WO2010106912A1 - 難燃性樹脂発泡体及び難燃性発泡部材 - Google Patents
難燃性樹脂発泡体及び難燃性発泡部材 Download PDFInfo
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- WO2010106912A1 WO2010106912A1 PCT/JP2010/053386 JP2010053386W WO2010106912A1 WO 2010106912 A1 WO2010106912 A1 WO 2010106912A1 JP 2010053386 W JP2010053386 W JP 2010053386W WO 2010106912 A1 WO2010106912 A1 WO 2010106912A1
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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
-
- 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
-
- 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
- C08J9/12—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 physical blowing agent
-
- 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
- C08J9/12—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 physical blowing agent
- C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/22—Plastics; Metallised plastics
- C09J7/26—Porous or cellular plastics
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- 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
- C09J7/29—Laminated material
-
- 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
- C08J2203/08—Supercritical fluid
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
- C09J2301/41—Additional features of adhesives in the form of films or foils characterized by the presence of essential components additives as essential feature of the carrier layer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/10—Presence of inorganic materials
- C09J2400/16—Metal
- C09J2400/163—Metal in the substrate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/24—Presence of a foam
- C09J2400/243—Presence of a foam in the substrate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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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
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249982—With component specified as adhesive or bonding agent
- Y10T428/249983—As outermost component
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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
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249986—Void-containing component contains also a solid fiber or solid particle
Definitions
- the present invention relates to a flame retardant foam that is flexible and has a high expansion ratio, and a flame retardant foam member formed using the flame retardant foam.
- an image display member fixed to an image display device such as a liquid crystal display, an electroluminescence display, a plasma display, or an optical member such as a camera or a lens fixed to a so-called “mobile phone” or “portable information terminal”
- a foam member is used when fixing to a predetermined part (fixing part or the like).
- a dustproof material having flame retardancy has been demanded from the viewpoint of product safety.
- an image display member mounted on an image display device such as a liquid crystal display, an electroluminescence display, or a plasma display, or an optical member such as a camera or lens mounted on a so-called “mobile phone” or “portable information terminal”
- the clearance (clearance; clearance) between the portions where the foam member is used is sufficiently large, so that the foam member can be used without much compression. Therefore, there was no need to worry about the compression repulsion force of the foam member.
- a foaming member for example, a gasket made of a foam base and a plastic film fixed to one side of the base (see Patent Document 1), and an electric / electronic device in which a foam is provided with an adhesive layer Sealing materials (see Patent Document 2) are known.
- an object of the present invention is to obtain a flame-retardant resin foam which is highly foamed and has excellent flexibility capable of following even a minute clearance.
- the present inventors have covered the surface of the flame retardant with a silicone having a high affinity with the resin, thereby releasing gas from the interface between the resin and the flame retardant during foaming. It was found that a flame-retardant resin foam having a high expansion ratio, which could not be achieved so far, was obtained. At the same time, it was found that coating the surface of the flame retardant with silicone having a high affinity with the resin improves the fluidity of the resin and makes it easier to obtain an increase in the expansion ratio.
- the present invention provides a resin foam comprising a resin and a flame retardant component, wherein the flame retardant component is a flame retardant coated with polysiloxane.
- the present invention provides a polysiloxane-coated metal hydroxide in which the polysiloxane-coated flame retardant is 30 to 60% by weight in the resin foam.
- the above resin foam is provided.
- the present invention provides the above resin having a compression load value at 50% compression of 3.0 N / cm 2 or less and having a flame resistance of HBF grade or higher in a grade determined by a flame resistance test of UL94 standard. Provide foam.
- the present invention provides the above resin foam having an expansion ratio of 9 times or more.
- the present invention provides the above resin foam having a density of 0.030 to 0.120 g / cm 3 .
- the present invention provides the resin foam, wherein the resin is a thermoplastic resin.
- the present invention provides the above resin foam having a closed cell structure or a semi-continuous semi-closed cell structure.
- the present invention provides the resin foam, wherein the resin foam is formed through a step of depressurizing after impregnating the resin with a high-pressure inert gas.
- the present invention provides the resin foam, wherein the inert gas during impregnation is carbon dioxide.
- the present invention provides the resin foam, wherein the inert gas during impregnation is in a supercritical state.
- the present invention provides a foamed member composed of the resin foam.
- the present invention provides the foamed member having an adhesive layer on one side or both sides of the resin foam.
- the present invention provides the foamed member, wherein the adhesive layer is formed on the resin foam via the film layer.
- the present invention provides the foamed member, wherein the adhesive layer is an acrylic adhesive layer.
- the foam of the present invention since it has the above-described configuration, it has high foaming, has excellent flexibility capable of following even a small clearance, and further has flame retardancy. .
- the resin foam of the present invention is a resin foam containing a resin and a flame retardant component, wherein the flame retardant component is a flame retardant coated with polysiloxane.
- the resin foam of the present invention is usually produced by foaming and molding a resin composition containing a resin and a flame retardant component.
- the resin composition contains at least a resin and a flame retardant component, and is a composition that forms a resin foam.
- the resin that is the material of the resin foam (foam) is not particularly limited as long as it is a polymer exhibiting thermoplasticity (thermoplastic polymer) and can be impregnated with high-pressure gas.
- thermoplastic polymers include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, a copolymer of ethylene and propylene, ethylene or propylene and other ⁇ -olefins.
- Olefin-based copolymers such as copolymers of ethylene and other ethylenically unsaturated monomers (for example, vinyl acetate, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, vinyl alcohol, etc.)
- Polystyrene such as polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin); polyamide such as 6-nylon, 66-nylon, 12-nylon; polyamideimide; polyurethane; polyimide; polyetherimide; Methyl methacrylate Which acrylic resins, polyvinyl chloride, polyvinyl fluoride; alkenyl aromatic resin; polyacetal; polycarbonate such as bisphenol-A based polycarbonate, polyethylene terephthalate, polyesters such as polybutylene terephthalate and poly (phenylene sulfide) and the like.
- the thermoplastic polymer also includes a thermoplastic elastomer that exhibits properties as a rubber at room temperature and exhibits thermoplasticity at a high temperature.
- thermoplastic elastomers include olefin elastomers such as ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-vinyl acetate copolymer, polybutene, polyisobutylene, and chlorinated polyethylene; Styrene elastomers such as butadiene-styrene copolymers, styrene-isoprene-styrene copolymers, styrene-isoprene-butadiene-styrene copolymers, and hydrogenated polymers thereof; thermoplastic polyester elastomers; thermoplastic polyurethane elastomers A thermoplastic acrylic elastomer and the like. These thermoplastic elastomers, for example, have a glass transition temperature
- Thermoplastic polymers can be used alone or in admixture of two or more. Moreover, any of thermoplastic elastomers, thermoplastic polymers other than thermoplastic elastomers, and mixtures of thermoplastic elastomers and thermoplastic polymers other than thermoplastic elastomers can be used as the foam material.
- thermoplastic elastomer and a thermoplastic polymer other than the thermoplastic elastomer examples include a mixture of an olefin elastomer such as an ethylene-propylene copolymer and an olefin polymer such as polypropylene.
- a flame retardant coated with polysiloxane is usually used as the flame retardant component.
- the flame retardant coated with polysiloxane has a structure in which a flame retardant that improves the flame retardancy of resin foam is coated with polysiloxane with high heat resistance, so it has higher flame resistance and heat resistance. Demonstrate.
- a flame retardant component has a high affinity with the resin due to the polysiloxane coating, so it has excellent dispersibility in the resin and does not impair the fluidity of the resin.
- foam-molding using no gas escape occurs at the interface between the resin and the flame retardant component.
- the amount of the flame retardant component used can be reduced, and this reduction in the amount of flame retardant component contributes to an improvement in the expansion ratio. .
- the flame retardant is not particularly limited, and known and commonly used flame retardants used for polyolefin resins and the like can be used. Of these, metal hydroxides are preferably used.
- the metal element in the metal hydroxide examples include aluminum (Al), magnesium (Mg), calcium (Ca), nickel (Ni), cobalt (Co), tin (Sn), zinc (Zn), and copper (Cu). , Iron (Fe), titanium (Ti), boron (B) and the like. Of these, aluminum, magnesium and the like are preferable.
- the metal hydroxide may be composed of one kind of metal element or may be composed of two or more kinds of metal elements. In the present invention, as the metal hydroxide composed of one kind of metal element, for example, aluminum hydroxide, magnesium hydroxide or the like is preferably used as the metal hydroxide composed of one kind of metal element.
- a composite metal hydroxide that is a metal hydroxide composed of two or more metal elements can also be suitably used.
- Specific examples of such composite metal hydroxides include sMgO. (1-s) NiO.cH 2 O [0 ⁇ s ⁇ 1, 0 ⁇ c ⁇ 1], sMgO. (1-s ) ZnO.cH 2 O [0 ⁇ s ⁇ 1, 0 ⁇ c ⁇ 1], sA1 2 O 3.
- (1-s) Fe 2 O 3 .cH 2 O [0 ⁇ s ⁇ 1, 0 ⁇ c ⁇ 3 ] Etc. are mentioned.
- a composite metal hydroxide composed of magnesium, nickel, and zinc is optimal.
- Metal hydroxides for example, magnesium oxide / nickel oxide hydrate and magnesium oxide / zinc oxide hydrate are particularly preferably used.
- the composite metal hydroxide may have a polyhedral shape or a thin flat plate shape. When a polyhedral composite metal hydroxide is used, a highly foamed resin foam can be obtained.
- the average particle size (average particle size) of the flame retardant (particularly the above metal hydroxide) is not particularly limited, but is preferably about 0.1 to 10 ⁇ m, and preferably about 0.2 to 7 ⁇ m.
- the average particle size can be measured by, for example, a laser particle size measuring device.
- a specific surface area becomes large and a flame retardance becomes high, so that a particle diameter is small.
- the particle diameter exceeds 10 ⁇ m, the expansion ratio tends to decrease, and it becomes difficult to obtain a highly foamed resin foam.
- the particle size is less than 0.1 ⁇ m, it may be difficult to handle because it tends to fly as dust.
- the flame retardant is polysiloxane coated, but the flame retardant before the polysiloxane coating may be surface-treated. That is, in the present invention, the polysiloxane-coated flame retardant is obtained by applying a surface treatment to a flame retardant as a core component, and further applying a polysiloxane coating to the flame retardant subjected to the surface treatment. Also good.
- the use of a surface-treated flame retardant as the flame retardant before polysiloxane coating is advantageous in that the adhesion to the polysiloxane coating is improved and the coating processability is improved.
- the surface treatment is not particularly limited, but a surface treatment method using a surface treatment agent can be employed. Although it does not restrict
- a surface treating agent can be used individually or in mixture of 2 or more types.
- the amount of the surface treatment agent used is not particularly limited.
- the amount is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the metal hydroxide.
- the amount is preferably 0.3 to 8 parts by weight. If the amount is less than 0.1 parts by weight, the effect of using the surface treatment agent may not be obtained. On the other hand, if the amount exceeds 10 parts by weight, the particle size becomes too large, causing gas escape during foaming. There is a case.
- the surface treatment method using a surface treatment agent is not particularly limited, but when a metal hydroxide is used as a flame retardant, for example, a dry method, a wet method, an integral blend method, etc., which are known and commonly used methods Is mentioned.
- the polysiloxane used for the coating of the flame retardant is not particularly limited as long as it is a polymer having a siloxane bond as a main skeleton, but a polyorganosiloxane having an average composition formula represented by the formula (1) is preferable.
- the molecular structure of polysiloxane is preferably a straight chain, but may partially include a branched chain structure.
- R represents a substituted or unsubstituted monovalent hydrocarbon group, and a represents a positive number.
- the carbon number of R in the polyorganosiloxane represented by the average composition formula (1) is usually 1 to 10, preferably 1 to 8.
- examples of the hydrocarbon group R include alkyl groups such as methyl group, ethyl group, propyl group, and butyl group; vinyl group, allyl group, butenyl group, and the like.
- the hydrocarbon groups R may all be the same group or different from each other.
- substituted hydrocarbon group as the hydrocarbon group R include, for example, chloromethyl group, chloropropyl group, 3,3,3-trifluoropropyl group, 2-cyanoethyl group and the like.
- the molecular structure of the polyorganosiloxane represented by the average composition formula (1) is preferably linear, but may be partially branched. Therefore, it is a positive number in the range of 1.95 to 2.05.
- the amount of polysiloxane is not particularly limited, but is 0.1 to 15% by weight based on the total amount of the flame retardant and polysiloxane in terms of flame retardancy and handling properties. Preferably, it is 1.0 to 10% by weight. If it is less than 0.1% by weight, the flame retardancy may not be improved, and there is concern about a decrease in fluidity. If it exceeds 15% by weight, the average particle size of the flame retardant component may become too large, and the expansion ratio may be lowered.
- the flame retardant coated with polysiloxane can be prepared by mixing and dispersing polysiloxane and flame retardant or kneading. Mixing and dispersing and kneading may be performed under a pressure of about 0.1 to 10 MPa.
- a metal oxide is preferable as the flame retardant, and a polyorganosiloxane represented by the average composition formula (1) is preferable as the polysiloxane coating the flame retardant.
- a metal oxide coated with a polyorganosiloxane represented by the average composition formula (1) is preferable.
- the content of the flame retardant component in the resin composition is preferably as small as possible from the viewpoint of obtaining a highly foamed foam.
- the content of a polysiloxane-coated flame retardant for example, polysiloxane-coated metal oxide
- the content of a polysiloxane-coated flame retardant is not particularly limited, but from the viewpoint of expansion ratio and flame retardancy, It is preferably 30 to 60% by weight, preferably 35 to 55% by weight, based on the total amount of the resin foam. When the amount is less than 30 parts by weight, flame retardancy may not be sufficiently obtained.
- the amount exceeds 60 parts by weight the expansion ratio decreases as the elongation viscosity of the resin composition increases, and foaming with high foaming is achieved. The body may not be obtained.
- additives may be added as necessary.
- the kind of additive is not specifically limited, Various additives normally used for foam molding can be used.
- additives include cell nucleating agents, crystal nucleating agents, plasticizers, lubricants, colorants (pigments, dyes, etc.), ultraviolet absorbers, antioxidants, anti-aging agents, fillers, reinforcing agents, and charging agents.
- examples thereof include an inhibitor, a surfactant, a vulcanizing agent, and a surface treatment agent.
- the addition amount of the additive can be appropriately selected within a range that does not impair the formation of bubbles and the like, and the addition amount used for normal resin foaming and molding can be adopted.
- an additive can be used individually or in combination of 2 or more types.
- the lubricant improves the fluidity of the resin and suppresses thermal degradation of the resin.
- the lubricant used in the present invention is not particularly limited as long as it has an effect on improving the fluidity of the resin.
- hydrocarbon lubricants such as liquid paraffin, paraffin wax, microwax and polyethylene wax
- stearic acid Fatty acid lubricants such as behenic acid and 12-hydroxystearic acid
- ester lubricants such as butyl stearate, monoglyceride stearate, pentaerythritol tetrastearate, hydrogenated castor oil and stearyl stearate.
- Such lubricants can be used alone or in combination of two or more.
- the amount of lubricant added is, for example, 0.5 to 10 parts by weight (preferably 0.8 to 8 parts by weight, more preferably 1 to 6 parts by weight) with respect to 100 parts by weight of the resin.
- the addition amount exceeds 10 parts by weight, the fluidity becomes too high and the expansion ratio may be lowered.
- it is less than 0.5 parts by weight, the fluidity cannot be improved, the stretchability at the time of foaming is lowered, and the foaming ratio may be lowered.
- the shrinkage-preventing agent has a function of effectively suppressing permeation of the foaming agent gas by forming a molecular film on the surface of the foam film.
- the shrinkage preventing agent used in the present invention is not particularly limited as long as it has an effect of suppressing the permeation of the blowing agent gas.
- fatty acid metal salts for example, stearic acid, behenic acid, 12-hydroxystearic acid
- Fatty acids such as aluminum, calcium, magnesium, lithium, barium, zinc, lead salts, etc.
- fatty acid amide [fatty acid amide (monoamide or bisamide) of about 12 to 38 carbon atoms (preferably about 12 to 22 carbon atoms)
- bisamide is preferably used to obtain a fine cell structure.
- Such anti-shrinkage agents can be used alone or in combination of two or more.
- the addition amount of the shrinkage inhibitor is, for example, 0.5 to 10 parts by weight (preferably 0.7 to 8 parts by weight, more preferably 1 to 6 parts by weight) with respect to 100 parts by weight of the resin. If the addition amount exceeds 10 parts by weight, gas efficiency is lowered in the cell growth process, so that a cell having a small cell diameter can be obtained, but there are also many unfoamed portions, which may reduce the foaming ratio. On the other hand, if the amount is less than 0.5 part by weight, the coating film is not sufficiently formed, and gas escape occurs at the time of foaming, causing shrinkage and reducing the foaming ratio.
- a lubricant such as stearic acid monoglyceride and a shrinkage preventing agent such as erucic acid amide or lauric acid bisamide may be used in combination.
- the resin composition can be obtained by a known / conventional method.
- the resin composition can be obtained by adding a flame retardant component (a flame retardant coated with a polysiloxane) and, if necessary, an additive to a resin that is a raw material of the foam and kneading.
- a flame retardant component a flame retardant coated with a polysiloxane
- an additive to a resin that is a raw material of the foam and kneading.
- kneading mixing, you may heat.
- the resin composition contains a flame retardant coated with polysiloxane, the resin has good handling properties without impairing the fluidity of the resin due to the flame retardant component.
- the resin composition has an elongational viscosity (temperature 180 ° C., shear rate 100 [1 / s]) measured by a capillary rheometer of 30 to 90 kPa ⁇ s, preferably 40 to 70 kPa ⁇ s. Since the resin composition has such an extensional viscosity, it is difficult for the bubble wall to break during the foam molding, and a high foaming ratio can be obtained. Further, the pressure at the die can be maintained even under a wide gap condition, and the thickness of the foam can be increased.
- the elongation viscosity of the resin composition is less than 30 kPa ⁇ s, a desired expansion ratio may not be obtained at the time of foam molding, or outgassing may occur.
- the elongation viscosity exceeds 90 kPa ⁇ s. In some cases, the moldability is lowered and a smooth foam surface cannot be obtained.
- the resin foam of the present invention is formed from a resin composition containing at least a resin and a flame retardant component.
- the method for producing the resin foam is not particularly limited, and examples thereof include commonly used methods such as a physical method and a chemical method.
- a general physical method is a method of forming bubbles by dispersing a low boiling point liquid (foaming agent) such as chlorofluorocarbons or hydrocarbons in a resin, and then heating to volatilize the foaming agent.
- a general chemical method is a method in which bubbles are formed by a gas generated by thermal decomposition of a compound (foaming agent) added to a resin.
- a method using a high-pressure inert gas as the foaming agent is preferable because a foam having a small cell diameter and a high cell density can be easily obtained.
- a method for forming the resin foam of the present invention from a resin composition by a method using a high-pressure inert gas as a foaming agent for example, a gas for impregnating a resin with an inert gas under high pressure is used.
- a gas for impregnating a resin with an inert gas under high pressure examples include an impregnation step, a pressure reduction step in which the pressure is reduced after the step to foam the resin, and a heating method in which bubbles are grown by heating as necessary.
- the unfoamed molded product after molding the resin composition in advance to obtain an unfoamed molded product, the unfoamed molded product may be impregnated with an inert gas, or after melting the resin composition, After impregnating the inert gas under pressure, it may be subjected to molding during decompression.
- These steps may be performed by either a batch method or a continuous method.
- the inert gas used in the present invention is not particularly limited as long as it is inert to the resin and can be impregnated, and examples thereof include carbon dioxide, nitrogen gas, and air. These gases may be mixed and used. Among these, carbon dioxide having a large amount of impregnation into the resin used as the material of the foam and having a high impregnation rate is preferable. Carbon dioxide is also preferred from the viewpoint of obtaining a clean resin foam with few impurities.
- the inert gas when impregnating the resin is in a supercritical state.
- the solubility of the gas in the resin is increased and high concentration can be mixed.
- the pressure drops rapidly after impregnation since the concentration is high as described above, the generation of bubble nuclei is increased, and the density of bubbles formed by the growth of the bubble nuclei is the same as the porosity. Since it becomes large, fine bubbles can be obtained.
- Carbon dioxide has a critical temperature of 31 ° C. and a critical pressure of 7.4 MPa.
- the impregnation amount of the inert gas into the resin is not particularly limited, but is preferably 1.0 to 10.0% by weight, preferably 1.5 to 7.5% based on the total amount of the resin from the viewpoint of pressure control during foaming. 5% by weight. If the amount of impregnation of the inert gas into the resin is too small, the control range of pressure control during foaming may be reduced, while if too large, pressure control becomes difficult.
- a resin foam can be formed as follows. That is, first, an unfoamed molded product (such as a resin sheet for foam molding) is formed by extruding the resin composition using an extruder such as a single screw extruder or a twin screw extruder. Alternatively, using a kneader equipped with rollers, cams, kneaders, and Banbury type blades, the resin composition is uniformly kneaded, and this is press-molded using a hot plate press, and then unfoamed. A product (such as a resin sheet for forming a foam).
- an extruder such as a single screw extruder or a twin screw extruder.
- a kneader equipped with rollers, cams, kneaders, and Banbury type blades the resin composition is uniformly kneaded, and this is press-molded using a hot plate press, and then unfoamed.
- a product (such as a resin sheet for
- the obtained unfoamed molded product is put in a pressure vessel, a high-pressure inert gas is introduced, and the inert gas is impregnated in the unfoamed molded product.
- the shape of the unfoamed molded product is not particularly limited, and may be any of a roll shape, a plate shape, and the like.
- the introduction of the high-pressure inert gas may be performed continuously or discontinuously.
- the pressure is released (usually up to atmospheric pressure) to generate bubble nuclei in the resin. Bubble nuclei may be grown at room temperature as they are, or may be grown by heating as necessary.
- a heating method a known or conventional method such as a water bath, an oil bath, a hot roll, a hot air oven, a far infrared ray, a near infrared ray, or a microwave can be adopted. After the bubbles are grown in this way, the shape is fixed rapidly by cooling with cold water or the like.
- a resin foam can be formed as follows. That is, a high-pressure inert gas is injected while kneading the resin composition using an extruder such as a single-screw extruder or a twin-screw extruder, and the resin is sufficiently impregnated in the resin, and then extruded and pressurized. Is released (usually up to atmospheric pressure), foaming and molding are performed simultaneously, and in some cases, the bubbles are grown by heating. After the bubbles are grown, the shape is fixed rapidly by cooling with cold water or the like.
- the pressure in the gas impregnation step is, for example, 6 MPa or more (for example, about 6 to 100 MPa), preferably 8 MPa or more (for example, about 8 to 100 MPa).
- 6 MPa the pressure at the time of foaming is remarkable, the bubble diameter becomes too large, a small average cell diameter (average bubble diameter) in the above range cannot be obtained, and the dustproof effect is reduced.
- the pressure is low, the amount of gas impregnation is relatively small compared to when the pressure is high, and the number of bubble nuclei formed is reduced due to a decrease in the bubble nucleus formation rate. This is because the bubble diameter becomes extremely large.
- the bubble diameter and the bubble density change greatly only by slightly changing the impregnation pressure, so that it is difficult to control the bubble diameter and the bubble density.
- the temperature in the gas impregnation step varies depending on the type of inert gas or resin to be used and can be selected in a wide range, but it is, for example, about 10 to 350 ° C. in consideration of operability.
- the impregnation temperature in the case of impregnating an inert gas into an unfoamed molded product such as a sheet is about 10 to 250 ° C., preferably about 40 to 230 ° C. in a batch system.
- the impregnation temperature in the case where the molten resin composition impregnated with gas is extruded and foaming and molding are simultaneously performed is generally about 60 to 350 ° C. in the continuous type.
- the temperature during impregnation is preferably 32 ° C. or higher, particularly 40 ° C. or higher in order to maintain a supercritical state.
- the decompression speed is not particularly limited, but is preferably about 5 to 300 MPa / second in order to obtain uniform fine bubbles.
- the heating temperature in the heating step is, for example, about 40 to 250 ° C., preferably about 60 to 250 ° C.
- the resin foam of the present invention is usually produced by foaming and molding using a resin composition containing a resin and a flame retardant component, and contains a flame retardant coated with polysiloxane as a flame retardant component. Has excellent flame retardancy. Specifically, it is preferable that the resin foam of the present invention has a flame retardancy equal to or higher than the HBF grade as a grade determined by a flame retardancy test of UL94 standard.
- the repulsive load value at the time of 50% compression of the resin foam is preferably 3.0 N / cm 2 or less, more preferably 2.0 N / cm 2 or less from the viewpoint of strain due to the repulsive force generated when used in equipment. It is.
- the repulsive load at the time of 50% compression of a resin foam is measured according to the compression hardness measuring method described in JISK6767.
- the expansion ratio is preferably 9 times or more (for example, 9 times to 50 times), more preferably 12 times or more (for example, from the viewpoint of impact absorption, light weight, and flexibility. 12 times to 30 times) is preferable. If the expansion ratio is less than 9 times, sufficient impact absorbability may not be obtained in the resin foam, or flexibility that can follow a minute clearance may not be obtained, while the expansion ratio exceeds 50 times. And strength may be significantly reduced.
- a specific example of the minute clearance is a clearance of 0.10 to 0.30 mm.
- the expansion ratio of the resin foam is calculated from the following formula.
- Foaming ratio (times) (density before foaming) / (density after foaming)
- the density before foaming is, for example, the density of an unfoamed molded product or a resin before foaming when a resin foam is formed by impregnating a molten resin with an inert gas after melting the resin composition.
- the density after foaming corresponds to the density of the following resin foam.
- the density is preferably 0.030 to 0.120 g / cm 3 , more preferably 0.045 to 0.100 g / cm 3 in terms of impact absorption and flexibility. is there. If it is less than 0.030 g / cm 3 , the strength may be remarkably reduced. On the other hand, if it exceeds 0.120 g / cm 3 , sufficient impact absorbability may not be obtained or minute clearance may not be followed. .
- the cell structure is a closed cell structure or a semi-continuous semi-closed cell structure (a mixture of a closed cell structure and a semi-continuous semi-closed cell structure).
- the ratio is not particularly limited).
- a cell structure in which the closed cell structure part is 80% or more (in particular, 90% or more) in the resin foam is preferable.
- the flame retardancy of the resin foam is controlled by selecting the resin, selecting the type of flame retardant to be coated, selecting the polysiloxane structure, adjusting the amount of flame retardant component, etc. be able to.
- the resilience load, density, expansion ratio, and cell structure at 50% compression of the resin foam are the types of resin, types of foaming agent, flame retardant components and other additives.
- operating conditions such as temperature, pressure, and time in the gas impregnation process
- operating conditions such as pressure reduction speed, temperature, and pressure in the decompression process, heating temperature after decompression, etc. It can be adjusted by selecting and setting.
- the resin foam of the present invention has both flexibility and flame retardancy, and is highly foamed and lightweight. Moreover, it can follow a minute clearance. For this reason, it can use suitably as a sealing material, a buffer sealing material, an impact-absorbing material, a dustproof material, a soundproof material, and a waterproofing material.
- the resin foam of the present invention has the above-mentioned characteristics and can fill a minute clearance between high-density parts, it can be used for various members or parts, electronic parts, electronic devices, and the like. It is particularly useful for downsizing and thinning. For example, it can be suitably used for liquid crystal display devices such as liquid crystal displays, electroluminescence displays, and plasma displays, and mobile communication devices such as mobile phones and portable information terminals.
- liquid crystal display devices such as liquid crystal displays, electroluminescence displays, and plasma displays
- mobile communication devices such as mobile phones and portable information terminals.
- the flame retardant foam member is composed of at least the resin foam.
- the flame retardant foamed member may be composed of only a resin foam, or another layer or a substrate (particularly an adhesive layer, etc.) is provided on one or both sides of the resin foam. It may be a configuration.
- the flame-retardant foam member has a configuration in which an adhesive layer is provided on one or both surfaces of the resin foam, it is possible to fix or temporarily fix a member or component such as an optical member to the adherend. .
- the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives (natural rubber-based pressure-sensitive adhesives, synthetic rubber-based pressure-sensitive adhesives), silicone-based pressure-sensitive adhesives, and polyester-based pressure-sensitive adhesives.
- Known pressure-sensitive adhesives such as adhesives, urethane-based pressure-sensitive adhesives, polyamide-based pressure-sensitive adhesives, epoxy-based pressure-sensitive adhesives, vinyl alkyl ether-based pressure-sensitive adhesives, and fluorine-based pressure-sensitive adhesives can be appropriately selected and used.
- An adhesive can be used individually or in combination of 2 or more types.
- the pressure-sensitive adhesive may be any type of pressure-sensitive adhesive such as an emulsion-based pressure-sensitive adhesive, a hot-melt pressure-sensitive adhesive, a solvent-based pressure-sensitive adhesive, an oligomer-based pressure-sensitive adhesive, or a solid-based pressure-sensitive adhesive.
- an acrylic pressure-sensitive adhesive is suitable as the pressure-sensitive adhesive from the viewpoint of preventing contamination of the adherend.
- the pressure-sensitive adhesive layer can be formed by using a known or conventional forming method.
- a method of applying a pressure-sensitive adhesive on a predetermined site or surface coating method
- a pressure-sensitive adhesive film on a release film such as a release liner
- examples thereof include a method (transfer method) of applying an agent to form an adhesive layer and then transferring the adhesive layer onto a predetermined site or surface.
- a known or conventional coating method such as a casting method, a roll coater method, a reverse coater method, a doctor blade method
- a known or conventional coating method such as a casting method, a roll coater method, a reverse coater method, a doctor blade method
- the thickness of the adhesive layer is usually about 2 to 100 ⁇ m (preferably 10 to 100 ⁇ m). The thinner the adhesive layer is, the higher the effect of preventing the adhesion of dust and dirt at the end portion.
- the adhesion layer may have any form of a single layer or a laminated body.
- the adhesive layer may be formed on the foam via another layer (lower layer).
- a lower layer include a base material layer (particularly, a film layer), other adhesive layers, an intermediate layer, an undercoat layer, and the like.
- the adhesive layer is formed only on one side (one side) of the foam
- another layer may be formed on the other side of the foam, for example, other types of adhesives. Examples thereof include a layer and a base material layer.
- the resin foam constituting the flame-retardant foam member or the flame-retardant foam member may be processed so as to have a desired shape or thickness. For example, by slicing the flame retardant foamed member, a flame retardant foamed member having a desired thickness can be obtained. In addition, various shapes may be processed according to the device or equipment used.
- the flame-retardant foamed member can be suitably used as, for example, a sealing material, a buffer sealing material, an impact absorbing material, a dustproof material, a soundproof material, and a waterproof material.
- the flame-retardant foamed member is particularly preferably used inside an electronic device or the like. This is because the resin foam constituting the flame-retardant foam member is excellent in flexibility, and since an inert gas such as carbon dioxide is usually used as a foaming agent during production, generation of harmful substances and This is because there is no residual pollutant and it is clean.
- the flame-retardant foam member is used, for example, when various members or parts (for example, optical members) are attached (attached) to a predetermined part. In particular, it is preferably used even when a small member or component (for example, a small optical member) is mounted on a thin product.
- an optical member attached (attached) using a flame-retardant foaming member for example, an image display member attached to an image display device such as a liquid crystal display, an electroluminescence display, a plasma display (particularly, a small image display) Member) and a camera or lens (particularly, a small camera or lens) mounted on a mobile communication device such as a so-called “mobile phone” or “portable information terminal”.
- an image display member attached to an image display device such as a liquid crystal display, an electroluminescence display, a plasma display (particularly, a small image display) Member) and a camera or lens (particularly, a small camera or lens) mounted on a mobile communication device such as a so-called “mobile phone” or “portable information terminal”.
- a member to be attached (mounted) using a flame-retardant foaming member a battery, an HDD (hard disk drive), and the like can be given.
- Example 1 Polypropylene [melt flow rate (MFR): 0.35 g / 10 min]: 45 parts by weight, polyolefin elastomer [melt flow rate (MFR): 6 g / 10 min, JIS A hardness: 79 °]: 55 parts by weight, polysiloxane coating Treated magnesium hydroxide (trade name “FRX-100” manufactured by Shin-Etsu Chemical Co., Ltd., average particle size: 1.0 ⁇ m, coating amount: 6.0% by weight): 60 parts by weight, carbon (trade name “Asahi # 35” Asahi Carbon Co., Ltd.): 10 parts by weight, stearic acid monoglyceride: 1 part by weight, and fatty acid bisamide (lauric acid bisamide): 1 part by weight in a biaxial kneader manufactured by Japan Steel Works (JSW), After knead
- the pellets were put into a single screw extruder manufactured by Nippon Steel Works, and carbon dioxide gas was injected under an atmosphere of 220 ° C. at a pressure of 13 (12 after injection) MPa. Carbon dioxide gas was injected at a ratio of 6.0% by weight with respect to the total amount of the polymer. After sufficiently saturating the carbon dioxide gas, it was cooled to a temperature suitable for foaming and then extruded from a die to obtain a foam.
- Example 2 Polypropylene [melt flow rate (MFR): 0.35 g / 10 min]: 45 parts by weight, polyolefin elastomer [melt flow rate (MFR): 6 g / 10 min, JIS A hardness: 79 °]: 55 parts by weight, polysiloxane coating Treated magnesium hydroxide (trade name “FRX-100” manufactured by Shin-Etsu Chemical Co., Ltd., average particle size: 1.0 ⁇ m, coating amount: 6.0 wt%): 90 parts by weight, carbon (trade name “Asahi # 35” Asahi Carbon Co., Ltd.): 10 parts by weight, stearic acid monoglyceride: 1 part by weight, and fatty acid bisamide (lauric acid bisamide): 1 part by weight in a biaxial kneader manufactured by Japan Steel Works (JSW), After knead
- the pellets were put into a single screw extruder manufactured by Nippon Steel Works, and carbon dioxide gas was injected under an atmosphere of 220 ° C. at a pressure of 13 (12 after injection) MPa. Carbon dioxide gas was injected at a ratio of 6.0% by weight with respect to the total amount of the polymer. After sufficiently saturating the carbon dioxide gas, it was cooled to a temperature suitable for foaming and then extruded from a die to obtain a foam.
- Example 3 Polypropylene [melt flow rate (MFR): 0.35 g / 10 min]: 45 parts by weight, polyolefin elastomer [melt flow rate (MFR): 6 g / 10 min, JIS A hardness: 79 °]: 55 parts by weight, polysiloxane coating Treated magnesium hydroxide (trade name “FRX-100” manufactured by Shin-Etsu Chemical Co., Ltd., average particle size: 1.0 ⁇ m, coating amount: 6.0% by weight): 120 parts by weight, carbon (trade name “Asahi # 35” Asahi Carbon Co., Ltd.): 10 parts by weight, stearic acid monoglyceride: 1 part by weight, and fatty acid bisamide (lauric acid bisamide): 1 part by weight in a biaxial kneader manufactured by Japan Steel Works (JSW), After knead
- the pellets were put into a single screw extruder manufactured by Nippon Steel Works, and carbon dioxide gas was injected under an atmosphere of 220 ° C. at a pressure of 13 (12 after injection) MPa. Carbon dioxide gas was injected at a ratio of 6.0% by weight with respect to the total amount of the polymer. After sufficiently saturating the carbon dioxide gas, it was cooled to a temperature suitable for foaming and then extruded from a die to obtain a foam.
- Example 4 Polypropylene [melt flow rate (MFR): 0.35 g / 10 min]: 50 parts by weight, polyolefin elastomer [melt flow rate (MFR): 6 g / 10 min, JIS A hardness: 79 °]: 50 parts by weight, polysiloxane coating Treated magnesium hydroxide (trade name “FRX-100” manufactured by Shin-Etsu Chemical Co., Ltd., average particle size: 1.0 ⁇ m, coating amount: 6.0% by weight): 120 parts by weight, carbon (trade name “Asahi # 35” Asahi Carbon Co., Ltd.): 10 parts by weight, stearic acid monoglyceride: 1 part by weight, and fatty acid bisamide (lauric acid bisamide): 1 part by weight in a biaxial kneader manufactured by Japan Steel Works (JSW), After knead
- the pellets were put into a single screw extruder manufactured by Nippon Steel Works, and carbon dioxide gas was injected under an atmosphere of 220 ° C. at a pressure of 13 (12 after injection) MPa. Carbon dioxide gas was injected at a ratio of 6.0% by weight with respect to the total amount of the polymer. After sufficiently saturating the carbon dioxide gas, it was cooled to a temperature suitable for foaming and then extruded from a die to obtain a foam.
- Example 5 Polypropylene [melt flow rate (MFR): 0.35 g / 10 min]: 50 parts by weight, polyolefin elastomer [melt flow rate (MFR): 6 g / 10 min, JIS A hardness: 79 °]: 50 parts by weight, polysiloxane coating Treated magnesium hydroxide (trade name “FRX-100” manufactured by Shin-Etsu Chemical Co., Ltd., average particle size: 1.0 ⁇ m, coating amount: 6.0% by weight): 75 parts by weight, carbon (trade name “Asahi # 35” Asahi Carbon Co., Ltd.): 10 parts by weight, stearic acid monoglyceride: 1 part by weight, and fatty acid bisamide (lauric acid bisamide): 1 part by weight in a biaxial kneader manufactured by Japan Steel Works (JSW), After knead
- the pellets were put into a single screw extruder manufactured by Nippon Steel Works, and carbon dioxide gas was injected under an atmosphere of 220 ° C. at a pressure of 13 (12 after injection) MPa. Carbon dioxide gas was injected at a ratio of 6.0% by weight with respect to the total amount of the polymer. After sufficiently saturating the carbon dioxide gas, it was cooled to a temperature suitable for foaming and then extruded from a die to obtain a foam.
- Example 6 Polypropylene [melt flow rate (MFR): 0.35 g / 10 min]: 65 parts by weight, polyolefin elastomer [melt flow rate (MFR): 6 g / 10 min, JIS A hardness: 79 °]: 35 parts by weight, polysiloxane coating Treated magnesium hydroxide (trade name “FRX-100” manufactured by Shin-Etsu Chemical Co., Ltd., average particle size: 1.0 ⁇ m, coating amount: 6.0% by weight): 75 parts by weight, carbon (trade name “Asahi # 35” Asahi Carbon Co., Ltd.): 10 parts by weight, stearic acid monoglyceride: 1 part by weight, and fatty acid bisamide (lauric acid bisamide): 1 part by weight in a biaxial kneader manufactured by Japan Steel Works (JSW), After knead
- the pellets were put into a single screw extruder manufactured by Nippon Steel Works, and carbon dioxide gas was injected under an atmosphere of 220 ° C. at a pressure of 13 (12 after injection) MPa. Carbon dioxide gas was injected at a ratio of 6.0% by weight with respect to the total amount of the polymer. After sufficiently saturating the carbon dioxide gas, it was cooled to a temperature suitable for foaming and then extruded from a die to obtain a foam.
- the pressure of the resin at this time is measured by a pressure sensor installed near the entrance of the capillary.
- the pressure thus measured was calculated as a viscosity value by the following equation.
- P 0 (P S ⁇ L L -P L ⁇ L L) / (L L -L S)
- P 0 Pressure loss [MPa]
- P L Pressure loss measured with a long die [MPa]
- P S Pressure loss measured with a short die [MPa]
- L L Long die length [mm]
- L S Length of short die [mm] From this, the extensional viscosity ⁇ [kPa ⁇ s] was calculated by the following equation.
- the foam is punched with a 40 mm ⁇ 40 mm punching blade mold, and the dimensions of the punched sample are measured. Further, the thickness is measured with a 1/100 dial gauge having a measurement terminal diameter ( ⁇ ) of 20 mm. The volume of the foam was calculated from these values. Next, the weight of the foam is measured with an upper pan balance having a minimum scale of 0.01 g or more. From these values, the density (g / cm 3 ) of the foam was calculated. The density of the foam means the density after foaming.
- compression load value at 50% compression It measured according to the compression hardness measuring method of the foam described in JIS K 6767. A test piece obtained by cutting a foam into a circular shape with a diameter of 20 mm was compressed to 50% of the initial thickness at a speed of 10 mm / min, and the load value (N) after 20 seconds was measured and obtained. The value obtained was converted per unit area (1 cm 2 ), and the compression load value (N / cm 2 ) at 50% compression was determined.
- the resin foam and the flame-retardant foam member of the present invention have flexibility and flame retardancy, and are highly foamed and lightweight. Moreover, it can follow a minute clearance.
- it can be suitably used as a sealing material, a buffer sealing material, an impact absorbing material, a dustproof material, a soundproofing material, a waterproofing material, and the like.
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Abstract
Description
樹脂組成物は、少なくとも樹脂及び難燃成分を含んでおり、樹脂発泡体を形成する組成物である。
本発明の樹脂発泡体は、樹脂と難燃成分とを少なくとも含む樹脂組成物から形成される。本発明の樹脂発泡体において、樹脂発泡体を製造する方法としては、特に制限されず、例えば、物理的方法、化学的方法等の通常用いられる方法が挙げられる。一般的な物理的方法は、クロロフルオロカーボン類又は炭化水素類などの低沸点液体(発泡剤)を樹脂に分散させ、次に加熱し発泡剤を揮発することにより気泡を形成させる方法である。また、一般的な化学的方法は、樹脂に添加した化合物(発泡剤)の熱分解により生じたガスにより気泡を形成させる方法である。しかし、一般的な物理的方法は、発泡剤として用いられる物質の可燃性や毒性、及びオゾン層破壊などの環境への影響が懸念される。また、一般的な化学的方法では、発泡ガスの残渣が発泡体中に残存するため、特に低汚染性の要求が高い電子機器用途においては、腐食性ガスやガス中の不純物による汚染が問題となる。しかも、これらの物理的方法及び化学的方法では、いずれにおいても、微細な気泡構造を形成することは難しく、特に300μm以下の微細気泡を形成することは極めて困難である。
本発明の樹脂発泡体は、通常、樹脂及び難燃成分を含む樹脂組成物を用いて、発泡・成形することにより作製され、難燃成分としてポリシロキサンコーティングされた難燃剤を含むことから、高度な難燃性を有する。具体的には、本発明の樹脂発泡体は、UL94規格の難燃性試験で判定されるグレードでHBFグレード以上の難燃性を有することが好ましい。
発泡倍率(倍)=(発泡前の密度)/(発泡後の密度)
なお、発泡前の密度は、例えば、未発泡成形物の密度や、樹脂組成物を溶融してから、溶融した樹脂に不活性ガスを含浸させて樹脂発泡体を形成する場合の発泡前の樹脂組成物の密度に相当する。また、発泡後の密度は、下記の樹脂発泡体の密度に相当する。
難燃性発泡部材は、少なくとも前記樹脂発泡体から構成されている。具体的には、難燃性発泡部材は、樹脂発泡体のみからなる構成であってもよいし、樹脂発泡体の片面又は両面に、他の層や基材(特に粘着層など)が設けられている構成であってもよい。
ポリプロピレン[メルトフローレート(MFR):0.35g/10min]:45重量部、ポリオレフィン系エラストマー[メルトフローレート(MFR):6g/10min、JIS A硬度:79°]:55重量部、ポリシロキサンコーティング処理された水酸化マグネシウム(商品名「FRX-100」信越化学工業社製、平均粒径:1.0μm、コーティング量:6.0重量%):60重量部、カーボン(商品名「旭♯35」旭カーボン株式会社製):10重量部、ステアリン酸モノグリセリド:1重量部、及び脂肪酸ビスアミド(ラウリン酸ビスアミド):1重量部を、日本製鋼所(JSW)社製の二軸混練機にて、200℃の温度で混練した後、ストランド状に押出し、水冷後ペレット状に成形した。このペレットを、日本製鋼所社製の単軸押出機に投入し、220℃の雰囲気下、13(注入後12)MPaの圧力で、二酸化炭素ガスを注入した。二酸化炭素ガスは、ポリマー全量に対して6.0重量%の割合で注入した。二酸化炭素ガスを十分飽和させた後、発泡に適した温度まで冷却後、ダイから押出して、発泡体を得た。
ポリプロピレン[メルトフローレート(MFR):0.35g/10min]:45重量部、ポリオレフィン系エラストマー[メルトフローレート(MFR):6g/10min、JIS A硬度:79°]:55重量部、ポリシロキサンコーティング処理された水酸化マグネシウム(商品名「FRX-100」信越化学工業社製、平均粒径:1.0μm、コーティング量:6.0重量%):90重量部、カーボン(商品名「旭♯35」旭カーボン株式会社製):10重量部、ステアリン酸モノグリセリド:1重量部、及び脂肪酸ビスアミド(ラウリン酸ビスアミド):1重量部を、日本製鋼所(JSW)社製の二軸混練機にて、200℃の温度で混練した後、ストランド状に押出し、水冷後ペレット状に成形した。このペレットを、日本製鋼所社製の単軸押出機に投入し、220℃の雰囲気下、13(注入後12)MPaの圧力で、二酸化炭素ガスを注入した。二酸化炭素ガスは、ポリマー全量に対して6.0重量%の割合で注入した。二酸化炭素ガスを十分飽和させた後、発泡に適した温度まで冷却後、ダイから押出して、発泡体を得た。
ポリプロピレン[メルトフローレート(MFR):0.35g/10min]:45重量部、ポリオレフィン系エラストマー[メルトフローレート(MFR):6g/10min、JIS A硬度:79°]:55重量部、ポリシロキサンコーティング処理された水酸化マグネシウム(商品名「FRX-100」信越化学工業社製、平均粒径:1.0μm、コーティング量:6.0重量%):120重量部、カーボン(商品名「旭♯35」旭カーボン株式会社製):10重量部、ステアリン酸モノグリセリド:1重量部、及び脂肪酸ビスアミド(ラウリン酸ビスアミド):1重量部を、日本製鋼所(JSW)社製の二軸混練機にて、200℃の温度で混練した後、ストランド状に押出し、水冷後ペレット状に成形した。このペレットを、日本製鋼所社製の単軸押出機に投入し、220℃の雰囲気下、13(注入後12)MPaの圧力で、二酸化炭素ガスを注入した。二酸化炭素ガスは、ポリマー全量に対して6.0重量%の割合で注入した。二酸化炭素ガスを十分飽和させた後、発泡に適した温度まで冷却後、ダイから押出して、発泡体を得た。
ポリプロピレン[メルトフローレート(MFR):0.35g/10min]:50重量部、ポリオレフィン系エラストマー[メルトフローレート(MFR):6g/10min、JIS A硬度:79°]:50重量部、ポリシロキサンコーティング処理された水酸化マグネシウム(商品名「FRX-100」信越化学工業社製、平均粒径:1.0μm、コーティング量:6.0重量%):120重量部、カーボン(商品名「旭♯35」旭カーボン株式会社製):10重量部、ステアリン酸モノグリセリド:1重量部、及び脂肪酸ビスアミド(ラウリン酸ビスアミド):1重量部を、日本製鋼所(JSW)社製の二軸混練機にて、200℃の温度で混練した後、ストランド状に押出し、水冷後ペレット状に成形した。このペレットを、日本製鋼所社製の単軸押出機に投入し、220℃の雰囲気下、13(注入後12)MPaの圧力で、二酸化炭素ガスを注入した。二酸化炭素ガスは、ポリマー全量に対して6.0重量%の割合で注入した。二酸化炭素ガスを十分飽和させた後、発泡に適した温度まで冷却後、ダイから押出して、発泡体を得た。
ポリプロピレン[メルトフローレート(MFR):0.35g/10min]:50重量部、ポリオレフィン系エラストマー[メルトフローレート(MFR):6g/10min、JIS A硬度:79°]:50重量部、ポリシロキサンコーティング処理された水酸化マグネシウム(商品名「FRX-100」信越化学工業社製、平均粒径:1.0μm、コーティング量:6.0重量%):75重量部、カーボン(商品名「旭♯35」旭カーボン株式会社製):10重量部、ステアリン酸モノグリセリド:1重量部、及び脂肪酸ビスアミド(ラウリン酸ビスアミド):1重量部を、日本製鋼所(JSW)社製の二軸混練機にて、200℃の温度で混練した後、ストランド状に押出し、水冷後ペレット状に成形した。このペレットを、日本製鋼所社製の単軸押出機に投入し、220℃の雰囲気下、13(注入後12)MPaの圧力で、二酸化炭素ガスを注入した。二酸化炭素ガスは、ポリマー全量に対して6.0重量%の割合で注入した。二酸化炭素ガスを十分飽和させた後、発泡に適した温度まで冷却後、ダイから押出して、発泡体を得た。
ポリプロピレン[メルトフローレート(MFR):0.35g/10min]:65重量部、ポリオレフィン系エラストマー[メルトフローレート(MFR):6g/10min、JIS A硬度:79°]:35重量部、ポリシロキサンコーティング処理された水酸化マグネシウム(商品名「FRX-100」信越化学工業社製、平均粒径:1.0μm、コーティング量:6.0重量%):75重量部、カーボン(商品名「旭♯35」旭カーボン株式会社製):10重量部、ステアリン酸モノグリセリド:1重量部、及び脂肪酸ビスアミド(ラウリン酸ビスアミド):1重量部を、日本製鋼所(JSW)社製の二軸混練機にて、200℃の温度で混練した後、ストランド状に押出し、水冷後ペレット状に成形した。このペレットを、日本製鋼所社製の単軸押出機に投入し、220℃の雰囲気下、13(注入後12)MPaの圧力で、二酸化炭素ガスを注入した。二酸化炭素ガスは、ポリマー全量に対して6.0重量%の割合で注入した。二酸化炭素ガスを十分飽和させた後、発泡に適した温度まで冷却後、ダイから押出して、発泡体を得た。
ポリプロピレン[メルトフローレート(MFR):0.35g/10min]:45重量部、ポリオレフィン系エラストマー[メルトフローレート(MFR):6g/10min、JIS A硬度:79°]:55重量部、シランカップリング剤処理された水酸化マグネシウム(商品名「キスマ5A」協和化学工業社製、平均粒径0.8μm):10重量部、カーボン(商品名「旭♯35」旭カーボン株式会社製):10重量部、ステアリン酸モノグリセリド:1重量部、及び脂肪酸ビスアミド(ラウリン酸ビスアミド):1重量部を、日本製鋼所(JSW)社製の二軸混練機にて、200℃の温度で混練した後、ストランド状に押出し、水冷後ペレット状に成形した。このペレットを、日本製鋼所社製の単軸押出機に投入し、220℃の雰囲気下、13(注入後12)MPaの圧力で、二酸化炭素ガスを注入した。二酸化炭素ガスは、ポリマー全量に対して6.0重量%の割合で注入した。二酸化炭素ガスを十分飽和させた後、発泡に適した温度まで冷却後、ダイから押出して、発泡体を得た。
ポリプロピレン[メルトフローレート(MFR):0.35g/10min]:45重量部、ポリオレフィン系エラストマー[メルトフローレート(MFR):6g/10min、JIS A硬度:79°]:55重量部、シランカップリング剤処理された水酸化マグネシウム(商品名「キスマ5A」協和化学工業社製、平均粒径0.8μm):60重量部、カーボン(商品名「旭♯35」旭カーボン株式会社製):10重量部、ステアリン酸モノグリセリド:1重量部、及び脂肪酸ビスアミド(ラウリン酸ビスアミド):1重量部を、日本製鋼所(JSW)社製の二軸混練機にて、200℃の温度で混練した後、ストランド状に押出し、水冷後ペレット状に成形した。このペレットを、日本製鋼所社製の単軸押出機に投入し、220℃の雰囲気下、13(注入後12)MPaの圧力で、二酸化炭素ガスを注入した。二酸化炭素ガスは、ポリマー全量に対して6.0重量%の割合で注入した。二酸化炭素ガスを十分飽和させた後、発泡に適した温度まで冷却後、ダイから押出して、発泡体を得た。
ポリプロピレン[メルトフローレート(MFR):0.35g/10min]:45重量部、ポリオレフィン系エラストマー[メルトフローレート(MFR):6g/10min、JIS A硬度:79°]:55重量部、シランカップリング剤処理された水酸化マグネシウム(商品名「キスマ5A」協和化学工業社製、平均粒径0.8μm):90重量部、カーボン(商品名「旭♯35」旭カーボン株式会社製):10重量部、ステアリン酸モノグリセリド:1重量部、及び脂肪酸ビスアミド(ラウリン酸ビスアミド):1重量部を、日本製鋼所(JSW)社製の二軸混練機にて、200℃の温度で混練した後、ストランド状に押出し、水冷後ペレット状に成形した。このペレットを、日本製鋼所社製の単軸押出機に投入し、220℃の雰囲気下、13(注入後12)MPaの圧力で、二酸化炭素ガスを注入した。二酸化炭素ガスは、ポリマー全量に対して6.0重量%の割合で注入した。二酸化炭素ガスを十分飽和させた後、発泡に適した温度まで冷却後、ダイから押出して、発泡体を得た。
ポリプロピレン[メルトフローレート(MFR):0.35g/10min]:45重量部、ポリオレフィン系エラストマー[メルトフローレート(MFR):6g/10min、JIS A硬度:79°]:55重量部、シランカップリング剤処理された水酸化マグネシウム(商品名「キスマ5A」協和化学工業社製、平均粒径0.8μm):120重量部、カーボン(商品名「旭♯35」旭カーボン株式会社製):10重量部、ステアリン酸モノグリセリド:1重量部、及び脂肪酸ビスアミド(ラウリン酸ビスアミド):1重量部を、日本製鋼所(JSW)社製の二軸混練機にて、200℃の温度で混練した後、ストランド状に押出し、水冷後ペレット状に成形した。このペレットを、日本製鋼所社製の単軸押出機に投入し、220℃の雰囲気下、13(注入後12)MPaの圧力で、二酸化炭素ガスを注入した。二酸化炭素ガスは、ポリマー全量に対して6.0重量%の割合で注入した。二酸化炭素ガスを十分飽和させた後、発泡に適した温度まで冷却後、ダイから押出して、発泡体を得た。
実施例及び比較例に係る発泡体について、伸長粘度、発泡倍率、50%圧縮時の圧縮荷重値(50%圧縮荷重値)、及び難燃性を、測定又は評価した。これらの結果を表1に示した。
伸長粘度は以下の方法により測定した。
測定装置:ロザンドプレシジョン社製ツインキャピラリーレオメーター「RH7-2型」
ロングダイ:φ1mm、長さ16mm、入射角180°(L/D=16)
ショートダイ:φ1mm、長さ0.25mm、入射角180°(L/D=0.25)
キャピラリーレオメーターのキャピラリー中にペレット状の樹脂を投入し、180℃で10分程度加熱する。溶融した樹脂は、ピストンがある一定速度で押し下げられることによって、下側のキャピラリーを通して樹脂が押し出される。この時の樹脂の圧力をキャピラリーの入り口近くに設置された圧力センサーにより測定する。このようにして測定された圧力を、以下の式により粘度の値として算出した。
P0=(PS・LL-PL・LL)/(LL-LS)
P0:圧力損失[MPa]
PL:ロングダイで測定した圧力損失[MPa]
PS:ショートダイで測定した圧力損失[MPa]
LL:ロングダイの長さ[mm]
LS:ショートダイの長さ[mm]
これより、伸長粘度λ[kPa・s]は、以下の式により算出した。
λ=9(n+1)2P0/(32ηγ)
η:せん断速度[1/s]=(100[1/s])
γ:せん断粘度[kpa・s] τ=k・γnより算出され、τはせん断応力[kpa]である。
n:パワーローインデックス
k:定数
40mm×40mmの打抜き刃型にて発泡体を打抜き、打抜いた試料の寸法を測定する。また、測定端子の直径(φ)20mmである1/100ダイヤルゲージにて厚みを測定する。これらの値から発泡体の体積を算出した。次に、発泡体の重量を最小目盛り0.01g以上の上皿天秤にて測定する。これらの値より発泡体の密度(g/cm3)を算出した。なお、発泡体の密度は、発泡後の密度の意味である。
発泡前の密度を上記(密度)と同様の方法により測定し、下記式より求めた。
発泡倍率(倍)=(発泡前の密度)/(発泡後の密度)
発泡前の密度は実施例及び比較例のペレットの密度のことであり、また発泡後の密度は実施例及び比較例の発泡体の密度のことである。
JIS K 6767に記載されている発泡体の圧縮硬さ測定方法に準じて測定した。発泡体を直径20mmの円形状に切り出して得た試験片を、10mm/minの速度にて、初期厚みの50%まで圧縮を行ったのち20秒後の荷重値(N)を測定し、得た値を単位面積(1cm2)当たりに換算して、50%圧縮時の圧縮荷重値(N/cm2)を求めた。
UL-94規格の水平燃焼試験(試験方法・条件は、JIS K 6400-6に準拠)を実施することにより、難燃性を評価した。試験片(長さ:150±1mm、幅:50±1mm、厚さ:0.3mm及び1.2mm)を水平に保持し、38mm炎を60秒間接炎し、標線間100mmの燃焼速度及び燃焼挙動により判定を行った。
Claims (14)
- 樹脂及び難燃成分を含む樹脂発泡体であって、難燃成分がポリシロキサンコーティングされた難燃剤であることを特徴とする樹脂発泡体。
- ポリシロキサンコーティングされた難燃剤がポリシロキサンコーティングされた金属水酸化物であり、該ポリシロキサンコーティングされた金属水酸化物の含有量が樹脂発泡体中で30~60重量%である請求項1記載の樹脂発泡体。
- 50%圧縮時の圧縮荷重値が3.0N/cm2以下であり、UL94規格の難燃性試験で判定されるグレードでHBFグレード以上の難燃性を有する請求項1又は2に記載の樹脂発泡体。
- 発泡倍率が、9倍以上である請求項1~3の何れかの項に記載の樹脂発泡体。
- 密度が、0.030~0.120g/cm3である請求項1~4の何れかの項に記載の樹脂発泡体。
- 樹脂が、熱可塑性樹脂である請求項1~5の何れかの項に記載の樹脂発泡体。
- 独立気泡構造又は半連続半独立気泡構造を有している請求項1~6の何れかの項に記載の樹脂発泡体。
- 樹脂発泡体が、樹脂に高圧の不活性ガスを含浸させた後、減圧する工程を経て形成されている請求項1~7の何れかの項に記載の樹脂発泡体。
- 含浸時の不活性ガスが、二酸化炭素である請求項8記載の樹脂発泡体。
- 含浸時の不活性ガスが、超臨界状態である請求項8又は9に記載の樹脂発泡体。
- 請求項1~10の何れかの項に記載の樹脂発泡体から構成されている発泡部材。
- 樹脂発泡体の片面側又は両面側に、粘着層を有している請求項11記載の発泡部材。
- 粘着層が、フィルム層を介して、樹脂発泡体上に形成されている請求項12記載の発泡部材。
- 粘着層が、アクリル系粘着剤層である請求項12又は13に記載の発泡部材。
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WO2013168798A1 (ja) * | 2012-05-11 | 2013-11-14 | 日東電工株式会社 | 樹脂発泡体及び発泡シール材 |
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CN110621184B (zh) | 2017-05-10 | 2021-05-04 | 耐克创新有限合伙公司 | 一种鞋类物品 |
JPWO2021106910A1 (ja) * | 2019-11-25 | 2021-06-03 | ||
JP7288397B2 (ja) | 2019-12-19 | 2023-06-07 | 日東電工株式会社 | 難燃断熱シートおよび難燃断熱材 |
EP4117932B1 (en) | 2020-05-29 | 2023-09-13 | Nike Innovate C.V. | Structurally-colored articles and methods for making and using structurally-colored articles |
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JP2005097566A (ja) * | 2003-08-22 | 2005-04-14 | Nitto Denko Corp | 発泡防塵材、および該発泡防塵材が用いられた防塵構造 |
WO2008041617A1 (fr) * | 2006-10-02 | 2008-04-10 | Nitto Denko Corporation | Mousse de résine polyoléfinique et son procédé de production |
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KR100720207B1 (ko) * | 2003-08-22 | 2007-05-21 | 닛토덴코 가부시키가이샤 | 발포 방진재 및 발포 방진재를 사용한 방진 구조 |
JP2006008873A (ja) * | 2004-06-28 | 2006-01-12 | Fujikura Ltd | 難燃性樹脂組成物及びこれを用いた電線・ケーブル |
JP5121243B2 (ja) * | 2006-03-30 | 2013-01-16 | Jsr株式会社 | ポリオレフィン系樹脂発泡体とその製造方法 |
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- 2010-03-03 CN CN2010800122244A patent/CN102356124B/zh not_active Expired - Fee Related
- 2010-03-03 KR KR1020117024538A patent/KR20110131294A/ko not_active Application Discontinuation
- 2010-03-03 WO PCT/JP2010/053386 patent/WO2010106912A1/ja active Application Filing
- 2010-03-03 US US13/256,806 patent/US20120003457A1/en not_active Abandoned
- 2010-03-12 TW TW99107359A patent/TW201038640A/zh unknown
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JP2003041038A (ja) * | 2001-07-26 | 2003-02-13 | Nitto Denko Corp | ゴム発泡体 |
JP2005097566A (ja) * | 2003-08-22 | 2005-04-14 | Nitto Denko Corp | 発泡防塵材、および該発泡防塵材が用いられた防塵構造 |
WO2008041617A1 (fr) * | 2006-10-02 | 2008-04-10 | Nitto Denko Corporation | Mousse de résine polyoléfinique et son procédé de production |
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WO2020208946A1 (ja) * | 2019-04-10 | 2020-10-15 | 日東電工株式会社 | 難燃発泡体および発泡部材 |
JP7572157B2 (ja) | 2019-04-10 | 2024-10-23 | 日東電工株式会社 | 難燃発泡体および発泡部材 |
Also Published As
Publication number | Publication date |
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CN102356124B (zh) | 2013-08-21 |
TW201038640A (en) | 2010-11-01 |
CN102356124A (zh) | 2012-02-15 |
US20120003457A1 (en) | 2012-01-05 |
KR20110131294A (ko) | 2011-12-06 |
JP2010242061A (ja) | 2010-10-28 |
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