WO2013042560A1 - 難燃粘着シート - Google Patents
難燃粘着シート Download PDFInfo
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- WO2013042560A1 WO2013042560A1 PCT/JP2012/072978 JP2012072978W WO2013042560A1 WO 2013042560 A1 WO2013042560 A1 WO 2013042560A1 JP 2012072978 W JP2012072978 W JP 2012072978W WO 2013042560 A1 WO2013042560 A1 WO 2013042560A1
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- sensitive adhesive
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- flame
- adhesive sheet
- retardant
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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
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
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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
- 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
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
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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
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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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
- C09J2461/00—Presence of condensation polymers of aldehydes or ketones
- C09J2461/006—Presence of condensation polymers of aldehydes or ketones 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
- C09J2475/00—Presence of polyurethane
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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
- C09J2477/00—Presence of polyamide
- C09J2477/006—Presence of polyamide 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
- C09J2479/00—Presence of polyamine or polyimide
- C09J2479/08—Presence of polyamine or polyimide polyimide
- C09J2479/086—Presence of polyamine or polyimide polyimide 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
- C09J2481/00—Presence of sulfur containing polymers
- C09J2481/006—Presence of sulfur containing polymers in the substrate
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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
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
- Y10T428/24967—Absolute thicknesses specified
- Y10T428/24975—No layer or component greater than 5 mils thick
Definitions
- the present invention relates to a flame retardant adhesive sheet. Specifically, the present invention relates to a flame-retardant pressure-sensitive adhesive sheet having excellent flame retardancy and high adhesive strength even if the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer does not contain a flame retardant.
- Flame resistance is required for materials used in various fields such as electronic parts, electronic equipment, aircraft, and nuclear power plants.
- flame retardancy is also imparted to members used in the above-mentioned fields, and adhesive tapes or sheets for fixing these members.
- flame retardants such as halides, phosphorus compounds, aluminum hydroxide, magnesium hydroxide, melamine in the base material and / or adhesive. Yes.
- Patent Documents 1 to 4 propose pressure-sensitive adhesive tapes in which a non-flammable pressure-sensitive adhesive is applied to a flame-retardant base material using various flame retardants.
- Patent Document 5 proposes a pressure-sensitive adhesive containing a microencapsulated solid flame retardant and an inorganic oxide.
- Patent Document 6 does not impair the flame retardancy of the film substrate and does not significantly reduce the adhesive properties by partially applying a flame retardant adhesive on the surface of the flame retardant substrate. Adhesive tape has been proposed.
- the present invention provides a flame-retardant pressure-sensitive adhesive sheet that achieves both excellent flame retardancy and adhesive strength without using a flame retardant for the pressure-sensitive adhesive and without partially applying the pressure-sensitive adhesive. This is the issue.
- the inventors of the present invention provide an adhesive sheet having a pressure-sensitive adhesive layer having a specific range of thickness, which is composed of a specific pressure-sensitive adhesive that does not contain a flame retardant, on at least one side of the flame-retardant substrate. It was found that can be solved. That is, the present invention provides the following [1] to [10].
- a flame-retardant pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on at least one side of a base material, wherein the base material has a flame retardancy conforming to VTM-0 in a test according to UL94 standard, and the pressure-sensitive adhesive layer
- the thickness per side of the adhesive layer is 0.6 ⁇ m or more and the total thickness of the adhesive layer is 2.2 ⁇ m or less, and the adhesive constituting the adhesive layer does not contain a flame retardant
- a flame-retardant pressure-sensitive adhesive sheet which is a urethane resin obtained by reacting the components (b4) and (b5) at a mass ratio [(b4) / (b5)] of 70/30 to 100/0.
- the base material is a base material containing neither a halogen-based flame retardant nor a phosphorus-based flame retardant.
- the substrate is a substrate containing no flame retardant.
- the substrate is a substrate made of polyimide resin, polyaramid resin, polyphenylene sulfide resin, or polyether ether ketone resin, or a substrate coated with these resins.
- the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer further contains (C) a crosslinking agent, and (A) the acrylic copolymer has a crosslinkable functional group capable of reacting with the (C) crosslinking agent.
- the flame-retardant pressure-sensitive adhesive sheet of the present invention can be formed into a thin film with sufficient adhesiveness by using a specific pressure-sensitive adhesive, so that the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer contains a flame retardant. Even if it does not do, it can be set as the sheet
- the flame-retardant pressure-sensitive adhesive sheet of the present invention is a flame-retardant pressure-sensitive adhesive sheet having a pressure-sensitive adhesive layer on at least one side of a substrate, and the structure of the flame-retardant pressure-sensitive adhesive sheet has a pressure-sensitive adhesive layer on one side or both sides of the substrate. If it is, it will not specifically limit.
- Drawing 1 is a figure showing one mode of composition of a flame retardant adhesive sheet of the present invention.
- the structure of the flame-retardant pressure-sensitive adhesive sheet of the present invention is not limited to the flame-retardant pressure-sensitive adhesive sheet 1a having the pressure-sensitive adhesive layer 12a on one side of the substrate 11, as shown in FIG. 1 (a), but as shown in FIG.
- the flame-retardant pressure-sensitive adhesive sheet 1b in which a release sheet 13a is further laminated on the pressure-sensitive adhesive layer 12a formed on one surface of the substrate 11 may be used.
- the flame-retardant adhesive sheet of this invention may be the flame-retardant adhesive sheet 1c which has the adhesive layers 12a and 12b on both surfaces of the base material 11 like FIG.1 (c), and this adhesive layer 12a.
- 12b may be a flame retardant adhesive sheet in which release sheets 13a and 13b (not shown) are further laminated.
- the base material used for the flame-retardant pressure-sensitive adhesive sheet of the present invention is not particularly limited as long as it has flame retardancy conforming to VTM-0 in a test according to the UL94 standard, and is preferably a resin base material.
- “conforms to VTM-0 in a test conforming to the UL94 standard” means that the VTM rank is VTM in the test conforming to the thin material vertical combustion test method of the flame retardant test standard UL94 issued by Under Laboratories. It means that it is determined to be ⁇ 0.
- a base material made of a resin having flame retardancy as a single resin a base material made of a resin having flame retardancy as a single resin, a base material made of a resin containing a flame retardant, a base material coated with the resin, and the like can be used.
- the resin having flame retardancy as a single resin include polyimide resins such as polyetherimide resin and polyphenylene etherimide resin, polyphenylene sulfide resin, and polyether ether ketone resin.
- a resin used for a base material composed of a resin containing a flame retardant in addition to the above resin having flame retardancy alone, polycarbonate resin, polystyrene resin, polyethylene resin, polyester resin, polyolefin resin, polyurethane resin, Examples thereof include phenol resin, urea resin, EVA resin, acrylic resin, acrylonitrile butadiene resin (ABS resin), epoxy resin, polystyrene-polycarbonate alloy resin, polystyrene-ABS alloy resin, polyamide resin and the like.
- flame retardants examples include organic flame retardants such as halogen flame retardants, phosphorus flame retardants, silicone compounds, melamine compounds, hindered amine compounds and guanidine compounds, and inorganic flame retardants such as antimony compounds and metal hydroxides. Examples include flame retardants. You may use the said flame retardant individually or in combination of 2 or more types.
- a base material coated with a resin having flame retardancy as described above or a resin containing a flame retardant may be used.
- the base material in this case include a base material obtained by coating a sheet-like or film-like plastic, paper such as impregnated paper, metal foil, woven fabric, non-woven fabric, etc. with any of the above resins.
- a base material made of polyimide resin, polyaramid resin, polyphenylene sulfide resin, or polyether ether ketone resin, or a base material coated with these resins is preferable.
- a base material that substantially does not contain any of the halogen-based flame retardant and the phosphorus-based flame retardant is preferable, and in particular, a base material that does not substantially include any of the flame retardant is preferably used.
- the base material used in the flame-retardant adhesive sheet of the present invention include Lumirror ZV10 (trade name, polyethylene terephthalate film coated with polyimide resin, manufactured by Toray Industries, Inc.), Torelina (trade name, polyphenylene) Sulfide resin film, manufactured by Toray Industries, Inc., Mikutron (trade name, polyaramid resin film, manufactured by Toray Industries, Inc.), Kapton (trade name, polyimide resin film, manufactured by Toray DuPont), Superior UT (trade name, polyether) Examples thereof include an imide-based resin film, manufactured by Mitsubishi Resin Co., Ltd., and dialamy (trade name, flame retardant-containing polyethylene terephthalate resin film, manufactured by Mitsubishi Resin Co., Ltd.).
- LAXRON Polyca SDB-3 (trade name, flame retardant-containing polycarbonate resin film, manufactured by Tokiwa Electric Co., Ltd.), Sun Lloyd Barrier (trade name, polyphenylene ether resin film, manufactured by Sumitomo Bakelite Co., Ltd.), Sun Lloyd Eco Sheet Polyca (Trade name, non-halogen flame retardant-containing polycarbonate resin film, manufactured by Sumitomo Bakelite Co., Ltd.), Ultem (trade name, polyetherimide resin film, manufactured by Asahi Glass Co., Ltd.), Lexan (trade name, polycarbonate resin film, manufactured by Asahi Glass Co., Ltd.) ), Baroques (trade name, polybutylene terephthalate resin film, manufactured by Asahi Glass Co., Ltd.), safety film (trade name, polyethylene resin film, manufactured by Oida Kogyo Co., Ltd.), and the like. Note that the present invention is not limited to these product examples.
- the thickness of the substrate is appropriately determined according to the use of the flame-retardant pressure-sensitive adhesive sheet, but is usually 1 to 100 ⁇ m, preferably 5 to 100 ⁇ m, more preferably 10 to 80 ⁇ m.
- the flame-retardant pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer on at least one side of the substrate.
- the thickness per side of the pressure-sensitive adhesive layer is 0.6 ⁇ m or more and the total thickness of the pressure-sensitive adhesive layer is 2.2 ⁇ m or less from the viewpoint of both flame retardancy and adhesiveness. It is. If the thickness per side of the pressure-sensitive adhesive layer is less than 0.6 ⁇ m, sufficient adhesive strength cannot be obtained, and if the total thickness of the pressure-sensitive adhesive layer exceeds 2.2 ⁇ m, sufficient flame retardancy cannot be obtained. .
- the “thickness per side of the pressure-sensitive adhesive layer” means the thickness of each pressure-sensitive adhesive layer provided on one or both sides of the substrate (each of Z1 and Z2 in FIGS. 1 (a) to 1 (c)).
- the “total thickness of the pressure-sensitive adhesive layer” is the total thickness of the pressure-sensitive adhesive layers provided on one or both sides of the substrate (for example, Z1 in FIGS. 1 (a) and 1 (b)).
- (C) is Z1 + Z2.)
- the thickness per side of the pressure-sensitive adhesive layer is 0.6 ⁇ m or more, preferably 0.8 to 2.1 ⁇ m, more preferably 1.0 to 1 .4 ⁇ m.
- the thickness of the pressure-sensitive adhesive layer per one side is 0.6 ⁇ m or more, preferably 0.8 to 1.6 ⁇ m, more preferably 1.0 to 1. 4 ⁇ m.
- the total thickness of the pressure-sensitive adhesive layer is 2.2 ⁇ m or less, preferably 0.6 to 2.1 ⁇ m, more preferably 0.8 to 2.0 ⁇ m.
- the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer used in the present invention is characterized by not containing a flame retardant.
- a flame retardant By not containing a flame retardant, it is preferable from the viewpoint of environmental friendliness and the adhesive strength of the adhesive sheet.
- the “flame retardant” here is the same as the above-mentioned flame retardant in the base material, and “does not contain a flame retardant” means that the adhesive does not substantially contain any of the above-mentioned flame retardants.
- the pressure-sensitive adhesive contains (A) an acrylic copolymer and (B) a urethane resin, and (C) a crosslinking agent, other additives, an organic solvent, and the like as necessary. be able to.
- each component contained in an adhesive is demonstrated.
- the pressure-sensitive adhesive used in the present invention contains (A) an acrylic copolymer.
- the (A) acrylic copolymer is an acrylic copolymer obtained through a polymerization reaction using a monomer mixture containing (meth) acrylic acid ester as a main component. Therefore, the (A) acrylic copolymer to be used contains at least a structural unit derived from a (meth) acrylic ester.
- (meth) acrylic acid means both acrylic acid and methacrylic acid, and the same applies to other similar terms.
- the content of the structural unit derived from the (meth) acrylic acid ester is preferably 70 to 99.9 mass in the total structural unit of the component (A) from the viewpoint of obtaining sufficient adhesive strength even if the pressure-sensitive adhesive layer is thinned. %, More preferably 80 to 99.5% by mass, still more preferably 85 to 99% by mass, and still more preferably 88 to 95% by mass.
- limiting in particular about the copolymerization form of (A) acrylic copolymer Any of a random, a block, and a graft copolymer may be sufficient.
- Examples of the (meth) acrylic acid ester that is a main component monomer of the acrylic copolymer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and butyl (meth) acrylate.
- Examples include dodecyl, myristyl (meth) acrylate, palmityl (meth) acrylate, stearyl (meth) acrylate, and the like.
- butyl (meth) acrylate is preferable from the viewpoint of obtaining sufficient adhesive strength even if the pressure-sensitive adhesive layer is thinned.
- (meth) acrylic acid esters may be used alone or in combination of two or more.
- the content of butyl acrylate is preferably 50 to 100 mass in the (meth) acrylate used, from the viewpoint of obtaining sufficient adhesive strength even if the pressure-sensitive adhesive layer is thinned. %, More preferably 70 to 100% by mass, still more preferably 80 to 100% by mass.
- the acrylic copolymer is an acrylic copolymer having a crosslinkable functional group obtained by polymerizing a monomer mixture containing the (meth) acrylic acid ester and a monomer having a crosslinkable functional group.
- a polymer is preferred.
- the crosslinkable functional group referred to here is a functional group capable of reacting with the crosslinking agent of the component (C) described later, and examples thereof include a carboxy group, a hydroxyl group, and an amino group. Among these, a carboxy group and / or a hydroxyl group are preferable from the viewpoint of reactivity with the crosslinking agent of the component (C), and a carboxy group is more preferable from the viewpoint of obtaining higher adhesive strength.
- the “carboxy group and / or hydroxyl group” means one or more selected from a carboxy group and a hydroxyl group.
- Examples of the monomer having a crosslinkable functional group include (meth) acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid and other ethylenically unsaturated carboxylic acids, (meth) acrylic acid 2-hydroxyethyl, (Meth) acrylic acid 4-hydroxybutyl, (meth) acrylic acid 2-hydroxypropyl, (meth) acrylic acid 3-hydroxypropyl, (meth) acrylic acid 2-hydroxybutyl, (meth) acrylic acid 3-hydroxybutyl, etc.
- (Meth) acrylic acid hydroxyalkyl ester (meth) acrylic acid monomethylaminoethyl, (meth) acrylic acid monoethylaminoethyl, (meth) acrylic acid monomethylaminopropyl, (meth) acrylic acid monoethylaminopropyl ( (Meth) acrylic acid monoalkylaminoalkyl and the like
- ethylenically unsaturated carboxylic acid (meth) acrylic acid hydroxyalkyl ester are preferable, An ethylenically unsaturated carboxylic acid is more preferable, and (meth) acrylic acid is still more preferable.
- the content of the monomer having a crosslinkable functional group is preferably 0 in the monomer mixture which is a raw material of the acrylic copolymer, from the viewpoint of obtaining sufficient adhesive strength even when the pressure-sensitive adhesive layer is thinned. 1 to 20% by mass, more preferably 0.5 to 15% by mass, and still more preferably 1 to 12% by mass.
- the acrylic copolymer may contain a structural unit derived from a monomer other than the above (hereinafter referred to as another monomer) as a structural unit.
- examples of other monomers include vinyl esters such as vinyl acetate and vinyl propionate, olefins such as ethylene, propylene, and isobutylene, halogenated olefins such as vinyl chloride and vinylidene chloride, styrene, methylstyrene, and vinyl.
- examples thereof include aromatic vinyl monomers such as toluene, diene monomers such as butadiene, isoprene and chloroprene, and nitrile monomers such as (meth) acrylonitrile. These monomers may be used alone or in combination of two or more.
- the method for obtaining the (A) acrylic copolymer from these monomer mixtures is not particularly limited, and can be carried out by a known polymerization method in the presence or absence of a solvent.
- a solvent to be used include ethyl acetate and toluene.
- a polymerization initiator may be used in the polymerization reaction.
- the polymerization initiator include azobisisobutyronitrile and benzoyl peroxide.
- the blending amount of these polymerization initiators is preferably 0.01 to 1 part by mass, more preferably 0.1 to 0.5 part by mass with respect to 100 parts by mass of the monomer mixture.
- the polymerization conditions are not particularly limited, but the polymerization is preferably performed at a polymerization temperature of 50 to 90 ° C. and a reaction time of 2 to 30 hours.
- the weight average molecular weight (Mw) of the (A) acrylic copolymer thus obtained is preferably from 300,000 to 1,500,000, more preferably from 400,000 to 1,000,000, from the viewpoint of improving adhesive performance and the like. More preferably, it is 500,000 to 800,000. If it is 300,000 or more, the cohesive force of the pressure-sensitive adhesive layer is improved, and sufficient adhesive force can be obtained. Moreover, if it is 1.5 million or less, the elasticity modulus of an adhesive layer will not become high too much and the fall of adhesive force can be suppressed.
- a weight average molecular weight means the value of standard polystyrene conversion measured by the gel permeation chromatography (GPC) method, and is specifically the value measured by the method as described in an Example. Means the same.
- the pressure-sensitive adhesive used in the present invention contains (B) a urethane resin (hereinafter also referred to as “component (B)”).
- component (B) a urethane resin
- the mass ratio [(A) / (B)] of (A) acrylic copolymer and (B) urethane resin is used to obtain an adhesive having an appropriate elastic modulus, and the adhesive layer is made into a thin film.
- the said mass ratio which shows the ratio of (A) component with respect to (B) component is 1/99 or more, the fall of the adhesive force by an elasticity modulus becoming too low can be avoided, What is 40/60 or less? In this case, it is possible to avoid a decrease in adhesive force due to an excessively high elastic modulus.
- Urethane resin used in the present invention is obtained by reacting (b3) a chain extender with a terminal isocyanate urethane prepolymer obtained by reacting (b1) a polyol and (b2) a polyvalent isocyanate compound. Urethane resin is preferred.
- polyol a compound having two or more hydroxyl groups in the molecule can be used, but a diol is preferably used from the viewpoint of suppressing gelation.
- examples of the polyol include alkanes such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 1,7-heptanediol.
- Examples include diols, alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol, and dipropylene glycol, polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polybutylene glycol, and polyoxyalkylene glycols such as polytetramethylene glycol.
- a polyalkylene glycol having a weight average molecular weight of 1,000 to 3,000 is more preferred.
- Examples of the polyvalent isocyanate compound include aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate.
- Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4 '-Toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 4,4', 4 "-triphenylmethane triisocyanate 1,4-tetramethylxylylene diisocyanate, 1,3-tetramethylxylylene diisocyanate, and the like.
- Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, Examples include 2,4,4-trimethylhexamethylene diisocyanate.
- Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, and methyl-2. , 4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis (cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane, etc. It is done.
- polyvalent isocyanate compounds are trimethylolpropane adduct-type modified products of the above polyisocyanates, burette-type modified products reacted with water, and isocyanurate-type modified products containing isocyanurate rings. Also good.
- polyvalent isocyanate compounds 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, 3 from the viewpoint of physical properties as an adhesive.
- -One or more selected from isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate and modified products thereof are preferable.
- isocyanates and modified products thereof are more preferable, and hexamethylene diisocyanate and modified products thereof are more preferable.
- the method for preparing the terminal isocyanate urethane prepolymer is not particularly limited.
- the reactor includes a component (b1) and a component (b2), a urethanization catalyst added as necessary, and a solvent used as necessary. And the like, and the like.
- the blending ratio of the components (b1) and (b2) is preferably from 1.1 to 3.0, more preferably from 1.2 to NCO group / OH group (molar ratio) from the viewpoint of using an isocyanate group as the terminal. It is preferable to mix and react so that it may become 2.5. If it is 1.1 or more, since gelation can be avoided, the tendency to thicken can be suppressed.
- the unreacted polyvalent isocyanate compound concentration in the terminal isocyanate urethane prepolymer does not become too high, and the reaction with the (b3) chain extender described later can proceed smoothly.
- the isocyanate group content (NCO%) in the terminal isocyanate urethane prepolymer is JIS K1603, although it varies depending on the reactivity of the components (b1) and (b2) used and the blending amount of (b3) chain extender.
- the value measured according to the above is preferably 0.5 to 12% by mass, more preferably 1 to 4% by mass. If it is 0.5 mass% or more, the reaction with the (b3) chain extender can be sufficiently advanced, and if it is 12 mass% or less, the reaction with the (b3) chain extender is sufficiently controlled. be able to.
- a tertiary amine type compound, an organometallic type compound, etc. are mentioned.
- the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) and the like.
- organometallic compounds include tin compounds and non-tin compounds.
- tin compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin Examples include acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate and the like.
- DBTDL dibutyltin dilaurate
- DBTDL dibutyltin diacetate
- dibutyltin sulfide tributyltin sulfide
- non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate.
- titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride
- lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate.
- Iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate
- cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate
- zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate
- zirconium naphthenate examples of zircon
- DBTDL tin 2-ethylhexanoate
- tetrabutyl titanate are preferable, and DBTDL is more preferable.
- the addition amount of the catalyst used in the reaction is preferably 0.0001 to 1 part by mass, more preferably 0.005 to 0.1 part by mass with respect to 100 parts by mass of the component (b1) from the viewpoint of reactivity. It is.
- solvent used as necessary in the reaction examples include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, esters such as ethyl acetate and butyl acetate, ketones such as methyl ethyl ketone (MEK), Examples include dimethylformamide and cyclohexanone. These solvents may be used alone or in combination of two or more.
- the reaction temperature in the reaction is preferably 120 ° C. or less, more preferably 70 to 100 ° C. If it is 120 degrees C or less, an alohanate reaction can suppress progress, the terminal isocyanate urethane prepolymer which has a predetermined molecular weight and structure can be synthesize
- the reaction time in the reaction is preferably 2 to 20 hours when the reaction temperature is 70 to 100 ° C., for example.
- the terminal isocyanate urethane prepolymer obtained as described above becomes a urethane resin by a chain extension reaction with the (b3) chain extender.
- the chain extender contains (b4) a compound having two hydroxyl groups and / or amino groups and (b5) a compound having three or more hydroxyl groups and / or amino groups, and (b4) component and (b5) The components are reacted at a mass ratio [(b4) / (b5)] of 70/30 to 100/0.
- the “compound having two hydroxyl groups and / or amino groups” means a compound having two functional groups selected from hydroxyl groups and amino groups, and “a compound having three or more hydroxyl groups and / or amino groups” Means a compound having three or more functional groups selected from a hydroxyl group and an amino group.
- the component (b4) is not particularly limited as long as it is a compound having two hydroxyl groups and / or amino groups, but from the viewpoint of further preventing a decrease in adhesive strength, aliphatic diol, aliphatic diamine, alkanolamine, bisphenol. At least one compound selected from the group consisting of aromatic diamines is preferred.
- the aliphatic diol include alkanediols such as 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, and 1,7-heptanediol.
- alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol.
- alkylene glycols such as ethylene glycol, propylene glycol, diethylene glycol and dipropylene glycol.
- alkanolamine examples include monoethanolamine, monopropanolamine, isopropanolamine and the like.
- bisphenol include bisphenol A and the like.
- aromatic diamine include diphenylmethanediamine, tolylenediamine, xylylenediamine, and the like. In addition, you may use these compounds individually or in combination of 2 or more types.
- the component (b5) is not particularly limited as long as it is a compound having three or more hydroxyl groups and / or amino groups, but a polyol such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, 1-amino- Examples include amino alcohols such as 2,3-propanediol, 1-methylamino-2,3-propanediol, N- (2-hydroxypropylethanolamine), and ethylene oxide or propylene oxide adducts of tetramethylxylylenediamine. . In addition, you may use these compounds individually or in combination of 2 or more types.
- the hydroxyl group and / or amino group in the components (b4) and (b5) are preferably a primary amino group, a secondary amino group, or a primary hydroxyl group from the viewpoint of reactivity with an isocyanate group.
- the component (b4) is more preferably an aliphatic diol, and even more preferably an alkanediol.
- the component (b5) is more preferably a polyol, and more preferably trimethylolpropane.
- the mass ratio [(b4) / (b5)] of the component (b4) and the component (b5) to be blended is 70/30 to 100/0, preferably 75/25 to 95/5, more preferably 80. / 20 to 90/10.
- the said mass ratio which shows the ratio of (b4) component with respect to (b5) component is 70/30 or more, even if it makes an adhesive layer thin, the fall of adhesive force can be suppressed and a urethane resin is obtained. In the chain extension reaction, gelation can be avoided and a desired pressure-sensitive adhesive can be obtained.
- Examples of the chain extension reaction include (1) a method in which a solution of a terminal isocyanate urethane prepolymer is charged into a reactor, and a chain extender is dropped into the reactor to cause a reaction, and (2) a chain extender is charged in the reactor. , A method in which a solution of a terminal isocyanate urethane prepolymer is dropped and reacted; (3) a method in which a solution of a terminal isocyanate urethane prepolymer is diluted with a solvent and then a predetermined amount of a chain extender is charged into the reactor and reacted. Is mentioned.
- the isocyanate group gradually decreases, it is easy to obtain a resin having a uniform composition, and therefore the method (1) or (3) is preferable.
- a solvent the same solvent as that which can be used for the above-mentioned terminal isocyanate urethane prepolymer production reaction can be used.
- the reaction temperature in the chain extension reaction is preferably 20 to 80 ° C. If it is 20 degreeC or more, chain extension reaction can be advanced at sufficient speed
- the reaction temperature is preferably not higher than the boiling point of the solvent, and particularly preferably 40 to 60 ° C. in the presence of MEK and ethyl acetate.
- the reaction time in the chain extension reaction is preferably 1 to 20 hours when the reaction temperature is 40 to 80 ° C., for example.
- An end terminator may be used to terminate the chain extension reaction.
- the terminal terminator include a compound having only one hydrogen capable of reacting with an isocyanate group or a compound having only one amino group.
- the compound having only one hydrogen capable of reacting with an isocyanate group include monool compounds such as methanol and ethanol.
- a compound having only one primary amino group or one secondary amino group can be used, and examples thereof include diethylamine and morpholine.
- a compound having only one primary amino group has two reactive hydrogens, but the reactive hydrogen remaining after one reactive hydrogen has reacted is substantially less reactive. Is equivalent to monofunctionality.
- the addition amount of the terminal stopper is preferably such that the terminal stopper is 1 mole or more and 2 moles or less with respect to 1 mole of the terminal isocyanate group remaining after the chain extension reaction. If the addition amount of the terminal terminator is 1 mol or more, an isocyanate group does not remain after the termination reaction, and thus the obtained urethane resin is stable. On the other hand, if the addition amount of the terminal terminator is 2 mol or less, low molecular weight urethane resin tends to decrease.
- the weight average molecular weight of the urethane resin is preferably 10,000 to 300,000, more preferably 30,000 to 250,000, and still more preferably 50,000 to 200,000. If it is 10,000 or more, it is preferable because the adhesive properties, particularly the adhesion holding force tends to be improved, and if it is 300,000 or less, gelation can be avoided.
- the pressure-sensitive adhesive used in the present invention increases the cohesive force to obtain a desired pressure-sensitive adhesive force. It is preferable to contain a crosslinking agent capable of reacting with the functional group.
- the crosslinking agent include an isocyanate crosslinking agent, an epoxy crosslinking agent, an aziridine crosslinking agent, a metal chelate crosslinking agent and an amine crosslinking agent, and an amino resin crosslinking agent.
- isocyanate crosslinking agent examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2, , 4'-diphenylmethane diisocyanate, 3-methyldiphenylmethane diisocyanate, hexamethylene diisocyanate, 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), 2,4'-methylenebis ( Cyclohexyl isocyanate) and polyisocyanate compounds such as lysine isocyanate.
- isocyanate crosslinking agent examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,3-xylylene diisocyanate, 1,4
- the polyvalent isocyanate compound may be a trimethylolpropane adduct type modified product of the above compound, a burette type modified product reacted with water, or an isocyanurate type modified product containing an isocyanurate ring.
- the epoxy-based crosslinking agent is not particularly limited as long as it has two or more epoxy groups or glycidyl groups in the molecule, but a polyfunctional epoxy compound containing two or more glycidyl groups in the molecule is preferable.
- the polyfunctional epoxy compound containing two or more glycidyl groups in the molecule include diglycidyl ether of bisphenol A and its oligomer, diglycidyl ether of hydrogenated bisphenol A and its oligomer, diglycidyl orthophthalate, isophthalate Acid diglycidyl ester, terephthalic acid diglycidyl ester, p-oxybenzoic acid glycidyl ester, tetrahydrophthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, succinic acid diglycidyl ester, adipic acid diglycidyl ester, sebacic acid di Glycidyl ester, ethylene glycol dig
- the aziridine-based crosslinking agent is not particularly limited, but specific examples thereof include 1,1 ′-(methylene-di-p-phenylene) bis-3,3-aziridinylurea and 1,1 ′-(hexamethylene) bis. -3,3-aziridinyl urea, 2,4,6-triaziridinyl-1,3,5-triazine, trimethylolpropane-tris- (2-aziridinylpropionate), and the like.
- metal chelate-based crosslinking agent examples include compounds in which acetylacetone, ethyl acetoacetate, and the like are coordinated to a polyvalent metal such as aluminum, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium, chromium, and zirconium. Etc.
- amine-based cross-linking agents include polyamines such as aliphatic polyamines (for example, triethylenetetramine, tetraethylenepentamine, ethylenediamine, N, N-dicinenamylidene-1,6-hexanediamine, trimethylenediamine, hexamethylenediamine carbamate, ethanolamine.
- polyamines such as aliphatic polyamines (for example, triethylenetetramine, tetraethylenepentamine, ethylenediamine, N, N-dicinenamylidene-1,6-hexanediamine, trimethylenediamine, hexamethylenediamine carbamate, ethanolamine.
- amino resin-based crosslinking agents examples include methoxylated methylol urea, methoxylated methylol N, N-ethylene urea, methoxylated methylol dicyandiamide, methoxylated methylol melamine, methoxylated methylol benzoguanamine, butoxylated methylol melamine, butoxylated methylol benzoguanamine, and the like.
- methoxylated methylol melamine, butoxylated methylol melamine, methylolated benzoguanamine and the like can be mentioned.
- an isocyanate-based crosslinking agent is preferable, and tolylene diisocyanate and a modified product thereof are more preferable.
- the content of the (C) cross-linking agent is preferably 0.01 to 100 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B) from the viewpoint of obtaining high adhesive strength even if the pressure-sensitive adhesive layer is thinned.
- the amount is 8 parts by mass, more preferably 0.05 to 5 parts by mass, still more preferably 0.1 to 3 parts by mass.
- the pressure-sensitive adhesive used in the present invention can be blended with other components as long as the effects of the present invention are not impaired.
- other components include ultraviolet absorbers, antioxidants, antiseptics, antifungal agents, plasticizers, antifoaming agents, and wettability adjusting agents.
- the flame-retardant pressure-sensitive adhesive sheet of the present invention may be one in which a release sheet is laminated on a pressure-sensitive adhesive layer, for example, as shown in FIG.
- a peeling sheet used for the flame-retardant adhesive sheet of this invention
- coated the release agent on the sheet base material is preferable.
- the release sheet may be one in which a release agent is applied to both surfaces of the sheet substrate and subjected to a release treatment, or may be one in which the release agent is applied to only one surface of the sheet substrate and subjected to the release treatment.
- the sheet substrate used for the release sheet for example, a paper substrate such as glassine paper, coated paper, cast coated paper, laminated paper obtained by laminating a thermoplastic resin such as polyethylene on these paper substrates, or polyethylene terephthalate, Examples thereof include polyester films such as polybutylene terephthalate and polyethylene naphthalate, and plastic films such as polyolefin films such as polypropylene and polyethylene.
- the release agent include rubber elastomers such as olefin resins, isoprene resins, butadiene resins, long chain alkyl resins, alkyd resins, fluorine resins, silicone resins, and the like.
- the thickness of the release sheet is not particularly limited, but is usually 20 to 200 ⁇ m, preferably 25 to 150 ⁇ m.
- the thickness after drying of the layer composed of the release agent in the release sheet is not particularly limited, but when the release agent is applied in a solution state, it is preferably 0.01 to 2.0 ⁇ m, more preferably 0.03 to 1.0 ⁇ m.
- the thickness of the plastic film is preferably 3 to 50 ⁇ m, more preferably 5 to 40 ⁇ m.
- the manufacturing method of the flame-retardant adhesive sheet of this invention is not specifically limited.
- the flame-retardant pressure-sensitive adhesive sheet 1a shown in FIG. 1 (a) can be produced by applying a pressure-sensitive adhesive on one surface of the substrate 11 and drying it to form the pressure-sensitive adhesive layer 12a.
- the flame-retardant adhesive sheet 1b shown in FIG.1 (b) after apply
- the base material 11 is bonded together to produce a single-sided pressure-sensitive adhesive sheet.
- the pressure-sensitive adhesive used in the present invention it is preferable to dilute the pressure-sensitive adhesive with an organic solvent in order to easily form a thin pressure-sensitive adhesive layer on the substrate.
- organic solvent to be used include toluene, ethyl acetate, methyl ethyl ketone, and the like. By blending these organic solvents into an adhesive solution having an appropriate solid content concentration, a thinned adhesive layer can be formed.
- the solid content concentration of the pressure-sensitive adhesive is preferably 5 to 60% by mass, more preferably 10 to 40% by mass.
- the pressure-sensitive adhesive solution has an appropriate viscosity, and workability is improved when the pressure-sensitive adhesive solution is applied.
- the said (A) acrylic copolymer and / or (B) urethane resin used for the said adhesive in the state contained in the organic solvent it dilutes using the same organic solvent, The said solid content concentration You may prepare an adhesive solution so that it may become.
- blended said organic solvent with a well-known coating method is mentioned.
- the coating method include known methods such as spin coating, spray coating, bar coating, knife coating, roll coating, blade coating, die coating, and gravure coating.
- the temperature condition for the heat treatment is preferably 70 to 150 ° C., more preferably 80 to 120 ° C.
- the treatment time of the heat treatment is preferably 30 seconds to 5 minutes, more preferably 40 to 180 seconds.
- the adhesive strength at normal temperature (23 ° C., 50% RH (relative humidity)) of the flame-retardant pressure-sensitive adhesive sheet of the present invention produced as described above is 3.0 N / 25 mm or more in the measurement method described in the examples. Will be.
- the flame-retardant pressure-sensitive adhesive sheet has flame retardancy conforming to VTM-0 in a test according to the UL94 standard. The flame retardancy can be specifically measured by the method described in Examples.
- the weight average molecular weight (Mw) shown in the description of the following examples is a value obtained by measurement under the following conditions using “HLC-8020” manufactured by Tosoh Corporation and converted to standard polystyrene. (Measurement condition) Column: “TSK gel GMHXL ( ⁇ 2)” “TSK gel G2000HXL” (both manufactured by Tosoh Corporation) Column temperature: 40 ° C Developing solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Detector: Differential refractometer
- Production Example 1 (Preparation of acrylic copolymer solution) As a monomer component, 90 parts by mass of butyl acrylate and 10 parts by mass of acrylic acid, 200 parts by mass of ethyl acetate as a solvent, and 0.2 parts by mass of azobisisobutyronitrile as a polymerization initiator are placed in a reactor. Mixed. After deaeration with nitrogen gas for 4 hours, the temperature was gradually raised to 60 ° C., followed by polymerization reaction with stirring for 24 hours, and an ethyl acetate solution containing an acrylic copolymer having a weight average molecular weight of 650,000 (solid content) A concentration of 33% by mass was obtained.
- Production Example 3 (Preparation of urethane resin solution (B-2))
- (b3) chain extender (b4) the amount of 1,4-butanediol used was 0.48 parts by mass, and (b5) 0.12 parts by mass of trimethylolpropane was added.
- (B-2; solid content concentration of 50% by mass) was obtained.
- the composition and the like are shown in Table 1.
- Example 1 (Production of flame retardant adhesive sheet) 25 parts by mass (solid content) of the acrylic copolymer-containing ethyl acetate solution obtained in Production Example 1, 100 parts by mass (solid content) of the urethane resin-containing toluene solution (B-1) obtained in Production Example 2, and crosslinking
- 2.25 parts by mass (solid content) of an isocyanate-based crosslinking agent manufactured by Nippon Polyurethane Co., Ltd., trade name “Coronate L”, ethyl acetate solution of trimethylolpropane-modified tolylene diisocyanate (solid content: 75% by mass)
- an adhesive solution 25 parts by mass (solid content) of the acrylic copolymer-containing ethyl acetate solution obtained in Production Example 1, 100 parts by mass (solid content) of the urethane resin-containing toluene solution (B-1) obtained in Production Example 2, and crosslinking
- This solution was applied to a silicone-treated 38 ⁇ m polyester film (product name “SP-PET 381031”, manufactured by Lintec Corporation) as a release sheet so that the thickness of the pressure-sensitive adhesive layer after drying was 1.0 ⁇ m.
- the base material is a polyethylene terephthalate (PET) film coated with polyimide resin on both sides (trade name “Lumirror ZV10 # 25”, manufactured by Toray Industries, Inc., thickness: 30 ⁇ m, UL94
- PET polyethylene terephthalate
- VTM-0 flame retardant adhesive sheet.
- the thickness and total thickness of each layer of the flame-retardant adhesive sheet were measured by observing the sheet cross section with an electron microscope (manufactured by Keyence Corporation, trade name “VHX-1000”).
- the prepared release sheet of the flame retardant adhesive sheet was peeled off, and a test according to the flame retardant test standard UL94 thin material vertical combustion test method issued by Under Laboratories was conducted to determine the VTM rank.
- the sample size of the flame-retardant pressure-sensitive adhesive sheet used for evaluation was 50 mm ⁇ 200 mm, and the test was conducted with the pressure-sensitive adhesive layer outside.
- the criteria for determining the VTM rank are as follows. VTM-0; burning time of the sample is within 10 seconds, and the absorbent cotton is not ignited by the burned material or falling object, and further, the burning up to the marked line (125 mm position from the lower end of the sample) is not recognized.
- VTM-1 The burning time of the sample is within 30 seconds, and the absorbent cotton is not ignited by the burned material or the falling object, and further, the burning up to the marked line is not recognized.
- VTM-2 The burning time of the sample is within 30 seconds, and burning up to the marked line is not observed.
- Table 2 those conforming to VTM-0 are "VTM-0", those not conforming to VTM-0 but conforming to VTM-1 are conforming to "VTM-1", VTM-0 and VTM-1 Those that did not conform to VTM-2 were designated as “VTM-2”, and those that did not conform to any of VTM-0, VTM-1, and VTM-2 were designated as “Fail”.
- Adhesive for adhesive strength test in the same manner as described above except that a 25 ⁇ m polyester film (trade name “T-100” manufactured by Mitsubishi Plastics, Inc.) was used in place of “Lumirror ZV10 # 25” as the base material. A sheet was produced. The release sheet was peeled off, and a test piece of the adhesive sheet cut to 25 mm ⁇ 300 mm was attached to an adherend (SUS304 steel plate) in an environment of 23 ° C. and 50% RH to obtain a sample for an adhesive strength test. Based on JIS Z0237, the adhesive force 24 hours after sticking was measured by a 180 ° peeling method at a pulling speed of 300 mm / min. The evaluation results are shown in Table 2.
- Examples 2 to 15 and Comparative Examples 1 to 14 A pressure-sensitive adhesive sheet was prepared in the same manner as in Example 1 except that the base material and the pressure-sensitive adhesive layer were changed as shown in Table 2. In addition, flame retardancy evaluation and adhesive strength test were performed in the same manner as in Example 1. The evaluation results are shown in Table 2.
- the pressure-sensitive adhesive sheets obtained in Examples 1 to 15 of the present invention have excellent flame retardancy and adhesive strength.
- the pressure-sensitive adhesive sheets obtained in Comparative Examples 5 and 7 had insufficient adhesive strength because the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer did not contain the component (A) or the component (B).
- the pressure-sensitive adhesive sheets obtained in Comparative Examples 1 to 4, 6 and 8 to 12 did not have sufficient flame retardancy because the total thickness of the pressure-sensitive adhesive layer exceeded 2.2 ⁇ m.
- the pressure-sensitive adhesive sheet obtained in Comparative Example 13 has insufficient adhesive strength because the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer contains melamine cyanurate, which is a flame retardant, and the pressure-sensitive adhesive sheet obtained in Comparative Example 14 The adhesive strength was insufficient because the thickness per side of the pressure-sensitive adhesive layer was less than 0.6 ⁇ m.
- the flame retardant pressure-sensitive adhesive sheet of the present invention can make the pressure-sensitive adhesive layer thin with sufficient adhesiveness by using a specific pressure-sensitive adhesive, the pressure-sensitive adhesive constituting the pressure-sensitive adhesive layer contains a flame retardant. Even if it does not exist, it can be set as the sheet
- the flame-retardant pressure-sensitive adhesive sheet is suitably used in small electronic devices such as portable electronic devices.
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Abstract
Description
一方、特許文献5には、マイクロカプセル化した固体の難燃剤及び無機酸化物を含有する粘着剤が提案されている。
さらに、特許文献6には、難燃性基材面に難燃性を有さない粘着剤を部分塗布することにより、フィルム基材の難燃性を損なわず、且つ、粘着特性を著しく低下させない粘着テープが提案されている。
また、特許文献5に記載の固体の難燃剤による難燃化は、難燃剤の添加に伴い粘着剤が硬くなり、粘着力が低下する。
更に、特許文献6に記載の粘着テープは、粘着剤を部分塗布しているため、生産歩留まりが低下し、また基材が薄い場合は、上記部分塗布により生じる段差によって意匠性が低下する懸念がある。
本発明は、このような背景の下、粘着剤に難燃剤を使用せず、かつ粘着剤の部分塗布をすることなく、優れた難燃性と粘着力を両立した難燃粘着シートを提供することを課題とする。
すなわち、本発明は、下記[1]~[10]を提供するものである。
[1]基材の少なくとも片面に粘着剤層を有する難燃粘着シートであって、前記基材が、UL94規格に準ずる試験においてVTM-0に適合する難燃性を有し、前記粘着剤層の片面あたりの厚みが0.6μm以上でかつ該粘着剤層の総厚みが2.2μm以下であり、該粘着剤層を構成する粘着剤が、難燃剤を含有せず、(A)アクリル系共重合体と、(B)ウレタン樹脂とを含有し、(B)ウレタン樹脂が、(b1)ポリオールと(b2)多価イソシアネート化合物とを反応させて得られる末端イソシアネートウレタンプレポリマーに、(b3)鎖延長剤を反応させて得られるものであり、(b3)鎖延長剤が、(b4)水酸基及び/又はアミノ基を2つ有する化合物及び(b5)水酸基及び/又はアミノ基を3つ以上有する化合物を含有し、(b4)成分と(b5)成分とを質量比〔(b4)/(b5)〕で70/30~100/0の割合で反応させてなるウレタン樹脂である、難燃粘着シート。
[2]基材が、ハロゲン系難燃剤及びリン系難燃剤のいずれも含有しない基材である、上記[1]に記載の難燃粘着シート。
[3]基材が、難燃剤を含有しない基材である、上記[1]に記載の難燃粘着シート。
[4]基材が、ポリイミド樹脂、ポリアラミド樹脂、ポリフェニレンサルファイド樹脂、又はポリエーテルエーテルケトン樹脂からなる基材、又はこれらの樹脂がコートされた基材である、上記[1]~[3]のいずれかに記載の難燃粘着シート。
[5](b1)ポリオールが、重量平均分子量1,000~3,000のグリコールである、上記[1]~[4]のいずれかに記載の難燃粘着シート。
[6]粘着剤層を構成する粘着剤が、さらに(C)架橋剤を含有し、かつ(A)アクリル系共重合体が、該(C)架橋剤と反応しうる架橋性官能基を有する、上記[1]~[5]のいずれかに記載の難燃粘着シート。
[7]架橋性官能基が、カルボキシ基及び/又は水酸基である、上記[6]に記載の難燃粘着シート。
[8](C)架橋剤が、イソシアネート系架橋剤である、上記[6]又は[7]に記載の難燃粘着シート。
[9](A)アクリル系共重合体と(B)ウレタン樹脂との質量比〔(A)/(B)〕が、1/99~40/60である、上記[1]~[8]のいずれかに記載の難燃粘着シート。
[10](A)アクリル系共重合体の重量平均分子量(Mw)が、30万~150万である、上記[1]~[9]のいずれかに記載の難燃粘着シート。
図1は、本発明の難燃粘着シートの構成の一態様を示す図である。本発明の難燃粘着シートの構成は、図1(a)のように、基材11の片面に粘着剤層12aを有する難燃粘着シート1aに限らず、図1(b)のように、基材11の片面に形成された粘着剤層12aの上に、更に剥離シート13aが積層された難燃粘着シート1bであってもよい。
また、本発明の難燃粘着シートは、図1(c)のように、基材11の両面に粘着剤層12a、12bを有する難燃粘着シート1cであってもよく、該粘着剤層12a、12bのそれぞれの上に、更に剥離シート13a、13b(図示せず)が積層された難燃粘着シートであってもよい。
本発明の難燃粘着シートに用いられる基材は、UL94規格に準ずる試験においてVTM-0に適合する難燃性を有するものであればよく、樹脂製の基材であることが好ましい。本発明において、「UL94規格に準ずる試験においてVTM-0に適合」とは、アンダーラボラトリーズ社発行のプラスチック材料の難燃性試験規格UL94の薄手材料垂直燃焼試験方法に準ずる試験において、VTMランクがVTM-0と判定されるものであることをいう。
樹脂単体で難燃性を有する樹脂としては、ポリエーテルイミド樹脂やポリフェニレンエーテルイミド樹脂等のポリイミド樹脂、ポリフェニレンサルファイド樹脂、ポリエーテルエーテルケトン樹脂等が挙げられる。
難燃剤としては、ハロゲン系難燃剤、リン系難燃剤、シリコーン系化合物、メラミン系化合物、ヒンダードアミン系化合物、グアニジン系化合物等の有機系難燃剤や、アンチモン系化合物、金属水酸化物等の無機系難燃剤が挙げられる。上記難燃剤は、単独で又は2種以上組み合わせて用いてもよい。
また、環境対応の観点から、ハロゲン系難燃剤、リン系難燃剤のいずれも実質的に含有しない基材が好ましく、特にいずれの難燃剤も実質的に含有しない基材を用いることが好ましい。
また、LAXRONポリカSDB-3(商品名、難燃剤含有ポリカーボネート樹脂フィルム、トキワ電気株式会社製)、サンロイドバリア(商品名、ポリフェニレンエーテル系樹脂フィルム、住友ベークライト株式会社製)、サンロイドエコシートポリカ(商品名、ノンハロゲン難燃剤含有ポリカーボネート樹脂フィルム、住友ベークライト株式会社製)、ウルテム(商品名、ポリエーテルイミド樹脂フィルム、旭硝子株式会社製)、レキサン(商品名、ポリカーボネート系樹脂フィルム、旭硝子株式会社製)、バロックス(商品名、ポリブチレンテレフタレート系樹脂フィルム、旭硝子株式会社製)、セフティーフィルム(商品名、ポリエチレン系樹脂フィルム、大井田工業株式会社製)等が挙げられる。なお、これらの製品例に限定されるわけではない。
本発明の難燃粘着シートは、上記基材の少なくとも片面に粘着剤層を有するものである。
本発明の難燃粘着シートにおいて、難燃性及び粘着性の両立の観点から、粘着剤層の片面あたりの厚みは0.6μm以上であり、かつ該粘着剤層の総厚みは2.2μm以下である。粘着剤層の片面あたりの厚みが0.6μm未満であると十分な粘着力が得られず、また該粘着剤層の総厚みが2.2μmを超えると、十分な難燃性が得られない。
なお、本発明において「粘着剤層の片面あたりの厚み」とは、基材の片面又は両面に設けられる粘着剤層のそれぞれの厚み(図1(a)~(c)のZ1、Z2の各々)を示し、「粘着剤層の総厚み」とは、基材の片面又は両面に設けられる粘着剤層の合計の厚み(例えば、図1(a)及び(b)ではZ1であり、図1(c)ではZ1+Z2である)を示す。
基材の片面にのみ粘着剤層が設けられる場合は、粘着剤層の片面あたりの厚みは、0.6μm以上であり、好ましくは0.8~2.1μm、より好ましくは1.0~1.4μmである。
基材の両面に粘着剤層が設けられる場合は、粘着剤層の片面あたりの厚みは、0.6μm以上であり、好ましくは0.8~1.6μm、より好ましくは1.0~1.4μmである。また粘着剤層の総厚みは、2.2μm以下であり、好ましくは0.6~2.1μm、より好ましくは0.8~2.0μmである。
本発明で用いられる粘着剤層を構成する粘着剤は、難燃剤を含有しないことを特徴とする。難燃剤を含有しないことで、環境対応の観点、及び粘着シートの粘着力の観点からも好ましい。なお、ここでいう「難燃剤」とは、基材において前記した難燃剤と同じであり、「難燃剤を含有しない」とは、粘着剤が、前記したいずれの難燃剤も実質的に含有しないことを意味する。
また、該粘着剤は、(A)アクリル系共重合体と、(B)ウレタン樹脂とを含有し、必要に応じて、(C)架橋剤、その他の添加剤、及び有機溶媒等を含有することができる。以下、粘着剤中に含まれる各成分について説明する。
本発明で用いられる粘着剤は、(A)アクリル系共重合体を含有する。本発明において、(A)アクリル系共重合体は、(メタ)アクリル酸エステルが主成分である単量体混合物を原料として、重合反応を経て得られるアクリル系共重合体である。そのため、用いる(A)アクリル系共重合体は、少なくとも(メタ)アクリル酸エステル由来の構成単位を含む。
なお、以下の記載において、例えば「(メタ)アクリル酸」とは、アクリル酸及びメタクリル酸の両方を意味し、他の類似用語も同様である。
なお、(A)アクリル系共重合体の共重合形態については特に制限はなく、ランダム、ブロック、グラフト共重合体のいずれであってもよい。
ここでいう架橋性官能基とは、後述する(C)成分の架橋剤と反応し得る官能基であって、カルボキシ基、水酸基、アミノ基等が挙げられる。これらの中でも、(C)成分の架橋剤との反応性の観点から、カルボキシ基及び/又は水酸基が好ましく、より高い粘着力を得られるという観点から、カルボキシ基がより好ましい。なお、「カルボキシ基及び/又は水酸基」とは、カルボキシ基及び水酸基から選ばれる1種以上をいう。
これらの中でも、架橋剤との反応性の観点、及び粘着剤層を薄膜化しても十分に高い粘着力を得る観点から、エチレン性不飽和カルボン酸、(メタ)アクリル酸ヒドロキシアルキルエステルが好ましく、エチレン性不飽和カルボン酸がより好ましく、(メタ)アクリル酸が更に好ましい。
他の単量体としては、例えば、酢酸ビニル、プロピオン酸ビニル等のビニルエステル類、エチレン、プロピレン、イソブチレン等のオレフィン類、塩化ビニル、ビニリデンクロリド等のハロゲン化オレフィン類、スチレン、メチルスチレン、ビニルトルエン等の芳香族ビニル単量体、ブタジエン、イソプレン、クロロプレン等のジエン系単量体、(メタ)アクリロニトリル等のニトリル系単量体等が挙げられる。これらの単量体は、単独で又は2種以上を組み合わせて用いてもよい。
また、重合反応に際し、重合開始剤を用いてもよい。重合開始剤としては、例えば、アゾビスイソブチロニトリル、ベンゾイルパーオキサイド等が挙げられる。これらの重合開始剤の配合量としては、単量体混合物100質量部に対し、好ましくは0.01~1質量部、より好ましくは0.1~0.5質量部である。
また、重合条件としては、特に限定されないが、重合温度50~90℃で、反応時間2~30時間の条件で行われることが好ましい。
なお、本発明において、重量平均分子量(Mw)は、ゲルパーミエーションクロマトグラフィー(GPC)法により測定した標準ポリスチレン換算の値を意味し、具体的には実施例に記載の方法により測定された値を意味する(以下同じ)。
本発明で用いられる粘着剤は、(B)ウレタン樹脂(以下、「(B)成分」ともいう)を含有する。粘着剤が(B)ウレタン樹脂を含有することで、粘着剤層を薄膜化しても十分に高い粘着力を得ることができる。
本発明において、(A)アクリル系共重合体と(B)ウレタン樹脂との質量比〔(A)/(B)〕は、適度な弾性率を有する粘着剤を得て、粘着剤層を薄膜化しても十分な粘着力を得る観点から、好ましくは1/99~40/60、より好ましくは5/95~30/70、更に好ましくは10/90~25/75である。(B)成分に対する(A)成分の割合を示す当該質量比が1/99以上であれば、弾性率が低くなりすぎることによる粘着力の低下を回避することができ、40/60以下であれば、弾性率が高くなりすぎることによる粘着力の低下を回避することできる。
(b1)ポリオールとしては、例えば、1,3-プロパンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、ネオペンチルグリコール、1,6-ヘキサンジオール、1,7-ヘプタンジオール等のアルカンジオール、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール等のアルキレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリブチレングリコール等のポリアルキレングリコール、ポリテトラメチレングリコール等のポリオキシアルキレングリコールが挙げられる。なお、これらの(b1)ポリオールは、単独で又は2種以上組み合わせて用いてもよい。
これらの(b1)ポリオールの中でも、得られる末端イソシアネートウレタンプレポリマーと(b3)鎖延長剤との反応においてゲル化を抑制する観点から、重量平均分子量1,000~3,000の中分子量のグリコールが好ましく、重量平均分子量1,000~3,000のポリアルキレングリコールがより好ましい。
芳香族ポリイソシアネートとしては、例えば、1,3-フェニレンジイソシアネート、1,4-フェニレンジイソシアネート、4,4’-ジフェニルメタンジイソシアネート、2,4-トリレンジイソシアネート、2,6-トリレンジイソシアネート、4,4’-トルイジンジイソシアネート、2,4,6-トリイソシアネートトルエン、1,3,5-トリイソシアネートベンゼン、ジアニシジンジイソシアネート、4,4’-ジフェニルエーテルジイソシアネート、4,4’,4”-トリフェニルメタントリイソシアネート、1,4-テトラメチルキシリレンジイソシアネート、1,3-テトラメチルキシリレンジイソシアネート等が挙げられる。
脂肪族ポリイソシアネートとしては、例えば、トリメチレンジイソシアネート、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、ペンタメチレンジイソシアネート、1,2-プロピレンジイソシアネート、2,3-ブチレンジイソシアネート、1,3-ブチレンジイソシアネート、ドデカメチレンジイソシアネート、2,4,4-トリメチルヘキサメチレンジイソシアネート等が挙げられる。
脂環式ポリイソシアネートとしては、例えば、3-イソシアネートメチル-3,5,5-トリメチルシクロヘキシルイソシアネート、1,3-シクロペンタンジイソシアネート、1,3-シクロヘキサンジイソシアネート、1,4-シクロヘキサンジイソシアネート、メチル-2,4-シクロヘキサンジイソシアネート、メチル-2,6-シクロヘキサンジイソシアネート、4,4’-メチレンビス(シクロヘキシルイソシアネート)、1,4-ビス(イソシアネートメチル)シクロヘキサン、1,4-ビス(イソシアネートメチル)シクロヘキサン等が挙げられる。
なお、これらの(b2)多価イソシアネート化合物は、上記ポリイソシアネートのトリメチロールプロパンアダクト型変性体、水と反応させたビュウレット型変性体、イソシアヌレート環を含有させたイソシアヌレート型変性体であってもよい。
(b1)と(b2)成分の配合比は、末端をイソシアネート基とする観点から、NCO基/OH基(モル比)が、好ましくは1.1~3.0、より好ましくは1.2~2.5となるように配合して反応させることが好ましい。1.1以上であれば、ゲル化を避けることができるため、増粘する傾向を抑制することができる。一方、3.0以下であれば、末端イソシアネートウレタンプレポリマー中の未反応多価イソシアネート化合物濃度が高くなり過ぎず、後述する(b3)鎖延長剤との反応をスムーズに進行させることができる。
3級アミン系化合物としては、トリエチルアミン、トリエチレンジアミン、N,N-ジメチルベンジルアミン、N-メチルモルホリン、1,8-ジアザビシクロ[5.4.0]ウンデセン-7(DBU)等が挙げられる。
有機金属系化合物としては、錫系化合物、非錫系化合物が挙げられる。
錫系化合物としては、例えば、ジブチル錫ジクロリド、ジブチル錫オキシド、ジブチル錫ジブロミド、ジブチル錫ジマレエート、ジブチル錫ジラウレート(DBTDL)、ジブチル錫ジアセテート、ジブチル錫スルフィド、トリブチル錫スルフィド、トリブチル錫オキシド、トリブチル錫アセテート、トリエチル錫エトキシド、トリブチル錫エトキシド、ジオクチル錫オキシド、トリブチル錫クロリド、トリブチル錫トリクロロアセテート、2-エチルヘキサン酸錫等が挙げられる。
非錫系化合物としては、例えば、ジブチルチタニウムジクロリド、テトラブチルチタネート、ブトキシチタニウムトリクロリド等のチタン系化合物、オレイン酸鉛、2-エチルヘキサン酸鉛、安息香酸鉛、ナフテン酸鉛等の鉛系化合物、2-エチルヘキサン酸鉄、鉄アセチルアセトネート等の鉄系化合物、安息香酸コバルト、2-エチルヘキサン酸コバルト等のコバルト系化合物、ナフテン酸亜鉛、2-エチルヘキサン酸亜鉛等の亜鉛系化合物、ナフテン酸ジルコニウム等が挙げられる。
これらの触媒の中でも、DBTDL、2-エチルヘキサン酸錫、テトラブチルチタネートが好ましく、DBTDLがより好ましい。なお、これらの触媒は、単独で又は2種以上組み合わせて用いてもよい。
(b3)鎖延長剤は、(b4)水酸基及び/又はアミノ基を2つ有する化合物及び(b5)水酸基及び/又はアミノ基を3つ以上有する化合物を含有し、(b4)成分と(b5)成分とを質量比〔(b4)/(b5)〕で70/30~100/0の割合で反応させてなるものである。なお、「水酸基及び/又はアミノ基を2つ有する化合物」とは、水酸基及びアミノ基から選ばれる官能基を2つ有する化合物をいい、「水酸基及び/又はアミノ基を3つ以上有する化合物」とは、水酸基及びアミノ基から選ばれる官能基を3つ以上有する化合物をいう。
脂肪族ジオールとしては、例えば、1,3-プロパンジオール、1,4-ブタンジオール、1,5-ペンタンジオール、ネオペンチルグリコール、1,6-ヘキサンジオール、1,7-ヘプタンジオール等のアルカンジオール、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール等のアルキレングリコールが挙げられる。
脂肪族ジアミンとしては、例えば、エチレンジアミン、1,3-プロパンジアミン、1,4-ブタンジアミン、1,5-ペンタンジアミン、1,6-ヘキサンジアミン等が挙げられる。
アルカノールアミンとしては、例えば、モノエタノールアミン、モノプロパノールアミン、イソプロパノールアミン等が挙げられる。
ビスフェノールとしては、例えば、ビスフェノールA等が挙げられる。
芳香族ジアミンとしては、例えば、ジフェニルメタンジアミン、トリレンジアミン、キシリレンジアミン等が挙げられる。なお、これらの化合物は、単独で又は2種以上組み合わせて用いてもよい。
また、上記のうち、(b4)成分としては脂肪族ジオールがより好ましく、アルカンジオールが更に好ましい。また、上記のうち、(b5)成分としてはポリオールがより好ましく、トリメチロールプロパンが更に好ましい。
配合する(b4)成分と(b5)成分との質量比〔(b4)/(b5)〕は、70/30~100/0であり、好ましくは75/25~95/5、より好ましくは80/20~90/10である。(b5)成分に対する(b4)成分の割合を示す当該質量比が70/30以上であれば、粘着剤層を薄膜化しても、粘着力の低下を抑えることができ、また、ウレタン樹脂を得る鎖延長反応の際、ゲル化を回避でき、所望の粘着剤を得ることができる。
溶剤としては、前記の末端イソシアネートウレタンプレポリマー生成反応に用い得るものと同様の溶剤を使用することができる。
なお、鎖延長反応における反応時間は、例えば、反応温度を40~80℃にした場合、好ましくは1~20時間である。
末端停止剤としては、例えば、イソシアネート基と反応可能な水素を1つだけ有する化合物又はアミノ基を1つだけ有する化合物が挙げられる。
イソシアネート基と反応可能な水素を1つだけ有する化合物としては、例えば、メタノール、エタノール等のモノオール化合物が挙げられる。
アミノ基を1つだけ有する化合物としては、1級アミノ基又は2級アミノ基を1つだけ有する化合物を使用することができ、例えば、ジエチルアミン、モルホリン等が挙げられる。
1級アミノ基を1つだけ有する化合物は、反応可能な水素を2つ有しているが、1つの反応可能な水素が反応した後に残った反応可能な水素は反応性が低いので、実質的に単官能と同等となる。
末端停止剤の添加量は、鎖延長反応後に残存する末端イソシアネート基の1モルに対して、末端停止剤が1モル以上2モル以下となる割合であることが好ましい。末端停止剤の添加量が1モル以上であれば、停止反応後にイソシアネート基が残らないため、得られるウレタン樹脂が安定である。一方、末端停止剤の添加量が2モル以下であれば、低分子量のウレタン樹脂が少なくなる傾向にある。
本発明で用いられる粘着剤は、(A)成分として架橋性官能基を有するアクリル系共重合体を用いる場合、凝集力を高めて所望の粘着力を得る観点から、(A)成分中の架橋性官能基と反応しうる架橋剤を含有することが好ましい。
架橋剤としては、イソシアネート系架橋剤、エポキシ系架橋剤、アジリジン系架橋剤、金属キレート系架橋剤及びアミン系架橋剤、アミノ樹脂系架橋剤等が挙げられる。
なお、多価イソシアネート化合物は、上記化合物のトリメチロールプロパンアダクト型変性体、水と反応させたビュウレット型変性体、イソシアヌレート環を含むイソシアヌレート型変性体であってもよい。
分子中に2つ以上のグリシジル基を含む多官能性エポキシ化合物としては、例えば、ビスフェノールAのジグリシジルエーテル及びそのオリゴマー、水素化ビスフェノールAのジグリシジルエーテル及びそのオリゴマー、オルソフタル酸ジグリシジルエステル、イソフタル酸ジグリシジルエステル、テレフタル酸ジグリシジルエステル、p-オキシ安息香酸グリシジルエステル、テトラハイドロフタル酸ジグリシジルエステル、ヘキサハイドロフタル酸ジグリシジルエステル、コハク酸ジグリシジルエステル、アジピン酸ジグリシジルエステル、セバシン酸ジグリシジルエステル、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、1,4-ブタンジオールジグリシジルエーテル、1,6-ヘキサンジオールジグリシジルエーテル及びポリアルキレングリコールジグリシジルエーテル類、トリメリット酸トリグリシジルエステル、トリグリシジルイソシアヌレート、1,4-ジグリシジルオキシベンゼン、ジグリシジルプロピレン尿素、グリセロールトリグリシジルエーテル、トリメチロールプロパンジ又はトリグリシジルエーテル、ペンタエリスリトールジ又はトリグリシジルエーテル、グリセロールアルキレンオキサイド付加物のトリグリシジルエーテル、ジグリシジルアニリン等のジグリシジルアミン等が挙げられる。
本発明で用いられる粘着剤には、本発明の効果を損なわない範囲で、その他の成分を配合することができる。その他の成分としては、例えば、紫外線吸収剤、酸化防止剤、防腐剤、防黴剤、可塑剤、消泡剤及び濡れ性調整剤等が挙げられる。
本発明の難燃粘着シートは、例えば図1(b)に示すように、粘着剤層の上に剥離シートが積層されたものであってもよい。
本発明の難燃粘着シートに用いられる剥離シートとしては、特に制限が無いが、取り扱い易さの観点から、シート基材上に剥離剤を塗布した剥離シートが好ましい。剥離シートは、シート基材の両面に剥離剤が塗布され剥離処理がされたものでもよく、シート基材の片面のみに剥離剤が塗布され剥離処理がされたものでもよい。
剥離シートに用いられるシート基材としては、例えば、グラシン紙、コート紙、キャストコート紙等の紙基材、これらの紙基材にポリエチレン等の熱可塑性樹脂をラミネートしたラミネート紙、又はポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート等のポリエステルフィルム、ポリプロピレンやポリエチレン等のポリオレフィンフィルム等のプラスチックフィルム等が挙げられる。
剥離剤としては、例えば、オレフィン系樹脂、イソプレン系樹脂、ブタジエン系樹脂等のゴム系エラストマー、長鎖アルキル系樹脂、アルキド系樹脂、フッ素系樹脂、シリコーン系樹脂等が挙げられる。
剥離シートにおける剥離剤からなる層の乾燥後の厚さとしては、特に限定されないが、剥離剤を溶液状態で塗布する場合は、好ましくは0.01~2.0μm、より好ましくは0.03~1.0μmである。剥離シートのシート基材としてプラスチックフィルムを用いる場合、該プラスチックフィルムの厚さは、好ましくは3~50μm、より好ましくは5~40μmである。
本発明の難燃粘着シートの製造方法は、特に限定されない。例えば、図1(a)に示す難燃粘着シート1aであれば、基材11の一方の面上に、粘着剤を塗布し、乾燥させて粘着剤層12aを形成して作製することができる。また、図1(b)に示す難燃粘着シート1bであれば、剥離シート13aの面上に、粘着剤を塗布し、乾燥させて粘着剤層12aを形成した後、該粘着剤層12a上に、基材11を貼り合わせ、片面粘着シートを作製する。
図1(c)に示す両面難燃粘着シート1cであれば、基材11の一方の面上に、粘着剤を塗布し、乾燥させて粘着剤層12aを形成した後、基材11の他方の面上に、同様に粘着剤を塗布し、乾燥させて粘着剤層12bを形成して作製することができる。
用いる有機溶媒としては、トルエン、酢酸エチル、メチルエチルケトン等が挙げられる。これらの有機溶媒を配合して、適度な固形分濃度の粘着剤溶液とすることで、薄膜化した粘着剤層を形成することができる。粘着剤の固形分濃度は、好ましくは5~60質量%、より好ましくは10~40質量%である。5質量%以上であれば、溶剤の使用量としては十分であり、60質量%以下であれば、粘着剤溶液が適度な粘度となり、該粘着剤溶液を塗布するに際して作業性が良好となる。
なお、上記粘着剤に用いられる前記(A)アクリル系共重合体及び/又は(B)ウレタン樹脂を有機溶媒に含有された状態で用いる場合、同じ有機溶媒を用いて希釈し、上記固形分濃度となるように粘着剤溶液を調製してもよい。
塗布方法としては、例えば、スピンコート法、スプレーコート法、バーコート法、ナイフコート法、ロールコート法、ブレードコート法、ダイコート法、グラビアコート法等の公知の方法が挙げられる。
また、溶剤や低沸点成分の残留を防ぐと共に、架橋剤が配合されている場合には架橋(反応)を進行させて粘着性を発現するために、基材や剥離シートに塗布した後、加熱処理をすることが好ましい。
加熱処理の温度条件は、好ましくは70~150℃、より好ましくは80~120℃である。加熱処理の処理時間は、好ましくは30秒~5分間、より好ましくは40~180秒間である。
以上のようにして作製される本発明の難燃粘着シートの常温(23℃、50%RH(相対湿度))での粘着力は、実施例に記載の測定方法において、3.0N/25mm以上のものとなる。
また、上記難燃粘着シートは、UL94規格に準ずる試験においてVTM-0に適合する難燃性を有するものとなる。該難燃性は、具体的には実施例に記載の方法により測定することができる。
(測定条件)
カラム:「TSK gel GMHXL(×2)」「TSK gel G2000HXL」(いずれも東ソー株式会社製)
カラム温度:40℃
展開溶媒:テトラヒドロフラン
流速:1.0mL/分
検出器:示差屈折計
(アクリル系共重合体溶液の調製)
単量体成分として、アクリル酸ブチル90質量部、及びアクリル酸10質量部、溶剤として、酢酸エチル200質量部、重合開始剤として、アゾビスイソブチロニトリル0.2質量部を反応器に入れ混合した。4時間窒素ガスで脱気を行い、60℃まで徐々に昇温した後、24時間撹拌しながら重合反応を行い、重量平均分子量が65万のアクリル系共重合体を含む酢酸エチル溶液(固形分濃度33質量%)を得た。
(ウレタン樹脂溶液(B-1)の調製)
(b1)ポリオールとしてポリプロピレングリコール(重量平均分子量:2,000)100質量部、(b2)多価イソシアネート化合物としてヘキサメチレンジイソシアネート10.1質量部(NCO基/OH基(モル比)=1.2)、触媒としてジブチル錫ジラウレート0.01質量部を混合し、85℃まで徐々に昇温した後に2時間撹拌し、末端イソシアネートウレタンプレポリマーを得た。
得られた末端イソシアネートウレタンプレポリマーに、トルエン110質量部を加え室温まで除冷した後に、(b3)鎖延長剤として、(b4)1,4-ブタンジオール0.60質量部を滴下し、70℃まで徐々に昇温した後、2時間撹拌し、重量平均分子量17万のウレタン樹脂のトルエン溶液(B-1;固形分濃度50質量%)を得た。組成等を表1に示す。
(ウレタン樹脂溶液(B-2)の調製)
製造例1において、(b3)鎖延長剤として、(b4)1,4-ブタンジオールの使用量を0.48質量部とし、さらに(b5)トリメチロールプロパン0.12質量部を加えた以外は、製造例2と同様にして、重量平均分子量14万のウレタン樹脂のトルエン溶液(B-2;固形分濃度50質量%)を得た。組成等を表1に示す。
(難燃粘着シートの作製)
製造例1で得たアクリル系共重合体含有酢酸エチル溶液25質量部(固形分)と、製造例2で得たウレタン樹脂含有トルエン溶液(B-1)100質量部(固形分)と、架橋剤として、イソシアネート系架橋剤(日本ポリウレタン株式会社製、商品名「コロネートL」、トリメチロールプロパン変性トリレンジイソシアネートの酢酸エチル溶液(固形分75質量%))2.25質量部(固形分)との混合物を、固形分濃度が10質量%となるように酢酸エチルで希釈し、粘着剤溶液を調製した。
この溶液を、剥離シートである、シリコーン処理された38μmポリエステルフィルム(リンテック株式会社製、商品名「SP-PET381031」)に、乾燥後の粘着剤層の厚さが1.0μmとなるように塗布し、100℃で1分間乾燥した後に、基材である、両面にポリイミド樹脂がコートされたポリエチレンテレフタレート(PET)フィルム(東レ株式会社製、商品名「ルミラーZV10#25」、厚み:30μm、UL94規格に準ずる試験においてVTM-0に適合)に転写し、難燃粘着シートを作製した。
なお、難燃粘着シートの各層の厚みならびに総厚みは、シート断面を電子顕微鏡(株式会社キーエンス製、商品名「VHX-1000」)で観測することで測定した。
作製した上記難燃粘着シートの剥離シートを剥離し、アンダーラボラトリーズ社発行のプラスチック材料の難燃性試験規格UL94の薄手材料垂直燃焼試験方法に準ずる試験を行い、VTMランクを判定した。評価に用いた難燃粘着シートのサンプルサイズは50mm×200mmであり、粘着剤層を外側にして試験を行った。
なお、VTMランクの判定基準は下記の通りである。
VTM-0;サンプルの燃焼時間が10秒以内であり、かつ燃焼物又は落下物による脱脂綿の着火が起こらず、更に標線(サンプル下端より125mmの位置)までの燃焼が認められない。
VTM-1;サンプルの燃焼時間が30秒以内であり、かつ燃焼物又は落下物による脱脂綿の着火が起こらず、更に標線までの燃焼が認められない。
VTM-2;サンプルの燃焼時間が30秒以内であり、かつ標線までの燃焼が認められない。
評価結果を表2に示す。なお、表2において、VTM-0に適合したものを「VTM-0」、VTM-0に適合せずVTM-1に適合したものを「VTM-1」、VTM-0ならびにVTM-1に適合せずVTM-2に適合したものを「VTM-2」、VTM-0とVTM-1とVTM-2のいずれにも適合しなかったものを「不合格」とした。
基材として「ルミラーZV10#25」の代わりに25μmポリエステルフィルム(三菱樹脂株式会社製、商品名「T-100」)を用いたこと以外は、前記と同様の方法で、粘着力試験用の粘着シートを作製した。
剥離シートを剥離し、23℃、50%RH環境下で、25mm×300mmにカットした上記粘着シートの試験片を被着体(SUS304鋼板)に貼付して、粘着力試験用サンプルとした。JIS Z0237に基づき、貼付24時間後の粘着力を、180°引き剥がし法により、引張り速度300mm/分にて測定した。評価結果を表2に示す。
基材及び粘着剤層を表2に記載のとおりに変更したこと以外は、実施例1と同様の方法で粘着シートを作製した。また、実施例1と同様の方法で難燃性評価及び粘着力試験を行った。評価結果を表2に示す。
一方、比較例5及び7で得られた粘着シートは、粘着剤層を構成する粘着剤が(A)成分又は(B)成分を含有しないため粘着力が不十分であった。また、比較例1~4、6及び8~12で得られた粘着シートは、粘着剤層の総厚みが2.2μmを超えるためいずれも十分な難燃性が得られなかった。
比較例13で得られた粘着シートは、粘着剤層を構成する粘着剤が難燃剤であるメラミンシアヌレートを含有しているため粘着力が不十分であり、比較例14で得られた粘着シートは、粘着剤層の片面あたりの厚みが0.6μm未満であるため粘着力が不十分であった。
11 基材
12a、12b 粘着剤層
13a 剥離シート
Claims (10)
- 基材の少なくとも片面に粘着剤層を有する難燃粘着シートであって、
前記基材が、UL94規格に準ずる試験においてVTM-0に適合する難燃性を有し、
前記粘着剤層の片面あたりの厚みが0.6μm以上でかつ該粘着剤層の総厚みが2.2μm以下であり、
該粘着剤層を構成する粘着剤が、難燃剤を含有せず、(A)アクリル系共重合体と、(B)ウレタン樹脂とを含有し、
(B)ウレタン樹脂が、(b1)ポリオールと(b2)多価イソシアネート化合物とを反応させて得られる末端イソシアネートウレタンプレポリマーに、(b3)鎖延長剤を反応させて得られるものであり、(b3)鎖延長剤が、(b4)水酸基及び/又はアミノ基を2つ有する化合物及び(b5)水酸基及び/又はアミノ基を3つ以上有する化合物を含有し、(b4)成分と(b5)成分とを質量比〔(b4)/(b5)〕で70/30~100/0の割合で反応させてなるウレタン樹脂である、難燃粘着シート。 - 基材が、ハロゲン系難燃剤及びリン系難燃剤のいずれも含有しない基材である、請求項1に記載の難燃粘着シート。
- 基材が、難燃剤を含有しない基材である、請求項1に記載の難燃粘着シート。
- 基材が、ポリイミド樹脂、ポリアラミド樹脂、ポリフェニレンサルファイド樹脂、又はポリエーテルエーテルケトン樹脂からなる基材、又はこれらの樹脂がコートされた基材である、請求項1~3のいずれかに記載の難燃粘着シート。
- (b1)ポリオールが、重量平均分子量1,000~3,000のグリコールである、請求項1~4のいずれかに記載の難燃粘着シート。
- 粘着剤層を構成する粘着剤が、さらに(C)架橋剤を含有し、かつ(A)アクリル系共重合体が、該(C)架橋剤と反応しうる架橋性官能基を有する、請求項1~5のいずれかに記載の難燃粘着シート。
- 架橋性官能基が、カルボキシ基及び/又は水酸基である、請求項6に記載の難燃粘着シート。
- (C)架橋剤が、イソシアネート系架橋剤である、請求項6又は7に記載の難燃粘着シート。
- (A)アクリル系共重合体と(B)ウレタン樹脂との質量比〔(A)/(B)〕が、1/99~40/60である、請求項1~8のいずれかに記載の難燃粘着シート。
- (A)アクリル系共重合体の重量平均分子量(Mw)が、30万~150万である、請求項1~9のいずれかに記載の難燃粘着シート。
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JP2013512678A JP5319857B1 (ja) | 2011-09-22 | 2012-09-07 | 難燃粘着シート |
CN201280031415.4A CN103635553B (zh) | 2011-09-22 | 2012-09-07 | 难燃粘着片 |
EP12833616.1A EP2752474B1 (en) | 2011-09-22 | 2012-09-07 | Flame retardant adhesive sheet |
US14/129,716 US9150760B2 (en) | 2011-09-22 | 2012-09-07 | Flame retardant adhesive sheet |
KR1020137034491A KR101443005B1 (ko) | 2011-09-22 | 2012-09-07 | 난연 점착 시트 |
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WO2013042560A1 true WO2013042560A1 (ja) | 2013-03-28 |
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PCT/JP2012/072978 WO2013042560A1 (ja) | 2011-09-22 | 2012-09-07 | 難燃粘着シート |
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US (1) | US9150760B2 (ja) |
EP (1) | EP2752474B1 (ja) |
JP (1) | JP5319857B1 (ja) |
KR (1) | KR101443005B1 (ja) |
CN (1) | CN103635553B (ja) |
TW (1) | TWI441895B (ja) |
WO (1) | WO2013042560A1 (ja) |
Cited By (1)
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JP2016117854A (ja) * | 2014-12-22 | 2016-06-30 | リンテック株式会社 | 粘着シート |
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JP5785861B2 (ja) * | 2011-11-30 | 2015-09-30 | リンテック株式会社 | 難燃粘着シート |
KR101730462B1 (ko) * | 2015-03-20 | 2017-05-11 | 토요잉크Sc홀딩스주식회사 | 점착제 및 점착 테이프 |
CN109476909B (zh) * | 2016-07-26 | 2021-04-23 | Dic株式会社 | 树脂组合物和层叠体 |
DE102016225906A1 (de) * | 2016-12-21 | 2018-06-21 | Tesa Se | Klebeband mit Flammschutzeigenschaften |
US20210130658A1 (en) * | 2017-10-31 | 2021-05-06 | Teraoka Seisakusho Co., Ltd. | Adhesive tape |
CN108314973A (zh) * | 2018-03-19 | 2018-07-24 | 深圳昌茂粘胶新材料有限公司 | 一种防火阻燃泡棉双面胶材料及其制备方法 |
CN110577803B (zh) | 2018-06-11 | 2021-11-26 | 3M创新有限公司 | 一种阻燃压敏胶粘合剂、阻燃压敏胶粘合片及其制备方法 |
CN109679546A (zh) * | 2018-09-29 | 2019-04-26 | 乐平市力邦化工有限公司 | 一种阻燃型氯丁/酚醛胶粘剂及其制备方法 |
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JPWO2013042560A1 (ja) | 2015-03-26 |
TWI441895B (zh) | 2014-06-21 |
JP5319857B1 (ja) | 2013-10-16 |
CN103635553B (zh) | 2016-05-11 |
US20140134414A1 (en) | 2014-05-15 |
EP2752474A1 (en) | 2014-07-09 |
US9150760B2 (en) | 2015-10-06 |
EP2752474B1 (en) | 2016-04-06 |
KR20140009588A (ko) | 2014-01-22 |
TW201317318A (zh) | 2013-05-01 |
EP2752474A4 (en) | 2015-04-29 |
CN103635553A (zh) | 2014-03-12 |
KR101443005B1 (ko) | 2014-09-22 |
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