WO2012141099A1 - 粘着シート - Google Patents
粘着シート Download PDFInfo
- Publication number
- WO2012141099A1 WO2012141099A1 PCT/JP2012/059522 JP2012059522W WO2012141099A1 WO 2012141099 A1 WO2012141099 A1 WO 2012141099A1 JP 2012059522 W JP2012059522 W JP 2012059522W WO 2012141099 A1 WO2012141099 A1 WO 2012141099A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sensitive adhesive
- pressure
- weight
- acrylic
- layer
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L25/00—Compositions of, 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 an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions 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; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
-
- 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
- C09J165/00—Adhesives based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Adhesives based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
- C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/385—Acrylic polymers
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/14—Protective coatings, e.g. hard coatings
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
- G02B1/16—Optical coatings produced by application to, or surface treatment of, optical elements having an anti-static effect, e.g. electrically conducting coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/13—Morphological aspects
- C08G2261/135—Cross-linked structures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/10—Definition of the polymer structure
- C08G2261/14—Side-groups
- C08G2261/142—Side-chains containing oxygen
- C08G2261/1424—Side-chains containing oxygen containing ether groups, including alkoxy
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
- C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
- C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
- C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/50—Physical properties
- C08G2261/51—Charge transport
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/70—Post-treatment
- C08G2261/76—Post-treatment crosslinking
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G2261/70—Post-treatment
- C08G2261/79—Post-treatment doping
- C08G2261/794—Post-treatment doping with polymeric dopants
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/58—Ethylene oxide or propylene oxide copolymers, e.g. pluronics
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34922—Melamine; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/16—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer
- C09J2301/162—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the structure of the carrier layer the carrier being a laminate constituted by plastic layers only
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
- C09J2433/006—Presence of (meth)acrylic polymer in the substrate
-
- 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
- C09J2465/00—Presence of polyphenylene
- C09J2465/006—Presence of polyphenylene in the substrate
-
- 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
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24479—Structurally defined web or sheet [e.g., overall dimension, etc.] including variation in thickness
- Y10T428/24612—Composite web or sheet
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2848—Three or more layers
Definitions
- the present invention relates to an adhesive sheet that can be re-peeled. More specifically, the present invention relates to a pressure-sensitive adhesive sheet that is excellent in appearance characteristics and that is excellent in prevention of an increase in adhesive strength over time, scratch resistance, and antistatic properties and that can be removed again.
- optical members including optical films such as polarizing plates, retardation plates, and antireflection plates, for the purpose of preventing scratches and dirt on the surface, improving cutting workability, and suppressing cracks
- a surface protective film is used by being attached to the surface of an optical member (see Patent Documents 1 and 2).
- a removable pressure-sensitive adhesive sheet in which a removable pressure-sensitive adhesive layer is provided on the surface of a plastic film substrate is generally used.
- Patent Documents 1 and 2 Conventionally, solvent-based acrylic pressure-sensitive adhesives have been used for these surface protective film applications as pressure-sensitive adhesives for forming the pressure-sensitive adhesive layer (see Patent Documents 1 and 2). Since it contains an organic solvent, conversion to a water-dispersed acrylic pressure-sensitive adhesive is attempted from the viewpoint of work environment at the time of coating (see Patent Documents 3 to 5).
- a water-insoluble crosslinking agent for the adhesive (or adhesive composition) forming the adhesive layer.
- a pressure-sensitive adhesive composition using a water-insoluble crosslinking agent for example, a re-peeling water-dispersed acrylic pressure-sensitive adhesive composition containing an oil-soluble crosslinking agent is known (see Patent Documents 6 and 7).
- the water-dispersed acrylic pressure-sensitive adhesive composition using a water-insoluble crosslinking agent does not sufficiently disperse large particles of the water-insoluble crosslinking agent in the pressure-sensitive adhesive composition. Due to this, when forming the pressure-sensitive adhesive layer, appearance defects such as “dents” are likely to occur on the surface of the pressure-sensitive adhesive layer. For this reason, particularly when using a water-insoluble crosslinking agent for the pressure-sensitive adhesive layer of the surface protective film, there may be a problem that it becomes difficult to inspect the adherend while the surface protective film is stuck. . In order to eliminate the dent caused by such a water-insoluble crosslinking agent, for example, a leveling agent is used.
- the water-dispersed acrylic pressure-sensitive adhesive composition generally has poor defoaming properties when it contains a surfactant such as the leveling agent or emulsifier. If air bubbles are included in the coating liquid during the formation of the pressure-sensitive adhesive layer, the air bubbles remain in the pressure-sensitive adhesive layer formed by application by the coating head, forming a dent on the surface of the pressure-sensitive adhesive layer, and the appearance of the pressure-sensitive adhesive layer This causes problems such as deterioration of the thickness of the pressure-sensitive adhesive layer, variation in the thickness of the pressure-sensitive adhesive layer, and residual bubble defects after drying of the pressure-sensitive adhesive layer. In order to improve antifoaming properties, it is effective to use an antifoaming agent.
- a pressure-sensitive adhesive formed from a water-dispersed acrylic pressure-sensitive adhesive composition which has excellent adhesiveness and removability (particularly an anti-adhesive property), and has reduced appearance defects such as “dents” and has excellent appearance characteristics.
- the layer is not obtained at present.
- adhesive residue (so-called “glue residue”) remains on the surface of the adherend (optical member, etc.) when the adhesive sheet is peeled off.
- Contamination of the adherend surface due to transfer of components contained in the adhesive layer to the adherend surface causes problems such as an adverse effect on the optical characteristics of the optical member. For this reason, the low adhesiveness with respect to a to-be-adhered body is strongly calculated
- the technique improves scratch resistance of the surface of the surface protective film, that is, the surface opposite to the surface (adhesive layer surface) to be attached to the adherend (surface of the base material side, sometimes referred to as “rear surface”)
- the technique include a technique of providing a hard surface layer (topcoat layer) on the back surface of the surface protective film.
- the surface protective film affixed to the adherend is observed from the back side (for example, observed in a bright room where external light enters or under a fluorescent lamp in the bright room) Then, the external appearance of the surface protection film looks entirely or partially whitish, thereby causing a problem that visibility of the adherend surface is lowered. Furthermore, when the thickness of the topcoat layer varies, the reflectance varies depending on the location, and the thick portion looks relatively white, thereby further reducing the visibility of the adherend surface.
- an object of the present invention is to have an acrylic pressure-sensitive adhesive layer on at least one side of a transparent film substrate having a topcoat layer, and to reduce appearance characteristics (such as dents and bubble defects).
- the present invention is to provide a pressure-sensitive adhesive sheet that is excellent in that it is difficult to look whitish), and that is also excellent in prevention of an increase in adhesive strength over time, scratch resistance, and antistatic properties.
- a raw material monomer having a specific composition is provided on at least one side of a transparent film substrate having a topcoat layer having a specific configuration in which variation in average thickness and thickness is controlled.
- a water-dispersed acrylic pressure-sensitive adhesive composition comprising a specific structure of polypropylene glycol (PPG) / polyethylene glycol (PEG) block copolymer (or a derivative thereof) as a constituent component.
- the present invention is a pressure-sensitive adhesive sheet having an acrylic pressure-sensitive adhesive layer on at least one side of a transparent film substrate, wherein the transparent film substrate comprises a base layer made of a resin material, and a first surface of the base layer A top coat layer provided on the top coat layer.
- the top coat layer is composed of polythiophene, an acrylic resin, and a melamine-based cross-linking agent.
- the average thickness D ave is 2 to 50 nm, and the thickness variation ⁇ D is 40% or less.
- the acrylic pressure-sensitive adhesive layer is composed of (meth) acrylic acid alkyl ester and carboxyl group-containing unsaturated monomer as essential raw material monomers, and contains (meth) acrylic acid alkyl ester in the total amount of raw material monomers. 70 to 99.5% by weight, carboxyl group-containing unsaturated monomer content is 0.5 to 10% by weight, and radical weight in the molecule Re-peeling water-dispersed acrylic pressure-sensitive adhesive composition containing an acrylic emulsion polymer (A) polymerized using a reactive emulsifier containing a functional functional group and a compound (B) represented by the following formula (I)
- the present invention provides a pressure-sensitive adhesive sheet, which is a pressure-sensitive adhesive layer formed more.
- the pressure-sensitive adhesive sheet is provided in which the resin material constituting the base layer contains polyethylene terephthalate or polyethylene naphthalate as a main resin component.
- the water-removable acrylic pressure-sensitive adhesive composition for re-peeling provides the pressure-sensitive adhesive sheet further comprising a water-insoluble crosslinking agent (C) having two or more functional groups capable of reacting with carboxyl groups in the molecule. .
- the pressure-sensitive adhesive sheet as a surface protective film for an optical member is provided.
- the pressure-sensitive adhesive sheet of the present invention Since the pressure-sensitive adhesive sheet of the present invention has the above-mentioned transparent film substrate, it is excellent in scratch resistance and antistatic properties, and hardly looks whitish. In addition, since the pressure-sensitive adhesive sheet of the present invention has the above acrylic pressure-sensitive adhesive layer, there are few appearance defects such as dents and bubble defects, and it has good removability and adhesiveness, particularly for adherends. Adhesive strength hardly increases over time. As described above, the pressure-sensitive adhesive sheet of the present invention has particularly excellent appearance characteristics by having the above-described configuration, and performs an appearance inspection of the adherend while it is still attached to the adherend (such as an optical member). It is easy and inspection accuracy can be improved. For this reason, the pressure-sensitive adhesive sheet of the present invention is particularly useful for surface protection of optical films.
- the pressure-sensitive adhesive sheet of the present invention has an acrylic pressure-sensitive adhesive layer on at least one side of the transparent film substrate.
- adhesive sheet includes a tape-shaped material, that is, an “adhesive tape”.
- the surface of the pressure-sensitive adhesive layer (acrylic pressure-sensitive adhesive layer) of the pressure-sensitive adhesive sheet of the present invention may be referred to as “pressure-sensitive adhesive surface”.
- the pressure-sensitive adhesive sheet of the present invention may be a double-sided pressure-sensitive adhesive sheet whose both surfaces are pressure-sensitive adhesive surfaces, or a single-sided pressure-sensitive adhesive sheet in which only one surface is a pressure-sensitive adhesive surface. Especially, it is preferable that it is a single-sided adhesive sheet from a viewpoint of protecting the surface of a to-be-adhered body. That is, the pressure-sensitive adhesive sheet of the present invention is preferably a pressure-sensitive adhesive sheet (single-sided pressure-sensitive adhesive sheet) having an acrylic pressure-sensitive adhesive layer on one side of the transparent film substrate.
- the pressure-sensitive adhesive sheet (single-sided pressure-sensitive adhesive sheet) preferably has a configuration in which one surface is a surface of a top coat layer described later and the other surface is a pressure-sensitive adhesive surface.
- the transparent film base material in the adhesive sheet of this invention has at least the base layer which consists of resin materials, and the below-mentioned topcoat layer provided on the 1st surface of this base layer.
- the transparent film substrate may have a configuration (laminated configuration) having the top coat layer only on one surface (first surface) side of the base layer, or both surfaces of the base layer (first surface and The structure (lamination structure) which has the said topcoat layer in the 2nd surface) side may be sufficient.
- the said transparent film base material is the structure (lamination structure of a "base layer / topcoat layer") which has the said topcoat layer only in the one surface (1st surface) side of the said base layer.
- the base layer of the transparent film substrate is a transparent film (thin film) molded body made of a resin material. That is, as the base layer, a resin film formed by molding various resin materials into a film shape can be preferably used. Although it does not specifically limit as a resin material which comprises the said base layer, The resin film excellent in the characteristic of 1 or 2 or more among transparency, mechanical strength, thermal stability, moisture shielding property, and isotropic property etc.
- polyester-based polymers such as polyethylene terephthalate (PET), polyethylene naphthalate, polybutylene terephthalate; cellulose-based polymers such as diacetylcellulose and triacetylcellulose; polycarbonate-based polymers
- PET polyethylene terephthalate
- cellulose-based polymers such as diacetylcellulose and triacetylcellulose
- polycarbonate-based polymers A resin material comprising an acrylic polymer such as polymethyl methacrylate as the main component (resin component) (a component occupying 50% by weight or more of the main component of the resin material, eg, 100% by weight of the resin material), More preferably polyethylene terephthalate or polyethylene
- the naphthalate is a resin material whose main component.
- the resin material examples include styrene polymers such as polystyrene and acrylonitrile-styrene copolymer; olefin polymers such as polyethylene, polypropylene, polyolefin having a cyclic or norbornene structure, and ethylene-propylene copolymer; vinyl chloride.
- Amide polymers such as nylon 6, nylon 6,6, aromatic polyamide; imide polymers; sulfone polymers; polyethersulfone polymers; polyetheretherketone polymers; polyphenylene sulfide polymers; polyvinyl alcohol polymers
- Polyoxymethylene polymers; epoxy polymers and the like can also be used.
- the base layer may be formed from a blend of two or more of the polymers.
- the base layer is more preferable as the anisotropy of optical properties (such as retardation) is smaller.
- the anisotropy of optical properties such as retardation
- the base layer may have a single layer structure or a structure in which a plurality of layers having different compositions are stacked. Especially, it is preferable that the said base layer is a single layer structure.
- the base layer may contain various additives such as an antioxidant, an ultraviolet absorber, an antistatic component, a plasticizer, and a colorant (pigment, dye, etc.) as necessary.
- corona discharge treatment, plasma treatment, ultraviolet irradiation treatment, acid treatment, alkali treatment, and application of a primer are applied to the first surface of the base layer (the surface on which the topcoat layer is provided).
- Surface treatment may be performed.
- Such surface treatment is performed, for example, for the purpose of improving the adhesion between the base layer and the topcoat layer, and in particular, polar groups such as hydroxyl groups (—OH groups) are present on the first surface of the base layer.
- Surface treatment as introduced is preferably employed.
- the same surface treatment as described above may be applied to the second surface of the base layer (usually the surface on which the acrylic pressure-sensitive adhesive layer is formed).
- Such surface treatment is performed, for example, for the purpose of improving the adhesion between the transparent film substrate and the acrylic pressure-sensitive adhesive layer (the anchoring property of the acrylic pressure-sensitive adhesive layer).
- the thickness of the base layer can be appropriately selected according to the application and purpose, and is not particularly limited, but is 10 to 200 ⁇ m in view of workability such as strength and handleability and cost and appearance inspection. It is preferably 15 to 100 ⁇ m, more preferably 20 to 70 ⁇ m.
- the refractive index of the base layer is not particularly limited, but is preferably 1.43 to 1.6, more preferably 1.45 to 1.5 from the viewpoint of appearance characteristics.
- the total light transmittance (according to JIS K7361-1) in the visible light wavelength region of the base layer is not particularly limited, but is preferably 80 to 97%, more preferably 85 to 95% from the viewpoint of appearance characteristics. .
- the arithmetic average roughness (Ra) of the surface of the base layer is not particularly limited.
- the arithmetic average roughness of the second surface (usually the surface on which the acrylic pressure-sensitive adhesive layer is formed) is 0.
- the thickness is preferably 001 to 1 ⁇ m, more preferably 0.01 to 0.7 ⁇ m.
- the acrylic pressure-sensitive adhesive layer in the pressure-sensitive adhesive sheet of the present invention has a high solvent-insoluble content, and thus the thickness accuracy of the coated surface (glue surface) decreases.
- the pressure-sensitive adhesive does not penetrate into the irregularities on the surface of the transparent film base material, and the contact area is reduced, so that the anchoring property of the acrylic pressure-sensitive adhesive layer to the transparent film base material is lowered.
- the arithmetic average roughness is less than 0.001 ⁇ m, blocking may easily occur, handling properties may decrease, and industrial production may be difficult.
- the topcoat layer of the transparent film substrate in the pressure-sensitive adhesive sheet of the present invention is a surface layer formed on at least the first surface side of the base layer, and contains at least polythiophene, an acrylic resin, and a melamine-based crosslinking agent as essential components. Composed.
- the pressure-sensitive adhesive sheet of the present invention can exhibit various functions such as scratch resistance, antistatic property, solvent resistance, printability, and print adhesion. In the case where the pressure-sensitive adhesive sheet of the present invention has the above functions, it can be preferably used particularly for surface protection of optical films.
- the acrylic resin in the topcoat layer is a basic component (base resin) that contributes to the formation of the topcoat layer, and the acrylic polymer is a base polymer (main component in the polymer component, that is, 50% by weight or more).
- a resin contained as a component That is, the content of the acrylic polymer in the acrylic resin (100% by weight) is 50% by weight or more (eg, 50 to 100% by weight), preferably 70 to 100% by weight, more preferably 90 to 100%. % By weight. *
- acrylic polymer is a polymer containing a monomer having at least one (meth) acryloyl group in one molecule (inside the molecule) (hereinafter sometimes referred to as “acrylic monomer”) as a main monomer component.
- acrylic monomer a monomer having at least one (meth) acryloyl group in one molecule (inside the molecule)
- the acrylic monomer content is 50% by weight or more.
- (meth) acryloyl group means an acryloyl group and / or a methacryloyl group (one or both of an acryloyl group and a methacryloyl group).
- the acrylic resin is not particularly limited, and various types of acrylic resins such as a thermosetting acrylic resin, an ultraviolet curable acrylic resin, an electron beam curable acrylic resin, and a two-component mixed acrylic resin can be used.
- the above-mentioned various types of acrylic resins can be used alone or in combination of two or more.
- acrylic having excellent scratch resistance for example, the result of evaluation of scratch resistance in the section “(Evaluation)” described later is good ( ⁇ )
- the acrylic resin can be grasped as a binder (binder resin) of polythiophene (antistatic component) in the top coat layer.
- the acrylic polymer that is the base polymer of the acrylic resin is not particularly limited, but is preferably an acrylic polymer containing methyl methacrylate (MMA) as a main monomer component (monomer component), more preferably, It is a copolymer of methyl methacrylate and one or more other monomers (preferably acrylic monomers other than methyl methacrylate).
- the copolymerization ratio of methyl methacrylate in the acrylic polymer is not particularly limited, but is 50% by weight or more (for example, 50 to 90% by weight) with respect to the total amount of monomer components (100% by weight) constituting the acrylic polymer. And more preferably 60% by weight or more (for example, 60 to 85% by weight).
- the monomer copolymerized with methyl methacrylate is not particularly limited, and examples thereof include (meth) acrylic acid alkyl esters other than methyl methacrylate, and more specifically, for example, (Meth) acrylic acid alkyl ester having a linear or branched alkyl group, (meth) acrylic acid alkyl ester (cycloalkyl (meth) acrylate) having an alicyclic alkyl group (cycloalkyl group), etc. Is preferably exemplified.
- the (meth) acrylic acid alkyl ester having a linear or branched alkyl group is not particularly limited.
- methyl acrylate, ethyl acrylate, n-butyl acrylate (BA) acrylic acid 2 -Alkyl acrylates having 1 to 12 carbon atoms of alkyl groups such as ethylhexyl (2EHA) (alkyl acrylate esters); alkyl groups such as ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate Examples thereof include alkyl methacrylate having 2 to 6 carbon atoms (methacrylic acid alkyl ester).
- the (meth) acrylic acid alkyl ester having an alicyclic alkyl group is not particularly limited.
- an acryl group having 5 to 7 carbon atoms in a cycloalkyl group such as cyclopentyl acrylate and cyclohexyl acrylate is used.
- Cycloalkyl; cycloalkyl methacrylate having 5 to 7 carbon atoms in the cycloalkyl group such as cyclopentyl methacrylate and cyclohexyl methacrylate (CHMA).
- the acrylic polymer for example, an acrylic polymer composed of a monomer component containing at least methyl methacrylate (MMA) and cyclohexyl methacrylate (CHMA) may be mentioned.
- the copolymerization ratio of cyclohexyl methacrylate is not particularly limited. For example, it is 25% by weight or less (for example, 0.1 to 25% by weight) based on the total amount of monomer components (100% by weight) constituting the acrylic polymer. ), More preferably 15% by weight or less (for example, 0.1 to 15% by weight).
- the acrylic polymer include, for example, methyl methacrylate (MMA) and a monomer component containing at least n-butyl acrylate (BA) and / or 2-ethylhexyl acrylate (2EHA).
- MMA methyl methacrylate
- BA n-butyl acrylate
- 2EHA 2-ethylhexyl acrylate
- the acrylic polymer comprised is mentioned.
- the copolymerization ratio of n-butyl acrylate and 2-ethylhexyl acrylate (when both are included, the total amount thereof) is not particularly limited.
- the total amount of monomer components constituting the acrylic polymer ( 100% by weight) is preferably 40% by weight or less (eg 1 to 40% by weight), more preferably 10 to 40% by weight, still more preferably 30% by weight or less (eg 3 to 30% by weight).
- it is 15 to 30% by weight.
- acrylic polymer examples include, for example, substantially methyl methacrylate (MMA), cyclohexyl methacrylate (CHMA), and n-butyl acrylate (BA) and / or acrylic acid 2-
- MMA substantially methyl methacrylate
- CHMA cyclohexyl methacrylate
- BA n-butyl acrylate
- acrylic acid 2- An acrylic polymer composed of a monomer component composed of ethylhexyl (2EHA) is exemplified. Specifically, it is composed of MMA, CHMA, and monomer components containing BA and / or 2EHA, and MMA, CHMA, BA, and 2EHA with respect to the total amount of monomer components (100% by weight) constituting the acrylic polymer.
- An acrylic polymer having a total content (total content) of 52% by weight or more is preferred.
- the above-mentioned acrylic polymer may be copolymerized with a monomer other than the above (other monomers) as long as the effects of the present invention are not significantly impaired.
- a monomer other than the above (other monomers) examples include carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid; acid anhydride group-containing monomers such as maleic anhydride and itaconic anhydride; vinyl acetate and propionic acid.
- Vinyl esters such as vinyl; aromatic vinyl compounds such as styrene and ⁇ -methylstyrene; amide group-containing monomers such as acrylamide and N, N-dimethylacrylamide; aminoethyl (meth) acrylate, (meth) acrylic acid N, Amino group-containing monomers such as N-dimethylaminoethyl; imide group-containing monomers such as cyclohexylmaleimide; epoxy group-containing monomers such as glycidyl (meth) acrylate; vinyl ethers such as (meth) acryloylmorpholine; methyl vinyl ether; Meta Acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl (meth) acrylate, hydroxydecyl (meth) acrylate, hydroxyl
- the copolymerization ratio of these “other monomers” (the total amount when two or more are used) is not particularly limited, but is preferably 20% by weight or less, more preferably 10% by weight or less, and still more preferably 5%. % By weight or less, most preferably 3% by weight or less.
- the “other monomer” may not be substantially copolymerized.
- the content of the other monomer is 0.1% with respect to the total amount of monomers (100% by weight) constituting the acrylic polymer. It may be not more than% by weight.
- the acrylic polymer has a copolymer composition that does not substantially contain a monomer having an acidic functional group (for example, acrylic acid or methacrylic acid).
- the content of the monomer having an acidic functional group is preferably 0.1% by weight or less with respect to the total amount of monomer components constituting the acrylic polymer.
- the “acidic functional group” means a functional group capable of exhibiting acidity such as a carboxyl group and an acid anhydride group, and the same applies to the following.
- the acrylic polymer has a copolymer composition including a monomer having a hydroxyl group (hydroxyl group-containing monomer). By copolymerizing the hydroxyl group-containing monomer, the adhesion of the topcoat layer to the base layer can be enhanced.
- the acrylic resin constituting the top coat layer may contain other resin components (excluding polythiophene) in addition to the acrylic polymer.
- content of the said other resin component in the said acrylic resin is less than 50 weight%.
- the polythiophene in the top coat layer is a component (antistatic component) having an action of preventing the pressure-sensitive adhesive sheet of the present invention from being charged.
- the pressure-sensitive adhesive sheet of the present invention exhibits excellent antistatic properties by including polythiophene in the topcoat layer, so that the surface is used in the processing or transporting process of articles that dislike static electricity such as liquid crystal cells and semiconductor devices. It can be particularly preferably used as a protective film.
- the polythiophene since the polythiophene has high hydrophobicity and is difficult to absorb moisture in a high humidity environment (humidified), it is less likely to cause whitening of the transparent film substrate (more specifically, whitening of the topcoat layer).
- a highly hygroscopic component for example, an ammonium salt
- the whitening of the substrate (more specifically, the topcoat layer) Whitening is likely to occur.
- the polythiophene includes, for example, an unsubstituted thiophene polymer and a substituted thiophene polymer such as 3,4-ethylenedioxythiophene.
- the polythiophene is preferably poly (3,4-ethylenedioxythiophene), which is a polymer of 3,4-ethylenedioxythiophene.
- the polystyrene equivalent weight average molecular weight (Mw) of the polythiophene is not particularly limited, but is preferably 40 ⁇ 10 4 or less (eg, 0.1 ⁇ 10 4 to 40 ⁇ 10 4 ), more preferably 0.5 ⁇ 10. 4 to 30 ⁇ 10 4 .
- Mw polystyrene equivalent weight average molecular weight
- the compatibility may be insufficient depending on the combination with other components constituting the top coat layer, resulting in a decrease in appearance characteristics or a decrease in solvent resistance.
- the scratch resistance may be inferior.
- the amount of polythiophene used is not particularly limited, but is preferably 10 to 200 parts by weight, more preferably 25 to 150 parts by weight based on 100 parts by weight of the acrylic polymer in the topcoat layer. Part by weight, more preferably 40 to 120 parts by weight. If the amount used is less than 10 parts by weight, the surface resistivity of the surface of the transparent film base on the topcoat layer side becomes too large, and the antistatic property may be lowered. On the other hand, if the amount used exceeds 200 parts by weight, the thickness variation ⁇ D of the topcoat layer tends to increase, and the pressure-sensitive adhesive sheet may appear partially whitish and the appearance characteristics may deteriorate. Further, depending on the combination with other components constituting the top coat layer, the compatibility of polythiophene may be insufficient, resulting in a decrease in appearance characteristics and a decrease in solvent resistance.
- a method for forming the topcoat layer As a method for forming the topcoat layer, as described later, when a method of applying a liquid composition (coating composition for forming the topcoat layer) to the surface of the base layer and drying or curing the composition is used,
- a polythiophene used for preparing the product a polythiophene in which the polythiophene is dissolved or dispersed in water (polythiophene aqueous solution or dispersion) can be preferably used.
- Such a polythiophene aqueous solution or dispersion is obtained by, for example, dissolving or dispersing a polythiophene having a hydrophilic functional group (which can be synthesized by a method such as copolymerizing a monomer having a hydrophilic functional group in the molecule) in water.
- a hydrophilic functional group include a sulfo group, an amino group, an amide group, an imino group, a hydroxyl group, a mercapto group, a hydrazino group, a carboxyl group, a quaternary ammonium group, and a sulfate ester group (—O—SO 3 H).
- phosphoric acid ester groups for example, —O—PO (OH) 2
- hydrophilic functional groups may form a salt.
- a commercial product such as a trade name “Denatron” series (manufactured by Nagase ChemteX Corporation) can be used.
- a polythiophene aqueous solution containing polystyrene sulfonate (which may be in a form in which PSS is added as a dopant to polythiophene) is particularly preferable in that stable charging characteristics can be obtained.
- the ratio of polythiophene to polystyrene sulfonate [polythiophene: polystyrene sulfonate] in the polythiophene aqueous solution containing PSS is not particularly limited, but is preferably 1: 5 to 1:10.
- the total content (total content) of polythiophene and polystyrene sulfonate in the polythiophene aqueous solution containing PSS is not particularly limited, but is preferably 1 to 5% by weight.
- a commercial product such as a trade name “Baytron” (manufactured by HC Stark) may be used.
- the total amount of polythiophene and polystyrene sulfonate is not particularly limited, but is 10 to 200 parts by weight with respect to 100 parts by weight of the acrylic polymer in the topcoat layer. The amount is preferably 25 to 150 parts by weight, more preferably 40 to 120 parts by weight.
- the top coat layer can provide a transparent film substrate having a small surface resistivity even when the top coat layer is thin.
- an acrylic resin mainly composed of an acrylic polymer having a copolymer composition that does not substantially contain a monomer having an acidic functional group is used as the acrylic resin, a better result can be obtained.
- the melamine-based crosslinking agent in the topcoat layer has at least one effect (especially, among scratch resistance improvement, solvent resistance improvement, print adhesion improvement, and friction coefficient reduction) by crosslinking the acrylic polymer. , To improve the scratch resistance).
- the said melamine type crosslinking agent is a compound which has a melamine structure.
- melamine crosslinking agent examples include, for example, monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine, and methylol melamine such as hexamethylol melamine; methoxymethyl melamine, ethoxymethyl melamine, propoxymethyl melamine, Alkoxymethyl melamines such as butoxymethyl melamine, hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxymethyl melamine, hexapentyloxymethyl melamine, hexahexyloxymethyl melamine, methoxybutyl melamine, ethoxybutyl melamine, Alkoxybutyl melamine such as propoxybutyl melamine and butoxybutyl melamine Such as alkoxyalkyl melamine
- Examples of the melamine-based crosslinking agent include trade names “Cymel 202”, “Cymel 212”, “Cymel 232”, “Cymel 235”, “Cymel 253”, “Cymel 266”, “Cymel 267”, “Cymel 270”.
- the amount of the melamine-based crosslinking agent used is not particularly limited, but is 5 to 100 with respect to 100 parts by weight of the acrylic polymer in the topcoat layer. Part by weight is preferable, more preferably 10 to 80 parts by weight, still more preferably 20 to 50 parts by weight. If the amount used is less than 5 parts by weight, the scratch resistance may be inferior. On the other hand, if the amount used exceeds 100 parts by weight, the printability may be inferior. Moreover, depending on the combination with the other component which comprises a topcoat layer, the compatibility of a melamine type crosslinking agent may be insufficient, and an external appearance characteristic may fall, or solvent resistance may fall.
- an acrylic polymer that does not substantially contain the monomer having the acidic functional group is used, and this is used in combination with a melamine-based cross-linking agent.
- the hardness tends to be higher and the adhesion of the topcoat layer to the base layer tends to be improved.
- the top coat layer preferably contains a lubricant in order to exhibit better scratch resistance with respect to the pressure-sensitive adhesive sheet of the present invention.
- a lubricant a known or commonly used lubricant can be used.
- a fluorine-based or silicone-based lubricant can be preferably used.
- silicone-based lubricants silicone-based lubricants (silicone-based lubricants) are preferable.
- the silicone-based lubricant include polydimethylsiloxane, polyether-modified polydimethylsiloxane, and polymethylalkylsiloxane.
- a lubricant containing a fluorine compound or a silicone compound having an aryl group or an aralkyl group may be used as the lubricant.
- the amount of the lubricant used is not particularly limited, but is preferably 5 to 90 parts by weight, more preferably 10 to 70 parts by weight, and still more preferably 15 parts by weight with respect to 100 parts by weight of the acrylic polymer in the topcoat layer. Above (for example, 15 to 50 parts by weight), particularly preferably 20 parts by weight or more, and most preferably 25 parts by weight or more. If the amount of lubricant used is less than 5 parts by weight, scratch resistance may be reduced. On the other hand, if the amount of the lubricant used exceeds 90 parts by weight, the printability may be insufficient, or the appearance characteristics of the topcoat layer (and thus the transparent film substrate or pressure-sensitive adhesive sheet) may deteriorate.
- the above-mentioned lubricant is presumed to reduce the coefficient of friction by bleeding on the surface of the topcoat layer and imparting slipperiness to the surface. Therefore, by using the lubricant appropriately, the scratch resistance can be improved through the reduction of the friction coefficient.
- the lubricant can make the surface tension of the composition for forming a topcoat layer, which will be described later, uniform, and can contribute to reducing the thickness unevenness of the topcoat layer and reducing interference fringes (and thus improving the appearance characteristics). Such an improvement in appearance characteristics is particularly significant in the surface protective film for optical members.
- the acrylic resin constituting the top coat layer is an ultraviolet curable acrylic resin
- a fluorine-based or silicone-based lubricant is added thereto, and a composition for forming a top coat layer described later is applied to the base layer.
- the lubricant bleeds to the surface of the coating film (interface with the air), which suppresses the inhibition of curing by oxygen when irradiated with ultraviolet rays, and the UV curable acrylic resin is sufficient even on the outermost surface of the topcoat layer. Can be cured.
- the top coat layer may contain an antistatic component other than polythiophene, an antioxidant, a colorant (pigment, dye, etc.), a fluidity modifier (thixotropic agent, an increase agent) as necessary, as long as the effects of the present invention are not impaired.
- Additives such as a viscosity agent, a film-forming aid, and a catalyst (for example, an ultraviolet polymerization initiator in a composition containing an ultraviolet curable acrylic resin) may be included.
- antistatic component other than the polythiophene a known or commonly used antistatic component can be used, and is not particularly limited.
- an organic or inorganic conductive substance, various antistatic agents, and the like can be used. .
- the organic conductive material is not particularly limited, and examples thereof include conductive polymers excluding polythiophene such as polyaniline, polypyrrole, polyethyleneimine, and allylamine polymers.
- the said conductive polymer can be used individually or in combination of 2 or more types. Moreover, you may use in combination with another antistatic component (an inorganic electroconductive substance, an antistatic agent, etc.).
- polyaniline for example, a commercial product such as a trade name “aqua-PASS” (manufactured by Mitsubishi Rayon Co., Ltd., an aqueous solution of polyaniline sulfonic acid) can be used.
- the inorganic conductive material is not particularly limited.
- the method for forming the top coat layer of the transparent film substrate in the pressure-sensitive adhesive sheet of the present invention is not particularly limited.
- the acrylic resin, polythiophene, melamine-based crosslinking agent, and additives used as necessary There is a technique including applying a liquid composition (topcoat layer forming composition) dispersed or dissolved in an appropriate solvent to the surface of the base layer. More specifically, for example, a method of forming the topcoat layer by applying the liquid composition to the surface of the base layer and drying, and performing a curing treatment (heat treatment, ultraviolet treatment, etc.) as necessary. Preferably it can be adopted.
- the solid content (NV) of the liquid composition is not particularly limited, but is preferably 5% by weight or less (for example, 0.05 to 5% by weight), more preferably 1% by weight. % Or less (for example, 0.1 to 1% by weight), more preferably 0.5% by weight or less, and particularly preferably 0.3% by weight or less.
- 5% by weight or less for example, 0.05 to 5% by weight
- % Or less for example, 0.1 to 1% by weight
- more preferably 0.5% by weight or less and particularly preferably 0.3% by weight or less.
- the lower limit of the solid content of the liquid composition is not particularly limited, but is preferably 0.05% by weight, more preferably 0.1% by weight. If the solid content is less than 0.05% by weight, repellency is likely to occur in the coating film depending on the material of the base layer, the surface condition, and the like, which may increase ⁇ D.
- the solvent constituting the liquid composition a solvent that can stably dissolve or disperse the components (acrylic resin, polythiophene, melamine-based crosslinking agent, etc.) of the topcoat layer is preferable.
- a solvent that can stably dissolve or disperse the components (acrylic resin, polythiophene, melamine-based crosslinking agent, etc.) of the topcoat layer is preferable.
- an organic solvent, water, these mixed solvents etc. can be used, for example.
- organic solvent examples include esters such as ethyl acetate; ketones such as methyl ethyl ketone, acetone and cyclohexanone; cyclic ethers such as tetrahydrofuran (THF) and dioxane; aromatic hydrocarbons such as toluene and xylene; methanol, One or more selected from aliphatic or alicyclic alcohols such as ethanol, n-propanol, isopropanol, and cyclohexanol; glycol ethers and the like can be used.
- a solvent containing glycol ethers as a main component for example, a solvent containing 50% by weight or more of glycol ethers is preferable.
- glycol ethers one or more selected from alkylene glycol monoalkyl ether and dialkylene glycol monoalkyl ether can be preferably used.
- examples thereof include monopropyl ether, diethylene glycol monobutyl ether, and diethylene glycol mono-2-ethylhexyl ether.
- the average thickness D ave of the top coat layer is 2 to 50 nm, preferably 2 to 30 nm, more preferably 2 to 20 nm, and further preferably 2 to 10 nm.
- the average thickness D ave of the top coat layer exceeds 50 nm, the appearance of the transparent film substrate looks whitish as a whole, and the appearance characteristics of the transparent film substrate (and thus the pressure-sensitive adhesive sheet having the transparent film substrate) are likely to deteriorate. Become.
- the average thickness D ave of the top coat layer is less than 2 nm, it is difficult to form the top coat layer uniformly.
- the average thickness D ave of the top coat layer is measured at five measurement points arranged at equal intervals along a straight line across the top coat layer (for example, a straight line across the top coat layer in the width direction). It can be obtained by measuring the thickness of the layer and calculating the arithmetic average value of the thickness at the five measurement points. In addition, it is preferable that the said measurement point is 2 cm or more (preferably 5 cm or more) apart from the adjacent measurement point.
- the thickness of the topcoat layer (the thickness of the topcoat layer at each measurement point) is measured, for example, by observing the cross section of the transparent film substrate (or adhesive sheet) with a transmission electron microscope (TEM).
- TEM transmission electron microscope
- a transparent film substrate (or adhesive sheet) is used as a sample, and after carrying out heavy metal dyeing treatment to clearly discriminate the topcoat layer, resin embedding is performed, and the above is performed by an ultrathin section method.
- the result obtained by TEM observation of the cross section of the sample can be adopted as the thickness of the top coat layer.
- TEM for example, a transmission electron microscope (model “H-7650”) manufactured by Hitachi, Ltd. can be used.
- the cross-sectional area of the topcoat layer is divided by the sample length in the field of view.
- the thickness of the top coat layer (average thickness in the field of view) was measured.
- staining may be abbreviate
- a calibration curve for the correlation between the thickness grasped by the TEM and the detection results by various thickness detectors for example, a surface roughness meter, an interference thickness meter, an infrared spectrometer, various X-ray diffractometers, etc.
- the thickness of the top coat layer may be determined by creating and calculating
- the thickness variation ⁇ D of the top coat layer is 40% or less (for example, 0 to 40%), preferably 30% or less, more preferably 25% or less, and still more preferably 20% or less.
- the thickness variation ⁇ D of the top coat layer is measured at five measurement points arranged at equal intervals along a straight line across the top coat layer (for example, a straight line across the top coat layer in the width direction).
- the said measurement point is 2 cm or more (preferably 5 cm or more) apart from the adjacent measurement point.
- the thickness at each measurement point of the topcoat layer may be directly measured by the above-described method (for example, by TEM observation, or the detection result obtained by an appropriate thickness detection device may be converted into the thickness by a calibration curve. ). More specifically, the average thickness D ave and the thickness variation ⁇ D of the topcoat layer can be measured according to the thickness measurement method described in Examples described later. When the thickness variation ⁇ D of the top coat layer is 40% or less, streaks and unevenness due to partial whitening are difficult to be visually recognized, and good appearance characteristics are exhibited. That is, the smaller the ⁇ D, the better the appearance characteristics. Further, when the ⁇ D is small is advantageous in terms of D ave is small and form a small transparent film substrate surface resistivity.
- the X-ray intensity variation ⁇ I by fluorescent X-ray (XRF) analysis of the topcoat layer is not particularly limited, but is preferably 40% or less (eg, 0 to 40%), more preferably 30% or less, and still more preferably Is 25% or less, particularly preferably 20% or less.
- the X-ray intensity variation ⁇ I is obtained by performing XRF analysis on five measurement points arranged at equal intervals along a straight line across the topcoat layer (for example, a straight line across the topcoat layer in the width direction).
- the said measurement point is 2 cm or more (preferably 5 cm or more) apart from the adjacent measurement point.
- the average X-ray intensity I ave is an arithmetic average value of the X-ray intensity I at the five measurement points.
- kcps number of X-ray photons incident through the counter tube window per second (count number)
- I ave and ⁇ I can be measured according to the X-ray intensity variation measurement method described in the examples described later.
- ⁇ I of the top coat layer is 40% or less, streaks and unevenness due to partial whitening are difficult to be visually recognized, and good appearance characteristics tend to be exhibited.
- the smaller the above-described thickness variation ⁇ D the smaller ⁇ I. Therefore, it ⁇ I is small, D ave is small and the surface resistivity is also advantageous to form a small transparent film substrate.
- the element to be subjected to the XRF analysis is not particularly limited as long as it is an element capable of XRF analysis among elements contained in the topcoat layer.
- a sulfur atom for example, a sulfur atom (S) derived from polythiophene contained in the topcoat layer
- a silicon atom for example, a silicon atom (Si) derived from a silicone-based lubricant contained in the topcoat layer
- a tin atom for example, a tin atom (Sn) derived from a tin oxide particle contained as a filler in the topcoat layer
- tin atom for example, a tin atom (Sn) derived from a tin oxide particle contained as a filler in the topcoat layer
- the variation ⁇ I of the X-ray intensity based on the XRF analysis of the sulfur atom is 40% or less, or the variation ⁇ I of the X-ray intensity based on the XRF analysis of the silicon atom is 40% or less.
- the XRF analysis can be performed as follows, for example. That is, as the XRF apparatus, a commercially available apparatus can be preferably used, and a spectral crystal can be appropriately selected and used, for example, a Ge crystal can be preferably used.
- the output setting and the like can be appropriately selected according to the apparatus to be used, and are not particularly limited. Usually, sufficient sensitivity can be obtained with an output of about 50 kV and 70 mA. More specifically, for example, the XRF analysis conditions described in Examples described later can be preferably employed.
- the X-ray intensity per area corresponding to a circle having a diameter of 30 mm is approximately 0.01 kcps or more (more preferably 0.03 kcps or more, for example, 0. It is preferable that an element to be analyzed is 05 to 3.00 kcps).
- the transparent film substrate in the pressure-sensitive adhesive sheet of the present invention is a transparent substrate.
- the total light transmittance (according to JIS K7361-1) in the visible light wavelength region of the transparent film substrate is not particularly limited, but is preferably 80 to 97%, more preferably 85 to 95%. is there.
- the haze of the transparent film substrate (according to JIS K7136) is not particularly limited, but is preferably 1.0 to 5.0%, more preferably 2.0 to 3.5%.
- the thickness of the transparent film substrate is not particularly limited, but is preferably 10 to 150 ⁇ m, more preferably 30 to 100 ⁇ m. If the thickness is less than 10 ⁇ m, the scratch preventing effect of the optical member may be impaired. On the other hand, if the thickness exceeds 150 ⁇ m, the cost may increase.
- the acrylic pressure-sensitive adhesive layer (pressure-sensitive adhesive layer) in the pressure-sensitive adhesive sheet of the present invention is a water-dispersed acrylic pressure-sensitive adhesive composition (re-peeling) containing the acrylic emulsion polymer (A) and the compound (B) as essential components.
- Water-dispersed acrylic pressure-sensitive adhesive composition) (sometimes referred to as “pressure-sensitive adhesive composition of the present invention”).
- the pressure-sensitive adhesive composition of the present invention preferably further contains a water-insoluble crosslinking agent (C).
- the acrylic emulsion polymer (A) in the pressure-sensitive adhesive composition of the present invention is a polymer comprising (meth) acrylic acid alkyl ester and a carboxyl group-containing unsaturated monomer as essential raw material monomers (raw material monomer components).
- the acrylic emulsion polymer (A) can be used alone or in combination of two or more.
- “(meth) acryl” means “acryl” and / or “methacryl” (one or both of “acryl” and “methacryl”).
- the (meth) acrylic acid alkyl ester is used as a main monomer component constituting the acrylic emulsion polymer (A), and has basic characteristics as a pressure-sensitive adhesive (or pressure-sensitive adhesive layer) such as adhesiveness and peelability. Play a role to express.
- alkyl acrylates tend to impart flexibility to the polymer forming the pressure-sensitive adhesive layer (acrylic pressure-sensitive adhesive layer) and exhibit the effect of exhibiting adhesiveness and adhesiveness in the pressure-sensitive adhesive layer.
- Alkyl esters tend to give the polymer forming the pressure-sensitive adhesive layer hardness and exert the effect of adjusting the removability of the pressure-sensitive adhesive layer.
- the (meth) acrylic acid alkyl ester is not particularly limited, but is a linear, branched or cyclic alkyl having 1 to 16 carbon atoms (more preferably 2 to 10, more preferably 4 to 8). And (meth) acrylic acid alkyl ester having a group.
- alkyl acrylate ester for example, an alkyl acrylate ester having an alkyl group having 2 to 14 carbon atoms (more preferably 4 to 8 carbon atoms) is preferable, and n-butyl acrylate, isobutyl acrylate, acrylic acid s -Having a linear or branched alkyl group such as butyl, isoamyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, nonyl acrylate, isononyl acrylate And alicyclic alkyl acrylates such as alkyl acrylate and isobornyl acrylate. Of these, 2-ethylhexyl acrylate, n-butyl acrylate, and isobornyl acrylate are preferable.
- alkyl methacrylate for example, alkyl methacrylate having an alkyl group having 1 to 16 carbon atoms (more preferably 1 to 8) is preferable, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, methacrylic acid.
- Methacrylic acid alkyl ester having a linear or branched alkyl group such as isopropyl acid, n-butyl methacrylate, isobutyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, bornyl methacrylate And alicyclic methacrylic acid alkyl ester such as isobornyl methacrylate.
- methyl methacrylate and n-butyl methacrylate are preferable.
- the above (meth) acrylic acid alkyl ester can be appropriately selected according to the intended adhesiveness and the like, and can be used alone or in combination of two or more.
- the content of the (meth) acrylic acid alkyl ester is 70 to 99.5% by weight in the total amount (total amount) (total raw material monomer) (100% by weight) of the raw material monomers constituting the acrylic emulsion polymer (A). More preferably, it is 85 to 99% by weight.
- the content exceeds 99.5% by weight the content of the carboxyl group-containing unsaturated monomer decreases, so that the anchoring property, low contamination and emulsion of the acrylic pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition In the case of less than 70% by weight, the adhesiveness and removability of the acrylic pressure-sensitive adhesive layer are lowered.
- the total amount (total content) of all the (meth) acrylic-acid alkylesters should just satisfy the said range.
- the content ratio of the alkyl acrylate ester to the alkyl methacrylate ester in the (meth) acrylic acid alkyl ester is not particularly limited, but is 100: 0. It is preferably about 30:70 (weight ratio), more preferably 100: 0 to 50:50.
- the carboxyl group-containing unsaturated monomer can exhibit a function of forming a protective layer on the surface of the emulsion particles made of the acrylic emulsion polymer (A) and preventing shear breakage of the emulsion particles. This is further improved by neutralizing the carboxyl group with a base.
- the stability of emulsion particles against shear failure is more generally referred to as mechanical stability.
- a polyfunctional compound that reacts with a carboxyl group for example, a polyfunctional epoxy compound
- it can be used as a crosslinking point in the formation stage of the acrylic pressure-sensitive adhesive layer by removing water. Can act.
- the adhesion (anchoring property) between the acrylic pressure-sensitive adhesive layer and the substrate can be improved via the polyfunctional compound.
- carboxyl group-containing unsaturated monomers include (meth) acrylic acid (acrylic acid, methacrylic acid), itaconic acid, maleic acid, fumaric acid, crotonic acid, carboxyethyl acrylate, carboxypentyl acrylate, and the like. Can be mentioned.
- the carboxyl group-containing unsaturated monomer includes acid anhydride group-containing unsaturated monomers such as maleic anhydride and itaconic anhydride.
- acrylic acid is preferable because it has a high relative concentration on the surface of the emulsion particles and can easily form a higher-density protective layer.
- carboxyl group-containing unsaturated monomer can be used individually or in combination of 2 or more types.
- the content of the carboxyl group-containing unsaturated monomer is 0.5 to 10% by weight in the total amount of raw material monomers (total raw material monomers) (100% by weight) constituting the acrylic emulsion polymer (A). It is preferably 1 to 5% by weight, more preferably 2 to 4% by weight.
- the carboxyl group-containing unsaturated monomer for example, acrylic acid
- the carboxyl group-containing unsaturated monomer is generally water-soluble, and thus polymerizes in water to cause thickening (increased viscosity).
- the acrylic pressure-sensitive adhesive layer is formed, the interaction with the functional group on the surface of the polarizing plate, which is the adherend, increases, and the adhesive force increases with time, making peeling difficult.
- a monomer component constituting the acrylic emulsion polymer (A)
- a monomer component may be used in combination.
- Examples of such a monomer component include amide group-containing monomers such as (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N-isopropyl (meth) acrylamide, and N, N— Amino group-containing monomers such as dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate may be added (used) in an amount of about 0.1 to 10% by weight.
- amide group-containing monomers such as (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N-isopropyl (meth) acrylamide
- N, N— Amino group-containing monomers such as dimethylaminoethyl (meth) acrylate and N, N-dimethylaminopropyl (meth) acrylate may be added (used) in an amount of about 0.1 to 10% by weight.
- (meth) acrylic acid aryl esters such as phenyl (meth) acrylate; vinyl esters such as vinyl acetate and vinyl propionate; styrene monomers such as styrene
- epoxy group-containing monomers such as glycidyl (meth) acrylate and allyl glycidyl ether, and polyfunctional monomers such as trimethylolpropane tri (meth) acrylate and divinylbenzene, You may add (use) in the ratio of less than weight%.
- hydrazide crosslinkers are used in combination with hydrazide-based crosslinking agents, and diacetone acrylamide (DAAM), allyl acetoacetate, 2- (acetoacetoxy) ethyl (meth) acrylate, etc., in particular for the purpose of improving low contamination.
- DAAM diacetone acrylamide
- a keto group-containing unsaturated monomer may be added (used) in a proportion of less than 10% by weight (preferably 0.5 to 5% by weight).
- Examples of the other monomer components include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl ( (Meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, (4-hydroxymethylcyclohexyl) methyl acrylate, N-methylol (meth) acrylamide, vinyl alcohol, allyl alcohol, 2-hydroxyethyl Hydroxyl group-containing unsaturated monomers such as vinyl ether, 4-hydroxybutyl vinyl ether and diethylene glycol monovinyl ether may be used.
- the hydroxyl group-containing unsaturated monomer preferably has a smaller addition amount (use amount) from the viewpoint of further reducing whitening contamination.
- the addition amount of the hydroxyl group-containing unsaturated monomer is preferably less than 1% by weight, more preferably less than 0.1% by weight, and still more preferably substantially free (for example, 0.05% by weight). Less than%).
- about 0.01 to 10% by weight may be added (used).
- the addition amount (usage amount) of the other monomer component is a content in the total amount (total raw material monomers) (100% by weight) of the raw material monomers constituting the acrylic emulsion polymer (A).
- the monomer component (raw material monomer) constituting the acrylic emulsion polymer (A) is selected from the group consisting of methyl methacrylate, isobornyl acrylate and vinyl acetate. It is preferred to use at least one selected monomer. Particularly preferred is methyl methacrylate.
- Monomer selected from the group consisting of the above monomers (methyl methacrylate, isobornyl acrylate and vinyl acetate) in the total amount (total raw material monomers) (100 wt%) of the raw material monomers constituting the acrylic emulsion polymer (A) ) Is preferably 1 to 15% by weight, more preferably 2 to 10% by weight, still more preferably 2 to 5% by weight.
- the content is less than 1% by weight, the effect of improving the appearance may not be obtained, and when it exceeds 15% by weight, the acrylic pressure-sensitive adhesive layer may become too hard and adhesion may be lowered.
- the acrylic emulsion polymer (A) in the present invention can be obtained by emulsion polymerization of the above raw material monomers (monomer mixture) with an emulsifier and a polymerization initiator.
- the emulsifier used for emulsion polymerization of the acrylic emulsion polymer (A) is a reactive emulsifier having a radical polymerizable functional group introduced into the molecule (a reactive emulsifier containing a radical polymerizable functional group). That is, the acrylic emulsion polymer (A) is an acrylic emulsion polymer polymerized using a reactive emulsifier containing a radical polymerizable functional group in the molecule.
- the reactive emulsifier containing the radical polymerizable reactive group may be used alone or in combination of two or more.
- the reactive emulsifier containing a radical polymerizable functional group is an emulsifier containing at least one radical polymerizable functional group in a molecule (in one molecule).
- the reactive emulsifier is not particularly limited, and various reactive emulsifiers having a radical polymerizable functional group such as vinyl group, propenyl group, isopropenyl group, vinyl ether group (vinyloxy group), and allyl ether group (allyloxy group). 1 type or 2 or more types can be selected and used.
- Use of the reactive emulsifier is preferable because the emulsifier is incorporated into the polymer and contamination from the emulsifier is reduced.
- the reactive emulsifier examples include nonionic anionic emulsifiers such as sodium polyoxyethylene alkyl ether sulfate, ammonium polyoxyethylene alkyl phenyl ether sulfate, sodium polyoxyethylene alkyl phenyl ether sulfate, sodium polyoxyethylene alkyl sulfosuccinate (nonionic).
- a reactive emulsifier having a form in which a radical polymerizable functional group (radical reactive group) such as a propenyl group or an allyl ether group is introduced into an anionic emulsifier having a hydrophilic hydrophilic group) (or corresponding to the form) Can be mentioned.
- a reactive emulsifier having a form in which a radical polymerizable functional group is introduced into an anionic emulsifier is referred to as an “anionic reactive emulsifier”.
- a reactive emulsifier having a form in which a radical polymerizable functional group is introduced into a nonionic anionic emulsifier is referred to as a “nonionic anionic reactive emulsifier”.
- an anionic reactive emulsifier in particular, a nonionic anionic reactive emulsifier
- the emulsifier is incorporated into the polymer, so that low contamination can be improved.
- the water-insoluble crosslinking agent (C) is a polyfunctional epoxy-based crosslinking agent having an epoxy group
- the reactivity of the crosslinking agent can be improved by its catalytic action.
- an anionic reactive emulsifier is not used, the crosslinking reaction is not completed by aging, and the adhesive force of the pressure-sensitive adhesive layer may change over time. Furthermore, there may be a problem that the adhesive force with the adherend increases with time due to unreacted carboxyl groups.
- anionic reactive emulsifier is incorporated in the polymer, a quaternary ammonium compound generally used as a catalyst for an epoxy crosslinking agent (see, for example, JP-A-2007-31585). It is preferable because it does not precipitate on the surface of the adherend and cannot cause whitening contamination.
- Examples of such reactive emulsifiers include the trade name “ADEKA rear soap SE-10N” (manufactured by ADEKA Corporation), the trade name “AQUALON HS-10” (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and the trade name “AQUALON”.
- Commercial products such as “HS-05” (Daiichi Kogyo Seiyaku Co., Ltd.) can also be used.
- impurity ions may be a problem
- an anionic emulsifier it is desirable to use an ammonium salt reactive emulsifier.
- an appropriate method such as an ion exchange resin method, a membrane separation method, or a precipitation filtration method for impurities using alcohol can be used.
- the amount (use amount) of the reactive emulsifier is not particularly limited, but is 0.1 to 5 with respect to 100 parts by weight of the total amount of raw material monomers (total raw material monomers) constituting the acrylic emulsion polymer (A). Part by weight is preferred, more preferably 0.5 to 3 parts by weight. If the blending amount exceeds 5 parts by weight, the cohesive force of the pressure-sensitive adhesive (pressure-sensitive adhesive layer) may be reduced to increase the amount of contamination on the adherend, and contamination with an emulsifier may occur. On the other hand, if the blending amount is less than 0.1 parts by weight, stable emulsification may not be maintained.
- the polymerization initiator used for emulsion polymerization of the acrylic emulsion polymer (A) is not particularly limited, and examples thereof include 2,2′-azobisisobutyronitrile and 2,2′-azobis (2-amidinopropane).
- Peroxide-based polymerization initiators redox initiators in combination with peroxides and reducing agents, such as peracids Combination of products and ascorbic acid (combination of hydrogen peroxide and ascorbic acid, etc.), combination of peroxide and iron (II) salt (combination of hydrogen peroxide and iron (II) salt, etc.), A redox polymerization initiator based on a combination of persulfate and sodium bisulfite can be used.
- the said polymerization initiator can be used individually or in combination of 2 or more types.
- the blending amount (use amount) of the polymerization initiator can be appropriately determined according to the type of the initiator and the raw material monomer, and is not particularly limited.
- the amount of the raw material monomer constituting the acrylic emulsion polymer (A) is not particularly limited.
- the amount is preferably 0.01 to 1 part by weight, more preferably 0.02 to 0.5 part by weight, based on 100 parts by weight of the total amount (total raw material monomers).
- the emulsion polymerization of the acrylic emulsion polymer (A) may be any method such as general batch polymerization, continuous dropping polymerization, or divided dropping polymerization, and the method is not particularly limited. From the viewpoint of reducing contamination, it is desirable to perform polymerization at the same time and at a low temperature (for example, 55 ° C. or less, preferably 30 ° C. or less). When polymerization is performed under such conditions, it is presumed that contamination is reduced because high molecular weight products are easily obtained and low molecular weight products are reduced.
- the above-mentioned acrylic emulsion polymer (A) is a polymer having a structural unit derived from a (meth) acrylic acid alkyl ester and a structural unit derived from a carboxyl group-containing unsaturated monomer as essential structural units.
- the content of the structural unit derived from the (meth) acrylic acid alkyl ester in the acrylic emulsion polymer (A) is preferably 70 to 99.5% by weight, more preferably 85 to 99% by weight.
- the content of the structural unit derived from the carboxyl group-containing unsaturated monomer in the acrylic emulsion polymer (A) is preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight, still more preferably. Is from 2 to 4% by weight.
- the solvent-insoluble content of the acrylic emulsion polymer (A) is preferably 70% (% by weight) or more, more preferably 75% by weight or more. More preferably, it is 80 weight% or more. If the solvent-insoluble content is less than 70% by weight, the acrylic emulsion polymer (A) contains a large amount of low molecular weight substances, so that the low molecular weight component in the pressure-sensitive adhesive layer cannot be sufficiently reduced only by the effect of crosslinking. There are cases where adherend contamination resulting from molecular weight components or the like occurs or the adhesive strength is too high.
- the solvent-insoluble content can be controlled by the polymerization initiator, reaction temperature, type of emulsifier and raw material monomer, and the like. Although the upper limit of the said solvent insoluble part is not specifically limited, For example, 99 weight% is preferable.
- the solvent insoluble content of the acrylic emulsion polymer (A) is a value calculated by the following “method for measuring the solvent insoluble content”.
- the total weight of the tetrafluoroethylene sheet and the kite string is also measured, and this weight is defined as the wrapping weight.
- the acrylic emulsion polymer (A) wrapped with a tetrafluoroethylene sheet and bound with a kite string (referred to as “sample”) is placed in a 50 ml container filled with ethyl acetate at 23 ° C. Let stand for 7 days. Then, the sample (after ethyl acetate treatment) is taken out from the container, transferred to an aluminum cup, dried in a dryer at 130 ° C. for 2 hours to remove ethyl acetate, the weight is measured, and the weight is immersed. After weight.
- the weight average molecular weight (Mw) of the solvent-soluble component (sometimes referred to as “sol component”) of the acrylic emulsion polymer (A) is not particularly limited, but is preferably 40,000 to 200,000, more preferably It is 50,000 to 150,000, more preferably 60,000 to 100,000.
- the weight average molecular weight of the solvent-soluble component of the acrylic emulsion polymer (A) is 40,000 or more, the wettability of the pressure-sensitive adhesive composition to the adherend is improved, and the adhesion to the adherend is improved. improves.
- the weight average molecular weight of the solvent-soluble component of the acrylic emulsion polymer (A) is 200,000 or less, the residual amount of the pressure-sensitive adhesive composition on the adherend is reduced, and the low contamination property is improved. .
- the weight average molecular weight of the solvent-soluble component of the acrylic emulsion polymer (A) is the treatment solution after the ethyl acetate treatment (ethyl acetate solution) obtained in the measurement of the solvent-insoluble component of the acrylic emulsion polymer (A).
- the measurement conditions are as follows.
- the content of the acrylic emulsion polymer (A) in the pressure-sensitive adhesive composition of the present invention is not particularly limited, but is preferably 80% by weight or more, more preferably 100% by weight of the nonvolatile content of the pressure-sensitive adhesive composition. Is 90 to 99% by weight.
- the compound (B) in the pressure-sensitive adhesive composition (water-dispersed acrylic pressure-sensitive adhesive composition) of the present invention is a compound represented by the following formula (I).
- R 1 and R 2 represent a linear or branched alkyl group or a hydrogen atom.
- R 1 and R 2 may be the same or different from each other.
- the linear or branched alkyl group is not particularly limited, and preferable examples include alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group.
- R 1 and R 2 are particularly preferably both hydrogen atoms.
- PO represents an oxypropylene group [—CH 2 CH (CH 3 ) O—].
- a and c are each a positive integer (an integer of 1 or more), preferably 1 to 100, more preferably 10 to 50, and still more preferably 10 to 30. a and c may be the same as or different from each other.
- EO represents an oxyethylene group [—CH 2 CH 2 O—].
- B is a positive integer (an integer of 1 or more), preferably 1 to 50, more preferably 1 to 30, and still more preferably 1 to 15.
- the addition form (copolymerization form) of EO and PO is a block type. That is, the compound (B) is a triblock having a block [polyoxypropylene block, polypropylene glycol (PPG) block] composed of PO on both sides of a block composed of EO [polyoxyethylene block, polyethylene glycol (PEG) block]. It is a copolymer or a derivative thereof.
- the compound (B) has a block-type structure in which the polyoxyethylene block is located at the center of the molecule, and has a structure in which a block composed of a hydrophobic group PO exists at both ends of the molecule. It is difficult to line up evenly at the interface and can exhibit defoaming properties.
- PPG-PEG-PPG triblock copolymer PEG-PPG-PEG triblock copolymer and polyoxyethylene-polyoxypropylene diblock copolymer having polyoxyethylene block at both ends of the molecule Since it is easy to line up uniformly at the gas-liquid interface, it has the effect of stabilizing the foam.
- the compound (B) has high hydrophobicity, it is unlikely to cause whitening contamination that occurs on the adherend in a high humidity environment, and the low contamination property is improved.
- a highly hydrophilic compound especially a water-soluble compound
- the compound dissolves in water and is easily transferred to the adherend, or the bleed compound swells on the adherend. Since it becomes easy to whiten, it is easy to cause whitening contamination.
- the pressure-sensitive adhesive layer (acrylic pressure-sensitive adhesive layer) formed from the pressure-sensitive adhesive composition of the present invention is hardly whitened (humidified whitening) even under humidified storage.
- the pressure-sensitive adhesive sheet is used for a surface protective film for an optical member, if the pressure-sensitive adhesive layer is whitened (that is, the pressure-sensitive adhesive sheet is whitened), the optical member inspection process may be hindered.
- Ratio of “total weight of EO” to “total weight of compound (B)” of the above compound (B) [(total weight of EO) / (total weight of compound (B)) ⁇ 100] (unit:% by weight) (%)) Is not particularly limited, but is preferably 50% by weight or less, more preferably 5 to 50% by weight, and still more preferably 10 to 30% by weight.
- the hydrophilic property of a compound (B) will become high and defoaming property may be lost.
- the said ratio is less than 5 weight%, the hydrophobicity of a compound (B) will become high too much, and it may cause a repellency.
- total weight of compound (B) means “the total amount of all compounds (B) in the pressure-sensitive adhesive composition of the present invention”
- total weight of EO means “this It is "the total amount of the weight of EO contained in all the compounds (B) in the pressure-sensitive adhesive composition of the invention”.
- the ratio of the “total weight of EO” to the “total weight of compound (B)” may be referred to as “EO content”. Examples of the method for measuring the EO content include NMR, chromatography (chromatography), and TOF-SIMS (time-of-flight secondary ion mass spectrometry).
- the number average molecular weight of the compound (B) in the pressure-sensitive adhesive composition of the present invention is preferably 1500 to 4000. If the number average molecular weight is less than 1500, the compatibility of the compound (B) with the system (the system of the pressure-sensitive adhesive composition) becomes too high, and the defoaming effect may not be obtained. On the other hand, if the number average molecular weight exceeds 4000, the incompatibility with the system becomes too high, so that the defoaming property becomes high, but it causes repelling when the pressure-sensitive adhesive composition is applied to a substrate or the like. There is.
- the compound (B) may be a commercially available product. Specifically, for example, trade names “Adeka Pluronic 25R-1”, “Adeka Pluronic 25R-2”, “Adeka Pluronic” manufactured by ADEKA Corporation. 17R-2 ",” Adeka Pluronic 17R-3 "; manufactured by BASF Japan Ltd.,” Pluronic RPE series ".
- the above compound (B) can be used alone or in admixture of two or more.
- the above compound (B) when blending the above compound (B) during the production of the pressure-sensitive adhesive composition of the present invention, it is preferable to blend only the compound (B) without using a solvent, from the viewpoint of improving blending workability, etc.
- a solvent examples include 2-ethylhexanol, butyl cellosolve, dipropylene glycol, ethylene glycol, propylene glycol, normal propyl alcohol, and isopropanol.
- the compounding amount of the compound (B) (content in the pressure-sensitive adhesive composition of the present invention) is not particularly limited, but is 0.01 to 1 part by weight with respect to 100 parts by weight of the acrylic emulsion polymer (A). More preferred is 0.02 to 0.8 parts by weight, even more preferred is 0.02 to 0.5 parts by weight, and most preferred is 0.02 to 0.3 parts by weight. When the blending amount is less than 0.01 parts by weight, defoaming properties may not be imparted, and when it exceeds 1 part by weight, contamination may easily occur.
- the cross-linking agent used in the pressure-sensitive adhesive composition of the present invention is not particularly limited, but a water-insoluble cross-linking agent is preferable from the viewpoint of being able to prevent an increase in adhesive force due to low contamination. Furthermore, a water-insoluble crosslinking agent (C) having two or more functional groups capable of reacting with a carboxyl group in the molecule (in one molecule) is preferable. In the present specification, the “water-insoluble crosslinking agent (C) having two or more functional groups capable of reacting with a carboxyl group in the molecule” may be simply referred to as “water-insoluble crosslinking agent (C)”. is there. That is, the pressure-sensitive adhesive composition of the present invention preferably further contains a water-insoluble crosslinking agent (C).
- the water-insoluble crosslinking agent (C) is a water-insoluble compound, and has two or more (for example, 2 to 6) functional groups capable of reacting with a carboxyl group in the molecule (in one molecule). It is.
- the number of functional groups that can react with a carboxyl group in one molecule is not particularly limited, but is preferably 3 to 5. As the number of functional groups capable of reacting with a carboxyl group in one molecule increases, the pressure-sensitive adhesive composition crosslinks more closely (that is, the cross-linked structure of the polymer forming the acrylic pressure-sensitive adhesive layer becomes dense). For this reason, it becomes possible to prevent the wetting and spreading of the pressure-sensitive adhesive layer after forming the acrylic pressure-sensitive adhesive layer.
- the functional group (carboxyl group) in the acrylic pressure-sensitive adhesive layer segregates on the adherend surface, and the acrylic pressure-sensitive adhesive layer and the adherend are separated. It becomes possible to prevent the adhesive force from increasing with time.
- the number of functional groups capable of reacting with a carboxyl group in one molecule exceeds 6 and is too large, a gelled product may be formed.
- the functional group capable of reacting with the carboxyl group in the water-insoluble crosslinking agent (C) is not particularly limited, and examples thereof include an epoxy group, an isocyanate group, and a carbodiimide group.
- an epoxy group is preferable from the viewpoint of reactivity.
- a glycidylamino group is preferable.
- the water-insoluble crosslinking agent (C) an epoxy-based crosslinking agent having an epoxy group is preferable, and among them, a crosslinking agent having a glycidylamino group (glycidylamino-based crosslinking agent) is preferable.
- the water-insoluble crosslinking agent (C) is an epoxy crosslinking agent (particularly glycidylamino crosslinking agent)
- the number of epoxy groups (particularly glycidylamino group) in one molecule is 2 or more (for example, 2 to 6) is preferable, and 3 to 5 is more preferable.
- the water-insoluble crosslinking agent (C) is a water-insoluble compound.
- water-insoluble means that the solubility in 100 parts by weight of water at 25 ° C. (the weight of the compound (crosslinking agent) that can be dissolved in 100 parts by weight of water) is 5 parts by weight or less, preferably 3 The amount is not more than parts by weight, more preferably not more than 2 parts by weight.
- the remaining crosslinking agent dissolves in moisture and is easily transferred to the adherend, and thus easily causes whitening contamination.
- the water-insoluble cross-linking agent has a higher contribution to the cross-linking reaction (reaction with a carboxyl group) than the water-soluble cross-linking agent, and has a high effect of preventing the adhesive force from increasing with time.
- the crosslinking reaction proceeds promptly by aging, and the adhesive force with the adherend increases with time due to unreacted carboxyl groups in the adhesive layer. Can be prevented.
- solubility with respect to water of said crosslinking agent can be measured as follows, for example.
- Measurement method of water solubility The same weight of water (25 ° C.) and the crosslinking agent are mixed using a stirrer at a rotation speed of 300 rpm for 10 minutes, and separated into an aqueous phase and an oil phase by centrifugation. Next, the aqueous phase is collected and dried at 120 ° C. for 1 hour, and the nonvolatile content in the aqueous phase (parts by weight of nonvolatile components relative to 100 parts by weight of water) is determined from the loss on drying.
- water-insoluble crosslinking agent (C) 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (for example, trade name “TETRAD-C” manufactured by Mitsubishi Gas Chemical Co., Ltd.) Etc.] [Solubility of 2 parts by weight or less with respect to 100 parts by weight of water at 25 ° C.] 1,3-bis (N, N-diglycidylaminomethyl) benzene (for example, Mitsubishi Gas Chemical Co., Ltd., trade name “TETRAD- X "etc.) [glycidylamino-based cross-linking agent such as solubility in 100 parts by weight of water at 25 ° C.
- Tris (2,3-epoxypropyl) isocyclicate for example, trade name“ Nissan Chemical Co., Ltd., trade name “ Other epoxy-based crosslinking agents such as “TEPIC-G” and the like] [solubility of 2 parts by weight or less with respect to 100 parts by weight of water at 25 ° C.] and the like.
- the said water-insoluble crosslinking agent (C) may be used independently and may use 2 or more types together.
- the water-insoluble cross-linking agent (C) is added at the time of preparing the pressure-sensitive adhesive composition of the present invention
- the water-insoluble cross-linking agent (C) is added to the liquid water-insoluble cross-linking agent (C) as it is ( May be added after being dissolved and / or diluted with an organic solvent (however, the amount of the organic solvent used is preferably as small as possible).
- the method of emulsifying the water-insoluble crosslinking agent (C) with an emulsifier is not preferable because the emulsifier bleeds and easily causes contamination (particularly whitening contamination).
- the blending amount of the water-insoluble crosslinking agent (C) (content in the pressure-sensitive adhesive composition of the present invention) is that of the carboxyl group-containing unsaturated monomer used as the raw material monomer of the acrylic emulsion polymer (A). It is preferable that the amount of the functional group capable of reacting with the carboxyl group of the water-insoluble crosslinking agent (C) is 0.3 to 1.3 mol with respect to 1 mol of the carboxyl group.
- the ratio of the “total number of functional groups capable of reacting with a group” [functional group capable of reacting with a carboxyl group / carboxyl group] (molar ratio) is preferably 0.3 to 1.3, more preferably 0.8. It is 4 to 1.1, more preferably 0.5 to 1.0.
- the water-insoluble crosslinking agent (C) is an epoxy crosslinking agent
- the [epoxy group / carboxyl group] (molar ratio) is preferably 0.3 to 1.3, and more preferably 0.8. It is 4 to 1.1, more preferably 0.5 to 1.0.
- the water-insoluble crosslinking agent (C) is a glycidylamino crosslinking agent, it is preferable that [glycidylamino group / carboxyl group] (molar ratio) satisfy the above range.
- water-insoluble crosslinking agent (C) having a functional group equivalent of 110 (g / eq) that can react with a carboxyl group is added (blended) to the pressure-sensitive adhesive composition, water-insoluble
- the number of moles of the functional group capable of reacting with the carboxyl group of the functional crosslinking agent (C) can be calculated as follows, for example.
- the pressure-sensitive adhesive composition of the present invention is a water-dispersed pressure-sensitive adhesive composition.
- the “water-dispersed type” means that it can be dispersed in an aqueous medium, that is, the pressure-sensitive adhesive composition of the present invention is a pressure-sensitive adhesive composition that can be dispersed in an aqueous medium.
- the aqueous medium is a medium (dispersion medium) containing water as an essential component, and may be a mixture of water and a water-soluble organic solvent in addition to water alone.
- the pressure-sensitive adhesive composition of the present invention may be a dispersion using the above aqueous medium or the like.
- the pressure-sensitive adhesive composition of the present invention may contain a polyfunctional hydrazide-based crosslinking agent as another crosslinking agent other than the water-insoluble crosslinking agent (C).
- a polyfunctional hydrazide-based crosslinking agent By using a polyfunctional hydrazide-based crosslinking agent, the removability of the acrylic pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition, the adhesiveness, and the anchoring property with the substrate can be improved.
- a polyfunctional hydrazide-based crosslinking agent (sometimes simply referred to as “hydrazide-based crosslinking agent”) is a compound having at least two hydrazide groups in a molecule (in one molecule). The number of hydrazide groups in one molecule is preferably 2 or 3, more preferably 2.
- the compound used as such a hydrazide-based cross-linking agent is not particularly limited.
- particularly preferred are adipic acid dihydrazide and sebacic acid dihydrazi
- hydrazide-based crosslinking agent for example, “Adipic acid dihydrazide (reagent)” manufactured by Tokyo Chemical Industry Co., Ltd., “Adipoil dihydrazide (reagent)” manufactured by Wako Pure Chemical Industries, Ltd. Etc. can be used.
- the blending amount of the hydrazide crosslinking agent (content in the pressure-sensitive adhesive composition of the present invention) is not particularly limited, but is a keto group-containing unsaturated monomer used as a raw material monomer for the acrylic emulsion polymer (A).
- the amount is preferably 0.025 to 2.5 mol, more preferably 0.1 to 2 mol, and still more preferably 0.2 to 1.5 mol, with respect to 1 mol of the keto group. If the blending amount is less than 0.025 mol, the effect of adding a crosslinking agent is small, the acrylic pressure-sensitive adhesive layer or pressure-sensitive adhesive sheet is delaminated, and a low molecular weight component remains in the polymer forming the acrylic pressure-sensitive adhesive layer. In some cases, whitening contamination of the adherend tends to occur. Moreover, when it exceeds 2.5 mol, an unreacted crosslinking agent component may cause a contamination.
- the pressure-sensitive adhesive composition of the present invention does not substantially contain a quaternary ammonium salt, and further preferably does not substantially contain a quaternary ammonium compound.
- These compounds are generally used as a catalyst or the like for improving the reactivity of the epoxy crosslinking agent. However, these compounds are not incorporated into the polymer forming the pressure-sensitive adhesive layer, and can move freely in the pressure-sensitive adhesive layer, so that they easily deposit on the adherend surface, and these compounds are contained in the pressure-sensitive adhesive composition.
- the content of the quaternary ammonium salt in the pressure-sensitive adhesive composition of the present invention is preferably less than 0.1% by weight, more preferably based on 100% by weight of the pressure-sensitive adhesive composition (nonvolatile content). Is less than 0.01% by weight, more preferably less than 0.005% by weight. Furthermore, it is preferable that the content of the quaternary ammonium compound satisfies the above range.
- the quaternary ammonium salt is not particularly limited, but specifically, for example, a compound represented by the following formula.
- R 3 , R 4 , R 5 , and R 6 represent an alkyl group, an aryl group, or a group derived therefrom (excluding a hydrogen atom, such as an alkyl group or an aryl group having a substituent).
- X ⁇ represents a counter ion.
- the quaternary ammonium salt and the quaternary ammonium compound are not particularly limited, but for example, water such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, etc.
- TMAH tetramethylammonium hydroxide
- tetraethylammonium hydroxide tetrapropylammonium hydroxide
- tetrabutylammonium hydroxide tetrabutylammonium hydroxide
- Alkylammonium oxide and its salts such as tetraphenylammonium hydroxide and its salts, trilaurylmethylammonium ion, didecyldimethylammonium ion, dicocoyldimethylammonium ion, distearyldimethylammonium ion, dioleyldimethylammonium ion Ion, cetyltrimethylammonium ion, stearyltrimethylammonium ion, behenyltrimethylammonium ion, cocoylbis (2-H Roxyethyl) methylammonium ion, polyoxyethylene (15) cocostearylmethylammonium ion, oleylbis (2-hydroxyethyl) methylammonium ion, cocobenzyldimethylammonium ion, laurylbis (2-hydroxyethyl) methylammonium ion, decylbis (2-
- the pressure-sensitive adhesive composition of the present invention is for improving the reactivity of the epoxy-based crosslinking agent in the same manner as the quaternary ammonium salt (or quaternary ammonium compound) from the viewpoint of low contamination. It is preferable not to add a tertiary amine and an imidazole compound which are generally used as a catalyst or the like. Therefore, it is preferable that the pressure-sensitive adhesive composition of the present invention does not substantially contain a tertiary amine and an imidazole compound.
- the content of the tertiary amine and the imidazole compound (the total content of the tertiary amine and the imidazole compound) in the pressure-sensitive adhesive composition of the present invention is not particularly limited, but the pressure-sensitive adhesive composition (Non-volatile content) It is preferably less than 0.1% by weight, more preferably less than 0.01% by weight, and still more preferably less than 0.005% by weight with respect to 100% by weight.
- tertiary amine examples include tertiary amine compounds such as triethylamine, benzyldimethylamine and ⁇ -methylbenzyl-dimethylamine.
- imidazole compound examples include 2-methylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 4-ethylimidazole, 4-dodecylimidazole, 2-phenyl-4-hydroxymethylimidazole, and 2-ethyl-4. -Hydroxymethylimidazole, 1-cyanoethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole and the like.
- the pressure-sensitive adhesive composition of the present invention may contain various additives other than those described above as long as the contamination is not affected.
- various additives include pigments, fillers, leveling agents, dispersants, plasticizers, stabilizers, antioxidants, ultraviolet absorbers, ultraviolet stabilizers, anti-aging agents, and antiseptics.
- the leveling agent is not particularly limited, and examples thereof include acetylene diol compounds (diol compounds having an acetylene bond in the molecule), fluorocarbon-modified polyacrylates, and the like.
- the amount of the leveling agent (content in the pressure-sensitive adhesive composition of the present invention) is not particularly limited, but is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the acrylic emulsion polymer (A). More preferably, it is 0.1 to 5 parts by weight.
- the said leveling agent may be used independently and may use 2 or more types together.
- the pressure-sensitive adhesive composition of the present invention can be prepared by mixing the acrylic emulsion polymer (A) and the compound (B). If necessary, the water-insoluble crosslinking agent (C), other crosslinking agents, and various additives may be mixed.
- the said mixing method can use the mixing method of a well-known and usual emulsion, although it does not specifically limit, For example, stirring using a stirrer is preferable.
- the stirring conditions are not particularly limited, but for example, the temperature is preferably 10 to 50 ° C, more preferably 20 to 35 ° C.
- the stirring time is preferably 5 to 30 minutes, more preferably 10 to 20 minutes.
- the stirring speed is preferably 10 to 2000 rpm, more preferably 30 to 1000 rpm.
- the timing of adding the compound (B) is not particularly limited, and the compound (B) may be added during the polymerization of the acrylic emulsion polymer (A), or the acrylic emulsion polymer (A after polymerization) ) And compound (B) may be mixed.
- the timing at which the water-insoluble crosslinking agent (C) is added is not particularly limited, but is preferably just before the application of the pressure-sensitive adhesive composition from the viewpoint of pot life.
- the pressure-sensitive adhesive composition obtained as described above is applied to at least one side of the transparent film substrate, and is dried as necessary to form an acrylic pressure-sensitive adhesive layer.
- a pressure-sensitive adhesive sheet having an acrylic pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention on at least one side of the film substrate can be obtained.
- Crosslinking is performed by dehydrating in the drying step, heating the pressure-sensitive adhesive sheet after drying, or the like.
- the acrylic pressure-sensitive adhesive layer is preferably formed by the so-called direct copying method in which the pressure-sensitive adhesive composition is directly applied to the surface of the transparent film substrate as described above.
- the acrylic pressure-sensitive adhesive layer has a high solvent-insoluble content
- a so-called transfer method in which an acrylic pressure-sensitive adhesive layer is once formed on a release film and then transferred (bonded) to the transparent film substrate is used. Since sufficient anchoring property (adhesion) of the acrylic pressure-sensitive adhesive layer may not be obtained, the direct copy method is preferably used.
- the pressure-sensitive adhesive sheet of the present invention may be a pressure-sensitive adhesive sheet having an acrylic pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition of the present invention on at least one side of the substrate, and the production method is not particularly limited.
- the thickness of the acrylic pressure-sensitive adhesive layer (after crosslinking) in the pressure-sensitive adhesive sheet of the present invention is not particularly limited, but is preferably 1 to 50 ⁇ m, more preferably 1 to 35 ⁇ m, and still more preferably 3 to 25 ⁇ m.
- the solvent-insoluble content of the acrylic pressure-sensitive adhesive layer is not particularly limited, but is preferably 90% by weight or more, and more preferably 95% by weight or more. When the solvent-insoluble content is less than 90% by weight, transfer of contaminants to the adherend increases, whitening contamination may occur, and re-peelability may be insufficient (heavy release).
- the upper limit of the solvent insoluble content of the acrylic pressure-sensitive adhesive layer (after crosslinking) is not particularly limited, for example, 99% by weight is preferable.
- crosslinking) can be measured by the method similar to the measuring method of the solvent insoluble matter of the above-mentioned acrylic emulsion type polymer.
- the glass transition temperature of the acrylic polymer (after crosslinking) forming the acrylic pressure-sensitive adhesive layer is not particularly limited, but is preferably ⁇ 70 to ⁇ 10 ° C., more preferably ⁇ 70 to ⁇ 20 ° C., and still more preferably. It is -70 to -40 ° C, most preferably -70 to -60 ° C. When the glass transition temperature exceeds ⁇ 10 ° C., the adhesive strength is insufficient, and there are cases where floating or peeling occurs during processing. If the temperature is lower than -70 ° C, heavy peeling occurs in a higher peeling speed (tensile speed) region, which may reduce work efficiency.
- the glass transition temperature of the acrylic polymer (after crosslinking) that forms this acrylic pressure-sensitive adhesive layer can be adjusted, for example, by the monomer composition when preparing the acrylic emulsion polymer (A).
- the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive force (180 ° peel test) against a polarizing plate (triacetylcellulose (TAC) plate) (with a surface arithmetic average roughness Ra of 50 nm or less) at a tensile rate of 0.3 m / min.
- the peeling force when peeling the pressure-sensitive adhesive sheet attached to the polarizing plate is preferably 0.01 to 5 N / 25 mm, more preferably 0.02 to 3 N / 25 mm, and still more preferably 0.03 to 2 N / mm. 25 mm, most preferably 0.04 to 1 N / 25 mm.
- the adhesive strength exceeds 5 N / 25 mm, it is difficult to peel off the adhesive sheet in the manufacturing process of the polarizing plate or the liquid crystal display device, and productivity and handleability may be reduced. If it is less than 0.01 N / 25 mm, the pressure sensitive adhesive sheet may float or peel off during the production process, and the protective function as a pressure sensitive adhesive sheet for surface protection may be reduced.
- the arithmetic average roughness Ra can be measured using, for example, P-15 (contact type surface shape measuring device) manufactured by KLA Tencor.
- the surface roughness is not particularly limited, and can be measured, for example, under the conditions of a measurement length of 1000 ⁇ m, a scanning speed of 50 ⁇ m / second, a scanning frequency of once, and a load of 2 mg.
- the total light transmittance (according to JIS K7361-1) in the visible light wavelength region of the pressure-sensitive adhesive sheet of the present invention is not particularly limited, but is preferably 80 to 97%, more preferably 85 to 95%.
- the haze (according to JIS K7136) of the pressure-sensitive adhesive sheet of the present invention is not particularly limited, but is preferably 1.0 to 3.5%, more preferably 2.0 to 3.2%. If the total light transmittance and / or haze of the pressure-sensitive adhesive sheet is out of the above range, it tends to be difficult to perform an appearance inspection of the adherend.
- the surface resistivity of the top coat layer surface of the transparent film substrate is not particularly limited, but is 100 ⁇ 10 8 ⁇ / ⁇ or less (for example, 0.1 ⁇ 10 8 to 100 ⁇ 10 8 ⁇ / ⁇ ), preferably 50 ⁇ 10 8 ⁇ / ⁇ or less (for example, 0.1 ⁇ 10 8 to 50 ⁇ 10 8 ⁇ / ⁇ ), and more preferably 1 ⁇ 10 8. ⁇ 50 ⁇ 10 8 ⁇ / ⁇ .
- the surface resistivity When the surface resistivity is 100 ⁇ 10 8 ⁇ / ⁇ or less, it can be preferably used particularly as a surface protective film used in processing or transporting an article that dislikes static electricity such as a liquid crystal cell or a semiconductor device.
- the value of the surface resistivity can be calculated from the value of the surface resistance measured under an atmosphere of 23 ° C. and relative humidity 55% RH using a commercially available insulation resistance measuring device. Specifically, the value of the surface resistivity obtained by the surface resistivity measuring method described in the examples described later can be preferably employed.
- the friction coefficient of the topcoat layer surface of the said transparent film base material ie, the topcoat layer surface of the adhesive sheet of this invention
- 0.4 or less is preferable.
- the friction coefficient is not particularly limited.
- the friction coefficient is not particularly limited, but is preferably 0.1 to 0.4, and more preferably 0.15 to 0.4.
- the friction coefficient is a value obtained by rubbing the surface of the top coat layer of the transparent film substrate (or the pressure-sensitive adhesive sheet of the present invention) with a vertical load of 40 mN, for example, in a measurement environment of 23 ° C. and a relative humidity of 50% RH. Can be adopted.
- a method of reducing (adjusting) the friction coefficient a method of adding various lubricants (leveling agents, etc.) to the top coat layer, a method of increasing the cross-linking density of the top coat layer by adding a cross-linking agent or adjusting film forming conditions Etc. can be adopted as appropriate.
- the surface of the top coat layer of the transparent film substrate that is, the surface of the top coat layer of the pressure-sensitive adhesive sheet of the present invention can be easily printed with oil-based ink or water-based ink (for example, using an oil-based marking pen) (“printability” It may be referred to as “.
- Such a surface protective film adheresive sheet is used to identify an identification number or the like of an adherend to be protected in the process of processing or transporting an adherend (for example, an optical component) bonded with the surface protective film. Suitable for displaying on a surface protective film.
- the pressure-sensitive adhesive sheet of the present invention is preferably a surface protective film that is excellent in printability in addition to appearance characteristics, and is particularly high in printing for oil-based inks that are alcohol-based and contain pigments. It is preferable to have properties. Further, it is preferable that the printed ink has a characteristic that it is difficult to remove by rubbing or transfer (sometimes referred to as “print adhesion”). The degree of the printability can be grasped by, for example, the following printability evaluation. (Printability (print adhesion) evaluation) After printing on the surface of the topcoat layer using an X stamper manufactured by Shachihata in a measurement environment of 23 ° C. and 50% RH, a cellophane adhesive tape manufactured by Nichiban Co., Ltd.
- the surface of the top coat layer of the transparent film substrate that is, the surface of the top coat layer of the pressure-sensitive adhesive sheet of the present invention is visible even if the print is wiped with alcohol (for example, ethyl alcohol) when the print is corrected or erased. It is preferable to have a solvent resistance that does not cause noticeable changes (whitening).
- the degree of the solvent resistance can be grasped by, for example, the following solvent resistance evaluation. (Solvent resistance evaluation) In a room (dark room) where outside light is blocked, the top coat layer surface is wiped 15 times with a cloth (cloth) soaked with ethyl alcohol, and the appearance is visually observed.
- the pressure-sensitive adhesive sheet of the present invention is excellent in whitening contamination deterrence of the adherend. This can be evaluated, for example, as follows.
- the pressure-sensitive adhesive sheet is bonded to a polarizing plate (trade name “SEG1425DUHC”, manufactured by Nitto Denko Corporation) under the conditions of 0.25 MPa and 0.3 m / min, left at 80 ° C. for 4 hours, and then peeled off. .
- the polarizing plate after the pressure-sensitive adhesive sheet is peeled is further left for 12 hours in an environment of 23 ° C. and 90% RH, and then the surface is observed. At this time, it is preferable that no whitening is observed on the surface of the polarizing plate.
- When whitening occurs on the polarizing plate as an adherend under humidification conditions (high humidity conditions) after sticking / peeling the pressure-sensitive adhesive sheet low contamination is not sufficient for use as a surface protective film for optical members.
- the pressure-sensitive adhesive sheet of the present invention can be a wound body, and can be wound into a roll while the acrylic pressure-sensitive adhesive layer is protected with a release film (separator).
- the back side of the pressure-sensitive adhesive sheet (the surface opposite to the side where the acrylic pressure-sensitive adhesive layer is provided, usually the surface of the topcoat layer) is a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid amide-based release agent A release treatment and / or antifouling treatment with an agent, silica powder or the like may be performed, and a back treatment layer (release treatment layer, antifouling treatment layer, etc.) may be provided.
- an acrylic pressure-sensitive adhesive layer / transparent film substrate / back treatment layer is preferable.
- the pressure-sensitive adhesive sheet of the present invention is excellent in adhesiveness and removability (easy releasability) and can be re-removed, so that it can be used for re-removal (for re-removal). That is, the adhesive sheet of the present invention is used for re-peeling [for example, masking tape for architectural curing, masking tape for automobile coating, masking tape for electronic parts (lead frame, printed circuit board, etc.), masking tape for sandblasting, etc.
- the pressure-sensitive adhesive sheet of the present invention has excellent appearance characteristics because the appearance failure of the pressure-sensitive adhesive layer such as dents and bubble defects is reduced and it does not look whitish despite having a topcoat layer. Moreover, the adhesive sheet of this invention can exhibit the outstanding scratch resistance and antistatic property by having the said topcoat layer. For this reason, the pressure-sensitive adhesive sheet of the present invention constitutes a panel such as a liquid crystal display, organic electroluminescence (organic EL), field emission display, etc., which requires particularly excellent appearance characteristics, scratch resistance, and antistatic properties.
- Surface protection for optical members optical plastic, optical glass, optical film, etc.
- polarizing plates such as polarizing plates, retardation plates, antireflection plates, wave plates, optical compensation films, brightness enhancement films, etc.
- binder solution 1 including 0.1 g of binder polymer 1
- 40 g of ethylene glycol monoethyl ether were added to a beaker having a capacity of 150 mL and stirred and mixed.
- 1.2 g of NV 4.0 wt% conductive polymer solution 1 (aqueous solution) containing polyethylene dioxythiophene (PEDT) and polystyrene sulfonate (PSS), 55 g of ethylene glycol monomethyl ether, and polyether were added to this beaker.
- PEDT polyethylene dioxythiophene
- PSS polystyrene sulfonate
- Modified polydimethylsiloxane leveling agent (lubricant solution) (BYK Chemie, trade name “BYK-300”, NV52% by weight) 0.05 g and melamine crosslinker (manufactured by Sanwa Chemical Co., Ltd., trade name “ Nicalac MW-30M ”(non-volatile content: 100%) (0.02 g) was added, and the mixture was stirred for about 20 minutes and mixed well.
- the top containing 48 parts by weight of conductive polymer, 26 parts by weight of lubricant, and 20 parts by weight of melamine crosslinking agent (all in terms of solid content) with respect to 100 parts by weight of binder polymer 1 (acrylic polymer).
- a composition for forming a coat layer (NV: 0.2% by weight) was prepared.
- the topcoat layer forming composition is applied to the corona-treated surface of a transparent polyethylene terephthalate film (PET film) having a thickness of 38 ⁇ m, a width of 30 cm, and a length of 40 cm. It applied so that the thickness after drying might be set to about 10 nm.
- PET film transparent polyethylene terephthalate film
- the coated material was heated at 130 ° C. for 2 minutes and dried to form a topcoat layer on one surface of the PET film.
- the transparent film base material (it may be called "the base material 1") which has a transparent topcoat layer on the single side
- Production Example 2 [Production Example of Transparent Film Base]
- the amount of conductive polymer solution 1 used was changed from 1.2 g to 2.5 g, and the amount of ethylene glycol monomethyl ether used was changed from 55 g to 17 g.
- the topcoat layer forming solution was applied so that the thickness after drying was about 20 nm.
- the transparent film base material it may be called "the base material 2" which has a transparent topcoat layer on the single side
- Production Example 3 [Production Example of Transparent Film Base]
- the amount of ethylene glycol monoethyl ether used was changed from 40 g to 19 g
- the amount of conductive polymer solution 1 used was changed from 1.2 g to 0.7 g
- ethylene glycol monomethyl ether was not used.
- the topcoat layer forming solution was applied so that the thickness after drying was about 40 nm.
- Production Example 4 [Production Example of Transparent Film Base]
- the amount of ethylene glycol monoethyl ether used was changed from 19 g to 15 g.
- the topcoat layer forming solution was applied so that the thickness after drying was about 50 nm.
- the transparent film base material (it may be called "the base material 4") which has a transparent topcoat layer on the single side
- binder solution 2 including 2.3 g of binder polymer 2
- 30 g of ethylene glycol monoethyl ether were placed in a beaker having a capacity of 150 mL and mixed with stirring.
- 14 g of NV 1.3 wt% conductive polymer solution 2 (aqueous solution) containing PEDT and PSS, 6 g of ethylene glycol monomethyl ether, and 0.5 g of a lubricant solution (BYK-300) were added to this beaker and stirred for about 30 minutes. And mixed well.
- a composition for forming a topcoat layer containing 8 parts by weight of a conductive polymer and 11 parts by weight of a lubricant (both based on solid content) is prepared with respect to 100 parts by weight of binder polymer 2 (acrylic polymer). did.
- the crosslinking agent is not mix
- the top coat layer forming composition is dried on a corona-treated surface of a transparent polyethylene terephthalate film (PET film) having a thickness of 38 ⁇ m, a width of 30 cm, and a length of 40 cm, which is corona-treated on one side, using a bar coater.
- the thickness of the coating was about 610 nm.
- the coated product was dried by heating at 80 ° C. for 2 minutes to form a topcoat layer.
- the transparent film base material (it may be called "the base material 5") which has a transparent topcoat layer on the single side
- ⁇ 2 g of the binder solution 3 (including 0.1 g of the binder polymer 3) and 40 g of ethylene glycol monoethyl ether were added to a beaker having a capacity of 150 mL and stirred and mixed. Furthermore, 1.2 g of NV 4.0 wt% conductive polymer solution 1 (aqueous solution) containing polyethylene dioxythiophene (PEDT) and polystyrene sulfonate (PSS), 55 g of ethylene glycol monomethyl ether, and polyether were added to this beaker.
- PEDT polyethylene dioxythiophene
- PSS polystyrene sulfonate
- Modified polydimethylsiloxane leveling agent (lubricant solution) (BYK Chemie, trade name “BYK-300”, NV52% by weight) 0.05 g and melamine crosslinker (manufactured by Sanwa Chemical Co., Ltd., trade name “ Nicalac MW-30M ”) and 0.02 g were added, and the mixture was stirred for about 20 minutes and mixed well.
- the binder polymer 3 acrylic polymer
- the top containing 48 parts by weight of the conductive polymer, 26 parts by weight of the lubricant, and 20 parts by weight of the melamine crosslinking agent (all in terms of solid content).
- a composition for forming a coat layer (NV: 0.2% by weight) was prepared.
- the topcoat layer forming composition is applied to the corona-treated surface of a transparent polyethylene terephthalate film (PET film) having a thickness of 38 ⁇ m, a width of 30 cm, and a length of 40 cm. It applied so that the thickness after drying might be set to about 8 nm.
- PET film transparent polyethylene terephthalate film
- the coated material was heated at 130 ° C. for 2 minutes and dried to form a topcoat layer on one surface of the PET film.
- the transparent film base material (it may be called "the base material 6") which has a transparent topcoat layer on the single side
- Table 1 shows the composition of the topcoat layer in the transparent film base materials (base materials 1 to 6) prepared above, and the evaluation results of these transparent film base materials according to the evaluation procedure described later.
- Production Example 7 [Production Example of Water-dispersed Acrylic Adhesive Composition] (Preparation of acrylic emulsion polymer) In a container, 90 parts by weight of water and 96 parts by weight of 2-ethylhexyl acrylate (2EHA), 4 parts by weight of acrylic acid (AA), nonionic anionic reactive emulsifier (Daiichi Kogyo Seiyaku ( After mixing 3 parts by weight of a trade name “AQUALON HS-10” manufactured by the same company, the mixture was stirred and mixed with a homomixer to prepare a monomer emulsion.
- 2EHA 2-ethylhexyl acrylate
- AA acrylic acid
- AA nonionic anionic reactive emulsifier
- AQUALON HS-10 trade name manufactured by the same company
- Production Example 8 [Production Example of Water-dispersed Acrylic Adhesive Composition] As shown in Table 2, as a reactive emulsifier, in the same manner as in Production Example 7, except that 3 parts by weight of “ADEKA rear soap SE-10N” was used instead of “AQUALON HS-10”, an aqueous dispersion type An acrylic pressure-sensitive adhesive composition (sometimes referred to as “pressure-sensitive adhesive 2”) was prepared.
- Production Example 9 [Production Example of Water-dispersed Acrylic Adhesive Composition] As shown in Table 2, the monomer raw material of the acrylic emulsion polymer was changed to 92 parts by weight of 2-ethylhexyl acrylate (2EHA), 4 parts by weight of methyl methacrylate (MMA), and 4 parts by weight of acrylic acid (AA). Except for this, a water-dispersed acrylic pressure-sensitive adhesive composition (sometimes referred to as “pressure-sensitive adhesive 3”) was prepared in the same manner as in Production Example 7.
- 2EHA 2-ethylhexyl acrylate
- MMA methyl methacrylate
- AA acrylic acid
- Production Example 10 [Production Example of Water-dispersed Acrylic Adhesive Composition] As shown in Table 2, in the same manner as in Production Example 8, except that 0.5 part by weight of “Adekapluronic 17R-3” was used instead of “Adekapluronic 25R-1” as the compound (B), A water-dispersed acrylic pressure-sensitive adhesive composition (sometimes referred to as “pressure-sensitive adhesive 4”) was prepared.
- Production Example 11 [Production Example of Water-dispersed Acrylic Adhesive Composition] As shown in Table 2, as compound (B), 0.5 parts by weight of “PPO-PEO-PPO” was used instead of “Adekapluronic 25R-1”, and water-insoluble crosslinking agent (C) was used. A water-dispersed acrylic pressure-sensitive adhesive composition (sometimes referred to as “pressure-sensitive adhesive 5”) in the same manner as in Production Example 7, except that 3 parts by weight of “tetrad-X” was used instead of “tetrad-C”. Prepared).
- pressure-sensitive adhesive 5 (sometimes referred to as “pressure-sensitive adhesive 5”) in the same manner as in Production Example 7, except that 3 parts by weight of “tetrad-X” was used instead of “tetrad-C”.
- Production Example 12 [Production Example of Water-dispersed Acrylic Adhesive Composition] As shown in Table 2, a water-dispersed acrylic pressure-sensitive adhesive composition (sometimes referred to as “pressure-sensitive adhesive 6”) was prepared in the same manner as in Production Example 7 except that the copolymer (B) was not used. Prepared).
- pressure-sensitive adhesive 6 a water-dispersed acrylic pressure-sensitive adhesive composition
- Production Example 13 [Production Example of Water-dispersed Acrylic Adhesive Composition] As shown in Table 2, production examples except that a compound other than the compound (B) (0.5 parts by weight of “POLYRan (EO-PO)”) was used instead of the copolymer as the compound (B). In the same manner as in No. 7, a water-dispersed acrylic pressure-sensitive adhesive composition (sometimes referred to as “pressure-sensitive adhesive 7”) was prepared.
- Production Example 14 [Production Example of Water-dispersed Acrylic Adhesive Composition] As shown in Table 2, Production Example 7 except that a compound other than the compound (B) (3.0 parts by weight of “PEO-PPO-PEO”) was used instead of the copolymer which is the compound (B). In the same manner, a water-dispersed acrylic pressure-sensitive adhesive composition (sometimes referred to as “pressure-sensitive adhesive 8”) was prepared.
- Production Example 15 [Production Example of Water-dispersed Acrylic Adhesive Composition] As shown in Table 2, the compounding amount of “Adekapluronic 25R-1” as the compound (B) was changed to 0.1 parts by weight with respect to 100 parts by weight of the acrylic emulsion polymer (solid content). Prepared a water-dispersed acrylic pressure-sensitive adhesive composition (sometimes referred to as “pressure-sensitive adhesive 9”) in the same manner as in Production Example 7.
- Table 2 shows the compositions of the water-dispersed acrylic pressure-sensitive adhesive compositions (pressure-sensitive adhesives 1 to 9) prepared above.
- Example 1 As shown in Table 3, the water-dispersed acrylic pressure-sensitive adhesive composition (pressure-sensitive adhesive 1) obtained above was placed on the side opposite to the topcoat layer of the transparent film base material (base material 1) obtained above. Using an applicator manufactured by Tester Sangyo Co., Ltd., the surface is coated (coated) so that the thickness after drying is 15 ⁇ m, and then dried in a hot air circulation oven at 120 ° C. for 2 minutes, and the pressure-sensitive adhesive after drying After bonding the silicone-treated surface of a PET film (Mitsubishi Resin Co., Ltd., “MRF38”) surface-treated with silicone to the layer, it was cured (aged) at 50 ° C. for 3 days to obtain an adhesive sheet.
- a PET film Mitsubishi Resin Co., Ltd., “MRF38”
- Comparative Examples 1 to 6 As shown in Table 3, the type of the water-dispersed acrylic pressure-sensitive adhesive composition and the transparent film substrate was changed, and a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1.
- the trade name “Diafoil T100G” (manufactured by Mitsubishi Chemical Corporation) used as a base material in Comparative Example 6 is a PET film (antistatic treated PET film) having an antistatic layer on one surface. .
- the antistatic layer contains a compound having an ammonium base as an antistatic agent.
- Topcoat layer thickness (average thickness and thickness variation) The thickness of the topcoat layer was measured by observing a cross section of the transparent film substrate produced in the production example with a transmission electron microscope (TEM). On the other hand, the surface of the top coat layer of the transparent film substrate is subjected to sulfur atoms (PEDT and PSS contained in the top coat layer) using an X-ray fluorescence analyzer (manufactured by Rigaku, XRF apparatus, model “ZSX-100e”). The peak intensity of (derived) was measured. X-ray fluorescence analysis was performed under the following conditions.
- the thickness of the topcoat layer at the five measurement positions was determined.
- the average thickness D ave was measured by arithmetically averaging the thickness of the top coat layer at the above five measurement points.
- ⁇ s Rs ⁇ E / V ⁇ ⁇ (D + d) / (D ⁇ d)
- ⁇ s the surface resistivity ( ⁇ / ⁇ )
- Rs the surface resistance ( ⁇ )
- E the applied voltage (V)
- V the measured voltage (V)
- D the inner diameter of the annular electrode on the surface.
- Cm and d represent the outer diameter (cm) of the inner circle of the surface electrode.
- a polarizing plate material: triacetyl cellulose (TAC), surface arithmetic average roughness Ra is about 21 nm in the MD direction, about 31 nm in the TD direction, and an average of about 26 nm in the MD direction and the TD direction. Pasted together).
- TAC triacetyl cellulose
- the adhesive strength (N / 25 mm) of the adhesive sheet to the polarizing plate was measured, and was defined as “adhesive strength after pasting and storage at 40 ° C. for 1 week”.
- the 180 ° peel test was performed using a tensile tester in an environment of 23 ° C. and 50% RH at a tensile speed of 0.3 m / min. If the difference between the initial adhesive strength and the adhesive strength after storage at 40 ° C for 1 week [(Adhesive strength after storage at 40 ° C for 1 week)-(initial adhesive strength)] is 0.10 N / 25 mm or less, the increase in adhesive strength is prevented. It can be judged that it is excellent in property.
- Appearance of adhesive sheet (appearance characteristics) The state of the acrylic pressure-sensitive adhesive layer surface of the pressure-sensitive adhesive sheets obtained in Examples and Comparative Examples was visually observed, and the number of defects (dents and bubbles) within the observation range of 10 cm long ⁇ 10 cm wide was measured. Together with the evaluation results of the appearance of the transparent film substrate, the appearance (appearance characteristics) of the pressure-sensitive adhesive sheet was comprehensively evaluated according to the following criteria. Appearance of the pressure-sensitive adhesive sheet is poor (x): When the appearance of the transparent film substrate is poor, or when the appearance of the transparent film substrate is good, but the number of the above defects is 101 or more Appearance is good ( ⁇ ): When the appearance of the transparent film substrate is good and the number of the above defects is 0 to 100
- the pressure-sensitive adhesive sheets (Examples) satisfying the provisions of the present invention had a good appearance, and the increase in adhesive strength over time after application was small. Moreover, it had excellent antistatic properties and scratch resistance. Furthermore, it was not whitened when stored under humidification.
- a comparative example in which the compound (B) is not added Comparative Examples 1 to 3
- a comparative example in which the average thickness and / or variation in thickness of the topcoat layer of the substrate do not satisfy the provisions of the present invention Comparative Example 4, In 5
- the appearance of the pressure-sensitive adhesive sheet was poor.
- the comparative example (comparative example 5) which does not contain a melamine type crosslinking agent as a structural component of a topcoat layer was also inferior in scratch resistance.
- Comparative Example (Comparative Example 2) using a compound other than Compound (B) in place of Compound (B) a large increase in haze value was observed due to humid storage, and whitening of the pressure-sensitive adhesive sheet was confirmed under humid storage. It was.
- the antistatic layer of the base material is not a topcoat layer having a structure containing polythiophene, an acrylic resin, and a melamine-based crosslinking agent (Comparative Example 6)
- an increase in haze value due to humidification storage is observed, and It was inferior in scratch property.
- the pressure-sensitive adhesive sheet of the present invention is used for re-peeling applications.
- optical members optical plastics
- polarizing plates such as polarizing plates, retardation plates, antireflection plates, wave plates, optical compensation films, and brightness enhancement films constituting panels
- liquid crystal displays organic electroluminescence (organic EL), and field emission displays
- Optical glass, optical film, etc. for surface protection (surface protection film for optical members, etc.).
- the pressure-sensitive adhesive sheet of the present invention can be used, for example, for surface protection and damage prevention in the manufacture of microfabricated parts such as semiconductors, circuits, various printed boards, various masks and lead frames, or for removing foreign substances, masking, etc. Can be used.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Laminated Bodies (AREA)
- Adhesive Tapes (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
R1O-(PO)a-(EO)b-(PO)c-R2 (I)
(式中、R1及びR2は、直鎖状又は分岐鎖状のアルキル基、又は、水素原子を表す。POはオキシプロピレン基、EOはオキシエチレン基を表す。a、b及びcは、それぞれ正の整数である。EOとPOの付加形態はブロック型である。)
本発明の粘着シートにおける透明フィルム基材は、樹脂材料からなるベース層と、該ベース層の第一面上に設けられた後述のトップコート層とを少なくとも有する。上記透明フィルム基材は、上記ベース層の一方の面(第一面)側にのみ上記トップコート層を有する構成(積層構成)であってもよいし、上記ベース層の両面(第一面及び第二面)側に上記トップコート層を有する構成(積層構成)であってもよい。中でも、上記透明フィルム基材は、上記ベース層の一方の面(第一面)側にのみ上記トップコート層を有する構成(「ベース層/トップコート層」の積層構成)であることが好ましい。
上記透明フィルム基材のベース層は、樹脂材料により構成された透明なフィルム状(薄膜状)の成型体である。即ち、上記ベース層としては、各種の樹脂材料をフィルム状に成型してなる樹脂フィルムを好ましく使用できる。上記ベース層を構成する樹脂材料としては、特に限定されないが、透明性、機械的強度、熱安定性、水分遮蔽性、及び等方性などのうち、1又は2以上の特性に優れた樹脂フィルムを形成し得る樹脂材料が好ましく、具体的には、例えば、ポリエチレンテレフタレート(PET)、ポリエチレンナフタレート、ポリブチレンテレフタレート等のポリエステル系ポリマー;ジアセチルセルロース、トリアセチルセルロース等のセルロース系ポリマー;ポリカーボネート系ポリマー;ポリメチルメタクリレート等のアクリル系ポリマーなどを主たる成分(樹脂成分)(上記樹脂材料の主成分、例えば、樹脂材料(100重量%)の50重量%以上を占める成分)とする樹脂材料が好ましく、より好ましくはポリエチレンテレフタレート又はポリエチレンナフタレートを主たる成分とする樹脂材料である。なお、上記樹脂材料には、例えば、ポリスチレン、アクリロニトリル-スチレン共重合体等のスチレン系ポリマー;ポリエチレン、ポリプロピレン、環状乃至ノルボルネン構造を有するポリオレフィン、エチレン-プロピレン共重合体等のオレフィン系ポリマー;塩化ビニル系ポリマー;ナイロン6、ナイロン6,6、芳香族ポリアミド等のアミド系ポリマー;イミド系ポリマー;スルホン系ポリマー;ポリエーテルスルホン系ポリマー;ポリエーテルエーテルケトン系ポリマー;ポリフェニレンスルフィド系ポリマー;ポリビニルアルコール系ポリマー;ポリオキシメチレン系ポリマー;エポキシ系ポリマーなども使用できる。上記ベース層は、上記ポリマーの二種以上のブレンド物から形成されたものであってもよい。上記ベース層は、光学特性(位相差等)の異方性が小さいほど好ましい。特に、光学部材用の表面保護フィルム用途においては、上記ベース層の光学的異方性を小さくすることが有益である。上記ベース層は、単層構造であってもよいし、組成の異なる複数の層が積層された構造であってもよい。中でも、上記ベース層は単層構造であることが好ましい。
本発明の粘着シートにおける透明フィルム基材のトップコート層は、上記ベース層の少なくとも第一面側に形成される表面層であり、少なくともポリチオフェン、アクリル樹脂、及びメラミン系架橋剤を必須の成分として構成される。上記トップコート層を有することにより、本発明の粘着シートは、耐スクラッチ性、帯電防止性、耐溶剤性、印字性、印字密着性などの各種機能を発揮することができる。本発明の粘着シートが上記機能を有する場合には、特に、光学フィルムの表面保護用途として好ましく使用できる。
後述の実施例では、加速電圧:100kV、倍率:60,000倍の条件で得られた断面画像について二値化処理を行った後、視野内のサンプル長さでトップコート層の断面積を除算することで、トップコート層の厚み(視野内の平均厚み)を実測した。
なお、重金属染色を行わなくてもトップコート層を十分明瞭に観察し得る場合には、重金属染色を省略してもよい。
あるいは、TEMにより把握される厚みと、各種の厚み検出装置(例えば、表面粗さ計、干渉厚み計、赤外分光測定機、各種X線回折装置等)による検出結果との相関につき、検量線を作成して計算することにより、トップコート層の厚みを求めてもよい。
上記トップコート層の厚みのバラツキΔDは、トップコート層を横切る直線(例えば、トップコート層を幅方向に横切る直線)に沿って均等な間隔で配置された5箇所の測定点について、上記トップコート層の厚みを測定し、これら測定値の最大値Dmaxと最小値Dminとの差を平均厚みDaveで割った値[ΔD(%)=(Dmax-Dmin)/Dave×100]として定義される。なお、上記測定点は、隣り合う測定点が2cm以上(好ましくは5cm以上)離れていることが好ましい。また、上記トップコート層の各測定点における厚みは、上述の方法(例えば、TEM観察により直接測定してもよいし、適当な厚み検出装置による検出結果を検量線により厚みに換算してもよい)により測定できる。
より具体的には、後述の実施例に記載の厚みの測定方法に従って、トップコート層の平均厚みDave、厚みのバラツキΔDを測定できる。
上記トップコート層の厚みのバラツキΔDが40%以下であると、部分的に白っぽくなることによるスジやムラが視認されにくくなり、良好な外観特性を発揮する。即ち、上記ΔDは小さいほど、より優れた外観特性を発揮できる。また、上記ΔDが小さいと、Daveが小さく、かつ表面抵抗率の小さな透明フィルム基材を形成する上でも有利である。
ここで、上記平均X線強度Iaveは、上記5箇所の測定点におけるX線強度Iの算術平均値である。X線強度の単位としては、通常、kcps(1秒あたりに計数管窓を通して入射するX線光量子の数(カウント数))を用いる。具体的には、例えば、後述する実施例に記載のX線強度のバラツキ測定方法に従って、Iave及びΔIを測定することができる。上記トップコート層のΔIが40%以下であると、部分的に白っぽくなることによるスジやムラが視認されにくくなり、良好な外観特性を発揮する傾向にある。なお、一般に、上述の厚みのバラツキΔDが小さいほどΔIも小さくなる。従って、ΔIが小さいことは、Daveが小さく、且つ表面抵抗率が小さな透明フィルム基材を形成する上でも有利である。
なお、測定精度を高める観点からは、所定のXRF分析の条件において、直径30mmの円に相当する面積あたりのX線強度が概ね0.01kcps以上(より好ましくは0.03kcps以上、例えば、0.05~3.00kcps)となる元素を分析対象とすることが好ましい。
本発明の粘着シートにおけるアクリル系粘着剤層(粘着剤層)は、アクリルエマルション系重合体(A)及び化合物(B)を必須の成分として含有する水分散型アクリル系粘着剤組成物(再剥離用水分散型アクリル系粘着剤組成物)(「本発明の粘着剤組成物」と称する場合がある)により形成される。本発明の粘着剤組成物は、さらに、非水溶性架橋剤(C)を含有することが好ましい。
本発明の粘着剤組成物におけるアクリルエマルション系重合体(A)は、(メタ)アクリル酸アルキルエステル及びカルボキシル基含有不飽和単量体を必須の原料モノマー(原料モノマー成分)として構成された重合体(アクリル系重合体)である。即ち、アクリルエマルション系重合体(A)は、(メタ)アクリル酸アルキルエステル及びカルボキシル基含有不飽和単量体を必須成分とするモノマー混合物より得られる重合体である。アクリルエマルション系重合体(A)は、単独で又は2種以上を組み合わせて使用することができる。なお、本明細書では、「(メタ)アクリル」とは「アクリル」及び/又は「メタクリル」(「アクリル」及び「メタクリル」のうち、いずれか一方又は両方)のことをいう。
(溶剤不溶分の測定方法)
アクリルエマルション系重合体(A):約0.1gを採取し、平均孔径0.2μmの多孔質テトラフルオロエチレンシート(商品名「NTF1122」、日東電工(株)製)に包んだ後、凧糸で縛り、その際の重量を測定し、該重量を浸漬前重量とする。なお、該浸漬前重量は、アクリルエマルション系重合体(A)(上記で採取したもの)と、テトラフルオロエチレンシートと、凧糸の総重量である。また、テトラフルオロエチレンシートと凧糸の合計重量も測定しておき、該重量を包袋重量とする。
次に、上記のアクリルエマルション系重合体(A)をテトラフルオロエチレンシートにて包み凧糸で縛ったもの(「サンプル」と称する)を、酢酸エチルで満たした50ml容器に入れ、23℃にて7日間静置する。その後、容器からサンプル(酢酸エチル処理後)を取り出して、アルミニウム製カップに移し、130℃で2時間、乾燥機中で乾燥して酢酸エチルを除去した後、重量を測定し、該重量を浸漬後重量とする。
そして、下記の式から溶剤不溶分を算出する。
溶剤不溶分(重量%)=(X-Y)/(Z-Y)×100 (1)
(式(1)において、Xは浸漬後重量であり、Yは包袋重量であり、Zは浸漬前重量である。)
[測定方法]
GPC測定は、東ソー(株)製GPC装置「HLC-8220GPC」を用いて行い、ポリスチレン換算値にて分子量を求める。測定条件は下記の通りである。
サンプル濃度:0.2wt%(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
本発明の粘着剤組成物(水分散型アクリル系粘着剤組成物)における化合物(B)は、下記式(I)で表される化合物である。
R1O-(PO)a-(EO)b-(PO)c-R2 (I)
また、上記化合物(B)を用いることにより、本発明の粘着剤組成物より形成された粘着剤層(アクリル系粘着剤層)は加湿保存下でも白化(吸湿白化)しにくい。粘着シートを光学部材用の表面保護フィルムに用いる場合には、粘着剤層が白化(即ち、粘着シートが白化)すると光学部材の検査工程に支障が生じる場合がある。
本発明の粘着剤組成物に使用する架橋剤は、特に限定されないが、低汚染で粘着力の上昇を妨げることが可能である観点から、非水溶性架橋剤が好ましい。さらに、分子中(1分子中)にカルボキシル基と反応し得る官能基を2個以上有する非水溶性架橋剤(C)が好ましい。本明細書においては、上記の「分子中にカルボキシル基と反応し得る官能基を2個以上有する非水溶性架橋剤(C)」を単に「非水溶性架橋剤(C)」と称する場合がある。即ち、本発明の粘着剤組成物は、非水溶性架橋剤(C)をさらに含むことが好ましい。
(水に対する溶解度の測定方法)
同重量の水(25℃)と架橋剤を、攪拌機を用いて回転数300rpm、10分の条件で混合し、遠心分離により水相と油相に分ける。次いで、水相を採取し120℃で1時間乾燥して、乾燥減量から水相中の不揮発分(水100重量部に対する不揮発成分の重量部)を求める。
非水溶性架橋剤(C)の有するカルボキシル基と反応し得る官能基のモル数 = [非水溶性架橋剤(C)の配合量(添加量)]/[官能基当量] = 4/110
例えば、非水溶性架橋剤(C)として、エポキシ当量が110(g/eq)のエポキシ系架橋剤を4g添加(配合)する場合、エポキシ系架橋剤の有するエポキシ基のモル数は、例えば、以下のように算出できる。
エポキシ系架橋剤の有するエポキシ基のモル数 = [エポキシ系架橋剤の配合量(添加量)]/[エポキシ当量] = 4/110
なお、上記アクリル系粘着剤層(架橋後)の溶剤不溶分は、上述のアクリルエマルション系重合体の溶剤不溶分の測定方法と同様の方法で測定することができる。具体的には、上述の「溶剤不溶分の測定方法」において、「アクリルエマルション系重合体(A)」を「アクリル系粘着剤層(架橋後)」に読み替えた方法で測定することができる。
上記摩擦係数は、例えば、23℃、相対湿度50%RHの測定環境下において、透明フィルム基材(又は本発明の粘着シート)のトップコート層の表面を垂直荷重40mNで擦過して求められる値を採用できる。上記摩擦係数を低下させる(調整する)手法としては、トップコート層に各種滑剤(レベリング剤等)を含有させる方法、架橋剤の添加や成膜条件の調整によりトップコート層の架橋密度を高める方法等を適宜採用できる。
(印字性(印字密着性)評価)
23℃、50%RHの測定環境下でシャチハタ社製Xスタンパ-を用いて、トップコート層表面上に印字を施した後、その印字の上からニチバン社製のセロハン粘着テープ(品番No.405、幅19mm)を貼り付け、次いで、剥離速度30m/分、剥離角度180°の条件で剥離する。その後、剥離後の表面を目視観察し、印字面積の50%以上が剥離された場合を×(印字性不良)、印字面積の50%以上が剥離されずに残った場合を○(印字性良好)と評価する。
(耐溶剤性評価)
外光を遮った室内(暗室)において、エチルアルコールを染み込ませたウェス(布)でトップコート層表面を15回拭き、その外観を目視観察する。その結果、エチルアルコールで拭いた部分と他の部分との間に外観上の相違が観察されなかった(エチルアルコールで拭いたことによる外観変化が見られない)場合を○(耐溶剤性良好)、拭きムラが確認された場合を×(耐溶剤性不良)と評価する。
(トップコート層形成用組成物の調製)
反応器にトルエン25gを装入し、反応器内の温度を105℃まで上げた後、メチルメタクリレート(MMA)30g、n-ブチルアクリレート(BA)10g、シクロヘキシルメタクリレート(CHMA)5g、アゾビスイソブチロニトリル0.2gを混合した溶液を上記反応器に、2時間かけて連続的に滴下した。滴下完了後、反応器内の温度を110~115℃に調整し、同温度に3時間保持して共重合反応を行った。3時間経過後、トルエン4gとアゾビスイソブチロニトリル0.1gとの混合液を反応器に滴下し、同温度に1時間保持した。その後、反応器内の温度を90℃まで冷却し、トルエンを投入してNV5重量%に調整し、バインダとしてのアクリル系ポリマー(バインダポリマー1;Tg48℃)をトルエン中に5重量%含む溶液(バインダ溶液1)を作製した。
次に、容量150mLのビーカーに、2gのバインダ溶液1(0.1gのバインダポリマー1を含む)と、40gのエチレングリコールモノエチルエーテルとを入れて攪拌混合した。さらに、このビーカーに、ポリエチレンジオキシチオフェン(PEDT)とポリスチレンスルホネート(PSS)を含むNV4.0重量%の導電性ポリマー溶液1(水溶液)を1.2gと、エチレングリコールモノメチルエーテル55gと、ポリエーテル変性ポリジメチルシロキサン系レベリング剤(滑剤溶液)(BYK Chemie社製、商品名「BYK-300」、NV52重量%)0.05gと、メラミン系架橋剤((株)三和ケミカル製、商品名「ニカラック MW-30M」、不揮発分100%)0.02gとを加え、約20分間攪拌して十分に混合した。このようにして、バインダポリマー1(アクリル系ポリマー)100重量部に対して、導電性ポリマー48重量部、滑剤26重量部、及びメラミン系架橋剤20重量部(いずれも固形分換算)を含むトップコート層形成用組成物(NV:0.2重量%)を調製した。
一方の面にコロナ処理が施された厚み38μm、幅30cm、長さ40cmの透明なポリエチレンテレフタレートフィルム(PETフィルム)のコロナ処理面に、上記トップコート層形成用組成物を、バーコーターを用いて乾燥後の厚みが約10nmとなるように塗布した。この塗布物を130℃で2分間加熱して乾燥させることにより、上記PETフィルムの一方の面にトップコート層を形成した。このようにして、PETフィルムの片面に透明なトップコート層を有する透明フィルム基材(「基材1」と称する場合がある)を作製した。
製造例1において、導電性ポリマー溶液1の使用量を1.2gから2.5gに変更し、エチレングリコールモノメチルエーテルの使用量を55gから17gに変更した。また、トップコート層形成用溶液の塗布は、乾燥後の厚みが約20nmとなるように実施した。その他の点については製造例1と同様にして、PETフィルムの片面に透明なトップコート層を有する透明フィルム基材(「基材2」と称する場合がある)を作製した。
製造例1において、エチレングリコールモノエチルエーテルの使用量を40gから19gに変更し、導電性ポリマー溶液1の使用量を1.2gから0.7gに変更し、エチレングリコールモノメチルエーテルは使用しなかった。また、トップコート層形成用溶液の塗布は、乾燥後の厚みが約40nmとなるように実施した。その他の点については製造例1と同様にして、PETフィルムの片面に透明なトップコート層を有する透明フィルム基材(「基材3」と称する場合がある)を作製した。
製造例3において、エチレングリコールモノエチルエーテルの使用量を19gから15gに変更した。また、トップコート層形成用溶液の塗布は、乾燥後の厚みが約50nmとなるように実施した。その他の点については製造例3と同様にして、PETフィルムの片面に透明なトップコート層を有する透明フィルム基材(「基材4」と称する場合がある)を作製した。
(トップコート層形成用組成物の調製)
反応器にトルエン25gを装入し、反応器内の温度を105℃まで上げた後、メチルメタクリレート(MMA)32g、n-ブチルアクリレート(BA)5g、メタクリル酸(MAA)0.7g、シクロヘキシルメタクリレート(CHMA)5g、アゾビスイソブチロニトリル0.2gを混合した溶液を上記反応器に、2時間かけて連続的に滴下した。滴下完了後、反応器内の温度を110~115℃に調整し、同温度に3時間維持して共重合反応を行った。3時間経過後、トルエン4gとアゾビスイソブチロニトリル0.1gとの混合液を反応器に滴下し、同温度に1時間保持した。その後、反応器内の温度を90℃まで冷却し、トルエン31gを投入して希釈した。このようにして、バインダとしてのアクリル系ポリマー(バインダポリマー2;Tg72℃)をトルエン中に約42重量%含む溶液(バインダ溶液2)を作製した。
次に、容量150mLのビーカーに、5.5gのバインダ溶液2(2.3gのバインダポリマー2を含む)と30gのエチレングリコールモノエチルエーテルとを入れて攪拌混合した。さらにこのビーカーに、PEDT及びPSSを含むNV1.3重量%の導電性ポリマー溶液2(水溶液)を14g、エチレングリコールモノメチルエーテル6g、滑剤溶液(BYK-300)0.5gを加え、約30分間攪拌して十分に混合した。このようにして、100重量部のバインダポリマー2(アクリル系ポリマー)に対して、導電性ポリマー8重量部及び滑剤11重量部(いずれも固形分基準)を含むトップコート層形成用組成物を調製した。なお、このトップコート層形成用組成物には架橋剤は配合されていない。
片面にコロナ処理が施された厚み38μm、幅30cm、長さ40cmの透明なポリエチレンテレフタレートフィルム(PETフィルム)のコロナ処理面に、上記トップコート層形成用組成物を、バーコーターを用いて乾燥後の厚みが約610nmとなるように塗布した。この塗布物を80℃で2分間加熱して乾燥させることにより、トップコート層を形成した。このようにして、PETフィルムの片面に透明なトップコート層を有する透明フィルム基材(「基材5」と称する場合がある)を作製した。
(トップコート層形成用組成物の調製)
反応器にトルエン25gを装入し、反応器内の温度を105℃まで上げた後、メチルメタクリレート(MMA)30g、n-ブチルアクリレート(BA)10g、シクロヘキシルメタクリレート(CHMA)5g、ヒドロキシエチルメタクリレート(HEMA)5g、アゾビスイソブチロニトリル0.2gを混合した溶液を上記反応器に、2時間かけて連続的に滴下した。滴下完了後、反応器内の温度を110~115℃に調整し、同温度に3時間維持して共重合反応を行った。3時間経過後、トルエン4gとアゾビスイソブチロニトリル0.1gとの混合液を反応器に滴下し、同温度に1時間保持した。その後、反応器内の温度を90℃まで冷却し、トルエンを投入して希釈した。このようにして、バインダとしてのアクリル系ポリマー(バインダポリマー3;Tg49℃)をトルエン中に約5重量%含む溶液(バインダ溶液3)を作製した。
次に、容量150mLのビーカーに、2gのバインダ溶液3(0.1gのバインダポリマー3を含む)と、40gのエチレングリコールモノエチルエーテルとを入れて攪拌混合した。さらに、このビーカーに、ポリエチレンジオキシチオフェン(PEDT)とポリスチレンスルホネート(PSS)を含むNV4.0重量%の導電性ポリマー溶液1(水溶液)を1.2gと、エチレングリコールモノメチルエーテル55gと、ポリエーテル変性ポリジメチルシロキサン系レベリング剤(滑剤溶液)(BYK Chemie社製、商品名「BYK-300」、NV52重量%)0.05gと、メラミン系架橋剤((株)三和ケミカル製、商品名「ニカラック MW-30M」)0.02gとを加え、約20分間攪拌して十分に混合した。このようにして、バインダポリマー3(アクリル系ポリマー)100重量部に対して、導電性ポリマー48重量部、滑剤26重量部、及びメラミン系架橋剤20重量部(いずれも固形分換算)を含むトップコート層形成用組成物(NV:0.2重量%)を調製した。
一方の面にコロナ処理が施された厚み38μm、幅30cm、長さ40cmの透明なポリエチレンテレフタレートフィルム(PETフィルム)のコロナ処理面に、上記トップコート層形成用組成物を、バーコーターを用いて乾燥後の厚みが約8nmとなるように塗布した。この塗布物を130℃で2分間加熱して乾燥させることにより、上記PETフィルムの一方の面にトップコート層を形成した。このようにして、PETフィルムの片面に透明なトップコート層を有する透明フィルム基材(「基材6」と称する場合がある)を作製した。
(アクリルエマルション系重合体の調製)
容器に、水90重量部、及び、表2に示すように、アクリル酸2-エチルヘキシル(2EHA)96重量部、アクリル酸(AA)4重量部、ノニオンアニオン系反応性乳化剤(第一工業製薬(株)製、商品名「アクアロンHS-10」)3重量部を配合した後、ホモミキサーにより攪拌混合し、モノマーエマルションを調製した。
次いで、冷却管、窒素導入管、温度計および攪拌機を備えた反応容器に、水50重量部、重合開始剤(過硫酸アンモニウム)0.01重量部、及び、上記で調製したモノマーエマルションのうち10重量%にあたる量を添加し、攪拌しながら、75℃で1時間乳化重合した。その後、さらに重合開始剤(過硫酸アンモニウム)0.05重量部を添加し、次いで、攪拌しながら、残りのモノマーエマルションの全て(90重量%にあたる量)を3時間かけて添加して、その後、75℃で3時間反応させた。次いで、これを30℃に冷却して、濃度10重量%のアンモニア水を加えてpH8に調整して、アクリルエマルション系重合体の水分散液を調製した。
上記で得られたアクリルエマルション系重合体の水分散液に、アクリルエマルション系重合体(固形分)100重量部に対して、化合物(B)である「アデカプルロニック25R-1」を1.0重量部、レベリング剤として「EFKA-3570」を0.2重量部、非水溶性架橋剤であるエポキシ系架橋剤[三菱ガス化学(株)製、商品名「テトラッド-C」、1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン、エポキシ当量:110、官能基数:4]3重量部を、攪拌機を用いて、23℃、300rpm、10分の攪拌条件で攪拌混合し、水分散型アクリル系粘着剤組成物(「粘着剤1」と称する場合がある)を調製した。
表2に示すように、反応性乳化剤として、「アクアロンHS-10」の代わりに、「アデカリアソープSE-10N」3重量部を使用したこと以外は製造例7と同様にして、水分散型アクリル系粘着剤組成物(「粘着剤2」と称する場合がある)を調製した。
表2に示すように、アクリルエマルション系重合体のモノマー原料を、アクリル酸2-エチルヘキシル(2EHA)92重量部、メタクリル酸メチル(MMA)4重量部、アクリル酸(AA)4重量部に変更したこと以外は製造例7と同様にして、水分散型アクリル系粘着剤組成物(「粘着剤3」と称する場合がある)を調製した。
表2に示すように、化合物(B)として、「アデカプルロニック25R-1」の代わりに、「アデカプルロニック17R-3」0.5重量部を使用したこと以外は製造例8と同様にして、水分散型アクリル系粘着剤組成物(「粘着剤4」と称する場合がある)を調製した。
表2に示すように、化合物(B)として、「アデカプルロニック25R-1」の代わりに、「PPO-PEO-PPO」0.5重量部を使用し、非水溶性架橋剤(C)として、「テトラッド-C」の代わりに、「テトラッド-X」3重量部を使用したこと以外は製造例7と同様にして、水分散型アクリル系粘着剤組成物(「粘着剤5」と称する場合がある)を調製した。
表2に示すように、化合物(B)である共重合体を用いなかったこと以外は製造例7と同様にして、水分散型アクリル系粘着剤組成物(「粘着剤6」と称する場合がある)を調製した。
表2に示すように、化合物(B)である共重合体の代わりに、化合物(B)以外の化合物(「POLYRan(EO-PO)」0.5重量部)を用いたこと以外は製造例7と同様にして、水分散型アクリル系粘着剤組成物(「粘着剤7」と称する場合がある)を調製した。
表2に示すように、化合物(B)である共重合体の代わりに、化合物(B)以外の化合物(「PEO-PPO-PEO」3.0重量部)を用いたこと以外は製造例7と同様にして、水分散型アクリル系粘着剤組成物(「粘着剤8」と称する場合がある)を調製した。
表2に示すように、化合物(B)である「アデカプルロニック25R-1」の配合量を、アクリルエマルション系重合体(固形分)100重量部に対して0.1重量部に変更したこと以外は製造例7と同様にして、水分散型アクリル系粘着剤組成物(「粘着剤9」と称する場合がある)を調製した。
表3に示すように、上記で得られた水分散型アクリル系粘着剤組成物(粘着剤1)を、上記で得られた透明フィルム基材(基材1)のトップコート層に対する反対側の表面に、テスター産業(株)製アプリケーターを用いて、乾燥後の厚みが15μmとなるように塗布(コーティング)し、その後、熱風循環式オーブンで120℃で2分間乾燥させ、乾燥後の粘着剤層にシリコーンで表面処理したPETフィルム(三菱樹脂(株)製、「MRF38」)のシリコーン処理面を貼り合わせた後、50℃で3日間養生(エージング)して粘着シートを得た。
表3に示すように、水分散型アクリル系粘着剤組成物、透明フィルム基材の種類を変更し、実施例1と同様にして粘着シートを得た。
なお、比較例6で基材として用いた商品名「ダイヤホイルT100G」(三菱化学(株)製)は、一方の表面に帯電防止層を有するPETフィルム(帯電防止処理されたPETフィルム)である。上記帯電防止層には、帯電防止剤としてアンモニウム塩基を有する化合物が含まれる。
上記で作製した透明フィルム基材、並びに、実施例および比較例で得られた粘着シートについて、下記の測定方法又は評価方法により評価を行った。なお、アクリルエマルション系重合体の溶剤不溶分、アクリルエマルション系重合体の溶剤可溶分の重量平均分子量、及びアクリル系粘着剤層(架橋後)の溶剤不溶分は、上述の測定方法で測定した。
評価結果を表1~3に示した。
製造例にて作製した透明フィルム基材の断面を透過型電子顕微鏡(TEM)にて観察することにより、トップコート層の厚みを測定した。
一方、上記透明フィルム基材のトップコート層表面につき、蛍光X線分析装置(Rigaku社製、XRF装置、型式「ZSX-100e」)を用いて硫黄原子(トップコート層に含まれるPEDT及びPSSに由来する)のピーク強度を測定した。蛍光X線分析は以下の条件で行った。
[蛍光X線分析]
装置:Rigaku社製XRF装置、型式「ZSX-100e」
X線源:縦型Rh管
分析範囲:直径30mmの円内
検出X線:S-Kα
分光結晶:Geクリスタル
出力:50kV、70mA
上記TEM観察により得られたトップコート層の厚み(実測値)及び上記蛍光X線分析の結果に基づいて、蛍光X線分析におけるピーク強度からトップコート層の厚みを把握する検量線を作製した。
上記検量線を用いて、上記透明フィルム基材のトップコート層の厚みを測定した。具体的には、トップコート層が形成された領域を幅方向(バーコーターの移動方向に直交する方向)に横切る直線に沿って、該幅方向の一端から他端に向かって幅の1/6、2/6、3/6、4/6、5/6進んだ位置について蛍光X線分析を行い、その結果(硫黄原子のX線強度(kcps))、トップコート層の組成(PEDT及びPSSの含有量)及び上記検量線から、上記5箇所の測定位置におけるトップコート層の厚みを求めた。平均厚みDaveは、上記5箇所の測定点におけるトップコート層の厚みを算術平均することにより測定した。厚みのバラツキΔDは、上記平均厚みDaveと、上記5箇所の測定点におけるトップコート層の厚みのうちの最大値Dmax及び最小値Dminとを、次式:ΔD=(Dmax-Dmin)/Dave×100(%);に代入することにより算出した。
上記の各位置(5箇所の測定位置)について蛍光X線分析を行って得られた硫黄原子のX線強度(kcps)を算術平均することにより、平均X線強度Iaveを求めた。また、この平均X線強度Iaveと各位置(5箇所の測定位置)におけるX線強度の最大値Imax及び最小値Iminとを、次式:ΔI=(Imax-Imin)/Iave×100(%);に代入することにより、X線強度のバラツキΔIを算出した。
外光の入る窓を有する室内(明室)にて、晴天の日中に、直射日光の当たらない窓際にて上記透明フィルム基材(基材1~6)の背面(トップコート層側の表面)を目視観察した。これらの観察結果に基づき、以下の基準にて透明フィルム基材の外観を評価した。
○(外観良好):ムラやスジが確認されなかった
×(外観不良):ムラやスジが確認された
JIS K6911に準拠し、絶縁抵抗計((株)三菱化学アナリテック製、商品名「Hiresta-up MCP-HT450」)を用いて、23℃、相対湿度55%の雰囲気下において、上記で作製した透明フィルム基材(基材1~6)のトップコート層側の表面の表面抵抗Rsを測定した。印加電圧は100Vとし、表面抵抗Rsの読み取りは測定開始から60秒後に行った。その結果から、次式に従って表面抵抗率を算出した。
ρs=Rs×E/V×π(D+d)/(D-d)
ここで、上記式中のρsは表面抵抗率(Ω/□)、Rsは表面抵抗(Ω)、Eは印加電圧(V)、Vは測定電圧(V)、Dは表面の環状電極の内径(cm)、dは表面電極の内円の外径(cm)をそれぞれ表す。
上記で作製した透明フィルム基材(基材1~6)から10cm2(幅10cm×長さ10cm)のサンプルを切り出した。外光の入る窓を有する室内(明室)にて、試験者が上記サンプルの背面(トップコート層側の表面)を爪で擦り、これによる傷のつき方によって耐スクラッチ性を評価した。具体的には、爪で擦った後のサンプルの背面を光学顕微鏡で観察し、トップコート層の脱落屑の存在が確認された場合を×(耐スクラッチ性不良)、このような脱落屑の存在が確認されなかった場合を○(耐スクラッチ性良好)と評価した。
(初期粘着力)
実施例、比較例で得られた粘着シート(サンプルサイズ:25mm幅×100mm長さ)を、貼り合わせ機(テスター産業(株)製、小型貼り合せ機)を用いて、0.25MPa、0.3m/分の条件で、偏光板(材質:トリアセチルセルロース(TAC)、表面の算術平均粗さRaがMD方向で約21nm、TD方向で約31nm、MD方向とTD方向の平均で約26nmである)に貼り合わせた。
上記の粘着シートと偏光板の貼り合わせサンプルを用い、23℃、50%RHの環境下、20分間放置後に、下記の条件に従って180°剥離試験を行い、粘着シートの偏光板に対する粘着力(N/25mm)を測定し、「初期粘着力」とした。
(40℃1週間貼付保存後粘着力)
実施例、比較例で得られた粘着シート(サンプルサイズ:25mm幅×100mm長さ)を、貼り合わせ機(テスター産業(株)製、小型貼り合せ機)を用いて、0.25MPa、0.3m/分の条件で、偏光板(材質:トリアセチルセルロース(TAC)、表面の算術平均粗さRaがMD方向で約21nm、TD方向で約31nm、MD方向とTD方向の平均で約26nmである)に貼り合わせた。
上記の粘着シートと偏光板の貼り合わせサンプルを用い、40℃の環境に1週間保存した後、23℃、50%RHの環境下に2時間放置し、その後、下記の条件に従って180°剥離試験を行い、粘着シートの偏光板に対する粘着力(N/25mm)を測定し、「40℃1週間貼付保存後粘着力」とした。
上記の180°剥離試験は、引張試験機を用いて、23℃、50%RHの環境下、引張速度0.3m/分で行った。
初期粘着力と40℃1週間貼付保存後粘着力の差[(40℃1週間貼付保存後粘着力)-(初期粘着力)]が、0.10N/25mm以下であれば、粘着力上昇防止性に優れていると判断できる。
実施例、比較例で得られた粘着シートを50℃、95%RHの環境に24時間放置(加湿保存)後、日本電色工業(株)製、「デジタルヘイズメーター(DIGITAL HAZEMETER) NDH-20D」にてヘイズ値を測定した(「加湿保存後のヘイズ値」とした)。測定は、50℃×95%RHの環境からサンプルを取り出した後3分以内に行った。また、比較のため、加湿保存前のヘイズ値も測定した(「加湿保存前のヘイズ値」とした)。
実施例、比較例で得られた粘着シートのアクリル系粘着剤層表面の状態を目視で観察し、縦10cm×横10cmの観察範囲内の欠点(凹み及び気泡)の個数を測定した。上記透明フィルム基材の外観の評価結果と合わせて、以下の基準で粘着シートの外観(外観特性)を総合的に評価した。
粘着シートの外観が不良(×) : 透明フィルム基材の外観が不良である場合、又は、透明フィルム基材の外観は良好であるが、上記欠点の個数が101個以上である場合
粘着シートの外観が良好(○) : 透明フィルム基材の外観が良好であり、上記欠点の個数が0~100個である場合
なお、以下では、「化合物(B)の総重量」に対する「EOの総重量」の割合を、「EO含有率」と表記した。
[原料モノマー]
2EHA : 2-エチルヘキシルアクリレート
MMA : メチルメタクリレート
AA : アクリル酸
[乳化剤]
HS-10 : 第一工業製薬(株)製、商品名「アクアロンHS-10」(ノニオンアニオン系反応性乳化剤)
SE-10N : (株)ADEKA製、商品名「アデカリアソープSE-10N」(ノニオンアニオン系反応性乳化剤)
[架橋剤]
テトラッドC : 三菱ガス化学(株)製、商品名「TETRAD-C(テトラッド-C)」(1,3-ビス(N,N-ジグリシジルアミノメチル)シクロヘキサン、エポキシ当量:110、官能基数:4)
テトラッドX : 三菱ガス化学(株)製、商品名「TETRAD-X(テトラッド-X)」(1,3-ビス(N,N-ジグリシジルアミノメチル)ベンゼン、エポキシ当量:100、官能基数:4)
[化合物(B)]
アデカプルロニック25R-1 : (株)ADEKA製、商品名「アデカプルロニック25R-1」(数平均分子量2800、EO含有率10重量%、有効成分100重量%)
アデカプルロニック17R-3 : (株)ADEKA製、商品名「アデカプルロニック17R-3」(数平均分子量2000、EO含有率30重量%、有効成分100重量%)
PPO-PEO-PPO : SIGMA-ALDRICH(シグマ-アルドリッチ)社製、ポリ(プロピレングリコール)-block-ポリ(エチレングリコール)-block-ポリ(プロピレングリコール)(数平均分子量2000、EO含有率50重量%、有効成分100重量%)
[化合物(B)以外の化合物]
POLYRan(EO-PO) : SIGMA-ALDRICH(シグマ-アルドリッチ)社製、ポリ[エチレングリコール-ran-プロピレングリコール](数平均分子量2500、EO含有率75重量%、有効成分100重量%)
PEO-PPO-PEO : SIGMA-ALDRICH(シグマ-アルドリッチ)社製、ポリ(エチレングリコール)-block-ポリ(プロピレングリコール)-block-ポリ(エチレングリコール)(数平均分子量1900、EO含有率50重量%、有効成分100重量%)
[レベリング剤]
EFKA-3570 : BASF製、中和されたフルオロカーボン変性ポリマー
[基材(透明フィルム基材)]
T100G : 帯電防止処理PETフィルム、商品名「ダイヤホイルT100G」(三菱化学(株)製)
一方、化合物(B)を添加しない比較例(比較例1~3)、並びに基材のトップコート層の平均厚み及び/又は厚みのバラツキが本発明の規定を満たさない比較例(比較例4、5)では、粘着シートの外観が不良であった。また、トップコート層の構成成分としてメラミン系架橋剤を含有しない比較例(比較例5)は、耐スクラッチ性にも劣っていた。化合物(B)の代わりに、化合物(B)以外の化合物を用いた比較例(比較例2)では、加湿保存によりヘイズ値の大きな上昇が見られ、加湿保存下で粘着シートの白化が確認された。さらに、基材の帯電防止層が、ポリチオフェン、アクリル樹脂、及びメラミン系架橋剤を含む構成のトップコート層ではない場合(比較例6)は、加湿保存によるヘイズ値の上昇が見られ、且つ耐スクラッチ性にも劣っていた。
Claims (4)
- 透明フィルム基材の少なくとも片面側にアクリル系粘着剤層を有する粘着シートであって、
前記透明フィルム基材が、樹脂材料からなるベース層と、該ベース層の第一面上に設けられたトップコート層とを有し、
前記トップコート層は、ポリチオフェン、アクリル樹脂、及びメラミン系架橋剤から構成され、平均厚みDaveが2~50nm、厚みのバラツキΔDが40%以下であり、
前記アクリル系粘着剤層が、(メタ)アクリル酸アルキルエステル及びカルボキシル基含有不飽和単量体を必須の原料モノマーとして構成され、原料モノマー全量中の(メタ)アクリル酸アルキルエステルの含有量が70~99.5重量%、カルボキシル基含有不飽和単量体の含有量が0.5~10重量%であり、かつ分子中にラジカル重合性官能基を含む反応性乳化剤を用いて重合されたアクリルエマルション系重合体(A)ならびに下記式(I)で表される化合物(B)を含有する再剥離用水分散型アクリル系粘着剤組成物より形成された粘着剤層であることを特徴とする粘着シート。
R1O-(PO)a-(EO)b-(PO)c-R2 (I)
(式中、R1及びR2は、直鎖状又は分岐鎖状のアルキル基、又は、水素原子を表す。POはオキシプロピレン基、EOはオキシエチレン基を表す。a、b及びcは、それぞれ正の整数である。EOとPOの付加形態はブロック型である。) - 前記ベース層を構成する樹脂材料が、ポリエチレンテレフタレートまたはポリエチレンナフタレートを主たる樹脂成分とする請求項1に記載の粘着シート。
- 前記再剥離用水分散型アクリル系粘着剤組成物が、分子中にカルボキシル基と反応し得る官能基を2個以上有する非水溶性架橋剤(C)をさらに含む請求項1又は2に記載の粘着シート。
- 光学部材用の表面保護フィルムである請求項1~3のいずれか1項に記載の粘着シート。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020137024180A KR101878010B1 (ko) | 2011-04-15 | 2012-04-06 | 점착 시트 |
CN201280018649.5A CN103476891B (zh) | 2011-04-15 | 2012-04-06 | 粘合片 |
US14/111,315 US20140037911A1 (en) | 2011-04-15 | 2012-04-06 | Pressure-sensitive adhesive sheet |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011091485A JP5751905B2 (ja) | 2011-04-15 | 2011-04-15 | 粘着シート |
JP2011091503A JP5751906B2 (ja) | 2011-04-15 | 2011-04-15 | 粘着シート |
JP2011-091509 | 2011-04-15 | ||
JP2011-091503 | 2011-04-15 | ||
JP2011091509A JP5791945B2 (ja) | 2011-04-15 | 2011-04-15 | 粘着シート |
JP2011-091485 | 2011-04-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012141099A1 true WO2012141099A1 (ja) | 2012-10-18 |
Family
ID=47009274
Family Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/059522 WO2012141099A1 (ja) | 2011-04-15 | 2012-04-06 | 粘着シート |
PCT/JP2012/059524 WO2012141100A1 (ja) | 2011-04-15 | 2012-04-06 | 粘着シート |
PCT/JP2012/059527 WO2012141101A1 (ja) | 2011-04-15 | 2012-04-06 | 粘着シート |
Family Applications After (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/059524 WO2012141100A1 (ja) | 2011-04-15 | 2012-04-06 | 粘着シート |
PCT/JP2012/059527 WO2012141101A1 (ja) | 2011-04-15 | 2012-04-06 | 粘着シート |
Country Status (5)
Country | Link |
---|---|
US (3) | US20140037950A1 (ja) |
KR (3) | KR101878010B1 (ja) |
CN (3) | CN103476891B (ja) |
TW (3) | TW201245396A (ja) |
WO (3) | WO2012141099A1 (ja) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103802703A (zh) * | 2014-01-26 | 2014-05-21 | 东莞广泽汽车饰件有限公司 | 一种汽车扶手生产工艺 |
JP2015027765A (ja) * | 2013-07-30 | 2015-02-12 | 日東電工株式会社 | 表面保護フィルムおよび光学部材 |
WO2017010766A1 (ko) * | 2015-07-10 | 2017-01-19 | 주식회사 엘지화학 | 가교성 조성물 |
Families Citing this family (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102858900B (zh) * | 2010-04-20 | 2013-12-25 | 日东电工株式会社 | 再剥离用水分散型丙烯酸系粘合剂组合物和粘合片 |
JP5611883B2 (ja) * | 2011-04-13 | 2014-10-22 | 日東電工株式会社 | 再剥離用水分散型アクリル系粘着剤組成物及び粘着シート |
US20140037950A1 (en) * | 2011-04-15 | 2014-02-06 | Nitto Denko Corporation | Pressure-sensitive adhesive sheet |
JP5599762B2 (ja) * | 2011-06-17 | 2014-10-01 | 富士フイルム株式会社 | インク組成物、インクセット、及び画像形成方法 |
JP6098289B2 (ja) * | 2013-03-28 | 2017-03-22 | デクセリアルズ株式会社 | 熱伝導性シート |
KR101391297B1 (ko) * | 2013-07-22 | 2014-05-02 | 동우 화인켐 주식회사 | 점착제 조성물 |
JP6092033B2 (ja) * | 2013-07-30 | 2017-03-08 | 日東電工株式会社 | 表面保護フィルムおよび光学部材 |
JP6092035B2 (ja) * | 2013-07-30 | 2017-03-08 | 日東電工株式会社 | 表面保護フィルムおよび光学部材 |
JP6419548B2 (ja) * | 2014-11-27 | 2018-11-07 | 日東電工株式会社 | 表面保護フィルム、表面保護フィルムの製造方法、及び、光学部材 |
EP3048141B1 (en) | 2015-01-26 | 2017-11-22 | Avery Dennison Corporation | Self adhesive fouling release coating composition |
CN105017986B (zh) * | 2015-07-28 | 2017-12-26 | 浙江欧丽数码喷绘材料有限公司 | 一种抗刮超薄可印刷单面胶及其制备方法和应用 |
JP6819600B2 (ja) * | 2015-09-30 | 2021-01-27 | 日本ゼオン株式会社 | 帯電防止ハードコートフィルムの製造方法、偏光板の製造方法、タッチパネルの製造方法、及び液晶表示装置の製造方法 |
US11831097B2 (en) * | 2016-06-30 | 2023-11-28 | The University Of Akron | UV-curable contact stabilization coating material for electrical contact surfaces |
KR101872600B1 (ko) * | 2016-09-06 | 2018-08-02 | (주)엘지하우시스 | 점착 조성물, 점착 필름 및 점착 필름을 적용하는 방법 |
JP6343364B2 (ja) * | 2017-04-19 | 2018-06-13 | 日東電工株式会社 | 粘着剤組成物、及び粘着シート |
WO2019123892A1 (ja) | 2017-12-19 | 2019-06-27 | 三菱ケミカル株式会社 | 無溶剤型アクリル系樹脂組成物、これを用いた無溶剤型アクリル系粘着剤、粘着シートおよび無溶剤型アクリル系樹脂組成物の製造方法 |
EP3775078A4 (en) * | 2018-03-30 | 2021-11-03 | Soken Chemical & Engineering Co., Ltd. | OPTICAL LAMINATE, ADHESIVE COMPOSITION AND PROTECTIVE MATERIAL |
CN108795307B (zh) * | 2018-07-04 | 2020-02-18 | 东莞市古川胶带有限公司 | 一种极薄双面胶带及其制备方法 |
KR102129099B1 (ko) * | 2018-08-03 | 2020-07-01 | 주식회사 이리스코스메틱 | 네일 스티커용 인쇄시트 |
TWI717895B (zh) * | 2018-11-12 | 2021-02-01 | 南韓商Lg化學股份有限公司 | 色彩轉換膜、製造其的方法、包含其的背光單元以及顯示器裝置 |
US20220135843A1 (en) * | 2018-12-20 | 2022-05-05 | Lg Chem, Ltd. | Acrylic Emulsion Pressure-Sensitive Adhesive Composition |
KR102289974B1 (ko) * | 2019-12-06 | 2021-08-13 | 주식회사 두산 | 점착 필름 |
JPWO2021192896A1 (ja) * | 2020-03-27 | 2021-09-30 | ||
CN114605902B (zh) * | 2020-12-08 | 2023-03-31 | 德莎欧洲股份公司 | 一种高耐磨pu涂层及其应用 |
KR102634998B1 (ko) * | 2023-11-24 | 2024-02-08 | (주) 아이프린팅 | 탈부착이 용이한 라벨지 인쇄방법 및 그에 의해 인쇄된 라벨지 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002309209A (ja) * | 2001-04-12 | 2002-10-23 | Nippon Carbide Ind Co Inc | 水性アクリル系感圧接着剤組成物 |
JP2003213232A (ja) * | 2001-11-15 | 2003-07-30 | Konishi Co Ltd | 両面粘着テープ |
JP2003238932A (ja) * | 2002-02-18 | 2003-08-27 | Arakawa Chem Ind Co Ltd | 粘着付与樹脂エマルジョンおよびその製造方法ならびに水系粘・接着剤組成物 |
JP2006052379A (ja) * | 2004-07-16 | 2006-02-23 | Nitto Denko Corp | 粘着剤組成物、粘着シート類及び表面保護フィルム |
JP2007211074A (ja) * | 2006-02-08 | 2007-08-23 | Nippon Synthetic Chem Ind Co Ltd:The | エマルジョン型粘着剤組成物の製造方法、及び粘着剤組成物 |
JP2007262318A (ja) * | 2006-03-29 | 2007-10-11 | Nitto Denko Corp | 粘着フィルムおよび画像表示装置 |
JP2009035722A (ja) * | 2007-07-11 | 2009-02-19 | Nitto Denko Corp | 粘着剤組成物、粘着型光学フィルムおよび画像表示装置 |
JP2011241386A (ja) * | 2010-04-20 | 2011-12-01 | Nitto Denko Corp | 水分散型アクリル系粘着剤組成物及び粘着シート |
Family Cites Families (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3753765A (en) * | 1971-09-20 | 1973-08-21 | Du Pont | Conductive carbon antistatic backing for photographic film |
JPH05331431A (ja) * | 1992-05-28 | 1993-12-14 | Achilles Corp | 導電性透明保護フィルム |
JPH0834963A (ja) | 1994-07-22 | 1996-02-06 | Sekisui Chem Co Ltd | アクリル系粘着剤組成物 |
JP3810490B2 (ja) * | 1996-10-14 | 2006-08-16 | 日東電工株式会社 | 再剥離型感圧接着剤とその接着シ―ト類 |
JP2001064607A (ja) | 1999-09-01 | 2001-03-13 | Nitto Denko Corp | 表面保護フィルム |
JP4572007B2 (ja) | 1999-11-02 | 2010-10-27 | 日東電工株式会社 | 水分散型再剥離用感圧接着剤とその接着シ―ト類 |
WO2002090474A1 (en) * | 2001-05-04 | 2002-11-14 | Coatings For Industry, Inc. | Coating composition |
JP2002363521A (ja) * | 2001-06-08 | 2002-12-18 | Nitto Denko Corp | 水分散型粘着剤組成物および粘着テープ |
JP2003027026A (ja) | 2001-07-17 | 2003-01-29 | Saiden Chemical Industry Co Ltd | 再剥離用水分散型感圧性接着剤 |
JP4063614B2 (ja) | 2002-08-30 | 2008-03-19 | 日東電工株式会社 | 再剥離用水分散型アクリル系粘着剤組成物及び粘着シート |
JP4507610B2 (ja) * | 2003-02-28 | 2010-07-21 | Dic株式会社 | 再剥離型水性粘着剤組成物及び粘着製品 |
JP3997262B2 (ja) | 2004-03-30 | 2007-10-24 | サンノプコ株式会社 | 消泡剤 |
JP4807965B2 (ja) | 2004-05-12 | 2011-11-02 | 日東電工株式会社 | 再剥離用水分散型アクリル系粘着シートおよびそれに用いる粘着剤組成物 |
TW200617124A (en) * | 2004-06-01 | 2006-06-01 | Nitto Denko Corp | Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet and surface protecting film |
JP4531628B2 (ja) * | 2004-09-16 | 2010-08-25 | 日東電工株式会社 | 粘着剤組成物、粘着シート類、および表面保護フィルム |
US8137788B2 (en) * | 2004-09-29 | 2012-03-20 | Toray Industries, Inc. | Laminated film |
CN100577413C (zh) * | 2004-09-29 | 2010-01-06 | 东丽株式会社 | 叠层薄膜 |
JP4714452B2 (ja) * | 2004-10-21 | 2011-06-29 | 日東電工株式会社 | 帯電防止性粘着型光学フィルム及び画像表示装置 |
JP4346086B2 (ja) * | 2004-10-21 | 2009-10-14 | 日東電工株式会社 | 帯電防止性粘着型光学フィルム及び画像表示装置 |
JP4367704B2 (ja) * | 2004-10-21 | 2009-11-18 | 日東電工株式会社 | 帯電防止性粘着型光学フィルム及び画像表示装置 |
WO2006043448A1 (ja) * | 2004-10-21 | 2006-04-27 | Nitto Denko Corporation | 帯電防止性粘着型光学フィルム及び画像表示装置 |
US7641946B2 (en) * | 2005-08-08 | 2010-01-05 | Nitto Denko Corporation | Adhesive film and image display device |
JP4900897B2 (ja) * | 2005-09-05 | 2012-03-21 | 日東電工株式会社 | 粘着テープ類およびその製造方法 |
JP5863157B2 (ja) * | 2006-12-18 | 2016-02-16 | 日東電工株式会社 | 粘着シート |
JP2008194886A (ja) * | 2007-02-09 | 2008-08-28 | Nippon Shokubai Co Ltd | 表面保護フィルム |
JP5518370B2 (ja) * | 2009-05-20 | 2014-06-11 | 日東電工株式会社 | 再剥離用水分散型アクリル系粘着剤組成物の製造方法、再剥離用水分散型アクリル系粘着剤組成物、粘着剤層及び粘着シート |
JP5117532B2 (ja) * | 2010-04-20 | 2013-01-16 | 日東電工株式会社 | 再剥離用水分散型アクリル系粘着剤組成物及び粘着シート |
US20140037950A1 (en) * | 2011-04-15 | 2014-02-06 | Nitto Denko Corporation | Pressure-sensitive adhesive sheet |
-
2012
- 2012-04-06 US US14/111,335 patent/US20140037950A1/en not_active Abandoned
- 2012-04-06 KR KR1020137024180A patent/KR101878010B1/ko active IP Right Grant
- 2012-04-06 WO PCT/JP2012/059522 patent/WO2012141099A1/ja active Application Filing
- 2012-04-06 CN CN201280018649.5A patent/CN103476891B/zh not_active Expired - Fee Related
- 2012-04-06 WO PCT/JP2012/059524 patent/WO2012141100A1/ja active Application Filing
- 2012-04-06 CN CN201280018622.6A patent/CN103476890B/zh active Active
- 2012-04-06 CN CN2012800186832A patent/CN103476892A/zh active Pending
- 2012-04-06 US US14/111,298 patent/US20140030511A1/en not_active Abandoned
- 2012-04-06 KR KR1020137023320A patent/KR101883518B1/ko active IP Right Grant
- 2012-04-06 US US14/111,315 patent/US20140037911A1/en not_active Abandoned
- 2012-04-06 KR KR1020137024182A patent/KR101883519B1/ko active IP Right Grant
- 2012-04-06 WO PCT/JP2012/059527 patent/WO2012141101A1/ja active Application Filing
- 2012-04-13 TW TW101113312A patent/TW201245396A/zh unknown
- 2012-04-13 TW TW101113313A patent/TWI582203B/zh active
- 2012-04-13 TW TW101113310A patent/TW201247833A/zh unknown
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002309209A (ja) * | 2001-04-12 | 2002-10-23 | Nippon Carbide Ind Co Inc | 水性アクリル系感圧接着剤組成物 |
JP2003213232A (ja) * | 2001-11-15 | 2003-07-30 | Konishi Co Ltd | 両面粘着テープ |
JP2003238932A (ja) * | 2002-02-18 | 2003-08-27 | Arakawa Chem Ind Co Ltd | 粘着付与樹脂エマルジョンおよびその製造方法ならびに水系粘・接着剤組成物 |
JP2006052379A (ja) * | 2004-07-16 | 2006-02-23 | Nitto Denko Corp | 粘着剤組成物、粘着シート類及び表面保護フィルム |
JP2007211074A (ja) * | 2006-02-08 | 2007-08-23 | Nippon Synthetic Chem Ind Co Ltd:The | エマルジョン型粘着剤組成物の製造方法、及び粘着剤組成物 |
JP2007262318A (ja) * | 2006-03-29 | 2007-10-11 | Nitto Denko Corp | 粘着フィルムおよび画像表示装置 |
JP2009035722A (ja) * | 2007-07-11 | 2009-02-19 | Nitto Denko Corp | 粘着剤組成物、粘着型光学フィルムおよび画像表示装置 |
JP2011241386A (ja) * | 2010-04-20 | 2011-12-01 | Nitto Denko Corp | 水分散型アクリル系粘着剤組成物及び粘着シート |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015027765A (ja) * | 2013-07-30 | 2015-02-12 | 日東電工株式会社 | 表面保護フィルムおよび光学部材 |
CN103802703A (zh) * | 2014-01-26 | 2014-05-21 | 东莞广泽汽车饰件有限公司 | 一种汽车扶手生产工艺 |
CN103802703B (zh) * | 2014-01-26 | 2015-12-02 | 东莞广泽汽车饰件有限公司 | 一种汽车扶手生产工艺 |
WO2017010766A1 (ko) * | 2015-07-10 | 2017-01-19 | 주식회사 엘지화학 | 가교성 조성물 |
WO2017010769A1 (ko) * | 2015-07-10 | 2017-01-19 | 주식회사 엘지화학 | 점착 편광판 |
US10851268B2 (en) | 2015-07-10 | 2020-12-01 | Lg Chem, Ltd. | Compound |
US10883020B2 (en) | 2015-07-10 | 2021-01-05 | Lg Chem, Ltd. | Pressure-sensitive adhesive polarizing plate |
US10883019B2 (en) | 2015-07-10 | 2021-01-05 | Lg Chem, Ltd. | Cross-linkable composition |
US10889735B2 (en) | 2015-07-10 | 2021-01-12 | Lg Chem, Ltd. | Cross-linkable composition |
Also Published As
Publication number | Publication date |
---|---|
TW201247833A (en) | 2012-12-01 |
KR20140019348A (ko) | 2014-02-14 |
CN103476890B (zh) | 2015-11-25 |
CN103476890A (zh) | 2013-12-25 |
KR20140061290A (ko) | 2014-05-21 |
KR20140019347A (ko) | 2014-02-14 |
WO2012141101A1 (ja) | 2012-10-18 |
KR101883518B1 (ko) | 2018-07-30 |
US20140030511A1 (en) | 2014-01-30 |
CN103476891A (zh) | 2013-12-25 |
TWI582203B (zh) | 2017-05-11 |
US20140037950A1 (en) | 2014-02-06 |
TW201245396A (en) | 2012-11-16 |
KR101878010B1 (ko) | 2018-07-12 |
US20140037911A1 (en) | 2014-02-06 |
KR101883519B1 (ko) | 2018-07-30 |
CN103476891B (zh) | 2015-05-13 |
CN103476892A (zh) | 2013-12-25 |
TW201247834A (en) | 2012-12-01 |
WO2012141100A1 (ja) | 2012-10-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2012141099A1 (ja) | 粘着シート | |
JP5791945B2 (ja) | 粘着シート | |
JP6092035B2 (ja) | 表面保護フィルムおよび光学部材 | |
JP5611883B2 (ja) | 再剥離用水分散型アクリル系粘着剤組成物及び粘着シート | |
TWI490297B (zh) | Water-dispersed acrylic pressure-sensitive adhesive composition and adhesive sheet | |
JP5719194B2 (ja) | 再剥離用水分散型アクリル系粘着剤組成物及び粘着シート | |
JP6092034B2 (ja) | 表面保護フィルムおよび光学部材 | |
JP6092033B2 (ja) | 表面保護フィルムおよび光学部材 | |
US20140295183A1 (en) | Pressure-sensitive adhesive composition, pressure-sensitive adhesive sheet and optical film | |
KR101944142B1 (ko) | 재박리용 수분산형 아크릴계 점착제 조성물 및 점착 시트 | |
JP6599618B2 (ja) | 粘着シート、及び、光学部材 | |
JP5113277B2 (ja) | 水分散型アクリル系粘着剤組成物及び粘着シート | |
JP6599619B2 (ja) | 粘着シート、及び、光学部材 | |
JP5751905B2 (ja) | 粘着シート | |
JP5751906B2 (ja) | 粘着シート | |
JP5623967B2 (ja) | 水分散型アクリル系粘着剤組成物及び粘着シート |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12771469 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20137024180 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14111315 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 12771469 Country of ref document: EP Kind code of ref document: A1 |