WO2013179944A1 - 樹脂発泡体及び発泡部材 - Google Patents
樹脂発泡体及び発泡部材 Download PDFInfo
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- WO2013179944A1 WO2013179944A1 PCT/JP2013/064041 JP2013064041W WO2013179944A1 WO 2013179944 A1 WO2013179944 A1 WO 2013179944A1 JP 2013064041 W JP2013064041 W JP 2013064041W WO 2013179944 A1 WO2013179944 A1 WO 2013179944A1
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- breaking strength
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- maximum breaking
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- 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
- C08J9/12—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
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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
- C08J9/0004—Use of compounding ingredients, the chemical constitution of which is unknown, broadly defined, or irrelevant
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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
- 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
- C08J2201/03—Extrusion of the foamable blend
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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
- C08J2203/06—CO2, N2 or noble gases
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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
- C08J2203/08—Supercritical fluid
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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
- C08J2205/00—Foams characterised by their properties
- C08J2205/06—Flexible foams
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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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08J2367/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the hydroxy and the carboxyl groups directly linked to aromatic rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2301/00—Additional features of adhesives in the form of films or foils
- C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
- C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2433/00—Presence of (meth)acrylic polymer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J2467/00—Presence of polyester
- C09J2467/006—Presence of polyester in the substrate
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
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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
- Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
- Y10T428/2852—Adhesive compositions
- Y10T428/2878—Adhesive compositions including addition polymer from unsaturated monomer
- Y10T428/2891—Adhesive compositions including addition polymer from unsaturated monomer including addition polymer from alpha-beta unsaturated carboxylic acid [e.g., acrylic acid, methacrylic acid, etc.] Or derivative thereof
Definitions
- the present invention relates to a resin foam and a foamed member. More specifically, a resin foam used for electrical or electronic devices (for example, mobile phones, mobile terminals, smartphones, tablet computers (tablet PCs), digital cameras, digital video cameras, video cameras, personal computers, home appliances, etc.) And a foamed member.
- electrical or electronic devices for example, mobile phones, mobile terminals, smartphones, tablet computers (tablet PCs), digital cameras, digital video cameras, video cameras, personal computers, home appliances, etc.
- a foamed member for example, mobile phones, mobile terminals, smartphones, tablet computers (tablet PCs), digital cameras, digital video cameras, video cameras, personal computers, home appliances, etc.
- Resin foams have excellent cushioning properties and are usefully used for seal materials, cushion materials, pad materials, and the like.
- polyolefin elastomer foams, urethane elastomer foams, polyester elastomer foams as dustproof materials and cushioning materials for liquid crystal displays, plasma displays, organic EL displays, etc. of electric or electronic devices such as mobile phones and digital cameras The body is used.
- Patent Document 1 As a resin foam, an uncrosslinked type or a crosslinked type polyolefin elastomer foam is known (see Patent Document 1). Moreover, a thermoplastic polyester foam suitable for miniaturization, weight reduction, and thickness reduction for electric or electronic devices is known (see Patent Document 2).
- Resin foam has the characteristics of suppressing elongation and tearing during assembly because it is compatible with recent changes in the shape of electrical or electronic equipment (for example, thinner, smaller, larger screens, etc.) Is becoming more sought after.
- the width of the portion where the resin foam is used is becoming narrower with the enlargement of the screen of a mobile phone, and the above-mentioned characteristics are remarkably required for the mobile phone.
- resin foams that are flexible under high compression are easy to tear, and may not be bonded to each other when they are assembled to an optical member casing or the like.
- an object of the present invention is to provide a resin foam that can maintain flexibility even under high compression and has excellent assembling properties. Furthermore, the other object of this invention is to provide the foam member which can maintain a softness
- the repulsive stress when compressed to 80% is 1.0 to 9.0 N / cm 2
- the maximum breaking strength defined below is 1.0 to 10.0 MPa
- the ratio between the specified maximum breaking strength and the breaking strength in the direction perpendicular to the maximum breaking strength direction is 1.0 to 5.0
- a resin foam is provided.
- Maximum breaking strength Measure the breaking strength of a sheet-like resin foam in any direction in the horizontal direction, and then rotate the arbitrary direction around the axis every 10 ° to measure the breaking strength in each direction. The direction in which the largest breaking strength is measured is the maximum breaking strength direction, and the breaking strength in the maximum breaking strength direction is the maximum breaking strength.
- the resin foam preferably further has an average cell diameter of 10 to 200 ⁇ m and an apparent density of 0.01 to 0.20 g / cm 3 .
- the resin constituting the resin foam is preferably a thermoplastic resin.
- the thermoplastic resin is preferably polyester.
- the resin foam is preferably formed through a step of depressurizing after impregnating the resin composition with a high-pressure gas.
- the gas is preferably an inert gas.
- the gas is preferably carbon dioxide gas.
- the above high-pressure gas is preferably a supercritical gas.
- the present invention provides a foamed member comprising the above resin foam.
- the foamed member preferably has an adhesive layer on the resin foam.
- the pressure-sensitive adhesive layer is preferably an acrylic pressure-sensitive adhesive layer.
- the resin foam of the present invention can maintain flexibility even under high compression and has excellent assemblability. Furthermore, since the foamed member of the present invention includes the resin foam, the flexibility can be maintained even under high compression, and the assemblability is excellent.
- the resin foam of the present invention has a repulsion stress of 1.0 to 9.0 N / cm 2 when compressed to 80%, a maximum breaking strength defined below of 1.0 to 10.0 MPa, The ratio between the maximum breaking strength specified below and the breaking strength in the direction perpendicular to the maximum breaking strength (maximum breaking strength / breaking strength in the direction perpendicular to the maximum breaking strength direction) is 1.0 to 5.0 is there.
- Maximum breaking strength With respect to a sheet-like resin foam, the breaking strength is measured in an arbitrary direction in the horizontal direction, and then the arbitrary breaking direction is rotated about every 10 ° (degrees) about the arbitrary direction, thereby breaking strength in each direction.
- the direction in which the largest breaking strength is measured is taken as the maximum breaking strength direction
- the breaking strength in the maximum breaking strength direction is taken as the maximum breaking strength.
- the maximum breaking strength defined above may be simply referred to as “maximum breaking strength”.
- “the ratio between the maximum breaking strength and the breaking strength in the direction perpendicular to the maximum breaking strength direction (maximum breaking strength / breaking strength in the direction perpendicular to the maximum breaking strength direction)” is simply referred to as “the strength ratio (maximum breaking strength). / Breaking strength in a direction perpendicular to the maximum breaking strength direction).
- the resin foam of the present invention is formed by foaming a composition (resin composition) containing at least the resin constituting the resin foam of the present invention.
- the said resin composition contains 70 weight% or more (preferably 80 weight% or more) resin with respect to the resin composition whole quantity (100 weight%).
- the repulsive stress when compressed to 80% of the resin foam of the present invention is 1.0 to 9.0 N / cm 2 , preferably 1.5 to 8.5 N / cm 2 , more preferably 2.0. To 8.0 N / cm 2 . Since the resin foam of the present invention has a repulsion stress of 1.0 N / cm 2 or more when compressed to 80%, an appropriate rigidity is obtained and it has good workability. Moreover, since the repulsion stress when compressed to 80% is 9.0 N / cm 2 or less, it has excellent flexibility. Since the resin foam of the present invention has a repulsive stress when compressed to 80% within the above range, it is rich in flexibility, even when used for sealing to a housing having only a narrow clearance, The housing will not be deformed.
- the repulsive stress when compressed to 80% means the compressive stress when the compression rate is 80%.
- the compression ratio of 80% means that the sheet-like resin foam is compressed to a state corresponding to 80% of the initial height in the thickness direction, that is, to a state in which the initial thickness is distorted by 80%. This means that the thickness of the sheet-like resin foam having a compression rate of 80% corresponds to a thickness of 20% of the initial thickness.
- the maximum breaking strength of the resin foam of the present invention is 1.0 to 10.0 MPa, preferably 1.0 to 8.5 MPa, more preferably 1.2 to 7.5 MPa. Since the resin foam of the present invention has a maximum breaking strength of 1.0 MPa or more, it is excellent in strength and is not easily torn or torn even if a force acts on the resin foam. In addition, plastic deformation hardly occurs. For this reason, it is excellent in assembly property and workability. Moreover, since the maximum breaking strength is 10.0 MPa or less, it does not become hard even under high compression, and is excellent in flexibility even under high compression.
- the resin foam of the present invention has a maximum breaking strength within the above range, even when it is used for sealing to a housing, it is torn or stretched when assembled to the housing (particularly plastic). Such as deformation) does not occur, and attachment does not become difficult.
- assembly attachment property means the ease of incorporating at the time of incorporating a resin foam in a predetermined place by a machine or a human hand.
- the maximum breaking strength is obtained as follows. With respect to the sheet-like resin foam, any one direction in the horizontal direction (direction perpendicular to the thickness direction) is defined, and then the 17 directions are obtained by rotating the arbitrary one direction every 10 ° about the axis. (See FIG. 1). The breaking strength is measured for each of the 18 directions defined above in the sheet-like resin foam. The direction in which the largest breaking strength is measured is defined as the maximum breaking strength direction, and the breaking strength in the maximum breaking strength direction is defined as the maximum breaking strength.
- the strength ratio (maximum breaking strength / breaking strength in the direction perpendicular to the maximum breaking strength direction) of the resin foam of the present invention is 1.0 to 5.0, preferably 1.0 to 4.5, more preferably. Is 1.0 to 4.0. Since the resin foam of the present invention has a strength ratio (maximum breaking strength / breaking strength in a direction perpendicular to the maximum breaking strength direction) within the above range, it is not extremely weak only in a specific direction. Excellent accuracy. For this reason, it is excellent in assemblability.
- the strength ratio (the maximum breaking strength / the breaking strength in the direction perpendicular to the maximum breaking strength direction) exceeds 5.0
- the sheet-like resin foam in the horizontal direction (the direction perpendicular to the thickness direction)
- the strength anisotropy of the resin is large and the strength of the resin foam is large
- the resin foam is easily cut.
- the variation in elongation becomes large, the accuracy is lowered, and in some cases, tearing, blurring, and breakage may occur.
- the breaking strength is determined based on the tensile strength and elongation terms of JIS K 6767.
- the resin foam of the present invention has a sheet-like or tape-like shape
- the length direction (MD direction, flow direction)
- the direction orthogonal to the maximum breaking strength direction is the width direction.
- TD direction the direction orthogonal to the maximum breaking strength direction
- the width direction is the maximum breaking strength direction
- the direction perpendicular to the maximum breaking strength direction is the length direction.
- the average cell diameter of the resin foam of the present invention is not particularly limited, but is preferably 10 to 200 ⁇ m, more preferably 15 to 150 ⁇ m, still more preferably 20 to 100 ⁇ m.
- the resin foam of the present invention preferably has an average cell diameter of 10 ⁇ m or more because excellent flexibility is easily obtained. Moreover, it is preferable for the average cell diameter to be 200 ⁇ m or less because the occurrence of pinholes can be suppressed, and it becomes easy to obtain excellent sealing properties and excellent dustproof properties.
- the cell diameter in the cell structure of the resin foam of the present invention is obtained, for example, by taking an enlarged image of the cell structure part (bubble structure part) of the cut surface with a digital microscope, obtaining the cell area, and converting to an equivalent circle diameter. Desired.
- the resin foam of the present invention preferably has a uniform and fine cell structure from the viewpoints of flexibility, sealing properties and dust resistance. Moreover, it is preferable not to include a coarse cell (particularly a cell having a cell diameter exceeding 300 ⁇ m).
- the cell structure of the resin foam of the present invention is not particularly limited, but it has a semi-continuous semi-closed cell structure (a mixture of closed-cell structure and open-cell structure from the viewpoint of strength, sealability, dustproof property, and flexibility. It is a cell structure, and the ratio is not particularly limited. In particular, a cell structure in which the closed cell structure part is 40% or less (preferably 30% or less) in the resin foam is preferable.
- the apparent density of the resin foam of the present invention is not particularly limited, but is preferably 0.01 to 0.20 g / cm 3 , more preferably 0.01 to 0.15 g / cm 3 .
- the density of the resin foam of the present invention is 0.01 g / cm 3 or more, good strength can be obtained, which is preferable.
- the density is 0.20 g / cm 3 or less because it has a high expansion ratio and can provide excellent flexibility. That is, when the apparent density of the resin foam of the present invention is 0.01 to 0.20 g / cm 3 , better foaming characteristics (high foaming ratio) can be obtained, moderate strength, excellent flexibility, It becomes easy to demonstrate excellent cushioning properties.
- the resin foam of the present invention has an average cell diameter of 10 to 200 ⁇ m from the viewpoint of obtaining a high foaming ratio while obtaining an appropriate strength, and obtaining excellent flexibility and excellent sealing properties and dust resistance.
- the apparent density is preferably 0.01 to 0.20 g / cm 3 .
- the shape of the resin foam of the present invention is not particularly limited, but is preferably a sheet or a tape. Further, it may be processed into an appropriate shape according to the purpose of use. For example, it may be processed into a linear shape, a circular shape, a polygonal shape, a frame shape (frame shape), or the like by cutting, punching, or the like.
- the thickness of the resin foam of the present invention is not particularly limited, but is preferably 0.05 to 3.0 mm, more preferably 0.06 to 2.8 mm, still more preferably 0.07 to 1.5 mm, particularly preferably. 0.08 to 1.0 mm.
- the resin that is the material of the resin foam of the present invention is not particularly limited, but a thermoplastic resin is preferably exemplified.
- the resin foam of the present invention may be composed of only one kind of resin, or may be composed of two or more kinds of resins.
- thermoplastic resin examples include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, copolymers of ethylene and propylene, ethylene or propylene and other ⁇ -olefins (for example, Copolymer with butene-1, pentene-1, hexene-1, 4-methylpentene-1, etc.), ethylene and other ethylenically unsaturated monomers (for example, vinyl acetate, acrylic acid, acrylic ester, Polyolefin resins such as copolymers with methacrylic acid, methacrylic acid esters, vinyl alcohol, etc.); styrene resins such as polystyrene, acrylonitrile-butadiene-styrene copolymers (ABS resins); 6-nylon, 66-nylon, Polyamide resin such as 12-nylon; polyamide Polyimide; Polyetherimide; Acrylic resin such as polymethyl methacrylate; Polyvinyl chloride; Poly
- thermoplastic resin may be used individually or in combination of 2 or more types.
- a thermoplastic resin is a copolymer
- the copolymer of any form of a random copolymer and a block copolymer may be sufficient.
- thermoplastic resin includes a rubber component and / or a thermoplastic elastomer component. Since the rubber component and the thermoplastic elastomer component have a glass transition temperature of room temperature or lower (for example, 20 ° C. or lower), they are remarkably excellent in flexibility and shape followability when formed into a resin foam.
- the resin foam of this invention may be formed with the resin composition containing said thermoplastic resin and a rubber component and / or a thermoplastic elastomer component.
- the rubber component or thermoplastic elastomer component is not particularly limited as long as it has rubber elasticity and can be foamed.
- natural rubber polyisobutylene, polyisoprene, chloroprene rubber, butyl rubber, nitrile butyl rubber and the like are used.
- olefin elastomer such as ethylene-propylene copolymer, ethylene-propylene-diene copolymer, ethylene-vinyl acetate copolymer, polybutene, chlorinated polyethylene; styrene-butadiene-styrene copolymer, styrene- Examples thereof include styrene elastomers such as isoprene-styrene copolymers and hydrogenated products thereof; polyester elastomers; polyamide elastomers; various thermoplastic elastomers such as polyurethane elastomers. Moreover, these rubber components or thermoplastic elastomer components may be used alone or in combination of two or more.
- thermoplastic resin rebound stress when compressed to 80% within a specific range, maximum breaking strength within a specific range, strength ratio within a specific range (perpendicular to the maximum breaking strength / maximum breaking strength direction)
- Polyester polyester (polyesters such as the above-mentioned polyester resins and polyester elastomers) are preferred from the viewpoint of obtaining flexibility and maintaining excellent flexibility even under high compression.
- a polyester elastomer is more preferable. That is, the resin foam of the present invention is more preferably a resin foam (polyester elastomer foam) formed from a resin composition containing a polyester elastomer.
- the polyester elastomer is not particularly limited as long as it is a resin having an ester bond site by reaction (polycondensation) between a polyol component and a polycarboxylic acid component.
- aromatic dicarboxylic acid divalent aromatic carboxylic acid
- polyester-based thermoplastic resins obtained by condensation polymerization of an acid and a diol component.
- aromatic dicarboxylic acid examples include terephthalic acid, isophthalic acid, phthalic acid, naphthalenecarboxylic acid (for example, 2,6-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, etc.), diphenyl ether dicarboxylic acid, 4,4 Examples include '-biphenyldicarboxylic acid.
- aromatic dicarboxylic acid may be used individually or in combination of 2 or more types.
- diol component examples include ethylene glycol, propylene glycol, trimethylene glycol, 1,4-butanediol (tetramethylene glycol), 2-methyl-1,3-propanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,7 -Heptanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-methyl-1,6-hexanediol, 1,8-octanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,3,5-trimethyl-1,3-pe Tandiol, 1,9
- the diol component may be a diol component in a polymer form such as polyether diol or polyester diol.
- the polyether diol include polyether diols such as polyethylene glycol obtained by ring-opening polymerization of ethylene oxide, propylene oxide, tetrahydrofuran and the like, polypropylene glycol, polytetramethylene glycol, and copolyether obtained by copolymerization thereof. Can be mentioned.
- a diol component may be used individually or in combination of 2 or more types.
- polyester thermoplastic resin examples include polyalkylene terephthalate resins such as polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, and polycyclohexane terephthalate. Moreover, the copolymer obtained by copolymerizing 2 or more types of the said polyalkylene terephthalate type-resin is also mentioned. When the polyalkylene terephthalate resin is a copolymer, it may be a copolymer in any form of a random copolymer, a block copolymer, and a graft copolymer.
- polyester elastomer examples include a polyester elastomer that is a block copolymer of a hard segment and a soft segment.
- polyester elastomer examples include, for example, (i) the aromatic dicarboxylic acid, and a hydroxyl group and a hydroxyl group among the diol components.
- a polyester formed by polycondensation with a diol component having 2 to 4 carbon atoms in the main chain between them is used as a hard segment, and the aromatic dicarboxylic acid and a hydroxyl group and a hydroxyl group of the diol component
- a polyester / polyether type copolymer having a soft segment is used as a hard segment, and polyester such as the above polyether diol
- a polyester / polyester type copolymer having a soft segment (iii) a polyester / polyester type having the same polyester as in (i) and (ii) above as a hard segment and an aliphatic polyester as a soft segment; And the like.
- the polyester elastomer constituting the polyester elastomer is preferably a block copolymer of a hard segment and a soft segment, more preferably the above ( a polyester-polyether type copolymer of ii) (polyester formed by polycondensation of an aromatic dicarboxylic acid and a diol component having 2 to 4 carbon atoms in the main chain between the hydroxyl group and the hydroxyl group) Is a polyester / polyether type copolymer having a hard segment and a polyether as a soft segment.
- polyester / polyether type copolymer of (ii) is a polyester / polyether type block copolymer having polybutylene terephthalate as a hard segment and polyether as a soft segment. Etc.
- the melt flow rate (MFR) at 230 ° C. of the resin constituting the resin foam of the present invention is not particularly limited, but is preferably 1.5 to 4.0 g / 10 min, more preferably 1.5 to 3.8 g. / 10 min, more preferably 1.5 to 3.5 g / 10 min. It is preferable that the melt flow rate (MFR) at 230 ° C. of the resin is 1.5 g / 10 min or more, since the moldability of the resin composition used for forming the resin foam of the present invention is improved. Moreover, it is preferable for the resin to have a melt flow rate (MFR) at 230 ° C.
- MFR at 230 ° C. refers to MFR measured at a temperature of 230 ° C. and a load of 2.16 kgf based on ISO 1133 (JIS K 7210).
- the resin foam of the present invention is preferably formed of a resin composition containing a resin having a melt flow rate (MFR) at 230 ° C. of 1.5 to 4.0 g / 10 min.
- MFR melt flow rate
- the resin foam of the present invention is a polyester elastomer foam
- MFR melt flow rate
- the resin composition forming the resin foam of the present invention preferably contains a foam nucleating agent in addition to the above-mentioned resin.
- a foam nucleating agent may be used individually or in combination of 2 or more types.
- the foaming nucleating agent is not particularly limited, but an inorganic material is preferable.
- the inorganic substance include hydroxides such as aluminum hydroxide, potassium hydroxide, calcium hydroxide, and magnesium hydroxide; clay (particularly hard clay); talc; silica; zeolite; and alkali such as calcium carbonate and magnesium carbonate.
- Earth metal carbonates for example, metal oxides such as zinc oxide, titanium oxide, and alumina; for example, various metal powders such as iron powder, copper powder, aluminum powder, nickel powder, zinc powder, titanium powder, alloy powder, etc.
- Metal powder mica; carbon particles; glass fiber; carbon tube; layered silicate;
- clay and alkaline earth metal carbonate are preferable, more preferably hard, from the viewpoint of suppressing the generation of coarse cells and easily obtaining a uniform and fine cell structure as the foam nucleating agent.
- Clay is preferable, more preferably hard, from the viewpoint of suppressing the generation of coarse cells and easily obtaining a uniform and fine cell structure as the foam nucleating agent.
- the hard clay is a clay containing almost no coarse particles.
- the hard clay is preferably a clay having a 166 mesh screen residue of 0.01% or less, and more preferably a clay having a 166 mesh screen residue of 0.001% or less.
- the sieve residue is a ratio (weight basis) to the whole although it remains without passing through the sieve.
- the hard clay is composed of aluminum oxide and silicon oxide as essential components.
- the total proportion of aluminum oxide and silicon oxide in the hard clay is preferably 80% by weight or more (for example, 80 to 100% by weight), more preferably 90% by weight with respect to the total amount of the hard clay (100% by weight). Or more (for example, 90 to 100% by weight).
- the hard clay may be fired.
- the average particle size (average particle size) of the hard clay is not particularly limited, but is preferably 0.1 to 10 ⁇ m, more preferably 0.2 to 5.0 ⁇ m, and still more preferably 0.5 to 1.0 ⁇ m. .
- the inorganic material is preferably surface-treated. That is, the foam nucleating agent is preferably a surface-treated inorganic substance.
- a surface treating agent used for the surface treatment of an inorganic substance it improves affinity with resin (especially polyester) by giving surface processing treatment, and at the time of foaming, shaping
- the said surface treating agent may be used individually or in combination of 2 or more types.
- the surface treatment in the inorganic material is a silane coupling treatment or a treatment with a higher fatty acid or a salt thereof.
- the aluminum compound is not particularly limited, but an aluminum coupling agent is preferable.
- the aluminum coupling agent include acetoalkoxyaluminum diisopropylate, aluminum ethylate, aluminum isopropylate, mono sec-butoxyaluminum diisopropylate, aluminum sec-butyrate, ethyl acetoacetate aluminum diisopropylate, aluminum tris. (Ethyl acetoacetate), aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (acetylacetonate), cyclic aluminum oxide isopropylate, cyclic aluminum oxide isostearate and the like.
- the silane compound is not particularly limited, but a silane coupling agent is preferable.
- the silane coupling agent include a vinyl group-containing silane coupling agent, a (meth) acryloyl group-containing silane coupling agent, an amino group-containing silane coupling agent, an epoxy group-containing silane coupling agent, Examples include mercapto group-containing silane coupling agents, carboxyl group-containing silane coupling agents, and halogen atom-containing silane coupling agents.
- examples of the silane coupling agent include vinyltrimethoxysilane, vinylethoxysilane, dimethylvinylmethoxysilane, dimethylvinylethoxysilane, methylvinyldimethoxysilane, methylvinyldiethoxysilane, vinyl-tris (2 -Methoxy) silane, vinyltriacetoxysilane, 2-methacryloxyethyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxy-propylmethyldimethoxysilane, 3-aminopropyl Trimethoxylane, 3-aminopropyltriethoxysilane, 2-aminoethyltrimethoxysilane, 3- [N- (2-aminoethyl) amino] propyltrimethoxysilane, 3- [N- (2- Minoethyl) amino] propyltri
- the titanate compound is not particularly limited, but a titanate coupling agent is preferable.
- the titanate coupling agent include isopropyl triisostearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, isopropyl tri (N-aminoethyl-aminoethyl) titanate, isopropyl tridecylbenzenesulfonyl titanate, tetraisopropyl bis (Dioctyl phosphite) titanate, tetraoctyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate, bis (dioctyl pyrophosphate) oxy Acetate titanate, bis (dioctyl pyrophosphate) ethylene titanate
- the epoxy compound is not particularly limited, but is preferably an epoxy resin or a monoepoxy compound.
- the epoxy resin include glycidyl ether type epoxy resins such as bisphenol A type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, and alicyclic epoxy resins.
- the monoepoxy compound include styrene oxide, glycidyl phenyl ether, allyl glycidyl ether, glycidyl (meth) acrylate, 1,2-epoxycyclohexane, epichlorohydrin, and glycidol.
- the isocyanate compound is not particularly limited, but is preferably a polyisocyanate compound or a monoisocyanate compound.
- the polyisocyanate compounds include aliphatic diisocyanates such as tetramethylene diisocyanate and hexamethylene diisocyanate; alicyclic diisocyanates such as isophorone diisocyanate and 4,4′-dicyclohexylmethane diisocyanate; diphenylmethane diisocyanate, and 2,4-tolylene diisocyanate.
- Aromatic diisocyanates such as isocyanate, 2,6-tolylene diisocyanate, phenylene diisocyanate, 1,5-naphthylene diisocyanate, xylylene diisocyanate, toluylene diisocyanate; free isocyanate groups by reaction of these diisocyanate compounds with polyol compounds
- the monoisocyanate compound include phenyl isocyanate and stearyl isocyanate.
- higher fatty acids or salts thereof include higher fatty acids such as oleic acid, stearic acid, palmitic acid, and lauric acid, and salts of the higher fatty acids (for example, metal salts).
- metal salts for example, metal salts.
- the metal atom in the metal salt of the higher fatty acid include alkali metal atoms such as sodium atom and potassium atom, alkaline earth metal atoms such as magnesium atom and calcium atom.
- the phosphoric acid esters are preferably phosphoric acid partial esters.
- the phosphoric acid partial esters include phosphoric acid partial esters in which phosphoric acid (such as orthophosphoric acid) is partially esterified (mono or diesterified) with an alcohol component (such as stearyl alcohol), or the phosphoric acid Examples include salts of partial esters (metal salts such as alkali metals).
- the method for surface treatment of the inorganic material with a surface treatment agent is not particularly limited, and examples thereof include a dry method, a wet method, and an integral blend method.
- the amount of the surface treatment agent when the surface treatment is performed on the inorganic material is not particularly limited, but is preferably 0.1 to 10 parts by weight, more preferably 0. 3 to 8 parts by weight.
- the 166 mesh sieve residue of the inorganic material is not particularly limited, but is preferably 0.01% or less, more preferably 0.001% or less. This is because, when the resin composition is foamed, if coarse particles are present, cell foam breakage is likely to occur. This is because the size of the particles exceeds the thickness of the cell wall.
- the average particle diameter (average particle diameter) of the inorganic substance is not particularly limited, but is preferably 0.1 to 10 ⁇ m, more preferably 0.2 to 5.0 ⁇ m, and still more preferably 0.5 to 1.0 ⁇ m. If the average particle size is less than 0.1 ⁇ m, it may not function sufficiently as a nucleating agent. On the other hand, if the average particle diameter exceeds 10 ⁇ m, it may cause gas loss during foaming of the resin composition, which is not preferable.
- the above foaming nucleating agent is capable of easily obtaining a fine cell structure by suppressing foam breakage during foaming due to the affinity with the resin and the generation of voids at the interface between the resin and the inorganic substance.
- a surface-treated inorganic material is preferred.
- the content of the foam nucleating agent in the resin composition is not particularly limited, but is preferably 0.1 to 20% by weight, more preferably 0.1 to 10%, based on the total amount of the resin composition (100% by weight). % By weight, more preferably 0.3 to 6% by weight.
- the content is 0.1% by weight or more, it is preferable because it is easy to obtain a resin foam having a uniform and fine cell structure by preventing the generation of coarse cells.
- the content is 20% by weight or less, it is possible to suppress the viscosity of the resin composition from significantly increasing, and further, it is possible to suppress outgassing during foaming of the resin composition, and a uniform cell structure is easily obtained. ,preferable.
- the resin composition preferably contains an epoxy-modified polymer.
- the epoxy-modified polymer acts as a crosslinking agent. Moreover, it acts as a modifier (resin modifier) that improves the melt tension and strain hardening degree of a resin composition (particularly a resin composition containing a polyester elastomer). For this reason, when the resin composition contains an epoxy-modified polymer (repulsive stress when compressed to 80% within a specific range, maximum breaking strength within a specific range, strength ratio within a specific range ( (Maximum breaking strength / breaking strength in a direction perpendicular to the maximum breaking strength direction), maintaining flexibility even under high compression, and easily obtaining excellent assemblability, which is preferable. Foaming makes it easy to obtain a fine cell structure, and the epoxy-modified polymers may be used alone or in combination of two or more.
- the epoxy-modified polymer is not particularly limited, but it is difficult to form a three-dimensional network structure as compared with a compound having a low molecular weight epoxy group, and a resin composition (especially a polyester elastomer is excellent in melt tension and strain hardening degree).
- Resin composition an epoxy-modified acrylic polymer which is a polymer having an epoxy group at the end or side chain of the main chain of the acrylic polymer, or the end or side chain of the main chain of polyethylene. It is preferably at least one polymer selected from epoxy-modified polyethylene, which is a polymer having an epoxy group.
- the weight average molecular weight of the epoxy-modified polymer is not particularly limited, but is preferably 5,000 to 10,000, more preferably 8,000 to 80,000, still more preferably 10,000 to 60,000, particularly preferably. 20,000 to 60,000. In addition, when the molecular weight is less than 5,000, the reactivity of the epoxy-modified polymer increases, and high foaming may not be achieved.
- the epoxy equivalent of the epoxy-modified polymer is not particularly limited, but is preferably 100 to 3000 g / eq, more preferably 200 to 2500 g / eq, still more preferably 300 to 2000 g / eq, and particularly preferably 800 to 1600 g / eq. It is.
- the epoxy equivalent of the epoxy-modified polymer is 3000 / eq or less, the melt tension and strain hardening degree of a resin composition (particularly a resin composition containing a polyester elastomer) can be sufficiently improved, and within a specific range.
- the viscosity of the epoxy-modified polymer (B-type viscosity, 25 ° C.) is not particularly limited, but is preferably 2000 to 4000 mPa ⁇ s, more preferably 2500 to 3200 mPa ⁇ s. It is preferable that the viscosity of the epoxy-modified polymer is 2000 mPa ⁇ s or more because it is easy to obtain a fine cell structure with high foaming by suppressing the destruction of the cell walls during foaming of the resin composition. On the other hand, it is preferable that the viscosity is 4000 mPa ⁇ s or less because the fluidity of the resin composition can be easily obtained, and the resin composition can be efficiently foamed.
- the epoxy-modified polymer preferably has a weight average molecular weight of 5,000 to 10,000 and an epoxy equivalent of 100 to 3000 g / eq.
- the content of the epoxy-modified polymer in the resin composition is not particularly limited, but is preferably 0.5 to 15.0 parts by weight, more preferably 0.001 parts by weight with respect to 100 parts by weight of the resin in the resin composition.
- the amount is 6 to 10.0 parts by weight, more preferably 0.7 to 7.0 parts by weight, and particularly preferably 0.8 to 3.0 parts by weight.
- the melt tension and strain hardening degree of the resin composition can be increased, and the resin composition (particularly a resin composition including a polyester-based elastomer) Melt tension and strain hardening degree can be sufficiently improved, and maximum breaking strength within a specific range and strength ratio within a specific range (maximum breaking strength / breaking strength in a direction perpendicular to the maximum breaking strength direction) are obtained. Therefore, it is easy to improve the assembly property, and it is easy to obtain a fine cell structure with high foaming, which is preferable.
- the content of the epoxy-modified polymer is 15.0 parts by weight or less, it is possible to suppress a problem that the viscosity of the resin composition becomes too high and cannot be highly foamed, and a highly foamed and fine cell structure is obtained. Since it becomes easy, it is preferable.
- the epoxy-modified polymer can prevent the polyester chain from being broken by hydrolysis (for example, hydrolysis due to moisture absorption of raw materials), thermal decomposition, oxidative decomposition, etc., and rebond the cut polyester chain. Therefore, the melt tension of the resin composition containing the polyester elastomer can be further improved.
- the epoxy-modified polymer since the epoxy-modified polymer has a large number of epoxy groups in one molecule, it is easier to form a branched structure than a conventional epoxy-based crosslinking agent, and the strain hardening degree of a resin composition containing a polyester-based elastomer Can be further improved.
- the resin composition preferably contains a lubricant.
- a lubricant When the resin composition contains a lubricant, the moldability of the resin composition is improved, which is preferable. The slipping property is improved, which is preferable because it can be easily extruded in a desired shape from, for example, an extruder.
- a lubricant may be used alone or in combination of two or more.
- aliphatic carboxylic acid and its derivative For example, aliphatic carboxylic acid anhydride, alkali metal salt of aliphatic carboxylic acid, alkaline earth metal salt of aliphatic carboxylic acid, etc. Is mentioned.
- Examples of the aliphatic carboxylic acid and derivatives thereof include lauric acid and derivatives thereof, stearic acid and derivatives thereof, crotonic acid and derivatives thereof, oleic acid and derivatives thereof, maleic acid and derivatives thereof, glutaric acid and derivatives thereof, behen Preference is given to fatty acid carboxylic acids having 3 to 30 carbon atoms such as acids and derivatives thereof, montanic acid and derivatives thereof, and derivatives thereof.
- fatty acid carboxylic acids having 3 to 30 carbon atoms and derivatives thereof stearic acid and derivatives thereof, montanic acid and derivatives thereof are preferable from the viewpoints of dispersibility in the resin composition, solubility, and the effect of improving the surface appearance.
- an alkali metal salt of stearic acid and an alkaline earth metal salt of stearic acid are preferable.
- zinc stearate and calcium stearate are more preferable.
- examples of the lubricant include acrylic lubricants.
- examples of commercially available acrylic lubricants include acrylic polymer external lubricants (trade name “METABREN L”, manufactured by Mitsubishi Rayon Co., Ltd.).
- an acrylic lubricant is preferable as the lubricant.
- the content of the lubricant in the resin composition is not particularly limited, but is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the resin in the resin composition. Parts, more preferably 1 to 8 parts by weight.
- the content of the lubricant is 0.1 parts by weight or more, the effect obtained by including the lubricant is easily obtained, which is preferable.
- the content of the lubricant is 20 parts by weight or less, it is preferable because the problem that air bubbles cannot be removed when foaming the resin composition and high foaming cannot be achieved can be suppressed.
- the resin composition may contain a cross-linking agent within a range that does not impair the effects of the present invention.
- the crosslinking agent is not particularly limited.
- epoxy crosslinking agent isocyanate crosslinking agent, silanol crosslinking agent, melamine resin crosslinking agent, metal salt crosslinking agent, metal chelate crosslinking agent, amino resin crosslinking agent. Agents and the like.
- a crosslinking agent may be used individually or in combination of 2 or more types.
- the resin composition may contain a crystallization accelerator as long as the effects of the present invention are not impaired.
- a crystallization accelerator for example, an olefin resin is mentioned.
- an olefin resin a resin having a broad molecular weight distribution and having a shoulder on the high molecular weight side, a micro-crosslinked resin (a slightly crosslinked resin), a long-chain branched resin, and the like are preferable.
- the olefin resin examples 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 another ⁇ -olefin (for example, butene- 1, copolymers with pentene-1, hexene-1, 4-methylpentene-1, etc., ethylene and other ethylenically unsaturated monomers (for example, vinyl acetate, acrylic acid, acrylic ester, methacrylic acid) , Methacrylic acid esters, vinyl alcohol, etc.) and the like.
- ⁇ -olefin for example, butene- 1, copolymers with pentene-1, hexene-1, 4-methylpentene-1, etc.
- ethylene and other ethylenically unsaturated monomers for example, vinyl acetate, acrylic acid, acrylic ester, methacrylic acid
- Methacrylic acid esters vinyl alcohol, etc.
- the olefin resin when the olefin resin is a copolymer, it may be a copolymer in any form of a random copolymer or a block copolymer. Moreover, an olefin resin may be used individually or in combination of 2 or more types.
- the resin composition may contain a flame retardant as long as the effects of the present invention are not impaired.
- a flame retardant for example, the powder particle (for example, various powdery flame retardants etc.) which has a flame retardance is mentioned, An inorganic flame retardant is mentioned preferably.
- the inorganic flame retardant may be, for example, a brominated flame retardant, a chlorine flame retardant, a phosphorus flame retardant, an antimony flame retardant, or the like.
- Non-halogen-non-antimony-based gas components are generated that are harmful to equipment and corrosive to equipment.
- Phosphorus flame retardants and antimony flame retardants are harmful and explosive.
- Inorganic flame retardants inorganic flame retardants free of halogen compounds and antimony compounds
- examples of the non-halogen-nonantimony inorganic flame retardant include aluminum hydroxide, magnesium hydroxide, hydrated metal compounds such as magnesium oxide / nickel oxide hydrate, magnesium oxide / zinc oxide hydrate, and the like. It is done. The hydrated metal oxide may be surface treated.
- the said flame retardant may be used individually or in combination of 2 or more types.
- additives may be included in the resin composition as necessary within a range not impairing the effects of the present invention.
- additives include crystal nucleating agents, plasticizers, colorants (carbon black, pigments, dyes, etc. for the purpose of black coloring), ultraviolet absorbers, antioxidants, anti-aging agents, reinforcing agents, Examples thereof include an antistatic agent, a surfactant, a tension modifier, a shrinkage inhibitor, a fluidity modifier, a vulcanizing agent, a surface treatment agent, a dispersion aid, and a polyester resin modifier.
- an additive may be used individually or in combination of 2 or more types.
- the resin composition has a repulsive stress when compressed to 80% within a specific range, a maximum breaking strength within a specific range, and a strength ratio within a specific range (maximum breaking strength / maximum breaking strength direction and orthogonal It is preferable that at least the following (i) to (iv) are included from the standpoint of obtaining a good assembling property while maintaining flexibility even under high compression.
- Type copolymer (ii): epoxy-modified polymer (iii): lubricant (preferably acrylic lubricant)
- Foam nucleating agent preferably a surface-treated inorganic material, more preferably a surface-treated hard clay)
- the method for producing the resin composition is not particularly limited, and examples thereof include mixing the resin and additives added as necessary. Note that heat may be applied during manufacture.
- the melt tension (take-off speed: 2.0 m / min) of the resin composition is not particularly limited, but is preferably 15 to 70 cN, more preferably 13 to 60 cN, still more preferably 15 to 55 cN, and particularly preferably 26 to 50 cN. It is.
- the resin composition has a melt tension of less than 10 cN, when the resin composition is foamed, the expansion ratio is low, independent bubbles are not easily formed, and the shape of the formed bubbles is uniform. It becomes difficult.
- the melt tension of the resin composition exceeds 70 cN, the fluidity is lowered, and foaming may be adversely affected.
- the melt tension refers to the tension when a specified apparatus is used and a molten resin extruded from a specified die at a specified temperature and extrusion speed is drawn into a strand at a specified take-up speed.
- a Capillary Extension Rheometer manufactured by Malvern was used, and the resin extruded at a constant speed of 8.8 mm / min from a capillary having a diameter of 2 mm and a length of 20 mm was taken up at a take-up speed of 2 m / min.
- the value is the melt tension.
- the melt tension is a value measured at a temperature of 10 ⁇ 2 ° C. from the melting point of the resin of the resin composition to the high temperature side. This is because the resin does not enter a molten state at a temperature lower than the melting point, and on the other hand, at a temperature greatly exceeding the melting point to the high temperature side, the resin becomes completely fluid and the melt tension cannot be measured.
- the strain hardening degree (strain rate: 0.1 [1 / s]) of the resin composition is not particularly limited, it has a uniform and dense cell structure and suppresses cell bubble breakage during foaming and is highly foamed. From the viewpoint of obtaining a foam, 2.0 to 5.0 is preferable, and 2.5 to 4.5 is more preferable.
- the strain hardening degree of the resin composition is a degree of strain hardening at the melting point of the resin of the resin composition.
- the degree of strain hardening deviates from the region (linear region) where uniaxial elongational viscosity gradually increases with increasing strain after the start of measurement, and the region where uniaxial elongational viscosity rises (nonlinear region). Is an index indicating the degree of increase in uniaxial elongational viscosity.
- the resin foam of the present invention is preferably formed by foam molding the above resin composition.
- the foaming method of the resin composition is not particularly limited, but a foaming method in which the resin composition is impregnated with a high-pressure gas and then depressurized (pressure is released) is preferable. That is, the resin foam of the present invention is preferably formed through a step of reducing the pressure after impregnating the resin composition with a high-pressure gas.
- the gas is not particularly limited, but an inert gas is preferable from the viewpoint of obtaining a clean resin foam.
- the inert gas refers to a gas that is inert to the resin composition and can be impregnated.
- the gas may be used as a mixture.
- the inert gas is not particularly limited, and examples thereof include carbon dioxide gas (carbon dioxide gas), nitrogen gas, helium, and air. Among these, carbon dioxide gas is preferable because it has a large amount of impregnation and a high impregnation rate.
- a foaming method of the resin composition a physical foaming method (foaming method by a physical method) and a chemical foaming method (foaming method by a chemical method) can also be mentioned.
- the physical foaming method there is concern about the flammability and toxicity of substances used as the foaming agent (foaming agent gas) and environmental impacts such as ozone layer destruction, but the foaming method using an inert gas is This is an environmentally friendly method in that no foaming agent is used.
- the residue of the foaming gas generated by the foaming agent remains in the foam, so that contamination by corrosive gas and impurities in the gas is a problem, especially for electronic devices where low pollution requirements are high. It may become.
- the above gas is preferably in a supercritical state from the viewpoint of increasing the impregnation rate into the resin composition.
- the solubility of the gas in the resin composition increases and high concentration can be mixed.
- the pressure drops suddenly after impregnation since it is possible to impregnate at a high concentration as described above, the generation of bubble nuclei increases, and the density of bubbles formed by the growth of the bubble nuclei has a porosity. Even if they are the same, they become larger, so that fine bubbles can be obtained.
- Carbon dioxide has a critical temperature of 31 ° C. and a critical pressure of 7.4 MPa.
- the resin foam of the present invention is preferably produced by impregnating a resin composition with a high-pressure gas.
- the resin composition is preliminarily formed into an appropriate shape such as a sheet.
- a batch method may be used in which the unfoamed resin molded product is impregnated with high-pressure gas and foamed by releasing the pressure, Alternatively, a continuous method may be used in which the resin composition is kneaded together with a high-pressure gas under pressure and molded, and simultaneously the pressure is released and molding and foaming are performed simultaneously.
- the resin foam of the present invention is manufactured by a batch method.
- the production method of the unfoamed resin molded body is not particularly limited.
- a method of molding using an extruder such as an extruder or a twin screw extruder; the resin composition is uniformly kneaded using a kneader equipped with blades such as a roller, a cam, a kneader, and a Banbury mold
- a method of press molding to a predetermined thickness using a hot plate press a method of molding a resin composition using an injection molding machine, and the like.
- the unfoamed resin molded body having a desired shape and thickness can be obtained.
- the unfoamed resin molded body may be manufactured by other molding methods besides extrusion molding, press molding, and injection molding.
- the shape of the unfoamed resin molded body is not limited to a sheet shape, and various shapes are selected according to the application. For example, a sheet shape, a roll shape, a prism shape, a plate shape, and the like can be given.
- the unfoamed resin molded body molded body made of a resin composition
- a pressure-resistant container high-pressure container
- the high-pressure gas may be introduced continuously or discontinuously.
- a heating method for growing bubble nuclei 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 may be employed.
- the resin foam of the present invention may be formed by impregnating a non-foamed molded article composed of the resin composition with a high-pressure gas and then foaming it through a pressure reducing step. Moreover, after impregnating the unfoamed molding comprised from the said resin composition with a high voltage
- a resin composition is injected (introduced) with high-pressure gas while kneading using an extruder such as a single-screw extruder or a twin-screw extruder,
- an extruder such as a single-screw extruder or a twin-screw extruder
- the kneading impregnation process in which the resin composition is sufficiently impregnated into the resin composition, the pressure is released by extruding the resin composition through a die provided at the tip of the extruder (usually up to atmospheric pressure), and molding and foaming simultaneously It may be produced by a molding decompression step to be performed.
- a heating step of growing bubbles by heating may be provided.
- the resin foam is obtained by rapidly cooling with cold water or the like to fix the shape.
- an injection molding machine or the like may be used in addition to the extruder.
- the resin foam of the present invention may be formed by impregnating a molten resin composition with a high-pressure gas and then foaming it through a pressure reducing step.
- the resin foam of the present invention may be formed by impregnating a molten resin composition with a high-pressure gas and then further heating it through a step of reducing the pressure.
- the mixing amount of the gas is not particularly limited, but is preferably 2 to 10% by weight, more preferably 2%, based on the total amount of the resin composition, for example. ⁇ 6% by weight.
- the pressure when impregnating the unfoamed resin molded body or resin composition with the gas is preferably 3 MPa or more (for example, 3 to 100 MPa), more preferably. Is 4 MPa or more (for example, 4 to 100 MPa).
- the pressure of the gas is lower than 3 MPa, the bubble growth during foaming is remarkable, the bubble diameter becomes too large, and disadvantages such as, for example, a decrease in the dustproof effect are likely to occur, which is not preferable.
- the temperature when impregnating the unfoamed resin molded article or the polyester elastomer composition with the high-pressure gas can be selected within a wide range, but the operability and the like can be selected. In consideration, 10 to 350 ° C. is preferable.
- the impregnation temperature when impregnating a sheet-like unfoamed resin molded body with a high-pressure gas is preferably 40 to 300 ° C, more preferably 100 to 250 ° C.
- the temperature when injecting and kneading the high-pressure gas into the resin composition is preferably 150 to 300 ° C., more preferably 210 to 250 ° C.
- 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 5 to 300 MPa / s in order to obtain uniform fine bubbles.
- the heating temperature in the heating step is not particularly limited, but is preferably 40 to 250 ° C, more preferably 60 to 250 ° C.
- a resin foam having a high expansion ratio can be produced, so that a thick resin foam can be obtained.
- the gap of the die attached to the tip of the extruder is as narrow as possible (usually 0.1 to 1). 0.0 mm). Therefore, in order to obtain a thick resin foam, the resin composition extruded through a narrow gap must be foamed at a high magnification. Conventionally, a foam that is formed because a high foaming magnification cannot be obtained. Has been limited to a thin thickness (for example, 0.5 to 2.0 mm).
- the resin foam of the present invention has excellent flexibility because the repulsive stress when compressed to 80% is within a specific range. In particular, it is excellent in flexibility even under high compression. Furthermore, since it is excellent in flexibility, it can follow a minute clearance (for example, a step of 0.1 mm). In addition, since the resin foam of the present invention is excellent in flexibility even under high compression, it is effective to cause deformation of the casing, deformation of the display, and poor appearance when attached to an electric or electronic device. Can be suppressed.
- the resin foam of the present invention has a maximum breaking strength within a specific range and a strength ratio (maximum breaking strength / breaking strength in a direction perpendicular to the maximum breaking strength direction) is within a specific range. And is capable of effectively suppressing plastic deformation, tearing, and tearing during assembly and processing. Therefore, the resin foam of the present invention is excellent in assemblability. Moreover, it is excellent in workability. In addition, even if the strength of the resin foam is high, the resin is inferior in isotropy of the strength.
- the resin foam of the present invention has the above-mentioned characteristics, when it is assembled to a portion having a small interval, the resin foam is stretched with tension so as to match the size of the interval, thereby reducing the width of the resin foam. However, tearing, cutting, variation in elongation, plastic deformation, and the like can be suppressed. For this reason, the resin foam of this invention can be assembled
- the resin foam of the present invention has the above characteristics, it is suitably used as a sealing material or a dustproof material for electrical equipment or electronic equipment. Further, it is preferably used as a shock absorbing material and a shock absorbing material, particularly as a shock absorbing material and a shock absorbing material for electric equipment or electronic equipment.
- the resin foam of the present invention may be used as a foam member. That is, the said foaming member is a member containing said resin foam of this invention.
- the foamed member may be composed of only the resin foam of the present invention, or other layers (particularly, a pressure-sensitive adhesive layer (adhesive layer), a base material layer, etc.) may be formed on the resin foam.
- a stacked structure may be used.
- the shape of the foamed member is not particularly limited, but a sheet shape (including a film shape) and a tape shape are preferable.
- the foamed member may be processed so as to have a desired shape, thickness, and the like. For example, various shapes may be processed according to the device, equipment, casing, member, and the like used.
- the foamed member preferably has an adhesive layer.
- the said foaming member is a sheet-like foaming member, it is preferable to have an adhesive layer in the single side
- a processing mount can be provided on the foamed member via the adhesive layer, and further fixed to an adherend (for example, a housing or a part). Or it can be temporarily fixed.
- the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer is not particularly limited.
- an acrylic pressure-sensitive adhesive such as a natural rubber-based pressure-sensitive adhesive, a synthetic rubber-based pressure-sensitive adhesive
- a silicone-based pressure-sensitive adhesive or a polyester-based pressure-sensitive adhesive
- an adhesive examples thereof include an adhesive, a urethane-based adhesive, a polyamide-based adhesive, an epoxy-based adhesive, a vinyl alkyl ether-based adhesive, and a fluorine-based adhesive.
- An adhesive may be used individually or in combination of 2 or more types.
- the pressure-sensitive adhesive may be any form of pressure-sensitive adhesive such as an emulsion-based pressure-sensitive adhesive, a solvent-based pressure-sensitive adhesive, a hot-melt pressure-sensitive adhesive, an oligomer-based pressure-sensitive adhesive, or a solid-type pressure-sensitive adhesive.
- an acrylic pressure-sensitive adhesive is preferable from the viewpoint of preventing contamination of the adherend. That is, the foam member preferably has an acrylic pressure-sensitive adhesive layer on the resin foam of the present invention.
- the thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably 2 to 100 ⁇ m, more preferably 10 to 100 ⁇ m.
- the thinner the pressure-sensitive adhesive layer the higher the effect of preventing the adhesion of dust and dirt at the end, so the thinner the adhesive layer is preferable.
- the pressure-sensitive adhesive layer may have either a single layer or a laminate.
- the pressure-sensitive adhesive layer may be provided via another layer (lower layer).
- a lower layer include other pressure-sensitive adhesive layers, intermediate layers, undercoat layers, and base material layers (particularly film layers and nonwoven fabric layers).
- the pressure-sensitive adhesive layer may be protected by a release film (separator) (for example, release paper, release film, etc.).
- the foamed member includes the resin foam of the present invention, it has excellent assemblability. Moreover, it is excellent in flexibility and excellent in compressibility even under high compression. Flexibility to follow minute clearances. Furthermore, workability is also excellent.
- the foamed member has the characteristics as described above, it is suitably used as a member used when various members or parts are attached (attached) to a predetermined site.
- the foamed member is suitably used as a member used when attaching (attaching) a component constituting the electrical or electronic device to a predetermined site in the electrical or electronic device.
- it is excellent in flexibility even under high compression, it is possible to effectively suppress the deformation of the casing, the deformation of the display, and the appearance defect when attached to an electric or electronic device.
- the foamed member is suitably used for electric or electronic equipment. That is, the foamed member may be a foamed member for electric or electronic equipment.
- the various members or parts that can be attached (mounted) using the foamed member are not particularly limited, and for example, various members or parts in electrical or electronic devices are preferable.
- Examples of such a member or component for electric or electronic equipment include an image display member (display unit) (particularly a small image display member) mounted on an image display device such as a liquid crystal display, an electroluminescence display, or a plasma display. ), Optical members or optical parts such as cameras and lenses (particularly small cameras and lenses) that are mounted on mobile communication devices such as so-called “mobile phones” and “portable information terminals”.
- the foamed member of the present invention for example, around the display unit such as LCD (liquid crystal display) or the display unit and the housing such as LCD (liquid crystal display) for the purpose of dust prevention, light shielding, buffering, etc. And a window portion).
- LCD liquid crystal display
- the housing such as LCD (liquid crystal display) for the purpose of dust prevention, light shielding, buffering, etc.
- a window portion for example, around the display unit such as LCD (liquid crystal display) or the display unit and the housing such as LCD (liquid crystal display) for the purpose of dust prevention, light shielding, buffering, etc. And a window portion).
- Example 1 Block copolymer of polybutylene terephthalate as a hard segment and polyether as a soft segment (trade name “Hytrel 5577”, manufactured by Toray DuPont Co., Ltd., 230 ° C. melt flow rate: 1.8 g / 10 min, melting point: 208 ° C.): 100 parts by weight, acrylic lubricant (trade name “METABBRENE L-1000”, manufactured by Mitsubishi Rayon Co., Ltd.): 5 parts by weight, hard clay treated with a silane coupling agent (trade name “ST” -301 ", manufactured by Shiraishi Calcium Co., Ltd .: 1 part by weight, carbon black (trade name” Asahi # 35 ", manufactured by Asahi Carbon Co., Ltd.): 5 parts by weight and an epoxy-based modifier (epoxy-modified acrylic polymer, weight) Average molecular weight (Mw): 50000, epoxy equivalent: 1200 g / eq, viscosity: 2850 mP ⁇ S)
- the pellets were put into a single screw extruder, and carbon dioxide gas was injected at a pressure of 17 (13 after injection) MP in an atmosphere of 240 ° C. After sufficiently saturating the carbon dioxide gas, it was cooled to a temperature suitable for foaming and extruded from a die to obtain a sheet-like polyester elastomer foam having a thickness of 2.0 mm.
- Example 2 Block copolymer of polybutylene terephthalate as a hard segment and polyether as a soft segment (trade name “Perprene P-90BD”, manufactured by Toyobo Co., Ltd., 230 ° C.
- the pellets were put into a single screw extruder, and carbon dioxide gas was injected at a pressure of 17 (13 after injection) MPa in an atmosphere of 240 ° C. After sufficiently saturating the carbon dioxide gas, it was cooled to a temperature suitable for foaming and extruded from a die to obtain a sheet-like polyester elastomer foam having a thickness of 2.0 mm.
- Example 3 Block copolymer of polybutylene terephthalate as a hard segment and polyether as a soft segment (trade name “Perprene P-90BD”, manufactured by Toyobo Co., Ltd., 230 ° C.
- the pellets were put into a single screw extruder, and carbon dioxide gas was injected at a pressure of 17 (13 after injection) MPa in an atmosphere of 240 ° C. After sufficiently saturating the carbon dioxide gas, it was cooled to a temperature suitable for foaming and extruded from a die to obtain a sheet-like polyester elastomer foam having a thickness of 2.0 mm.
- Block copolymer of polybutylene terephthalate as a hard segment and polyether as a soft segment (trade name “Hytrel 5577” manufactured by Toray DuPont Co., Ltd., 230 ° C.
- melt flow rate 1.8 g / 10 min
- acrylic lubricant trade name “Metablene L-1000”, manufactured by Mitsubishi Rayon Co., Ltd.
- polypropylene trade name “Newstrain SH9000”, manufactured by Nippon Polypro Co., Ltd.
- Magnesium 1 part by weight was kneaded with a twin-screw kneader at a temperature of 220 ° C., then extruded into a strand, cooled with water, cut into a pellet, and molded.
- the pellets were put into a single screw extruder, and carbon dioxide gas was injected at a pressure of 17 (13 after injection) MPa in an atmosphere of 240 ° C. After sufficiently saturating carbon dioxide gas, it was cooled to a temperature suitable for foaming and then extruded from a die to obtain a sheet-like polyester elastomer foam having a thickness of 2.5 mm.
- Block copolymer of polybutylene terephthalate as a hard segment and polyether as a soft segment (trade name “Hytrel 5577”, manufactured by Toray DuPont Co., Ltd., 230 ° C.
- melt flow rate 1.8 g / 10 min, melting point: 208 ° C.
- acrylic lubricant trade name “Metablene L-1000”, manufactured by Mitsubishi Rayon Co., Ltd.
- polypropylene trade name “Newstrain SH9000”, manufactured by Nippon Polypro Co., Ltd.
- magnesium hydroxide 1 part by weight
- carbon black trade name “Asahi # 35”, manufactured by Asahi Carbon Co., Ltd.
- an epoxy-based crosslinking agent trifunctional epoxy compound, trade name “TEPIC-G” Manufactured by Nissan Chemical Industries, Ltd., melting point: 90 to 125 ° C., epoxy equivalent: 110 g / q, viscosity: 100 cp or less, molecular weight: 297): 0.5 parts by weight, with a twin-screw kneader, kneaded at a temperature of 220 °
- the pellets were put into a single screw extruder, and carbon dioxide gas was injected at a pressure of 17 (13 after injection) MPa in an atmosphere of 240 ° C.
- the carbon dioxide gas was sufficiently saturated, cooled to a temperature suitable for foaming, and then extruded from a die to obtain a sheet-like polyester elastomer foam having a thickness of 2.2 mm.
- Comparative Example 4 Use a commercially available foam whose main component is a polyurethane having an average cell diameter of 160 ⁇ m, a repulsive stress of 9.5 N / cm 2 when compressed to 80%, and an apparent density of 0.15 g / cm 3 did. This foam was a sheet and had a thickness of 1.0 mm. Moreover, the repulsion stress (50% vs. repulsive load) at the time of 50% compression was 0.7 N / cm 2 .
- the foam was punched with a punching blade mold having a width of 30 mm and a length of 30 mm to obtain a sheet-like test piece.
- the dimensions of the test piece were measured with a caliper. Further, the thickness of the test piece was measured with a 1/100 dial gauge having a measurement terminal diameter ( ⁇ ) of 20 mm.
- the volume of the test piece was calculated from these values.
- a sheet-like test piece having a thickness of 0.5 mm, a width of 30 mm, and a length of 30 mm was obtained from the foam.
- the breaking strength was measured in the length direction in the horizontal direction, and further, the breaking direction in each direction was measured by rotating the length direction every 10 ° about the axis.
- the breaking strength was measured in 18 directions. In addition, in FIG. 1, it showed about 18 directions which measured the peel strength in the foam.
- the breaking strength was measured based on the terms of tensile strength and elongation of JIS K 6767.
- the breaking strength in the maximum breaking strength direction was taken as the maximum breaking strength (MPa). Furthermore, the breaking strength (MPa) in the direction orthogonal to the maximum breaking strength direction was determined. Then, from the maximum breaking strength and the breaking strength in the direction perpendicular to the maximum breaking strength direction, the ratio of the maximum breaking strength and the breaking strength in the direction perpendicular to the maximum breaking strength direction (strength ratio (maximum breaking strength / maximum breaking strength direction And the breaking strength in the direction perpendicular to the surface))).
- the foam was cut out in any 10 directions in the horizontal direction to obtain 10 sheet-like test pieces having a thickness of 0.5 mm, a width of 3 mm, and a length of 30 cm.
- the load was applied to the casing while applying a tension in the length direction of the test piece using a 1.0 N load.
- the length of the test piece after assembling is measured, and if it is within the range of 30.0 to 31.0 cm, the test is accepted, and those exceeding 31.0 cm (that is, those that have greatly expanded) or assembling Items that sometimes broke were rejected.
- test piece 21 The foam was cut out to obtain a sheet-like test piece (test piece 21) having a width of 50 mm, a length of 50 mm, and a thickness of 1.0 mm.
- the test piece is set on a jig (square, jig 2) as shown in FIG. 2 as shown in FIG. 2, and the test piece is placed on the upper surface side acrylic plate (acrylic plate 22a having a thickness of 1 mm).
- a microscope By compressing in the thickness direction, the state of deformation of the acrylic plate (acrylic plate 22a) on the upper surface side was observed with a microscope.
- spacers having a thickness of 0.4 mm were placed on the left and right ends of an acrylic plate having a thickness of 2 mm (acrylic plate 22b having a thickness of 2 mm) and sandwiched between the spacers.
- a test piece was installed in the center, and an acrylic plate having a thickness of 1 mm (acrylic plate 22a having a thickness of 1 mm) was installed on the upper surface.
- the bolts were tightened into a jig in a four-way diagonal line from the upper side of the acrylic plate (acrylic plate 22a with a thickness of 1 mm), and the force was applied uniformly in the thickness direction of the test piece. The piece was compressed in the thickness direction.
- the presence or absence of deformation of the upper surface side acrylic plate (acrylic plate 22a having a thickness of 1 mm) was observed with a microscope. The case where no deformation was observed was evaluated as “none”, while the case where deformation was observed was evaluated as “present”.
- melt tension For measuring the melt tension, a Capillary Extension Rheometer manufactured by Malvern was used, and a resin extruded at a constant speed of 8.8 mm / min from a capillary having a diameter of 2 mm and a length of 20 mm was taken out at a rate of 2 m / min. The tension at the time of take-off was taken as the melt tension. In addition, the pellet before foam molding was used for the measurement. The temperature at the time of measurement was 10 ⁇ 2 ° C. on the high temperature side from the melting point of the resin.
- strain hardening degree For the measurement, pellets before foam molding were used. The pellet was formed into a sheet having a thickness of 1 mm using a heated hot plate press, and a sheet was obtained. A sample (length: 10 mm, width: 10 mm, thickness: 1 mm) was cut out from the sheet. . From the above sample, the uniaxial elongation viscosity at a strain rate of 0.1 [1 / s] was measured using a uniaxial elongation viscometer (manufactured by TA Instruments). And the strain hardening degree was calculated
- Degree of strain hardening log ⁇ max / log ⁇ 0.2 ( ⁇ max indicates the extensional viscosity when the uniaxial extensional viscosity is the highest, and ⁇ 0.2 indicates the extensional viscosity when the strain ⁇ is 0.2.)
- the temperature at the time of measurement was the melting point of the resin.
- the “strength ratio” in Table 1 is “the ratio between the maximum breaking strength and the breaking strength in the direction perpendicular to the maximum breaking strength direction (strength ratio (maximum breaking strength / breaking strength in the direction perpendicular to the maximum breaking strength direction)). ) ".
- the examples show that the repulsive load (repulsive stress) is small under high compression, the maximum breaking strength is large while being flexible, and the strength ratio (maximum breaking strength / maximum breaking strength direction and Since the breaking strength in the direction perpendicular to the surface is small, the isotropic property is excellent. For this reason, it has excellent workability without stretching or tearing during assembly. Furthermore, when assembling, assembling and bonding can be performed with excellent workability.
- the resin foam and foamed member of the present invention can be used for electric or electronic devices (for example, mobile phones, mobile terminals, smartphones, tablet computers (tablet PCs), digital cameras, digital video cameras, video cameras, personal computers, home appliances, etc. ).
- electric or electronic devices for example, mobile phones, mobile terminals, smartphones, tablet computers (tablet PCs), digital cameras, digital video cameras, video cameras, personal computers, home appliances, etc. ).
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Abstract
Description
さらに、本発明の他の目的は、高圧縮下であっても柔軟性を維持でき、組み付け性に優れる発泡体部材を提供することにある。
最大破断強度:シート状の樹脂発泡体について、水平方向における任意の方向で破断強度を測定し、次にその任意の方向を軸に10°おきに回転させて、各方向における破断強度を測定し、最も大きい破断強度が測定された方向を最大破断強度方向とし、最大破断強度方向の破断強度を最大破断強度とする。
さらに、本発明の発泡部材は、上記樹脂発泡体を含むので、高圧縮下であっても柔軟性を維持でき、組み付け性に優れる。
最大破断強度:シート状の樹脂発泡体について、水平方向における任意の方向で破断強度を測定し、次にその任意の方向を軸に10°(度)おきに回転させて、各方向における破断強度を測定し、最も大きい破断強度が測定された方向を最大破断強度方向とし、最大破断強度方向の破断強度を最大破断強度とする。
なお、本明細書では、上記で規定される最大破断強度を、単に「最大破断強度」と称する場合がある。
また、「最大破断強度と、最大破断強度方向と直行する方向の破断強度との比(最大破断強度/最大破断強度方向と直行する方向の破断強度)」を、単に「強度比(最大破断強度/最大破断強度方向と直行する方向の破断強度)」と称する場合がある。
(i):230℃におけるメルトフローレート(MFR)が1.5~4.0g/10minであるポリエステル系エラストマー(好ましくは、230℃におけるメルトフローレート(MFR)が1.5~4.0g/10minであり、ハードセグメント及びソフトセグメントのブロック共重合体であるポリエステル系エラストマー、より好ましくは、230℃におけるメルトフローレート(MFR)が1.5~4.0g/10minであり、芳香族ジカルボン酸とヒドロキシル基とヒドロキシル基との間の主鎖中の炭素数が2~4であるジオール成分との重縮合により形成されるポリエステルをハードセグメントとし、ポリエーテルをソフトセグメントとする、ポリエステル・ポリエーテル型の共重合体)
(ii):エポキシ変性ポリマー
(iii):滑剤(好ましくはアクリル系滑剤)
(iv):発泡核剤(好ましくは表面処理加工された無機物、より好ましくは表面処理加工されたハードクレイ)
本発明の樹脂発泡体は発泡部材として用いられてもよい。つまり、上記発泡部材は、上記の本発明の樹脂発泡体を含む部材である。上記発泡部材は、例えば、上記の本発明の樹脂発泡体のみからなる構成であってもよいし、上記樹脂発泡体に他の層(特に粘着剤層(粘着層)、基材層など)が積層されている構成であってもよい。
ハードセグメントとしてのポリブチレンテレフタレートとソフトセグメントとしてのポリエーテルとのブロック共重合体(商品名「ハイトレル5577」、東レ・デュポン株式会社製、230℃のメルトフローレート:1.8g/10min、融点:208℃):100重量部、アクリル系滑剤(商品名「メタブレンL-1000」、三菱レイヨン株式会社製):5重量部、シランカップリング剤で表面処理加工されているハードクレイ(商品名「ST-301」、白石カルシウム株式会社製):1重量部、カーボンブラック(商品名「旭♯35」、旭カーボン株式会社製):5重量部及びエポキシ系改質剤(エポキシ変性アクリル系ポリマー、重量平均分子量(Mw):50000、エポキシ当量:1200g/eq、粘度:2850mPa・s):2重量部を、二軸混練機により、220℃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切断して成形した。このペレットを単軸押出機に投入し、240℃の雰囲気中、17(注入後13)MPの圧力で二酸化炭素ガスを注入した。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、厚みが2.0mmのシート状のポリエステル系エラストマー発泡体を得た。
ハードセグメントとしてのポリブチレンテレフタレートとソフトセグメントとしてのポリエーテルとのブロック共重合体(商品名「ペルプレン P-90BD」、東洋紡株式会社製、230℃のメルトフローレート:3.0g/10min、融点:204℃):100重量部、アクリル系滑剤(商品名「メタブレンL-1000」、三菱レイヨン株式会社製):5重量部、シランカップリング剤で表面処理加工されているハードクレイ(商品名「ST-301」、白石カルシウム株式会社製):1重量部、カーボンブラック(商品名「旭♯35」、旭カーボン株式会社製):5重量部及びエポキシ系改質剤(エポキシ変性アクリル系ポリマー、重量平均分子量(Mw):50000、エポキシ当量:1200g/eq、粘度:2850mPa・s):2重量部を、二軸混練機により、220℃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切断して成形した。このペレットを単軸押出機に投入し、240℃の雰囲気中、17(注入後13)MPaの圧力で二酸化炭素ガスを注入した。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、厚みが2.0mmのシート状のポリエステル系エラストマー発泡体を得た。
ハードセグメントとしてのポリブチレンテレフタレートとソフトセグメントとしてのポリエーテルとのブロック共重合体(商品名「ペルプレン P-90BD」、東洋紡株式会社製、230℃のメルトフローレート:3.0g/10min、融点:204℃):100重量部、アクリル系滑剤(商品名「メタブレンL-1000」、三菱レイヨン株式会社製):5重量部、シランカップリング剤で表面処理加工されているハードクレイ(商品名「ST-301」、白石カルシウム株式会社製):3重量部、カーボンブラック(商品名「旭♯35」、旭カーボン株式会社製):5重量部及びエポキシ系改質剤(エポキシ変性アクリル系ポリマー、重量平均分子量(Mw):50000、エポキシ当量:1200g/eq、粘度:2850mPa・s):2重量部を、二軸混練機により、220℃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切断して成形した。このペレットを単軸押出機に投入し、240℃の雰囲気中、17(注入後13)MPaの圧力で二酸化炭素ガスを注入した。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、厚みが2.0mmのシート状のポリエステル系エラストマー発泡体を得た。
ポリプロピレン(メルトフローレート(MFR):0.35g/10min):35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・):60重量部、水酸化マグネシウム:10重量部及びカーボン(商品名「旭♯35」、旭カーボン株式会社製):10重量部を、単軸押出機に投入した。220℃の雰囲気下、13(注入後は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、厚みが2.1mmのシート状のポリオレフィン系エラストマー発泡体を得た。
ハードセグメントとしてのポリブチレンテレフタレートとソフトセグメントとしてのポリエーテルとのブロック共重合体(商品名「ハイトレル5577」、東レ・デュポン株式会社製、230℃のメルトフローレート:1.8g/10min):100重量部、アクリル系滑剤(商品名「メタブレンL-1000」、三菱レイヨン株式会社製):5重量部、ポリプロピレン(商品名「ニューストレンSH9000」、日本ポリプロ株式会社製):1重量部及び水酸化マグネシウム:1重量部を、二軸混練機により、220℃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切断して成形した。このペレットを単軸押出機に投入し、240℃の雰囲気中、17(注入後13)MPaの圧力で二酸化炭素ガスを注入した。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、厚みが2.5mmのシート状のポリエステル系エラストマー発泡体を得た。
ハードセグメントとしてのポリブチレンテレフタレートとソフトセグメントとしてのポリエーテルとのブロック共重合体(商品名「ハイトレル5577」、東レ・デュポン株式会社製、230℃のメルトフローレート:1.8g/10min、融点:208℃):100重量部、アクリル系滑剤(商品名「メタブレンL-1000」、三菱レイヨン株式会社製):5重量部、ポリプロピレン(商品名「ニューストレンSH9000」、日本ポリプロ株式会社製):1重量部、水酸化マグネシウム:1重量部、カーボンブラック(商品名「旭♯35」、旭カーボン株式会社製):5重量部及びエポキシ系架橋剤(3官能エポキシ化合物、商品名「TEPIC-G」、日産化学工業株式会社製、融点:90~125℃、エポキシ当量:110g/eq、粘度:100cp以下、分子量:297):0.5重量部を、二軸混練機により、220℃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切断して成形した。このペレットを単軸押出機に投入し、240℃の雰囲気中、17(注入後13)MPaの圧力で二酸化炭素ガスを注入した。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、厚みが2.2mmのシート状のポリエステル系エラストマー発泡体を得た。
市販の、平均セル径が160μmであり、80%に圧縮したときの反発応力が9.5N/cm2であり、見掛け密度が0.15g/cm3であるポリウレタンが主成分の発泡体を使用した。
この発泡体はシート状であり、厚みは1.0mmであった。また、50%圧縮時の反発応力(50%対反発荷重)が0.7N/cm2であった。
実施例及び比較例の発泡体について、下記の測定又は評価を行った。そして、その結果を、表1に示した。
発泡体を、幅:30mm、長さ:30mmサイズの打ち抜き刃型にて打ち抜き、シート状の試験片とした。該試験片の寸法をノギスにより測定した。また、測定端子の直径(φ)が20mmである1/100ダイヤルゲージにて試験片の厚みを測定した。これらの値から試験片の体積を算出した。次に、試験片の重量を電子天秤にて測定した。試験片の体積と試験片の重量から、次式より、発泡体の見掛け密度(g/cm3)を算出した。
発泡体の見掛け密度(g/cm3)=(試験片の重量)/(試験片の体積)
デジタルマイクロスコープ(商品名「VHX-500」、キーエンス株式会社製)により、発泡体気泡部の拡大画像を取り込み、切断面の一定面積(1mm2)に表れた全てのセルの面積を、同計測機器の画像解析ソフト(商品名「Win ROOF」、三谷商事株式会社製)を用いて画像解析することにより測定した。そして、円相当径換算した後、セル数で平均化して、平均セル径(μm)を求めた。
JIS K 6767に記載されている圧縮硬さ測定法に準じて測定した。
発泡体を幅:30mm、長さ:30mmに切り出し、シート状の試験片とした。次に該試験片を、圧縮速度:10mm/minで、厚み方向に、圧縮率が80%になるまで圧縮したときの応力(N)を単位面積(1cm2)当たりに換算して反発力(N/cm2)とした。
発泡体より厚み0.5mm、幅:30mm、長さ30mmのシート状の試験片を得た。該試験片について、水平方向における長さ方向で破断強度を測定し、さらにその長さ方向を軸に10°おきに回転させて、各方向における破断強度を測定した。破断強度の測定は、18方向について行った。なお、図1に、発泡体において、剥離強度の測定を行った18方向について示した。
なお、破断強度は、JIS K 6767の引張強さ及び伸びの項に基づいて、測定した。
次に、最も大きい破断強度が測定された方向を最大破断強度方向とし、最大破断強度方向の破断強度を最大破断強度(MPa)とした。さらに、最大破断強度方向と直行する方向の破断強度(MPa)を求めた。
そして、最大破断強度及び最大破断強度方向と直行する方向の破断強度より、「最大破断強度と最大破断強度方向と直行する方向の破断強度との比(強度比(最大破断強度/最大破断強度方向と直行する方向の破断強度))」を求めた。
発泡体を水平方向における任意の10方向に切り出して、厚み0.5mm、幅3mm、長さ30cmのシート状の試験片を10個得た。
次に、試験片の長さ方向の一端を固定した状態で、1.0Nの荷重を用いて、試験片の長さ方向に張力を加えながら筐体への組付けを行った。この時、組み付け後の試験片の長さを測定し、30.0~31.0cmの範囲内であれば合格とし、31.0cmを超えたもの(つまり、大きく伸びてしまったもの)や組み付け時に切れてしまったものを不合格とした。
10個全ての試験片について、合格であった場合を「良好」と評価し、一方、1つでも不合格が含まれていた場合を「不良」と評価した。
発泡体を切り出して、幅50mm、長さ50mm、厚み1.0mmのシート状の試験片(試験片21)を得た。
試験片を図2に示されるような治具(正方形、治具2)に、図2に示すように試験片をセットし、上面側のアクリル板(厚み1mmのアクリル板22a)により試験片を厚み方向に圧縮して、上面側のアクリル板(アクリル板22a)の変形の状態をマイクロスコープにて観察した。
具体的には、厚み2mmのアクリル板(厚み2mmのアクリル板22b)の左右の端部に、厚み0.4mmのスペーサー(厚み0.4mmのスペーサー23)を設置し、上記スペーサーで挟まれた中央部に試験片(試験片21)を設置して、この上面に、厚み1mmのアクリル板(厚み1mmのアクリル板22a)を設置した。その後、両端のスペーサー部において、上面側のアクリル板(厚み1mmのアクリル板22a)側から四方対角線状にボルトを治具に締め込んで、試験片の厚み方向に均一に力をかけて、試験片を厚み方向に圧縮した。その際、上面側のアクリル板(厚み1mmのアクリル板22a)の変形の有無をマイクロスコープで観察した。そして、変形がみられない場合を「なし」と評価し、一方、変形がみられる場合を「あり」と評価した。
溶融張力の測定には、Malvern社製のCapillary Extrusion Rheometerを使用し、直径が2mm、長さが20mmのキャピラリーより、8.8mm/minの一定速度で押し出された樹脂を2m/minの引取速度で引き取ったときの張力を溶融張力とした。
なお、測定には、発泡成形前のペレットを用いた。また、測定時の温度は、樹脂の融点から高温側に10±2℃の温度とした。
測定には、発泡成形前のペレットを用いた。該ペレットを、加熱した熱板プレスを用いて、厚さ1mmのシート状に成形し、シートを得た、該シートからサンプル(たて:10mm、よこ:10mm、厚さ:1mm)を切り出した。
上記サンプルより、一軸伸長粘度計(ティー・エイ・インスツルメント社製)を用いて、歪速度0.1[1/s]での一軸伸長粘度を測定した。そして、下記式より、歪硬化度を求めた。
歪硬化度=logηmax/logη0.2
(ηmaxは一軸伸長粘度において最も高くなったときの伸長粘度を示し、η0.2は歪εが0.2の時の伸長粘度を示す。)
なお、測定時の温度は、樹脂の融点とした。
A 長さ方向
B 幅方向
C 破断強度を測定する方向
2 治具
21 発泡体
22a アクリル板
22b アクリル板
23 スペーサー
Claims (11)
- 80%に圧縮したときの反発応力が1.0~9.0N/cm2であり、下記で規定される最大破断強度が1.0~10.0MPaであり、下記で規定される最大破断強度と、最大破断強度方向と直行する方向の破断強度との比(最大破断強度/最大破断強度方向と直行する方向の破断強度)が1.0~5.0であることを特徴とする樹脂発泡体。
最大破断強度:シート状の樹脂発泡体について、水平方向における任意の方向で破断強度を測定し、次にその任意の方向を軸に10°おきに回転させて、各方向における破断強度を測定し、最も大きい破断強度が測定された方向を最大破断強度方向とし、最大破断強度方向の破断強度を最大破断強度とする。 - さらに、平均セル径が10~200μmであり、見かけ密度が0.01~0.20g/cm3である請求項1記載の樹脂発泡体。
- 前記樹脂発泡体を構成する樹脂が、熱可塑性樹脂である請求項1又は2記載の樹脂発泡体。
- 前記熱可塑性樹脂が、ポリエステルである請求項3記載の樹脂発泡体。
- 前記樹脂発泡体が、樹脂組成物に高圧のガスを含浸させた後、減圧する工程を経て形成される請求項1~4の何れか1項に記載の樹脂発泡体。
- 前記ガスが、不活性ガスである請求項5記載の樹脂発泡体。
- 前記ガスが、二酸化炭素ガスである請求項6又は7記載の樹脂発泡体。
- 前記の高圧のガスが、超臨界状態のガスである請求項5~7の何れか1項に記載の樹脂発泡体。
- 請求項1~8の何れか1項に記載の樹脂発泡体を含むことを特徴とする発泡部材。
- 前記樹脂発泡体上に粘着剤層を有する請求項9記載の発泡部材。
- 前記粘着剤層が、アクリル系粘着剤層である請求項10記載の発泡部材。
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| CN201380028500.XA CN104350092B (zh) | 2012-05-28 | 2013-05-21 | 树脂发泡体和发泡构件 |
| US14/403,822 US20150218422A1 (en) | 2012-05-28 | 2013-05-21 | Resin foam and foam material |
| KR1020147036296A KR102142840B1 (ko) | 2012-05-28 | 2013-05-21 | 수지 발포체 및 발포 부재 |
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| JP2014005452A (ja) * | 2012-05-31 | 2014-01-16 | Nitto Denko Corp | 熱可塑性樹脂発泡体及び発泡シール材 |
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| EP3571244B1 (en) * | 2017-01-20 | 2022-03-16 | DSM IP Assets B.V. | Foamed composition |
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| JP6358369B1 (ja) * | 2017-06-27 | 2018-07-18 | 東洋紡株式会社 | 熱可塑性ポリエステルエラストマー樹脂発泡成形体およびその製造方法 |
| JP6358368B1 (ja) * | 2017-06-27 | 2018-07-18 | 東洋紡株式会社 | 熱可塑性ポリエステルエラストマー樹脂組成物およびその発泡成形体 |
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| TWI783864B (zh) * | 2022-01-27 | 2022-11-11 | 合泰材料科技股份有限公司 | 低永久壓縮形變的減震墊 |
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|---|---|
| TW201400533A (zh) | 2014-01-01 |
| JP6039501B2 (ja) | 2016-12-07 |
| CN104350092B (zh) | 2017-08-29 |
| US20150218422A1 (en) | 2015-08-06 |
| KR20150027118A (ko) | 2015-03-11 |
| CN104350092A (zh) | 2015-02-11 |
| KR102142840B1 (ko) | 2020-08-10 |
| JP2014005443A (ja) | 2014-01-16 |
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