WO2015159738A1 - Feuille adhésive, et élément optique - Google Patents

Feuille adhésive, et élément optique Download PDF

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Publication number
WO2015159738A1
WO2015159738A1 PCT/JP2015/060625 JP2015060625W WO2015159738A1 WO 2015159738 A1 WO2015159738 A1 WO 2015159738A1 JP 2015060625 W JP2015060625 W JP 2015060625W WO 2015159738 A1 WO2015159738 A1 WO 2015159738A1
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WO
WIPO (PCT)
Prior art keywords
pressure
sensitive adhesive
meth
acid
adhesive sheet
Prior art date
Application number
PCT/JP2015/060625
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English (en)
Japanese (ja)
Inventor
賢一 片岡
天野　立巳
Original Assignee
日東電工株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日東電工株式会社 filed Critical 日東電工株式会社
Priority to KR1020167031650A priority Critical patent/KR102290158B1/ko
Priority to CN201580019596.2A priority patent/CN106255733B/zh
Publication of WO2015159738A1 publication Critical patent/WO2015159738A1/fr

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Classifications

    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • 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
    • 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
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • 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
    • C09J201/00—Adhesives based on unspecified macromolecular compounds
    • 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 an adhesive sheet and an optical member protected by the adhesive sheet.
  • the pressure-sensitive adhesive sheet of the present invention is a surface protective film used for the purpose of protecting the surface of an optical member such as a polarizing plate, a wave plate, a phase difference plate, an optical compensation film, a reflection sheet, and a brightness enhancement film used for a liquid crystal display, etc. Useful.
  • optical parts and electronic parts are transported or mounted on a printed circuit board, they are transferred in a state where individual parts are packaged with a predetermined sheet or with an adhesive tape attached.
  • surface protective films are particularly widely used in the field of optical and electronic components.
  • the surface protective film is generally used for the purpose of preventing scratches and dirt generated during the processing and transportation of the adherend by attaching it to the adherend (protected body) via an adhesive applied to the support film side.
  • Patent Document 1 a panel of a liquid crystal display is formed by bonding an optical member such as a polarizing plate or a wave plate to a liquid crystal cell via an adhesive.
  • the surface protection film is bonded together through the adhesive, and the damage
  • the adherend when the adherend is processed with the surface protective film bonded, a high-temperature treatment may be performed.
  • the adhesive strength of the adhesive layer may greatly increase, and then
  • the surface protective film is no longer needed, when the film is peeled off and removed, the polarized light that is the adherend in the peeling process is accompanied by an increase in the size and thickness of the liquid crystal display panel that is the adherend. Since damage to the plate and the liquid crystal cell is likely to occur, light peeling is required when peeling at high speed after high-temperature treatment.
  • the object of the present invention is to prevent an increase in the adhesive strength at high temperatures with the lapse of time in order to eliminate the problems in the conventional adhesive sheet (adhesive strength increase prevention property, adhesive strength stability), and adhesive strength during high-speed peeling. Is to provide a pressure-sensitive adhesive sheet excellent in removability and workability and excellent in shearing force.
  • the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition on one or both sides of a support film, and the pressure-sensitive adhesive layer has a pressure-sensitive adhesive surface on the TAC surface at 23 ° C. for 30 minutes.
  • Adhesive strength (A) at a peeling speed of 30 m / min after sticking and Adhesive strength (B) at a peeling speed of 30 m / min after sticking the adhesive face of the pressure-sensitive adhesive layer to the TAC face at 70 ° C. for 1 week.
  • the adhesive force ratio (B / A) is less than 2.
  • the pressure-sensitive adhesive composition preferably contains a (meth) acrylic polymer having a hydroxyl group and a carboxyl group.
  • the pressure-sensitive adhesive composition contains a crosslinking agent, and the crosslinking agent contains an aromatic isocyanate compound and an aliphatic isocyanate compound.
  • the pressure-sensitive adhesive sheet of the present invention preferably contains 5.1% by mass or more of a hydroxyl group-containing (meth) acrylic monomer with respect to the total amount of monomer components constituting the (meth) acrylic polymer.
  • the pressure-sensitive adhesive sheet of the present invention contains 0.01% by mass or more and less than 0.5% by mass of a carboxyl group-containing (meth) acrylic monomer with respect to the total amount of monomer components constituting the (meth) acrylic polymer. Is preferred.
  • the pressure-sensitive adhesive sheet of the present invention has an antistatic layer on one side of the support film opposite to the pressure-sensitive adhesive layer, and the antistatic layer comprises polyaniline sulfonic acid as a conductive polymer component, a polyester resin as a binder, and It is preferably formed from an antistatic composition containing an isocyanate-based crosslinking agent as a crosslinking agent.
  • the antistatic agent composition preferably further contains a fatty acid amide as a lubricant.
  • the optical member of the present invention is preferably protected by the pressure-sensitive adhesive sheet.
  • the pressure-sensitive adhesive sheet of the present invention can prevent an increase in pressure-sensitive adhesive strength at high temperatures (adhesive strength increase prevention property, pressure-sensitive adhesive strength), has low pressure-sensitive adhesive strength during high-speed peeling, and has excellent removability and workability. Furthermore, since it is excellent in shearing force, unnecessary curling and unintended curling can be suppressed on the adherend when it is bonded to the adherend, which is useful.
  • the pressure-sensitive adhesive sheet (surface protective film) of the present invention is generally in the form of a pressure-sensitive adhesive sheet, pressure-sensitive adhesive tape, pressure-sensitive adhesive label, pressure-sensitive adhesive film, etc., and particularly optical components (for example, liquid crystals such as polarizing plates and wave plates). It is suitable as a surface protective film for protecting the surface of the optical component during processing or transport of the optical component used as a display panel component.
  • the pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet is typically formed continuously, but is not limited to such a form, for example, a pressure-sensitive adhesive formed in a regular or random pattern such as a spot or stripe. It may be an agent layer. Further, the pressure-sensitive adhesive sheet disclosed herein may be in the form of a roll or a single sheet.
  • Typical examples of the pressure-sensitive adhesive sheet (surface protective film) disclosed herein include those having a pressure-sensitive adhesive layer on one side or both sides of the support film (base material), or antistatic provided on one side of the support film. And a layer having a pressure-sensitive adhesive layer provided on the surface of the base support film opposite to the antistatic layer.
  • the pressure-sensitive adhesive sheet is used by attaching this pressure-sensitive adhesive layer to an adherend (the surface of an optical component such as a polarizing plate).
  • the pressure-sensitive adhesive sheet before use (that is, before sticking to the adherend) is protected by a release liner whose surface (sticking surface to the adherend) is at least the pressure-sensitive adhesive layer side.
  • the form may be sufficient. Or the form by which the adhesive layer contact
  • the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition on one side or both sides of a support film.
  • the resin material constituting the support film can be used without any particular limitation. For example, transparency, mechanical strength, thermal stability, moisture shielding properties, isotropic properties, flexibility, dimensional stability, etc. It is preferable to use one having excellent characteristics.
  • the pressure-sensitive adhesive composition can be applied by a roll coater or the like, and can be wound into a roll, which is useful.
  • the support 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; A plastic film composed of a resin material having an acrylic polymer such as methyl methacrylate as a main resin component (a main component of the resin component, typically a component occupying 50% by mass or more) is used as the support film. It can be preferably used.
  • polyester polymers such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), and polybutylene terephthalate
  • cellulose polymers such as diacetyl cellulose and triacetyl cellulose
  • polycarbonate polymers A plastic film composed of a resin material having an acrylic polymer such as methyl methacrylate as a main resin component (a main component of the resin component, typically a component occupying 50% by mass or more) is used
  • 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 support film made of a blend of two or more of the above-described polymers may be used.
  • the support 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 is one having a polymer material (polyester resin) having a main skeleton based on an ester bond such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or 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 support film for the pressure-sensitive adhesive sheet, such as excellent optical characteristics and dimensional stability, and has the property of being easily charged as it is.
  • various additives such as an antioxidant, an ultraviolet absorber, a plasticizer, and a colorant (pigment, dye, etc.) may be blended as necessary.
  • corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and application of a primer are applied to the first surface of the support film (the surface on which the antistatic layer is provided).
  • the surface treatment may be performed.
  • Such a surface treatment can be, for example, a treatment for enhancing the adhesion between the support film and the antistatic layer.
  • Surface treatment in which polar groups such as hydroxyl groups (—OH groups) are introduced on the surface of the support film can be preferably employed.
  • the surface treatment similar to the above may be given to the 2nd surface (surface on the side in which an adhesive layer is formed) of a support film.
  • Such a surface treatment may be a treatment for enhancing the adhesion between the film and the pressure-sensitive adhesive layer (the anchoring property of the pressure-sensitive adhesive layer).
  • the pressure-sensitive adhesive sheet of the present invention can have an antistatic layer on the support film, but when it has an antistatic function, a plastic film that has been subjected to antistatic treatment is used as the support film. It is also possible to do. Use of the support film is preferable because charging of the pressure-sensitive adhesive sheet itself when peeled can be suppressed. Further, the support film is a plastic film, and by applying an antistatic treatment to the plastic film, it is possible to reduce the charge of the pressure-sensitive adhesive sheet itself and to have an excellent antistatic ability to the adherend.
  • antistatic resin which consists of an antistatic agent and a resin component, a conductive polymer, and a conductive substance.
  • examples thereof include a method of applying a conductive resin, a method of depositing or plating a conductive material, a method of kneading an antistatic agent, and the like.
  • the thickness of the support film is usually about 5 to 200 ⁇ m, preferably about 10 to 100 ⁇ m. When the thickness of the support 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 pressure-sensitive adhesive sheet (surface protective film) of the present invention has the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition, and the pressure-sensitive adhesive composition has adhesiveness.
  • the pressure-sensitive adhesive composition used in the present invention preferably contains a (meth) acrylic polymer having a hydroxyl group and a carboxyl group.
  • a (meth) acrylic polymer having the hydroxyl group and the carboxyl group By using the (meth) acrylic polymer having the hydroxyl group and the carboxyl group, the hydroxyl group can easily control the crosslinking, and the carboxyl group improves the shearing force, Since an increase in adhesive strength over time can be prevented, this is a preferred embodiment.
  • the shearing force of the adhesive (layer) curling based on the adherend can be suppressed by adhering the adhesive to the adherend, and between the adhesive and the adherend (interface) ) Is preferable because the occurrence of slippage and deviation in the above can be suppressed.
  • the (meth) acrylic polymer refers to an acrylic polymer and / or a methacrylic polymer
  • the (meth) acrylate refers to acrylate and / or meth
  • the (meth) acrylic polymer uses the hydroxyl group-containing (meth) acrylic monomer as a monomer component, it becomes easy to control the crosslinking of the pressure-sensitive adhesive composition, and thus improves the wettability by flow. And the cohesive force of the pressure-sensitive adhesive (layer), the reduction of the pressure-sensitive adhesive force at the time of peeling (light peelability), and the balance with the shearing force are easily controlled. Furthermore, when an antistatic agent is added to the pressure-sensitive adhesive, the hydroxyl group has an appropriate interaction with an ionic compound that is an antistatic agent, unlike a carboxyl group or a sulfonate group that can generally act as a crosslinking site. Therefore, it can be suitably used also in terms of antistatic properties.
  • the pressure-sensitive adhesive sheet of the present invention preferably contains 5.1% by mass or more of a hydroxyl group-containing (meth) acrylic monomer with respect to the total amount of monomer components constituting the (meth) acrylic polymer, more preferably The content is 5.3 to 15% by mass, more preferably 7 to 12% by mass. Within the above range, the balance between the wettability of the pressure-sensitive adhesive composition and the cohesive force and shear force of the pressure-sensitive adhesive (layer) can be easily controlled, which is preferable.
  • hydroxyl group-containing (meth) acrylic monomer examples 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 and the like.
  • the pressure-sensitive adhesive sheet of the present invention contains 0.01% by mass or more and less than 0.5% by mass of a carboxyl group-containing (meth) acrylic monomer with respect to the total amount of monomer components constituting the (meth) acrylic polymer. More preferably, it is 0.01 or more and less than 0.4 mass%, More preferably, it is 0.01 or more and less than 0.3 mass%, Most preferably, it is 0.01 or more and less than 0.2 mass%. Within the above range, an increase in adhesive force over time can be suppressed, and the removability, the adhesive force increase preventing property, and the workability are excellent. In addition to the cohesive force of the pressure-sensitive adhesive layer, it is excellent in shearing force and is preferable.
  • an acid functional group such as a carboxyl group having a large polar action
  • an acid functional group such as a carboxyl group interacts with the ionic compound when an ionic compound is blended as an antistatic agent. As a result, ion conduction is hindered, conductivity efficiency is lowered, and sufficient antistatic properties may not be obtained.
  • Examples of the carboxyl group-containing (meth) acrylic monomer include (meth) acrylic acid, carboxylethyl (meth) acrylate, carboxylpentyl (meth) acrylate, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, 2 -(Meth) acryloyloxypropyl hexahydrophthalic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl maleic acid, carboxy Examples include polycaprolactone mono (meth) acrylate and 2- (meth) acryloyloxyethyl tetrahydrophthalic acid.
  • the pressure-sensitive adhesive composition used in the present invention is not particularly limited as long as it contains the (meth) acrylic polymer and has a tacky (meth) acrylic polymer, but as a main component of the monomer component, A (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms is preferably used, and more preferably a (meth) acrylic monomer having an alkyl group having 4 to 14 carbon atoms.
  • a (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms is preferably used, and more preferably a (meth) acrylic monomer having an alkyl group having 4 to 14 carbon atoms.
  • As said (meth) acrylic-type monomer 1 type (s) or 2 or more types can be used as a main component.
  • the “main component” means that the blending ratio is the highest.
  • 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 pressure-sensitive adhesive sheet of the present invention when used as a surface protective film, 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 (meth) acrylate, n-tetradecyl (meth) acrylate, etc.
  • Suitable examples include (meth) acrylates having an alkyl group having 6 to 14 carbon atoms.
  • a (meth) acrylate 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 it has excellent removability.
  • the pressure-sensitive adhesive sheet of the present invention comprises 50 to 94.99 masses of the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms based on the total amount of monomer components constituting the (meth) acrylic polymer. %, More preferably 60 to 94.9% by mass, still more preferably 70 to 94.8% by mass, and most preferably 80 to 94.7% by mass.
  • an adhesive composition has moderate wettability and is excellent also in the cohesion force of an adhesive (layer), and is preferable.
  • the glass transition temperature and release 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.
  • the other polymerizable monomer can be used without particular limitation as long as it does 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 that functions as an adhesive (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.
  • Examples of the amide group-containing monomer include acrylamide, methacrylamide, diethylacrylamide, N-vinylpyrrolidone, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, and N, N-diethyl.
  • Examples include methacrylamide, 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, isobutyl vinyl ether, and the like.
  • other polymerizable monomers other than the carboxyl group-containing (meth) acrylic monomer, the hydroxyl group-containing (meth) acrylic monomer, and the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms Is preferably 0 to 40% by mass, more preferably 0 to 30% by mass, based on the total amount of monomer components (total monomer components) constituting the (meth) acrylic polymer.
  • the (meth) acrylic polymer has a weight average molecular weight of 100,000 to 5,000,000, preferably 200,000 to 4,000,000, more preferably 300,000 to 3,000,000.
  • weight average molecular weight is smaller than 100,000, there is a tendency for adhesive residue to occur due to the reduced cohesive force of the resulting pressure-sensitive adhesive (layer).
  • the weight average molecular weight exceeds 5,000,000, the fluidity of the polymer is lowered and the adherend (for example, a polarizing plate as an optical member) is insufficiently wetted. There is a tendency to cause blisters generated between the agent composition layer.
  • a weight average molecular weight means what was obtained by measuring by GPC (gel permeation chromatography).
  • the glass transition temperature (Tg) of the (meth) acrylic polymer is preferably 0 ° C. or lower, more preferably ⁇ 10 ° C. or lower, and further preferably ⁇ 20 ° C. or lower (usually ⁇ 100 ° C. or higher). .
  • the glass transition temperature is higher than 0 ° C., the polymer is difficult to flow, for example, the wettability to the adherend (for example, a polarizing plate as an optical member) is insufficient, and the adhesive composition of the adherend and the adhesive sheet There is a tendency to cause blisters generated between the material layers.
  • the glass transition temperature is ⁇ 61 ° C. or lower, an adhesive composition excellent in wettability to the adherend and light peelability can be easily obtained.
  • the glass transition temperature of a (meth) acrylic-type polymer can be adjusted in the said range by changing the monomer component and composition ratio to be used suitably.
  • the polymerization method of the (meth) acrylic polymer used in the present invention is not particularly limited and can be polymerized by known methods such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, etc. In view of characteristics such as low contamination to the adherend and solution, solution polymerization is a more preferable embodiment. Further, the polymer obtained may be any of a random copolymer, a block copolymer, an alternating copolymer, a graft copolymer, and the like.
  • the pressure-sensitive adhesive composition can contain an antistatic agent (antistatic component), and the antistatic agent can contain an ionic compound.
  • antistatic component antistatic component
  • the ionic compound include alkali metal salts and / or ionic compounds having a low melting point (melting point of 150 ° C. or lower). By containing these ionic compounds, excellent antistatic properties can be imparted.
  • the content of the ionic compound is preferably 1 part by mass or less, more preferably 0.001 to 0.9 part by mass, and more preferably 0.001 part by mass with respect to 100 parts by mass of the (meth) acrylic polymer. 005 to 0.8 part by mass. It is preferable for it to be in the above-mentioned range since it is easy to achieve both antistatic properties and low contamination.
  • the pressure-sensitive adhesive composition may contain an organopolysiloxane having a polyoxyalkylene chain.
  • organopolysiloxane a known organopolysiloxane having a polyoxyalkylene chain can be appropriately used.
  • trade names are X-22-4952, X-22-4272, X-22-6266, KF-6004, KF-889, KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-640, KF-642, KF-643, KF- 6022, X-22-6191, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6017, X-22-2516 (manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-201, SF8427 , SF8428, FZ-2162, SH3749, FZ-77, L-7001, FZ-2104, F -2110, L-7002, FZ-2122, FZ
  • the above-mentioned organopolysiloxane 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 mass, more preferably 0.03 to 3 parts by mass, and still more preferably 100 parts by mass of the (meth) acrylic polymer. Is 0.05 to 1 part by mass. 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 preferably contains a crosslinking agent, and the crosslinking agent is an aromatic isocyanate compound, and an aliphatic isocyanate compound (both isocyanate compounds are combined, It may be referred to as an isocyanate compound or an isocyanate crosslinking agent).
  • the cross-linking agent is a pressure-sensitive adhesive sheet having more excellent heat resistance by appropriately adjusting the selection and addition ratio of the cross-linking agent according to the structural unit and the structural ratio of the (meth) acrylic polymer. Pressure-sensitive adhesive layer) can be obtained.
  • the crosslinking agent contains an aromatic isocyanate compound and an aliphatic isocyanate compound, it is useful because it can prevent an increase in adhesive strength with time (preventing an increase in adhesive strength).
  • crosslinking agent used for this invention an epoxy compound, a melamine resin, an aziridine derivative, a metal chelate compound, etc. are used suitably other than the said aromatic isocyanate type compound and an aliphatic isocyanate type compound. Can do.
  • these crosslinking agents may be used individually by 1 type, and may mix and use 2 or more types.
  • aliphatic isocyanate compounds include aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), and dimer acid diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, and isophorone diisocyanate (IPDI). And alicyclic isocyanates.
  • aromatic isocyanate compound include aromatic isocyanates such as 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate (XDI).
  • modified polyisocyanates obtained by modifying the above isocyanate compounds (isocyanate-based crosslinking agents) with allophanate bonds, biuret bonds, isocyanurate bonds, uretdione bonds, urea bonds, carbodiimide bonds, uretonimine bonds, oxadiazine trione bonds, etc. .
  • isocyanate crosslinking agent for example, as a commercial product of the isocyanate compound (isocyanate crosslinking agent), trade names Takenate 300S, Takenate 500, Takenate D110N, Takenate D140N, Takenate D165N, Takenate D178N (above, Mitsui Chemicals), Sumidur T80, Sumi Joule L, Death Module N3400 (manufactured by Sumika Bayer Urethane Co., Ltd.), Millionate MR, Millionate MT, Coronate L, Coronate HL, Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) and the like.
  • isocyanate crosslinking agent trade names Takenate 300S, Takenate 500, Takenate D110N, Takenate D140N, Takenate D165N, Takenate D178N (above, Mitsui Chemicals), Sumidur T80, Sumi Joule L, Death Module N3400 (
  • isocyanate compounds may be used as a mixture of two or more kinds, and a bifunctional isocyanate compound and a trifunctional or higher isocyanate compound may be used in combination.
  • a cross-linking agent By using a cross-linking agent in combination, it is possible to prevent the pressure-sensitive adhesive force from increasing with time or to obtain a pressure-sensitive adhesive sheet excellent in shearing force.
  • 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 commercially available product names HDU, TAZM, TAZO (manufactured by Mutual Yakugyo 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 (total) of the crosslinking agent used in the present invention is preferably 0.01 to 10 parts by mass, and 0.1 to 8 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer. It is more preferably contained, more preferably 0.5 to 5 parts by mass, and most preferably 1.0 to 4 parts by mass.
  • the content is less than 0.01 parts by mass, the crosslinking formation by the crosslinking agent becomes insufficient, the cohesive force of the pressure-sensitive adhesive composition becomes small, and sufficient heat resistance may not be obtained. There is a tendency to cause the rest.
  • the mixing ratio of the aromatic isocyanate compound and the aliphatic isocyanate compound is not particularly limited.
  • (aromatic isocyanate compound / aliphatic isocyanate compound) (mass ratio) is 3 / 1 to 1/50 is preferable, 2/1 to 1/40 is more preferable, and 1/1 to 1/30 is still more preferable.
  • the blending ratio is useful because it can prevent an increase in adhesive strength over time.
  • the pressure-sensitive adhesive composition may further contain a crosslinking catalyst in order to make any of the above-described crosslinking reactions proceed more effectively.
  • cross-linking catalysts include tin-based catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, 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-2,4-dionato) iron, tris (nonane-4,6-dionato) iron, tris ( 2,2,6,6-tetramethylheptane-3,5-dionato) iron, tris (tridecan-6,8-dionato) iron, tris (1-phenylbutane-1, -Dionato) iron, tris (hexafluoroacetylacetonato) iron, tris (ethyl acetoacetate) iron, tris (acetoacetate-n-propyl) iron, tris (isopropy
  • the content (amount of use) of the crosslinking catalyst is not particularly limited, but is preferably about 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 mass is more preferable.
  • the speed of the crosslinking reaction is high, and the pot life of the pressure-sensitive adhesive composition becomes long, which is a preferred embodiment.
  • the pressure-sensitive adhesive composition of the present invention may contain a polyoxyalkylene chain-containing compound that does not contain organopolysiloxane.
  • a polyoxyalkylene chain-containing compound 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) ), Polyester compounds having a polyoxyalkylene chain (and derivatives thereof), acrylic compounds having a polyoxyalkylene chain (and derivatives thereof), and the like. Moreover, you may mix
  • polyether compound having a polyoxyalkylene chain examples include block copolymers of polypropylene glycol (PPG) -polyethylene glycol (PEG), block copolymers of PPG-PEG-PPG, and 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 Examples of such compounds include terminal acetylated PPG and the like.
  • the acrylic compound having a polyoxyalkylene chain include a (meth) acrylate polymer having an oxyalkylene group.
  • the added mole number of oxyalkylene units is preferably 1 to 50, more preferably 2 to 30, and further preferably 2 to 20 from the viewpoint of coordination of the ionic compound.
  • the terminal of the oxyalkylene group 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 ethylene glycol group-containing (meth) acrylates, such as methoxy-polyethylene glycol (meth) acrylate type such as methoxy-diethylene glycol (meth) acrylate, methoxy-triethylene glycol (meth) acrylate, ethoxy-diethylene glycol Ethoxy-polyethylene glycol (meth) acrylate type such as (meth) acrylate, ethoxy-triethylene glycol (meth) acrylate, butoxy-diethylene glycol (meth) acrylate Butoxy-polyethylene glycol (meth) acrylate type such as butoxy-triethylene glycol (meth) acrylate, phenoxy-polyethylene glycol (meth) acryl
  • the monomer unit (component) other monomer units (components) other than the (meth) acrylic acid alkylene oxide can be used.
  • specific examples of other monomer units 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 a (poly) ethylene oxide chain at least partially.
  • 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. can get.
  • an adhesive composition excellent in low contamination can be obtained.
  • the mass of the (poly) ethylene oxide chain in the entire compound is preferably 5 to 90% by mass, more preferably 5 to 85% by mass, and still more preferably 5 to 80% by mass. Most preferably, it is 5 to 75% by mass.
  • the molecular weight of the polyoxyalkylene chain-containing compound not containing the organopolysiloxane is preferably a number average molecular weight (Mn) of 50,000 or less, more preferably 200 to 30,000, still more preferably 200 to 10,000, and more preferably 200 to 5,000. Those are particularly preferably used. When Mn is larger than 50000, the compatibility with the acrylic polymer is lowered and the pressure-sensitive adhesive layer tends to be whitened. If Mn is less than 200, contamination with the polyoxyalkylene compound may easily occur. In addition, Mn means the value of polystyrene conversion obtained by GPC (gel permeation chromatography) here.
  • the compounding amount of the polyoxyalkylene chain-containing compound not containing the organopolysiloxane can be, for example, 0.005 to 20 parts by mass, preferably 0 with respect to 100 parts by mass of the (meth) acrylic polymer. 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and most preferably 0.1 to 1 part by mass. If the blending amount is too small, the effect of preventing bleeding of the antistatic component is reduced, and if it is too much, contamination by the polyoxyalkylene compound may easily occur.
  • the pressure-sensitive adhesive composition may contain an acrylic oligomer.
  • the acrylic oligomer preferably has a weight average molecular weight of 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.
  • it functions as a tackifier resin, improves adhesion (adhesion) properties, and is effective in suppressing the lifting of the pressure-sensitive adhesive sheet.
  • a (meth) acrylic acid ester monomer can be used.
  • the acrylic oligomer may be a (meth) acrylic monomer having an alicyclic structure, such as dicyclopentanyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyloxyethyl methacrylate, dicyclopentanyl.
  • Such (meth) acrylic monomers can be used alone or in combination of two or more.
  • the acrylic oligomer may be obtained by copolymerizing another monomer component (copolymerizable monomer) copolymerizable with the (meth) acrylic monomer. Is possible.
  • the weight average molecular weight of the acrylic oligomer is 1000 or more and less than 30000, preferably 1500 or more and less than 20000, and more preferably 2000 or more and less than 10,000.
  • the weight average molecular weight is 30000 or more, the adhesion (adhesion) property is lowered.
  • the weight average molecular weight is less than 1000, the molecular weight becomes low, which causes a decrease in the adhesive strength of the adhesive sheet.
  • the pressure-sensitive adhesive composition may contain a compound that causes keto-enol tautomerism as a crosslinking retarder.
  • a compound that causes keto-enol tautomerism can be preferably employed in a pressure-sensitive adhesive composition containing a cross-linking agent or a pressure-sensitive adhesive composition that can be used by blending a cross-linking agent.
  • an embodiment including a compound that causes the keto-enol tautomerism can be preferably employed.
  • blending can be suppressed, and the effect of extending the pot life of an adhesive composition may be implement
  • the crosslinking agent When at least an isocyanate compound is used as the crosslinking agent, it is particularly meaningful to contain a compound that causes keto-enol tautomerism. This technique can be preferably applied when, for example, the pressure-sensitive adhesive composition is in an organic solvent solution or a solvent-free form.
  • various ⁇ -dicarbonyl compounds can be used. Specific examples include acetylacetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, 6-methylheptane-2,4-dione, 2,6-dimethylheptane- ⁇ -diketones such as 3,5-dione; acetoacetates such as methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, tert-butyl acetoacetate; ethyl propionyl acetate, ethyl propionyl acetate, isopropyl propionyl acetate, propionyl acetate propionyl acetates such as tert-butyl; isobutyryl acetates such as ethyl isobutyryl acetates such as ethyl isobutyryl acetate
  • the content of the compound that causes keto-enol tautomerism can be, for example, 0.1 to 20 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer, and usually 0.5 to 15 parts by mass. It is appropriate to set it to parts by mass (for example, 1 to 10 parts by mass). If the amount of the compound is too small, it may be difficult to achieve a sufficient use effect. On the other hand, if the compound is used more than necessary, it may remain in the pressure-sensitive adhesive layer and reduce the cohesive force.
  • the pressure-sensitive adhesive composition used for the pressure-sensitive adhesive sheet of the present invention may contain other known additives, such as powders such as colorants and pigments, surfactants, plasticizers, and pressure-sensitive adhesives.
  • the pressure-sensitive adhesive sheet of the present invention is characterized in that it has a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition (formed by crosslinking the pressure-sensitive adhesive composition) on one side or both sides of the support film.
  • the crosslinking of the pressure-sensitive adhesive composition is generally performed after application of the pressure-sensitive adhesive composition, but it is also possible to transfer a pressure-sensitive adhesive layer comprising the pressure-sensitive adhesive composition after crosslinking to a support film or the like.
  • the method for forming the pressure-sensitive adhesive layer on the support film is not particularly limited. For example, the pressure-sensitive adhesive composition is applied to the support film, and the polymerization solvent is dried and removed to form the pressure-sensitive adhesive layer on the support film. It is produced by forming.
  • curing may be performed for the purpose of adjusting the component transfer of the pressure-sensitive adhesive layer or adjusting the crosslinking reaction.
  • one or more solvents other than the polymerization solvent are newly added to the pressure-sensitive adhesive composition so that the pressure-sensitive adhesive composition can be uniformly applied on the support film. You may add to.
  • a known method used for the production of pressure-sensitive adhesive sheets 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 pressure-sensitive adhesive sheet of the present invention is usually prepared so that the thickness of the pressure-sensitive adhesive layer is preferably 3 to 100 ⁇ m, more preferably about 5 to 50 ⁇ m. It is preferable for the thickness of the pressure-sensitive adhesive layer to be within the above-mentioned range, since it is easy to obtain a suitable balance between removability and adhesion (adhesion).
  • a separator can be bonded to the surface of the pressure-sensitive adhesive layer for the purpose of protecting the pressure-sensitive adhesive surface as necessary.
  • the material constituting the separator includes paper and plastic film, but 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.
  • polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer examples thereof include a coalesced film, a polyethylene terephthalate film, a polybutylene terephthalate film, a polyurethane film, and an ethylene-vinyl acetate copolymer film.
  • the thickness of the separator 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.
  • mold release and antifouling treatment with a silicone type, fluorine type, long chain alkyl type or fatty acid amide type release agent, silica powder, etc., coating type, kneading type, vapor deposition type It is also possible to carry out antistatic treatment such as.
  • the pressure-sensitive adhesive sheet of the present invention is a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed from a pressure-sensitive adhesive composition on one or both sides of a support film, and the pressure-sensitive adhesive layer is attached to the TAC surface at 23 ° C. for 30 minutes.
  • the ratio (B / A) is less than 2, preferably 0.5 to 1.9, and more preferably 0.7 to 1.8.
  • the adhesive strength (A) at a peeling speed of 30 m / min after pasting the adhesive surface of the pressure-sensitive adhesive layer to the TAC surface at 23 ° C. for 30 minutes is preferably 2.0 N / 25 mm or less, more preferably 0. 1 to 1.9 N / 25 mm, more preferably 0.1 to 1.8 N / 25 mm. If the adhesive strength (A) exceeds 2.0 N / 25 mm, the adhesive sheet (surface protective film) is difficult to peel off from the adherend, and the workability of peeling when the adhesive sheet is no longer necessary, This is not preferable because the adherend is damaged by the peeling process.
  • the adhesive strength (B) at a peeling speed of 30 m / min after pasting the adhesive surface of the pressure-sensitive adhesive layer to the TAC surface at 70 ° C. for 1 week is preferably less than 4.0 N / 25 mm, more preferably 0.1 to 3.5 N / 25 mm, more preferably 0.1 to 3.0 N / 25 mm.
  • the pressure-sensitive adhesive force (B) is 4.0 N / 25 mm or more, the pressure-sensitive adhesive sheet (surface protective film) is hardly peeled off from the adherend, and the workability of peeling when the pressure-sensitive adhesive sheet becomes unnecessary is further deteriorated. Is not preferred because it will damage the adherend in the peeling step.
  • the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive surface (A) at a peeling speed of 30 m / min after pasting the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer to the TAC surface at 23 ° C. for 30 minutes, and the pressure-sensitive adhesive surface of the pressure-sensitive adhesive layer.
  • Adhesive strength ratio (B / A) to adhesive strength (B) at a peeling speed of 30 m / min after 1 week pasting on TAC surface at 70 ° C. is less than 2, preferably 0.5 to 1.9. More preferably, it is 0.7 to 1.8. By being in the said range, it is excellent in removability and workability
  • the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer having a pressure-sensitive adhesive area of 1 cm 2 bonded to a TAC polarizing plate and sheared when peeled in the shear direction at a peeling rate of 0.06 mm / min after being stuck at 23 ° C. for 30 minutes.
  • the force is preferably 10 N / cm 2 or more, more preferably 10 to 50 N / cm 2 , and still more preferably 10 to 40 N / cm 2 . If the shearing force is within the above range, it can withstand the force in the shearing direction that occurs when the adherend tries to curl, and the adhesive sheet does not slip or slip, and the adherend is curled. Since it can suppress, it is preferable.
  • the pressure-sensitive adhesive sheet of the present invention has an antistatic layer on one side of the support film opposite to the pressure-sensitive adhesive layer, and the antistatic layer comprises polyaniline sulfonic acid as a conductive polymer component, a polyester resin as a binder, and It is preferably formed from an antistatic composition containing an isocyanate-based crosslinking agent as a crosslinking agent.
  • the pressure-sensitive adhesive sheet has an antistatic layer (topcoat layer)
  • the antistatic property of the pressure-sensitive adhesive sheet is improved, which is a preferred embodiment.
  • the antistatic layer preferably contains polyaniline sulfonic acid as a conductive polymer component.
  • the polyaniline sulfonic acid is “water-soluble”, but can be fixed in the antistatic layer by using an isocyanate-based crosslinking agent described later, and water resistance can be improved.
  • an antistatic layer having an excellent surface resistance value with time can be obtained, which is a preferred embodiment.
  • the conductive polymer used in forming the antistatic layer is “water-dispersible”, aggregates are generated when the antistatic layer is formed using the water-dispersible conductive polymer-containing solution. This is not preferable because it tends to be easy and cannot be applied uniformly, and the surface resistance value with time tends to be extremely inferior.
  • the amount of the conductive polymer used is preferably 10 to 200 parts by weight, more preferably 25 to 150 parts by weight, even more preferably 100 parts by weight of the binder contained in the antistatic layer (topcoat layer). Is 40 to 120 parts by mass. 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 support film may be reduced or the transparency may be decreased. There is a risk of lowering, which is not preferable.
  • the polyaniline sulfonic acid used as the conductive polymer component preferably has a polystyrene equivalent weight average molecular weight (Mw) of 5 ⁇ 10 5 or less, 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.
  • the conductive polymer component used in the invention preferably contains polyaniline sulfonic acid, a polyester resin as the binder, and an isocyanate-based cross-linking agent as the cross-linking agent, and the essential component dissolved in water (conductive polymer aqueous solution) Or simply referred to as an aqueous solution).
  • Such an aqueous conductive polymer solution is prepared by, for example, dissolving a conductive polymer having a hydrophilic functional group (which can be synthesized by a method such as copolymerizing a monomer having a hydrophilic functional group in the molecule) in water. can do.
  • the hydrophilic functional group 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.
  • the antistatic layer disclosed herein contains polyaniline sulfonic acid (polyaniline type) as an essential component as the conductive polymer component.
  • polyaniline type polyaniline type
  • one or more other antistatic components conductive polymer
  • Organic conductive materials other than the above, inorganic conductive materials, antistatic agents, etc. may be included together.
  • 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 only a conductive polymer.
  • the embodiment consisting 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 their derivatives, imidazolines and their derivatives, alanine and their derivatives; 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), ATO (antimony oxide / tin oxide), and the like. 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 single ion having a cationic, anionic or zwitterionic ion conductive group.
  • examples thereof include an ion conductive polymer obtained by polymerizing or copolymerizing a monomer.
  • the antistatic layer preferably contains a polyester resin as a binder.
  • the polyester resin is preferably a resin material containing polyester as a main component (typically exceeding 50% by mass, preferably 75% by mass or more, for example, 90% by mass 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). Selected from one or more compounds (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, naphthalenedicarboxylic acid, and acid anhydrides thereof; adipic acid, sebacic acid, azelaic acid, succinic acid, Aliphatic dicarboxylic acids such as fumaric acid, maleic acid, highmic 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, naphthalenedicarboxylic acid, and acid anhydrides thereof
  • adipic acid, sebacic acid, azelaic acid, succinic acid Aliphatic dicarboxylic acids such as fumaric acid, maleic acid, high
  • 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.
  • alkylene oxide adducts 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 MD-1480” manufactured by Toyobo Co., Ltd. can be used.
  • the antistatic layer is a resin other than a polyester resin as a binder as long as the performance of the pressure-sensitive adhesive sheet (surface protective film) disclosed herein (for example, performance such as antistatic properties) is not significantly impaired.
  • one or more resins selected from acrylic resins, acrylic-urethane resins, acrylic-styrene resins, acrylic-silicone resins, silicone resins, polysilazane resins, polyurethane resins, fluororesins, polyolefin resins, etc. Further, it can be contained.
  • 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 mass is preferable.
  • the proportion of the binder in the whole antistatic layer can be, for example, 50 to 95% by mass, and usually 60 to 90% by mass is appropriate.
  • the antistatic layer (topcoat layer) preferably uses a fatty acid amide as a lubricant.
  • a further release treatment for example, a treatment in which a known release treatment agent such as a silicone release agent or a long-chain alkyl release agent is applied and dried
  • a further release treatment for example, a treatment in which a known release treatment agent such as a silicone release agent or a long-chain alkyl release agent is applied and dried
  • a further release treatment for example, a treatment in which a known release treatment agent such as a silicone release agent or a long-chain alkyl release agent is applied and dried
  • an antistatic layer (topcoat layer) having both sufficient slipping property and printing adhesion can be obtained, which can be a preferable mode.
  • the aspect in which the surface of the antistatic layer is not further peeled can prevent whitening due to the peeling treatment agent (for example, whitening due to storage under heating and humidification conditions). This is preferable. It is also advantageous from the viewpoint of solvent resistance.
  • fatty acid amide examples include lauric acid amide, palmitic acid amide, stearic acid amide, behenic acid amide, hydroxy stearic acid amide, oleic acid amide, erucic acid amide, N-oleylparticic acid amide, N-stearyl stearic acid.
  • the ratio of the lubricant to the whole antistatic layer can be 1 to 50% by mass, and usually 5 to 40% by mass is appropriate.
  • the ratio of the lubricant to the whole antistatic layer can be 1 to 50% by mass, and usually 5 to 40% by mass is appropriate.
  • the antistatic layer contains other lubricant in addition to the fatty acid amide, as long as the application effect is not greatly impaired.
  • examples of such other lubricants include various waxes such as petroleum wax (paraffin wax, etc.), mineral wax (montan wax, etc.), higher fatty acid (cellotic acid, etc.), and neutral fat (palmitic acid triglyceride, etc.). It is done.
  • a general silicone-based lubricant, a fluorine-based lubricant, and the like may be supplemented.
  • the technology disclosed herein can be preferably implemented in an embodiment that does not substantially contain such a silicone-based lubricant, a fluorine-based lubricant and the like.
  • a silicone compound used for a purpose other than the lubricant for example, as an antifoaming agent for a coating material for forming an antistatic layer described later
  • the antistatic layer preferably contains an isocyanate-based crosslinking agent as a crosslinking agent.
  • an isocyanate-based crosslinking agent By using the isocyanate-based crosslinking agent, the water-soluble polyaniline sulfonic acid, which is an essential component when forming the antistatic layer, can be fixed in the binder, has excellent water resistance, and further improves printing adhesion. The effect can be realized.
  • 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-based crosslinking agent include isocyanate-based crosslinking agents that can be used in the preparation of general pressure-sensitive adhesive layers and antistatic layers (topcoat layers) (for example, used in the above-mentioned pressure-sensitive adhesive layers).
  • Isocyanate compounds (isocyanate-based cross-linking agents)) alcohols, phenols, thiophenols, amines, imides, oximes, lactams, active methylene compounds, mercaptans, imines, ureas, diaryl compounds And those blocked with sodium bisulfite can be used.
  • the antistatic layer in the technology disclosed herein includes an antistatic component, an antioxidant, a colorant (pigment, dye, etc.), a fluidity modifier (thixotropic agent, thickener, etc.), a film-forming as necessary. It may contain additives such as auxiliaries, surfactants (antifoaming agents, etc.), preservatives and the like.
  • the antistatic layer is a liquid composition (for forming an antistatic layer) in which essential components such as the conductive polymer component and additives used as necessary are dissolved in an appropriate solvent (such as water).
  • an appropriate solvent such as water
  • a method of applying the coating material to the first surface of the support 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 mass or less (typically 0.05 to 5% by mass), and usually 1% by mass or less (typically 0.10 to 10%). 1 mass%) is appropriate.
  • the NV of the coating material is, for example, 0.05 to 0.50 mass% (for example, 0.10 to 0.40 mass%).
  • a more uniform antistatic layer can be formed by using a low NV coating material.
  • a solvent capable of stably dissolving 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), glycol ethers such as dialkylene glycol monoalkyl ether; and the like can be used.
  • 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 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). The appearance of the film) can easily become uneven. On the other hand, if it is too thick, the properties (optical properties, dimensional stability, etc.) of the support film may be affected.
  • the surface resistance value ( ⁇ / ⁇ ) measured on the surface of the antistatic layer is preferably less than 1.0 ⁇ 10 11 . More preferably, it is less than 5.0 ⁇ 10 10 , and further preferably less than 2.0 ⁇ 10 10 .
  • the pressure-sensitive adhesive sheet exhibiting a surface resistance value within the above range can be suitably used as a pressure-sensitive adhesive sheet used in processing or transporting an article that dislikes static electricity such as a liquid crystal cell or a semiconductor device.
  • 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.
  • the pressure-sensitive adhesive sheet (surface protective film) disclosed herein has a property that the back surface (surface of the antistatic layer) can be easily printed with water-based ink or oil-based ink (for example, using an oil-based marking pen).
  • Such an adhesive sheet describes the identification number of the adherend to be protected on the surface adhesive sheet in the course of processing or transporting the adherend (for example, an optical component) performed with the adhesive sheet attached. Suitable for display. Therefore, it is preferable that it is an adhesive sheet excellent in printability.
  • the solvent is alcohol-based and has high printability for oil-based inks containing pigments.
  • the pressure-sensitive adhesive sheet disclosed herein preferably has a solvent resistance that does not cause a noticeable change in appearance even if the print is wiped with alcohol (for example, ethyl alcohol) when the print is corrected or erased. .
  • the pressure-sensitive adhesive sheet (surface protective film) disclosed herein can be implemented in a mode that further includes other layers in addition to the support film (base material), the pressure-sensitive adhesive layer, and the antistatic layer.
  • Examples of the arrangement of the “other layer” include a space between the first surface (back surface) of the support film and the antistatic layer, a space between the second surface (front surface) of the support film and the pressure-sensitive adhesive layer, and the like.
  • the layer disposed between the front surface of the support film and the pressure-sensitive adhesive layer can be, for example, an undercoat layer (anchor layer) or an antistatic layer that enhances the anchoring property of the pressure-sensitive adhesive layer with respect to the second surface.
  • the pressure-sensitive adhesive sheet may be configured such that an antistatic layer is disposed on the front surface of the support film, an anchor layer is disposed on the antistatic layer, and a pressure-sensitive adhesive layer is disposed thereon.
  • the optical member of the present invention is preferably protected by the pressure-sensitive adhesive sheet.
  • the pressure-sensitive adhesive sheet can prevent an increase in adhesive strength over time (at a high temperature), has low adhesive strength at high-speed peeling, and has excellent removability and workability, so that it can protect the surface during processing, transportation, shipping, etc. Since it can be used for applications, it is useful for protecting the surface of the optical member (polarizing plate or the like). Moreover, since the said adhesive sheet is excellent in shearing force, it can suppress the curling of the adherend (optical member) to which the said adhesive sheet was bonded, and since it is excellent in handleability, it becomes useful.
  • the glass transition temperature Tg (° C.) was determined by the following formula using the following literature values as the glass transition temperature Tgn (° C.) of the homopolymer of each monomer.
  • Tg + 273 ⁇ [Wn / (Tgn + 273)] [Wherein Tg (° C.) is the glass transition temperature of the copolymer, Wn ( ⁇ ) is the mass fraction of each monomer, Tgn (° C.) is the glass transition temperature of the homopolymer of each monomer, and n is the type of each monomer Represents.
  • a TAC polarizing plate manufactured by Nitto Denko Corp., SEG1423DU polarizing plate, width: 70 mm, length: 100 mm
  • SEG1423DU polarizing plate width: 70 mm, length: 100 mm
  • the adhesive force (A) is preferably 2.0 N / 25 mm or less, more preferably 0.1 to 1.9 N / 25 mm, and still more preferably 0.1 to 1.8 N / 25 mm. If the adhesive strength (A) exceeds 2.0 N / 25 mm, the adhesive sheet (surface protective film) is difficult to peel off from the adherend, and the workability of peeling when the adhesive sheet is no longer necessary, This is not preferable because the adherend is damaged by the peeling process.
  • a TAC polarizing plate manufactured by Nitto Denko Corp., SEG1423DU polarizing plate, width: 70 mm, length: 100 mm
  • SEG1423DU polarizing plate width: 70 mm, length: 100 mm
  • the adhesive strength with time (B) when peeled at a peeling speed of 30 m / min (high speed peeling) and a peeling angle of 180 ° with a universal tensile tester. ) (N / 25 mm). The measurement was performed in an environment of 23 ° C. ⁇ 50% RH.
  • the adhesive force (B) is preferably less than 4.0 N / 25 mm, more preferably 0.1 to 3.5 N / 25 mm, and still more preferably 0.1 to 3.0 N / 25 mm.
  • the pressure-sensitive adhesive force (B) is 4.0 N / 25 mm or more, the pressure-sensitive adhesive sheet (surface protective film) is hardly peeled off from the adherend, and the workability of peeling when the pressure-sensitive adhesive sheet becomes unnecessary is further deteriorated. Is not preferred because it will damage the adherend in the peeling step.
  • the adhesive strength (A) and the adhesive strength ratio (B / A) to the adhesive strength (B) are less than 2, preferably 0.5 to 1.9, more preferably 0. .7 to 1.8. By being in the said range, it is excellent in removability and workability
  • the said adhesive force ratio is evaluated as a parameter
  • the shear force (N / cm 2 ) is preferably 10 or more, more preferably 10 to 50, and still more preferably 10 to 40. If the shearing force is within the above range, it can withstand the force in the shearing direction that occurs when the adherend tries to curl, and the adhesive sheet does not slip or slip, and the adherend is curled. Since it can suppress, it is preferable.
  • Measurement was performed according to JIS-K-6911 using a resistivity meter (manufactured by Mitsubishi Chemical Analytic, Hiresta UP MCP-HT450 type) in an atmosphere of temperature 23 ° C. and humidity 50% RH.
  • the surface resistance value ( ⁇ / ⁇ ) on the surface of the antistatic layer in the present invention is preferably 1. for both initial and room temperature (23 ° C. ⁇ 50% RH) ⁇ 1 week (7 days). It is less than 0 ⁇ 10 11 , more preferably less than 5.0 ⁇ 10 10 , and even more preferably less than 2.0 ⁇ 10 10 .
  • the pressure-sensitive adhesive sheet (surface protective film) exhibiting a surface resistance value within the above range is suitably used as a pressure-sensitive adhesive sheet used in the processing or transporting of articles that dislike static electricity such as liquid crystal cells and semiconductor devices. obtain.
  • slipperiness (dynamic frictional force) (N) in this invention Preferably it is 5 or less, More preferably, it is 4.5 or less, More preferably, it is 4 or less.
  • slipperiness (dynamic frictional force) (N) Preferably it is 5 or less, More preferably, it is 4.5 or less, More preferably, it is 4 or less.
  • (meth) acrylic polymer > 94.5 parts by mass of 2-ethylhexyl acrylate (2EHA), 5.32 parts by mass of 4-hydroxyethyl acrylate (HEA), acrylic acid in a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser (AA) 0.18 parts by mass, 2,2′-azobisisobutyronitrile 0.2 parts by mass and 150 parts by mass of ethyl acetate as a polymerization initiator were charged, and nitrogen gas was introduced while gently stirring.
  • the polymerization temperature was kept at around 65 ° C. for 6 hours to prepare a (meth) acrylic polymer solution (40% by mass).
  • the acrylic polymer had a weight average molecular weight of 520,000 and a glass transition temperature (Tg) of ⁇ 67 ° C. (see the column of the pressure-sensitive adhesive composition 1 in Table 1).
  • Methylolpropane / tolylene diisocyanate manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate L
  • 1 part by mass solid content 1 part by mass
  • isocyanurate of hexamethylene diisocyanate which is an aliphatic isocyanate compound (Nippon Polyurethane Industry)
  • As a crosslinking catalyst 1 part by mass (Coronate HX) (solid content 1 part by mass). 3 parts by mass (0.03 parts by mass of solid content) of dibutyltin dilaurate (1% by mass ethyl acetate solution) was added, and the mixture was stirred to prepare an adhesive composition 1 (solution).
  • aqueous solution for antistatic layer (back treatment agent A)> Polyester resin Vylonal MD-1480 (25% aqueous solution, manufactured by Toyobo Co., Ltd.) as a binder, polyaniline sulfonic acid (aquaPASS, weight average molecular weight 40,000, manufactured by Mitsubishi Rayon Co.) as a conductive polymer, and hexamethylene blocked with diisopropylamine as a crosslinking agent Isocyanurate of diisocyanate, lubricant, oleic amide in water / ethanol (1/3) mixed solvent, binder in solid content of 100 parts by mass, conductive polymer in solid content of 75 parts by mass, and crosslinker in solid form 10 parts by weight and 30 parts by weight of solid lubricant were added and stirred for about 20 minutes to mix thoroughly. In this way, an aqueous solution for an antistatic layer having an NV of about 0.4% was prepared.
  • aqueous solution for antistatic layer (back treatment agent B)> Polyester resin Vylonal MD-1480 (25% aqueous solution, manufactured by Toyobo Co., Ltd.) as a binder, polyaniline sulfonic acid (aquaPASS, weight average molecular weight 40,000, manufactured by Mitsubishi Rayon Co.) as a conductive polymer, and hexamethylene blocked with diisopropylamine as a crosslinking agent A diisocyanate isocyanurate body in a water / ethanol (1/3) mixed solvent, a binder in a solid content of 100 parts by mass, a conductive polymer in a solid content of 75 parts by mass, and a crosslinking agent in a solids content of 10 parts by mass. In addition, it was stirred for about 20 minutes and mixed well. In this way, an aqueous solution for an antistatic layer having an NV of about 0.4% was prepared.
  • aqueous solution for antistatic layer (back treatment agent C)> Polyester resin Vylonal MD-1480 (25% aqueous solution, manufactured by Toyobo Co., Ltd.) as the binder, poly (3,4-ethylenedioxythiophene) (PEDOT) 0.5% and polystyrene sulfonate (weight average molecular weight 150,000) as the conductive polymer (PSS) 0.8% aqueous solution (Bytron P, manufactured by HC Stark), water / ethanol (1/1) mixed solvent of isocyanurate of hexamethylene diisocyanate blocked with diisopropylamine as a crosslinking agent
  • 100 parts by mass of the binder in a solid amount, 50 parts by mass of the conductive polymer in a solid content, and 10 parts by mass of the cross-linking agent in a solid amount were added, and the mixture was sufficiently mixed by stirring for about 20 minutes. In this way, an aqueous solution for an antistatic layer having an aqueous solution,
  • aqueous solution for antistatic layer (back treatment agent D)> Polyester resin Vylonal MD-1480 (25% aqueous solution, manufactured by Toyobo Co., Ltd.) as a binder, and polyaniline sulfonic acid (aquaPASS, weight average molecular weight 40,000, manufactured by Mitsubishi Rayon Co.) as a conductive polymer is mixed in water / ethanol (1/3). To the solvent, 100 parts by mass of the binder in a solid amount and 75 parts by mass of the conductive polymer in a solid content were added, and the mixture was stirred and mixed well for about 20 minutes. In this way, an aqueous solution for an antistatic layer having an NV of about 0.4% was prepared.
  • ⁇ Preparation of support film with antistatic layer> One surface (first surface) is subjected to corona treatment on a transparent polyethylene terephthalate (PET) film (polyester film) having a thickness of 38 ⁇ m, a width of 30 cm, and a length of 40 cm.
  • PET polyethylene terephthalate
  • One of the aqueous solutions of D) was applied so that the thickness after drying was 30 nm.
  • the coated material was heated to 130 ° C. for 1 minute and dried to prepare a support film with an antistatic layer having an antistatic layer on the first surface of the PET film.
  • ⁇ Example 1> ⁇ Production of adhesive sheet>
  • the pressure-sensitive adhesive composition 1 (solution) was applied to the surface opposite to the antistatic layer of the support film with the antistatic layer and heated at 130 ° C. for 1 minute to form a pressure-sensitive adhesive layer having a thickness of 15 ⁇ m. .
  • the adhesive strength ratio (B / A) is included in a desired range, and the adhesive strength with time at high temperature increases with respect to the initial adhesive strength at the time of high-speed peeling. It was confirmed that the shear strength was excellent.
  • the adhesive force ratio (B / A) deviates from the desired range, the initial adhesive force during high-speed peeling is high, and the increase in adhesive force over time at high temperatures is large.
  • the adhesive strength increase preventing property adheresive strength stability
  • removability workability
  • shear force were inferior to those of the examples.
  • a desired raw material (conductive polymer component: polyaniline sulfonic acid, binder: polyester resin, and crosslinking agent: isocyanate-based crosslinking agent) is blended as an antistatic layer (antistatic agent composition).
  • conductive polymer component polyaniline sulfonic acid
  • binder polyester resin
  • crosslinking agent isocyanate-based crosslinking agent

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesive Tapes (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Polarising Elements (AREA)

Abstract

L'invention fournit une feuille adhésive qui permet d'inhiber l'élévation d'une force d'adhérence au fil du temps à haute température (propriété d'inhibition d'élévation de force d'adhérence, stabilité de force d'adhérence), dont la force d'adhérence lors d'un pelage rapide est limitée à un niveau bas, qui se révèle excellente en terne de propriétés de pelages répétés et d'usinabilité, et qui présente un excellent effort de cisaillement. La feuille adhésive de l'invention possède une couche adhésive formée par une composition d'agent adhésif sur une face ou sur les deux faces d'un film support. En outre, cette feuille adhésive est caractéristique en ce qu'un rapport de force d'adhérence (B/A) entre une force d'adhérence (A) lorsque la vitesse de pelage est de 30m/min après mise en adhésion pendant 30 minutes à 23°C d'une face d'adhésion de ladite couche adhésive sur une face TAC, et une force d'adhérence (B) lorsque la vitesse de pelage est de 30m/min après mise en adhésion pendant une semaine à 70°C de la face d'adhésion de ladite couche adhésive sur la face TAC, est inférieur à 2.
PCT/JP2015/060625 2014-04-16 2015-04-03 Feuille adhésive, et élément optique WO2015159738A1 (fr)

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CN111621234A (zh) * 2019-02-27 2020-09-04 琳得科株式会社 粘着片、反复弯曲层叠构件及反复弯曲器件

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JP6269769B1 (ja) * 2016-09-30 2018-01-31 東洋インキＳｃホールディングス株式会社 粘着シート
JP2018053212A (ja) * 2016-09-30 2018-04-05 日立化成株式会社 粘着フィルム
JP2018077355A (ja) * 2016-11-09 2018-05-17 日東電工株式会社 積層光学フィルム、及び画像表示装置
JP6829097B2 (ja) * 2017-02-08 2021-02-10 日本カーバイド工業株式会社 保護フィルム用粘着剤組成物及び被着体の表面保護フィルム
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KR102290864B1 (ko) * 2018-10-30 2021-08-23 산진 옵토일렉트로닉스 (쑤저우) 컴퍼니 리미티드 점착제 조성물
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KR102475814B1 (ko) * 2019-05-22 2022-12-08 주식회사 엘지화학 점착제 조성물
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