CN113825820A - Thermoplastic elastomer composition for damping member - Google Patents
Thermoplastic elastomer composition for damping member Download PDFInfo
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- CN113825820A CN113825820A CN201980096594.1A CN201980096594A CN113825820A CN 113825820 A CN113825820 A CN 113825820A CN 201980096594 A CN201980096594 A CN 201980096594A CN 113825820 A CN113825820 A CN 113825820A
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- hydrogenated
- styrene
- polymer block
- thermoplastic
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- 239000000203 mixture Substances 0.000 title claims abstract description 74
- 229920002725 thermoplastic elastomer Polymers 0.000 title claims abstract description 55
- 238000013016 damping Methods 0.000 title claims abstract description 53
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 177
- 229920001971 elastomer Polymers 0.000 claims abstract description 81
- 239000000806 elastomer Substances 0.000 claims abstract description 63
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 62
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 62
- -1 diene compound Chemical class 0.000 claims abstract description 58
- 229920000642 polymer Polymers 0.000 claims abstract description 50
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 35
- 229920001400 block copolymer Polymers 0.000 claims abstract description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 97
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 45
- 229920005989 resin Polymers 0.000 claims description 31
- 239000011347 resin Substances 0.000 claims description 31
- 229920001955 polyphenylene ether Polymers 0.000 claims description 27
- 239000005060 rubber Substances 0.000 claims description 18
- 239000004743 Polypropylene Substances 0.000 claims description 12
- 150000001412 amines Chemical class 0.000 claims description 12
- 239000004611 light stabiliser Substances 0.000 claims description 12
- 229920001155 polypropylene Polymers 0.000 claims description 12
- 239000004902 Softening Agent Substances 0.000 claims description 10
- 239000002530 phenolic antioxidant Substances 0.000 claims description 6
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- 238000011156 evaluation Methods 0.000 description 8
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- 238000004519 manufacturing process Methods 0.000 description 7
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- 229920006132 styrene block copolymer Polymers 0.000 description 7
- NXXYKOUNUYWIHA-UHFFFAOYSA-N 2,6-Dimethylphenol Chemical compound CC1=CC=CC(C)=C1O NXXYKOUNUYWIHA-UHFFFAOYSA-N 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical group CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 5
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- 239000000843 powder Substances 0.000 description 5
- QQOMQLYQAXGHSU-UHFFFAOYSA-N 2,3,6-Trimethylphenol Chemical compound CC1=CC=C(C)C(O)=C1C QQOMQLYQAXGHSU-UHFFFAOYSA-N 0.000 description 4
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- GVLZQVREHWQBJN-UHFFFAOYSA-N 3,5-dimethyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(C)=CC2=C1 GVLZQVREHWQBJN-UHFFFAOYSA-N 0.000 description 3
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- 229910052623 talc Inorganic materials 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
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- 229920001519 homopolymer Polymers 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
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- 229920005992 thermoplastic resin Polymers 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical group CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- OPLCSTZDXXUYDU-UHFFFAOYSA-N 2,4-dimethyl-6-tert-butylphenol Chemical compound CC1=CC(C)=C(O)C(C(C)(C)C)=C1 OPLCSTZDXXUYDU-UHFFFAOYSA-N 0.000 description 1
- DKCPKDPYUFEZCP-UHFFFAOYSA-N 2,6-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=C1O DKCPKDPYUFEZCP-UHFFFAOYSA-N 0.000 description 1
- KUNNUNBSGQSGDY-UHFFFAOYSA-N 2-butyl-6-methylphenol Chemical compound CCCCC1=CC=CC(C)=C1O KUNNUNBSGQSGDY-UHFFFAOYSA-N 0.000 description 1
- GRXOKDOOUFYKLX-UHFFFAOYSA-N 3,5-dichloro-7-oxabicyclo[2.2.1]hepta-1(6),2,4-triene Chemical compound ClC1=C(O2)C(Cl)=CC2=C1 GRXOKDOOUFYKLX-UHFFFAOYSA-N 0.000 description 1
- KXRLIZRDCCQKDZ-UHFFFAOYSA-N 3-ethyl-5-methyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound CC1=C(O2)C(CC)=CC2=C1 KXRLIZRDCCQKDZ-UHFFFAOYSA-N 0.000 description 1
- UDBVWWVWSXSLAX-UHFFFAOYSA-N 4-[2,3-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butyl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)C(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)CC1=CC(C(C)(C)C)=C(O)C=C1C UDBVWWVWSXSLAX-UHFFFAOYSA-N 0.000 description 1
- APMOEFCWQRJOPS-UHFFFAOYSA-N 5-ethenyl-1,5-dimethylcyclohexa-1,3-diene Chemical compound CC1=CC=CC(C)(C=C)C1 APMOEFCWQRJOPS-UHFFFAOYSA-N 0.000 description 1
- NGNBLQAYJAKWKR-UHFFFAOYSA-N 5-methyl-3-phenyl-7-oxabicyclo[2.2.1]hepta-1,3,5-triene Chemical compound O1C=2C(C)=CC1=CC=2C1=CC=CC=C1 NGNBLQAYJAKWKR-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 101100097985 Caenorhabditis elegans mars-1 gene Proteins 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- FLPKSBDJMLUTEX-UHFFFAOYSA-N bis(1,2,2,6,6-pentamethylpiperidin-4-yl) 2-butyl-2-[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]propanedioate Chemical compound C1C(C)(C)N(C)C(C)(C)CC1OC(=O)C(C(=O)OC1CC(C)(C)N(C)C(C)(C)C1)(CCCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 FLPKSBDJMLUTEX-UHFFFAOYSA-N 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- GJKZSOHUVOQISW-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;styrene Chemical compound C=CC=C.CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 GJKZSOHUVOQISW-UHFFFAOYSA-N 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 239000003484 crystal nucleating agent Substances 0.000 description 1
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- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012765 fibrous filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000010299 mechanically pulverizing process Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000000790 scattering method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
Abstract
The invention provides a thermoplastic elastomer composition for a damping member, a damping member and a rotor for a motor using the same, wherein the thermoplastic elastomer composition comprises a hydrogenated thermoplastic styrene elastomer A and a hydrogenated thermoplastic styrene elastomer B at a mass ratio of 5/95-55/45 (hydrogenated thermoplastic styrene elastomer A/hydrogenated thermoplastic styrene elastomer B), the A hardness is 50 or less, the hydrogenated thermoplastic styrene elastomer A is a hydrogenated product of a block copolymer comprising a styrene polymer block (S1) and a conjugated diene compound polymer block (B1), the 1, 2-vinyl bond content of the conjugated diene compound polymer block (B1) is 50 mass% or more, and the hydrogenated thermoplastic styrene elastomer B is a block copolymer comprising a styrene polymer block (S2) and a conjugated diene compound polymer block (B2) The content of 1, 2-vinyl bonds in the conjugated diene compound polymer block (B2) is less than 50% by mass, and the thermoplastic elastomer composition for damping members of the present invention can be used for damping members suitable for noise/vibration countermeasures for household electric appliances, automobile parts, sporting goods and the like.
Description
Technical Field
The present invention relates to a thermoplastic elastomer composition for damping members suitable for noise and vibration countermeasures for home electric appliances, automobile parts, sporting goods, and the like, a damping member using the thermoplastic elastomer composition, and a rotor for a motor.
Background
As typical uses of the damping member, for example, there are: in electric equipment such as an air conditioner, a heat pump water heater, and an air cleaner, it is known that a bearing portion or the like provided to support a rotating shaft of a motor or a power transmission member is provided in a rotor of a brushless motor, and a vibration-proof rubber is inserted between the rotating shaft and an outer core having a permanent magnet, a ferrite magnet, an electromagnetic steel plate, or the like, thereby suppressing sound and vibration generated by the motor, and preventing deterioration of the entire equipment due to vibration while pursuing quietness.
Patent document 1 discloses: by integrally molding the core and the vibration-proof material using the elastic body instead of embedding rubber in the rotor of the motor, the vibration-proof material can be prevented from being deviated or falling off.
As a thermoplastic elastomer having high damping performance, a styrene-isoprene-styrene block copolymer, a styrene-isoprene-butadiene-styrene block copolymer, and a hydrogenated product thereof are known, and these elastomers have excellent damping performance as compared with vulcanized rubbers, but have a problem of large compression set. If the compression set of the damping material used for the bearing portion is large, the position of the outer core of the rotor or the position of the support of the rotating shaft may fluctuate with time, resulting in poor engagement with the rotation transmitting member or contact between the rotor and the housing, and therefore improvement is required.
Patent document 2 discloses a thermoplastic resin composition containing a polyphenylene ether-based resin, a conjugated diene-alkenyl aromatic-based copolymer, and a polystyrene-based resin, which is excellent in dimensional accuracy and dimensional stability and also excellent in damping performance, but the polyphenylene ether-based resin itself does not have a damping performance to be satisfied, and therefore, it is suggested that a specific conjugated diene-alkenyl aromatic-based copolymer needs to be used in combination in order to improve the damping performance. Preferred fillers include: fibrous fillers such as glass fibers, and scaly fillers such as mica and talc.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 6-86485;
patent document 2: japanese patent laid-open No. 11-080535.
Disclosure of Invention
Problems to be solved by the invention
In patent document 1, when an elastic body is integrally molded with a rotor having a complicated shape, if the filling property is poor, voids may be generated to deteriorate the weight balance of the rotor, and therefore, the elastic body to be used needs high moldability, but patent document 1 does not disclose what kind of material can be used as the elastic body having both damping property and moldability.
Further, it is known that the needle-like or layer-like filler described in patent document 2 has been conventionally a preferable filler as a damping material, and may be collectively referred to as a damping filler, but the moldability as a thermoplastic composition tends to be lowered by blending the filler.
Therefore, as the thermoplastic elastomer composition, a thermoplastic elastomer composition excellent in damping property is known, and a damping filler for improving the damping property is also known, but for an application further requiring moldability or compression set resistance, the problem is not sufficiently solved, and a solution is required.
The subject of the invention is to provide: a thermoplastic elastomer composition for a damping member excellent in damping properties, compression set resistance and moldability, a damping member using the thermoplastic elastomer composition, and a rotor for a motor.
Means for solving the problems
The present invention relates to the following [1] to [6 ]:
[1] a thermoplastic elastomer composition for a damping member, which comprises a hydrogenated thermoplastic styrene elastomer A and a hydrogenated thermoplastic styrene elastomer B in a mass ratio of 5/95-55/45 (hydrogenated thermoplastic styrene elastomer A/hydrogenated thermoplastic styrene elastomer B), wherein the hydrogenated thermoplastic styrene elastomer A is a hydrogenated product of a block copolymer comprising a styrene polymer block (S1) and a conjugated diene compound polymer block (B1), the 1, 2-vinyl bond content of the conjugated diene compound polymer block (B1) is 50 mass% or more, the hydrogenated thermoplastic styrene elastomer B is a hydrogenated product of a block copolymer comprising a styrene polymer block (S2) and a conjugated diene compound polymer block (B2), and the conjugated diene compound polymer block (B2) is 1, the 2-vinyl bond content is less than 50 mass%, and the composition contains 10-200 parts by mass of polyphenylene ether resin, 50-1000 parts by mass of softening agent for rubber, and 10-300 parts by mass of ground calcium carbonate, relative to 100 parts by mass of the total of the hydrogenated thermoplastic styrene elastomer A and the hydrogenated thermoplastic styrene elastomer B, and the A hardness is less than 50.
[2]Above-mentioned [1]The thermoplastic elastomer composition comprises ground calcium carbonate having a volume-based median diameter of 0.5 to 10μm, the specific surface area of 0.3-3.0 m2/g；
[3] The thermoplastic elastomer composition according to the above [1] or [2], which further contains a phenolic antioxidant and a hindered amine light stabilizer;
[4] the thermoplastic elastomer composition according to any one of the above [1] to [3], which further comprises polypropylene;
[5] a damping member which is a molded body of the thermoplastic elastomer composition according to any one of the above [1] to [4 ]; and
[6] a rotor for a motor, the rotor comprising the damper member according to [5 ].
Effects of the invention
The thermoplastic elastomer composition of the present invention exhibits the effect of excellent damping properties as a damping member, and also excellent compression set resistance and moldability.
Detailed Description
The thermoplastic elastomer composition of the present invention comprises:
a hydrogenated thermoplastic styrene-based elastomer A which is a hydrogenated product of a block copolymer comprising a styrene-based polymer block (S1) and a conjugated diene compound polymer block (B1), wherein the weight average molecular weight is 50% by mass or more of the 1, 2-vinyl bond content of the conjugated diene compound polymer block (B1); and
a hydrogenated thermoplastic styrene-based elastomer B which is a hydrogenated product of a block copolymer comprising a styrene-based polymer block (S2) and a conjugated diene compound polymer block (B2), wherein the conjugated diene compound polymer block (B2) has a 1, 2-vinyl bond content of less than 50% by mass; and
polyphenylene ether resin, a softening agent for rubber, and ground calcium carbonate.
The specific properties of the thermoplastic elastomer are derived from a structure in which a soft segment (soft phase) composed of a soft rubber component and a hard segment (hard phase) composed of a hard resin component are separated. Further, the softening agent for rubber is held in the soft segment portion and is held in accordance with the length of the soft segment portion.
The hydrogenated thermoplastic styrene-based elastomer a has a 1, 2-vinyl bond content of 50 mass% or more and is excellent in damping properties, but when only the hydrogenated thermoplastic styrene-based elastomer a is used, the length of the soft segment portion in the molecular chain having many branches becomes short, and therefore the softening agent for rubber is not easily held, and the composition may become sticky. Accordingly, the composition of the present invention contains the hydrogenated thermoplastic styrene-based elastomer B having a 1, 2-vinyl bond content of less than 50 mass%. Since the hydrogenated thermoplastic styrene-based elastomer B has a long molecular chain with few branches, the length of the soft segment portion becomes long, and the softening agent for rubber is easily held. By using the hydrogenated thermoplastic styrene-based elastomer A and the hydrogenated thermoplastic styrene-based elastomer B in combination, the improvement in damping properties and tackiness can be improved. In the present invention, the 1, 2-vinyl bond amount means the total amount of 1, 2-vinyl bond and 3, 4-vinyl bond. In the case where the conjugated diene compound polymer block (B1) has a polybutadiene unit, the 1, 2-vinyl bonding unit and the 3, 4-vinyl bonding unit form the same structure, and therefore the difference in effect due to the difference in structure can be ignored, and all the bonding units have more side chains than the 1, 4-vinyl bonding unit, and therefore exhibit a damping effect. On the other hand, in the case where the conjugated diene compound polymer block (B1) has isoprene units, there is a difference in the shape of side chains in the 1, 2-vinyl bonding units and 3, 4-vinyl bonding units, and the 3, 4-vinyl bonding has side chains with a larger volume, so that the damping effect becomes larger. Therefore, in the conjugated diene compound polymer block (B1), a block having a larger total amount of 1, 2-vinyl bonds and 3, 4-vinyl bonds than 1, 4-vinyl bonds is preferable, and a block having a larger amount of 3, 4-vinyl bonds is more preferable in the total amount of 1, 2-vinyl bonds and 3, 4-vinyl bonds.
Further, the present invention is characterized by containing heavy calcium carbonate.
Calcium carbonate generally used as a filler is roughly classified into the following 2 types: natural calcium carbonate (ground calcium carbonate) obtained by mechanically pulverizing and classifying limestone; and synthetic calcium carbonate (light calcium carbonate) obtained by dissolving limestone once in a raw material and chemically synthesizing the limestone. Since ground calcium carbonate is a ground product, it has a substantially amorphous ground shape, and may have various particle sizes or particle size distributions. On the other hand, light calcium carbonate is precipitated from a solution by a chemical reaction, and thus produced by a production method into light calcium carbonate having a certain particle shape, which is spindle-shaped and has a micron-sized major axis, and colloidal calcium carbonate having a cubic primary particle size.
It is known that light calcium carbonate has been used as a filler for natural rubber since long and that a rubber having light calcium carbonate dispersed therein as ultrafine particles and having a large specific surface area has an improved tensile strength, but has a tendency to easily aggregate in a non-polar molten resin from the viewpoint of the properties of light calcium carbonate having a hydrophilic surface as fine particles, and therefore, in order to disperse the light calcium carbonate in the resin, it is necessary to perform a surface treatment with an organic acid such as stearic acid.
Since the thermoplastic elastomer composition is similar in use and properties to natural rubber, light calcium carbonate for rubber is often blended as an additive, but in the thermoplastic elastomer composition of the present invention for damping members, the necessity of particularly improving the tensile strength is low, and on the other hand, it is found that moldability or compression set resistance is deteriorated when light calcium carbonate is blended, and these problems are solved by blending heavy calcium carbonate having a specific particle size.
The hydrogenated thermoplastic styrene-based elastomer A is composed of a styrene-based polymer block (S1) and a conjugated diene compound polymer block (B1), and a part or all of the conjugated diene compound polymer block (B1) is hydrogenated. The hydrogenation rate is preferably 80% or more, more preferably 90% or more. In the present invention, the hydrogenation ratio can be determined by the ratio of the hydrogenation to the hydrogenation before and after1The content of the carbon-carbon double bond derived from the conjugated diene compound in the block copolymer was measured by H-NMR spectroscopy and determined from the measured value.
Examples of the styrene-based polymer block (S1) include: and styrene monomers such as styrene, o-methylstyrene, p-tert-butylstyrene, 1, 3-dimethylstyrene, α -methylstyrene, vinylnaphthalene, and vinylanthracene.
As the conjugated diene compound polymer block (B1), there can be mentioned: and polymer blocks of conjugated diene compounds such as butadiene, isoprene and 1, 3-pentadiene.
Examples of the hydrogenated thermoplastic styrene-based elastomer a include: styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-propylene-styrene block copolymer (SEEPS), hydrogenated products of polystyrene-polyisoprene-polystyrene (SIS), and the like.
From the viewpoint of compression set resistance and moldability, the weight average molecular weight of the hydrogenated thermoplastic styrene-based elastomer A is preferably 50,000 to 500,000, more preferably 100,000 to 300,000, and still more preferably 200,000 to 250,000.
From the viewpoint of heat resistance, the styrene monomer content in the hydrogenated thermoplastic styrene-based elastomer a is preferably 20% by mass or more, and more preferably 20 to 40% by mass.
The hydrogenated thermoplastic styrene-based elastomer A is preferably a block copolymer composed of at least 2 styrene-based polymer blocks (S1) and at least 1 conjugated diene compound polymer block (B1).
The 1, 2-vinyl bond content of the conjugated diene compound polymer block (B1) in the hydrogenated thermoplastic styrene-based elastomer A is 50 mass% or more, preferably 50 to 80 mass%. Such a hydrogenated thermoplastic styrene-based elastomer a has a bulky structure with many branches in the elastomer molecular chain. Therefore, when vibration energy is applied to the composition of the present invention, the probability of collision between molecules is increased, the vibration energy is efficiently converted into heat energy, and good damping properties are imparted to the composition of the present invention.
The hydrogenated thermoplastic styrene-based elastomer B is a hydrogenated product of a block copolymer comprising a styrene-based polymer block (S2) and a conjugated diene compound polymer block (B2), and the conjugated diene compound polymer block (B2) has a 1, 2-vinyl bond content of less than 50% by mass. The hydrogenation rate is preferably 80% or more, more preferably 90% or more. In the present invention, the hydrogenation ratio can be determined by the ratio of the hydrogenation to the hydrogenation before and after1The content of the carbon-carbon double bond derived from the conjugated diene compound in the block copolymer was measured by H-NMR spectroscopy and determined from the measured value.
The 1, 2-vinyl bond content of the conjugated diene compound polymer block (B2) is preferably 20 to 45 mass%, more preferably 30 to 40 mass%.
Examples of the styrene-based polymer block (S2) and the conjugated diene compound polymer block (B2) include the same blocks as those of the styrene-based polymer block (S1) and the conjugated diene compound polymer block (B1).
Therefore, examples of the hydrogenated thermoplastic styrene-based elastomer B include, in the same manner as the hydrogenated thermoplastic styrene-based elastomer a: styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), styrene-ethylene-propylene-styrene block copolymer (SEEPS), hydrogenated products of polystyrene-polyisoprene-polystyrene (SIS), and the like.
The hydrogenated thermoplastic styrene-based elastomer B preferably has a weight average molecular weight of 50,000 to 500,000, more preferably 150,000 to 450,000, and still more preferably 200,000 to 400,000, from the viewpoint of compression set resistance and moldability.
From the viewpoint of heat resistance, the styrene monomer content in the hydrogenated thermoplastic styrene-based elastomer B is preferably 20% by mass or more, and more preferably 20 to 40% by mass.
The hydrogenated thermoplastic styrene-based elastomer B is preferably a block copolymer composed of at least 2 styrene-based polymer blocks (S2) and at least 1 conjugated diene compound polymer block (B2).
The mass ratio of the hydrogenated thermoplastic styrene elastomer A to the hydrogenated thermoplastic styrene elastomer B (hydrogenated thermoplastic styrene elastomer A/hydrogenated thermoplastic styrene elastomer B) is 5/95-55/45, preferably 10/90-50/50, and more preferably 20/80-40/60.
In the thermoplastic elastomer composition, the total content of the hydrogenated thermoplastic styrene-based elastomer a and the hydrogenated thermoplastic styrene-based elastomer B is preferably 10 to 40% by mass, and more preferably 15 to 35% by mass.
Polyphenylene ether resins are known to be resins excellent in heat resistance, mechanical strength, insulation properties, etc., and are used as heat-resistant resin materials, and also used in combination with styrene resins to improve impact resistance of the styrene resins because of their good compatibility with the styrene resins. In the present invention, there is an effect of enhancing the association of the styrene blocks of the thermoplastic styrene-based elastomer to improve heat resistance, and also an effect of improving compression set resistance.
The polyphenylene ether resin is not particularly limited, and examples thereof include: homopolymers composed of a repeating unit represented by the formula (a), copolymers having a repeating unit represented by the formula (a), and the like:
[ chemical formula 1]
(in the formula, R1、R2、R3And R4Each independently a monovalent group selected from the group consisting of a hydrogen atom, a halogen atom, a primary alkyl group having 1 to 7 carbon atoms, a secondary alkyl group having 1 to 7 carbon atoms, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbonoxy group, and a halohydrocarbonoxy group having at least 2 carbon atoms separating the halogen and oxygen atoms).
Such polyphenylene ether resin is not particularly limited, and known polyphenylene ether resins can be used. Specific examples of polyphenylene ether include: homopolymers such as poly (2, 6-dimethyl-1, 4-phenylene ether), poly (2-methyl-6-ethyl-1, 4-phenylene ether), poly (2-methyl-6-phenyl-1, 4-phenylene ether), poly (2, 6-dichloro-1, 4-phenylene ether), and the like; copolymers of 2, 6-dimethylphenol with other phenols (e.g., 2,3, 6-trimethylphenol, 2-methyl-6-butylphenol, etc.), etc., and among these, poly (2, 6-dimethyl-1, 4-phenylene ether), copolymers of 2, 6-dimethylphenol with 2,3, 6-trimethylphenol, and more preferably poly (2, 6-dimethyl-1, 4-phenylene ether) are preferred.
The method for producing the polyphenylene ether resin is not particularly limited, and conventionally known methods can be used. Specific examples of the method for producing a polyphenylene ether include: for example, a method described in U.S. Pat. No. 3306874 or the like for producing a copolymer by oxidative polymerization of 2, 6-xylenol using a complex of a cuprous salt and an amine as a catalyst, or a method described in U.S. Pat. No. 3306875, U.S. Pat. No. 3257357, U.S. Pat. No. 3257358, Japanese patent publication No. 52-17880, Japanese patent application laid-open No. 50-51197, and Japanese patent application laid-open No. 63-152628.
The polyphenylene ether preferably has a number average molecular weight of 5,000 to 40,000, more preferably 10,000 to 20,000, from the viewpoint of melt flowability.
The polyphenylene ether resin in the invention may be a modified polyphenylene ether resin. The modified polyphenylene ether is not particularly limited, and examples thereof include: and products obtained by grafting or adding a styrene polymer or a derivative thereof to the above polyphenylene ether. The proportion of the mass increase by grafting or addition is not particularly limited, and is preferably 0.01 mass% or more, and is preferably 10 mass% or less, more preferably 7 mass% or less, and still more preferably 5 mass% or less in the modified polyphenylene ether resin.
The method for producing the modified polyphenylene ether is not particularly limited, and examples thereof include: and a method of reacting the polyphenylene ether with a styrene polymer or a derivative thereof in the presence or absence of a radical generator in a molten state, a solution state or a slurry state at 80 to 350 ℃.
The content of the polyphenylene ether resin is 10 to 200 parts by mass, preferably 15 to 100 parts by mass, and more preferably 20 to 80 parts by mass, based on 100 parts by mass of the total of the hydrogenated thermoplastic styrene-based elastomer A and the hydrogenated thermoplastic styrene-based elastomer B.
The content of the polyphenylene ether resin in the thermoplastic elastomer composition is preferably 2 to 50% by mass, more preferably 5 to 20% by mass.
Examples of the rubber softener include: among these, at least 1 selected from paraffin-based oils and naphthenic-based oils is preferable, and paraffin-based oils are more preferable, from the viewpoint of good affinity with the styrene-based block copolymer and less bleeding.
The dynamic viscosity of the rubber softener at 40 ℃ is preferably 30mm from the viewpoint that volatilization at the time of heating and melting can be prevented when the dynamic viscosity is high and the bleeding resistance is also good2More preferably 60mm or more in terms of the thickness of the film2(ii) at least s, more preferably 80mm2A length of 150mm or more, preferably 150mm2More than s, preferably 500mm from the viewpoint of easy handling when the dynamic viscosity is low2Less than s, more preferably 450mm2(ii) less than s, more preferably 400mm2The ratio of the water to the water is less than s.
If the content of the softening agent for rubber is too small, the flexibility of the composition is lowered and the damping performance is lowered. In addition, if the softening agent is too much, oil bleeding is likely to occur. From the above viewpoint, the content of the softening agent is 50 to 1000 parts by mass, preferably 60 to 300 parts by mass, and more preferably 70 to 200 parts by mass, based on 100 parts by mass of the total of the hydrogenated thermoplastic styrene-based elastomer a and the hydrogenated thermoplastic styrene-based elastomer B.
The content of the rubber softener in the thermoplastic elastomer composition is preferably 5 to 60% by mass, and more preferably 20 to 50% by mass.
The heavy calcium carbonate of the present invention is preferably calcium carbonate having a larger particle size and a smaller specific surface area than light calcium carbonate, i.e., calcium carbonate having a lower proportion of fine particles. The ground calcium carbonate preferably used in the present invention has excellent melt fluidity when forming a composition, hardly affects the hardness of the composition, and exhibits unexpected characteristics of excellent compression set resistance of a molded article. The reason is presumed to be as follows: since the composition is free of pores and contains a small amount of fine particles, the melt viscosity of the composition is low, while since the composition is amorphous and approximately spherical, the composition has good adhesion to the resin and does not impair the melt flowability of the resin composition.
From the above viewpoint, the volume-based median diameter of the ground calcium carbonate is preferably 0.5 to 10μm, more preferably 0.7 to 8.0μm, more preferably 1.0 to 5.0μm, more preferably 1.0 to 3.0μm。
In addition, the specific surface area of the heavy calcium carbonate is preferably 0.1-8.0 m2A concentration of 0.3 to 3.0m2A specific ratio of 0.5 to 2.4 m/g2A specific ratio of 0.7 to 1.7 m/g2/g。
Although the method for producing heavy calcium carbonate is not particularly limited, it is a general characteristic of heavy calcium carbonate produced by pulverizing natural stone, that crystalline limestone is coarsely/intermediately pulverized by using a jaw crusher, hammer mill or the like according to a predetermined method, finely pulverized by using a hammer mill, vertical roll mill, vibration ball mill or the like, and further subjected to an air classification operation by using a turbo classifier, Turboplex or the like, whereby heavy calcium carbonate having a desired particle size distribution can be obtained.
For example, ground calcium carbonate having a small content of fine particles can be obtained by classifying particles having a specific particle size from a ground mixture of natural calcium carbonate. Even if the average particle size is the same, a large amount of fine particles or coarse particles are contained in the material whose average particle size is reduced by only the intensive grinding step, and the proportion of fine particles or coarse particles can be reduced by concentrating the ground calcium carbonate having a specific particle size by a method such as a vibrating screen or air classification.
In the present invention, the ground calcium carbonate having a specific particle size distribution is characterized in that: it is effective for improving moldability and compression set characteristics. The most common laser diffraction particle size distribution meter is excellent in that the breadth of the particle size distribution or the median diameter as a representative value can be easily determined as a method for measuring the particle size, but the lower limit of the measurable value is 0.1μSince m is about m, the content of fine particles below m cannot be accurately measured. On the other hand, the specific surface area measured by a gas adsorption method known as the so-called BET method is a measurement method that strongly indicates the influence of fine particles. In particular, it is effective in the measurement of heavy calcium carbonate having no porosity and no pore volume. Therefore, the heavy calcium carbonate preferred in the present invention can be preferably determined by combining the particle size measurement based on the laser diffraction type particle size distribution meter with the specific surface area measurement according to the gas adsorption method.
The heavy calcium carbonate in the present invention may be surface-treated. As a method of surface treatment, a method using an organic acid such as stearic acid, a method using a silane coupling agent, or the like is known, and effects such as improvement of dispersibility or improvement of adhesion to a resin component by surface treatment are known, but in heavy calcium carbonate, since it is originally a ground mineral, the particle shape is necessarily amorphous, and for example, adhesion to a resin is excellent as compared with a spherical filler, and further, since the particle diameter is large, dispersibility is excellent, surface treatment is not necessarily required.
The content of the ground calcium carbonate is 10 to 300 parts by mass, preferably 15 to 200 parts by mass, and more preferably 20 to 100 parts by mass, based on 100 parts by mass of the total of the hydrogenated thermoplastic styrene-based elastomer A and the hydrogenated thermoplastic styrene-based elastomer B.
In addition, in the thermoplastic elastomer composition, the content of the ground calcium carbonate is preferably 3 to 50% by mass, more preferably 10 to 30% by mass.
From the viewpoint of moldability, the thermoplastic elastomer composition of the present invention preferably further contains polypropylene.
The polypropylene may be homopolypropylene, which is a propylene homopolymer, or may be block polypropylene, random polypropylene, or the like, and homopolypropylene is preferable from the viewpoint of heat resistance and damping properties.
From the viewpoint of moldability, the melt mass flow rate of polypropylene at 230 ℃ under a nominal load of 21N is preferably 0.1 to 100g/10 min, more preferably 0.5 to 80g/10 min, further preferably 1 to 50g/10 min, and further preferably 1 to 20g/10 min.
The flexural modulus of the polypropylene is preferably 50 to 2000MPa, more preferably 100 to 1850MPa, further preferably 200 to 1700MPa, and further preferably 800 to 1700MPa from the viewpoint of damping properties and flexibility.
The content of the polypropylene is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and still more preferably 5 to 20 parts by mass, based on 100 parts by mass of the total of the hydrogenated thermoplastic styrene-based elastomer A and the hydrogenated thermoplastic styrene-based elastomer B.
The content of polypropylene in the thermoplastic elastomer composition is preferably 0.2 to 30% by mass, more preferably 1 to 10% by mass.
The thermoplastic elastomer composition of the present invention preferably contains an antioxidant. Since the polyphenylene ether resin contained in the thermoplastic elastomer composition of the present invention has a high softening temperature, it is preferable to increase the temperature at the time of melt-kneading the composition, and in this case, scorching or discoloration is likely to occur. It is common knowledge to use an antioxidant in combination with the thermal discoloration during melt kneading, and examples of the antioxidant include: 2, 6-di-tert-butyl-p-cresol, 2, 6-di-tert-butylphenol, 2, 4-dimethyl-6-tert-butylphenol, 4' -dihydroxydiphenyl, tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, phenol antioxidants such as tetrakis [ methylene-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] methane, 3,9 bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ] -1, 1-dimethylethyl } -2,4,8, 10-tetraoxaspiro-5, 5-undecane, phosphite antioxidants, thioether antioxidants and the like. Among these, phenol antioxidants and phosphite antioxidants are preferable, and phenol antioxidants are more preferable.
The content of the antioxidant in the thermoplastic elastomer composition is preferably 0.1 to 5.0% by mass, more preferably 0.15 to 2.0% by mass.
The thermoplastic elastomer composition of the present invention preferably contains both a phenolic antioxidant and a hindered amine light stabilizer. The hindered amine-based light stabilizer is generally used for preventing discoloration due to light deterioration, but in the present invention, when a phenol-based antioxidant is used in combination, the effect of preventing discoloration due to heat is remarkably improved even under high temperature conditions for melting a polyphenylene ether resin. When a filler having a large specific surface area, such as talc, which is known as a damping filler, is further used, there is a possibility that the effect of preventing thermal discoloration is reduced by adsorption of a hindered amine-based light stabilizer, but when used in combination with ground calcium carbonate as in the present invention, it is found that such a phenomenon does not occur, and an unexpected effect is exhibited even by those skilled in the art.
The Hindered Amine Light stabilizer in the present invention is generally abbreviated as HALS (Hindered Amine Light Stabilizers), and is preferably a compound having a 2,2,6, 6-tetramethylpiperidine skeleton in the molecule. HALS is commercially available, and among them, a compound having a hindered phenol structure in the molecule has a large effect on resistance to thermal discoloration, and is more preferable when used in combination with a phenolic antioxidant. Examples of hindered amine light stabilizers having a hindered phenol structure in the molecule include Tinuvin 144 manufactured by BASF Japan, and sanol LS-2626 manufactured by Sanko Lifetech.
The mass ratio of the phenolic antioxidant to the hindered amine light stabilizer (phenolic antioxidant/hindered amine light stabilizer) is preferably 0.2 to 10, more preferably 0.5 to 5, and still more preferably 1 to 3.
The content of the hindered amine light stabilizer in the thermoplastic elastomer composition is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.5% by mass.
The thermoplastic elastomer composition of the present invention may further contain additives such as an anti-blocking agent, a heat stabilizer, an ultraviolet absorber, a lubricant, a crystal nucleating agent, a foaming agent, and a coloring agent.
The thermoplastic elastomer composition of the present invention may contain other thermoplastic resins or thermoplastic elastomers within a range not impairing the effects of the present invention.
The thermoplastic elastomer composition of the present invention is obtained by appropriately mixing hydrogenated thermoplastic styrene-based elastomer a, hydrogenated thermoplastic styrene-based elastomer B, polyphenylene ether resin, softening agent for rubber and ground calcium carbonate, and if necessary, further appropriately mixing additives such as antioxidant, light stabilizer and polypropylene, and then cooling and solidifying the mixture.
The "mixing" in the present invention is not particularly limited as long as it is a method of mixing various raw materials well, and the raw materials may be mixed by dissolving in an organic solvent capable of dissolving the various raw materials or by melt-kneading.
When melt kneading is performed, a general extruder can be used, and a twin-screw extruder is preferably used in order to improve the kneading state. The supply (feeding) into the extruder was as follows: the respective components may be mixed in advance using a mixing device such as a henschel mixer, and the resultant mixture may be supplied from one hopper; the respective components may be charged into two hoppers and supplied while being quantitatively fed by a screw or the like below the hoppers.
The product obtained by mixing the raw materials constituting the thermoplastic elastomer composition can be formed into a pellet, powder, sheet or the like according to the use. For example, the polymer is melt-kneaded by an extruder and extruded into strands (strands), and the strands are cut into pellets such as cylindrical pellets or rice-grain pellets by a cutter while being cooled in cold water. The obtained pellets are usually molded into a predetermined sheet-like molded article or a mold molded article by injection molding or extrusion molding. Further, the melt-kneaded product may be granulated using a rough mill or the like to be used as a molding material. An intermediate product obtained by pasting a paperboard or the like to a sheet-like thermoplastic elastomer composition can also be produced.
From the viewpoint of damping properties, the A hardness of the thermoplastic elastomer composition of the present invention is 50 or less, preferably 20 to 48, and more preferably 30 to 45.
From the viewpoint of flowability and moldability, the thermoplastic elastomer composition of the present invention preferably has a melt mass flow rate at 200 ℃ under a nominal load of 49N of 0.5 to 6.0g/10 minutes, more preferably 1.3 to 3.5g/10 minutes, and further preferably 1.5 to 2.5g/10 minutes.
The thermoplastic elastomer composition of the present invention is suitably heat-molded by a conventional method to obtain a molded article. The apparatus for producing the molded article may use any molding machine capable of melting a moldable material, and examples thereof include: kneaders, extrusion molding machines, injection molding machines, pressure molding machines, blow molding machines, mixing rolls, and the like.
The thermoplastic elastomer composition of the present invention is excellent in damping properties, and therefore the molded body thereof is used as a damping member. Further, from the viewpoint of excellent damping properties, compression set resistance and moldability, it is possible to stably suppress vibration and noise for a long period of time by using the same as a rotary bearing of a motor.
Therefore, the present invention also provides a rotor for a motor, which is provided with the damping member of the present invention.
A brushless rotor is preferable as the rotor for the motor, and a general rotor for the brushless motor is composed of 4 parts of a shaft of the rotor, an inner peripheral portion of a fixed shaft, a magnetic body such as an electromagnetic steel plate or a permanent magnet which becomes an outer peripheral portion of the rotor, and a coupling (fastening) member which connects the inner peripheral portion and the outer peripheral portion, and may have an outer layer composed of a magnet member on a surface of the outer peripheral portion as necessary, in addition to these parts. In the rotor, the damping member of the present invention may be used as a connecting member to be filled between the inner circumferential portion and the outer circumferential portion and integrally molded, or may be molded as a separate member from other members and fitted between the inner circumferential portion and the outer circumferential portion by assembly.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Various physical properties of the raw materials used in the examples and comparative examples were measured by the following methods.
< component A and component B (hydrogenated thermoplastic styrene-based elastomer) >)
[ styrene monomer content ]
The content of styrene and/or styrene derivative was determined by measuring proton NMR with a nuclear magnetic resonance apparatus (DPX-400, BRUKER, Germany) and quantifying the characteristic group of styrene. The content of other monomer units can also be determined by proton NMR measurement.
[ weight average molecular weight (Mw) ]
The molecular weight was measured by gel permeation chromatography in terms of polystyrene under the following measurement conditions, and the weight average molecular weight was determined.
Measuring apparatus
Seed and seed pumps: manufactured by JASCO (Japan Spectroscopy Co., Ltd.), PU-980;
seed and pillar temperature box: showa Denko K.K., AO-50;
seed and seed detectors: hitachi, RI (differential refractometer) detector L-3300;
seed and pillar species: "K-805L (8.0X 300 mm)" and "K-804L (8.0X 300 mm)" manufactured by Showa Denko K.K.K.K. of 1 root each were used in series;
seed and pillar temperature: 40 ℃;
and (4) seed and protection: K-G (4.6X 10 mm);
seed and seed eluents: chloroform;
seed and effluent flow rate: 1.0 ml/min;
seed concentration: about 1 mg/ml;
filtering a seed and seed sample solution: pore diameter of 0.45 made of polytetrafluoroethyleneμm, a disposable filter;
standard samples for seed dressing standard curves: polystyrene manufactured by Showa Denko K.K.
[ amount of 1, 2-vinyl linkage in the conjugated diene Compound Polymer Block ]
Dissolving the block copolymer before hydrogenation in CDCl3Determination of1H-NMR spectrum [ device: JNM-Lambda 500 (manufactured by Nippon electronics Co., Ltd.), measurement temperature: 50 deg.C]The 1, 2-vinyl bond amount or the total of the 1, 2-vinyl bond amount and the 3, 4-vinyl bond amount is calculated from the ratio of the total peak area of the structural units derived from the conjugated diene compound to the peak area corresponding to each of the 1, 2-vinyl bond unit and the 3, 4-vinyl bond unit in the isoprene unit, the 1, 2-vinyl bond unit in the butadiene unit, and the peak area corresponding to each of the bond units in the case of a mixture of isoprene and butadiene.
< component C (polyphenylene ether resin) >)
[ number average molecular weight (Mn) ]
The molecular weight was measured by the same method as the weight average molecular weight of the components A and B, and the number average molecular weight was calculated.
< ingredient D (softener for rubber) >)
[ dynamic viscosity ]
Measured at a temperature of 40 ℃ according to JIS Z8803.
< ingredient E (ground calcium carbonate, etc.) >)
[ volume-based median diameter ]
A0.1 g sample was dispersed in 10mL deionized water according to the laser diffraction/scattering method specified in JIS M8511, and dispersed with 70w of ultrasonic waves for 30 seconds, and the resulting slurry was measured for particle size distribution by using "Mastersizer 2000" manufactured by Malvern, with the value of 50% of the cumulative fraction on a volume basis as the volume-based median diameter.
[ specific surface area ]
The specific surface area was measured in accordance with JIS Z8830 "method for measuring specific surface area of powder (solid) based on gas adsorption". Specifically, a sample was weighed into a glass cuvette, and the absolute value of the amount of gas adsorbed was increased or decreased by an appropriate amount so as to fall within the measurable range of the apparatus, and the amount of nitrogen adsorbed was measured by "AUTOSORB-1" manufactured by Malvern corporation, and the specific surface area was calculated. This is a so-called BET specific surface area, and the more the fine particles, the larger the specific surface area.
< ingredient F (Polypropylene) >)
Melt Mass Flow Rate (MFR)
Measured according to ASTM D1238 at 230 ℃ under a nominal load of 21.2N.
[ flexural modulus of elasticity ]
Measured by a method according to JIS K7171.
Production example of ground calcium carbonate
The white crystalline limestone was coarsely pulverized by a hammer mill to obtain coarsely pulverized material passing through a vibrating screen having a mesh size of 10 mm. Then, the coarsely pulverized product was finely pulverized together with zirconia balls by a batch vibration ball mill, and heavy calcium carbonates a to c having particle sizes shown in table 1 were produced.
The calcium carbonates a to c were further classified by an air flow classifier (manufactured by Nisshin ENGINEERING, TC-15) and classified into 3 types of classified fine powder, classified medium-sized powder, and classified coarse powder shown in Table 1.
[ Table 1]
TABLE 1
Examples 1 to 12 and comparative examples 1 to 4
(1) Preparation of thermoplastic elastomer composition (pellets)
Materials shown in table 9 except the softener were dry-mixed, and then the softener was infiltrated thereinto to prepare a mixture. Then, the mixture was melt-kneaded under the following conditions using an extruder, extruded into strands, and cut into pellets having a diameter of about 3mm and a thickness of about 3mm with a cutter while cooling in cold water, to produce thermoplastic elastomer compositions.
[ melting and kneading conditions ]
An extruder: KZW32TW-60MG-NH (trade name, manufactured by TECHNOVEL, Inc.);
temperature of the cylinder: 180-220 ℃;
screw rotation speed: 300 r/min.
The details of the raw materials described in table 9 used in examples and comparative examples are as follows.
[ Table 2]
TABLE 2 [ component A ]
[ Table 3]
TABLE 3 [ ingredient B ]
[ Table 4]
TABLE 4 [ component C ]
[ Table 5]
TABLE 5 [ ingredient D ]
[ Table 6]
TABLE 6 [ ingredient E ]
[ Table 7]
TABLE 7 [ component F ]
[ Table 8]
TABLE 8 [ other ingredients ]
(2) Production of molded article of thermoplastic elastomer composition
The pellets were injection molded under the following conditions to prepare a plate having a width of 125mm, a length of 125mm and a thickness of 2 mm.
[ conditions for injection Molding ]
An injection molding machine: 100MSIII-10E (trade name, manufactured by Mitsubishi heavy industries, Ltd.);
injection molding temperature: 200 ℃;
injection molding pressure: 30 percent;
injection molding time: 10 seconds;
temperature of the die: at 40 ℃.
The thermoplastic elastomer compositions obtained in examples and comparative examples were evaluated as follows using the pellets or the plate. The results are shown in Table 9.
[ flexibility (A hardness) ]
The plate was used, and measurement was carried out in accordance with JIS K6253-3A type.
[ formability ]
(1) Melt Mass Flow Rate (MFR)
The determination was carried out using the particles according to ASTM D1238 at 200 ℃ under a nominal load of 49N.
(2) Surface texture of molded article
The surface properties of the plate were visually observed and evaluated according to the following evaluation criteria.
< evaluation Standard >
Very good: the plate has no sink mark/flow mark, and has good mirror surface;
o: the surface of the plate is slightly fuzzy, but has no sink mark/flow mark;
and (delta): any sink mark/flow mark is generated on the plate;
x: both sink marks/flow marks are produced on the plate.
[ tackiness ]
The surface of the plate was touched with a finger to determine whether or not there was any significant stickiness, and the evaluation was performed according to the following evaluation criteria.
< evaluation Standard >
Very good: the surface was smooth and completely felt no stickiness;
o: while not following the fingers, a little stickiness was felt;
x: the sheet was sticky to such an extent as to follow the fingers when touched with the fingers.
[ resistance to Heat discoloration ]
The plates were heated in a 120 ℃ gear oven for 500 hours. The color difference between the plate before heating and the plate after heating was visually compared, and the evaluation was performed according to the following evaluation criteria.
< evaluation Standard >
Very good: even if viewed side by side, no color difference is perceived by eye;
o: if the color difference is not recognized by separate comparison, but if the color difference is recognized, the color is changed to such an extent that the color difference is perceived;
x: discoloration upon heating occurred clearly.
[ damping Property (loss tangent (tan) ]δ))]
A plate cut to a width of 12mm was placed as a test piece on ARES G-2 manufactured by TA Instruments, and the viscoelasticity was measured at 30Hz in a torsion mode (torsion) at a length of 25mm at a temperature rise rate of 5 ℃/min between-60 ℃ and 200 ℃, and the loss tangent (tan) at 20 ℃ was calculatedδ)。
[ compression set resistance ]
The disc-shaped molded article was used as a test piece and measured by a compression set test prescribed in JIS K6262. Specifically, the plate was punched out into a disk shape, 7 pieces were stacked, and measurement pieces having a diameter and a thickness of 29.0. + -. 0.5mm (diameter) and 12.5. + -. 0.5mm (thickness) respectively were prepared by hot pressing, and the initial dimension was measured at a standard temperature (23.2. + -. 2 ℃ C.). The test piece was held between compression plates having spacers of 9.3 to 9.4mm in thickness, and the test piece was held at 70 ℃ for 24 hours under 25 vol% compression, and then the compression plates were removed at a standard temperature, left for 30 minutes, and the thickness of the center portion of the test piece was measured to calculate the value of compression set.
[ Table 9]
From the above results, it is clear that: the compositions of examples 1 to 12 were excellent in damping properties, compression set resistance and moldability, and were excellent in flexibility, and were suppressed in stickiness and discoloration due to heat. Among them, the comparison between examples 1,2 and 4 and examples 6 and 7 shows that: by adjusting the particle size of the ground calcium carbonate, the above characteristics are maintained at a higher level.
On the other hand, in comparative example 1 using precipitated calcium carbonate, the composition becomes hard and the damping property is lowered, and in comparative example 2 using talc, although the damping property and the compression set resistance are both good, stickiness and thermochromic are generated and the moldability is poor. In comparative example 3 in which no polyphenylene ether resin was used and comparative example 4 in which no filler was used, the flowability was good, but the compression set resistance was poor.
[ noise measurement ]
The fan motor is removed from an outdoor unit of a commercial household indoor air conditioner having a brushless rotor, and the rotor is removed by disassembling a casing of the motor. The vibration-proof material inserted around the shaft in the rotor as a connecting member was removed, the vibration-proof material molded into the same shape using the thermoplastic elastomer composition of example 1 or comparative example 1 was inserted, the rotor using the thermoplastic elastomer composition of example 1 or comparative example 1 was reconfigured, and the rotor was returned to the fan motor and mounted to the outdoor unit.
The outdoor unit was placed in a thermostatic chamber at 70 ℃ and continuously operated for 3000 hours with the fan motor rotating at a constant speed of 1000rpm, and the a characteristic sound pressure at the start of operation and after the continuous operation was measured by the method according to JIS Z8731 using a digital noise meter "MRS-1" manufactured by CUSTOM corporation. The results are shown in Table 10.
[ Table 10]
Watch 10
From the results of the noise measurement, it is found that: in example 1, the increase in noise was suppressed even after continuous operation, as compared with comparative example 1.
Industrial applicability
The thermoplastic elastomer composition for damping members of the present invention can be used for damping members suitable for noise/vibration countermeasures for household electric appliances, automobile parts, sporting goods, and the like.
Claims (6)
1. A thermoplastic elastomer composition for a damping member, which comprises a hydrogenated thermoplastic styrene elastomer A and a hydrogenated thermoplastic styrene elastomer B in a mass ratio of 5/95-55/45 (hydrogenated thermoplastic styrene elastomer A/hydrogenated thermoplastic styrene elastomer B), wherein the hydrogenated thermoplastic styrene elastomer A is a hydrogenated product of a block copolymer comprising a styrene polymer block (S1) and a conjugated diene compound polymer block (B1), the 1, 2-vinyl bond content of the conjugated diene compound polymer block (B1) is 50 mass% or more, the hydrogenated thermoplastic styrene elastomer B is a hydrogenated product of a block copolymer comprising a styrene polymer block (S2) and a conjugated diene compound polymer block (B2), and the conjugated diene compound polymer block (B2) is 1, the 2-vinyl bond content is less than 50 mass%, and the composition contains 10-200 parts by mass of polyphenylene ether resin, 50-1000 parts by mass of softening agent for rubber, and 10-300 parts by mass of ground calcium carbonate, relative to 100 parts by mass of the total of the hydrogenated thermoplastic styrene elastomer A and the hydrogenated thermoplastic styrene elastomer B, and the A hardness is less than 50.
2. The thermoplastic elastomer composition according to claim 1, wherein the volume-based median diameter of the ground calcium carbonate is 0.5 to 10μm, the specific surface area of 0.3-3.0 m2/g。
3. The thermoplastic elastomer composition according to claim 1 or 2, which further contains a phenolic antioxidant and a hindered amine light stabilizer.
4. The thermoplastic elastomer composition according to any one of claims 1 to 3, which further comprises polypropylene.
5. A damping member which is a molded article of the thermoplastic elastomer composition according to any one of claims 1 to 4.
6. A rotor for a motor, comprising the damping member according to claim 5.
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| PCT/JP2019/020135 WO2020235006A1 (en) | 2019-05-21 | 2019-05-21 | Thermoplastic elastomer composition for damping member |
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| JP4901106B2 (en) * | 2005-01-27 | 2012-03-21 | 東レ・ダウコーニング株式会社 | Thermoplastic elastomer composition for vehicle molding and glass plate with vehicle molding |
| JP5288760B2 (en) * | 2007-10-03 | 2013-09-11 | アロン化成株式会社 | Thermoplastic resin blend, composite material, and method for producing composite material |
| JP5506314B2 (en) * | 2009-09-30 | 2014-05-28 | 日東電工株式会社 | Damping composition, damping material and damping sheet |
| JP5507182B2 (en) * | 2009-09-30 | 2014-05-28 | 株式会社クラレ | Hot melt sealant |
| JP2012219150A (en) * | 2011-04-06 | 2012-11-12 | Sumitomo Rubber Ind Ltd | Highly damping composition |
| JP6060453B2 (en) * | 2012-11-09 | 2017-01-18 | 北川工業株式会社 | Damping material |
| JP2014118516A (en) * | 2012-12-18 | 2014-06-30 | Sumitomo Rubber Ind Ltd | High-damping composition and vibration control damper |
| WO2015087954A1 (en) * | 2013-12-11 | 2015-06-18 | 株式会社クラレ | Sealant |
| JP2018197329A (en) * | 2017-05-25 | 2018-12-13 | 株式会社カネカ | Room temperature-curable composition |
| JP2019001950A (en) * | 2017-06-19 | 2019-01-10 | 東レ株式会社 | Polyamide resin for vibration damping member, polyamide resin composition for vibration damping member, and molded product of them |
| JP7224131B2 (en) * | 2017-10-11 | 2023-02-17 | 株式会社カネカ | Curable composition |
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- 2019-05-21 WO PCT/JP2019/020135 patent/WO2020235006A1/en active Application Filing
- 2019-05-21 CN CN201980096594.1A patent/CN113825820A/en active Pending
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| JPS62256845A (en) * | 1986-04-30 | 1987-11-09 | Asahi Chem Ind Co Ltd | High filler composition |
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| JP2013159635A (en) * | 2012-02-01 | 2013-08-19 | Bridgestone Corp | Thermoplastic elastomer composition |
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