WO2014003043A1 - 粘着性組成物及び粘着性発泡シート - Google Patents
粘着性組成物及び粘着性発泡シート Download PDFInfo
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- WO2014003043A1 WO2014003043A1 PCT/JP2013/067469 JP2013067469W WO2014003043A1 WO 2014003043 A1 WO2014003043 A1 WO 2014003043A1 JP 2013067469 W JP2013067469 W JP 2013067469W WO 2014003043 A1 WO2014003043 A1 WO 2014003043A1
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- rubber
- adhesive
- foam sheet
- pressure
- resin
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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
- C09J7/10—Adhesives in the form of films or foils without carriers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B25/00—Layered products comprising a layer of natural or synthetic rubber
- B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
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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
- C08L21/00—Compositions of unspecified rubbers
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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
- C09J201/00—Adhesives based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C09J7/241—Polyolefin, e.g.rubber
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/26—Porous or cellular plastics
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- B32B2250/02—2 layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2266/02—Organic
- B32B2266/0207—Materials belonging to B32B25/00
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- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/77—Uncured, e.g. green
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- B32B2307/00—Properties of the layers or laminate
- B32B2307/10—Properties of the layers or laminate having particular acoustical properties
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- B32B2405/00—Adhesive articles, e.g. adhesive tapes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2605/00—Vehicles
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2207/00—Foams characterised by their intended use
- C08J2207/02—Adhesive
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2445/00—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers
- C08J2445/02—Characterised by the use of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Derivatives of such polymers of coumarone-indene polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2457/00—Characterised by the use of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C08J2457/02—Copolymers of mineral oil hydrocarbons
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2493/00—Characterised by the use of natural resins; Derivatives thereof
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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
- C08K2201/00—Specific properties of 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
- C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
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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
- C09J2301/41—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the carrier 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
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/24—Presence of a foam
- C09J2400/243—Presence of a foam in the substrate
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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
- C09J2409/00—Presence of diene rubber
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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
- C09J2421/00—Presence of unspecified rubber
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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
- C09J2421/00—Presence of unspecified rubber
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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
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- Y10T428/2883—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer of diene monomer [e.g., SBR, SIS, etc.]
Definitions
- the present invention relates to a pressure-sensitive adhesive composition, and further relates to a pressure-sensitive adhesive foam sheet based on the pressure-sensitive adhesive composition.
- a rubber foam material is filled in the space of the automobile body in order to satisfy the requirements such as the quiet performance of the interior space of the automobile.
- a rubber-based foam material is generally made of an unfoamed thermosetting foam sheet in which a foaming agent, a vulcanizing agent, etc. are blended with unvulcanized rubber, and an inner wall of a hollow portion of a steel plate for an automobile body that constitutes the gap.
- a drying and heating process such as an electrodeposition coating line.
- the said thermosetting foam sheet is normally made into the laminated body in which the adhesion layer was laminated
- Such a thermosetting foam sheet is described in, for example, Japanese Patent Publication No. 7-119399.
- the laminate-type thermosetting foam sheet is packed in a stacked state after production, and stored in a warehouse or the like until it is actually used, so when left for a long time, due to the load from above,
- the pressure-sensitive adhesive in the pressure-sensitive adhesive layer may protrude from the side surface of the foamed sheet, and adjacent sheets may be integrated with each other, or the sheet may be in close contact with the packaging container, resulting in poor handling.
- This tendency increases as the application time of the load becomes longer, and is particularly noticeable in the case where the load is stored while being transported or stacked in a warehouse or the like.
- Such a phenomenon is called cold flow, and measures such as a reduction in the amount of oil in the adhesive layer and an increase in the amount of filler are taken to suppress this phenomenon.
- the adhesiveness and workability of the adhesive composition constituting the adhesive layer may deteriorate.
- the cold flow property tends to increase.
- Japanese Patent Application Laid-Open No. 2006-206454 describes suppression of cold flow by adding a styrenic thermoplastic elastomer. However, no means for achieving both good processability and adhesiveness is disclosed.
- the present invention has been made in view of such problems, and provides a pressure-sensitive adhesive composition that can form a pressure-sensitive adhesive layer that has both good pressure-sensitive adhesiveness and processability and that has a reduced cold flow.
- a first object is to provide a pressure-sensitive adhesive foam sheet having a pressure-sensitive adhesive layer made of the pressure-sensitive adhesive composition and having reduced cold flow.
- the first object of the present invention is to 100 parts by weight of unvulcanized rubber, and This is achieved by an adhesive composition containing 20 to 100 parts by weight of an adhesive hydrocarbon resin having a softening point of 40 ° C. or less.
- the adhesive hydrocarbon resin is selected from the group consisting of coumarone resin, aliphatic petroleum resin, aromatic petroleum resin, aliphatic / aromatic copolymer petroleum resin, terpene resin, rosin resin, and phenolic resin. It is preferable to consist of at least one kind.
- the unvulcanized rubber is preferably selected from the group consisting of natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, butyl rubber, and modified rubber obtained by terminally modifying these rubbers.
- the second object of the present invention is to An adhesive layer comprising the adhesive composition, and This is achieved by an adhesive foam sheet comprising a foamable rubber layer comprising a foaming agent, a vulcanizing agent and unvulcanized rubber.
- the volume expansion ratio of the foamable rubber layer is preferably 500% or more.
- the foaming agent includes azodicarbonamide, azobisisobutyronitrile, azodicarbonbarium, N, N′-dinitrosopentamethylenetetramine, N, N′-dimethyl-N, N′-dinitrosotephthalamide, 4, 4'-oxysbis (benzenesulfonylhydrazide), hydrazodicarbonamide, paratoluenesulfonylhydrazide, diphenylsulfone-3,3'-disulfonylhydrazide, allylbis (sulfonylhydrazide), p-toluylenesulfonyl semicarbazide, 4,4'- It is preferably selected from the group consisting of oxybis (benzenesulfonyl semicarbazide), sodium bicarbonate, ammonium carbonate, and anhydrous sodium nitrate.
- the vulcanizing agent is preferably sulfur or a sulfur-based vulcanizing agent.
- the unvulcanized rubber is preferably selected from the group consisting of natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, butyl rubber, and modified rubber obtained by terminally modifying these rubbers.
- the pressure-sensitive adhesive foam sheet of the present invention is preferably a hexahedron having an upper surface, a bottom surface, and four side surfaces.
- the pressure-sensitive adhesive composition of the present invention has both good pressure-sensitive adhesiveness and processability, and can form a pressure-sensitive adhesive layer in which cold flow is suppressed.
- the adhesive hydrocarbon resin in the adhesive composition of the present invention is a coumarone resin, aliphatic petroleum resin, aromatic petroleum resin, aliphatic / aromatic copolymer petroleum resin, terpene resin, rosin resin, and phenolic
- a coumarone resin aliphatic petroleum resin, aromatic petroleum resin, aliphatic / aromatic copolymer petroleum resin, terpene resin, rosin resin, and phenolic
- the unvulcanized rubber in the adhesive composition of the present invention is selected from the group consisting of natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, butyl rubber, and modified rubber obtained by terminally modifying these rubbers.
- the pressure-sensitive adhesive layer and the workability are further improved, and a pressure-sensitive adhesive layer in which cold flow is suppressed can be formed.
- the pressure-sensitive adhesive foam sheet of the present invention includes a foamable rubber layer containing a foaming agent, a vulcanizing agent and unvulcanized rubber, it has thermosetting and foaming properties. Therefore, the pressure-sensitive adhesive foam sheet of the present invention can be foamed and cured by heating.
- the volume expansion ratio of the foamable rubber layer is 500% or more, for example, the voids in the automobile body can be efficiently filled, and the quietness in the automobile can be improved.
- the pressure-sensitive adhesive foam sheet of the present invention is a hexahedron having an upper surface, a bottom surface, and four side surfaces, it is particularly excellent in handleability and can be densely laminated.
- the adhesive foam sheet of this invention is provided with the adhesive layer which has high adhesiveness, it can prevent reliably falling off from an automobile body steel plate, for example after sticking to the space
- the adhesive composition of the present invention is 100 parts by weight of unvulcanized rubber, and 20 to 100 parts by weight of an adhesive hydrocarbon resin having a softening point of 40 ° C. or lower is included.
- the adhesive composition of this invention is equipped with the favorable adhesiveness and workability, and can comprise the adhesion layer by which the cold flow was suppressed.
- the adhesive foam sheet of the present invention is An adhesive layer comprising the adhesive composition of the present invention, and A foamable rubber layer containing a foaming agent, a vulcanizing agent and unvulcanized rubber is provided.
- a cold flow is prevented thru
- the adhesive layer can be easily manufactured, and deterioration of the adhesiveness of the adhesive layer can be suppressed.
- the pressure-sensitive adhesive composition of the present invention contains unvulcanized rubber.
- the type of unvulcanized rubber is not particularly limited, but diene-based unvulcanized rubber is preferable.
- the diene-based unvulcanized rubber can be appropriately selected from known ones.
- the diene-based unvulcanized rubber for example, at least one selected from natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, butyl rubber, and modified rubber obtained by terminally modifying these rubbers can be used. Styrene butadiene rubber is preferred from the viewpoint of processability and foamability.
- Such unvulcanized rubber can be used alone or as a blend.
- the amount of unvulcanized rubber used is not particularly limited. For example, it is 10 to 90% by weight, preferably 15 to 70% by weight, and more preferably 20 to 50% by weight based on the weight of the entire pressure-sensitive adhesive composition. %.
- the pressure-sensitive adhesive composition of the present invention contains a pressure-sensitive adhesive hydrocarbon resin having a softening point of 40 ° C. or lower.
- adhesive hydrocarbon resins having a softening point of 40 ° C. or lower include coumarone resins, aliphatic petroleum resins, aromatic petroleum resins, aliphatic / aromatic copolymer petroleum resins, terpene resins, rosin resins, and phenolic resins. At least one selected from the group consisting of resins can be used. These can be used alone or in admixture of two or more.
- a coumarone resin, an aliphatic petroleum resin, an aromatic petroleum resin, or an aliphatic / aromatic copolymer petroleum resin is preferable from the viewpoint of adhesiveness and processability.
- the softening point of the adhesive hydrocarbon resin blended in the adhesive composition of the present invention is 40 ° C. or less, preferably 35 ° C. or less, more preferably 0 to 35 ° C., and still more preferably 10 ⁇ 30 ° C. When the softening point exceeds 40 ° C., the effect of the present invention cannot be exhibited.
- the softening point as used in the present invention can be measured according to the ring and ball method of JISK6220-1.
- the amount of the sticky hydrocarbon resin having a softening point of 40 ° C. or lower is 20 to 100 parts by weight, preferably 25 to 100 parts by weight, more preferably 30 to 30 parts by weight with respect to 100 parts by weight of the unvulcanized rubber. 100 parts by weight. Further, based on the total weight of the pressure-sensitive adhesive composition, it can be, for example, 3 to 50% by weight, preferably 4 to 40% by weight, more preferably 5 to 30% by weight.
- a tackifying resin having a softening point in the range of 70 ° C. to 150 ° C. can be blended with the adhesive composition of the present invention.
- the tackifying resin include coumarone resin, aliphatic petroleum resin, aromatic petroleum resin, aliphatic / aromatic copolymer petroleum resin, terpene resin, rosin resin, phenol having a softening point in the range of 70 ° C to 150 ° C. It is possible to use at least one hydrocarbon resin selected from the group consisting of a resin.
- the pressure-sensitive adhesive composition of the present invention may be used in combination with various conventionally known oils, anti-aging agents, colorants, inorganic fillers, processing aids, and other additives as long as the effects of the present invention are not hindered. Good.
- the pressure-sensitive adhesive composition of the present invention can be produced by mixing and kneading the above components by a conventionally known method such as a kneader, an internal mixer, or a two-roll.
- the pressure-sensitive adhesive foam sheet of the present invention comprises a pressure-sensitive adhesive layer containing the pressure-sensitive adhesive composition of the present invention, and a foamable rubber layer containing a foaming agent, a vulcanizing agent and unvulcanized rubber.
- the pressure-sensitive adhesive foam sheet of the present invention includes a pressure-sensitive adhesive layer on part or all of its surface for reliable sticking to an automobile body steel plate or the like.
- the thickness of the pressure-sensitive adhesive layer is not particularly limited, but can be, for example, in the range of 0.1 to 10 mm, more preferably in the range of 0.5 mm to 5 mm, and still more preferably in the range of 1 mm to 3 mm.
- the said adhesion layer contains the adhesive composition of this invention.
- the amount of the pressure-sensitive adhesive composition used can be appropriately determined according to the target degree of pressure-sensitive adhesiveness. For example, 1 to 100% by weight, preferably 80 to 99% by weight, more preferably based on the total weight of the pressure-sensitive adhesive layer. It can be 90 to 95% by weight.
- the said adhesion layer can be manufactured by implementing well-known shaping
- the pressure-sensitive adhesive foam sheet of the present invention includes a foamable rubber layer that can be foamed and cured by heating. By foaming / curing the foamable rubber layer, it is possible to fill a space in an automobile body steel plate or the like.
- the thickness of the foamable rubber layer is not particularly limited, but can be, for example, in the range of 0.1 to 10 mm, more preferably in the range of 0.5 mm to 8 mm, and still more in the range of 1 mm to 6 mm. preferable.
- the foaming agent contained in the foamable rubber layer can be appropriately selected from known ones such as azodicarbonamide (ADCA), azobisisobutyronitrile, azodicarbonbarium, N, N′-dinitroso. Pentamethylenetetramine, N, N′-dimethyl-N, N′-dinitrosotephthalamide, 4,4′-oxysbis (benzenesulfonylhydrazide), hydrazodicarbonamide, paratoluenesulfonylhydrazide, diphenylsulfone-3,3 ′ -Disulfonylhydrazide, allylbis (sulfonylhydrazide), p-toluylenesulfonyl semicarbazide, 4,4'-oxybis (benzenesulfonyl semicarbazide), sodium hydrogen carbonate, ammonium carbonate, anhydrous sodium nitrate and the like. These can be used alone or in
- the amount of the foaming agent to be used can be appropriately determined according to the physical properties of the desired foam based on the foaming ratio and the like. For example, 0.5 to 20% by weight, preferably 1 to 10% based on the total weight of the foamable rubber layer. % By weight, more preferably 2 to 5% by weight.
- the volume expansion ratio of the foamable rubber layer is preferably 500% or more, more preferably 600% or more, and even more preferably 700% or more.
- the volume expansion ratio is 500% or more, the void can be completely filled when used for filling a void in an automobile body.
- urea may be used as a foaming aid.
- the vulcanizing agent can be appropriately selected from known ones and used, and examples thereof include sulfur or sulfur-based vulcanizing agents such as thiurams and dithiocarbamates.
- Thiurams include tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, tetramethylthiuram monosulfide, N, N'-dimethyl-N, N'-diphenylthiuram disulfide, dipentamethylenethiuram disulfide, dipentamethylene
- the dithiocarbamates include zinc dimethylthiocarbamate, zinc diethylthiocarbamate, zinc N-ethyl-N-phenyldithiocarbamate, zinc dibenzyldithiocarbamate and the like. Can be mentioned. These can be used individually or in mixture of 2 or more types. In particular, in the present invention, it is preferable to use te
- the amount of the vulcanizing agent used can be, for example, 0.5 to 5% by weight, preferably 1 to 3% by weight, based on the total weight of the foamable rubber layer.
- a vulcanization accelerator can be used in combination with the vulcanizing agent as long as the effects of the present invention are not impaired.
- the vulcanization accelerator include guanidines, thiazoles, sulfenamides, dithiocarbamic acids, xanthogens, aldehyde ammonias, aldehyde amines, thioureas and the like. Note that the above thiurams, dithiocarbamates and the like may be used as vulcanization accelerators. These can be used individually or in mixture of 2 or more types.
- the unvulcanized rubber can be appropriately selected from known ones, and a diene-based unvulcanized rubber is preferable.
- the diene-based unvulcanized rubber can be appropriately selected from known ones.
- As the diene-based unvulcanized rubber for example, at least one selected from natural rubber, isoprene rubber, butadiene rubber, styrene butadiene rubber, butyl rubber, and modified rubber obtained by terminally modifying these rubbers can be used. Styrene butadiene rubber is preferred from the viewpoint of processability and foamability.
- Such unvulcanized rubber can be used alone or as a blend.
- the amount of unvulcanized rubber used is not particularly limited. For example, it is 10 to 90% by weight, preferably 20 to 85% by weight, more preferably 30 to 80% by weight based on the total weight of the foamable rubber layer. %.
- the unvulcanized rubber contained in the foamable rubber layer may be of a different type / composition from the unvulcanized rubber contained in the adhesive composition contained in the adhesive layer, but is preferably the same type / composition. .
- foamable rubber layer various conventionally known oils, anti-aging agents, colorants, inorganic fillers, processing aids, and other additives may be used in combination as long as the effects of the present invention are not impaired.
- an adhesive may be mix
- the above components are first mixed and kneaded by a conventionally known method such as a kneader, an internal mixer, a two-roll, etc. to obtain a thermosetting foam composition.
- a conventionally known method such as a kneader, an internal mixer, a two-roll, etc.
- thermosetting foamed composition is formed into a sheet shape to form a foamable rubber layer.
- the foamable rubber layer can be produced, for example, by performing a known molding process such as extrusion molding, calendar roll molding, press molding or the like using the thermosetting foam composition. From the viewpoint of productivity, extrusion molding is preferred.
- extrusion molding is preferred.
- mold it changes with compositions of a composition, in order to suppress progress of hardening, decomposition
- the pressure-sensitive adhesive foam sheet of the present invention is, for example, coextrusion molding using a multilayer die provided with two nozzles using each composition constituting the foamable rubber layer and the pressure-sensitive adhesive layer, and sandwiching the two sheets with a roll. It can manufacture by implementing well-known shaping
- the shape of the contact surface of the foamable rubber layer and the adhesive layer is arbitrary, and the cross section thereof may be a geometric shape represented by a straight line, a curved line, or a combination thereof.
- the other layer may be formed by coextrusion using a multilayer die with three nozzles.
- the foamable rubber layer and the adhesive layer contain unvulcanized rubber having an unsaturated bond
- photopolymerization is caused by the energy of electromagnetic waves on or near the surface of the foamable rubber layer and / or the adhesive layer subjected to electromagnetic wave irradiation. Done.
- the unvulcanized rubber is thinly crosslinked and cured on the electromagnetic wave irradiation surface to form a protective film. Since components such as the crosslinking agent in the foamable rubber layer and the adhesive layer cannot pass through the protective film, even if the component moves toward the sheet surface, the component does not ooze out from the electromagnetic wave irradiation surface.
- ultraviolet light having a wavelength of 400 nm or less is preferably used, a wavelength of 10 nm to 400 nm is more preferable, and a wavelength of 200 nm to 400 nm is even more preferable.
- the ultraviolet ray either UVB having a wavelength of 280 to 315 nm or UVA having a wavelength of 315 to 400 nm can be used.
- the electromagnetic wave source is not particularly limited, and an arbitrary light source can be used.
- an ultraviolet light source is particularly preferable.
- an arbitrary ultraviolet light source such as an ultraviolet lamp such as an ultraviolet laser or a xenon lamp, or an ultraviolet light emitting LED can be used.
- a light source including ultraviolet rays can be used, and a fluorescent lamp and sunlight can also be used.
- the light source for example, those having an irradiation intensity of 60 to 300 kJ / m 2 per hour can be used, and those having an irradiation intensity of 90 to 250 kJ / m 2 are preferable.
- the electromagnetic wave irradiation amount is not particularly limited. Therefore, the wavelength of the electromagnetic wave, the intensity of the electromagnetic wave, and the irradiation time of the electromagnetic wave can be appropriately adjusted under the condition that the electromagnetic wave irradiation surface is cured.
- a crosslinked / cured film is formed on the surface of the foamed sheet without heating the foamed sheet, preferably by irradiation with electromagnetic waves, preferably with ultraviolet radiation, so that the sheet does not foam. Therefore, the pressure-sensitive adhesive foam sheet of the present invention remains unfoamed, and can be used, for example, for filling the void by inserting it as a non-foamed material into the void of the automobile body and then heating and foaming.
- the form of the adhesive foam sheet of this invention is not specifically limited, From the point of usability and a preservability, it is preferable that it is a hexahedron shape which has an upper surface, a bottom face, and four side surfaces. In this case, it is preferable that electromagnetic waves are irradiated on the upper surface, at least one of the side surfaces, and / or the lower surface. In the case of irradiating the side surface with electromagnetic waves, it is preferable to irradiate as many side surfaces as possible, and it is preferable to irradiate all four side surfaces with electromagnetic waves.
- the pressure-sensitive adhesive foam sheet of the present invention is hexahedral, it is preferably in the form of a substantially rectangular parallelepiped, and more preferably in the form of a thin plate.
- the pressure-sensitive adhesive foam sheet of the present invention is in the form of a thin plate, irradiation of electromagnetic waves on the side surfaces may be omitted, but it is preferable to irradiate at least the upper surface with electromagnetic waves.
- the sheet thickness when the pressure-sensitive adhesive foam sheet of the present invention is in the form of a thin plate is not particularly limited, but can be, for example, in the range of 1-20 mm, more preferably in the range of 2 mm-10 mm. A range of ⁇ 5 mm is even more preferred.
- the pressure-sensitive adhesive composition of the present invention has both good pressure-sensitive adhesiveness and processability, and can form a pressure-sensitive adhesive layer in which cold flow is suppressed. Therefore, it is possible to easily produce an adhesive layer having high adhesiveness and usable for various applications.
- the adhesive foam sheet of the present invention Moreover, cold flow is suppressed in the adhesive foam sheet of the present invention. Therefore, even if left in a stacked state for a long time, due to the load from above, the adhesive in the adhesive layer in the adhesive foam sheet protrudes from the side surface of the foam sheet, adjacent sheets are integrated, It can be prevented or reduced that the sheet is in close contact with the packaging container and the handling property is deteriorated.
- workability is improved without impairing the sticking property to an automobile body or the like, the adhesiveness, and the foamability which is the original performance of the thermosetting foam sheet. It is possible.
- thermosetting foam sheet of the present invention is, for example, a foam material that has a sound absorption effect by being foamed and cured by being appropriately heated after being attached to the inner wall of a hollow portion such as the inside of a void of an automobile body steel plate. Form. Thereby, the quietness of the interior space of a car can be improved. Therefore, the thermosetting foam sheet of the present invention can be used as a void filler for automobile bodies.
- Example 1 to 4 and Comparative Examples 1 to 4 Each component shown in Table 1 below was mixed and kneaded with an open kneader to prepare an adhesive composition (the numerical values in Table 1 represent parts by weight relative to 100 parts by weight of rubber). The obtained pressure-sensitive adhesive composition was pressed with an oil press to produce an unvulcanized sheet having a thickness of 2 mm.
- the unvulcanized sheets (adhesive materials) of Examples 1 to 4 and Comparative Examples 1 to 4 are cut into a length of 25 mm and a width of 25 mm, and are shown in FIG. 1 as cold-rolled steel sheets having a length of 100 mm, a width of 25 mm, and a thickness of 0.8 mm. Then, a 2 kg weight was placed for 5 seconds and pressed, and then the steel sheet was pulled in the direction of 180 degrees (left and right direction in FIG. 1) at a tensile speed of 300 mm / min, and the shear strength was measured. The index was determined by setting the tensile shear strength of Comparative Example 1 to 100. A higher index indicates better adhesion. The results are also shown in Table 1.
- the unvulcanized sheets of Examples 1 to 4 and Comparative Examples 1 to 4 were cut into a length of 50 mm and a width of 30 cm, and 10 sheets were stacked to prepare a test piece having a thickness of 20 mm.
- the obtained test piece was stored at room temperature, the thickness after 72 hours was measured, and the thickness retention was calculated from the ratio of the thickness after 72 hours to the initial thickness. The higher the thickness retention, the more difficult the cold flow. The results are also shown in Table 1.
- Resin A softening point 90 ° C: Rutgers hydrocarbon resin TT90
- Resin B softening point 30 ° C: Rutgers hydrocarbon resin TT30
- Resin C softening point 10 ° C: Rutgers Coumarone Resin G10
- Comparative Examples 2 and 3 have a good thickness retention compared to Comparative Example 1, but the penetration is low and the processability is not good. Moreover, the improvement of shear strength was not seen. About the comparative example 4, although the penetration and the shear strength were favorable, the big improvement was not seen by the thickness retention. On the other hand, Examples 1 to 4 showed good penetration and shear strength and improved thickness retention.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Adhesive Tapes (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
100重量部の未加硫ゴム、及び、
20~100重量部の軟化点40℃以下の粘着性炭化水素系樹脂
を含む粘着性組成物によって達成される。
前記粘着性組成物を含む粘着層、並びに、
発泡剤、加硫剤及び未加硫ゴムを含む発泡性ゴム層
を備える粘着性発泡シート
によって達成される。
100重量部の未加硫ゴム、及び、
20~100重量部の軟化点40℃以下の粘着性炭化水素系樹脂
を含む。これにより、本発明の粘着性組成物は良好な粘着性及び加工性を共に備えており、且つ、コールドフローが抑制された粘着層を構成することができる。
本発明の粘着性組成物を含む粘着層、並びに、
発泡剤、加硫剤及び未加硫ゴムを含む発泡性ゴム層
を備える。これにより、本発明の粘着性発泡シートではコールドフローが防止乃至低減される。また、粘着層の製造が容易であり、且つ、粘着層の粘着性の劣化をも抑制することもできる。
下記表1に示す各成分をオープンニーダーで混合・混練して粘着性組成物を調製した(表1中の数値はゴム100重量部に対する重量部を表す)。得られた粘着性組成物を油庄プレス機によりプレスして厚み2mmの未加硫シートを作成した。
実施例1~4及び比較例1~4の前記未加硫シートを縦50mm、横30mmに切り出し、10枚重ね厚み20mmの試験片を作成した。JISK2207に準拠し、得られた試験片の針入度を測定した。針入度の数値が大きい程柔軟であり、加工性が良好であることを示す。結果を表1に併せて示す。
実施例1~4及び比較例1~4の前記未加硫シート(粘着材)を縦25mm、横25mmに切り出し、縦100mm、横25mm、厚み0.8mmの冷却圧延鋼板材に図1に示すように挟み、2kgの重りを5秒間載せて圧着後、引張速度300mm/分にて鋼板を180度の方向(図1の左右方向)に引張り、せん断強度を測定した。比較例1の引張りせん断強度を100として指数を求めた。指数が高いほど粘着牲が良好であることを示す。結果を表1に併せて示す。
実施例1~4及び比較例1~4の前記未加硫シートを縦50mm、横30cmに切り出し、10枚重ねて厚み20mmの試験片を作成した。得られた試験片を室温にて保管し、72時間後の厚みを測定し、初期厚みに対する72時間後の厚みの比率から厚み保持率を算出した。厚み保持率が高いほどコールドフローしにくいことを示す。結果を表1に併せて示す。
Claims (9)
- 100重量部の未加硫ゴム、及び、
20~100重量部の軟化点40℃以下の粘着性炭化水素系樹脂
を含む粘着性組成物。 - 前記粘着性炭化水素系樹脂が、クマロン樹脂、脂肪族石油樹脂、芳香族石油樹脂、脂肪族/芳香族共重合系石油樹脂、テルペン樹脂、ロジン樹脂、及び、フェノール系樹脂からなる群より選択される少なくとも1種からなる、請求項1記載の粘着性組成物。
- 前記未加硫ゴムが、天然ゴム、イソプレンゴム、ブタジエンゴム、スチレンブタジエンゴム、ブチルゴム、及び、これらのゴムを末端変性した変性ゴムからなる群より選択される、請求項1又は2記載の粘着性組成物。
- 請求項1乃至3のいずれかに記載の粘着性組成物を含む粘着層、並びに、
発泡剤、加硫剤及び未加硫ゴムを含む発泡性ゴム層
を備える粘着性発泡シート。 - 前記発泡性ゴム層の体積発泡倍率が500%以上である、請求項4記載の粘着性発泡シート。
- 前記発泡剤が、アゾジカルボンアミド、アゾビスイソブチロニトリル、アゾジカルボンバリウム、N,N’-ジニトロソペンタメチレンテトラミン、N,N’-ジメチル-N,N’-ジニトロソテレフタルアミド、4,4’-オキシスビス(ベンゼンスルホニルヒドラジド)、ヒドラゾジカルボンアミド、パラトルエンスルホニルヒドラジド、ジフェニルスルホン-3,3’-ジスルホニルヒドラジド、アリルビス(スルホニルヒドラジド)、p-トルイレンスルホニルセミカルバジド、4,4’-オキシビス(ベンゼンスルホニルセミカルバジド)、炭酸水素ナトリウム、炭酸アンモニウム、及び、無水硝酸ナトリウムからなる群より選択される、請求項4又は5記載の粘着性発泡シート。
- 前記加硫剤が、硫黄又は硫黄系加硫剤である、請求項4乃至6のいずれかに記載の粘着性発泡シート。
- 前記未加硫ゴムが、天然ゴム、イソプレンゴム、ブタジエンゴム、スチレンブタジエンゴム、ブチルゴム、及び、これらのゴムを末端変性した変性ゴムからなる群より選択される、請求項4乃至7のいずれかに記載の粘着性発泡シート。
- 上面、底面、4つの側面を有する六面体状である、請求項4乃至8のいずれかに記載の粘着性発泡シート。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/410,759 US20150191631A1 (en) | 2012-06-27 | 2013-06-26 | Adhesive composition and adhesive foam sheet |
CN201380033714.6A CN104411759A (zh) | 2012-06-27 | 2013-06-26 | 粘合性组合物及粘合性发泡片材 |
EP13809387.7A EP2907842A4 (en) | 2012-06-27 | 2013-06-26 | ADHESIVE COMPOSITION AND HAFTSCHAUMSTOFFFOLIE |
BR112014031700A BR112014031700A2 (pt) | 2012-06-27 | 2013-06-26 | composição adesiva e folha espumável adesiva. |
IN2523MUN2014 IN2014MN02523A (ja) | 2012-06-27 | 2014-12-11 |
Applications Claiming Priority (2)
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JP2012-143909 | 2012-06-27 | ||
JP2012143909A JP2014005423A (ja) | 2012-06-27 | 2012-06-27 | 粘着性組成物及び粘着性発泡シート |
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PCT/JP2013/067469 WO2014003043A1 (ja) | 2012-06-27 | 2013-06-26 | 粘着性組成物及び粘着性発泡シート |
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US (1) | US20150191631A1 (ja) |
EP (1) | EP2907842A4 (ja) |
JP (1) | JP2014005423A (ja) |
CN (1) | CN104411759A (ja) |
BR (1) | BR112014031700A2 (ja) |
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JP7231128B2 (ja) * | 2020-12-15 | 2023-03-01 | Dic株式会社 | 接着シート、並びに物品及び物品の製造方法 |
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JP2014005423A (ja) | 2014-01-16 |
EP2907842A4 (en) | 2016-06-29 |
EP2907842A1 (en) | 2015-08-19 |
CN104411759A (zh) | 2015-03-11 |
BR112014031700A2 (pt) | 2017-06-27 |
IN2014MN02523A (ja) | 2015-07-17 |
US20150191631A1 (en) | 2015-07-09 |
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