WO2013141171A1 - 発泡性封止材、発泡性封止部材、封止発泡体および空間の封止方法 - Google Patents
発泡性封止材、発泡性封止部材、封止発泡体および空間の封止方法 Download PDFInfo
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- WO2013141171A1 WO2013141171A1 PCT/JP2013/057523 JP2013057523W WO2013141171A1 WO 2013141171 A1 WO2013141171 A1 WO 2013141171A1 JP 2013057523 W JP2013057523 W JP 2013057523W WO 2013141171 A1 WO2013141171 A1 WO 2013141171A1
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J15/00—Sealings
- F16J15/02—Sealings between relatively-stationary surfaces
- F16J15/021—Sealings between relatively-stationary surfaces with elastic packing
- F16J15/022—Sealings between relatively-stationary surfaces with elastic packing characterised by structure or material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0019—Use of organic additives halogenated
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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
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/02—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles for articles of definite length, i.e. discrete articles
- B29C44/12—Incorporating or moulding on preformed parts, e.g. inserts or reinforcements
- B29C44/18—Filling preformed cavities
- B29C44/188—Sealing off parts of the cavities
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0066—Use of inorganic compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/104—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
- C08J9/105—Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof containing sulfur
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
- C08J2201/026—Crosslinking before of after foaming
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2207/00—Foams characterised by their intended use
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
- C08J2423/28—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by reaction with halogens or halogen-containing compounds
Definitions
- the present invention relates to a foamable sealing material, a foamable sealing member, a sealing foam, and a method for sealing a space, and more specifically, a sealing foam for sealing a space, a sealing method, and a sealing foam.
- the present invention relates to a foamable sealing member and a foamable sealing material.
- a foam is not used to prevent engine vibration and noise or wind noise from being transmitted to the vehicle interior. It is known to fill and seal.
- a filling foam composition containing an ethylene / vinyl acetate copolymer and 4,4′-oxybis (benzenesulfonylhydrazide) is prepared, and this is placed in the internal space of the hollow member, and then heated. It has been proposed to fill the internal space of the hollow member with a filling foam obtained by foaming and seal the internal space with the filling foam (see, for example, Patent Document 1 below).
- the internal space of the hollow member disposed in the vicinity of the engine room is also filled with foam for filling. It has been proposed to arrange the composition and seal the internal space with a foam.
- the foam since the hollow member is exposed to a high temperature by heat generated from the engine, the foam needs to have excellent flame retardance that can effectively suppress combustion due to the high temperature exposure.
- An object of the present invention is to provide a sealing foam having excellent flame retardancy while having excellent sealing properties, a foamable sealing member for forming the same, a foamable sealing material, and a space sealing by them. It is to provide a stopping method.
- the foamable sealing material of the present invention contains a polymer, a foaming agent, and a flame retardant, and the flame retardant comprises 5 to 110 parts by mass of a metal hydroxide, 100% by mass of the polymer, and a halogen-based organic compound. It is characterized by containing 5 to 110 parts by mass of a compound and capable of foaming to seal a space.
- the metal hydroxide is aluminum hydroxide and / or magnesium hydroxide.
- the halogen-based organic compound is a bromine-based organic compound and / or a chlorine-based organic compound.
- the bromine-based organic compound may be ethylene bis (pentabromophenyl) and / or decabromodiphenyl oxide, and the chlorine-based organic compound may be chlorinated polyethylene. Is preferred.
- the foamable sealing member of the present invention comprises the foamable sealing material described above and an attachment member attached to the foamable sealing material and attachable to the internal space of the hollow member.
- the stopping material contains a polymer, a foaming agent, and a flame retardant, and the flame retardant is 5 to 110 parts by mass of a metal hydroxide and 5 to 110 parts by mass of a halogenated organic compound with respect to 100 parts by mass of the polymer.
- the foamable sealing material is characterized by being foamable in order to seal the internal space.
- the sealing foam of the present invention is a sealing foam obtained by foaming the above-described foamable sealing material, and the foamable sealing material comprises a polymer, a foaming agent, and a flame retardant.
- the flame retardant contains 5 to 110 parts by mass of a metal hydroxide and 5 to 110 parts by mass of a halogenated organic compound with respect to 100 parts by mass of the polymer.
- the space sealing method of the present invention includes a step of installing the foamable sealing material in the space, and a step of foaming the foamable sealing material to obtain a sealing foam
- the foamable sealing material contains a polymer, a foaming agent, and a flame retardant, and the flame retardant comprises 5 to 110 parts by mass of a metal hydroxide, 5 to 110 parts of a halogen-based organic compound with respect to 100 parts by mass of the polymer. It is characterized by containing 110 mass parts.
- the foamable sealing material of the present invention provided in the foamable sealing member of the present invention contains a polymer, a foaming agent, and a flame retardant, and the flame retardant contains a specific combination of a metal hydroxide and a halogenated organic compound. Contains in proportion.
- the sealing foam of the present invention obtained by foaming the foamable sealing material of the present invention has a high expansion ratio, and has excellent flame retardancy while being excellent in sealing performance.
- the method for sealing a space arranges a foamable sealing material in the space, and then foams the foamable sealing material to obtain a sealing foam.
- the space can be reliably sealed by the foam.
- FIG. 1 is a process diagram of a method for sealing an internal space of a hollow member disposed in or near an engine room in an automobile with the foamable sealing material, foamable sealing member, and sealing foam of the present invention.
- FIG. 1 (a) shows a step of attaching a mounting member to a foamable sealing material to produce a foamable sealing member, and installing this on a hollow member.
- FIG. A step of sealing the internal space of the hollow member with the sealing foam by foaming the foamable sealing material is shown.
- the foamable sealing material of the present invention can be foamed to seal a space, and specifically contains a polymer, a foaming agent, and a flame retardant.
- polymer examples include a resin and / or rubber obtained by polymerization of a monomer having at least one ethylenically unsaturated double bond. These polymers can be used alone or in combination of two or more.
- the resin examples include vinyl polymers (vinyl monomer polymers) such as vinyl copolymers and olefin polymers.
- examples of the resin also include polyvinyl butyral resin and polyvinyl chloride resin.
- the resin is preferably a vinyl polymer, more preferably a vinyl copolymer or an olefin polymer.
- vinyl copolymer examples include a copolymer of a vinyl group-containing ester and an olefin.
- vinyl group-containing ester examples include fatty acid vinyl esters and (meth) acrylates.
- fatty acid vinyl ester examples include vinyl acetate, vinyl propionate and vinyl butyrate.
- (Meth) acrylate is acrylate and / or methacrylate, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, and butyl (meth) acrylate. .
- Vinyl group-containing esters can be used alone or in combination.
- the vinyl group-containing ester is preferably a fatty acid vinyl ester, and more preferably vinyl acetate.
- olefin examples include ethylene and propylene. Olefin can be used alone or in combination.
- ethylene is preferable.
- vinyl copolymer for example, ethylene / vinyl acetate copolymer (EVA), ethylene / vinyl propionate copolymer, ethylene / vinyl butyrate copolymer, ethylene / propylene / vinyl acetate copolymer are used.
- EVA ethylene / vinyl acetate copolymer
- ethylene / vinyl propionate copolymer ethylene / vinyl butyrate copolymer
- ethylene / propylene / vinyl acetate copolymer ethylene / propylene / vinyl acetate copolymer
- Olefin / fatty acid vinyl ester copolymers such as polymers, for example, ethylene / methyl (meth) acrylate copolymer, ethylene / ethyl (meth) acrylate copolymer (EEA / EMA), ethylene / propyl (meth) acrylate copolymer Examples thereof include olefin / (meth) acrylate copolymers such as polymers and ethylene / butyl (meth) acrylate copolymers.
- the above vinyl copolymer is a block copolymer or a random copolymer.
- Vinyl copolymers can be used alone or in combination of two or more.
- an olefin / fatty acid vinyl ester copolymer is preferable, and EVA is more preferable.
- the content of vinyl group-containing ester (specifically, fatty acid vinyl ester, preferably vinyl acetate) in the vinyl copolymer is, for example, 5 to 60% by mass, preferably 10 to 45% by mass.
- the olefin polymer is a hydrocarbon polymer that does not substantially have an oxygen atom-containing portion such as an ester bond in the molecule, and is specifically an olefin polymer.
- olefin examples include those similar to the olefin exemplified as the monomer for forming the vinyl copolymer.
- olefin polymer examples include polyethylene (ethylene homopolymer), polypropylene (propylene homopolymer), and ethylene / propylene copolymer.
- the olefin polymer can be used alone or in combination.
- Preferred examples of the olefin polymer include polyethylene.
- the resin for example, in addition to a resin obtained by polymerization of a monomer having at least one ethylenically unsaturated double bond, a resin made of a polycondensate such as a polyester resin or a polyamide resin can be used.
- Examples of rubber include conjugated diene polymers.
- the conjugated diene polymer is a polymer of a monomer containing a conjugated diene, and examples thereof include styrene / butadiene rubber (SBR), polybutadiene rubber (BR), and ethylene / propylene / diene rubber (EPDM).
- SBR styrene / butadiene rubber
- BR polybutadiene rubber
- EPDM ethylene / propylene / diene rubber
- EPDM is a synthetic rubber obtained by copolymerization of ethylene, propylene and diene. Specifically, it is obtained by further copolymerizing diene with an ethylene / propylene copolymer (EPM).
- EPM ethylene / propylene copolymer
- diene examples include 5-ethylidene-5-norbornene, 1,4-hexadiene, dicyclopentadiene, and the like. Preferably, 5-ethylidene-5-norbornene is used.
- the diene content of EPDM is, for example, 1 to 20% by mass, preferably 3 to 10% by mass.
- the ethylene content is, for example, 50 to 97% by mass, preferably 60 to 95% by mass.
- the melt flow rate (MFR) of the polymer is, for example, 10.0 g / 10 min or less, preferably 7.5 g / 10 min or less, and for example, 1.0 g / 10 min or more, preferably 1.5 g / 10 min. That's it.
- MFR is determined by a measuring method based on JISK7210 (1999) and JISK6922-1 (1997). Specifically, the MFR of the vinyl copolymer is determined by measurement at a heating temperature of 190 ° C. and a load of 21.18 N in accordance with JISK7210 (1999), and the MFR of the olefin polymer conforms to JISK6922-1 (1997). It is determined by measurement at a heating temperature of 190 ° C. and a load of 21.18N.
- the Mooney viscosity of the polymer is, for example, 50 ML 1 + 4 (100 ° C.) or less, preferably 40 ML 1 + 4 (100 ° C.) or less, and for example, 5 ML 1 + 4 (100 ° C.) or more, preferably Also more than 10ML 1 + 4 (100 ° C). Mooney viscosity is determined by measurement at a heating temperature of 100 ° C. in accordance with ASTM D 1646.
- the blending ratio of the polymer is, for example, 10 to 90% by mass, preferably 25 to 85% by mass with respect to the foamable sealing material.
- foaming agent examples include heat-decomposable foaming agents such as inorganic foaming agents and organic foaming agents.
- Examples of the inorganic foaming agent include ammonium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, ammonium nitrite, sodium borohydride, azides and the like.
- organic foaming agent examples include N-nitroso compounds (N, N′-dinitrosopentamethylenetetramine, N, N′-dimethyl-N, N′-dinitrosotephthalamide, etc.), azo compounds (for example, , Azobisisobutyronitrile, azodicarbonamide (ADCA), barium azodicarboxylate, etc.), fluorinated alkanes (eg, trichloromonofluoromethane, dichloromonofluoromethane, etc.), hydrazine compounds (eg, p-toluenesulfonyl) Hydrazide, diphenylsulfone-3,3′-disulfonylhydrazide, 4,4′-oxybis (benzenesulfonylhydrazide) (OBSH), allylbis (sulfonylhydrazide), etc.), semicarbazide compounds (for example, p-tolu
- the foaming agent examples include gas-filled microcapsule foaming agents, and more specifically, heat-expandable substances (eg, isobutane, pentane, etc.) are microcapsules (eg, vinylidene chloride, acrylonitrile). And thermally expandable fine particles encapsulated in a microcapsule made of a thermoplastic resin such as acrylic acid ester or methacrylic acid ester. As such thermally expandable fine particles, for example, commercially available products such as microspheres (trade name, manufactured by Matsumoto Yushi Co., Ltd.) are used.
- heat-expandable substances eg, isobutane, pentane, etc.
- microcapsules eg, vinylidene chloride, acrylonitrile
- thermally expandable fine particles encapsulated in a microcapsule made of a thermoplastic resin such as acrylic acid ester or methacrylic acid ester.
- thermally expandable fine particles for example, commercially available products such as microsphere
- foaming agents can be used alone or in combination of two or more.
- foaming agents azo compounds and hydrazine compounds are preferable, and ADCA and OBSH are more preferable.
- the blending ratio of the foaming agent is, for example, 5 to 30 parts by mass, preferably 10 to 25 parts by mass with respect to 100 parts by mass of the polymer. If the blending ratio of the foaming agent is less than the above range, the foam for sealing obtained from the foamable sealing material has a low foaming ratio, and in order to seal the space, the foamable sealing material must have a large shape. It is necessary to form, and attachment workability
- Flame retardant contains metal hydroxide and halogenated organic compound.
- the metal hydroxide is solid, for example, aluminum (Al), magnesium (Mg), calcium (Ca), nickel (Ni), cobalt (Co), tin (Sn), zinc (Zn), copper
- Al aluminum
- Mg magnesium
- Ca calcium
- Ni nickel
- Co cobalt
- Sn tin
- Zn zinc
- copper examples thereof include metal hydroxides of metal elements such as (Cu) and iron (Fe).
- metal hydroxide examples include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, nickel hydroxide, cobalt hydroxide, tin hydroxide, zinc hydroxide, copper hydroxide, and iron hydroxide.
- Metal hydroxides can be used alone or in combination.
- the metal hydroxide is preferably aluminum hydroxide or magnesium hydroxide from the viewpoint of flame retardancy.
- metal hydroxide such as the Hydrite series (aluminum hydroxide, manufactured by Showa Denko KK), Kisuma series (magnesium hydroxide, manufactured by Kyowa Chemical Industry Co., Ltd.), and the like.
- Examples of the shape of the metal hydroxide include a spherical shape, a needle shape, and a plate shape.
- the average value of the maximum length of the metal hydroxide (in the case of a spherical shape, the average particle diameter) is, for example, 1 nm to 100 ⁇ m, preferably 5 nm to 50 ⁇ m, more preferably 10 nm to 1 ⁇ m.
- metal hydroxide is, for example, aluminum hydroxide or magnesium hydroxide
- water is generated by thermal decomposition as shown in the following formula (1) or formula (2).
- the residual time of the foaming sealing material and the sealing foam (burning the sample molded from the foaming sealing material and the sealing foam, The time during which the red heat of the sample lasts after the flame of the sample disappears can be shortened, and excellent flame retardancy can be imparted to the foamable sealing material and the sealing foam.
- the mixing ratio of the metal hydroxide is 5 to 110 parts by weight, preferably 5 to 80 parts by weight, more preferably 10 to 60 parts by weight, and still more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the polymer. 40 parts by mass.
- the expansion ratio may be reduced.
- the mixing ratio of the metal hydroxide is less than the above range, the flame retardancy may be lowered.
- the halogen-based organic compound is an organic compound that is solid and has a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom in the molecule.
- a fluorine-based compound that contains a fluorine atom in the molecule Organic compounds, chlorine-based organic compounds containing chlorine atoms in the molecule, bromine-based organic compounds containing bromine atoms in the molecule, iodine-based organic compounds containing iodine atoms in the molecule, multiple types of halogen atoms in the molecule And organic compounds having.
- a chlorine type organic compound and a bromine type organic compound are mentioned.
- chlorinated organic compound examples include chlorinated polyolefins such as chlorinated polyethylene obtained by chlorinating polyethylene, and chlorinated rubbers such as chloroprene rubber.
- chlorinated polyolefin is mentioned, More preferably, a chlorinated polyethylene is mentioned.
- brominated organic compounds examples include brominated aromatic compounds such as tetrabromobisphenol A, ethylenebis (pentabromophenyl), ethylenebistetrabromophthalimide, tetrabromophthalic anhydride, brominated polystyrene, such as tetrabromocyclooctane.
- Brominated alicyclic compounds such as dibromomethyl-dibromocyclohexane, hexabromocyclododecane, for example, brominated ethers such as decabromodiphenyl oxide (decabromodiphenyl ether), tetradecabromodiphenoxybenzene, TBA-bisdibromopropyl ether Compound etc. are mentioned.
- the bromine-based organic compound is preferably a bromine-based aromatic compound or a bromine-based ether compound, and more preferably ethylenebis (pentabromophenyl) or decabromo from the viewpoints of flame retardancy, stability, and handleability.
- Diphenyl oxide is mentioned.
- halogen-based organic compound for example, Elastylene series (chlorine-based organic compound, manufactured by Showa Denko KK), SAYTEX series (bromine-based organic compound, manufactured by Albemarle), etc. are used.
- the halogen content in the halogen-based organic compound is, for example, 5 to 95% by mass, preferably 10 to 90% by mass.
- the chlorine content relative to the chlorine organic compound is, for example, 10 to 60% by mass, preferably 20 to 50% by mass.
- the bromine content with respect to the bromine-based organic compound is, for example, 45 to 99 mass%, preferably 55 to 95 mass%.
- hydrogen halide specifically, hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide
- Examples of the shape of the halogen-based organic compound include a spherical shape, a needle shape, and a plate shape.
- the average value of the maximum length is, for example, 1 nm to 100 ⁇ m, Preferably, it is 100 nm to 20 ⁇ m.
- the melting point of the halogen-based organic compound is, for example, 200 to 400 ° C., preferably 250 to 375 ° C.
- the melting point of the halogen-based organic compound can be set to 100 to 200 ° C., preferably 125 to 175 ° C., for example.
- the blending ratio of the halogen-based organic compound is 5 to 110 parts by mass, preferably 5 to 80 parts by mass, more preferably 10 to 60 parts by mass, and still more preferably 20 to 100 parts by mass with respect to 100 parts by mass of the polymer. 50 parts by mass.
- the expansion ratio may decrease.
- flame retardancy may be reduced.
- the ratio of the metal hydroxide to the halogen-based organic compound is, for example, 1/10 to 10/1, preferably 1/3 to 3/1, based on mass (metal hydroxide / halogen-based organic compound). It is. If the above ratio is within the above range, corrosion and environmental load can be reduced while imparting excellent flame retardancy to the foamable sealing material and the sealing foam.
- the blending ratio of the flame retardant that is, the total amount of the metal hydroxide and the halogenated organic compound is, for example, 10 to 220 parts by mass, preferably 10 to 160 parts by mass, more preferably 100 parts by mass of the polymer. It is 20 to 120 parts by mass, and more preferably 40 to 100 parts by mass.
- the flame retardant contains the metal hydroxide and the halogen-based organic compound described above, the foaming seal with less corrosion and environmental load while imparting excellent flame retardancy to the foamable sealing material and the sealing foam.
- a stop material and a sealing foam can be provided.
- foamable sealing material examples include a foaming aid, a crosslinking agent, a crosslinking aid, a rust inhibitor, and a filler, a lubricant, a plasticizer, an anti-aging agent, an antioxidant, a pigment, and a colorant.
- known additives such as fungicides, flame retardants (flame retardants excluding metal hydroxides and halogenated organic compounds), softeners, and the like can be added at an appropriate ratio.
- foaming aid examples include urea compounds, for example, higher fatty acids such as salicylic acid and stearic acid or metal salts thereof (for example, zinc salts), for example, metal oxides such as zinc oxide.
- urea compounds for example, higher fatty acids such as salicylic acid and stearic acid or metal salts thereof (for example, zinc salts), for example, metal oxides such as zinc oxide.
- the foaming aid can be used alone or in combination.
- foaming aid preferably, higher fatty acid zinc and metal oxide are used.
- the blending ratio of the foaming aid is, for example, 1 to 100 parts by weight, preferably 5 to 50 parts by weight with respect to 100 parts by weight of the foaming agent.
- the blending ratio of the foaming aid is, for example, 1 to 20 parts by mass, preferably 2 to 10 parts by mass with respect to 100 parts by mass of the polymer.
- crosslinking agent examples include organic peroxides.
- the organic peroxide is a radical generator that can be decomposed by heating to generate free radicals to crosslink the polymer.
- DCP dicumyl peroxide
- 1,3-bis Tertiary butyl peroxyisopropyl) benzene, tertiary butyl peroxyketone, tertiary butyl peroxybenzoate, and the like.
- the crosslinking agent can be used alone or in combination of two or more.
- DCP is preferable.
- the blending ratio of the crosslinking agent is, for example, 0.1 to 10 parts by mass, preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the polymer. If the blending ratio of the crosslinking agent is less than the above range, there is little increase in viscosity due to crosslinking, and foam breakage may occur due to gas pressure during foaming. Moreover, when the mixture ratio of a crosslinking agent exceeds the said range, it bridge
- crosslinking aid examples include ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate (TMPTA / TMPTMA), pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol hexa.
- (Meth) acryloyl group-containing compounds containing a plurality of (meth) acryloyl groups such as (meth) acrylates, for example, allyl group-containing compounds such as triallyl isocyanurate (TAIC), triallyl cyanurate (TAC), for example, Hydroxyimino group-containing compounds such as p-quinonedioxime (oximes), for example, imino group and amino group-containing compounds such as guanidine, for example, imides such as N, N′-m-phenylenebismaleimide Containing compounds, for example, carboxyl group-containing compounds such as zinc acrylate (e.g., an unsaturated fatty acid metal salt), for example, a vinyl group-containing compounds such as 1,2-polybutadiene, for example, and sulfur compounds such as sulfur.
- TAIC triallyl isocyanurate
- TAC triallyl cyanurate
- Hydroxyimino group-containing compounds such as p-quino
- crosslinking aids can be used alone or in combination of two or more.
- crosslinking aid preferably a (meth) acryloyl group-containing compound, more preferably TMPTA, TMPTMA, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc.
- (meth) acryloyl group-containing compounds containing three or more (meth) acryloyl groups.
- the blending ratio of the crosslinking aid is, for example, 1 to 20 parts by mass, preferably 2 to 15 parts by mass with respect to 100 parts by mass of the crosslinking agent.
- the blending ratio of the crosslinking aid is, for example, 0.05 to 1.5 parts by mass, preferably 0.1 to 1.0 part by mass with respect to 100 parts by mass of the polymer.
- the rust preventive is not particularly limited, and examples thereof include basic oxides described in JP-A-2005-97586, and specifically include calcium oxide, magnesium oxide, ferrous oxide, and second oxide. Examples include iron.
- the rust inhibitor can be used alone or in combination.
- magnesium oxide is preferable.
- the average particle diameter of the rust inhibitor is, for example, 1 nm to 100 ⁇ m.
- the blending ratio of the rust preventive is, for example, 0.05 to 50 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the foaming agent.
- each above-mentioned component is mix
- the foamable sealing material can be prepared by kneading the above-described components with, for example, a mixing roll, a pressure kneader, an extruder, or the like.
- the kneading conditions are such that the heating temperature is, for example, 50 to 130 ° C., preferably 95 to 120 ° C., and the heating time is, for example, 0.5 to 30 minutes, preferably 1 to 20 minutes.
- the obtained kneaded product can be prepared as a preform (preform) by forming it into a predetermined shape.
- the kneaded material is directly formed into a predetermined shape (for example, a sheet shape) by calendar molding or press molding.
- a predetermined shape for example, a sheet shape
- the kneaded product can be pelletized with a pelletizer or the like and molded into a predetermined shape with an injection molding machine or an extrusion molding machine.
- the molding temperature is, for example, 60 to 120 ° C., preferably 75 to 115 ° C.
- sealing foam of this invention can be formed by heating the foaming sealing material of this invention obtained in this way on appropriate conditions, and making it foam.
- the encapsulated foam of the present invention thus obtained has a volume expansion ratio (density before foaming / density after foaming) of, for example, 4 times or more, preferably 6 times or more, more preferably 10 times or more, More preferably, it is 14 times or more, for example, 40 times or less.
- the volume expansion ratio of the sealing foam is appropriately set according to the type of the foaming agent, and when the foaming agent is an azo compound (specifically, ADCA), for example, 6 times or more, preferably When the foaming agent is a hydrazine-based compound (specifically, OBSH), for example, 4 times or more, preferably 6 times or more, more preferably 10 times or more, and further preferably 14 times or more.
- ADCA azo compound
- OBSH hydrazine-based compound
- Such a volume expansion ratio can improve the sealing performance of the sealing foam with respect to the space.
- the sealing foam does not burn up to the marked line B (that is, self-extinguish (flame disappears), for example, in the measurement based on the “FMVSS No. 302” combustion test (ISO6795, JIS D1201) described in detail later. I.e., self-extinguishing)), that is, the prescribed burning rate cannot be measured, preferably self-extinguishing at a position within 200 mm from the tip, and more preferably self-extinguishing at a location within 100 mm from the tip. More preferably, the film self-extinguishes at a position within 50 mm from the tip, and particularly preferably, the film self-extinguishes at a position within 30 mm from the tip.
- the sealing foam of this invention obtained in this way can provide various effects, such as reinforcement, vibration suppression, soundproofing, dustproofing, heat insulation, buffering, and watertightness, to various members that partition the space.
- it is suitable as a foaming filler for various industrial products such as reinforcing materials, vibration-proofing materials, soundproofing materials, dustproofing materials, heat insulating materials, cushioning materials, water-stopping materials, etc. Can be used.
- Examples of the member that divides the space sealed by the sealing foam of the present invention include two members that are opposed to each other with an interval, for example, a hollow member in which an internal space is formed.
- the foamable sealing material is installed between the above-described members or in the internal space of the hollow member, and then the foamable seal is installed.
- the material is heated and foamed to form a sealing foam, and the sealing foam is filled between the members or in the internal space of the hollow member. Thereby, between the members or the internal space of the hollow member is sealed with the sealing foam.
- the sealing foam when the sealing foam is filled in the internal space of the hollow member, for example, first, an attachment member that can be attached to the hollow member is attached to the foamable sealing material, and the foamable sealing material is attached. A foamable sealing member including a stopper and an attachment member is produced. Next, the attachment member is attached to the hollow member so that the foamable sealing material is disposed in the internal space, and then the foamable sealing material is foamed by heating to form a sealing foam. As a result, the sealing foam is filled into the internal space of the hollow member to seal the internal space.
- Examples of such a hollow member include a hollow member provided in or near the engine room in an automobile.
- the attachment member is attached to the hollow member, and then foamed, the internal space of the hollow member is sealed with the sealing foam.
- a foamable sealing member is first prepared.
- the mounting member is attached to, for example, one member so that the foamable sealing material is disposed between the two members, and then the foamable sealing material is foamed by heating to form a sealing foam. Form. In this way, the sealing foam is filled between the two members, and the gap is sealed.
- FIG. 1 is a process diagram of a method for sealing an internal space of a hollow member disposed in or near an engine room in an automobile with the foamable sealing material, foamable sealing member, and sealing foam of the present invention.
- FIG. 1 (a) shows a step of attaching a mounting member to a foamable sealing material to produce a foamable sealing member, and installing this on a hollow member.
- FIG. A step of sealing the internal space of the hollow member with the sealing foam by foaming the foamable sealing material is shown.
- the internal space of the hollow member disposed in or near the engine room in the automobile is sealed using an embodiment of the foamable sealing material, foamable sealing member, and sealing foam of the present invention. The method will be described with reference to FIG.
- the foamable sealing sheet 1 molded into a predetermined shape is installed in the hollow member 2.
- the foamable sealing sheet 1 is formed into a sheet shape from a foamable sealing material.
- the thickness of the foamable sealing sheet 1 is appropriately set according to the expansion ratio and / or the internal space of the hollow member 2, and is, for example, 0.01 to 10 mm, preferably 0.05 to 5 mm.
- the hollow member 2 includes an inner panel 4 and an outer panel 5 having a substantially concave cross section.
- the inner panel 4 is formed so that the center portion projects from the peripheral end portion to one side in the thickness direction of the hollow member 2 (the lower side in FIG. 1).
- the outer panel 5 is formed so that the center portion projects from the peripheral end portion to the other side in the thickness direction of the hollow member 2 (upper side in FIG. 1).
- the mounting member 3 is attached to the foamable sealing sheet 1, and the foaming seal provided with the mounting member 3 and the foamable sealing sheet 1 is provided.
- the stop member 6 is produced.
- the attachment member 3 can also be insert-molded with a kneaded material at the time of shaping
- the attachment member 3 of the foamable sealing member 6 is attached to the inner panel 4.
- the peripheral end portions of the inner panel 4 and the outer panel 5 are brought into contact with each other and joined together.
- the hollow member 2 is formed as a closed cross section.
- the hollow member 2 is heated at, for example, 140 ° C. or higher and 180 ° C. or lower, preferably 160 ° C. or higher and 180 ° C. or lower, using heat in the drying line process during subsequent baking coating.
- the sealing foam 9 can be formed by foaming the foamable sealing sheet 1 as shown in FIG.1 (b).
- the sealing foam 9 can fill and seal the inner space of the hollow member 2 with almost no gap.
- the shape, installation position, arrangement direction, and arrangement number of the foamable sealing sheet 1 are appropriately selected according to the shape of the hollow member 2 and the like.
- the foaming sealing sheet 1 with which the above-mentioned foaming sealing member 6 is equipped contains a polymer, a foaming agent, and a flame retardant, and a flame retardant is a specific combination of a metal hydroxide and a halogenated organic compound. Contains in proportion.
- the sealing foam 9 obtained by foaming the foamable sealing sheet 1 has a high expansion ratio, and has excellent flame retardancy while being excellent in sealing performance.
- the above-described method for sealing the internal space of the hollow member 2 is to place the foamable sealing sheet 1 in the internal space and then foam the foamable sealing sheet 1 to obtain the sealing foam 9.
- the internal space of the hollow member 2 can be reliably sealed by the sealing foam 9 having excellent flame retardancy.
- Examples 1 to 12 and Comparative Examples 1 to 6 Each component was kneaded for 10 minutes at a rotation speed of 15 min ⁇ 1 and about 110 ° C. with a 6-inch mixing roll according to the formulation of Tables 1 to 3, and then kneaded (foamable sealing material, foamable filler). ) was prepared. Thereafter, the prepared kneaded product was molded into a foamable sealing sheet having a thickness of 2.5 mm by hot pressing at 110 ° C.
- the sealing foam was cut into a size of 100 mm ⁇ 356 mm to prepare a sample, and the burning rate in the longitudinal direction of the sample was measured.
- a marked line A is drawn along the width direction from the one end (tip) in the longitudinal direction of the sample along the width direction, and the width direction from the marked line A to the other side 254 mm in the width direction.
- a marked line B was drawn along Thereafter, a flame was applied to one end in the longitudinal direction of the sample, and the combustion state proceeding from the tip to the mark B through the mark A was observed, and the burning rate of the sample between the marks A and B was measured.
- EVA Trade name “Evaflex EV460”, ethylene / vinyl acetate copolymer, MFR 2.5 g / 10 min (according to JISK7210 (1999), heating temperature 190 ° C., load 21.18 N), vinyl acetate content 19% by weight, Mitsui DCP manufactured by DuPont Chemical Co., Ltd .: trade name “Park Mill D-40MBK”, dicumyl peroxide, DCP content 40% by mass, silica + EPDM content 60% by mass, OBSH manufactured by NOF Corporation: trade name “Selmic SX”, 4, 4 '-Oxybis (benzenesulfonylhydrazide) (OBSH), magnesium oxide manufactured by Sankyo Kasei Co., Ltd .: trade name “Kyowa Mag 150”, average particle size 18 nm, aluminum hydroxide manufactured by Kyowa Chemical Industry Co., Ltd .: trade name “Hijilite H32
- Ethylene bis (pentabromophenyl) trade name “SAYTEX 8010”, melting point: 350 ° C., bromine content 82% by mass, average particle size 5 ⁇ m
- Albemarle Made decabromodiphenyl oxide trade name “SAYTEX 102E”, melting point: 304 ° C., bromine content 83% by mass, average particle size 6 ⁇ m
- Showa Denko TMPTA Trade name “TMP3A”, trimethylolpropane triacrylate
- Osaka Organic Chemical Industry ADCA Trade name “Vinole AC # 3C”, Azodicarbonamide, Eiwa Chemical Co., Ltd.
- Zinc oxide Trade name “Zinc oxide” "Type 2", zinc stearate manufactured by Mitsui Mining & Mining Co., Ltd. -P ", PE manufactured by Nippon Steel Chemical Co., Ltd .: Sumikasen G201, polyethylene, melt flow rate: 2 g / 10 min (according to JIS K6922-1 (1997), heating temperature 190 ° C., load 21.18 N)
- EPT Trade name “Mitsui EPT X-3012P”, EPDM, Mooney viscosity: 15 ML 1 + 4 (100 ° C.) (ASTM D 1646), heating temperature 100 ° C., ethylene content 71.8 mass%, diene content 3. 6% by mass
- EPT Trade name “Mitsui EPT X-3012P”, EPDM, Mooney viscosity: 15 ML 1 + 4 (100 ° C.) (ASTM D 1646), heating temperature 100 ° C., ethylene content 71.8 mass%, diene content 3. 6% by mass
- Sealing foam made by foaming sealing material fills the space of various members, for example, reinforcing material, vibration proofing material, soundproofing material, dustproofing material, heat insulating material, buffer material, waterstop material, etc. It can be used as a foaming filler for various industrial products.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- General Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
2Al(OH)3 → Al2O3 + 3H2O (2)
また、これらの熱分解は、吸熱反応である。とりわけ、水酸化アルミニウムまたは水酸化マグネシウムは、200~400℃の広い温度範囲にわたって、上記した吸熱反応が進行する。
各成分を、表1~表3の配合処方に従って、6インチミキシングロールにて回転数15min-1、約110℃で、10分間混練して、混練物(発泡性封止材、発泡性充填材)を調製した。その後、調製した混練物を、110℃の熱プレスにて、厚み2.5mmの発泡性封止シートを成形した。
各実施例および各比較例で得られた発泡性封止シートについて、以下の項目についてそれぞれ評価した。それらの結果を、表1~表3に示す。
(1) 発泡倍率
発泡性封止シートを、直径19mmの円板状に打ち抜き加工してサンプルを作製し、作製したサンプルを、180℃で、20分間加熱することにより、サンプルを発泡させた。つまり、封止発泡体を得た。そして、発泡前後の封止発泡体の密度から、発泡倍率を算出した。
(2) 難燃性
「FMVSSNo.302」燃焼試験(ISO6795、JIS D1201)に準拠して、「(1) 発泡倍率」において得られた封止発泡体の難燃性を評価した。
EVA:商品名「エバフレックスEV460」、エチレン・酢酸ビニル共重合体、MFR2.5g/10min(JISK7210(1999)に準拠、加熱温度190℃、荷重21.18N)、酢酸ビニル含量19重量%、三井・デュポンケミカル社製
DCP:商品名「パークミルD-40MBK」、ジクミルパーオキサイド、DCP含量40質量%、シリカ+EPDM含量60質量%、日本油脂社製
OBSH:商品名「セルマイクSX」、4,4’-オキシビス(ベンゼンスルホニルヒドラジド)(OBSH)、三協化成社製
酸化マグネシウム:商品名「キョーワマグ150」、平均粒子径18nm、協和化学工業社製
水酸化アルミニウム:商品名「ハイジライトH32」、平均粒子径18nm、昭和電工社製
水酸化マグネシウム:商品名「キスマ5A」、平均粒子径0.8μm、協和化学工業社製
エチレンビス(ペンタブロモフェニル):商品名「SAYTEX 8010」、融点:350℃、臭素含量82質量%、平均粒子径5μm、アルベマール社製
デカブロモジフェニルオキサイド:商品名「SAYTEX 102E」、融点:304℃、臭素含量83質量%、平均粒子径6μm、アルベマール社製
塩素化ポリエチレン:エラスレン401A、融点:140℃、塩素含量40質量%、昭和電工社製
TMPTA:商品名「TMP3A」、トリメチロールプロパントリアクリレート、大阪有機化学工業製
ADCA:商品名「ビニホールAC♯3C」、アゾジカルボンアミド、永和化成社製
酸化亜鉛:商品名「酸化亜鉛2種」、三井金属鉱山社製
ステアリン酸亜鉛:商品名「SZ-P」、日堺化学社製
PE:スミカセンG201、ポリエチレン、メルトフローレート:2g/10min(JIS K6922-1(1997)に準拠、加熱温度190℃、荷重21.18N)
EPT:商品名「三井EPT X-3012P」、EPDM、ムーニー粘度:15ML1+4(100℃)(ASTM D 1646)に準拠、加熱温度100℃、エチレン含量71.8質量%、ジエン含量3.6質量%
なお、上記発明は、本発明の例示の実施形態として提供したが、これは単なる例示に過ぎず、限定的に解釈してはならない。当該技術分野の当業者によって明らかな本発明の変形例は、後記特許請求の範囲に含まれる。
Claims (7)
- ポリマーと発泡剤と難燃剤とを含有し、
前記難燃剤は、前記ポリマー100質量部に対して、
金属水酸化物5~110質量部と、
ハロゲン系有機化合物5~110質量部と
を含有し、
空間を封止するために発泡可能であることを特徴とする、発泡性封止材。 - 前記金属水酸化物が、水酸化アルミニウムおよび/または水酸化マグネシウムであることを特徴とする、請求項1に記載の発泡性封止材。
- 前記ハロゲン系有機化合物が、臭素系有機化合物および/または塩素系有機化合物であることを特徴とする、請求項1に記載の発泡性封止材。
- 前記臭素系有機化合物が、エチレンビス(ペンタブロモフェニル)および/またはデカブロモジフェニルオキサイドであり、
前記塩素系有機化合物が、塩素化ポリエチレンである
ことを特徴とする、請求項3に記載の発泡性封止材。 - 発泡性封止材と、
前記発泡性封止材に装着され、中空部材の内部空間に取り付け可能な取付部材と
を備え、
前記発泡性封止材は、ポリマーと発泡剤と難燃剤とを含有し、
前記難燃剤は、前記ポリマー100質量部に対して、
金属水酸化物5~110質量部と、
ハロゲン系有機化合物5~110質量部と
を含有し、
前記発泡性封止材は、前記内部空間を封止するために発泡可能である
ことを特徴とする、発泡性封止部材。 - 発泡性封止材を発泡させることによって得られる
封止発泡体であって、
前記発泡性封止材は、ポリマーと発泡剤と難燃剤とを含有し、
前記難燃剤は、前記ポリマー100質量部に対して、
金属水酸化物5~110質量部と、
ハロゲン系有機化合物5~110質量部と
を含有することを特徴とする、封止発泡体。 - 発泡性封止材を空間に設置する工程、および、
前記発泡性封止材を発泡させて、封止発泡体を得る工程
を備え、
前記発泡性封止材は、ポリマーと発泡剤と難燃剤とを含有し、
前記難燃剤は、前記ポリマー100質量部に対して、
金属水酸化物5~110質量部と、
ハロゲン系有機化合物5~110質量部と
を含有する
ことを特徴とする、空間の封止方法。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/384,222 US20150014934A1 (en) | 2012-03-21 | 2013-03-15 | Foamable sealing material, foamable sealing member, sealing foam, and method for sealing space |
KR1020147025713A KR20140146068A (ko) | 2012-03-21 | 2013-03-15 | 발포성 봉지재, 발포성 봉지 부재, 봉지 발포체 및 공간의 봉지 방법 |
CN201380014974.9A CN104204052A (zh) | 2012-03-21 | 2013-03-15 | 发泡性密封材料、发泡性密封构件、密封发泡体以及空间的密封方法 |
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JP2012-064238 | 2012-03-21 | ||
JP2012064238A JP5412542B2 (ja) | 2012-03-21 | 2012-03-21 | 発泡性封止材、発泡性封止部材、封止発泡体および空間の封止方法 |
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JP (1) | JP5412542B2 (ja) |
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KR102123726B1 (ko) * | 2017-08-25 | 2020-06-26 | 주식회사 가람매트 | 장치물 내장재용 발포폼 |
US20210261232A1 (en) * | 2020-02-20 | 2021-08-26 | The Boeing Company | System and method of fabricating sandwich panels with a foamable material |
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- 2013-03-15 CN CN201380014974.9A patent/CN104204052A/zh active Pending
- 2013-03-15 US US14/384,222 patent/US20150014934A1/en not_active Abandoned
- 2013-03-15 KR KR1020147025713A patent/KR20140146068A/ko not_active Application Discontinuation
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JP2003041038A (ja) * | 2001-07-26 | 2003-02-13 | Nitto Denko Corp | ゴム発泡体 |
JP2005097586A (ja) * | 2003-09-02 | 2005-04-14 | Nitto Denko Corp | 充填発泡用組成物、充填発泡部材および充填用発泡体 |
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CN104204052A (zh) | 2014-12-10 |
US20150014934A1 (en) | 2015-01-15 |
JP2013194183A (ja) | 2013-09-30 |
KR20140146068A (ko) | 2014-12-24 |
JP5412542B2 (ja) | 2014-02-12 |
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