WO2023054341A1 - 防振ゴム組成物および防振ゴム部材 - Google Patents
防振ゴム組成物および防振ゴム部材 Download PDFInfo
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- WO2023054341A1 WO2023054341A1 PCT/JP2022/035894 JP2022035894W WO2023054341A1 WO 2023054341 A1 WO2023054341 A1 WO 2023054341A1 JP 2022035894 W JP2022035894 W JP 2022035894W WO 2023054341 A1 WO2023054341 A1 WO 2023054341A1
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- Prior art keywords
- vibration
- rubber composition
- mass
- component
- parts
- Prior art date
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- 239000005060 rubber Substances 0.000 title claims abstract description 100
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- 238000013016 damping Methods 0.000 title claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000006229 carbon black Substances 0.000 claims abstract description 39
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- 229920003244 diene elastomer Polymers 0.000 claims description 23
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 6
- UTTHLMXOSUFZCQ-UHFFFAOYSA-N benzene-1,3-dicarbohydrazide Chemical compound NNC(=O)C1=CC=CC(C(=O)NN)=C1 UTTHLMXOSUFZCQ-UHFFFAOYSA-N 0.000 claims description 6
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims description 6
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 5
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- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 5
- 229960002447 thiram Drugs 0.000 description 5
- 238000010276 construction Methods 0.000 description 4
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 4
- 238000009661 fatigue test Methods 0.000 description 4
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- 229920001084 poly(chloroprene) Polymers 0.000 description 4
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- 239000000725 suspension Substances 0.000 description 4
- -1 3-triethoxysilylpropyl Chemical group 0.000 description 3
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 3
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
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- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
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- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
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- GQWNEBHACPGBIG-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-[2-(1,3-benzothiazol-2-ylsulfanylamino)ethoxy]ethanamine Chemical compound C1=CC=C2SC(SNCCOCCNSC=3SC4=CC=CC=C4N=3)=NC2=C1 GQWNEBHACPGBIG-UHFFFAOYSA-N 0.000 description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
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- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
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- 238000005406 washing Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- MACMAADVRVVHBD-VMPITWQZSA-N (e)-1-(2,4-dihydroxyphenyl)-3-(2-hydroxyphenyl)prop-2-en-1-one Chemical compound OC1=CC(O)=CC=C1C(=O)\C=C\C1=CC=CC=C1O MACMAADVRVVHBD-VMPITWQZSA-N 0.000 description 1
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
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- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
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- ALHNLFMSAXZKRC-UHFFFAOYSA-N benzene-1,4-dicarbohydrazide Chemical compound NNC(=O)C1=CC=C(C(=O)NN)C=C1 ALHNLFMSAXZKRC-UHFFFAOYSA-N 0.000 description 1
- VTEKOFXDMRILGB-UHFFFAOYSA-N bis(2-ethylhexyl)carbamothioylsulfanyl n,n-bis(2-ethylhexyl)carbamodithioate Chemical compound CCCCC(CC)CN(CC(CC)CCCC)C(=S)SSC(=S)N(CC(CC)CCCC)CC(CC)CCCC VTEKOFXDMRILGB-UHFFFAOYSA-N 0.000 description 1
- HCOMFAYPHBFMKU-UHFFFAOYSA-N butanedihydrazide Chemical compound NNC(=O)CCC(=O)NN HCOMFAYPHBFMKU-UHFFFAOYSA-N 0.000 description 1
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- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
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- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
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- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
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- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- ZWLFGLCGZUVIEA-UHFFFAOYSA-N nonanedihydrazide Chemical compound NNC(=O)CCCCCCCC(=O)NN ZWLFGLCGZUVIEA-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- VLDHWMAJBNWALQ-UHFFFAOYSA-M sodium;1,3-benzothiazol-3-ide-2-thione Chemical compound [Na+].C1=CC=C2SC([S-])=NC2=C1 VLDHWMAJBNWALQ-UHFFFAOYSA-M 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
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- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- ASAOXGWSIOQTDI-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSSSCC[Si](OCC)(OCC)OCC ASAOXGWSIOQTDI-UHFFFAOYSA-N 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- KLFNHRIZTXWZHT-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltrisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSCCC[Si](OCC)(OCC)OCC KLFNHRIZTXWZHT-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- JSXKIRYGYMKWSK-UHFFFAOYSA-N trimethoxy-[2-(2-trimethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CO[Si](OC)(OC)CCSSSSCC[Si](OC)(OC)OC JSXKIRYGYMKWSK-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- NQRACKNXKKOCJY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSCCC[Si](OC)(OC)OC NQRACKNXKKOCJY-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- PGNWIWKMXVDXHP-UHFFFAOYSA-L zinc;1,3-benzothiazole-2-thiolate Chemical compound [Zn+2].C1=CC=C2SC([S-])=NC2=C1.C1=CC=C2SC([S-])=NC2=C1 PGNWIWKMXVDXHP-UHFFFAOYSA-L 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L21/00—Compositions of unspecified rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
- F16F1/00—Springs
- F16F1/36—Springs made of rubber or other material having high internal friction, e.g. thermoplastic elastomers
- F16F1/3605—Springs made of rubber or other material having high internal friction, e.g. thermoplastic elastomers characterised by their material
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
- C08K5/22—Compounds containing nitrogen bound to another nitrogen atom
- C08K5/24—Derivatives of hydrazine
- C08K5/25—Carboxylic acid hydrazides
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
- F16F2224/00—Materials; Material properties
- F16F2224/02—Materials; Material properties solids
- F16F2224/025—Elastomers
Definitions
- the present invention relates to an anti-vibration rubber composition and an anti-vibration rubber member used for anti-vibration applications in vehicles such as railway vehicles.
- the functions required for anti-vibration rubber for railroad vehicles include, for example, high durability, suppression of spring deterioration (low spring deterioration property) that occurs during running vibration, and insulation.
- a rubber composition which is a material for anti-vibration rubber, contains a polymer such as a diene rubber and a filler such as silica or carbon black.
- silica as a filler are excellent in durability and insulation, but have the property of not being able to satisfy the low spring deterioration property.
- those using carbon black as a filler can satisfy the low spring deterioration property, but have the property of being disadvantageous in durability and insulation.
- the various anti-vibration rubber compositions disclosed in the above-mentioned patent documents do not satisfy all the functions required for anti-vibration rubber for railway vehicles (high durability, low spring deterioration, insulation). , in fact, it is not possible to solve the above problems. That is, even in the anti-vibration rubber composition using a blend of silica and carbon black, high durability, low spring deterioration, and insulation as described above are contradictory characteristics, so these functions are all required. It is currently difficult even for those skilled in the art to fully satisfy. Therefore, there is still room for improvement in this respect.
- the present invention has been made in view of such circumstances, and provides an anti-vibration rubber composition and an anti-vibration rubber member that can satisfy all of high durability, low spring deterioration, and insulation at a high level. offer.
- the inventors of the present invention have conducted research focusing on the factors that make it impossible to solve the above problems even when silica and carbon black are used as fillers in combination with the diene rubber, which is the polymer of the anti-vibration rubber composition. piled up.
- silica has the property of being agglomerated easily, and the agglomerates are easily loosened when the anti-vibration rubber is vibrated.
- the chemical bond at the interface with the rubber is poor, and it easily becomes the starting point of cracks, which is a factor that reduces the durability of the anti-vibration rubber.
- this is a factor that lowers the insulating properties of rubber.
- the gist of the present invention is the following [1] to [6].
- a vibration-damping rubber composition containing a polymer component consisting of component (A) below and components (B) to (D) below, wherein (B) is added to 100 parts by mass of component (A)
- the proportion of component is 0.1 to 5 parts by mass
- the proportion of component (C) is 10 to 40 parts by mass
- the proportion of component (D) is 10 to 30 parts by mass
- component (C) has a BET specific surface area of 18 to 40 m 2 /g.
- A a diene rubber
- B a dihydrazide compound
- C Carbon black.
- Silica Silica.
- a silane coupling agent (E) is at least one selected from the group consisting of mercapto-based silane coupling agents and sulfide-based silane coupling agents.
- the dihydrazide compound (B) is at least one selected from adipic acid dihydrazide and isophthalic acid dihydrazide.
- a vibration-isolating rubber member comprising a vulcanized body of the vibration-isolating rubber composition according to any one of [1] to [4].
- the anti-vibration rubber member according to [5] which is a rubber anti-vibration member for railway vehicles.
- the anti-vibration rubber composition of the present invention contains a diene rubber polymer, a dihydrazide compound, carbon black having a BET specific surface area within a specific range, and silica. be. Therefore, it is possible to satisfy high durability, low spring deterioration, and insulation at a high level. For this reason, it can exhibit excellent performance particularly as a material for anti-vibration rubber for railway vehicles.
- a vibration-insulating rubber composition (hereinafter referred to as "the present vibration-insulating rubber composition") which is one embodiment of the present invention comprises, as described above, a polymer component consisting of the following (A) component, and the following ( A vibration-damping rubber composition containing components B) to (D), wherein the ratio of component (B) is 0.1 to 5 parts by mass per 100 parts by mass of component (A), and component (C) is 10 to 40 parts by mass, component (D) is 10 to 30 parts by mass, and component (C) has a BET specific surface area of 18 to 40 m 2 /g.
- A a diene rubber
- B a dihydrazide compound
- C Carbon black.
- Silica Silica.
- the present anti-vibration rubber composition uses a polymer composed of the diene rubber (A), and does not use a polymer other than the diene rubber (A).
- a diene rubber containing natural rubber (NR) as a main component is preferably used as the diene rubber (A).
- NR natural rubber
- main component means that 50% by mass or more of the diene rubber (A) is natural rubber, and is meant to include those in which the diene rubber (A) consists only of natural rubber. . In this way, by using natural rubber as a main component, the strength and dynamic magnification can be reduced.
- diene rubbers other than natural rubber examples include butadiene rubber (BR), styrene-butadiene rubber (SBR), chloroprene rubber (CR), isoprene rubber (IR), acrylonitrile-butadiene rubber (NBR), ethylene- Propylene-diene rubber (EPDM), butyl rubber (IIR), chloroprene rubber (CR), and the like. These are used alone or in combination of two or more. It is desirable to use these diene-based rubbers together with natural rubber.
- the present anti-vibration rubber composition contains the dihydrazide compound (B) in a specific proportion.
- the dihydrazide compound (B) include compounds represented by the following general formula (1).
- dihydrazide compound (B) examples include adipic acid dihydrazide, isophthalic acid dihydrazide, phthalic acid dihydrazide, terephthalic acid dihydrazide, succinic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, oxalic acid dihydrazide, and dodecanoic acid dihydrazide. be done. These are used alone or in combination of two or more. Among them, adipic acid dihydrazide and isophthalic acid dihydrazide are preferable from the viewpoint of lowering the dynamic magnification.
- the content of the dihydrazide compound (B) is, as described above, from the viewpoint of obtaining the effects of the present invention (high durability, low spring deterioration, and insulation at high levels). It is 0.1 to 5 parts by mass, preferably 0.5 to 4 parts by mass, more preferably 0.75 to 3 parts by mass, based on 100 parts by mass of the diene rubber (A).
- the present anti-vibration rubber composition contains carbon black (C) in a specific proportion.
- the carbon black (C) one having a BET specific surface area of 18 to 40 m 2 /g is used.
- those with a BET specific surface area of 18 to 35 m 2 /g are used, and those with a BET specific surface area of 18 to 30 m 2 /g are more preferably used. That is, if the BET specific surface area of the carbon black (C) is too large, the desired insulating effect cannot be obtained, and if the BET specific surface area is too small, durability will be reduced.
- the BET specific surface area of the carbon black (C) is obtained by, for example, degassing the sample at 200 ° C. for 15 minutes, using a mixed gas (N 2 : 70%, He: 30%) as an adsorption gas, BET It can be measured with a specific surface area measuring device (4232-II, manufactured by Microdata).
- Various grades of carbon black such as FEF grade, MAF grade, GPF grade, SRF grade, FT grade, and MT grade are used as the grade of the carbon black (C) from the viewpoint of reinforcement, durability, and insulation. . These are used alone or in combination of two or more. Among them, FEF grade carbon black is preferably used from the above viewpoint.
- the content of the carbon black (C) is, as described above, from the viewpoint of obtaining the effects of the present invention (all of high durability, low spring deterioration, and insulation at a high level). It is 10 to 40 parts by mass, preferably 20 to 40 parts by mass, more preferably 30 to 40 parts by mass, based on 100 parts by mass of the diene rubber (A).
- the present anti-vibration rubber composition contains silica (D) in a specific proportion.
- silica (D) for example, wet silica, dry silica, colloidal silica, and the like are used. And these are used individually or in combination of 2 or more types.
- the silica (D) preferably has a BET specific surface area of 20 to 380 m 2 /g, more preferably 30 to 330 m 2 . /g of silica.
- the BET specific surface area of the silica (D) is obtained by, for example, degassing the sample at 200 ° C. for 15 minutes, using a mixed gas (N 2 : 70%, He: 30%) as an adsorption gas, BET ratio It can be measured with a surface area measuring device (4232-II, manufactured by Microdata).
- the content of the silica (D) is, as described above, the diene It is 10 to 30 parts by mass, preferably 15 to 30 parts by mass, more preferably 20 to 30 parts by mass, based on 100 parts by mass of the rubber (A).
- the present anti-vibration rubber composition may contain a silane coupling agent (E), if necessary.
- a silane coupling agent (E) By including the silane coupling agent (E) in this way, the silica (D) and the diene rubber (A) are bonded via the silane coupling agent (E), and the durability of the anti-vibration rubber is enhanced. be able to improve.
- the silane coupling agent (E) include mercapto-based silane coupling agents, sulfide-based silane coupling agents, amine-based silane coupling agents, epoxy-based silane coupling agents, and vinyl-based silane coupling agents. They are used singly or in combination of two or more.
- the silane coupling agent (E) is a mercapto-based silane coupling agent or a sulfide-based silane coupling agent
- the vulcanization density is increased, and it is particularly effective for low dynamic magnification and durability. preferable.
- Examples of the mercapto-based silane coupling agent include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and the like. These are used alone or in combination of two or more.
- sulfide-based silane coupling agent examples include bis-(3-(triethoxysilyl)-propyl)-disulfide, bis(3-triethoxysilylpropyl) trisulfide, bis-(3-(triethoxysilyl) -propyl)-tetrasulfide, bis(3-trimethoxysilylpropyl) disulfide, bis(2-triethoxysilylethyl) tetrasulfide, bis(2-trimethoxysilylethyl) tetrasulfide, bis(3-triethoxysilylpropyl) ) disulfide, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyl tetrasulfide, 2-trie
- Examples of the amine-based silane coupling agent include 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2- aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-(N-phenyl)aminopropyltrimethoxysilane and the like. These are used alone or in combination of two or more.
- epoxy-based silane coupling agent examples include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane and the like. These are used alone or in combination of two or more.
- vinyl-based silane coupling agent examples include vinyltriethoxysilane, vinyltrimethoxysilane, vinyl-tris( ⁇ -methoxyethoxy)silane, vinyldimethylchlorosilane, vinyltrichlorosilane, vinyltriisopropoxysilane, and vinyl-tris. (2-methoxyethoxy)silane and the like. These are used alone or in combination of two or more.
- the content of these silane coupling agents (E) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the diene rubber (A) because of its excellent low dynamic magnification and durability. It is preferably in the range of 0.3 to 8 parts by mass.
- the component (E) in addition to the components (A) to (D), which are essential components, the component (E), a vulcanizing agent, a vulcanization accelerator, a vulcanizing aid, and an anti-aging agent , process oil, etc., may be contained as appropriate.
- vulcanizing agent examples include sulfur (powder sulfur, precipitated sulfur, insoluble sulfur), sulfur-containing compounds such as alkylphenol disulfide, and the like. These are used alone or in combination of two or more.
- the content of the vulcanizing agent is preferably in the range of 0.1 to 10 parts by mass, particularly preferably in the range of 0.3 to 5 parts by mass, based on 100 parts by mass of the diene rubber (A). . That is, if the content of the vulcanizing agent is too small, vulcanization reactivity tends to be poor. This is because there is a tendency to decrease.
- vulcanization accelerator examples include thiuram-based, sulfenamide-based, guanidine-based, thiazole-based, aldehyde-ammonia-based, aldehyde-amine-based, and thiourea-based vulcanization accelerators. These are used alone or in combination of two or more. Among these, a combination of a thiuram-based vulcanization accelerator and at least one vulcanization accelerator selected from sulfenamide-based, guanidine-based, and thiazole-based vulcanization accelerators is used because it provides excellent compression set. is preferred.
- the content of the vulcanization accelerator is preferably in the range of 0.1 to 10 parts by mass, particularly preferably in the range of 0.3 to 5 parts by mass, based on 100 parts by mass of the diene rubber (A). be.
- thiuram-based vulcanization accelerator examples include tetramethylthiuram disulfide (TMTD), tetraethylthiuram disulfide (TETD), tetrabutylthiuram disulfide (TBTD), tetrakis(2-ethylhexyl)thiuram disulfide (TOT), and tetrabenzylthiuram. disulfide (TBzTD) and the like. These are used alone or in combination of two or more.
- TMTD tetramethylthiuram disulfide
- TETD tetraethylthiuram disulfide
- TBTD tetrabutylthiuram disulfide
- TOT tetrakis(2-ethylhexyl)thiuram disulfide
- TBzTD tetrabenzylthiuram. disulfide
- sulfenamide vulcanization accelerator examples include N-oxydiethylene-2-benzothiazolylsulfenamide (NOBS), N-cyclohexyl-2-benzothiazolylsulfenamide (CBS), Nt -Butyl-2-benzothiazolesulfenamide (BBS), N,N'-dicyclohexyl-2-benzothiazolesulfenamide and the like. These are used alone or in combination of two or more.
- guanidine-based vulcanization accelerator examples include N,N'-diphenylthiourea, trimethylthiourea, N,N'-diethylthiourea, and N,N'-dibutylthiourea. These are used alone or in combination of two or more.
- Examples of the thiazole vulcanization accelerator include dibenzothiazyl disulfide (MBTS), 2-mercaptobenzothiazole (MBT), 2-mercaptobenzothiazole sodium salt (NaMBT), and 2-mercaptobenzothiazole zinc salt (ZnMBT). etc. These are used alone or in combination of two or more. Among these, dibenzothiazyl disulfide (MBTS) and 2-mercaptobenzothiazole (MBT) are preferably used because of their excellent vulcanization reactivity.
- vulcanization aid examples include zinc oxide (ZnO), stearic acid, magnesium oxide, and the like. These are used alone or in combination of two or more.
- the content of the vulcanization aid is preferably in the range of 0.1 to 10 parts by mass, particularly preferably in the range of 0.3 to 7 parts by mass, based on 100 parts by mass of the diene rubber (A). be.
- anti-aging agent examples include carbamate-based anti-aging agents, phenylenediamine-based anti-aging agents, phenol-based anti-aging agents, diphenylamine-based anti-aging agents, quinoline-based anti-aging agents, imidazole-based anti-aging agents, and waxes. mentioned. These are used alone or in combination of two or more.
- the content of the antioxidant is preferably in the range of 0.5 to 15 parts by mass, particularly preferably in the range of 1 to 10 parts by mass, based on 100 parts by mass of the diene rubber (A).
- process oil examples include naphthenic oil, paraffinic oil, aromatic oil, and the like. These are used alone or in combination of two or more.
- the content of the process oil is preferably in the range of 1 to 35 parts by mass, particularly preferably in the range of 3 to 30 parts by mass, based on 100 parts by mass of the diene rubber (A).
- the present anti-vibration rubber composition uses components (A) to (D), which are essential components thereof, in specific proportions, and furthermore, if necessary, component (E) and other materials listed above.
- a kneader such as a kneader, Banbury mixer, open roll, or twin-screw stirrer.
- the kneading involves kneading materials other than the vulcanizing agent and the vulcanization accelerator at 100 to 170°C for 3 to 10 minutes (preferably at 120 to 150°C for 3 to 5 minutes) using a Banbury mixer. Then, a vulcanizing agent and a vulcanization accelerator are blended and kneaded at 30 to 80°C for 3 to 10 minutes (preferably at 30 to 60°C for 3 to 5 minutes) using an open roll. is desirable.
- the present anti-vibration rubber composition obtained in this manner obtains the effects of the present invention (high durability, low spring loss, insulation properties) by satisfying the following condition ( ⁇ ). is satisfied at a high level), it is preferable.
- ( ⁇ ) ⁇ G′ represented by the following formula (I) is 5.0 or less.
- ⁇ G' is preferably 4.5 or less from the viewpoint of obtaining the effects of the present invention.
- ⁇ G′ represented by the above formula (I) is an index for evaluating the cohesiveness of the filler, as described in JP-A-2006-47070, and ⁇ G′ is A smaller value indicates a higher degree of dispersion of the filler.
- G'1 and G'2 can be measured by, for example, a rubber processing tester, a curastometer, a dynamic viscoelasticity measurement, or the like. More specifically, it is measured by RPA2000 manufactured by Alpha Technology.
- this anti-vibration rubber composition is vulcanized at a high temperature (150-170°C) for 5-30 minutes to form a rubber anti-vibration member (vulcanized body).
- the hardness (JIS-A hardness) of the surface of the anti-vibration rubber member (vulcanized body) is usually 60-85, preferably 65-80.
- the hardness can be measured with an Asker rubber hardness tester (P1-A type) manufactured by Kobunshi Keiki Co., Ltd.
- the anti-vibration rubber member (vulcanized body) can achieve 80,000 times or more expansion and contraction at breakage in the expansion and contraction fatigue test conducted according to JIS K 6260.
- the number of expansions and contractions at breakage is 100,000 times or more, and more preferably, the number of expansions and contractions at breakage is 120,000 times or more.
- the anti-vibration rubber member (vulcanized body) has a volume resistivity of 1 measured under the following conditions according to JIS K 6271-1:2015 (vulcanized rubber and thermoplastic rubber-determination of electrical resistivity). ⁇ 10 9 ⁇ cm or more can be achieved. Preferably, a volume resistivity of 1 ⁇ 10 11 ⁇ cm or more is achieved, and more preferably a volume resistivity of 1 ⁇ 10 13 ⁇ cm or more is achieved.
- Measurement method Double ring electrode method Guard electrode: outer diameter 80 mm, inner diameter 70 mm Main electrode: 50mm Sample outside dimensions: 100 mm ⁇ 100 mm Sample thickness: 2mm Applied voltage: 1V Detection current range: 200pA to 20mA
- the vibration-isolating rubber member made of the vulcanized body of the present vibration-isolating rubber composition can satisfy all of high durability, low spring deterioration, and insulation at a high level. It can exhibit excellent performance as a material for anti-vibration rubber for railway vehicles.
- it can also be used as a structural member for engine mounts, stabilizer bushes, suspension bushes, motor mounts, subframe mounts, etc. used in automobiles and the like.
- electric vehicles electric vehicles (EV), fuel cell vehicles (FCV), plug-in hybrid vehicles (PHV), hybrid vehicles (HV), etc.) that are powered by electric motors.
- vibration control dampers for computer hard disk drives, vibration control dampers for general home appliances such as washing machines, construction vibration control walls in the construction and housing fields, and vibration control (vibration control) dampers. It can also be used for seismic damping (vibration damping) devices and seismic isolation devices.
- Isophthalic acid dihydrazide (IDH) manufactured by Otsuka Chemical Co., Ltd.
- Carbon black (iii) SEAST SRA (BET specific surface area: 18 m 2 /g) manufactured by Tokai Carbon Co., Ltd.
- Silane coupling agent (i) Sulfide-based silane coupling agent (EVONIK DEGUSSA, Si-69)
- Anti-aging agent Antigen 6C manufactured by Sumitomo Chemical Co., Ltd.
- a vibration-insulating rubber composition was prepared by blending and kneading the respective materials in the proportions shown in Tables 1 and 2 below.
- materials other than the vulcanizing agent and the vulcanization accelerator are kneaded using a Banbury mixer at 140° C. for 5 minutes, then the vulcanizing agent and the vulcanization accelerator are blended, and the open roll is mixed. was kneaded for 5 minutes at 60°C.
- Each anti-vibration rubber composition is press-molded (vulcanized) under the conditions of 150° C. for 30 minutes, and the hardness (JIS-A hardness) of the rubber surface is measured using an Asker rubber hardness tester (P1-A type) (polymer meter company). Then, the reinforcing properties were evaluated according to the following criteria. O (very good): Hardness is 60 or more. ⁇ (poor): Hardness less than 60.
- volume resistivity VR ( ⁇ cm) was measured. Specifically, the volume resistivity VR was obtained under the following conditions. Measurement method: Double ring electrode method Guard electrode: outer diameter 80 mm, inner diameter 70 mm Main electrode: 50mm Sample outside dimensions: 100 mm ⁇ 100 mm Sample thickness: 2mm Applied voltage: 1V Detection current range: 200pA to 20mA Insulation properties were evaluated according to the following criteria. ⁇ (very good): Volume resistivity VR is 1 ⁇ 10 9 ⁇ cm or more. ⁇ (poor): Volume resistivity VR is less than 1 ⁇ 10 9 ⁇ cm.
- the vulcanizates of the anti-vibration rubber compositions of the examples are excellent in durability (high durability), spring deterioration (low spring deterioration), and insulation properties.
- the result shows the characteristics required for
- the anti-vibration rubber composition of Comparative Example 1 contained too little dihydrazide compound and the carbon black was insufficiently dispersed, resulting in the formation of conductive paths and poor insulation.
- the dispersibility of carbon black and silica was insufficient, resulting in the generation of agglomerates, and the agglomerates collapsed during endurance vibration, causing a load reduction, resulting in poor spring resistance.
- the anti-vibration rubber composition of Comparative Example 2 had an excessively high content of the dihydrazide compound, and the viscosity of the rubber was remarkably increased, resulting in poor durability.
- the anti-vibration rubber composition of Comparative Example 3 contained too little carbon black, resulting in poor reinforcing properties (hardness).
- the anti-vibration rubber composition of Comparative Example 4 contained too much carbon black, resulting in poor insulation due to the formation of conductive paths.
- the BET specific surface area of the carbon black shows a value exceeding the stipulation of the present invention, and as the surface area increases, the conductivity increases, resulting in poor insulation. rice field.
- the BET specific surface area of the carbon black shows a value less than the value specified in the present invention, and the interface between the rubber and the carbon black tends to become a crack initiation point during endurance vibration. Therefore, the durability was poor.
- the anti-vibration rubber composition of Comparative Example 7 had too little silica content, resulting in inferior reinforcing properties (hardness).
- the anti-vibration rubber composition of Comparative Example 8 had an excessively high content of silica, and the agglomerates of silica collapsed during endurance vibration to cause load reduction, resulting in poor spring resistance.
- the BET specific surface area of the carbon black shows a value exceeding the stipulations of the present invention. rice field.
- a vibration-isolating rubber member made of a vulcanized body of the present vibration-isolating rubber composition can satisfy all of high durability, low spring deterioration, and insulation at a high level, so it is particularly suitable for railway vehicles. It can exhibit excellent performance as a material for vibration rubber. In addition to the above applications, it can also be used as a structural member for engine mounts, stabilizer bushes, suspension bushes, motor mounts, subframe mounts, etc. used in automobiles and the like. In particular, due to its high insulating properties, it is used in electric vehicles (electric vehicles (EV), fuel cell vehicles (FCV), plug-in hybrid vehicles (PHV), hybrid vehicles (HV), etc.) that are powered by electric motors.
- electric vehicles electric vehicles (EV), fuel cell vehicles (FCV), plug-in hybrid vehicles (PHV), hybrid vehicles (HV), etc.) that are powered by electric motors.
- vibration control dampers for computer hard disk drives, vibration control dampers for general home appliances such as washing machines, construction vibration control walls in the construction and housing fields, and vibration control (vibration control) dampers. It can also be used for seismic damping (vibration damping) devices and seismic isolation devices.
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Abstract
Description
通常、防振ゴムの材料となるゴム組成物には、ジエン系ゴム等のポリマーの他、シリカ、カーボンブラック等の充填材が配合されている。ここで、充填材としてシリカを使用したものは、耐久性と絶縁性に優れるが、低ばね低下性を満たし得ないといった性質がある。一方、充填材としてカーボンブラックを使用したものは、低ばね低下性を満たし得るが、耐久性と絶縁性が不利となる性質がある。
このように、防振ゴム組成物の充填材配合において、シリカの単独配合、あるいはカーボンブラックの単独配合では、高耐久性、低ばね低下性、絶縁性を全て満足させることは困難である。
また、シリカとカーボンブラックとをブレンドして防振ゴム組成物の充填材に使用するといったことも、従来において適宜行われている(例えば、特許文献1~6参照)。
すなわち、シリカとカーボンブラックとをブレンドして用いた防振ゴム組成物においても、前記のような、高耐久性、低ばね低下性、絶縁性は、背反特性となるため、これらの機能を全て充分に満足させることは、たとえ当業者であっても困難なのが現状である。そのため、この点において、未だ改善の余地がある。
そこで、本発明者らは、前記カーボンブラックとして、比表面積の小さな(特定のBET比表面積を示す)カーボンブラックを用い、さらに、前記カーボンブラックおよびシリカの分散性を向上させるため、ジヒドラジド化合物を加えることを想起した。そして、各種実験の結果、意外にも、前記の各種材料の割合を本発明に規定された特定の範囲内としたところ、鉄道車両用防振ゴムに要求される機能(高耐久性、低ばね低下性、絶縁性)を全て満足させることが実現可能となることを突き止めた。
[1] 下記の(A)成分からなるポリマー成分と、下記の(B)~(D)成分を含有する防振ゴム組成物であって、(A)成分100質量部に対し、(B)成分の割合が0.1~5質量部であり、(C)成分の割合が10~40質量部であり、(D)成分の割合が10~30質量部であり、かつ、(C)成分が、BET比表面積18~40m2/gのものである、防振ゴム組成物。
(A)ジエン系ゴム。
(B)ジヒドラジド化合物。
(C)カーボンブラック。
(D)シリカ。
[2] さらに、シランカップリング剤(E)を含有する、[1]に記載の防振ゴム組成物。
[3] 前記シランカップリング剤(E)が、メルカプト系シランカップリング剤およびスルフィド系シランカップリング剤からなる群から選ばれた少なくとも一つである、[2]に記載の防振ゴム組成物。
[4] 前記ジヒドラジド化合物(B)が、アジピン酸ジヒドラジドおよびイソフタル酸ジヒドラジドから選ばれた少なくとも一つである、[1]~[3]のいずれかに記載の防振ゴム組成物。
[5] [1]~[4]のいずれかに記載の防振ゴム組成物の加硫体からなる防振ゴム部材。
[6] 鉄道車両用防振ゴム部材である、[5]に記載の防振ゴム部材。
(A)ジエン系ゴム。
(B)ジヒドラジド化合物。
(C)カーボンブラック。
(D)シリカ。
前記のように、本防振ゴム組成物は、ジエン系ゴム(A)からなるポリマーを用いており、ジエン系ゴム(A)以外のポリマーは使用しない。前記ジエン系ゴム(A)としては、好ましくは、天然ゴム(NR)を主成分とするジエン系ゴムが用いられる。ここで、「主成分」とは、前記ジエン系ゴム(A)の50質量%以上が天然ゴムであるものを示し、前記ジエン系ゴム(A)が天然ゴムのみからなるものも含める趣旨である。このように、天然ゴムを主成分とすることにより、強度や低動倍率化の点で優れるようになる。
また、天然ゴム以外のジエン系ゴムとしては、例えば、ブタジエンゴム(BR)、スチレン-ブタジエンゴム(SBR)、クロロプレンゴム(CR)、イソプレンゴム(IR)、アクリロニトリル-ブタジエンゴム(NBR)、エチレン-プロピレン-ジエンゴム(EPDM)、ブチルゴム(IIR)、クロロプレンゴム(CR)等が挙げられる。これらは単独でもしくは二種以上併せて用いられる。なお、これらのジエン系ゴムは、天然ゴムと併用することが望ましい。
本防振ゴム組成物には、先に述べたように、特定の割合でジヒドラジド化合物(B)が含まれる。ジヒドラジド化合物(B)としては、例えば、下記の一般式(1)に示す化合物が挙げられる。
また、本防振ゴム組成物には、先に述べたように、特定の割合でカーボンブラック(C)が含まれる。前記カーボンブラック(C)としては、BET比表面積18~40m2/gのものが用いられる。好ましくは、BET比表面積18~35m2/gのものが用いられ、より好ましくは、BET比表面積18~30m2/gのものが用いられる。
すなわち、前記カーボンブラック(C)のBET比表面積が大きすぎると、所望の絶縁効果が得られず、BET比表面積が小さすぎると、耐久性が低下するといった問題があるからである。
なお、前記カーボンブラック(C)のBET比表面積は、例えば、試料を200℃で15分間脱気した後、吸着気体として混合ガス(N2:70%、He:30%)を用いて、BET比表面積測定装置(マイクロデータ社製、4232-II)により測定することができる。
また、本防振ゴム組成物には、先に述べたように、特定の割合でシリカ(D)が含まれる。前記シリカ(D)としては、例えば、湿式シリカ、乾式シリカ、コロイダルシリカ等が用いられる。そして、これらは単独でもしくは二種以上併せて用いられる。
なお、前記シリカ(D)のBET比表面積は、例えば、試料を200℃で15分間脱気した後、吸着気体として混合ガス(N2:70%、He:30%)を用いて、BET比表面積測定装置(マイクロデータ社製、4232-II)により測定することができる。
本防振ゴム組成物には、必要に応じ、シランカップリング剤(E)を含有することができる。このように、シランカップリング剤(E)を含有させることにより、シリカ(D)とジエン系ゴム(A)がシランカップリング剤(E)を介して結合し、より防振ゴムの耐久性を向上させることができるようになる。
前記シランカップリング剤(E)としては、例えば、メルカプト系シランカップリング剤、スルフィド系シランカップリング剤、アミン系シランカップリング剤、エポキシ系シランカップリング剤、ビニル系シランカップリング剤等が、単独でもしくは二種以上併せて用いられる。なかでも、前記シランカップリング剤(E)が、メルカプト系シランカップリング剤やスルフィド系シランカップリング剤であることが、加硫密度が上がり、低動倍率、耐久性に特に効果があるため、好ましい。
ここで、本防振ゴム組成物は、その必須成分である(A)~(D)成分を特定の割合で用い、さらに、必要に応じて前記(E)成分や、前記列記したその他の材料を用いて、これらをニーダー,バンバリーミキサー,オープンロール,二軸スクリュー式撹拌機等の混練機を用いて混練することにより、調製することができる。
(α)下記の式(I)で示されるΔG’が5.0以下。
ΔG'=G’1/G’2……(I)
[式(I)中、G’1は、周波数11Hz、振れ角0.28%、40℃での、未加硫ゴム組成物の貯蔵弾性率であり、G’2は、周波数11Hz、振れ角42%、40℃での、未加硫ゴム組成物の貯蔵弾性率を示す。]
測定方法:二重リング電極法
ガード電極:外径80mm、内径70mm
主電極:50mm
試料外寸法:100mm×100mm
サンプル厚さ:2mm
印加電圧:1V
検知電流範囲:200pA~20mA
ばね低下性={(F2-F1)/F1}×100 (%)……(II)
また、前記用途以外にも、自動車の車両等に用いられるエンジンマウント、スタビライザブッシュ、サスペンションブッシュ、モーターマウント、サブフレームマウント等の構成部材としても用いることができる。なかでも、絶縁性等が高いことから、電動モーターを動力源とする電気自動車(電気自動車(EV)の他、燃料電池自動車(FCV)、プラグインハイブリッド車(PHV)、ハイブリッド車(HV)等も含む)用の、モーターマウント、サスペンションブッシュ、サブフレームマウント等の構成部材(電気自動車用防振ゴム部材)の用途にも、有利に用いることができる。
また、絶縁性等が高いことから、コンピューターのハードディスクの制振ダンパー、洗濯機等の一般家電製品の制振ダンパー、建築・住宅分野における建築用制震壁,制震(制振)ダンパー等の制震(制振)装置および免震装置の用途にも用いることができる。
大塚化学社製、アジピン酸ジヒドラジド(ADH)
大塚化学社製、イソフタル酸ジヒドラジド(IDH)
東海カーボン社製、シーストV(BET比表面積27m2/g)
旭カーボン社製、旭#60(BET比表面積40m2/g)
東海カーボン社製、シーストSRA(BET比表面積18m2/g)
キャボットジャパン社製、ショウブラックN330(BET比表面積75m2/g)
旭カーボン社製、旭#15(BET比表面積12m2/g)
旭カーボン社製、旭#65(BET比表面積42m2/g)
東ソー・シリカ社製、ニップシールVN3(BET比表面積180~230m2/g)
スルフィド系シランカップリング剤(EVONIK DEGUSSA社製、Si-69)
メルカプト系シランカップリング剤(MOMENTIVE社製、NXT Z45)
堺化学工業社製、酸化亜鉛二種
日油社製、ビーズステアリン酸さくら
住友化学社製、アンチゲン6C
日本サン石油社製、サンセン410
三新化学工業社製、サンセラーCZ-G
軽井沢製錬所社製
前記各材料を、後記の表1および表2に示す割合で配合して混練することにより、防振ゴム組成物を調製した。なお、前記混練は、まず、加硫剤と加硫促進剤以外の材料を、バンバリーミキサーを用いて140℃で5分間混練し、ついで、加硫剤と加硫促進剤を配合し、オープンロールを用いて60℃で5分間混練することにより行った。
各防振ゴム組成物に対し、RPA2000(アルファテクノロジー社製)により、周波数11Hz、40℃での、未加硫ゴム組成物の貯蔵弾性率(振れ角0.28%での貯蔵弾性率G’1、および、振れ角42%での貯蔵弾性率G’2)を測定した。そして、前記測定結果をもとに、下記の式(I)で示されるΔG’を算出した。
ΔG’=G’1/G’2 ……(I)
各防振ゴム組成物を、150℃×30分間の条件でプレス成形(加硫)し、そのゴム表面の硬度(JIS-A硬度)を、アスカーゴム硬度計(P1-Aタイプ)(高分子計器社製)により測定した。そして、下記の基準に従い、補強性の評価を行った。
〇(very good):硬度が60以上。
×(poor) :硬度が60未満。
各防振ゴム組成物を、150℃×30分間の条件でプレス成形(加硫)し、厚み2mmのゴムシートを作製した。そして、このゴムシートから、JIS3号ダンベルを打ち抜き、このダンベルを用い、JIS K 6260に準じて伸縮疲労試験を行った。
そして、その破断時の伸縮回数を測定し、下記の基準に従い、耐久性の評価を行った。
○(very good):伸縮回数が8万回以上。
×(poor) :伸縮回数が8万回未満。
各防振ゴム組成物を、150℃×30分間の条件でプレス成形(加硫)して得られたサンプルに対し、JIS K 6271-1:2015(加硫ゴムおよび熱可塑性ゴム-電気抵抗率の求め方)に従って、体積抵抗率VR(Ω・cm)を測定した。
具体的には、以下の条件で、体積抵抗率VRを求めた。
測定方法:二重リング電極法
ガード電極:外径80mm、内径70mm
主電極:50mm
試料外寸法:100mm×100mm
サンプル厚さ:2mm
印加電圧:1V
検知電流範囲:200pA~20mA
そして、下記の基準に従い、絶縁性の評価を行った。
〇(very good):体積抵抗率VRが1×109Ω・cm以上。
×(poor) :体積抵抗率VRが1×109Ω・cm未満。
各防振ゴム組成物を、150℃×30分間の条件でプレス成形(加硫)して得られた防振ゴムサンプルについて、3Hzの周波数で圧縮方向に4mm、引張方向に15mmの伸縮を繰り返す耐久疲労試験を実施し、15mm引張時の荷重(初期荷重F1、および伸縮回数3000回時点の荷重F2)を測定した。そして、前記測定結果をもとに、下記の式(II)で示されるばね低下性を算出した。
ばね低下性={(F2-F1)/F1}×100 (%)……(II)
そして、下記の基準に従い、ばね低下性の評価を行った。
〇(very good):ばね低下性が-20%以上。
×(poor) :ばね低下性が-20%未満。
比較例2の防振ゴム組成物は、そのジヒドラジド化合物の含有量が多すぎ、ゴムの粘度が著しく上がるため耐久性に劣る結果となった。
比較例3の防振ゴム組成物は、そのカーボンブラックの含有量が少なすぎ、補強性(硬度)に劣る結果となった。
比較例4の防振ゴム組成物は、そのカーボンブラックの含有量が多すぎ、導電パス形成により絶縁性に劣る結果となった。
比較例5の防振ゴム組成物は、そのカーボンブラックのBET比表面積が、本発明の規定を超える値を示すものであり、表面積の増加に伴い導電性が上がるため絶縁性に劣る結果となった。
比較例6の防振ゴム組成物は、そのカーボンブラックのBET比表面積が、本発明の規定未満の値を示すものであり、耐久加振時にゴムとカーボンブラックとの界面が亀裂発生起点となり易いため耐久性に劣る結果となった。
比較例7の防振ゴム組成物は、そのシリカの含有量が少なすぎ、補強性(硬度)に劣る結果となった。
比較例8の防振ゴム組成物は、そのシリカの含有量が多すぎ、シリカ同士の凝集塊が耐久加振中に崩れて荷重低下を引き起こすため、ばね低下性に劣る結果となった。
比較例9の防振ゴム組成物は、そのカーボンブラックのBET比表面積が、本発明の規定を超える値を示すものであり、表面積の増加に伴い導電性が上がるため絶縁性に劣る結果となった。
また、前記用途以外にも、自動車の車両等に用いられるエンジンマウント、スタビライザブッシュ、サスペンションブッシュ、モーターマウント、サブフレームマウント等の構成部材としても用いることができる。なかでも、絶縁性等が高いことから、電動モーターを動力源とする電気自動車(電気自動車(EV)の他、燃料電池自動車(FCV)、プラグインハイブリッド車(PHV)、ハイブリッド車(HV)等も含む)用の、モーターマウント、サスペンションブッシュ、サブフレームマウント等の構成部材(電気自動車用防振ゴム部材)の用途にも、有利に用いることができる。
また、絶縁性等が高いことから、コンピューターのハードディスクの制振ダンパー、洗濯機等の一般家電製品の制振ダンパー、建築・住宅分野における建築用制震壁,制震(制振)ダンパー等の制震(制振)装置および免震装置の用途にも用いることができる。
Claims (6)
- 下記の(A)成分からなるポリマー成分と、下記の(B)~(D)成分を含有する防振ゴム組成物であって、(A)成分100質量部に対し、(B)成分の割合が0.1~5質量部であり、(C)成分の割合が10~40質量部であり、(D)成分の割合が10~30質量部であり、かつ、(C)成分が、BET比表面積18~40m2/gのものである、防振ゴム組成物。
(A)ジエン系ゴム。
(B)ジヒドラジド化合物。
(C)カーボンブラック。
(D)シリカ。 - さらに、シランカップリング剤(E)を含有する、請求項1記載の防振ゴム組成物。
- 前記シランカップリング剤(E)が、メルカプト系シランカップリング剤およびスルフィド系シランカップリング剤からなる群から選ばれた少なくとも一つである、請求項2記載の防振ゴム組成物。
- 前記ジヒドラジド化合物(B)が、アジピン酸ジヒドラジドおよびイソフタル酸ジヒドラジドから選ばれた少なくとも一つである、請求項1~3のいずれか一項に記載の防振ゴム組成物。
- 請求項1~4のいずれか一項に記載の防振ゴム組成物の加硫体からなる防振ゴム部材。
- 鉄道車両用防振ゴム部材である、請求項5記載の防振ゴム部材。
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JP2020164634A (ja) * | 2019-03-29 | 2020-10-08 | 住友理工株式会社 | 防振ゴム組成物および防振ゴム部材 |
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2022
- 2022-09-27 CN CN202280021083.5A patent/CN116981731A/zh active Pending
- 2022-09-27 WO PCT/JP2022/035894 patent/WO2023054341A1/ja active Application Filing
- 2022-09-27 EP EP22876207.6A patent/EP4317296A1/en active Pending
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2023
- 2023-10-04 US US18/480,512 patent/US20240026129A1/en active Pending
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WO2020066550A1 (ja) * | 2018-09-26 | 2020-04-02 | 住友理工株式会社 | 防振ゴム組成物および防振ゴム部材 |
JP2020164634A (ja) * | 2019-03-29 | 2020-10-08 | 住友理工株式会社 | 防振ゴム組成物および防振ゴム部材 |
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US20240026129A1 (en) | 2024-01-25 |
EP4317296A1 (en) | 2024-02-07 |
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