WO2018056167A1 - Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, and optical member - Google Patents
Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet, and optical member Download PDFInfo
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- WO2018056167A1 WO2018056167A1 PCT/JP2017/033269 JP2017033269W WO2018056167A1 WO 2018056167 A1 WO2018056167 A1 WO 2018056167A1 JP 2017033269 W JP2017033269 W JP 2017033269W WO 2018056167 A1 WO2018056167 A1 WO 2018056167A1
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- pressure
- sensitive adhesive
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- acrylate
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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
- 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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- 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
- 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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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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
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- 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
- 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
- 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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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
Definitions
- the present invention relates to a pressure-sensitive adhesive composition, a pressure-sensitive adhesive sheet, and an optical member.
- the pressure-sensitive adhesive sheet obtained from the pressure-sensitive adhesive composition is used for application to a plastic product or the like that is likely to generate static electricity (for example, a liquid crystal display panel, a plasma display panel (PDP), an organic electroluminescence (EL) display, etc.).
- a plastic product or the like that is likely to generate static electricity
- static electricity for example, a liquid crystal display panel, a plasma display panel (PDP), an organic electroluminescence (EL) display, etc.
- PDP plasma display panel
- EL organic electroluminescence
- it is used for the purpose of protecting the surface of an optical member (for example, a polarizing plate, a wave plate, a retardation plate, an optical compensation film, a reflection sheet, a brightness enhancement film used for a liquid crystal display). It is useful as a surface protective film.
- the surface protective film (also referred to as a surface protective sheet) generally has a configuration in which an adhesive layer is provided on a film-like base film (support). Such a 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.
- 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 layer.
- a polarizing plate to be bonded to a liquid crystal cell is once manufactured in a roll form, and then unwound from this roll and cut into a desired size according to the shape of the liquid crystal cell.
- a measure is taken to attach a surface protective film to one side or both sides (typically, one side) of the polarizing plate. This surface protective film is peeled off and removed when it is no longer needed.
- 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, the surface protection film is subjected to an antistatic treatment. For example, as a surface layer (topcoat layer, back layer) of the surface protection film, an antistatic layer is formed or an antistatic coating is applied. Thus, an antistatic function is provided (see Patent Documents 1 and 2).
- an ionic compound such as an alkali metal salt or an ionic liquid that functions as an antistatic agent is included in the pressure-sensitive adhesive. (See Patent Document 3).
- the pressure-sensitive adhesive layer surface containing the ionic compound is attached to an optical member such as a polarizing plate and stored in a high temperature (warming) environment, the ionic compound penetrates from the surface of the optical member. As a result, the antistatic ability of the ionic compound is lowered, and the optical member cannot be sufficiently protected.
- the present invention has been intensively studied in view of the above circumstances. As a result, even when the optical member such as a polarizing plate is pasted and stored in a high temperature environment, the antistatic property and the stability of the stripping voltage with time are stable. It aims at providing the adhesive composition which can achieve property, the adhesive sheet formed with the said adhesive composition, and the optical member to which the said adhesive sheet is affixed.
- the pressure-sensitive adhesive composition of the present invention comprises a pressure-sensitive polymer and an ionic group-containing silicone represented by the following formula (1).
- R 1 to R 4 may be the same or different and include any of an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, an alicyclic group, a fluorine-substituted alkyl group, and an ionic group, One or more of R 1 to R 4 contain an ionic group, and n is an integer of 0 to 100.
- the pressure-sensitive adhesive composition of the present invention preferably contains an oxyalkylene group-containing compound.
- the pressure-sensitive adhesive composition of the present invention preferably contains at least one selected from the group consisting of acrylic pressure-sensitive adhesives, urethane-based pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives.
- the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition on at least one surface of a base film, and contains the ionic group inside and / or on the surface of the pressure-sensitive adhesive layer.
- a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition on at least one surface of a base film, and contains the ionic group inside and / or on the surface of the pressure-sensitive adhesive layer.
- silicone is present.
- a separator is attached to the surface of the pressure-sensitive adhesive layer opposite to the surface that contacts the base film.
- the ionic group-containing silicone is preferably present on the surface of the separator that contacts the pressure-sensitive adhesive layer.
- the optical member of the present invention is preferably attached with the pressure-sensitive adhesive sheet or a pressure-sensitive adhesive sheet obtained by peeling the separator from the pressure-sensitive adhesive sheet.
- the present invention uses a pressure-sensitive adhesive composition containing a specific ionic group-containing silicone, so that a pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer formed of the pressure-sensitive adhesive composition is used for an optical member such as a polarizing plate. Even when pasted and stored in a high temperature environment, it is useful because it can achieve excellent antistatic properties and stability over time of the stripping voltage.
- the pressure-sensitive adhesive sheet disclosed herein is generally in a form referred to as a pressure-sensitive adhesive tape, pressure-sensitive adhesive label, pressure-sensitive adhesive film, etc., and particularly used as an optical component (for example, a liquid crystal display panel component such as a polarizing plate or a wave plate). It is suitable as a surface protective film for protecting the surface of the optical component during processing or transport of the optical component.
- 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 pressure-sensitive adhesive sheet (surface protective film) of the present invention has a 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 substrate 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
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- cellulose polymers such as diacetyl cellulose and triacetyl cellulose
- polycarbonate 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 mass or more) such as an acrylic polymer such as polymethyl methacrylate; It can be preferably used as the substrate film.
- 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 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 base film for a surface protective film, such as excellent optical characteristics and dimensional stability, and has a 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.
- a known or conventional surface treatment such as corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and application of a primer may be performed.
- Such surface treatment can be, for example, a treatment for improving the adhesion between the base film and the pressure-sensitive adhesive layer (the anchoring property of the pressure-sensitive adhesive layer).
- a plastic film subjected to an antistatic treatment can be used as the base film.
- the substrate film is preferable because charging of the pressure-sensitive adhesive sheet itself when peeled is suppressed.
- the base 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.
- a conventionally well-known method can be used, for example, 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 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 pressure-sensitive adhesive sheet disclosed herein can be practiced in a mode that further includes other layers in addition to the base film and the pressure-sensitive adhesive layer.
- the other layer include an undercoat layer (anchor layer) that improves the anchoring property of the antistatic layer and the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive sheet of the present invention has the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition.
- a pressure-sensitive adhesive composition for example, an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a synthetic rubber-based pressure-sensitive adhesive, a natural rubber-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, and the like can be used.
- Acrylic adhesive using a (meth) acrylic polymer which is at least one selected from the group consisting of an acrylic adhesive, a urethane adhesive, and a silicone adhesive, particularly preferably an adhesive polymer Is to use the agent.
- the (meth) acrylic polymer which is a pressure-sensitive polymer constituting the acrylic pressure-sensitive adhesive
- the (meth) acrylic polymer is an alkyl having 1 to 14 carbon atoms as a raw material monomer constituting the pressure-sensitive adhesive layer.
- a (meth) acrylic monomer having a group can be used as the main monomer.
- As said (meth) acrylic-type monomer 1 type (s) or 2 or more types can be used.
- a pressure-sensitive adhesive sheet (surface protective film) having excellent properties and removability 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 (meth) acrylic polymer preferably contains a hydroxyl group-containing (meth) acrylic monomer as a raw material monomer.
- a hydroxyl group containing (meth) acrylic-type monomer 1 type (s) or 2 or more types can be used.
- hydroxyl groups have moderate interactions with ionic group-containing silicones, which are antistatic components (antistatic agents), and oxyalkylene group-containing compounds. Therefore, it can be suitably used also in terms of antistatic properties.
- 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, etc. .
- the hydroxyl group-containing (meth) acrylic monomer is preferably contained in an amount of 25% by mass or less, more preferably 20% by mass or less, based on 100% by mass of the total amount of monomer components constituting the (meth) acrylic polymer. More preferably, the content is 0.1 to 15% by mass, and most preferably 1 to 10% by mass. 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 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 polymerizable monomer other than the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms used in the (meth) acrylic polymer, and the hydroxyl group-containing (meth) acrylic monomer A carboxyl group-containing (meth) acrylic monomer can be used.
- the pressure-sensitive adhesive sheet pressure-sensitive adhesive layer
- the cohesive force of the pressure-sensitive adhesive layer and the shearing force are excellent, which is preferable.
- carboxyl group-containing (meth) acrylic monomer examples include (meth) acrylic acid, carboxylethyl (meth) acrylate, carboxylpentyl (meth) acrylate, and the like.
- the carboxyl group-containing (meth) acrylic monomer is preferably 0 to 5% by mass and preferably 0 to 3% by mass with respect to 100% by mass of the total amount of monomer components constituting the (meth) acrylic polymer. More preferably, it is 0 to 2% by mass, still more preferably 0 to 0.19% by mass.
- the amount exceeds 5% by mass, a large number of acid functional groups such as carboxyl groups having a large polar action are present, and when an ionic group-containing silicone or an oxyalkylene group-containing compound as an antistatic component is blended, the antistatic component
- the interaction of an acid functional group such as a carboxyl group is not preferable because ionic conduction is hindered, conductivity efficiency is lowered, and sufficient antistatic properties may not be obtained.
- the total amount of monomer components constituting the (meth) acrylic polymer is 100% by mass.
- the carboxyl group-containing (meth) acrylic monomer is preferably contained in an amount of 0.01 to 0.19% by mass.
- the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms the hydroxyl group-containing (meth) acrylic monomer, and the carboxyl group-containing (meth) acrylic used in the (meth) acrylic polymer.
- Any other polymerizable monomer other than the 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 functioning as an improvement in peeling strength (adhesive strength) such as a vinyl ether monomer or as a crosslinking base point can be appropriately used.
- a nitrogen-containing monomer such as a cyano group-containing monomer, an amide group-containing monomer, an imide group-containing monomer, an amino group-containing monomer, and N-acryloylmorpholine.
- a nitrogen-containing monomer is useful because it can secure an appropriate peeling force (adhesive strength) that does not cause floating or peeling, and can provide a pressure-sensitive adhesive sheet (surface protective film) excellent in shearing force.
- These polymerizable monomers can be used alone or in combination of two or more.
- Examples of the cyano group-containing monomer include acrylonitrile and methacrylonitrile.
- 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.
- 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.
- 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.
- the polymerizable monomer other than the (meth) acrylic monomer having an alkyl group having 1 to 14 carbon atoms, the hydroxyl group-containing (meth) acrylic monomer, and the carboxyl group-containing (meth) acrylic monomer The amount is preferably 0 to 50% by mass, more preferably 0 to 20% by mass, based on 100% by mass of the total amount of monomer components constituting the (meth) acrylic polymer.
- the other polymerizable monomers can be appropriately adjusted in order to obtain desired characteristics.
- the (meth) acrylic polymer may further contain an alkylene oxide group-containing reactive monomer as a monomer component.
- the average addition mole number of the oxyalkylene unit of the alkylene oxide group-containing reactive monomer is 1 to 40 from the viewpoint of compatibility with the ionic group-containing silicone as the antistatic component and the oxyalkylene group-containing compound. It is preferably 3 to 40, more preferably 4 to 35, and particularly preferably 5 to 30. When 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. When the average number of added moles is greater than 40, the interaction with the ionic group-containing silicone or the oxyalkylene group-containing compound is large, and the viscosity of the pressure-sensitive adhesive composition tends to increase, making coating difficult. This is not preferable. Note that the terminal of the oxyalkylene chain may be a hydroxyl group or may be substituted with another functional group.
- the alkylene oxide group-containing reactive monomer may be used alone or in combination of two or more, but the total content is the total amount of monomer components of the (meth) acrylic polymer. Among these, 0 to 20% by mass is preferable, and 0 to 10% by mass is more preferable. If the content of the alkylene oxide group-containing reactive monomer exceeds 20% by mass, the interaction with the ionic group-containing silicone and the oxyalkylene group-containing compound is increased, ionic conduction is hindered, and antistatic properties are reduced. This 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 reactive monomer-containing (meth) acrylic polymer having an ethylene oxide group as a base polymer, the compatibility between the base polymer and the ionic group-containing silicone or oxyalkylene group-containing compound is improved, and the adherence to the adherend is improved. Bleed is suitably suppressed, and a low-staining 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.
- the (meth) acrylic polymer preferably has a weight average molecular weight (Mw) of 100,000 to 5,000,000, more preferably 200,000 to 4,000,000, still more preferably 300,000 to 3,000,000, and most preferably 300,000 to 950,000. It is.
- 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 weight average molecular weight exceeds 5 million, the fluidity of the polymer is lowered, and the wettability to the adherend (for example, polarizing plate) becomes insufficient, and the adherend and the adhesive sheet (surface protective film) There is a tendency to cause blisters generated between the pressure-sensitive adhesive 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 (usually ⁇ 100 ° C. or higher).
- the glass transition temperature is higher than 0 ° C., the polymer hardly flows, for example, the wettability to the polarizing plate which is an optical member becomes insufficient, and between the polarizing plate and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet (surface protective film). There is a tendency to cause blisters to occur.
- the glass transition temperature is ⁇ 61 ° C. or lower, an adhesive layer excellent in wettability to a polarizing plate and light release properties 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 is not particularly limited, and can be polymerized by known methods such as solution polymerization, emulsion polymerization, bulk polymerization, suspension polymerization, etc. From the viewpoint of characteristics such as low contamination to the adherend (protected body), 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.
- urethane-based pressure-sensitive adhesive can be adopted when a urethane-based pressure-sensitive adhesive is used for the pressure-sensitive adhesive layer.
- a urethane type adhesive Preferably, what consists of a urethane type polymer which is an adhesive polymer obtained by making a polyol and a polyisocyanate compound react is mentioned.
- the polyol include polyether polyol, polyester polyol, polycarbonate polyol, and polycaprolactone polyol.
- the polyisocyanate compound include diphenylmethane diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, and the like.
- any appropriate silicone-based pressure-sensitive adhesive can be adopted.
- a silicone-based pressure-sensitive adhesive one obtained by blending or agglomerating a silicone-based polymer that is a pressure-sensitive polymer can be preferably used.
- silicone pressure-sensitive adhesive examples include addition reaction curable silicone pressure-sensitive adhesives and peroxide curable silicone pressure-sensitive adhesives.
- peroxides benzoyl peroxide and the like
- an addition reaction curable silicone pressure-sensitive adhesive is preferable.
- the curing reaction of the addition reaction curable silicone pressure-sensitive adhesive for example, when obtaining a polyalkyl silicone pressure-sensitive adhesive, generally, a method of curing a polyalkylhydrogensiloxane composition with a platinum catalyst can be mentioned.
- the pressure-sensitive adhesive composition of the present invention is characterized by containing a pressure-sensitive polymer and an ionic group-containing silicone represented by the following formula (1).
- the adhesive layer is stuck on the surface of the adherend (for example, a polarizing plate) under a high temperature environment by the low surface free energy of the silicone chain.
- the ionic group-containing silicone does not penetrate into the adherend (from the adherend surface to the inside of the adherend) and tends to stay on the surface of the adhesive layer.
- the charging characteristics are stable, the antistatic performance is maintained for a long time, and this is a preferred embodiment.
- the “inside” of the pressure-sensitive adhesive layer is, for example, included in the pressure-sensitive adhesive layer when the pressure-sensitive adhesive layer is formed using the pressure-sensitive adhesive composition containing the ionic group-containing silicone. Point to.
- the “surface” of the pressure-sensitive adhesive layer refers to, for example, when the pressure-sensitive adhesive layer is formed using the pressure-sensitive adhesive composition in which the ionic group-containing silicone is blended or not blended.
- the ionic group-containing silicone is previously applied (laminated) to the separator surface to be attached, and when the separator is attached to the pressure-sensitive adhesive layer, from the separator surface, This refers to the case where the ionic group-containing silicone is transferred (transferred) to the surface of the pressure-sensitive adhesive layer.
- R 1 to R 4 may be the same or different, and are an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, an alicyclic group, a fluorine-substituted alkyl group, an ion One of R 1 to R 4 is included, and an ionic group is included in one or more of R 1 to R 4 .
- n is an integer of 0 to 100.
- the ionic group contained in one or more of R 1 to R 4 is preferably an ionic group having an ammonium cation group or a phosphonium cation group.
- one or more of R 1 to R 4 are preferably composed of a cation structure and an anion component represented by the following formula (a) or (b), or represented by (c) or (d)
- the zwitterionic structure is preferred.
- R 5 to R 7 in the above formula (a) may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms, an aryl group, or a fluorine-substituted alkyl group.
- m is an integer of 1 to 10.
- R 8 to R 10 in the above formula (b) may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms, an aryl group, or a fluorine-substituted alkyl group.
- m is an integer of 1 to 10.
- the anion component is not particularly limited.
- R 11 and R 12 in the above formula (c) may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms, an aryl group, or a fluorine-substituted alkyl group, and R 11 and R 12 are A ring may be formed, and in that case, an alkylene group is represented.
- m is an integer of 1 to 10
- p is an integer of 1 to 6.
- R 13 and R 14 in the above formula (d) may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms, an aryl group, or a fluorine-substituted alkyl group, and R 13 and R 14 are A ring may be formed, and in that case, an alkylene group is represented.
- m is an integer of 1 to 10
- p is an integer of 1 to 6.
- ionic group-containing silicone contains silicone chains, it is stored in a high-temperature environment with the adhesive layer attached to the surface of the adherend (eg, polarizing plate) due to the low surface free energy of the silicone chains. Even in this case, the ionic group-containing silicone does not penetrate into the adherend (from the adherend surface to the inside of the adherend) and tends to stay on the pressure-sensitive adhesive layer surface. The characteristics are stable, antistatic performance is maintained for a long time, and it can be suitably used as an antistatic agent.
- ionic group-containing silicone examples include, for example, commercially available product names X-40-2450 and X-40-2750 (manufactured by Shin-Etsu Chemical Co., Ltd.). These compounds may be used alone or in combination of two or more.
- the content of the ionic group-containing silicone is 100 parts by mass of an adhesive polymer (main polymer, for example, (meth) acrylic polymer, urethane polymer, silicone polymer, etc.) constituting the pressure-sensitive adhesive composition.
- main polymer for example, (meth) acrylic polymer, urethane polymer, silicone polymer, etc.
- it is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 7.5 parts by mass, still more preferably 0.03 to 5.5 parts by mass, and most preferably 0.04 to 4. 8 parts by mass.
- the amount is preferably 0.01 to 5.5 parts by mass with respect to 100 parts by mass of the adhesive polymer.
- the pressure-sensitive adhesive composition of the present invention preferably contains an oxyalkylene group-containing compound, more preferably contains an organopolysiloxane having an oxyalkylene chain, and contains an organopolysiloxane having an oxyalkylene main chain. More preferably.
- organopolysiloxane a known organopolysiloxane having a polyoxyalkylene main chain can be used as appropriate, and is preferably represented by the following formula (2).
- 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 the oxyalkylene chain may be an alkoxy group or a hydroxyl group.
- either R 1 or R 2 may be a hydroxyl group, or may be an alkyl group or an alkoxy group, and a part of the alkyl group or alkoxy group is substituted with a hetero atom. It may be.
- n is an integer of 1 to 300.
- organopolysiloxane those having a siloxane-containing site (siloxane site) as the main chain and an oxyalkylene chain bonded to the end of the main chain are used.
- siloxane site siloxane site
- oxyalkylene chain bonded to the end of the main chain
- R 1 and / or R 2 in the formula has an oxyalkylene chain containing a hydrocarbon group having 1 to 6 carbon atoms, and the oxyalkylene chain includes an oxymethylene group, an oxyethylene group, an oxyalkylene chain. 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, and more preferably 20 to 150.
- n is within the above range, the compatibility with the base polymer is balanced and a preferred embodiment is obtained.
- 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 in the main chain include, for example, commercially available products having trade names of X-22-4952, X-22-4272, X-22-6266, KF-6004, Examples thereof include KF-889 (manufactured by Shin-Etsu Chemical Co., Ltd.), BY16-201, SF8427 (manufactured by Toray Dow Corning), and IM22 (manufactured by Asahi Kasei Wacker). These compounds may be used alone or in combination of two or more.
- organosiloxane having (bonding) an oxyalkylene chain it is also possible to use an organosiloxane having (bonding) an oxyalkylene chain in the side chain. It is more preferable to use an organosiloxane having an oxyalkylene chain.
- organopolysiloxane a known organopolysiloxane having a polyoxyalkylene side chain can be used as appropriate, and is preferably represented by the following formula (3).
- 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. However, m and n are not 0 at the same time.
- 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 an ethylene group or a propylene group in order to increase the concentration of an antistatic component (for example, an ionic group-containing silicone) that can be dissolved in the polyoxyalkylene side chain. It is preferable.
- 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 having an oxyalkylene chain in the side chain include, for example, trade names KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF as commercially available products.
- 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 pressure-sensitive adhesive composition may contain an oxyalkylene group-containing compound that does not contain organopolysiloxane.
- an oxyalkylene group-containing compound that does not contain organopolysiloxane.
- oxyalkylene group-containing compound not containing the organopolysiloxane examples include, for example, polyoxyalkylene alkylamine, polyoxyalkylene diamine, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene alkyl phenyl ether.
- Nonionic surfactants such as polyoxyalkylene alkyl ether, polyoxyalkylene alkyl allyl ether, polyoxyalkylene alkyl phenyl allyl ether; polyoxyalkylene alkyl ether sulfate ester salt, polyoxyalkylene alkyl ether phosphate ester salt, Oxyalkylene alkylphenyl ether sulfate ester salt, polyoxyalkylene alkylphenyl ether phosphate Anionic surfactants such as salt of salts; other cationic surfactants having polyoxyalkylene chains (polyalkylene oxide chains), amphoteric surfactants, polyether compounds having polyoxyalkylene chains (and their Derivatives), acrylic compounds having a polyoxyalkylene chain (and derivatives thereof), and the like. Moreover, you may mix
- Such polyoxyalkylene chain-containing compounds may
- polyether compound (polyether component) having a polyoxyalkylene chain examples include a block copolymer of polypropylene glycol (PPG) -polyethylene glycol (PEG), a block copolymer of PPG-PEG-PPG, Examples thereof include a block copolymer of PEG-PPG-PEG.
- the derivative of the polyether compound having a polyoxyalkylene chain include an oxypropylene group-containing compound (PPG monoalkyl ether, PEG-PPG monoalkyl ether, etc.) whose terminal is etherified, and oxypropylene whose terminal is acetylated Group-containing compounds (terminal acetylated PPG and the like), and the like.
- the acrylic compound having a polyoxyalkylene chain include a (meth) acrylate polymer having an oxyalkylene group.
- the number of added 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 group-containing silicone.
- 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
- monomer units (components) other than the (meth) acrylic acid alkylene oxide carboxyl group-containing (meth) acrylate, phosphoric acid group-containing (meth) acrylate, cyano group-containing (meth) acrylate, vinyl esters , Aromatic vinyl compounds, acid anhydride group-containing (meth) acrylates, hydroxyl group-containing (meth) acrylates, amide group-containing (meth) acrylates, amino group-containing (meth) acrylates, epoxy group-containing (meth) acrylates, N- Acryloylmorpholine, vinyl ethers, and the like can be used as appropriate.
- 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 mass of the (poly) ethylene oxide chain in the entire polyoxyalkylene chain-containing compound not containing the organopolysiloxane is preferably 5 to 90% by mass, 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 the value of polystyrene conversion obtained by GPC (gel permeation chromatography) here.
- the content of the oxyalkylene group-containing compound is 100 parts by mass of an adhesive polymer (main polymer such as (meth) acrylic polymer, urethane polymer, silicone polymer, etc.) constituting the pressure-sensitive adhesive composition.
- main polymer such as (meth) acrylic polymer, urethane polymer, silicone polymer, etc.
- the antistatic property and light releasability (removability) of the pressure-sensitive adhesive sheet of the present invention can be easily achieved, which is preferable.
- 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.
- the pressure-sensitive adhesive composition is an acrylic pressure-sensitive adhesive containing the (meth) acrylic polymer
- the constitutional unit, the structural ratio, the selection and addition ratio of the cross-linking agent, etc. are appropriately determined.
- an isocyanate compound As the cross-linking 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 compounds include aliphatic polyisocyanates such as trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate (HDI), dimer acid diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate (IPDI), 1, Alicyclic isocyanates such as 3-bis (isocyanatomethyl) cyclohexane, aromatic isocyanates such as 2,4-tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, xylylene diisocyanate (XDI), and the isocyanate compound Allophanate bond, biuret bond, isocyanurate bond, uretdione bond, urea bond, carbodiimide bond Uretonimine bond, polyisocynate modified products thereof obtained by modifying the like oxadiazinetrione bond
- These isocyanate compounds may be used alone, or may be used in combination of two or more, and a bifunctional isocyanate compound and a trifunctional or higher isocyanate compound may be used in combination.
- a cross-linking agent in combination it is possible to achieve both stickiness and resilience (adhesiveness to a curved surface), and a pressure-sensitive adhesive sheet with better adhesion reliability can be obtained.
- the blending ratio (mass ratio) of both compounds is [bifunctional isocyanate compound] / [3
- the functional or higher isocyanate compound] (mass ratio) is preferably 0.1 / 99.9 to 50/50, more preferably 0.1 / 99.9 to 20/80, and 0.1 / 99 9.9 to 10/90 is more preferable, 0.1 / 99.9 to 5/95 is more preferable, and 0.1 / 99.9 to 1/99 is most preferable.
- 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 of the crosslinking agent used in the present invention is, for example, preferably 0.01 to 20 parts by mass, and 0.1 to 15 parts by mass with respect to 100 parts by mass of the (meth) acrylic polymer. More preferred is 0.5 to 10 parts by mass, still more preferred is 1 to 6 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 resulting pressure-sensitive adhesive layer becomes small, and sufficient heat resistance may not be obtained, It tends to cause glue residue.
- the pressure-sensitive adhesive composition may further contain a cross-linking catalyst for more effectively proceeding with any of the cross-linking reactions described above.
- 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 of the crosslinking catalyst is not particularly limited, but is preferably about 0.0001 to 1 part by mass, for example, 0.001 to 0.5 part with respect to 100 parts by mass of the (meth) acrylic polymer. Part by mass is more preferable. Within the above range, when the pressure-sensitive adhesive layer is formed, the speed of the cross-linking reaction is high, and the pot life of the pressure-sensitive adhesive composition is lengthened.
- the pressure-sensitive adhesive composition may contain a compound that causes keto-enol tautomerism.
- 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
- 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 may contain other known additives, for example, powders such as lubricants, colorants, pigments, plasticizers, tackifiers, low molecular weight polymers, surface lubrication.
- powders such as lubricants, colorants, pigments, plasticizers, tackifiers, low molecular weight polymers, surface lubrication.
- the pressure-sensitive adhesive sheet of the present invention is formed by forming the pressure-sensitive adhesive layer on at least one surface of a substrate film.
- the pressure-sensitive adhesive composition is generally crosslinked after the pressure-sensitive adhesive composition is applied.
- the method for forming the pressure-sensitive adhesive layer on the base film is not particularly limited.
- the pressure-sensitive adhesive layer is formed by applying the pressure-sensitive adhesive composition (solution) to the base film and removing the polymerization solvent by drying. It is produced by forming on a base film. Thereafter, curing may be performed for the purpose of adjusting the component transfer of the pressure-sensitive adhesive layer or adjusting the crosslinking reaction.
- the pressure-sensitive adhesive composition when the pressure-sensitive adhesive composition is applied on the base film to prepare a pressure-sensitive adhesive sheet, the pressure-sensitive adhesive composition includes at least one solvent other than the polymerization solvent so that the pressure-sensitive adhesive composition can be uniformly applied onto the base film. May be newly added.
- a known method used for the production of pressure-sensitive adhesive tapes is used as a method for forming the pressure-sensitive adhesive layer when producing the pressure-sensitive adhesive sheet of the present invention.
- a known method used for the production of pressure-sensitive adhesive tapes 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 3 to 100 ⁇ m, preferably about 5 to 50 ⁇ m. It is preferable for the thickness of the pressure-sensitive adhesive layer to be within the above range because it is easy to obtain an appropriate balance between removability and adhesiveness.
- the total thickness of the pressure-sensitive adhesive sheet of the present invention is preferably 8 to 300 ⁇ m, more preferably 10 to 200 ⁇ m, and most preferably 20 to 100 ⁇ m. Within the above range, the adhesive properties (removability, adhesiveness, etc.), workability, and appearance properties are excellent and a preferred embodiment is obtained.
- the said total thickness means the sum total of the thickness containing all layers, such as a base film, an adhesive layer, and another layer.
- a separator is attached to the surface of the pressure-sensitive adhesive layer opposite to the surface that contacts the base film.
- the 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 because of its 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 ionic group-containing silicone is preferably present (applied) on the surface of the separator that contacts the pressure-sensitive adhesive layer (see FIG. 1).
- the separator is attached to the pressure-sensitive adhesive layer due to the presence of the ionic group-containing silicone on the surface of the separator that contacts the pressure-sensitive adhesive layer (applied or forming a coating film)
- the ionic group-containing silicone is transferred (transferred) from the separator surface to the pressure-sensitive adhesive layer surface, and the pressure-sensitive adhesive layer is attached to the surface of the adherend (for example, a polarizing plate) in a high-temperature environment.
- the ionic group-containing silicone does not penetrate into the adherend (from the surface of the adherend to the inside of the adherend), and the release charging characteristics are stable over time, and antistatic performance over a long period of time. Is maintained, which is a preferred embodiment.
- the optical member of the present invention is preferably pasted (protected) by the pressure-sensitive adhesive sheet. Since the pressure-sensitive adhesive sheet is excellent in antistatic properties and stability over time of the stripping voltage, it can be used for surface protection applications (surface protection film) during processing, transportation, shipment, etc. It is useful for protecting the surface. 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 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 mass (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 pressure-sensitive adhesive sheet according to each example was cut to a size of 70 mm in width and 130 mm in length, the release liner was peeled off, and then bonded to a glass plate (manufactured by Nitto Denko Corporation, SEG1423DU polarizing plate, width: 70 mm, length) : 100 mm) was pressure-bonded with a hand roller so that one end of the pressure-sensitive adhesive sheet protruded 30 mm from the end of the polarizing plate. After this sample was left in an environment of 23 ° C. ⁇ 50% RH for one day, it was set at a predetermined position on a sample fixing base 30 having a height of 20 mm as shown in FIG.
- the end of the pressure-sensitive adhesive sheet (surface protective film) 1 that protruded 30 mm from the polarizing plate 20 was fixed to an automatic winder (not shown), and was peeled so that the peeling angle was 150 ° and the peeling speed was 30 m / min.
- the potential measuring device 40 model “STATIRON DZ-4”, manufactured by Sicid Electrostatic Co., Ltd.) in which the potential of the adherend (polarizing plate) surface generated at this time is fixed at a position 30 mm in height from the center of the polarizing plate 20. ), The “initial peel voltage” was measured. The measurement was performed in an environment of 23 ° C. and 50% RH.
- the pressure-sensitive adhesive sheet according to each example was cut to a size of 70 mm in width and 130 mm in length, the release liner was peeled off, and then bonded to a glass plate (manufactured by Nitto Denko Corporation, SEG1423DU polarizing plate, width: 70 mm, length) : 100 mm) was pressure-bonded with a hand roller so that one end of the pressure-sensitive adhesive sheet protruded 30 mm from the end of the polarizing plate. After leaving this sample in an environment of 70 ° C. for 120 hours, as shown in FIG. 2, it was set at a predetermined position on a sample fixing base 30 having a height of 20 mm.
- the end of the pressure-sensitive adhesive sheet (surface protective film) 1 that protruded 30 mm from the polarizing plate 20 was fixed to an automatic winder (not shown), and was peeled so that the peeling angle was 150 ° and the peeling speed was 30 m / min.
- the potential measuring device 40 model “STATIRON DZ-4”, manufactured by Sicid Electrostatic Co., Ltd.) in which the potential of the adherend (polarizing plate) surface generated at this time is fixed at a position 30 mm in height from the center of the polarizing plate 20. ), “70 ° C. storage peeling voltage” was measured. The measurement was performed in an environment of 23 ° C. and 50% RH.
- peeling voltage (kV) absolute value
- it is 0.55 or less, More preferably, it is 0.5 or less, Furthermore, Preferably, it is 0.45 or less.
- the pressure-sensitive adhesive sheet peeled off at the initial stage and after storage at 70 ° C. for 120 hours is not charged, is excellent in antistatic properties and peeling charging characteristics over time, and is excellent in workability. .
- Antistatic by diluting 10 parts by weight of antistatic agent (manufactured by Solvex, Microsolver RMd-142, mainly composed of tin oxide and polyester resin) with a mixed solvent consisting of 30 parts by weight of water and 70 parts by weight of methanol An agent solution was prepared. The obtained antistatic agent solution was applied onto a polyethylene terephthalate (PET) film (thickness: 38 ⁇ m) using a Meyer bar and dried at 130 ° C. for 1 minute to remove the solvent and remove the antistatic layer (thickness). Thickness: 0.2 ⁇ m) to form an antistatic film.
- PET polyethylene terephthalate
- Example 2 Instead of the acrylic polymer (1) used in Example 1, the acrylic polymer (2) was used. Further, instead of the ionic group-containing silicone X-40-2450, the ionic group-containing silicone X-40-2750 was used. A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that was used.
- Example 3 Instead of the acrylic polymer (1) used in Example 1, an acrylic polymer (2) was used, and 0.5 parts by mass of an oxyalkylene group-containing compound KF353 (manufactured by Shin-Etsu Chemical Co., Ltd.) containing an organopolysiloxane was added. And the adhesive sheet was produced by the method similar to Example 1.
- an acrylic polymer (2) was used, and 0.5 parts by mass of an oxyalkylene group-containing compound KF353 (manufactured by Shin-Etsu Chemical Co., Ltd.) containing an organopolysiloxane was added.
- the adhesive sheet was produced by the method similar to Example 1.
- Example 4 Instead of the acrylic polymer (1) used in Example 1, an acrylic polymer (2) was used, and an oxyalkylene group-containing compound latemul PD-420 (manufactured by Kao Corporation) 0.2 containing no organopolysiloxane was used. A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 with the addition of parts by mass.
- Examples 5 to 7 Instead of the acrylic polymer (1) used in Example 1, the acrylic polymer (2) was used, and X-40-2450 was used in the same manner as in Example 1, using the addition amount described in the table. An adhesive sheet was prepared.
- Example 9> (Preparation of silicone adhesive solution)
- a silicone adhesive “X-40-3229” (solid content 60 mass%, manufactured by Shin-Etsu Chemical Co., Ltd.) is 100 mass parts in solid content, and as a platinum catalyst, “CAT-PL-50T” (Shin-Etsu Chemical Co., Ltd.). 0.5 parts by mass), 0.5 parts by mass of ionic group-containing silicone X-40-2450 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 100 parts by mass of toluene as a solvent were blended to obtain a silicone pressure-sensitive adhesive solution. . And the adhesive sheet which adjusted the heating conditions etc. and the thickness of the adhesive layer obtained by the method similar to Example 1 was produced.
- Example 5 A pressure-sensitive adhesive sheet was produced in the same manner as in Example 3 except that EMIFSI was used instead of the ionic group-containing silicone used in Example 3.
- Table 1 shows the results of the above-described blending contents, various measurements and evaluations for the pressure-sensitive adhesive sheets according to Examples and Comparative Examples. The abbreviations in Table 1 will be described below.
- KF353 Organopolysiloxane having an oxyalkylene chain (HLB value: 10), manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-353
- PD420 Oxyalkylene group-containing compound containing no organopolysiloxane (HLB value: 12.6), manufactured by Kao Corporation, trade name: Latemul PD-420
- the pressure-sensitive adhesive sheet disclosed herein protects the optical member during production, transportation and the like of an optical member used as a component of a liquid crystal display panel, a plasma display panel (PDP), an organic electroluminescence (EL) display, or the like. Therefore, it is suitable as a surface protective film.
- surface protective films optical surfaces
- optical members such as polarizing plates (polarizing films) for liquid crystal display panels, wave plates, phase difference plates, optical compensation films, brightness enhancement films, light diffusion sheets, and reflective sheets It is useful as a protective film.
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Abstract
Description
(R1~R4は、同一でも異なっていてもよく、炭素数1~10のアルキル基、アルコキシ基、アリール基、アリサイクリック基、フッ素置換アルキル基、イオン性基のいずれかを含み、R1~R4のうち1つ以上にイオン性基を含む。nは0~100の整数である。) That is, the pressure-sensitive adhesive composition of the present invention comprises a pressure-sensitive polymer and an ionic group-containing silicone represented by the following formula (1).
(R 1 to R 4 may be the same or different and include any of an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, an alicyclic group, a fluorine-substituted alkyl group, and an ionic group, One or more of R 1 to R 4 contain an ionic group, and n is an integer of 0 to 100.)
ここに開示される粘着シートは、一般に、粘着テープ、粘着ラベル、粘着フィルム等と称される形態のものであり、特に光学部品(例えば、偏光板、波長板等の液晶ディスプレイパネル構成要素として用いられる光学部品)の加工時や搬送時に光学部品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。 <Overall structure of adhesive sheet (surface protective film)>
The pressure-sensitive adhesive sheet disclosed herein is generally in a form referred to as a pressure-sensitive adhesive tape, pressure-sensitive adhesive label, pressure-sensitive adhesive film, etc., and particularly used as an optical component (for example, a liquid crystal display panel component such as a polarizing plate or a wave plate). It is suitable as a surface protective film for protecting the surface of the optical component during processing or transport of the optical component. 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. In addition, the surface protective film disclosed herein may be in the form of a roll or a single sheet.
本発明の粘着シート(表面保護フィルム)は、基材フィルムを有す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。 <Base film>
The pressure-sensitive adhesive sheet (surface protective film) of the present invention has a base film. In the technology disclosed herein, 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. In particular, since the base film has flexibility, 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.
本発明の粘着シートは、前記粘着剤層を有し、前記粘着剤層は粘着剤組成物から形成されるものであり、前記粘着剤組成物としては、粘着性を有するものであれば、特に制限なく使用できる。前記粘着剤組成物としては、例えば、アクリル系粘着剤、ウレタン系粘着剤、合成ゴム系粘着剤、天然ゴム系粘着剤、シリコーン系粘着剤等を使用することもでき、中でも、より好ましくは、アクリル系粘着剤、ウレタン系粘着剤、及び、シリコーン系粘着剤からなる群より選択される少なくとも1種であり、特に好ましくは、粘着性ポリマーである(メタ)アクリル系ポリマーを使用するアクリル系粘着剤を使用することである。 <Adhesive composition>
The pressure-sensitive adhesive sheet of the present invention has the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive layer is formed from a pressure-sensitive adhesive composition. Can be used without limitation. As the pressure-sensitive adhesive composition, for example, an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, a synthetic rubber-based pressure-sensitive adhesive, a natural rubber-based pressure-sensitive adhesive, a silicone-based pressure-sensitive adhesive, and the like can be used. Acrylic adhesive using a (meth) acrylic polymer, which is at least one selected from the group consisting of an acrylic adhesive, a urethane adhesive, and a silicone adhesive, particularly preferably an adhesive polymer Is to use the agent.
本発明の粘着剤組成物は、粘着性ポリマー、及び、下記式(1)で表されるイオン性基含有シリコーンを含有することを特徴とする。前記粘着剤組成物に、イオン性基含有シリコーンを含むことで、シリコーン鎖の低表面自由エネルギーにより、粘着剤層を被着体(例えば、偏光板)表面に貼付した状態で、高温環境下で保存した場合であっても、被着体中に前記イオン性基含有シリコーンが(被着体表面から被着体内部へ)浸透せず、粘着剤層表面に留まろうとするため、経時でも剥離帯電特性が安定し、長期で帯電防止性能が維持され、好ましい態様となる。なお、前記粘着剤層の「内部」とは、例えば、前記イオン性基含有シリコーンを配合した前記粘着剤組成物を用いて粘着剤層を形成した場合に、前記粘着剤層中に含まれる場合を指す。また、前記粘着剤層の「表面」とは、例えば、前記イオン性基含有シリコーンを配合した、もしくは、配合していない前記粘着剤組成物を用いて粘着剤層を形成した場合に、前記粘着剤層表面を保護するため貼付されるセパレータ表面に、予め、前記イオン性基含有シリコーンが塗布(積層)しておき、前記セパレータを前記粘着剤層の貼付した場合に、前記セパレータ表面から、前記イオン性基含有シリコーンが前記粘着剤層表面に転写(移行)される場合を指す。
なお、上記式(1)中のR1~R4は、同一でも異なっていてもよく、炭素数1~10のアルキル基、アルコキシ基、アリール基、アリサイクリック基、フッ素置換アルキル基、イオン性基のいずれかを含み、R1~R4のうち1つ以上にイオン性基を含む。nは0~100の整数である。 <Ionic group-containing silicone>
The pressure-sensitive adhesive composition of the present invention is characterized by containing a pressure-sensitive polymer and an ionic group-containing silicone represented by the following formula (1). By containing the ionic group-containing silicone in the pressure-sensitive adhesive composition, the adhesive layer is stuck on the surface of the adherend (for example, a polarizing plate) under a high temperature environment by the low surface free energy of the silicone chain. Even when stored, the ionic group-containing silicone does not penetrate into the adherend (from the adherend surface to the inside of the adherend) and tends to stay on the surface of the adhesive layer. The charging characteristics are stable, the antistatic performance is maintained for a long time, and this is a preferred embodiment. The “inside” of the pressure-sensitive adhesive layer is, for example, included in the pressure-sensitive adhesive layer when the pressure-sensitive adhesive layer is formed using the pressure-sensitive adhesive composition containing the ionic group-containing silicone. Point to. In addition, the “surface” of the pressure-sensitive adhesive layer refers to, for example, when the pressure-sensitive adhesive layer is formed using the pressure-sensitive adhesive composition in which the ionic group-containing silicone is blended or not blended. In order to protect the surface of the agent layer, the ionic group-containing silicone is previously applied (laminated) to the separator surface to be attached, and when the separator is attached to the pressure-sensitive adhesive layer, from the separator surface, This refers to the case where the ionic group-containing silicone is transferred (transferred) to the surface of the pressure-sensitive adhesive layer.
In the above formula (1), R 1 to R 4 may be the same or different, and are an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, an alicyclic group, a fluorine-substituted alkyl group, an ion One of R 1 to R 4 is included, and an ionic group is included in one or more of R 1 to R 4 . n is an integer of 0 to 100.
上記式(a)中のR5~R7は、同一でも異なっていてもよく、炭素数1~10のアルキル基、アリール基、フッ素置換アルキル基のいずれかを示す。mは1~10の整数である。
R 5 to R 7 in the above formula (a) may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms, an aryl group, or a fluorine-substituted alkyl group. m is an integer of 1 to 10.
上記式(b)中のR8~R10は、同一でも異なっていてもよく、炭素数1~10のアルキル基、アリール基、フッ素置換アルキル基のいずれかを示す。mは1~10の整数である。
R 8 to R 10 in the above formula (b) may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms, an aryl group, or a fluorine-substituted alkyl group. m is an integer of 1 to 10.
上記式(c)中のR11、R12は、同一でも異なっていてもよく、炭素数1~10のアルキル基、アリール基、フッ素置換アルキル基のいずれかを示し、R11、R12は環を形成していてもよく、その場合はアルキレン基を表す。mは1~10の整数、pは1~6の整数である。
R 11 and R 12 in the above formula (c) may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms, an aryl group, or a fluorine-substituted alkyl group, and R 11 and R 12 are A ring may be formed, and in that case, an alkylene group is represented. m is an integer of 1 to 10, and p is an integer of 1 to 6.
上記式(d)中のR13、R14は、同一でも異なっていてもよく、炭素数1~10のアルキル基、アリール基、フッ素置換アルキル基のいずれかを示し、R13、R14は環を形成してもよく、その場合はアルキレン基を表す。mは1~10の整数、pは1~6の整数である。
R 13 and R 14 in the above formula (d) may be the same or different and each represents an alkyl group having 1 to 10 carbon atoms, an aryl group, or a fluorine-substituted alkyl group, and R 13 and R 14 are A ring may be formed, and in that case, an alkylene group is represented. m is an integer of 1 to 10, and p is an integer of 1 to 6.
本発明の粘着剤組成物は、オキシアルキレン基含有化合物を含有することが好ましく、中でも、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より好ましく、オキシアルキレン主鎖を有するオルガノポリシロキサンを含有することが、更に好ましい。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。 <Oxyalkylene group-containing compound>
The pressure-sensitive adhesive composition of the present invention preferably contains an oxyalkylene group-containing compound, more preferably contains an organopolysiloxane having an oxyalkylene chain, and contains an organopolysiloxane having an oxyalkylene main chain. More preferably. By using the organopolysiloxane, it is presumed that the surface free energy on the surface of the pressure-sensitive adhesive is reduced and light release is realized.
なお、上記式(2)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。 As the organopolysiloxane, a known organopolysiloxane having a polyoxyalkylene main chain can be used as appropriate, and is preferably represented by the following formula (2).
In the above formula (2), 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 the oxyalkylene chain may be an alkoxy group or a hydroxyl group. In addition, either R 1 or R 2 may be a hydroxyl group, or may be an alkyl group or an alkoxy group, and a part of the alkyl group or alkoxy group is substituted with a hetero atom. It may be. n is an integer of 1 to 300.
なお、上記式(3)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。) In addition to the above-described organosiloxane having (bonding) an oxyalkylene chain, it is also possible to use an organosiloxane having (bonding) an oxyalkylene chain in the side chain. It is more preferable to use an organosiloxane having an oxyalkylene chain. As the organopolysiloxane, a known organopolysiloxane having a polyoxyalkylene side chain can be used as appropriate, and is preferably represented by the following formula (3).
In the above formula (3), 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, and m and n are integers from 0 to 1000. However, m and n are not 0 at the same time. a and b are integers from 0 to 100. However, a and b are not 0 at the same time. )
本発明の粘着シート(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、前記粘着剤組成物が、前記(メタ)アクリル系ポリマーを含有するアクリル系粘着剤の場合、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粘着シート(粘着剤層)を得ることができる。 <Crosslinking agent>
In the pressure-sensitive adhesive sheet (surface protective film) of the present invention, 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. For example, in the case where the pressure-sensitive adhesive composition is an acrylic pressure-sensitive adhesive containing the (meth) acrylic polymer, the constitutional unit, the structural ratio, the selection and addition ratio of the cross-linking agent, etc. are appropriately determined. By adjusting and crosslinking, a pressure-sensitive adhesive sheet (pressure-sensitive adhesive layer) having more excellent heat resistance can be obtained.
本発明の粘着シートは、前記粘着剤層を基材フィルムの少なくとも片面に形成してなるものであるが、その際、粘着剤組成物の架橋は、粘着剤組成物の塗布後に行うのが一般的であるが、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。 <Adhesive layer and adhesive sheet (surface protective film)>
The pressure-sensitive adhesive sheet of the present invention is formed by forming the pressure-sensitive adhesive layer on at least one surface of a substrate film. In this case, the pressure-sensitive adhesive composition is generally crosslinked after the pressure-sensitive adhesive composition is applied. As a matter of course, it is also possible to transfer a pressure-sensitive adhesive layer comprising a pressure-sensitive adhesive composition after crosslinking to a substrate film or the like.
本発明の粘着シートには、前記粘着剤層の前記基材フィルムと接触する面と反対面に、セパレータが貼付することが好ましい。前記セパレータは、必要に応じて粘着面を保護する目的で、粘着剤層表面にセパレータを貼り合わせることが可能である。 <Separator>
In the pressure-sensitive adhesive sheet of the present invention, it is preferable that a separator is attached to the surface of the pressure-sensitive adhesive layer opposite to the surface that contacts the base film. The 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.
本発明の光学部材は、前記粘着シートにより貼付(保護)されていることが好ましい。前記粘着シートは、帯電防止性と剥離帯電圧の経時安定性に優れるため、加工、搬送、出荷時等の表面保護用途(表面保護フィルム)に使用できるため、前記光学部材(偏光板など)の表面を保護するために、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。 <Optical member>
The optical member of the present invention is preferably pasted (protected) by the pressure-sensitive adhesive sheet. Since the pressure-sensitive adhesive sheet is excellent in antistatic properties and stability over time of the stripping voltage, it can be used for surface protection applications (surface protection film) during processing, transportation, shipment, etc. It is useful for protecting the surface. 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.
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質量%(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。 <Measurement of weight average molecular weight (Mw)>
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 mass (THF solution)
Sample injection volume: 10 μl
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.
各例に係る粘着シートを幅70mm、長さ130mmのサイズにカットし、剥離ライナーを剥離した後、ガラス板に貼り合わせた偏光板(日東電工社製、SEG1423DU偏光板、幅:70mm、長さ:100mm)の表面に、粘着シートの片方の端部が偏光板の端から30mmはみ出すようにして、ハンドローラーにて圧着した。
このサンプルを23℃×50%RHの環境下に1日放置した後、図2に示すように、高さ20mmのサンプル固定台30の所定の位置にセットした。偏光板20から30mmはみ出した粘着シート(表面保護フィルム)1の端部を自動巻取り機(図示せず)に固定し、剥離角度150°、剥離速度30m/minとなるように剥離した。このときに発生する被着体(偏光板)表面の電位を、偏光板20の中央から高さ30mmの位置に固定してある電位測定器40(シシド静電気社製、型式「STATIRON DZ-4」)にて、「初期剥離帯電圧」を測定した。測定は、23℃、50%RHの環境下で行った。 <Measurement of initial peeling voltage>
The pressure-sensitive adhesive sheet according to each example was cut to a size of 70 mm in width and 130 mm in length, the release liner was peeled off, and then bonded to a glass plate (manufactured by Nitto Denko Corporation, SEG1423DU polarizing plate, width: 70 mm, length) : 100 mm) was pressure-bonded with a hand roller so that one end of the pressure-sensitive adhesive sheet protruded 30 mm from the end of the polarizing plate.
After this sample was left in an environment of 23 ° C. × 50% RH for one day, it was set at a predetermined position on a
各例に係る粘着シートを幅70mm、長さ130mmのサイズにカットし、剥離ライナーを剥離した後、ガラス板に貼り合わせた偏光板(日東電工社製、SEG1423DU偏光板、幅:70mm、長さ:100mm)の表面に、粘着シートの片方の端部が偏光板の端から30mmはみ出すようにして、ハンドローラーにて圧着した。
このサンプルを70℃の環境下に120時間放置した後、図2に示すように、高さ20mmのサンプル固定台30の所定の位置にセットした。偏光板20から30mmはみ出した粘着シート(表面保護フィルム)1の端部を自動巻取り機(図示せず)に固定し、剥離角度150°、剥離速度30m/minとなるように剥離した。このときに発生する被着体(偏光板)表面の電位を、偏光板20の中央から高さ30mmの位置に固定してある電位測定器40(シシド静電気社製、型式「STATIRON DZ-4」)にて、「70℃保存剥離帯電圧」を測定した。測定は、23℃、50%RHの環境下で行った。 <Measurement of 70 ° C storage peeling voltage>
The pressure-sensitive adhesive sheet according to each example was cut to a size of 70 mm in width and 130 mm in length, the release liner was peeled off, and then bonded to a glass plate (manufactured by Nitto Denko Corporation, SEG1423DU polarizing plate, width: 70 mm, length) : 100 mm) was pressure-bonded with a hand roller so that one end of the pressure-sensitive adhesive sheet protruded 30 mm from the end of the polarizing plate.
After leaving this sample in an environment of 70 ° C. for 120 hours, as shown in FIG. 2, it was set at a predetermined position on a
各例に係る粘着シートを幅50mm、長さ80mmのサイズにカットし、セパレータを剥離した後、TAC偏光板(日東電工社製、SEG1423DU偏光板、幅:70mm、長さ:100mm)に気泡を入れながらハンドローラーにて圧着し、評価サンプルを作製した。上記評価サンプルを70℃の環境下に120時間放置した後、粘着シートを被着体から手で剥離し、その際の被着体表面の気泡跡を目視にて観察した。なお、評価は、気泡跡が認められなかった場合を○、気泡跡が認められた場合を×とした。 <Presence of contamination (contamination resistance)>
After the pressure-sensitive adhesive sheet according to each example was cut to a size of 50 mm in width and 80 mm in length and the separator was peeled off, bubbles were formed in the TAC polarizing plate (manufactured by Nitto Denko Corporation, SEG1423DU polarizing plate, width: 70 mm, length: 100 mm). While being put, it was pressure-bonded with a hand roller to prepare an evaluation sample. The evaluation sample was allowed to stand in an environment of 70 ° C. for 120 hours, and then the pressure-sensitive adhesive sheet was peeled off from the adherend by hand, and the bubble marks on the adherend surface at that time were visually observed. In the evaluation, a case where no bubble trace was observed was marked as ◯, and a case where a bubble trace was recognized was marked as x.
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)96質量部、2-ヒドロキシエチルアクリレート(HEA)4質量部、重合開始剤として2,2’-アゾビスイソブチロニトリル0.2質量部、酢酸エチル150質量部を仕込み、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、アクリル系ポリマー(1)溶液(40質量%)を調製した。前記アクリル系ポリマー(1)の重量平均分子量(Mw)は、54万であった。 <Preparation of acrylic polymer (1)>
In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser, 96 parts by mass of 2-ethylhexyl acrylate (2EHA), 4 parts by mass of 2-hydroxyethyl acrylate (HEA), 2 as a polymerization initiator , 2'-azobisisobutyronitrile and 0.2 parts by weight of ethyl acetate were charged, nitrogen gas was introduced while gently stirring, and the temperature in the flask was kept at around 65 ° C. for 6 hours. Reaction was performed and the acrylic polymer (1) solution (40 mass%) was prepared. The acrylic polymer (1) had a weight average molecular weight (Mw) of 540,000.
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)91質量部、4-ヒドロキシブチルアクリレート(4HBA)9質量部、アクリル酸(AA)0.02質量部、重合開始剤として2,2’-アゾビスイソブチロニトリル0.2質量部、酢酸エチル150質量部を仕込み、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、アクリル系ポリマー(2)溶液(40質量%)を調製した。前記アクリル系ポリマー(2)の重量平均分子量(Mw)は、54万であった。 <Preparation of acrylic polymer (2)>
In a four-necked flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube, and a condenser, 91 parts by mass of 2-ethylhexyl acrylate (2EHA), 9 parts by mass of 4-hydroxybutyl acrylate (4HBA), acrylic acid (AA) 0.02 parts by mass, 0.22 parts by mass of 2,2′-azobisisobutyronitrile as a polymerization initiator and 150 parts by mass of ethyl acetate were introduced, nitrogen gas was introduced while gently stirring, and the liquid in the flask A polymerization reaction was carried out for 6 hours while maintaining the temperature at around 65 ° C. to prepare an acrylic polymer (2) solution (40 mass%). The acrylic polymer (2) had a weight average molecular weight (Mw) of 540,000.
〔アクリル系粘着剤溶液の調製〕
上記アクリル系ポリマー(1)溶液(40質量%)を酢酸エチルで20質量%に希釈し、この溶液500質量部(固形分100質量部)に、イオン性基含有シリコーン(X-40-2450、信越化学工業社製)を酢酸エチルで10%に希釈した溶液5質量部(固形分0.5質量部)、架橋剤として、3官能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)2質量部(固形分2質量部)、架橋触媒としてジラウリン酸ジブチルスズ(1質量%酢酸エチル溶液)3質量部(固形分0.03質量部)を加えて、混合攪拌を行い、アクリル系粘着剤溶液を調製した。 <Example 1>
[Preparation of acrylic adhesive solution]
The acrylic polymer (1) solution (40% by mass) is diluted with ethyl acetate to 20% by mass, and ionic group-containing silicone (X-40-2450, 5 parts by weight (manufactured by Shin-Etsu Chemical Co., Ltd.) diluted to 10% with ethyl acetate (solid content 0.5 parts by weight), and isocyanurate of hexamethylene diisocyanate, a trifunctional isocyanate compound (made by Tosoh Corporation) as a crosslinking agent , Coronate HX) 2 parts by mass (solid content 2 parts by mass), 3 parts by mass of dibutyltin dilaurate (1% by mass ethyl acetate solution) (solid content 0.03 parts by mass) as a crosslinking catalyst, mixed and stirred, An acrylic pressure-sensitive adhesive solution was prepared.
帯電防止剤(ソルベックス社製、マイクロソルバーRMd-142、酸化スズとポリエステル樹脂を主成分とする)10質量部を、水30質量部とメタノール70質量部からなる混合溶媒で希釈することにより帯電防止剤溶液を調製した。
得られた帯電防止剤溶液を、ポリエチレンテレフタレート(PET)フィルム(厚さ:38μm)上にマイヤーバーを用いて塗布し、130℃で1分間乾燥することにより溶剤を除去して帯電防止層(厚さ:0.2μm)を形成し、帯電防止処理フィルムを作製した。 [Preparation of antistatic film]
Antistatic by diluting 10 parts by weight of antistatic agent (manufactured by Solvex, Microsolver RMd-142, mainly composed of tin oxide and polyester resin) with a mixed solvent consisting of 30 parts by weight of water and 70 parts by weight of methanol An agent solution was prepared.
The obtained antistatic agent solution was applied onto a polyethylene terephthalate (PET) film (thickness: 38 μm) using a Meyer bar and dried at 130 ° C. for 1 minute to remove the solvent and remove the antistatic layer (thickness). Thickness: 0.2 μm) to form an antistatic film.
上記アクリル系粘着剤溶液を、上記の帯電防止処理フィルムの帯電防止処理面とは反対の面に塗布し、130℃で2分間加熱して、厚さ15μmの粘着剤層を形成した。次いで、上記粘着剤層の表面に、片面にシリコーン処理を施したポリエチレンテレフタレートフィルム(厚さ25μm)のシリコーン処理面を貼り合わせ、粘着シートを作製した。 [Production of adhesive sheet (surface protective film)]
The acrylic pressure-sensitive adhesive solution was applied to the surface opposite to the antistatic surface of the antistatic film and heated at 130 ° C. for 2 minutes to form a pressure-sensitive adhesive layer having a thickness of 15 μm. Next, a silicone-treated surface of a polyethylene terephthalate film (thickness 25 μm) having a silicone treatment on one side was bonded to the surface of the pressure-sensitive adhesive layer to produce a pressure-sensitive adhesive sheet.
実施例1で使用したアクリル系ポリマー(1)の代わりに、アクリル系ポリマー(2)を用い、さらにイオン性基含有シリコーンX-40-2450の代わりに、イオン性基含有シリコーンX-40-2750を用いた以外は、実施例1と同様の方法で、粘着シートを作製した。 <Example 2>
Instead of the acrylic polymer (1) used in Example 1, the acrylic polymer (2) was used. Further, instead of the ionic group-containing silicone X-40-2450, the ionic group-containing silicone X-40-2750 was used. A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 except that was used.
実施例1で使用したアクリル系ポリマー(1)の代わりに、アクリル系ポリマー(2)を用い、さらにオルガノポリシロキサンを含むオキシアルキレン基含有化合物KF353(信越化学社製)0.5質量部を添加し、実施例1と同様の方法で、粘着シートを作製した。 <Example 3>
Instead of the acrylic polymer (1) used in Example 1, an acrylic polymer (2) was used, and 0.5 parts by mass of an oxyalkylene group-containing compound KF353 (manufactured by Shin-Etsu Chemical Co., Ltd.) containing an organopolysiloxane was added. And the adhesive sheet was produced by the method similar to Example 1. FIG.
実施例1で使用したアクリル系ポリマー(1)の代わりに、アクリル系ポリマー(2)を用い、さらにオルガノポリシロキサンを含まないオキシアルキレン基含有化合物のラテムルPD-420(花王社製)0.2質量部を添加し、実施例1と同様の方法で、粘着シートを作製した。 <Example 4>
Instead of the acrylic polymer (1) used in Example 1, an acrylic polymer (2) was used, and an oxyalkylene group-containing compound latemul PD-420 (manufactured by Kao Corporation) 0.2 containing no organopolysiloxane was used. A pressure-sensitive adhesive sheet was produced in the same manner as in Example 1 with the addition of parts by mass.
実施例1で使用したアクリル系ポリマー(1)の代わりに、アクリル系ポリマー(2)を用い、X-40-2450を表中に記載の添加量を用い、実施例1と同様の方法で、粘着シートを作製した。 <Examples 5 to 7>
Instead of the acrylic polymer (1) used in Example 1, the acrylic polymer (2) was used, and X-40-2450 was used in the same manner as in Example 1, using the addition amount described in the table. An adhesive sheet was prepared.
〔ウレタン系粘着剤溶液の調製〕
ポリオールとして、ヒドロキシル基を3個有するポリオールであるプレミノールS3011(旭硝子社製、Mn=10000)85質量部、ヒドロキシル基を3個有するポリオールであるサンニックスGP3000(三洋化成社製、Mn=3000)13質量部、ヒドロキシル基を3個有するポリオールであるサンニックスGP1000(三洋化成社製、Mn=1000)2質量部、架橋剤としてイソシアネート化合物(コロネートHX:C/HX、日本ポリウレタン社製)18質量部、触媒として、鉄(III)アセチルアセトナート (東京化成工業社製)0.04質量部、イオン性基含有シリコーンX-40-2450(信越化学工業社製)0.5質量部、希釈溶剤として酢酸エチル210質量部を配合し、ウレタン系粘着剤溶液を得た。そして、実施例1と同様の方法で、加熱条件等や得られる粘着剤層の厚みを調整した粘着シートを作製した。 <Example 8>
[Preparation of urethane adhesive solution]
As a polyol, 85 parts by mass of Preminol S3011 (manufactured by Asahi Glass Co., Ltd., Mn = 10000) which is a polyol having three hydroxyl groups, Sanniks GP3000 (manufactured by Sanyo Chemical Co., Ltd., Mn = 3000) 13 which is a polyol having three hydroxyl groups 2 parts by mass of Sannix GP1000 (Sanyo Kasei Co., Ltd., Mn = 1000) which is a polyol having three hydroxyl groups, 18 parts by mass of an isocyanate compound as a crosslinking agent (Coronate HX: C / HX, manufactured by Nippon Polyurethane Co., Ltd.) As a catalyst, iron (III) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.04 parts by mass, ionic group-containing silicone X-40-2450 (manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 parts by mass, as a diluting solvent 210 mass parts of ethyl acetate was mix | blended and the urethane type adhesive solution was obtained. And the adhesive sheet which adjusted the heating conditions etc. and the thickness of the adhesive layer obtained by the method similar to Example 1 was produced.
〔シリコーン系粘着剤溶液の調製〕
シリコーン系粘着剤として、「X-40-3229](固形分60質量%、信越化学工業社製)を固形分で100質量部、白金触媒として、「CAT-PL-50T」(信越化学工業社製)0.5質量部、イオン性基含有シリコーンX-40-2450(信越化学工業社製)0.5質量部、溶剤としてトルエン100質量部を配合して、シリコーン系粘着剤溶液を得た。そして、実施例1と同様の方法で、加熱条件等や得られる粘着剤層の厚みを調整した粘着シートを作製した。 <Example 9>
(Preparation of silicone adhesive solution)
As a silicone adhesive, “X-40-3229” (solid content 60 mass%, manufactured by Shin-Etsu Chemical Co., Ltd.) is 100 mass parts in solid content, and as a platinum catalyst, “CAT-PL-50T” (Shin-Etsu Chemical Co., Ltd.). 0.5 parts by mass), 0.5 parts by mass of ionic group-containing silicone X-40-2450 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 100 parts by mass of toluene as a solvent were blended to obtain a silicone pressure-sensitive adhesive solution. . And the adhesive sheet which adjusted the heating conditions etc. and the thickness of the adhesive layer obtained by the method similar to Example 1 was produced.
実施例2で用いたイオン性基含有シリコーンの代わりに、表1中に記載のイオン性化合物を用いた以外は、実施例2と同様の方法で、粘着シートを作製した。 <Comparative Examples 1 to 4>
Instead of the ionic group-containing silicone used in Example 2, an adhesive sheet was prepared in the same manner as in Example 2 except that the ionic compounds listed in Table 1 were used.
実施例3で用いたイオン性基含有シリコーンの代わりに、EMIFSIを用いた以外は、実施例3と同様の方法で、粘着シートを作製した。 <Comparative Example 5>
A pressure-sensitive adhesive sheet was produced in the same manner as in Example 3 except that EMIFSI was used instead of the ionic group-containing silicone used in Example 3.
KF353:オキシアルキレン鎖を有するオルガノポリシロキサン(HLB値:10)、信越化学工業社製、商品名:KF-353
PD420:オルガノポリシロキサンを含まないオキシアルキレン基含有化合物(HLB値:12.6)、花王社製、商品名:ラテムルPD-420 [Oxyalkylene group-containing compound]
KF353: Organopolysiloxane having an oxyalkylene chain (HLB value: 10), manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KF-353
PD420: Oxyalkylene group-containing compound containing no organopolysiloxane (HLB value: 12.6), manufactured by Kao Corporation, trade name: Latemul PD-420
X-40-2450:イオン性基含有シリコーン、信越化学社製、有効成分55%
X-40-2750:イオン性基含有シリコーン、信越化学社製、有効成分100%
LiTFSI:リチウムビス(トリフルオロメタンスルホニル)イミド、アルカリ金属塩、東京化成社製、有効成分100%
EMIFSI:1-エチル-3-メチルイミダゾリウムビス(フルオロスルホニル)イミド、イオン液体、第一工業製薬社製、有効成分100%
BMPTFSI:1-ブチル-3-メチルピリジニウムビス(トリフルオロメタンスルホニル)イミド、イオン液体、アルドリッチ社製、有効成分100%
MTOATFSI:メチルトリオクチルアンモニウムビス(トリフルオロメタンスルホニル)イミド、和光純薬工業社製、有効成分100% [Ionic compound (antistatic component)]
X-40-2450: ionic group-containing silicone, manufactured by Shin-Etsu Chemical Co., Ltd., 55% active ingredient
X-40-2750: Silicone containing ionic group, manufactured by Shin-Etsu Chemical Co., Ltd., 100% active ingredient
LiTFSI: lithium bis (trifluoromethanesulfonyl) imide, alkali metal salt, manufactured by Tokyo Chemical Industry Co., Ltd., 100% active ingredient
EMISI: 1-ethyl-3-methylimidazolium bis (fluorosulfonyl) imide, ionic liquid, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., 100% active ingredient
BMPTFSI: 1-butyl-3-methylpyridinium bis (trifluoromethanesulfonyl) imide, ionic liquid, manufactured by Aldrich, 100% active ingredient
MTOATFSI: Methyl trioctyl ammonium bis (trifluoromethanesulfonyl) imide, manufactured by Wako Pure Chemical Industries, Ltd., 100% active ingredient
1’:セパレータ付き粘着シート(表面保護フィルム)
10:アクリル板
11:セパレータ
12:イオン性基含有シリコーン塗布膜
13:粘着剤層
14:基材フィルム
20:偏光板
30:サンプル固定台
40:電位測定器
1: Adhesive sheet (surface protective film)
1 ': Adhesive sheet with separator (surface protective film)
DESCRIPTION OF SYMBOLS 10: Acrylic board 11: Separator 12: Ionic group containing silicone coating film 13: Adhesive layer 14: Base film 20: Polarizing plate 30: Sample fixing stand 40: Potential measuring device
Claims (7)
- 粘着性ポリマー、及び、下記式(1)で表されるイオン性基含有シリコーンを含有することを特徴とする粘着剤組成物。
(R1~R4は、同一でも異なっていてもよく、炭素数1~10のアルキル基、アルコキシ基、アリール基、アリサイクリック基、フッ素置換アルキル基、イオン性基のいずれかを含み、R1~R4のうち1つ以上にイオン性基を含む。nは0~100の整数である。) A pressure-sensitive adhesive composition comprising a pressure-sensitive polymer and an ionic group-containing silicone represented by the following formula (1).
(R 1 to R 4 may be the same or different and include any of an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryl group, an alicyclic group, a fluorine-substituted alkyl group, and an ionic group, One or more of R 1 to R 4 contain an ionic group, and n is an integer of 0 to 100.) - オキシアルキレン基含有化合物を含有することを特徴とする請求項1に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1, comprising an oxyalkylene group-containing compound.
- アクリル系粘着剤、ウレタン系粘着剤、及び、シリコーン系粘着剤からなる群より選択される少なくとも1種を含有することを特徴とする請求項1又は2に記載の粘着剤組成物。 The pressure-sensitive adhesive composition according to claim 1 or 2, comprising at least one selected from the group consisting of an acrylic pressure-sensitive adhesive, a urethane-based pressure-sensitive adhesive, and a silicone-based pressure-sensitive adhesive.
- 基材フィルムの少なくとも片面に、請求項1~3のいずれかに記載の粘着剤組成物より形成される粘着剤層を有し、
前記粘着剤層の内部、及び/又は、表面に、前記イオン性基含有シリコーンが存在することを特徴とする粘着シート。 Having a pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition according to any one of claims 1 to 3, on at least one side of the base film;
The pressure-sensitive adhesive sheet, wherein the ionic group-containing silicone is present inside and / or on the surface of the pressure-sensitive adhesive layer. - 前記粘着剤層の前記基材フィルムと接触する面と反対面に、セパレータが貼付されていることを特徴とする請求項4に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 4, wherein a separator is affixed to the surface of the pressure-sensitive adhesive layer opposite to the surface in contact with the base film.
- 前記セパレータの前記粘着剤層と接触する面に、前記イオン性基含有シリコーンが存在することを特徴とする請求項5に記載の粘着シート。 The pressure-sensitive adhesive sheet according to claim 5, wherein the ionic group-containing silicone is present on a surface of the separator that contacts the pressure-sensitive adhesive layer.
- 請求項4に記載の粘着シート、又は、請求項5又は6に記載の粘着シートから前記セパレータを剥離した粘着シートが貼付されていることを特徴とする光学部材。
An optical member comprising the pressure-sensitive adhesive sheet according to claim 4 or a pressure-sensitive adhesive sheet obtained by peeling the separator from the pressure-sensitive adhesive sheet according to claim 5 or 6.
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JP2020003675A (en) * | 2018-06-28 | 2020-01-09 | 日東電工株式会社 | Adhesive composition, surface protection film, and optical film |
JP7465283B2 (en) | 2019-04-22 | 2024-04-10 | サムスン エスディアイ カンパニー,リミテッド | Silicone-based adhesive protective film and optical member including same |
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Also Published As
Publication number | Publication date |
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JP6670389B2 (en) | 2020-03-18 |
KR102117416B1 (en) | 2020-06-01 |
KR20190054143A (en) | 2019-05-21 |
JPWO2018056167A1 (en) | 2019-07-18 |
TW201817845A (en) | 2018-05-16 |
TWI727098B (en) | 2021-05-11 |
CN109790438A (en) | 2019-05-21 |
CN109790438B (en) | 2021-08-31 |
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