WO2006051952A1 - 複合材 - Google Patents
複合材 Download PDFInfo
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- WO2006051952A1 WO2006051952A1 PCT/JP2005/020875 JP2005020875W WO2006051952A1 WO 2006051952 A1 WO2006051952 A1 WO 2006051952A1 JP 2005020875 W JP2005020875 W JP 2005020875W WO 2006051952 A1 WO2006051952 A1 WO 2006051952A1
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- Prior art keywords
- composite material
- alloy
- thermoplastic elastomer
- room temperature
- mass
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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
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
- B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
- B29C45/14778—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the article consisting of a material with particular properties, e.g. porous, brittle
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
- C22C18/04—Alloys based on zinc with aluminium as the next major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2221/00—Use of unspecified rubbers as reinforcement
- B29K2221/003—Thermoplastic elastomers
Definitions
- the present invention relates to a polymer'metal composite material comprising a combination of a thermoplastic elastomer or a composition containing the same and an alloy having superplasticity at room temperature. More specifically, the present invention relates to a polymer 'metal composite material having properties such as flexibility and workability possessed by a polymer compound and properties such as conductivity, gas barrier property, moisture barrier property and electromagnetic wave shielding property possessed by a metal. Relates to a composite material having a combined force of a cured product of an active energy ray-curable resin composition and an alloy having superplasticity at room temperature.
- Patent Document 1 Japanese Patent No. 3194185
- Patent Document 2 Japanese Patent No. 2972481
- Patent Document 3 Japanese Patent No. 2790568
- Patent Document 4 Japanese Patent Publication No. 7-81179
- Patent Document 5 Japanese Patent No. 2564387
- the present invention has been made in view of the above circumstances, and has characteristics such as flexibility, workability, and conductivity, gas barrier properties, moisture barrier properties, and electromagnetic wave shielding properties of metals. It aims at providing the composite material which has.
- the present inventors have found that a polymer molded body using a thermoplastic elastomer and a thin film made of an alloy having superplasticity at room temperature on the surface thereof. It has been found that the above object can be achieved by a polymer / metal composite material having the following. In addition, it is seen that the above object is achieved by a composite material in which a thin film made of a superplastic plastic alloy at room temperature is laminated on a base material made of a cured product of an active energy ray-curable resin composition. Issued. The present invention has been completed on the basis of strong knowledge.
- the present invention provides the following composite material.
- a composite material comprising a thermoplastic molded body made of a thermoplastic elastomer or a composition containing the same, and a thin film made of an alloy having superplasticity at room temperature on the surface thereof.
- composition is a composition in which 0.1 to 50 parts by mass of polyolefin resin and 0 to 500 parts by mass of a softening agent are mixed with 100 parts by mass of a thermoplastic elastomer.
- Thermoplastic Elastomer The composite material according to 1 or 2 above, which is a polystyrene-based thermoplastic elastomer.
- SIBS Styrene-isobutylene-styrene block copolymer
- SEBS styrene ethylene Z butylene styrene block copolymer
- SEPS styrene ethylene Z propylene styrene block copolymer
- thermoplastic elastomer 80 ° or less according to JIS-A standards.
- the composite material according to 7 above which is an active energy ray-curable resin composition and a composition mainly comprising acrylic-modified urethane.
- the thickness of the thin film made of superplastic alloy at room temperature is ⁇ !
- An alloy that has superplasticity at room temperature is a Zn—A1 alloy containing Zn: 30-80% by mass, the balance being A1 and inevitable impurities, with an average grain size of 5 ⁇ m or less.
- Zn—A1 alloy consisting of A1 and inevitable impurities, with an average grain size of 5 ⁇ m or less
- a Zn-A1 alloy having a phase or a ′ phase and a ⁇ phase as a main structure, and a structure in which a ⁇ phase having an average crystal grain size of 0.05 m or less is finely dispersed in the ⁇ phase or ⁇ ′ phase.
- the composite material according to any one of 1 to 9.
- the composite material A of the present invention has a polymer molded body made of a thermoplastic elastomer or a composition containing the same and a thin film made of an alloy having superplasticity at room temperature on the surface thereof.
- thermoplastic elastomer is not particularly limited, and is appropriately selected from conventionally known thermoplastic elastomers according to the use of the composite material A.
- thermoplastic elastomer include, for example, polystyrene-based thermoplastic elastomers, polyolefin-based thermoplastic elastomers, polygen-based thermoplastic elastomers, polychlorinated bur-based thermoplastic elastomers, chlorinated polyethylene-based thermoplastic elastomers, and polyurethanes.
- Thermoplastic elastomer, polyester thermoplastic elastomer, polyamide thermoplastic elastomer, fluorine resin And other thermoplastic elastomers are examples of the thermoplastic elastomer.
- thermoplastic elastomer has a hardness of 80 ° or less according to the JIS-A standard.
- these thermoplastic elastomers may be used singly or in combination of two or more, but the surface strength such as balance between physical properties and cache properties is also polystyrene-based thermoplastic. U, who prefers an elastomer.
- the polystyrene-based thermoplastic elastomer has an aromatic vinyl polymer block (hard segment) and a rubber block (soft segment), and the aromatic bullet polymer portion forms a physical crosslink.
- the rubber block provides rubber elasticity.
- aromatic bur compounds that form aromatic bulle polymer blocks include styrene, ⁇ -methyl styrene; a-ethyl styrene; ⁇ -alkyl-substituted styrene such as a -methyl-p-methyl styrene, ⁇ -methyl Styrene; m-methyl styrene; ⁇ -methino styrene; 2, 4 dimethyl styrene; ethyl styrene; 2, 4, 6 trimethino styrene; o- t butino styrene; ⁇ - t butyl styrene; p cyclohexyl Nuclear alkyl-substituted styrene such as styrene, o chlorostyrene; m-chlorostyrene; p-chlorostyrene; p bromostyrene; 2-methyl
- This polystyrene-based thermoplastic elastomer has, for example, styrene butadiene styrene block copolymer (SBS), styrene isoprene styrene block copolymer (SIS), styrene isobutylene styrene block, depending on the arrangement format of the soft segments therein.
- SBS styrene butadiene styrene block copolymer
- SIS styrene isoprene styrene block copolymer
- SIS styrene isobutylene styrene block
- SIBS Lock copolymer
- SEBS styrene ethylene Z butylene styrene block copolymer
- SEPS styrene ethylene Z propylene styrene block copolymer
- Crystalline poly Examples thereof include a diblock copolymer of ethylene and polystyrene.
- SIBS small cell lung disease 2019
- SEBS small cell lung disease 2019
- SEPS small cell lung disease 2019
- composition containing a thermoplastic elastomer, 0.1 to 50 parts by mass of the polyolefin resin and 0.1 to 5 parts by mass of the thermoplastic elastomer with respect to 100 parts by mass of the thermoplastic elastomer.
- a composition containing ⁇ 500 parts by mass is preferred.
- thermoplastic elastomer is as described above, and SIBS, SEBS and S
- the softening agent is blended to reduce the hardness of the thermoplastic elastomer.
- any low molecular weight material with a force average molecular weight of less than 20000 can be selected from those conventionally used as softeners for plastics and rubber.
- Preferred physical properties are those having a viscosity at 100 ° C. of 5 ⁇ 10 2 Pa ′s or less, particularly 1 ⁇ 10 2 Pa ′s or less.
- the number average molecular weight is less than 20000, particularly 10000 or less, particularly 5000 or less.
- a softening agent usually a liquid or liquid at room temperature is preferably used.
- the softening agent having such properties can be appropriately selected from, for example, various types of rubber or mineral oil softeners such as mineral oils and synthetics.
- mineral oils include process oils such as naphthenes and norafines.
- non-aromatic oils especially mineral oils paraffinic oils, naphthenic oils, or synthetic polyisobutylenes are mentioned.
- System oil power One or two or more kinds selected, and those having a number average molecular weight of 450 to 5000 are preferred! /.
- softeners may be used alone or in combination of two or more as long as they have good compatibility with each other.
- the blending amount of these softeners is not particularly limited, but is usually selected in the range of 1 to L000 parts by mass, preferably 1 to 500 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer. If this quantity ⁇ mass part or more, sufficient low hardness can be achieved, the resulting polymer molded body (hereinafter referred to as May be simply referred to as a “molded body”. ), And if it is 1000 parts by mass or less, the softening agent does not bleed and the mechanical strength of the molded article is sufficient.
- the blending amount of the softener is preferably selected within the above range depending on the molecular weight of the thermoplastic elastomer and the type of other components added to the elastomer.
- the elastomer composition according to the present invention may be blended with a polyphenylene ether resin if desired for the purpose of improving the compression set of the molded article.
- polyphenylene ether resin known ones can be used. Specifically, poly (2, 6 dimethyl-1, 4 phenylene ether), poly (2-methyl-6 ethyl 1, 4-phenylene ether), poly (2, 6 diphenyl 1, 4 phenylene ether), poly (2-methyl 6-phenol 1, 4 phenylene ether), poly (2, 6 dichloro) 1, 4 phenolic ethers), and other copolymer of 2,6 dimethylphenol and monovalent phenols (eg 2, 3, 6 trimethylphenol and 2-methyl-6-butylphenol). Polyphenylene ether copolymers such as these can also be used. Of these, poly (2, 6 dimethyl-1,4 phenol ether) and copolymers of 2, 6 dimethyl phenol and 2, 3, 6 trimethyl phenol are preferred. , 4 phenol ether) is preferred.
- the blending amount of the polyphenylene ether resin can be suitably selected in the range of 10 to 250 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer.
- the blending amount is 250 parts by mass or less, the hardness of the obtained molded body is not excessively high and becomes moderate, and when it is 10 parts by mass or more, the effect of improving the compression set of the molded body obtained by blending is obtained. It will be enough.
- thermoplastic elastomer according to the present invention or a composition containing the thermoplastic elastomer includes clay, diatomaceous earth, silica, talc, barium sulfate, calcium carbonate, magnesium carbonate, metal oxide, my strength, graphite, Flaky inorganic additives such as aluminum hydroxide, various metal powders, glass powders, ceramic powders, granular or powdered solid fillers such as granular or powdered polymers, and other various natural or artificial shorts Fibers, long fibers (various polymers, fibers, etc.) can be blended.
- clay diatomaceous earth
- silica silica
- talc barium sulfate
- calcium carbonate calcium carbonate
- magnesium carbonate magnesium carbonate
- metal oxide metal oxide
- my strength graphite
- Flaky inorganic additives such as aluminum hydroxide, various metal powders, glass powders, ceramic powders, granular or powdered solid fillers such as granular or powdered poly
- hollow organic fillers such as inorganic hollow fillers such as glass balloons and silica balloons, polyvinylidene fluoride, polyvinylidene fluoride copolymers, etc.
- inorganic hollow fillers such as glass balloons and silica balloons
- polyvinylidene fluoride polyvinylidene fluoride copolymers
- gas can be mixed mechanically during mixing.
- thermoplastic elastomer according to the present invention or a composition containing the same may be used in combination with additives such as a known rosin component in order to improve various properties.
- a resin component for example, polyolefin resin, polystyrene resin, etc. can be used alone or in combination. By adding these, the workability and heat resistance of the elastomer composition according to the present invention can be improved.
- Polyolefin resins include, for example, polyethylene, isotactic polypropylene, a copolymer of propylene and a small amount of ⁇ -aged refin (for example, propylene-ethylene copolymer, propylene-methyl-4-pentene copolymer). Polymer), poly (4-methyl-1-pentene), polybutene and the like.
- ⁇ -aged refin for example, propylene-ethylene copolymer, propylene-methyl-4-pentene copolymer.
- Polymer poly (4-methyl-1-pentene
- polybutene polybutene and the like.
- polystyrene resin those obtained by either a radical polymerization method or an ionic polymerization method can be suitably used as long as they are obtained by a known production method.
- the number average molecular weight of polystyrene rosin can be selected from the range of preferably ⁇ 5,000 to 500,000, more preferably ⁇ 10,000 to 20000, and the molecular weight distribution [weight average molecular weight (Mw) and number average molecular weight (Mn) The ratio (MwZMn)] is preferably less than 5! /.
- this polystyrene resin examples include polystyrene, styrene-butadiene block copolymer having a styrene unit content of 60% by mass or more, rubber-reinforced polystyrene, polymethylstyrene, polypt-butylstyrene, and the like. You may use together 1 type, or 2 or more types. Furthermore, a copolymer obtained by polymerizing a mixture of monomers constituting these polymers can also be used.
- the said polyolefin resin and polystyrene resin can also be used together.
- these resins when these resins are added to the elastomer composition according to the present invention, when a polystyrene resin is used in combination as compared with the case of adding a polyolefin resin alone, Hardness tends to increase. Therefore, the hardness of the resulting molded article can be adjusted by selecting these blending ratios. In this case, it is preferable to select a range force of 95Z5 to 5Z95 (mass ratio) for the ratio of polyolefin resin Z-polystyrene resin.
- the blending amount is preferably 0 to about LOO parts by mass with respect to 100 parts by mass of the thermoplastic elastomer,
- the blending amount of the resin component exceeds 100 parts by mass, the hardness of the resulting molded product will not be too high.
- polyolefin resin it is more preferable to blend the above-mentioned softener in an amount of 1 to 500 parts by mass with respect to 100 parts by mass of the thermoplastic elastomer.
- thermoplastic elastomer according to the present invention or a composition containing the thermoplastic elastomer according to the present invention includes, as necessary, other flame retardants, antibacterial agents, hindered amine light stabilizers, ultraviolet absorbers.
- the silicone polymer preferably has a weight average molecular weight of 10,000 or more, preferably 100,000 or more.
- the silicone polymer improves the surface tackiness of a molded product using the elastomeric yarn and the composition.
- the silicone polymer may be a general-purpose thermoplastic polymer such as polyethylene, polypropylene, or polystyrene blended at a high concentration to improve handling.
- blended products with polypropylene have good workability and physical properties.
- a material for example, a material that is easily available as a silicone concentrate BY27 series general-purpose type, which is commercially available from Toray Dow Koung Silicorn Co., Ltd., may be used.
- the surface condition of the molded product can be improved by blending the silicone polymer.
- the miscibility with the thermoplastic elastomer used in the invention is not always good. This can be easily imagined because the chemical composition of each polymer is very different. Therefore, the silicone polymer may be separated depending on the content of the blend and the molding conditions of the molded body.
- a polymer having relatively good miscibility with the above thermoplastic elastomer for example, a graft polymer obtained by chemically bonding a silicone polymer to a polyolefin resin, is used to change the state.
- a material for example, a material marketed as a BY27 series graft type from Toray Dow Cowing Silicone Co., Ltd. may be used.
- the method for producing the elastomer composition according to the present invention is not particularly limited, and a known method can be applied.
- the above components and optional additive components are melted using a heating kneader, such as a single screw extruder, twin screw extruder, roll, Banbury mixer, probender, kneader, high shear mixer, etc. It can be easily produced by kneading and, if desired, adding a crosslinking agent such as organic peroxide, a crosslinking aid or the like, or mixing these necessary components at the same time and heating and kneading them. it can.
- a heating kneader such as a single screw extruder, twin screw extruder, roll, Banbury mixer, probender, kneader, high shear mixer, etc. It can be easily produced by kneading and, if desired, adding a crosslinking agent such as organic peroxide, a crosslinking aid or the like, or mixing
- thermoplastic material prepared by kneading a polymer organic material and a softening agent is prepared in advance, and this material is further mixed with one or more polymer organic materials of the same type or different type from those used here. You can also
- the elastomer composition according to the present invention can be crosslinked by adding a crosslinking agent such as an organic peroxide, a crosslinking aid or the like.
- a crosslinking agent such as an organic peroxide, a crosslinking aid or the like.
- the alloy having superplasticity at room temperature (hereinafter referred to as "room temperature superplastic alloy”) used in the present invention is not particularly limited, and any conventionally known room temperature superplastic alloy may be used. You can select as appropriate.
- superplasticity means the following. That is, many eutectics such as Al-33% Cu (eutectic), Zn-22% A1 (eutectoid), Sn-38% Pb (eutectic), or alloys close to it, have crystal grains In a fine state, the plastic film may exhibit a large plastic deformation with an elongation to break of about 1000%. This is called superplasticity.
- Superplastic alloys are used as a material when large deformation is required, such as drawing.
- Examples of the room temperature superplastic alloy used in the present invention include the following alloys.
- Zinc Al alloy containing 75 to 99% by mass of zinc, the balance being aluminum and inevitable impurities, with the average crystal grain size of 5 ⁇ m or less as a phase or a ′ phase, and ⁇ phase as the main structure
- a Zn—A1 alloy having a structure in which
- the alloys (1) and (2) are Zn-Al alloys described in JP-A-11-222643, and the elongation at room temperature is a value exceeding 160%.
- the thickness of the thin film made of room temperature superplastic alloy is usually about 10 ⁇ m to 5 ⁇ m, preferably from the viewpoint of desired required characteristics, balance between repeated deformation and economy, etc. Is between 50 nm and l ⁇ m.
- the thickness of the polymer molded body made of the thermoplastic elastomer or a composition containing the same is a force depending on the use of the composite material A Usually 0.1 to: about LOmm, preferably 0.5 to 5 mm It is. Furthermore, when the composite material A is used as a tube body, the inner diameter is a force appropriately selected depending on the application, and is usually about 0.1 to 3 mm, preferably 0.5 to 2 mm.
- the composite material A of the present invention is obtained by subjecting the thermoplastic elastomer or a composition containing the thermoplastic elastomer to a conventionally known method such as an extrusion molding method, an injection molding method, a calender molding method, a solution casting method and the like. Can be adopted.
- the composite material A of the present invention is obtained by laminating a thin film made of a room temperature superplastic alloy on a base material made of the above thermoplastic elastomer or a composition containing the thermoplastic elastomer, and then by a conventionally known method, for example, in a tube shape. It may be rolled into a tube body.
- the method for producing the substrate there are no particular restrictions on the method for producing the substrate, and conventionally known methods such as extrusion molding, injection molding, calendar molding, and solution casting can be employed.
- the method of laminating a thin film that also has room temperature superplastic alloy strength is not particularly limited.
- a conventionally known metal such as a vacuum deposition method, a sputtering method, an ion plating method, a plating method, a thermal spraying method, an injection method, etc.
- a thin film lamination method can be applied.
- the composite material B of the present invention is obtained by laminating a thin film made of an alloy having superplasticity at room temperature on a base material made of a cured product of an active energy ray-curable resin composition.
- the active energy ray-curable resin composition used in the composite material B of the present invention include a resin composition mainly composed of acrylic-modified urethane.
- acrylic-modified urethane examples include a polyether polyol urethane acrylate oligomer, a polyester polyol urethane acrylate oligomer, a urethane acrylate oligomer having both an ether group and an ester group in the molecule, and a carbonate having a carbonate group.
- examples thereof include urethane acrylate oligomers of diols.
- Polyether polyols include, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol mononor, 1,3 butylene glycol norole, 1,4-butylene glycol norole, and 1,6 hexanediol.
- Neopentyl glycol, cyclohexane dimethanol, 2,2 bis (4-hydroxycyclohexyl) propane, bisphenol A, etc. can be used in combination with ethylene oxide or propylene oxide.
- Polyester polyol can be obtained by reacting an alcohol component with an acid component.
- a compound or a compound to which ⁇ -force prolatatatone is added may be used as an alcohol component, and a dibasic acid such as adipic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, or an anhydride thereof may be used as an acid component. it can.
- a compound obtained by reacting the above-mentioned alcohol component, acid component, and ⁇ -force prolatatone at the same time can also be used as the polyester polyol.
- Examples of the carbonate diol include diphenyl carbonate, bis-black-mouthed phenolate, dinaphthinorecarbonate, phenolate norenocarbonate, phenenole chlorophenolate carbonate, 2 trinoleate 4 tolyl carbonate, dimethyl carbonate, Dialkyl carbonates such as jetyl carbonate or dialkyl carbonates and diols such as 1, 6 hexane Diol, neopentyl glycol, 1,4 butanediol, 1,8 octanediol, 1,4-cyclohexanedimethanol, 2 methylpropanediol, dipropylene glycol, dibutylene glycol or the above diol compounds and oxalic acid, malonic acid, It can be obtained by an ester exchange reaction with a reaction product of a dicarboxylic acid such as succinic acid, adipic acid, azelaic acid, hexahydrophthal
- the carbonate diol thus obtained is a monocarbonate diol having one carbonate structure in the molecule or a polycarbonate diol having two or more carbonate structures in the molecule.
- particularly preferred acrylic-modified urethane is a urethane acrylate oligomer of polyether polyol and polyester polyol
- examples of the organic diisocyanate include isophorone diisocyanate, 4,4, -dicyclohexylene methacrylate. Diisocyanate and hexamethylene diisocyanate are particularly preferred.
- a known photopolymerization initiator can be blended with the active energy ray-curable resin composition used in the present invention.
- the photopolymerization initiator include benzoin alkyl ethers such as benzoin ethyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; 2, 2 2-hydroxy-1-2-methylpropiophenone, 4′-isopropyl-2-hydroxy-1-2-methylpropiophenone, 4′dodecyl-2-hydroxy 2-methylpropiophenone, etc .; benzyldimethyl ketal Anthraquinone series such as 1-hydroxycyclohexyl phenol ketone, 2-ethyl anthraquinone, 2-chloro anthraquinone and the like; and thixanthone series photopolymerization initiators can also be mentioned.
- photopolymerization initiators may be used alone or in combination of two or more.
- the blending amount is preferably 1 to 3 parts by mass, more preferably 0.5 to 5 parts by mass per 100 parts by mass of the acrylic-modified urethane as the main component.
- the viscosity at a temperature of 23 ° C and a shear rate of 1.0 Z seconds is usually about 100 to 10,000 Pa's, preferably 200 to 5000 Pa's. More preferably, it is 500 to 1000 Pa's. When this viscosity is lOOPa's or more, the fluidity does not become too large and the shape of the substrate can be maintained.
- the shape shaping of the substrate is good.
- the thickness of the thin film made of room temperature superplastic alloy is usually about 10 ⁇ m to 5 ⁇ m, preferably from the viewpoint of desired required characteristics, balance between repeated deformation and economic efficiency. Is between 50 nm and l ⁇ m.
- the thickness of the base material which is a cured product of the active energy ray-curable resin composition, is a force depending on the use of the resulting composite material B.
- LOmm preferably about 0. 5 to 5 mm.
- the composite material B of the present invention is obtained by laminating a thin film made of a room temperature superplastic alloy on a base material made of a cured product of an active energy ray-curable resin composition.
- a method for producing a base material there is no particular limitation.
- an active energy ray-curable resin composition is extruded to form an uncured resin base material having a predetermined thickness.
- a method of producing a cured resin base material by irradiating active energy rays from an active energy line irradiation device can be employed.
- Active energy rays used for curing include ultraviolet rays and electron beams, ⁇ rays, j8 rays, ⁇ rays, etc. Ionizing radiation.
- the resin composition contains a photopolymerization initiator and Z or a photosensitizer.
- ionizing radiation such as an electron beam or ⁇ -ray
- curing can proceed promptly without containing a photopolymerization initiator or a photosensitizer.
- the ultraviolet light source include a xenon lamp, a low pressure mercury lamp, a high pressure mercury lamp, and an ultrahigh pressure mercury lamp.
- an inert gas atmosphere such as nitrogen gas or carbon dioxide gas or an atmosphere with a reduced oxygen concentration is preferred, and the ultraviolet curable resin composition can be cured even in a normal air atmosphere.
- the irradiation atmosphere temperature can usually be 10-200 ° C.
- the method of laminating a thin film that also has room temperature superplastic alloy strength is not particularly limited.
- a conventionally known metal such as a vacuum deposition method, a sputtering method, an ion plating method, a plating method, a thermal spraying method, an injection method, etc.
- a thin film lamination method can be applied.
- Applications of the composite material of the present invention include, for example, the automobile field, the air conditioner and refrigerator fields, the printer field, the painting field, the medical 'pharmaceutical field, the food field, etc., or the fluid in general households. It is suitable as a transport tube body. Specifically, it is used as an automobile fuel hose, torque converter hose, power steering hose, air conditioner hose, refrigeration machine hose, paint transport hose, propane gas hose, general household rubber hose, etc. be able to.
- Elastomer compositions were prepared by kneading the components having the compositions shown in Table 1. Using this elastomer composition, a sheet having a thickness of 2 mm was produced by injection molding under the production conditions of a mold temperature of 80 ° C and a resin temperature of 170 ° C. On this sheet, an alloy thin film with a thickness of 10 Onm was formed using a general-purpose vapor deposition system, with an alloy thin film of 78% ⁇ ⁇ -22% ⁇ 1 made into a fine crystal structure by a heat treatment process. A sample was made. The above Zn-A1 alloy is the one described in “Sakurai; Proceedings of Architectural Institute of Japan, A-1, pp255-2565 (2000)”. The following evaluation was performed about the obtained sample. The results are shown in Table 1.
- the air permeability of the composite material was obtained by a method based on JIS K7126A, and the air permeability of the resin sheet was shown as an index, and the air permeability was obtained.
- the KEC method of the Kansai Electronics Industry Promotion Center was used to determine the electromagnetic shielding properties of the composite materials, and the electromagnetic shielding properties of the resin sheet were expressed as 100, and the electromagnetic shielding properties were obtained.
- Example 1 samples were prepared in the same manner except that pure aluminum was used instead of the Zn—A1 alloy, and the same evaluation was performed. The results are shown in Table 1.
- Example 1 a sample was prepared in the same manner except that the alloy thin film was not provided, and the same evaluation was performed. The results are shown in Table 1.
- Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Composition of base material (parts by mass)
- Polymer A SEPS polymer with a weight average molecular weight of 100,000
- Polymer B SEPS polymer with a weight average molecular weight of 70,000
- Polypropylene resin manufactured by Chisso Corporation, trade name: Polypro CF3031
- Additive A A mixture of equal amounts of silicone polymer and polypropylene resin
- Additive B Silicone polymer grafted on polypropylene resin
- Additive C Modified polyphenylene ether (Asahi Kasei Co., Ltd., trade name: Zylon X0108)
- UV-curable resin composition UV-crosslinked urethane Ecllipse made by Emmenty Specialties Inc. in the United States, containing acrylic-modified urethane, was used.
- This UV-crosslinked urethane has a viscosity of 620 Pa's at 23 ° C and a shear rate of 1.0 Zsec.
- the relationship between the common logarithm of viscosity (y) and the common logarithm of shear rate (X) y —0. 456x + 3. It's 74.
- the UV curable resin composition is extruded using a CENTURY C720 manufactured by NORDSON and irradiated with ultraviolet light.
- a sheet with a thickness of 2 mm was produced.
- an alloy thin film with a thickness of lOOnm was formed using a general-purpose vapor deposition system, using a 78% Zn-22% A1 alloy with a fine crystal structure by a heating process, and a composite material was produced.
- the Zn-A1 alloy is one described in "Sakurai; Proceedings of the Architectural Institute of Japan, A-1, pp255-2565 (2000)".
- the obtained composite material was evaluated in the same manner as in Example 1 and the like. The results are shown in Table 2.
- Example 6 Comparative Example 3 In Example 6, a composite material was produced and evaluated in the same manner as in Example 6 except that pure aluminum was used instead of the Zn—A1 alloy. The results are shown in Table 2.
- Example 6 The same evaluation as in Example 6 was performed on the sheet without the alloy thin film in Example 6. The results are shown in Table 2.
- the air permeability is shown as a relative value when the metal thin film is not provided and the sheet (Comparative Example 4) has an air permeability of 100.
- the composite material A of the present invention has properties such as the flexibility and workability of the polymer compound, and the conductivity, gas barrier property, moisture barrier property, and electromagnetic wave shielding property of the metal, Suitable for applications such as fluid transportation.
- the composite material B of the present invention comprises an electromagnetic wave absorbing material, an electromagnetic wave shielding molded product, a gas barrier film, a moisture barrier film, a gasket for electronic equipment, a seal or a sealant, a liquid channel, tubes, a liquid seal. Suitable for applications such as a stopper.
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Abstract
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JP2004-330902 | 2004-11-15 | ||
JP2004330901A JP2006137152A (ja) | 2004-11-15 | 2004-11-15 | 複合材 |
JP2004-330901 | 2004-11-15 | ||
JP2004330902A JP2006137153A (ja) | 2004-11-15 | 2004-11-15 | 複合材 |
JP2005-017206 | 2005-01-25 | ||
JP2005017206A JP2006205395A (ja) | 2005-01-25 | 2005-01-25 | 高分子・金属複合体 |
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Cited By (2)
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WO2006136436A1 (en) * | 2005-06-24 | 2006-12-28 | Dsm Ip Assets B.V. | Styrene block copolymers as infill material in artificial turf systems |
WO2012014826A1 (en) | 2010-07-28 | 2012-02-02 | Canon Kabushiki Kaisha | Elastic member for inkjet |
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JPS60222248A (ja) * | 1984-04-18 | 1985-11-06 | 住友電気工業株式会社 | 超塑性合金ラミネ−トテ−プ及びそれを用いたしや水層付電力ケ−ブル |
JPH0848849A (ja) * | 1994-06-03 | 1996-02-20 | Sumitomo Chem Co Ltd | スチレン系樹脂組成物、シール層フィルム、シーラントフィルムおよび容器 |
JPH09268367A (ja) * | 1996-04-01 | 1997-10-14 | Hitachi Ltd | プラズマ処理による薄膜形成装置及び薄膜形成方法 |
JP2003130014A (ja) * | 2001-10-23 | 2003-05-08 | Kobe Steel Ltd | ボルト摩擦接合方法およびボルト摩擦接合用フィラー材 |
WO2004011246A1 (ja) * | 2002-07-30 | 2004-02-05 | Jujo Chemical Co.,Ltd. | アルミニウム積層体の作成方法およびアルミニウム積層体 |
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JPS60222248A (ja) * | 1984-04-18 | 1985-11-06 | 住友電気工業株式会社 | 超塑性合金ラミネ−トテ−プ及びそれを用いたしや水層付電力ケ−ブル |
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JP2003130014A (ja) * | 2001-10-23 | 2003-05-08 | Kobe Steel Ltd | ボルト摩擦接合方法およびボルト摩擦接合用フィラー材 |
WO2004011246A1 (ja) * | 2002-07-30 | 2004-02-05 | Jujo Chemical Co.,Ltd. | アルミニウム積層体の作成方法およびアルミニウム積層体 |
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Publication number | Priority date | Publication date | Assignee | Title |
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WO2006136436A1 (en) * | 2005-06-24 | 2006-12-28 | Dsm Ip Assets B.V. | Styrene block copolymers as infill material in artificial turf systems |
WO2012014826A1 (en) | 2010-07-28 | 2012-02-02 | Canon Kabushiki Kaisha | Elastic member for inkjet |
EP2598335A4 (en) * | 2010-07-28 | 2018-03-14 | Canon Kabushiki Kaisha | Elastic member for inkjet |
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