WO2012133343A1 - 粘着剤組成物及び光学部材用フィルム - Google Patents
粘着剤組成物及び光学部材用フィルム Download PDFInfo
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- WO2012133343A1 WO2012133343A1 PCT/JP2012/057800 JP2012057800W WO2012133343A1 WO 2012133343 A1 WO2012133343 A1 WO 2012133343A1 JP 2012057800 W JP2012057800 W JP 2012057800W WO 2012133343 A1 WO2012133343 A1 WO 2012133343A1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
- C09J7/38—Pressure-sensitive adhesives [PSA]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/08—Homopolymers or copolymers of acrylic acid esters
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/10—Block or graft copolymers containing polysiloxane sequences
- C09J183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/105—Compounds containing metals of Groups 1 to 3 or of Groups 11 to 13 of the Periodic Table
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/318—Applications of adhesives in processes or use of adhesives in the form of films or foils for the production of liquid crystal displays
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/408—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the adhesive layer
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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2483/00—Presence of polysiloxane
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- 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
- Y10T428/2852—Adhesive compositions
- Y10T428/2857—Adhesive compositions including metal or compound thereof or natural rubber
Definitions
- the present invention relates to an adhesive composition and a film for optical members.
- the liquid crystal display panel Since the liquid crystal display panel is thin and light and consumes less power, it has been used in recent years as a screen display device for various information-related devices such as personal computers.
- an optical member such as a polarizing plate or a retardation plate is used together with a glass cell (liquid crystal cell) containing liquid crystal as a main body.
- optical members are usually adhesively coated with a surface protective film so that the surface is not contaminated or damaged during each process such as punching, inspection, transportation, and liquid crystal display panel assembly. It is formed as a long optical member laminate. Then, the surface protective film is peeled and removed from the optical member when the surface protection is no longer necessary.
- the surface protective film for an optical member has an adhesive force that adheres to the surface of the optical member to such an extent that the optical member does not deviate or fall off from the surface while the surface protection of the optical member is required.
- the edge of the surface protection film that has been turned up has a property (familiarity) that naturally returns to its original state. It is also needed.
- the surface protective film is attached to protect the optical member so that the surface of the optical member is not contaminated or damaged.
- the surface of the protective film is subjected to external stress such as collision between objects and bonding. Easy environment. Therefore, it is also necessary that the pressure-sensitive adhesive layer has a property of being able to be peeled off without being transferred to the optical member even when subjected to such external stress (glue resistance).
- optical members and surface protection films are generally made of plastic, they have high electrical insulation, and static electricity is generated during friction and peeling. Therefore, it is inevitable that static electricity is generated when the surface protective film is peeled from the optical member.
- static electricity is generated when the surface protective film is peeled off from the optical member, dust and dust are adsorbed on the surface of the optical film, resulting in inconvenience for the product.
- JP 2009-275128 A discloses an adhesive containing an acrylic copolymer, a metal salt, and an organopolysiloxane having a polyoxyalkylene group.
- Japanese Patent Application Laid-Open No. 2009-275128 it may be difficult to satisfy all of the suppression of generation of static electricity due to peeling charging, the adhesiveness, and the anti-glue transfer resistance.
- An object of the present invention is to provide a pressure-sensitive adhesive composition that suppresses generation of static electricity due to peeling electrification and is excellent in adhesiveness and adhesive transfer resistance, and a film for optical members using the same.
- the present invention includes the following aspects. (1) 40% by mass to 80% by mass of a structural unit derived from an alkyl (meth) acrylate having an alkyl group having 1 to 5 carbon atoms, and an alkyl (meth) acrylate having an alkyl group having 6 to 18 carbon atoms An acrylic copolymer (A) containing 10% by mass to 59.9% by mass of a structural unit derived from an ester and 0.1% by mass to 10% by mass of a structural unit derived from a monomer having a hydroxyl group; A structural unit derived from a monomer other than the polyoxyalkylene group-containing monomer and a structural unit derived from a polyoxyalkylene group-containing monomer having an average addition mole number of alkylene oxide units of 20 or more, A polyoxyal having a content of structural units derived from the polyoxyalkylene group-containing monomer of 60% by mass or less and a weight average molecular weight of 3,000 to 100,000 A pressure-sensitive adhesive containing a
- the content of the polyoxyalkylene group-containing copolymer (B) and the content of the alkali metal salt (C) with respect to 100 parts by mass of the acrylic copolymer (A) are each 0.05 mass.
- the pressure-sensitive adhesive composition according to (1) or (2), wherein the pressure-sensitive adhesive composition is 0.01 to 2.0 parts by mass and 0.01 to 0.6 parts by mass.
- the content of the dimethylpolysiloxane compound (D) with respect to 100 parts by mass of the acrylic copolymer (A) is from 0.01 parts by mass to 1.0 part by mass. It is an adhesive composition as described in any one.
- an optical member comprising: a base material; and a pressure-sensitive adhesive layer that is provided on the base material and is a coating film of the pressure-sensitive adhesive composition according to any one of (1) to (6) above. It is a film.
- the present invention it is possible to provide a pressure-sensitive adhesive composition that suppresses the generation of static electricity due to peeling electrification and is excellent in adhesiveness and adhesive transfer resistance, and a film for optical members using the same.
- the pressure-sensitive adhesive composition of the present invention has 40 to 80% by mass of a structural unit derived from an alkyl (meth) acrylate having an alkyl group having 1 to 5 carbon atoms and an alkyl group having 6 to 18 carbon atoms.
- a structural unit derived from a polyoxyalkylene group-containing monomer having an average addition mole number of alkylene oxide units of 20 or more, and a monomer other than the polyoxyalkylene group-containing monomer The content of the structural unit derived from the polyoxyalkylene group-containing monomer is 60% by mass or less, and the weight average molecular weight is 3,000 to 100,000.
- a polyoxyalkylene group-containing copolymer (B), an alkali metal salt (C), a dimethylpolysiloxane compound (D) having a polyoxyalkylene group in the molecule and having an HLB value of 9 or less. contains.
- the pressure-sensitive adhesive composition may contain other components as necessary.
- the pressure-sensitive adhesive composition having the above-mentioned specific structure is suppressed in the generation of static electricity due to peeling charging, and is excellent in adhesiveness and anti-glue transfer resistance.
- (meth) acryl is used to mean at least one of “acryl” and “methacryl”.
- (meth) acrylate is used to mean at least one of “acrylate” and “methacrylate”.
- a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
- the amount of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.
- the pressure-sensitive adhesive composition comprises a structural unit derived from a (meth) acrylic acid alkyl ester having a C 1-5 alkyl group having a content of 40% by mass to 80% by mass, A structural unit derived from a (meth) acrylic acid alkyl ester having an alkyl group having 6 to 18 carbon atoms with a content of 10% by mass to 59.9% by mass, and a content of 0.1% by mass to 10% by mass % Of at least one acrylic copolymer having a structural unit derived from a monomer having a hydroxyl group.
- structural unit derived from (meth) acrylic acid alkyl ester means a structural unit formed by addition polymerization of (meth) acrylic acid alkyl ester with another monomer. The same applies to “derived structural units” and the like.
- the acrylic copolymer (A) contains a structural unit derived from a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 5 carbon atoms in a content of 40% by mass to 80% by mass.
- the optical member has an adhesive force that adheres to the surface to such an extent that the optical member does not deviate or fall off from the surface.
- the alkyl group of the above (meth) acrylic acid alkyl ester has 1 to 5 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably an alkyl group having 4 carbon atoms.
- Examples of the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 5 carbon atoms include methyl (meth) acrylate, ethyl (eta) acrylate, n-butyl (meth) acrylate, and i-butyl (meth) acrylate. S-butyl (meth) acrylate, t-butyl (meth) acrylate and the like. Of these, n-butyl (meth) acrylate and i-butyl (meth) acrylate, which are alkyl esters of (meth) acrylic acid having an alkyl group having 4 carbon atoms, are preferred because of the excellent balance between tackiness and conformability.
- the acrylic copolymer (A) may contain one or more structural units derived from a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 5 carbon atoms.
- the content of the structural unit derived from the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 5 carbon atoms is 40% by mass to 80% by mass. % To 70% by mass, more preferably 40% to 60% by mass.
- the content of the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 5 carbon atoms is less than 40% by mass in the total mass of the acrylic copolymer (A), it is necessary to protect the surface of the optical member. In some cases, the optical member may be displaced or fall off from the surface.
- the content of the alkyl (meth) acrylate having an alkyl group having 1 to 5 carbon atoms exceeds 80% by mass in the total mass of the acrylic copolymer (A), the conformability and the anti-glue transfer Tend to decrease.
- the acrylic copolymer (A) contains a structural unit derived from a (meth) acrylic acid alkyl ester having an alkyl group having 6 to 18 carbon atoms at a content of 10% by mass to 59.9% by mass.
- the alkyl group of the above (meth) acrylic acid alkyl ester has 6 to 18 carbon atoms, but is preferably an alkyl group having 6 to 10 carbon atoms, particularly preferably an alkyl group having 8 carbon atoms, from the viewpoint of adhesion to the substrate. It is a group.
- Examples of the (meth) acrylic acid alkyl ester having an alkyl group having 6 to 18 carbon atoms include n-octyl (meth) acrylate, i-octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and n-nonyl.
- (Meth) acrylate, i-nonyl (meth) acrylate, n-decyl (meth) acrylate, n-dodecyl (meth) acrylate, stearyl (meth) acrylate and the like can be mentioned.
- n-octyl (meth) acrylate at least selected from the group consisting of n-octyl (meth) acrylate, i-octyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, which are alkyl esters of (meth) acrylic acid having an alkyl group having 8 carbon atoms.
- n-octyl (meth) acrylate i-octyl (meth) acrylate
- 2-ethylhexyl (meth) acrylate alkyl esters of (meth) acrylic acid having an alkyl group having 8 carbon atoms.
- 2-ethylhexyl acrylate is particularly preferable.
- the acrylic copolymer (A) may contain one or more structural units derived from a (meth) acrylic acid alkyl ester having an alkyl group having 6 to 18 carbon atoms.
- the content of the structural unit derived from the (meth) acrylic acid alkyl ester having an alkyl group having 6 to 18 carbon atoms is 10% by mass to 59.9% by mass. It is preferably 30% by mass to 58% by mass, and more preferably 40% by mass to 58% by mass.
- the content of the structural unit derived from the (meth) acrylic acid alkyl ester having an alkyl group having 6 to 18 carbon atoms is less than 10% by mass in the total mass of the acrylic copolymer (A), Tends to decrease.
- the acrylic copolymer (A) contains a structural unit derived from a monomer having a hydroxyl group at a content of 0.1% by mass to 10% by mass. Thereby, it has the moderate adhesive force with respect to a to-be-adhered body, and is excellent also in removability.
- the monomer having a hydroxyl group include a (meth) acrylic monomer having a hydroxyl group and other monomers having a hydroxyl group.
- Examples of the (meth) acrylic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth).
- the compatibility and copolymerization with other monomers when the acrylic copolymer (A) is synthesized are good, and the crosslinking reaction with a crosslinking agent. From the viewpoint of satisfactory, it is preferable to use at least one selected from the group consisting of 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
- the acrylic copolymer (A) may contain one or more structural units derived from a monomer having a hydroxyl group.
- the content of the structural unit derived from the monomer having a hydroxyl group is 0.1 to 10% by mass in the total mass of the acrylic copolymer (A). More preferably, the content is 2% by mass to 5% by mass.
- the content of the structural unit derived from the monomer having a hydroxyl group is less than 0.1% by mass, the cohesive force is insufficient and the adherend tends to be contaminated. On the other hand, if it exceeds 10% by mass, the conformability tends to decrease.
- the acrylic copolymer (A) is a structural unit derived from a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 5 carbon atoms, and an alkyl (meth) acrylate having an alkyl group having 6 to 18 carbon atoms.
- a structural unit derived from another monomer other than these may be further included as necessary.
- the acrylic copolymer (A) may contain one or more structural units derived from other monomers.
- Examples of other monomers include monomers other than acrylic monomers, monomers having functional groups other than hydroxyl groups, and the like.
- Examples of the monomer having a functional group other than a hydroxyl group include a carboxy group-containing monomer, a glycidyl group-containing monomer, an amide group or N-substituted amide group-containing monomer, and a tertiary amino group-containing monomer. Etc.
- monomers other than acrylic monomers include aromatic monovinyl monomers such as styrene, ⁇ -methylstyrene, t-butylstyrene, p-chlorostyrene, chloromethylstyrene, and vinyltoluene; for example, acrylonitrile and methacrylonitrile.
- aromatic monovinyl monomers such as styrene, ⁇ -methylstyrene, t-butylstyrene, p-chlorostyrene, chloromethylstyrene, and vinyltoluene
- vinyl cyanide monomers vinyl ester monomers such as vinyl formate, vinyl acetate, vinyl propionate, vinyl versatate; and various derivatives thereof.
- carboxy group-containing monomer examples include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, itaconic acid, citraconic acid, cinnamic acid, succinic acid monohydroxyethyl (meth) acrylate, and maleic acid.
- Examples of the glycidyl group-containing monomer include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, glycidyl vinyl ether, 3,4-epoxycyclohexyl vinyl ether, glycidyl (meth) allyl ether, 3,4 -Epoxycyclohexyl (meth) allyl ether and the like.
- Examples of the amide group or N-substituted amide group-containing monomer include acrylamide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, and N-ethoxy. Examples thereof include methyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide, N-tert-butylacrylamide, N-octylacrylamide, diacetone acrylamide and the like.
- tertiary amino group-containing monomer examples include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide and the like.
- the acrylic copolymer (A) further includes a structural unit derived from another monomer
- the content is preferably 10% by mass or less, more preferably 3% by mass or less. preferable.
- Content ratio of structural unit derived from ester structural unit derived from (meth) acrylic acid alkyl ester having alkyl group having 6 to 18 carbon atoms / (meth) acrylic acid alkyl ester having alkyl group having 1 to 5 carbon atoms
- the structural unit derived from is not particularly limited.
- the content ratio is preferably 0.35 to 1.5, more preferably 0.7 to 1.5, from the viewpoints of suppressing generation of static electricity due to peeling, adhesiveness, and resistance to adhesive transfer. preferable.
- the content ratio of the structural unit derived from the monomer having a hydroxyl group to the structural unit derived from the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 5 carbon atoms There are no particular restrictions on the structural unit derived from a monomer having a hydroxyl group / the structural unit derived from a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 5 carbon atoms.
- the content ratio is preferably 0.04 to 0.13 from the viewpoint of suppressing generation of static electricity due to peeling, adhesiveness, and transferability.
- Content ratio of a structural unit derived from a monomer having a hydroxyl group to a total content of a structural unit derived from an alkyl ester hereinafter, also referred to as “structural unit derived from an alkyl (meth) acrylate”) (hydroxyl group)
- the structural unit derived from the monomer having the structural unit derived from the (meth) acrylic acid alkyl ester There are no particular restrictions on the structural unit derived from the monomer having the structural unit derived from the (meth) acrylic acid alkyl ester.
- the content ratio is preferably 0.02 to 0.05 from the viewpoints of suppression of generation of static electricity due to peeling, adhesiveness, and resistance to adhesive transfer.
- the acrylic copolymer (A) is preferably an acrylic copolymer (A) having a weight average molecular weight (Mw) of 200,000 to 1,000,000, and a weight average molecular weight (Mw) of 300,000 to 700,000. It is more preferable that If the weight average molecular weight (Mw) is at least the lower limit value, the adhesive force at the time of re-peeling is not excessively increased, and the surface protective film can be easily peeled off, which is preferable.
- the resulting adhesive composition layer has excellent fluidity, and even when used for adherends such as polarizing plates having fine irregularities on the surface, the adhesive composition is This is preferable because the surface of an adherend such as a polarizing plate can be sufficiently wetted and has excellent conformability.
- the number average molecular weight (Mn) of the acrylic copolymer (A) is preferably 30,000 to 100,000. If the number average molecular weight (Mn) is at least the lower limit value, the adhesive force at the time of re-peeling is not excessively increased and the surface protective film can be easily peeled off, which is preferable. On the other hand, if the upper limit is not exceeded, the resulting adhesive composition layer has excellent fluidity, and the adhesive composition is polarized even when used for an optical member such as a polarizing plate having fine irregularities on the surface. It is preferable because the surface of the adherend such as a plate can be sufficiently wetted and has excellent conformability.
- the dispersity (Mw / Mn) which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the acrylic copolymer (A) is not particularly limited. For example, it is preferably 3 to 10 from the viewpoints of suppressing generation of static electricity due to peeling, adhesiveness, and resistance to paste transfer.
- the weight average molecular weight (Mw) and number average molecular weight (Mn) of the acrylic copolymer (A) are values measured by the following method. (Measurement method of weight average molecular weight and number average molecular weight)
- the weight average molecular weight (Mw) of the acrylic copolymer (A) is measured according to the following procedures (1) to (3). (1) An acrylic copolymer solution is applied to a release sheet and dried at 100 ° C. for 2 minutes to obtain a film-like acrylic copolymer. (2) The film-like acrylic copolymer obtained in (1) above is dissolved in tetrahydrofuran so that the solid content is 0.2% by mass. (3) The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the acrylic copolymer are measured using gel permeation chromatography (GPC) under the following conditions.
- GPC gel permeation chromatography
- GPC HLC-8220 GPC [manufactured by Tosoh Corporation] Column: 4 TSK-GEL GMHXL used Mobile phase solvent: Tetrahydrofuran Flow rate: 0.6 ml / min Column temperature: 40 ° C
- the glass transition temperature (Tg) of the acrylic copolymer (A) is preferably ⁇ 45 ° C. or lower, more preferably ⁇ 80 ° C. to ⁇ 45 ° C., and ⁇ 80 ° C. to ⁇ 60 ° C. More preferably.
- a Tg of ⁇ 45 ° C. or lower is preferable because it has sufficient conformability.
- the glass transition temperature (Tg) of the acrylic copolymer (A) is a value obtained by converting the absolute temperature (K) obtained by the calculation of the following formula 1 into Celsius temperature (° C.).
- Formula 1 1 / Tg w 1 / Tg 1 + w 2 / Tg 2 +... + W (k-1) / Tg (k-1) + w k / Tg k
- Tg 1 , Tg 2 ,..., Tg (k ⁇ 1) , Tg k are the glass transition temperatures of the homopolymers of the respective monomer components constituting the acrylic copolymer. (K) is shown respectively.
- the content of the acrylic copolymer (A) in the pressure-sensitive adhesive composition is, for example, in the total mass of the pressure-sensitive adhesive composition from the viewpoints of suppression of generation of static electricity due to peeling, pressure-sensitive adhesiveness, and anti-glue transfer resistance. It is preferably 90 to 98% by mass.
- the pressure-sensitive adhesive composition includes a structural unit derived from a polyoxyalkylene group-containing monomer having an average addition mole number of alkylene oxide units of 20 or more, and the polyoxyalkylene group. Including a structural unit derived from a monomer other than the containing monomer, the content of the structural unit derived from the polyoxyalkylene group-containing monomer is 60% by mass or less, and the weight average molecular weight It contains at least one polyoxyalkylene group-containing copolymer (B) having a molecular weight of 3,000 to 100,000.
- polyoxyalkylene group-containing monomer examples include polyoxyalkylene group-containing (meth) acrylic monomers having a polyoxyethylene group and a polyoxypropylene group.
- polyoxyalkylene group-containing (meth) acrylic monomers include polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, and polypropylene glycol (meth) acrylate. Can be mentioned.
- At least one selected from the group consisting of methoxypolyethylene glycol (meth) acrylate and methoxypolypropylene glycol (meth) acrylate is preferable, and methoxypolyethylene glycol (meth) acrylate is more preferable.
- the average number of added moles of alkylene oxide units in the polyoxyalkylene group-containing monomer is not particularly limited as long as it is 20 or more. When the average number of added moles of alkylene oxide units is less than 20, sufficient antistatic effect may not be exhibited depending on the combination with an alkali metal salt described later.
- the average added mole number of the alkylene oxide unit is preferably 20 to 100, more preferably 20 to 50. When the average added mole number of the alkylene oxide unit is within the above range, more excellent antistatic effect and adhesiveness can be exhibited.
- the content of the structural unit derived from the polyoxyalkylene group-containing monomer in the polyoxyalkylene group-containing copolymer (B) is 60 mass in the total mass of the polyoxyalkylene group-containing copolymer (B). %, Preferably 10% to 60% by weight, more preferably 10% to 30% by weight. When the content of the structural unit derived from the polyoxyalkylene group-containing monomer exceeds 60% by mass, the tackiness tends to decrease.
- the polyoxyalkylene group-containing copolymer (B) further includes at least one other structural unit other than the structural unit derived from the polyoxyalkylene group-containing monomer.
- the monomer that can form other structural units include (meth) acrylic acid alkyl ester, monomers having a functional group such as a carboxy group, and a hydroxyl group.
- Examples of the (meth) acrylic acid alkyl ester include a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 5 carbon atoms and an alkyl group having 6 to 18 carbon atoms in the acrylic copolymer (A). Examples include (meth) acrylic acid alkyl esters.
- the substrate is preferably at least one kind of (meth) acrylic acid alkyl ester having an alkyl group having 1 to 5 carbon atoms, and has an alkyl group having 3 to 5 carbon atoms ( More preferably, it is at least one of (meth) acrylic acid alkyl esters, and more preferably at least one of (meth) acrylic acid alkyl esters having an alkyl group having 4 carbon atoms.
- Specific examples of the (meth) acrylic acid alkyl ester having an alkyl group having 1 to 5 carbon atoms are the same as described above.
- Examples of the monomer having a functional group such as a carboxy group or a hydroxyl group include a monomer having a hydroxyl group in the acrylic copolymer (A) and other monomers.
- the polyoxyalkylene group-containing copolymer (B) includes, as other structural units, structural units derived from (meth) acrylic acid alkyl esters. It preferably contains at least one kind, more preferably contains at least one structural unit derived from a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 5 carbon atoms, and an alkyl group having 3 to 5 carbon atoms.
- it contains at least one structural unit derived from (meth) acrylic acid alkyl ester having n-butyl (meth) acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, and a structural unit derived from at least one selected from the group consisting of t-butyl (meth) acrylate. It is particularly preferred.
- the content of other structural units in the polyoxyalkylene group-containing copolymer (B) is preferably 40 to 90% by mass in the total mass of the polyoxyalkylene group-containing copolymer (B). More preferably, it is -90 mass%.
- the content of other structural units is within the above range, there is a tendency to be more excellent in suppressing generation of static electricity due to peeling charging and to exhibit better adhesiveness.
- the polyoxyalkylene group-containing copolymer (B) includes a structural unit derived from a (meth) acrylic acid alkyl ester as another structural unit in addition to the structural unit derived from the polyoxyalkylene group-containing monomer.
- the content ratio of the structural unit derived from the (meth) acrylic acid alkyl ester to the structural unit derived from the polyoxyalkylene group-containing monomer in the polyoxyalkylene group-containing copolymer (B) is From the viewpoint of tackiness, it is preferably 0.1 to 0.5.
- the polyoxyalkylene group-containing copolymer (B) has a weight average molecular weight (Mw) of 3,000 to 100,000, preferably 5,000 to 60,000, more preferably 5,000. ⁇ 30,000. If the weight average molecular weight (Mw) is less than 3,000, sufficient adhesive strength may not be obtained. Moreover, when a weight average molecular weight (Mw) exceeds 100,000, the compatibility in an adhesive composition may fall.
- the weight average molecular weight (Mw) of the said polyoxyalkylene group containing copolymer (B) can be measured by the method similar to the measuring method of the weight average molecular weight (Mw) of the said acrylic copolymer (A).
- the content of the polyoxyalkylene group-containing copolymer (B) in the pressure-sensitive adhesive composition is 0.05 to 2.0 parts by mass with respect to 100 parts by mass of the acrylic copolymer (A). It is preferably 0.1 to 1.5 parts by mass, more preferably 0.2 to 1.0 part by mass. If the content of the polyoxyalkylene group-containing copolymer (B) is 0.05 parts by mass or more with respect to 100 parts by mass of the acrylic copolymer (A), a more excellent antistatic effect tends to be obtained. There is. If the content of the polyoxyalkylene group-containing copolymer (B) is 2.0 parts by mass or less with respect to 100 parts by mass of the acrylic copolymer (A), contamination of the adherend is more effective. Tend to be suppressed.
- the acrylic copolymer (A) and the polyoxyalkylene group-containing copolymer (B) are constituent units contained in these copolymers. It can be produced by polymerizing a mixture of monomers capable of forming.
- the polymerization method of the copolymer is not particularly limited, and can be appropriately selected from known methods such as a solution polymerization method, an emulsion polymerization method, and a suspension polymerization method.
- the pressure-sensitive adhesive composition of the present invention is produced using the copolymer obtained by polymerization, it is preferably polymerized by a solution polymerization method because the treatment process is relatively simple and can be performed in a short time.
- a predetermined organic solvent, a monomer, a polymerization initiator, and a chain transfer agent used as necessary are charged in a polymerization tank, and stirred in a nitrogen stream at the reflux temperature of the organic solvent.
- a known method such as heating for several hours.
- the weight average molecular weight and dispersion degree of the acrylic copolymer (A) and the polyoxyalkylene group-containing copolymer (B) are easily adjusted by the reaction temperature, time, amount of solvent, type and amount of catalyst. be able to.
- Examples of the organic solvent used for the polymerization of the acrylic copolymer (A) and the polyoxyalkylene group-containing copolymer (B) include benzene, toluene, ethylbenzene, n-propylbenzene, and t-butyl.
- Aromatic hydrocarbons such as benzene, o-xylene, m-xylene, p-xylene, tetralin, decalin, aromatic naphtha; for example, n-hexane, n-heptane, n-octane, i-octane, n-decane
- Aliphatic or alicyclic hydrocarbons such as dipentene, petroleum spirit, petroleum naphtha and turpentine oil; for example, ethyl acetate, n-butyl acetate, n-amyl acetate, 2-hydroxyethyl acetate, 2-butoxyethyl acetate
- Esters such as 3-methoxybutyl acetate, methyl benzoate; acetone, methyl ethyl ketone, Ketones such as chill-i-butyl ketone, isophorone, cyclohexanone, methylcyclohexanone
- organic peroxides examples include t-butyl hydroperoxide, cumene hydroxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide, caproyl peroxide, di-i-propyl peroxydicarbonate, di- 2-ethylhexyl peroxydicarbonate, t-butyl peroxybivalate, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 2,2-bis (4,4-di-t -Amylperoxycyclohexyl) propane, 2,2-bis (4,4-di-t-octylperoxycyclohexyl) propane, 2,2-bis (4,4-di- ⁇ -cumylperoxycyclohexyl) propane, 2,2-bis (4,4-di-di-di-
- azo compound examples include 2,2′-azobis-i-butyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile, 2,2′-azobis-4-methoxy-2,4-dimethylvalero. A nitrile etc. are mentioned.
- a chain transfer agent is usually not used, but the object and effect of the present invention are not impaired. In range, it is possible to use as needed.
- the chain transfer agent include cyanoacetic acid; alkyl esters having 1 to 8 carbon atoms of cyanoacetic acid; bromoacetic acid; alkyl esters having 1 to 8 carbon atoms of bromoacetic acid; anthracene, phenanthrene, fluorene, 9-phenylfluorene.
- Aromatic compounds such as p-nitroaniline, nitrobenzene, dinitrobenzene, p-nitrobenzoic acid, p-nitrophenol and p-nitrotoluene; benzoquinone, 2,3,5,6-tetra Benzoquinone derivatives such as methyl-p-benzoquinone; borane derivatives such as tributylborane; carbon tetrabromide, carbon tetrachloride, 1,1,2,2-tetrabromoethane, tribromoethylene, trichloroethylene, bromotrichloromethane, tri Bromomethane, 3-chloro-1-propene, etc.
- Halogenated hydrocarbons Aldehydes such as chloral and furaldehyde: Alkyl mercaptans having 1 to 18 carbon atoms; Aromatic mercaptans such as thiophenol and toluene mercaptan; Alkyl esters having 1 to 10 carbon atoms of mercaptoacetic acid and mercaptoacetic acid C1-12 hydroxyalkyl mercaptans; terpenes such as vinylene and terpinolene; and the like.
- Aldehydes such as chloral and furaldehyde: Alkyl mercaptans having 1 to 18 carbon atoms; Aromatic mercaptans such as thiophenol and toluene mercaptan; Alkyl esters having 1 to 10 carbon atoms of mercaptoacetic acid and mercaptoacetic acid C1-12 hydroxyalkyl mercaptans; terpenes such as vinylene and terpinolene; and the like.
- the polymerization temperature is generally in the range of about 30 to 180 ° C.
- a purification step for purifying the polymer obtained by the polymerization reaction may be provided. Thereby, when an unreacted monomer is contained in a polymer obtained by a solution polymerization method or the like, the monomer can be removed.
- the purification step can be appropriately selected from commonly used purification methods. For example, it can be purified by reprecipitation with methanol or the like.
- the pressure-sensitive adhesive composition contains at least one alkali metal salt (C).
- the alkali metal salt (C) is a metal salt having lithium, sodium, potassium or the like as a cation. Specifically, cations such as Li + , Na + , K + , Cl ⁇ , Br ⁇ , I ⁇ , BF 4 ⁇ , PF 6 ⁇ , SCN ⁇ , ClO 4 ⁇ , CF 3 SO 3 ⁇ , (CF Metal salts composed of anions such as 3 SO 2 ) 2 N ⁇ , (C 2 F 5 SO 2 ) 2 N ⁇ , (CF 3 SO 2 ) 3 C — are preferably used.
- a lithium salt such as 3 C is preferably used.
- LiCF 3 SO 3 and Li (CF 3 SO 2 ) 2 N are particularly preferable because they have good antistatic effects and metal corrosivity.
- These alkali metal salts may be used alone or in combination of two or more.
- the content of the alkali metal salt in the pressure-sensitive adhesive composition is preferably 0.01 parts by mass to 0.6 parts by mass with respect to 100 parts by mass of the acrylic copolymer (A). More preferably, it is from 0.2 to 0.2 parts by mass.
- the content of the alkali metal salt is 0.01 parts by mass or more with respect to 100 parts by mass of the acrylic copolymer (A)
- more excellent charging characteristics tend to be obtained.
- it is 0.6 mass part or less, there exists a tendency which can suppress the contamination of a to-be-adhered body more effectively.
- the pressure-sensitive adhesive composition contains at least one dimethylpolysiloxane compound (D) having a polyoxyalkylene group in the molecule and an HLB value of 9 or less.
- the dimethylpolysiloxane compound (D) has a polyoxyalkylene group in its molecule and has an antistatic performance by having an HLB value in a specific range, and further constitutes a pressure-sensitive adhesive composition. It is excellent in compatibility with a resin such as a copolymer, and can exhibit appropriate tackiness.
- polyoxyalkylene group examples include a polyoxyethylene group, a polyoxypropylene group, a polyoxybutylene group, and groups derived from these block copolymers.
- the polyoxyalkylene group may be contained as a side chain of the dimethylpolysiloxane compound (D) or as a terminal group of the dimethylpolysiloxane compound (D). From the viewpoint, it is preferably contained as a side chain of the dimethylpolysiloxane compound (D).
- the terminal of the polyoxyalkylene group may be any of a hydroxyl group, an alkoxy group, and an acyloxy group.
- the dimethylpolysiloxane compound (D) has an HLB value of 9 or less.
- HLB value of the dimethylpolysiloxane compound (D) exceeds 9, anti-glue resistance and anti-peeling performance tend to deteriorate.
- the HLB value is preferably 5 or more and 8 or less.
- the HLB value is a scale indicating the balance between hydrophilicity and hydrophobicity of the dimethylpolysiloxane compound (D).
- the definition of the Griffin method calculated by the following formula 2 is followed.
- the catalog data is preferentially adopted.
- a commonly used method can be used without any particular limitation.
- a method of appropriately selecting the molecular weight of the dimethylpolysiloxane compound and the content of the polyoxyalkylene group that is a hydrophilic group can be exemplified.
- dimethylpolysiloxane compound (D) having a polyoxyalkylene group and having an HLB value of 9 or less include, for example, “L-7001” (HLB value 5), “L-7002” (HLB value 8). ), “SF-8427” (HLB value 9), “SF-8428” (HLB value 0), “SH-3749” (HLB value 6), “SH-3773M” (HLB value 8), “SH-8400” (HLB value 7) [above, manufactured by Toray Dow Co., Ltd.].
- the content of the dimethylpolysiloxane compound (D) in the pressure-sensitive adhesive composition is 100 parts by weight of the acrylic copolymer (A) from the viewpoints of compatibility with the copolymer, surface uneven distribution, and pressure-sensitive adhesiveness. On the other hand, it is preferably from 0.01 part by weight to 1.0 part by weight, more preferably from 0.1 part by weight to 0.5 part by weight.
- the content of the dimethylpolysiloxane compound (D) having a polyoxyalkylene group in the pressure-sensitive adhesive composition is not less than the above lower limit value, the pressure-sensitive adhesive even when the protective film surface is subjected to external stress. It is preferable because the layer can be peeled off without being transferred to the optical member, and the generation of static electricity due to peeling charging can be suppressed. Further, if the content of the dimethylpolysiloxane compound (D) having a polyoxyalkylene group in the pressure-sensitive adhesive composition is not more than the above upper limit value, the adhesiveness may change over time or excessive on the surface of the optical member. It tends to be suppressed that the dimethylsiloxane compound remains and contaminates the surface, which is preferable.
- the pressure-sensitive adhesive composition preferably contains at least one crosslinking agent.
- the crosslinking agent is preferably at least one isocyanate compound, and more preferably at least one polyvalent isocyanate compound.
- a cross-linking agent preferably an isocyanate compound
- isocyanate compound examples include aromatic isocyanates such as xylylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, and tolylene diisocyanate; for example, hexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated products of the above aromatic isocyanate compounds.
- aromatic isocyanates such as xylylene diisocyanate, diphenylmethane diisocyanate, triphenylmethane triisocyanate, and tolylene diisocyanate
- hexamethylene diisocyanate isophorone diisocyanate
- hydrogenated products of the above aromatic isocyanate compounds examples include aliphatic or alicyclic isocyanates; dimer or trimer of these isocyanate compounds or isocyanate compound derivatives derived from various isocyanates such as adducts of these isocyanate compounds and polyols such as
- isocyanate compounds can be used alone or in admixture of two or more.
- Examples of the isocyanate compound include “Coronate HX”, “Coronate HL-S”, “Coronate 2234”, “Aquanate 200”, “Aquanate 210” (manufactured by Nippon Polyurethane Co., Ltd.), “Desmodule N3400”, “Death” Module N3300 (manufactured by Sumitomo Bayer Urethane Co., Ltd.), Duranate E-405-80T, Duranate 24A-100, Duranate TSE-100 (Asahi Kasei Kogyo Co., Ltd.), Takenate D-110N
- Commercially available products such as “Takenate D-120N”, “Takenate M-631N”, “MT-Olestar NP1200” (manufactured by Mitsui Takeda Chemical Co., Ltd.) can be suitably used.
- the content of these isocyanate compounds in the pressure-sensitive adhesive composition is preferably 0.01 parts by mass to 15 parts by mass, and 0.5 parts by mass with respect to 100 parts by mass of the acrylic copolymer (A). More preferably, it is ⁇ 5.0 parts by mass.
- the said adhesive composition may further contain curing catalysts, such as dibutyltin dilaurate and dioctyltin dilaurate, as needed.
- the pressure-sensitive adhesive composition includes the above-mentioned acrylic copolymer (A), polyoxyalkylene group-containing copolymer (B), alkali metal salt (C), dimethylpolysiloxane compound (D), and as necessary.
- other additives may be further contained.
- Other additives can be appropriately selected as necessary from additives usually used in pressure-sensitive adhesive compositions. Examples of other additives include a weather resistance stabilizer, a tackifier, a plasticizer, a softener, and an inorganic filler.
- the pressure-sensitive adhesive composition may further contain a solvent as necessary.
- the solvent is not particularly limited as long as it can dissolve the pressure-sensitive adhesive composition. It can be appropriately selected from those exemplified as the organic solvent for polymerization described above according to the purpose and the like.
- the pressure-sensitive adhesive composition includes an acrylic copolymer (A), a polyoxyalkylene group-containing copolymer (B), an alkali metal salt (C), a dimethylpolysiloxane compound (D), and as necessary. It can be prepared by mixing an isocyanate compound and a curing catalyst by a commonly used method.
- the pressure-sensitive adhesive composition of the present invention is used, for example, to form a pressure-sensitive adhesive layer on at least one surface of an appropriate transparent surface protective substrate by a conventionally known method in order to produce a surface protective film for an optical member. Used.
- the film for optical members of the present invention includes a base material and a pressure-sensitive adhesive layer that is provided on the base material and is a coating film of the pressure-sensitive adhesive composition.
- the film for optical members may further include other components as necessary.
- the said film for optical members is used suitably as a surface protection film for optical members.
- the substrate for the optical member film of the present invention is not particularly limited as long as it is a substrate to which the adhesive composition can be applied.
- a substrate containing a resin is preferable.
- the resin constituting the base material include polyester resin, acetate resin, polyether sulfone resin, polycarbonate resin, polyamide resin, and polyimide resin from the viewpoint of inspection and management of optical members through fluoroscopy. And films made of polyolefin resin, acrylic resin, and the like.
- a polyester resin is preferable, and a polyethylene terephthalate resin is particularly preferable in consideration of practicality.
- the thickness of the base material can be generally 500 ⁇ m or less.
- the thickness is preferably 5 ⁇ m to 500 ⁇ m, more preferably 5 ⁇ m to 300 ⁇ m, and still more preferably 10 ⁇ m to 200 ⁇ m.
- These base materials may be provided with an antistatic layer on one side or both sides for the purpose of preventing antistatic at the time of peeling.
- the surface of the substrate on the side where the pressure-sensitive adhesive layer is provided may be subjected to a corona discharge treatment or the like in order to improve the adhesion with the pressure-sensitive adhesive layer.
- the thickness of the pressure-sensitive adhesive layer formed on the substrate can be appropriately set according to the adhesive force required for the optical member film, the optical member surface roughness, and the like. Generally, it can be set to 1 ⁇ m to 100 ⁇ m. The thickness is preferably 5 ⁇ m to 50 ⁇ m, more preferably 15 ⁇ m to 30 ⁇ m. The thickness of the pressure-sensitive adhesive layer on the substrate is obtained as an arithmetic average value obtained by measuring the thickness at three points using a micrometer.
- the above-mentioned pressure-sensitive adhesive composition is diluted as it is or with an appropriate solvent as necessary, and this is directly applied and dried on a substrate which is a surface protective base film, and the solvent is removed.
- a removal method can be employed. First, on the release sheet made of an appropriate film such as paper or polyester film subjected to a release treatment with a silicone resin or the like, the pressure-sensitive adhesive composition is applied and dried by heating to form a pressure-sensitive adhesive layer. Next, the adhesive layer side of the release sheet can be pressed against a base material that is a surface protective base film, and the adhesive layer can be transferred onto the base material.
- the application method of the pressure-sensitive adhesive composition is not particularly limited, and can be appropriately selected from commonly used application methods. Examples of the application method include blade coating, direct coating, and knife coating.
- the optical member film thus obtained is laminated on the surface of the optical member to protect the surface of the optical member from being contaminated or damaged, and when the optical member is processed into a liquid crystal display panel or the like.
- the optical member film is left in a state where it is laminated on the optical member, and is subjected to various processes such as punching, inspection, transportation, and assembly of a liquid crystal display panel. If necessary, autoclave treatment, high temperature aging treatment, etc. When the surface pressure is no longer required, the film is peeled off from the optical member.
- Dispersity which is the ratio of the solid content, glass transition temperature (Tg), weight average molecular weight (Mw), viscosity, weight average molecular weight (Mw) of the resulting acrylic copolymer (A-1) solution to the number average molecular weight Table 1 shows (Mw / Mn).
- Tg glass transition temperature
- Mw weight average molecular weight
- Mw weight average molecular weight
- Mw weight average molecular weight
- Table 1 shows (Mw / Mn).
- “-” indicates that it is not blended.
- the “solid content” is the amount of residue obtained by removing the solvent from the acrylic copolymer solution.
- the viscosity was measured using a BH viscometer at 25 ° C. and a rotation speed of 10 rpm.
- the glass transition temperature (Tg) is calculated by the method described above, and the weight average molecular weight (Mw) is measured by the method described above.
- each compound in Table 1, 2 is as follows.
- the glass transition temperature (Tg) of the homopolymer of each monomer shown below was used for calculation of the glass transition temperature (Tg) in Table 1, respectively.
- EA ethyl acrylate (Tg: -27 ° C)
- MA methyl acrylate (Tg: 5 ° C.)
- t-BMA t-butyl methacrylate
- MePEGMA methoxypolyethylene glycol methacrylate, average added mole number of alkylene oxide unit is 23
- Example 1 Preparation of pressure-sensitive adhesive composition for film for optical member
- Acrylic copolymer (A-1) obtained in Production Example A-1 in a four-necked flask equipped with a stirring blade and a thermometer 100 parts by mass of a solution (however, 50 parts by mass as solid content), 0.6 parts by mass of the polyoxyalkylene group-containing copolymer (B-1) obtained in Production Example B-1 (however, acrylic copolymer) 0.05 parts by mass of LiCF 3 SO 3 (hereinafter sometimes abbreviated as “LiTFS”) as an active metal salt (C) with respect to 100 parts by mass of the union (A).
- LiCF 3 SO 3 hereinafter sometimes abbreviated as “LiTFS”
- a test pressure-sensitive adhesive sheet was obtained as an optical member film as follows. On a polyethylene terephthalate (PET) film [trade name; Teijin Tetron Film, Type G2, thickness 38 ⁇ m; manufactured by Teijin DuPont Films Ltd.], using an applicator, the coating amount after drying is 20 g / m 2
- PET polyethylene terephthalate
- the pressure-sensitive adhesive composition was applied to the film, dried at 100 ° C. for 60 seconds with a hot-air circulating drier to form a pressure-sensitive adhesive layer, and then the pressure-sensitive adhesive on the release film surface-treated with a silicone-based release agent. After placing the layers so that they contact each other and pressing and bonding them through a pressure nip roll, curing was performed at 23 ° C. and 50% RH for 3 days to obtain a test pressure-sensitive adhesive sheet.
- Examples 2 to 16, Comparative Examples 1 to 9 Adhesives for optical member films as shown in Table 3 in the same manner as in Example 1 except that the blending conditions of Examples and Comparative Examples shown in Table 3 were applied instead of the blending conditions of Example 1.
- Each agent composition was prepared.
- test pressure-sensitive adhesive sheets were prepared according to the above-described test pressure-sensitive adhesive sheet preparation methods.
- LiTFS LiCF 3 SO 3
- LiTFSI Li (CF 3 SO 2 ) 2 N
- alkali metal salt (C) N-3300 an isocyanate compound having an isocyanurate structure which is a trimer of hexamethylene diisocyanate manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Desmodur N3300, active ingredient 100% by mass
- Siloxane compounds the ends of the polyoxyalkylene group is a methoxy group
- HLB value 14 KP-355: manufactured by Shin-Etsu Chemical Co., Ltd., dimethylpolysiloxane compound having a polyoxyalkylene group introduced therein
- HLB value 10 DBTDL: Dibutyltin dilaurate, curing catalyst
- the adhesive strength at a peeling speed of 300 mm / min is 0.07 N / 25 mm or more, there is no deviation on the surface of the optical member or falling off the surface while the surface protection of the optical member is required. preferable. Moreover, if the adhesive force at a peeling speed of 30 m / min is 2.0 N / 25 mm or less, the peeling workability is good and preferable.
- test pressure-sensitive adhesive sheet was peeled off from the test sample, and the transfer state of the pressure-sensitive adhesive composition to the clear polarizing film was evaluated according to the following evaluation criteria by visual observation from the surface of the clear polarizing film. The results are shown in Table 4.
- the potential of the polarizing plate surface generated at this time was measured with a potential measuring device (KSD-0303 manufactured by Kasuga Electric Co., Ltd.) fixed at a predetermined position as shown in FIG. The measurement was performed in an environment of 23 ° C. and 50% RH. The results are shown in Table 4. If the absolute value of the stripping voltage when stripping at a stripping rate of 30 m / min is 0.3 kV or less, when the surface protective film is stripped from the optical member, there is little generation of static electricity due to stripping charging, and the liquid crystal display device This is preferable because the circuit is not destroyed or dust or dust is not adsorbed on the surface of the optical member.
- the pressure-sensitive adhesive composition of the present invention has little generation of static electricity due to peeling charging, and is excellent in adhesiveness and anti-glue transfer resistance. Furthermore, it turns out that it is excellent also in conformability and base-material adhesiveness.
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Abstract
Description
(1) 炭素数1~5のアルキル基を有する(メタ)アクリル酸アルキルエステルに由来する構成単位を40質量%~80質量%、炭素数6~18のアルキル基を有する(メタ)アクリル酸アルキルエステルに由来する構成単位を10質量%~59.9質量%、及び水酸基を有する単量体に由来する構成単位を0.1質量%~10質量%含有するアクリル系共重合体(A)と、アルキレンオキシド単位の平均付加モル数が20以上であるポリオキシアルキレン基含有単量体に由来する構成単位及び前記ポリオキシアルキレン基含有単量体以外の単量体に由来する構成単位を含み、前記ポリオキシアルキレン基含有単量体に由来する構成単位の含有率が60質量%以下であり、重量平均分子量が3,000~100,000であるポリオキシアルキレン基含有共重合体(B)と、アルカリ金属塩(C)と、分子内にポリオキシアルキレン基を有し、HLB値が9以下であるジメチルポリシロキサン化合物(D)と、を含有する粘着剤組成物である。
本発明の粘着剤組成物は、炭素数1~5のアルキル基を有する(メタ)アクリル酸アルキルエステルに由来する構成単位を40質量%~80質量%、炭素数6~18のアルキル基を有する(メタ)アクリル酸アルキルエステルに由来する構成単位を10質量%~59.9質量%、及び水酸基を有する単量体に由来する構成単位を0.1質量%~10質量%含有するアクリル系共重合体(A)と、アルキレンオキシド単位の平均付加モル数が20以上であるポリオキシアルキレン基含有単量体に由来する構成単位及び前記ポリオキシアルキレン基含有単量体以外の単量体に由来する構成単位を含み、前記ポリオキシアルキレン基含有単量体に由来する構成単位の含有率が60質量%以下であり、重量平均分子量が3,000~100,000であるポリオキシアルキレン基含有共重合体(B)と、アルカリ金属塩(C)と、分子内にポリオキシアルキレン基を有し、HLB値が9以下であるジメチルポリシロキサン化合物(D)と、を含有する。前記粘着剤組成物は必要に応じてその他の成分を含んでいてもよい。
上記特定の構成を有する粘着剤組成物は、剥離帯電による静電気の発生が抑制され、粘着性、耐糊転着性に優れる。
上記粘着剤組成物は、含有率が40質量%~80質量%である炭素数1~5のアルキル基を有する(メタ)アクリル酸アルキルエステルに由来する構成単位と、含有率が10質量%~59.9質量%である炭素数6~18のアルキル基を有する(メタ)アクリル酸アルキルエステルに由来する構成単位と、含有率が0.1質量%~10質量%である水酸基を有する単量体に由来する構成単位とを有するアクリル系共重合体の少なくとも1種を含む。ここで「(メタ)アクリル酸アルキルエステルに由来する構成単位」とは(メタ)アクリル酸アルキルエステルが他の単量体と付加重合して形成される構成単位を意味し、「単量体に由来する構成単位」等についても同様である。
上記アクリル系共重合体(A)は、炭素数1~5のアルキル基を有する(メタ)アクリル酸アルキルエステルに由来する構成単位を1種単独でも、2種以上含んでいてもよい。
上記アクリル系共重合体(A)は、炭素数6~18のアルキル基を有する(メタ)アクリル酸アルキルエステルに由来する構成単位を1種単独でも、2種以上含んでいてもよい。
上記アクリル系共重合体(A)は、水酸基を有する単量体に由来する構成単位を1種単独でも、2種以上含んでいてもよい。
(重量平均分子量及び数平均分子量の測定方法)
アクリル系共重合体(A)の重量平均分子量(Mw)は、下記(1)~(3)の手順に従って測定する。
(1)アクリル系共重合体溶液を剥離シートに塗布し、100℃で2分間乾燥し、フィルム状のアクリル系共重合体を得る。
(2)上記(1)で得られたフィルム状のアクリル系共重合体をテトラヒドロフランにて固形分0.2質量%になるように溶解させる。
(3)下記条件にて、ゲルパーミエーションクロマトグラフィー(GPC)を用いて、アクリル系共重合体の重量平均分子量(Mw)及び数平均分子量(Mn)を測定する。
GPC : HLC-8220 GPC〔東ソー(株)製〕
カラム : TSK-GEL GMHXL 4本使用
移動相溶媒 : テトラヒドロフラン
流速 : 0.6ml/min
カラム温度 : 40℃
式1 1/Tg=w1/Tg1+w2/Tg2+・・・・・・・・・+w(k-1)/Tg(k-1)+wk/Tgk
式1中、Tg1、Tg2、・・・・・・・、Tg(k-1)、Tgkは、アクリル系共重合体を構成する各単量体成分の単独重合体のガラス転移温度(K)をそれぞれ示す。w1、w2、・・・・・・、w(k-1)、wkは、アクリル系共重合体を構成する各単量体成分の質量分率をそれぞれ表わし、w1+w2+・・・・・+w(k-1)+wk=1である。
上記粘着剤組成物は、アルキレンオキシド単位の平均付加モル数が20以上であるポリオキシアルキレン基含有単量体に由来する構成単位及び前記ポリオキシアルキレン基含有単量体以外の単量体に由来する構成単位を含み、前記ポリオキシアルキレン基含有単量体に由来する構成単位の含有率が、その含有率が60質量%以下であり、重量平均分子量3,000~100,000であるポリオキシアルキレン基含有共重合体(B)の少なくとも1種を含有する。
上記粘着剤組成物は、アルカリ金属塩(C)の少なくとも1種を含有する。アルカリ金属塩(C)は、リチウム、ナトリウム、カリウム等をカチオンとする金属塩である。具体的には、Li+、Na+、K+等のカチオンと、Cl-、Br-、I-、BF4 -、PF6 -、SCN-、ClO4 -、CF3SO3 -、(CF3SO2)2N-、(C2F5SO2)2N-、(CF3SO2)3C-等のアニオンから構成される金属塩が好適に用いられる。特に、LiBr、LiI、LiBF4、LiPF6、LiSCN、LiClO4、LiCF3SO3、Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(CF3SO2)3Cなどのリチウム塩が好ましく用いられる。中でもLiCF3SO3、及びLi(CF3SO2)2Nは、帯電防止効果、金属腐食性が良好であるため特に好ましい。これらのアルカリ金属塩は単独で使用してもよく、また2種以上を混合して使用してもよい。
上記粘着剤組成物は、分子内にポリオキシアルキレン基を有し、HLB値が9以下であるジメチルポリシロキサン化合物(D)の少なくとも1種を含有する。上記ジメチルポリシロキサン化合物(D)が、その分子内にポリオキシアルキレン基を有し、HLB値が特定の範囲であることで、優れた帯電防止性能を示し、さらに粘着剤組成物を構成する上記共重合体等の樹脂との相溶性に優れ、また適度な粘着性を示すことができる。
式2 {(親水性基部分の式量の総和)/(界面活性剤の分子量)}×20
上記粘着剤組成物は、架橋剤の少なくとも1種を含むことが好ましい。上記架橋剤としてはイソシアネート化合物の少なくとも1種であることが好ましく、多価イソシアネート化合物の少なくとも1種であることがより好ましい。粘着剤組成物の構成成分が架橋剤(好ましくは、イソシアネート化合物)により架橋されることにより、粘着剤組成物の凝集力がより向上し、粘着特性により優れる粘着剤組成物を得ることができる。
また上記粘着剤組成物は、必要に応じてジブチルスズジラウレート、ジオクチルスズジラウレート等の硬化触媒を更に含んでいてもよい。
本発明の光学部材用フィルムは、基材と、該基材上に設けられ、上記粘着剤組成物の塗膜である粘着剤層とを備える。上記光学部材用フィルムは必要に応じてその他の構成要素を更に備えていてもよい。上記光学部材用フィルムは光学部材用の表面保護フィルムとして好適に用いられる。
粘着剤組成物の塗布方法は特に制限されず、通常用いられる塗布方法から適宜選択して用いることができる。塗布方法としては例えば、ブレードコーティング、ダイレクトコーティング、ナイフコーティング等を挙げることができる。
(製造例A-1)
温度計、攪拌機、窒素導入管及び還流冷却器を備えた反応容器内に、酢酸エチル35.0質量部を入れた。別の容器に2-エチルヘキシルアクリレート(2EHA)55.0質量部、n-ブチルアクリレート(BA)42.0質量部、4-ヒドロキシブチルアクリレート(4HBA)3.0質量部を入れて混合して単量体混合物を調製し、その中の15質量%を反応容器中に加え、次いで窒素雰囲気下で攪拌しながら還流温度まで加熱した。その後、残りの単量体混合物の全量と、酢酸エチル10質量部、トルエン10質量部、アゾビスイソブチロニトリル0.1質量部とを混合した混合液を、100分かけて還流温度の反応容器に逐次添加し、引き続いて45分間還流温度を維持したまま反応させた。さらにその後、酢酸エチル15質量部とt-ブチルパーオキシピバレート0.2質量部とを混合した溶液を60分かけて還流温度の反応容器に逐次添加し、引き続いてさらに80分間還流状態にて反応させた。反応終了後、酢酸エチルにて適宜希釈して固形分50質量%のアクリル系共重合体(A-1)溶液を得た。得られたアクリル系共重合体(A-1)溶液の固形分、ガラス転移温度(Tg)、重量平均分子量(Mw)、粘度、重量平均分子量(Mw)の数平均分子量に対する比である分散度(Mw/Mn)を表1に示す。なお、表1中の「-」は未配合であることを示す。
また、「固形分」とはアクリル系共重合体溶液から溶媒を除去した残渣量である。粘度は、BH型粘度計を用いて25℃、回転数10rpmで測定した。ガラス転移温度(Tg)は既述の方法で算出したものであり、重量平均分子量(Mw)は既述の方法で測定したものである。
単量体組成を表1に示す単量体組成に変更し、適宜開始剤量等を調整したこと以外は製造例A-1と同様にしてアクリル系共重合体(A-2)~(A-12)溶液を製造した。得られたアクリル系共重合体溶液の固形分、ガラス転移温度(Tg)、重量平均分子量(Mw)、分散度(Mw/Mn)を表1に示す。
(製造例B-1)
攪拌羽根、温度計、窒素ガス導入管、冷却器、滴下ロートを備えた反応容器内に、メチルエチルケトン100.0質量部を入れ、窒素雰囲気下で攪拌しながら還流温度まで過熱した。滴下ロートに、予め混合しておいた、メトキシポリエチレングリコールメタクリレート(アルキレンオキシド単位の平均付加モル数:23)10質量部、t-ブチルメタクリレート90質量部、メチルエチルケトン100質量部、アゾビスイソブチロニトリル5.0質量部の混合溶液を入れ、120分かけて還流温度の反応容器に逐次添加した。その後、240分間還流温度を維持したまま反応させ、反応を終了した。得られたポリオキシアルキレン基含有共重合体(B-1)溶液の固形分、重量平均分子量(Mw)を表2に示す。
単量体組成を表2に示す単量体組成に変更し、適宜開始剤量等を調整する以外は製造例B-1と同様にしてシド鎖含有共重合体(B-2)、(B-3)溶液を製造した。得られたポリオキシアルキレン基含有共重合体溶液の固形分、重量平均分子量(Mw)を表2に示す。
2EHA:2-エチルヘキシルアクリレート(Tg:-76℃)
n-OA:n-オクチルアクリレート(Tg:-80℃)
BA:n-ブチルアクリレート(Tg:-57℃)
EA:エチルアクリレート(Tg:-27℃)
MA:メチルアクリレート(Tg:5℃)
4HBA:4-ヒドロキシブチルアクリレート(Tg:-30℃)
t-BMA:t-ブチルメタクリレート
MePEGMA:メトキシポリエチレングリコールメタクリレート、アルキレンオキシド単位の平均付加モル数は23
攪拌羽根、温度計を備えた四つ口フラスコに、製造例A-1で得られたアクリル系共重合体(A-1)溶液100質量部(ただし、固形分として50質量部)、製造例B-1で得られたポリオキシアルキレン基含有共重合体(B-1)溶液0.6質量部(ただし、アクリル系共重合体(A)100質量部に対して、有効成分として0.4質量部)、アルカリ金属塩(C)としてLiCF3SO3(以下、「LiTFS」と略称することがある)0.05質量部(ただし、アクリル系共重合体(A)100質量部に対して、有効成分として0.1質量部)、ジブチルスズジラウレート0.01質量部(ただし、アクリル系共重合体(A)100質量部に対して、有効成分として0.02質量部)を仕込み、フラスコ内の液温を25℃付近に保って4.0時間混合撹拌を行い、アクリル系共重合体混合溶液を得た。これにジメチルシロキサン化合物(D)として、SH-8400 0.075質量部(ただし、アクリル系共重合体(A)100質量部に対して、有効成分として0.15質量部)、イソシアネート化合物としてN3300 0.75質量部(住化バイエルウレタン(株)製ヘキサメチレンジイソシアネートの3量体であるイソシアヌレート構造を有するイソシアネート化合物、アクリル系共重合体(A)100質量部に対して、有効成分として1.5質量部)を添加し、十分に攪拌して、表3に示す光学部材用フィルム用の粘着剤組成物を得た。
上記で得られた粘着剤組成物を用いて以下のようにして、光学部材用フィルムとして試験用粘着シートを得た。
ポリエチレンテレフタレート(PET)フィルム〔商品名;帝人テトロンフィルム、タイプG2、厚み38μm;帝人デュポンフィルム(株)製〕上に、アプリケーターを用いて、乾燥後の塗工量が20g/m2となるように粘着剤組成物を塗布し、100℃で60秒間熱風循環式乾燥機にて乾燥して粘着剤層を形成した後、シリコーン系離型剤で表面処理された離型フィルム上に該粘着剤層面が接するように載置し、加圧ニップロールを通して圧着して貼り合わせた後、23℃、50%RHで3日間養生を行って試験用粘着シートを得た。
実施例1の配合条件の代わりに表3に示した各実施例及び比較例の配合条件を適用したこと以外は、実施例1と同様にして表3に示すような光学部材用フィルム用の粘着剤組成物をそれぞれ作製した。これらの粘着剤組成物を用い、上記試験用粘着シートの作製方法に従って試験用粘着シートをそれぞれ作製した。
LiTFS:LiCF3SO3、アルカリ金属塩(C)
LiTFSI:Li(CF3SO2)2N、アルカリ金属塩(C)
N-3300:住化バイエルウレタン(株)製ヘキサメチレンジイソシアネートの3量体であるイソシアヌレート構造を有するイソシアネート化合物、商品名:デスモジュールN3300、有効成分100質量%、架橋剤(イソシアネート化合物)
SH-8400:東レ・ダウ(株)製、側鎖にポリオキシアルキレン基を導入したジメチルシロキサン化合物、ポリオキシアルキレン基の末端はアセチルオキシ基、HLB値=7、ジメチルポリシロキサン化合物(D)成分
L-7001:東レ・ダウ(株)製、側鎖にポリオキシアルキレン基を導入したジメチルシロキサン化合物、ポリオキシアルキレン基の末端はメトキシ基、HLB値=5、ジメチルポリシロキサン化合物(D)成分
SH-3773M:東レ・ダウ(株)製、側鎖にポリオキシアルキレン基を導入したジメチルシロキサン化合物、ポリオキシアルキレン基の末端は水酸基、HLB値=8、ジメチルポリシロキサン化合物(D)成分
FZ-2104:東レ・ダウ(株)製、側鎖にポリオキシアルキレン基を導入したジメチルシロキサン化合物、ポリオキシアルキレン基の末端はメトキシ基、HLB値=14
KP-355:信越化学工業(株)製、ポリオキシアルキレン基を導入したジメチルポリシロキサン化合物、HLB値=10
DBTDL:ジブチルスズジラウレート、硬化触媒
(粘着力)
上記で作製した試験用粘着シートを25mm×150mmにカットしたのち、この試験用粘着シート片を、卓上ラミネート機を用いて、離型フィルムを剥がしつつ、粘着剤層面をアンチグレア処理された偏光フィルムに圧着して試験サンプルとした。この試験サンプルを23℃、50%RHの条件下で24時間放置した後、180゜剥離における粘着力を剥離速度300mm/分(低速)、もしくは30m/分(高速)にて測定した。結果を表4に示した。
剥離速度300mm/分における粘着力が0.07N/25mm以上であれば、光学部材の表面保護が必要とされる間、該部材の表面上でずれを生じたり表面から脱落したりすることがなく好ましい。
また、剥離速度30m/分における粘着力が2.0N/25mm以下であれば、剥離作業性が良好であり好ましい。
上記で作製した試験用粘着シートを20mm×150mmにカットしたのち、この試験用粘着シート片を、卓上ラミネ-ト機を用いて、離型フィルムを剥がしつつ、粘着剤層面をクリア偏光フィルム(表面処理を施していない)に圧着して試験サンプルとした。この試験サンプルのPETフィルム表面にボールペンを垂直に固定し、500gの荷重をかけ1mm/sの速度で試料30mmの距離を3往復ボールペンで引っかき、引っかき試験を行った。引っかき試験後、試験サンプルから試験用粘着シートを剥離し、クリア偏光フィルムの表面から目視観察により、粘着剤組成物のクリア偏光フィルムへの転着状態を、下記評価基準に従って評価した。結果を表4に示した。
A:粘着剤組成物の転着が全く認められなかった。
B:粘着剤組成物の転着がほとんど認められなかったが、薄く転着の痕跡が認められた。
C:粘着剤組成物の転着が多少認められ、実用上問題があるレベルであった。
D:粘着剤組成物の転着が認められた。
上記で作製した試験用粘着シートを200mm×150mmにカットしたのち、離型フィルムを剥がして、粘着剤層面をアンチグレア処理された偏光フィルムに23℃、50%RHの条件下で中心部分より貼り合せ、自然重力により濡れ広がる時間を測定し、下記評価基準に従って評価した。結果を表4に示した。
A:端部まで完全になじむ時間が45秒未満であった。
B:端部まで完全になじむ時間が45秒以上60秒未満であった。
C:端部まで完全になじむ時間が60秒以上、又は端部まで完全になじまなかった。
上記で作製した試験用粘着シートを25mm×150mmにカットしたのち、この試験用粘着シート片を、卓上ラミネート機を用いて、離型フィルムを剥がしつつ、粘着剤層面をアンチグレア処理された偏光フィルムに圧着して試験サンプルとした。この試験サンプルを23℃、50%RHの条件下で24時間放置(コンディショニング処理)した後、180゜剥離、剥離速度30m/分(高速剥離条件)で剥離した。このときの発生する偏光板表面の電位を図1に示すように所定の位置に固定してある電位測定機〔春日電機(株)製KSD-0303〕にて測定した。測定は、23℃、50%RHの環境下で行った。結果を表4に示した。
剥離速度30m/分で剥離した際の、剥離帯電圧の絶対値が0.3kV以下であれば、光学部材から表面保護フィルムを剥離する際に、剥離帯電による静電気の発生が少なく、液晶表示装置の回路が破壊したり、光学部材表面にごみや埃を吸着したりすることがなく好ましい。
上記で作製した試験用粘着シートを作製した離型フィルムを剥がし、粘着剤層にカッターにて、2mm幅×2mm幅で100個のクロスカット部分を形成した。指にてクロスカット部を3回強くこすり、こすった箇所の粘着剤層が基材から剥離したかどうか目視にて観察した。また剥離したクロスカット部分の数を計数し、クロスカット部分の総数に対する比率(%)を求め、下記評価基準に従って評価した。結果を表4に示した。
A:剥離は無かった、または5%未満の剥離部分が見られたが、実用上問題ない程度であった。
B:クロスカット部分の5%以上の剥離部分が見られ、実用上問題となる程度であった。
C:全面的に剥離が見られた。
本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的かつ個々に記された場合と同程度に、本明細書に参照により取り込まれる。
Claims (7)
- 炭素数1~5のアルキル基を有する(メタ)アクリル酸アルキルエステルに由来する構成単位を40質量%~80質量%、炭素数6~18のアルキル基を有する(メタ)アクリル酸アルキルエステルに由来する構成単位を10質量%~59.9質量%、及び水酸基を有する単量体に由来する構成単位を0.1質量%~10質量%含有するアクリル系共重合体(A)と、
アルキレンオキシド単位の平均付加モル数が20以上であるポリオキシアルキレン基含有単量体に由来する構成単位及び前記ポリオキシアルキレン基含有単量体以外の単量体に由来する構成単位を含み、前記ポリオキシアルキレン基含有単量体に由来する構成単位の含有率が60質量%以下であり、重量平均分子量が3,000~100,000であるポリオキシアルキレン基含有共重合体(B)と、
アルカリ金属塩(C)と、
分子内にポリオキシアルキレン基を有し、HLB値が9以下であるジメチルポリシロキサン化合物(D)と、
を含有する粘着剤組成物。 - 前記ジメチルポリシロキサン化合物(D)のHLB値が、5以上8以下である請求項1に記載の粘着剤組成物。
- 前記アクリル系共重合体(A)100質量部に対する前記ポリオキシアルキレン基含有共重合体(B)の含有量、及び前記アルカリ金属塩(C)の含有量が、それぞれ0.05質量部~2.0質量部、及び0.01質量部~0.6質量部である請求項1又は請求項2に記載の粘着剤組成物。
- 前記アクリル系共重合体(A)100質量部に対する前記ジメチルポリシロキサン化合物(D)の含有量が0.01質量部~1.0質量部である請求項1~請求項3のいずれか1項に記載の粘着剤組成物。
- 前記炭素数1~5のアルキル基を有する(メタ)アクリル酸アルキルエステルがn-ブチル(メタ)アクリレートである請求項1~請求項4のいずれか1項に記載の粘着剤組成物。
- 前記炭素数6~18のルキル基を有する(メタ)アクリル酸アルキルエステルが2-エチルヘキシルアクリレートである請求項1~請求項5のいずれか1項に記載の粘着剤組成物。
- 基材と、
前記基材上に設けられ、請求項1~請求項6のいずれか1項に記載の粘着剤組成物の塗膜である粘着剤層と、
を備える光学部材用フィルム。
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| CN201280015512.4A CN103459537B (zh) | 2011-03-28 | 2012-03-26 | 粘合剂组合物及光学构件用薄膜 |
| JP2013507570A JP5848327B2 (ja) | 2011-03-28 | 2012-03-26 | 粘着剤組成物及び光学部材用フィルム |
| US14/008,296 US20140037955A1 (en) | 2011-03-28 | 2012-03-26 | Pressure-sensitive adhesive composition and film for optical member |
| KR1020137027566A KR101880697B1 (ko) | 2011-03-28 | 2012-03-26 | 점착제 조성물 및 광학 부재용 필름 |
| EP12765221.2A EP2692811A4 (en) | 2011-03-28 | 2012-03-26 | ADHESIVE COMPOSITION AND FILM FOR AN OPTICAL ELEMENT |
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| US (1) | US20140037955A1 (ja) |
| EP (1) | EP2692811A4 (ja) |
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| JP7650551B1 (ja) * | 2024-07-22 | 2025-03-25 | サイデン化学株式会社 | 再剥離用粘着剤組成物、表面保護フィルム、及び粘着剤層付き光学部材 |
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| JP6497476B1 (ja) * | 2018-09-20 | 2019-04-10 | 東洋インキScホールディングス株式会社 | 粘着剤および粘着シート |
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| Publication number | Publication date |
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| CN103459537B (zh) | 2015-09-30 |
| EP2692811A4 (en) | 2015-01-21 |
| JPWO2012133343A1 (ja) | 2014-07-28 |
| TW201245368A (en) | 2012-11-16 |
| CN103459537A (zh) | 2013-12-18 |
| KR101880697B1 (ko) | 2018-07-20 |
| TWI529228B (zh) | 2016-04-11 |
| JP5848327B2 (ja) | 2016-01-27 |
| EP2692811A1 (en) | 2014-02-05 |
| US20140037955A1 (en) | 2014-02-06 |
| KR20140013036A (ko) | 2014-02-04 |
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