子部品関連の技術分野における帯電防止性表面保護フィルムとして非常に有用となる。
本発明の表面保護フィルムは、前記粘着剤組成物が、帯電防止助剤であるオキシアルキレン鎖を有するオルガノポリシロキサンを含有することが好ましく、オキシアルキレン側鎖を有するオルガノポリシロキサンを含有することがより好ましい。前記オルガノポリシロキサンを使用することにより、粘着剤表面の表面自由エネルギーが低下し、軽剥離化を実現しているものと推測される。また、前記粘着剤組成物に含まれるイオン性化合物と共に、帯電防止性を向上させることが推測される。
(式中、R1及び/又はR2は、炭素数1~6のオキシアルキレン鎖を有し、前記オキシアルキレン鎖中のアルキレン基は、直鎖又は分岐していてもよく、前記オキシアルキレン鎖の末端が、アルコキシ基、又は、ヒドロキシル基であってもよい。また、R1又はR2のいずれか一方が、ヒドロキシル基でもよく、又は、アルキル基、アルコキシ基であってもよく、前記アルキル基、アルコキシ基の一部が、ヘテロ原子で置換された官能基であってもよい。nは、1~300の整数である。)
(式中、R1は1価の有機基、R2,R3及びR4はアルキレン基、R5は水素もしくは有機基、m及びnは0~1000の整数。但し、m, nが同時に0となることはない。a及びbは0~100の整数。但し、a, bが同時に0となることはない。)
本発明の表面保護フィルムは、前記粘着剤組成物が、架橋剤を含有することが好ましい。また、本発明においては、前記粘着剤組成物を用いて、粘着剤層とすることができる。例えば、前記(メタ)アクリル系ポリマーの構成単位、構成比率、架橋剤の選択および添加比率等を適宜調節して架橋することにより、より耐熱性に優れた表面保護フィルム(粘着剤層)を得ることができる。
前記粘着剤組成物には、さらに、上述したいずれかの架橋反応をより効果的に進行させるための架橋触媒を含有させることができる。かかる架橋触媒として、例えばジラウリン酸ジブチルスズ、ジラウリン酸ジオクチルスズなどのスズ系触媒、トリス(アセチルアセトナト)鉄(トリス(アセチルアセトナート)鉄)、トリス(ヘキサン-2,4-ジオナト)鉄、トリス(ヘプタン-2,4-ジオナト)鉄、トリス(ヘプタン-3,5-ジオナト)鉄、トリス(5-メチルヘキサン-2,4-ジオナト)鉄、トリス(オクタン-2,4-ジオナト)鉄、トリス(6-メチルヘプタン-2,4-ジオナト)鉄、トリス(2,6-ジメチルヘプタン-3,5-ジオナト)鉄、トリス(ノナン-2,4-ジオナト)鉄、トリス(ノナン-4,6-ジオナト)鉄、トリス(2,2,6,6-テトラメチルヘプタン-3,5-ジオナト)鉄、トリス(トリデカン-6,8-ジオナト)鉄、トリス(1-フェニルブタン-1,3-ジオナト)鉄、トリス(ヘキサフルオロアセチルアセトナト)鉄、トリス(アセト酢酸エチル)鉄、トリス(アセト酢酸-n-プロピル)鉄、トリス(アセト酢酸イソプロピル)鉄、トリス(アセト酢酸-n-ブチル)鉄、トリス(アセト酢酸-sec-ブチル)鉄、トリス(アセト酢酸-tert-ブチル)鉄、トリス(プロピオニル酢酸メチル)鉄、トリス(プロピオニル酢酸エチル)鉄、トリス(プロピオニル酢酸-n-プロピル)鉄、トリス(プロピオニル酢酸イソプロピル)鉄、トリス(プロピオニル酢酸-n-ブチル)鉄、トリス(プロピオニル酢酸-sec-ブチル)鉄、トリス(プロピオニル酢酸-tert-ブチル)鉄、トリス(アセト酢酸ベンジル)鉄、トリス(マロン酸ジメチル)鉄、トリス(マロン酸ジエチル)鉄、トリメトキシ鉄、トリエトキシ鉄、トリイソプロポキシ鉄、塩化第二鉄などの鉄系触媒を用いることができる。これら架橋触媒は、1種でもよく、2種以上を併用してもよい。
前記粘着剤組成物には、さらに架橋遅延剤を含んでいてもよい。前記架橋遅延剤としては、特に限定されず、例えば、アセト酢酸メチル、アセト酢酸エチル、アセト酢酸オクチル、アセト酢酸オレイル、アセト酢酸ラウリル、アセト酢酸ステアリル等のβ-ケトエステルや、アセチルアセトン、2,4-ヘキサンジオン、ベンゾイルアセトン等のβ-ジケトンや、イソプロピルアルコール等が挙げられる。中でも、アセチルアセトンを用いることができる。前記架橋遅延剤は、単独で又は2種以上組み合わせて使用することができる。
さらに、前記粘着剤組成物には、(メタ)アクリル系オリゴマーを含有してもよい。前記(メタ)アクリル系オリゴマーの重量平均分子量(Mw)は、1000以上30000未満が好ましく、より好ましくは1500以上20000未満、さらに好ましくは2000以上10000未満である。重量平均分子量が30000以上であると、粘着力の向上効果が充分には得られない場合がある。また、1000未満であると、低分子量となるため粘着力や保持特性の低下を引き起こす場合がある。本発明において、(メタ)アクリル系オリゴマーの重量平均分子量の測定は、GPC法によりポリスチレン換算して求めることができる。
本発明の表面保護フィルムは、樹脂材料からなる基材フィルムと、前記基材フィルムの片面に、前記粘着剤層と、前記基材フィルムの前記粘着剤層を有する面とは反対面に、帯電防止成分を含む前記帯電防止層と、前記粘着剤層の前記基材フィルムを有する面とは反対面に、離型フィルムと、が設けられていることを特徴とする(帯電防止層/基材フィルム/粘着剤層/離型フィルム)。また、前記基材フィルムと前記粘着剤層との間に、更に、前記帯電防止層を有することが好ましい(帯電防止層/基材フィルム/帯電防止層/粘着剤層/離型フィルム)。なお、前記粘着剤層は、粘着剤組成物の架橋により形成されるが、粘着剤組成物の塗布後に行うのが一般的である。ただし、架橋後の粘着剤組成物からなる粘着剤層を基材フィルムなどに転写することも可能である。
本発明の表面保護フィルムには、前記粘着剤層の粘着面を保護する目的で、前記粘着剤層の前記基材フィルムを有する面とは反対面に、離型フィルムと、が設けられ、前記離型フィルムの離型処理面が、シリコーン成分を含まないことを特徴とする。なお、「シリコーン成分を含まない」とは、実質的に含まないことを意味し、離型フィルムの離型処理面のケイ素(Si)元素比率が、0.5atomic%以下であることを示す。また、「シリコーン成分」とは、例えば、ポリジメチルシロキサン等が挙げられる。なお、ケイ素(Si)の元素比率については、X線光電子分光法による測定に基づき、離型フィルムの離型処理面(離型層表面)のケイ素原子(Si)の元素比率(atomic%)を算出した。なお、測定装置、測定条件を以下に示す。
測定装置:ULVAC PHI製 PHI Quantera SXM
X線源:モノクロAlKα
XRay Setting:100μmφ[15kV、25W]
光電子取出し角:試料表面に対して45°
本発明の光学部材は、前記表面保護フィルムにより保護されることが好ましい。前記表面保護フィルムは、帯電防止性を有する粘着剤層や帯電防止層を有することで、剥離帯電防止性に優れ、更に離型フィルムの離型処理面がシリコーン成分を含まないため、耐汚染性に優れ、表面保護フィルム自体のカールが抑制されるため、加工、搬送、出荷検査時等において、剥がれたりすることがなく、前記光学部材(偏光板など)の表面を傷や汚染などから保護することができ、有用なものとなる。特に静電気が発生しやすいプラスチック製品などに用いることができるため、帯電が特に深刻な問題となる光学・電子部品関連の技術分野において、帯電防止用途に非常に有用となる。
本発明の表示装置は、前記表面保護フィルムにより保護されることが好ましい。前記表面保護フィルムは、帯電防止性を有する粘着剤層や帯電防止層を有することで、剥離帯電防止性に優れ、更に離型フィルムの離型処理面がシリコーン成分を含まないため、耐汚染性に優れ、表面保護フィルム自体のカールが抑制されるため、加工、搬送、出荷検査時等において、剥がれたりすることがなく、前記表示装置を傷や汚染などから保護することができ、有用なものとなる。特に静電気が発生しやすいプラスチック製品などに用いることができるため、帯電が特に深刻な問題となる光学・電子部品関連の技術分野において、帯電防止用途に非常に有用となる。
ガラス転移温度Tg(℃)は、各モノマーによるホモポリマーのガラス転移温度Tgn(℃)として下記の文献値を用い、下記式により求めた。
式:1/(Tg+273)=Σ[Wn/(Tgn+273)]
式中、Tg(℃)は共重合体のガラス転移温度、Wn(-)は各モノマーの重量分率、Tgn(℃)は各モノマーによるホモポリマーのガラス転移温度、nは各モノマーの種類を表す。
文献値:
2-エチルヘキシルアクリレート(2EHA):-70℃
4-ヒドロキブチルアクリレート(HBA):-32℃
アクリル酸(AA):106℃
重量平均分子量(Mw)は、東ソー株式会社製GPC装置(HLC-8220GPC)を用いて測定を行った。測定条件は下記の通りである。
サンプル濃度:0.2重量%(THF溶液)
サンプル注入量:10μl
溶離液:THF
流速:0.6ml/min
測定温度:40℃
カラム:
サンプルカラム;TSKguardcolumn SuperHZ-H(1本)+TSKgel SuperHZM-H(2本)
リファレンスカラム;TSKgel SuperH-RC(1本)
検出器:示差屈折計(RI)
なお、重量平均分子量はポリスチレン換算値にて求めた。
得られた離型フィルム付きの表面保護フィルムを幅10mm×縦50mmに裁断し、裁断したサンプルの上部である幅10mm×縦10mm部分の離型フィルム側の表面に両面テープを用いて、支持体であるアクリル板(縦70mm、横100mm、厚さ1mm)にハンドローラーにて圧着し、固定した。
続いて、表面保護フィルムが固定されていないアクリル板の上部をチャックで挟み、両面テープでアクリル板に固定されている離型フィルム付きの表面保護フィルムから、アクリル板で固定されていない部分の離型フィルムを表面保護フィルムから裁断・剥離し、離型フィルムが剥離された状態の表面保護フィルムの下部をチャックで挟んで固定し、引張り速度0.06m/分で、せん断方向に引っ張ったときの、せん断力の最大値をせん断力(N/cm2)とした。
表面保護フィルムを幅50mm、長さ80mmのサイズにカットし、表面保護フィルムの粘着剤層表面に貼付された離型フィルムを剥離した後、幅70mm、長さ100mmにカットしたガラス板(松浪硝子社製)表面に、ハンドローラーを用いて、貼り付け、40℃×92%RHに7日間放置した後、表面保護フィルムを剥離し、ガラス表面の汚染を目視にて確認した。
(評価基準)
汚染がなかった場合:○
汚染があった場合:×
得られた離型フィルム付きの表面保護フィルムを幅50mm、長さ100mmのサイズにカットし、カットした表面保護フィルムの帯電防止層側に両面粘着テープを用いて、ハンドローラーにてアクリル板(三菱ケミカル製、アクリライトL)に圧着し、この表面保護フィルムの粘着剤層表面から離型フィルムを、剥離角度150°、剥離速度3m/分の速度で剥離した。この時に発生する剥離直後の粘着剤層表面の電位(kV)を、表面保護フィルムの中央から高さ100mmの位置に固定してある表面電位計(春日電機社製、KSD-0103)で測定した。測定は、23℃、50%RHの環境下で行った。
なお、「離型フィルム剥離時の剥離帯電圧」により、表面保護フィルム自体の「帯電防止性」を評価した。
得られた離型フィルム付きの表面保護フィルムを幅50mm、長さ110mmのサイズにカットし、離型フィルムを剥離した後、あらかじめ除電しておいたガラス板(松浪硝子製、幅50mm、長さ100mm)に、ハンドローラーを用いて圧着した。
このサンプルを23℃×50%RHの環境下に1日放置した後、高さ20mmのサンプル固定台の所定の位置にセットした。
上記ガラス板から10mmはみ出した表面保護フィルムの端部を自動巻取り機に固定し、剥離角度150°、剥離速度10m/分となるように剥離した。このときに発生する被着体(ガラス)表面の電位(kV)を、ガラスの中央から高さ100mmの位置に固定してある表面電位計(春日電機社製、KSD-0103)にて測定した。測定は、23℃、50%RHの環境下で行った。
なお、「表面保護フィルム剥離時の剥離帯電圧」により、被着体から表面保護フィルムを剥離する際の「帯電防止性(剥離帯電防止性)」を評価した。
得られた離型フィルム付きの表面保護フィルムを25mmの幅に切断し、離型フィルムを剥離して、表面保護フィルムの粘着剤層表面をガラス板(松浪硝子製、青板縁磨品、OF1)に2kgのローラーを用いて貼りあわせ、23℃、相対湿度50%の環境下に20分程度放置し、サンプルとした。
続いて、上記サンプルである表面保護フィルムを0.3m/分の速度で180°の角度でガラス板より引き剥し、表面保護フィルムのガラス板に対する剥離力を測定し、対ガラス粘着力(N/25mm)とした。
〔(メタ)アクリル系ポリマーの調製〕
攪拌羽根、温度計、窒素ガス導入管、冷却器を備えた四つ口フラスコに、2-エチルヘキシルアクリレート(2EHA)100重量部、4-ヒドロキブチルアクリレート(HBA)10重量部、アクリル酸(AA)0.02重量部、重合開始剤として2,2’-アゾビスイソブチロニトリル(AIBN)0.2重量部、酢酸エチル234重量部を仕込み、緩やかに攪拌しながら窒素ガスを導入し、フラスコ内の液温を65℃付近に保って6時間重合反応を行い、(メタ)アクリル系ポリマー溶液(30重量%)を調製した。前記(メタ)アクリル系ポリマーの重量平均分子量(Mw)は65万、ガラス転移温度(Tg)は、-67.6℃であった。
ジシクロペンタニルメタクリレート(DCPMA、メタクリル酸ジシクロペンタニル)60重量部、メチルメタクリレート(MMA、メタクリル酸メチル)40重量部、連鎖移動剤としてのα-チオグリセロール3.5重量部、及び重合溶媒としてのトルエン100重量部を、4つ口フラスコに投入し、これらを窒素雰囲気下にて70℃で1時間撹拌した。
次に、重合開始剤として2,2’-アゾビスイソブチロニトリル0.2重量部を4つ口フラスコに投入し、70℃で2時間反応させ、続いて、80℃で2時間反応させた。その後、反応液を130℃の温度雰囲気下に投入し、トルエン、連鎖移動剤、及び未反応モノマーを乾燥除去し、固形状の(メタ)アクリル系オリゴマーを得た。前記(メタ)アクリル系オリゴマーの重量平均分子量(Mw)は、5100であった。
前記(メタ)アクリル系ポリマー溶液(30重量%)を酢酸エチルで20重量%に希釈し、この溶液500重量部(固形分100重量部)に、帯電防止助剤であるオキシアルキレン鎖を有するオルガノポリシロキサン(信越化学工業社製、商品名:KF-353)0.225重量部、帯電防止剤であるイオン性化合物のリチウムビス(トリフルオロメタンスルホニル)イミド(東京化成工業社製、LiTFSI)0.0675重量部(固形分0.0675重量部)、前記アクリル系オリゴマー1.5重量部、架橋剤として、脂肪族系イソシアネート化合物であるヘキサメチレンジイソシアネートのイソシアヌレート体(東ソー社製、コロネートHX:C/HX)1重量部(固形分1重量部)、及び、架橋触媒として、トリス(アセチルアセトナート)鉄(日本化学産業社製、商品名「ナーセム第二鉄」、有効成分100重量%)0.0075重量部を加えて、混合攪拌を行い、アクリル系粘着剤溶液(粘着剤組成物)を調製した。
バインダとしてのポリエステル樹脂を25%含む分散液(商品名「バイナロールMD-1480」東洋紡株式会社製、(飽和共重合ポリエステル樹脂の水分散液)(バインダ分散液)を用意した。また、滑り剤としてのカルナバワックス(ワックスエステル)の水分散液(滑り剤分散液)を用意した。さらに、導電性ポリマーとしてのポリ(3,4-ジオキシチオフェン)(PEDOT)0.5%およびポリスチレンスルホネート(数平均分子量15万)(PSS)0.8%を含む水溶液(商品名「Baytron P」、H.C.Stark社製品)(導電性ポリマー水溶液)を用意した。
水とエタノールとの混合溶媒に、上記バインダ分散液を固形分量で100部と、上記滑り剤分散液を固形分量で30部と、上記導電性ポリマー水溶液を固形分量で50部と、メラミン系架橋剤とを加え、約20分間攪拌して十分に混合した。このようにして、NV(不揮発分)約0.5%の帯電防止層用水溶液(帯電防止剤組成物)を調製した。
基材フィルムとして、厚さ50μm、幅30cm、長さ40cmの透明なポリエチレンテレフタレート(PET)フィルム(三菱ケミカル社製、商品名:T100C50)を用意した。このPETフィルムに上記帯電防止層用水溶液をバーコーターで塗付し、130℃に2分間加熱して乾燥させ、続いて基材フィルムのもう一方の面にも同様に、上記帯電防止層用水溶液をバーコーターで塗付し、130℃に2分間加熱して乾燥させ、基材フィルムの両面に厚さ30nmの帯電防止層を有する帯電防止層(両面)付き基材フィルムを作製した。
冷却器を備えた反応容器にキシレン(太陽化学製、キシロール)を200重量部、オクタデシルイソシアネート(大原パラヂウム化学株式会社製、R-NCO)を600重量部入れ、撹拌しながら加熱しキシレンが還流し始めた点から、ポリビニルアルコール(クラレ製、クラレポバール205)100重量部を少量ずつ、10分間隔で2時間にわたって添加した。
ポリビニルアルコールを添加し終えた後、さらに2時間還流を行い、反応を完了させた。得られた反応混合物を約80℃まで冷却した後、メタノール中に加えたところ、反応生成物が白色沈殿として析出したので、この沈殿を濾別し、キシレン140重量部を加え、加熱して完全に溶解させた後、再びメタノールを加えて沈殿させるという操作を数回繰り返した後、沈殿物をメタノールで洗浄し、乾燥粉砕して得た粉末を水で0.3重量%に希釈し、離型剤組成物(溶液)を得た。この離型剤組成物を、基材である厚み25μmのPETフィルム(三菱ケミカル製、ダイアホイルT100C25)に塗布し、130℃で1分間乾燥させ、離型層を形成し、シリコーン成分不使用の離型フィルムを作製した。なお、乾燥後の離型層の厚みは20nmであり、X線光電子分光法による測定により、離型フィルムの離型処理面のケイ素原子(Si)の元素比率(atomic%)は検出下限を下回り(未満であり)、検出できず、離型処理面がシリコーン成分を(実質的に)含まないことを確認した。
前記アクリル系粘着剤溶液を、前記帯電防止層(両面)付き基材フィルムの帯電防止層が基材フィルムと接触している一方の面に塗布し、130℃で30秒間加熱して、厚さ20μmの粘着剤層を形成した。次いで、前記粘着剤層の表面に、前記シリコーン成分不使用の離型フィルムの離型層を有する面(離型層側)を貼り合わせ、表面保護フィルムを作製した(図2参照)。
表1及び表2の記載に基づき、粘着剤層、(帯電防止層付き)基材フィルム、及び、離型フィルムに基づきを調製した。なお、調製条件等については、実施例1と同様にして、最終的に表面保護フィルムを作製した。また、実施例1と異なる基材フィルムや離型フィルムについては、以下に記載のものを使用した。
実施例3においては、基材フィルムとして、厚さ38μm、幅30cm、長さ40cmの透明なポリエチレンテレフタレート(PET)フィルム(三菱ケミカル社製、商品名:T100C38)を用意した。このPETフィルムに上記帯電防止層用水溶液をバーコーターで塗付し、130℃に2分間加熱して乾燥させることで、乾燥後の厚みが10nmとなるように帯電防止層を有する帯電防止層(片面)付き基材フィルムを作製した(図1参照)。
比較例4においては、基材フィルムとして、厚さ38μm、幅30cm、長さ40cmの透明なポリエチレンテレフタレート(PET)フィルム(三菱ケミカル社製、商品名:T100C38)を用意した。このPETフィルムを帯電防止層なしの基材フィルムとして使用した。
比較例1及び2においては、シリコーン離型剤(信越化学工業社製、商品名:KS-847H)を100重量部、シリコーン硬化触媒(信越化学工業社製、商品名:CAT-PL-50T)を3.3重量部入れ、トルエン(出光石油化学社製)、ヘキサン(丸善石油化学社製、ノルマルヘキサン)、メチルエチルケトン(出光興産社製、MEK)が1:2:1の重量比でなる混合溶剤で0.3重量%に希釈し、離型剤組成物(溶液)を得た。この離型剤組成物を、基材である厚み25μmのPETフィルム(三菱樹脂社製、ダイアホイルT100-25)に塗布し、130℃で1分間乾燥させ、シリコーン系離型層を有する離型フィルムを作製した。なお、離型層の乾燥後の厚みは20nmであった。
1’:帯電防止層
2 :基材フィルム
3 :粘着剤層
4 :離型フィルム
10:表面保護フィルム
Claims (4)
- 樹脂材料からなる基材フィルムと、
前記基材フィルムの片面に、ベースポリマーとしての(メタ)アクリル系ポリマーと、帯電防止成分としてのイオン性化合物と、を含有する粘着剤組成物より形成される粘着剤層と、
前記基材フィルムの前記粘着剤層を有する面とは反対面に、帯電防止成分を含む帯電防止層と、
前記粘着剤層の前記基材フィルムを有する面とは反対面に、離型フィルムと、が設けられ、
前記離型フィルムの離型処理面が、シリコーン成分を含まないことを特徴とする表面保護フィルム。 - 前記基材フィルムと前記粘着剤層との間に、更に、帯電防止成分を含む帯電防止層を有することを特徴とする請求項1に記載の表面保護フィルム。
- 請求項1又は2に記載の表面保護フィルムにより保護されることを特徴とする光学部材。
- 請求項1又は2に記載の表面保護フィルムにより保護されることを特徴とする表示装置。
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- 2019-03-28 WO PCT/JP2019/013615 patent/WO2019194069A1/ja active Application Filing
- 2019-03-28 JP JP2020512202A patent/JPWO2019194069A1/ja active Pending
- 2019-03-28 CN CN201980022754.8A patent/CN111918942A/zh active Pending
- 2019-04-01 TW TW108111485A patent/TW201942285A/zh unknown
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2014024993A (ja) * | 2012-07-27 | 2014-02-06 | Nitto Denko Corp | 粘着シート |
JP2016132211A (ja) * | 2015-01-21 | 2016-07-25 | ユニチカ株式会社 | 離型フィルム |
JP2016145341A (ja) * | 2015-01-30 | 2016-08-12 | 日東電工株式会社 | セパレータ付き光学用表面保護フィルム |
JP2017031278A (ja) * | 2015-07-30 | 2017-02-09 | 日東電工株式会社 | セパレータ付き光学用表面保護フィルム |
JP2017170660A (ja) * | 2016-03-19 | 2017-09-28 | 三菱ケミカル株式会社 | 積層フィルム |
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CN111918942A (zh) | 2020-11-10 |
TW201942285A (zh) | 2019-11-01 |
KR20200138316A (ko) | 2020-12-09 |
JPWO2019194069A1 (ja) | 2021-04-15 |
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