JP2020075944A - Rubber composition for vibrationproof rubber, and vibrationproof rubber - Google Patents
Rubber composition for vibrationproof rubber, and vibrationproof rubber Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 100
- 239000005060 rubber Substances 0.000 title claims abstract description 100
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 10
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 10
- 229920001194 natural rubber Polymers 0.000 claims abstract description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 5
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 4
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000000304 alkynyl group Chemical group 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 4
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000003247 decreasing effect Effects 0.000 abstract 1
- 238000004073 vulcanization Methods 0.000 description 24
- 239000003795 chemical substances by application Substances 0.000 description 19
- 239000006229 carbon black Substances 0.000 description 18
- 235000019241 carbon black Nutrition 0.000 description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 15
- 229910052717 sulfur Inorganic materials 0.000 description 15
- 239000011593 sulfur Substances 0.000 description 15
- 230000003712 anti-aging effect Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000004636 vulcanized rubber Substances 0.000 description 9
- 238000013329 compounding Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 229920005549 butyl rubber Polymers 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 229920003049 isoprene 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
- 239000003921 oil Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 0 *N(*)c(cc1)ccc1NC(C=CC(O*)=O)=O Chemical compound *N(*)c(cc1)ccc1NC(C=CC(O*)=O)=O 0.000 description 1
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229920005557 bromobutyl Polymers 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001973 fluoroelastomer Polymers 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 229920002681 hypalon Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- SIBJEXQCOCKLSR-YSMBQZINSA-M sodium;(z)-4-(4-aminoanilino)-4-oxobut-2-enoate Chemical compound [Na+].NC1=CC=C(NC(=O)\C=C/C([O-])=O)C=C1 SIBJEXQCOCKLSR-YSMBQZINSA-M 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
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Abstract
Description
本発明は、防振ゴム用ゴム組成物に関し、特に自動車用エンジンマウントなどの防振部材として好適に用いることができる防振ゴム用ゴム組成物および防振ゴムに関するものである。 The present invention relates to a rubber composition for vibration isolating rubber, and more particularly to a rubber composition for vibration isolating rubber and a vibration isolating rubber that can be suitably used as a vibration isolating member such as an engine mount for automobiles.
自動車などの車両にはエンジンや車体の振動を吸収し、乗り心地の向上や騒音を防止するために防振ゴムが用いられている。かかる防振ゴムにおいては、動倍率（動的バネ定数／静的バネ定数）の低減と耐久性の向上とを高いレベルで両立することが求められる。かかる動倍率は車内騒音の指標となるものであり、低いほど良好である。 BACKGROUND ART Anti-vibration rubber is used in vehicles such as automobiles in order to absorb vibrations of an engine and a vehicle body, improve riding comfort and prevent noise. In such an anti-vibration rubber, it is required to reduce the dynamic magnification (dynamic spring constant / static spring constant) and improve the durability at a high level. The dynamic ratio is an index of vehicle interior noise, and the lower the better, the better.
下記特許文献１では、ゴム成分を一部変性し、かつ特定の性状を有するカーボンブラック含有するゴム組成物を原料として使用することにより、低動倍率化した防振ゴムの開発を試みているが、防振ゴムの低動倍率化および耐久性の向上の点でさらなる改良の余地があった。 In Patent Document 1 below, an attempt has been made to develop an anti-vibration rubber having a low dynamic magnification by partially modifying a rubber component and using a rubber composition containing carbon black having specific properties as a raw material. However, there was room for further improvement in terms of lowering the dynamic ratio and improving the durability of the anti-vibration rubber.
本発明は上記実情に鑑みてなされたものであり、その目的は、低動倍率化と耐久性向上との両立が可能な防振ゴムの原料となる防振ゴム用ゴム組成物、および防振ゴムを提供することにある。 The present invention has been made in view of the above circumstances, and an object thereof is to provide a rubber composition for a vibration isolating rubber, which is a raw material of a vibration isolating rubber capable of achieving both low dynamic magnification and improved durability, and an antivibration. To provide rubber.
上記課題を解決すべく、本発明者は、天然ゴムを特定量含有するゴム組成物において、特定の化合物を配合することにより、その加硫ゴムの動倍率の低減と耐久性の向上とが両立できることを見出した。本発明は、上記の検討の結果なされたものであり、下記の如き構成により上述の目的を達成するものである。 In order to solve the above-mentioned problems, the present inventor has a rubber composition containing a specific amount of natural rubber, by blending a specific compound, it is possible to reduce the dynamic ratio of the vulcanized rubber and improve the durability at the same time. I found that I could do it. The present invention has been made as a result of the above studies, and achieves the above object by the following configurations.
すなわち、本発明に係る防振ゴム用ゴム組成物は、ゴム成分の全量を１００質量部としたとき、天然ゴムを６０質量部以上含有し、かつ下記式（Ｉ）に記載の化合物：
本発明に係る防振ゴム用ゴム組成物は、ゴム成分の全量を１００質量部としたとき、天然ゴムを６０質量部以上含有し、前記式（Ｉ）に記載の化合物を０．１〜５質量部含有するため、最終的にかかる防振ゴム用ゴム組成物を加硫成形してなる防振ゴムは、動倍率の低減と耐久性の向上とが両立されている。 The rubber composition for anti-vibration rubber according to the present invention contains natural rubber in an amount of 60 parts by mass or more when the total amount of the rubber component is 100 parts by mass, and the compound represented by the formula (I) is contained in an amount of 0.1 to 5 parts by mass. Since the anti-vibration rubber is obtained by vulcanizing and molding the rubber composition for anti-vibration rubber, the anti-vibration rubber finally has both a reduction in dynamic ratio and an improvement in durability.
本発明に係る防振ゴム用ゴム組成物は、ゴム成分の全量を１００質量部としたとき、天然ゴムを６０質量部以上含有し、前記式（Ｉ）に記載の化合物０．１〜５質量部含有する。 The rubber composition for anti-vibration rubber according to the present invention contains natural rubber in an amount of 60 parts by mass or more when the total amount of the rubber component is 100 parts by mass, and contains 0.1 to 5 parts by mass of the compound represented by the formula (I). Contains part.
本発明に係る防振ゴム用ゴム組成物は、ゴム成分の全量を１００質量部としたとき、天然ゴムを６０質量部以上含有する。かかる防振ゴム用ゴム組成物は、天然ゴム以外のジエン系ゴムを含有してもよく、例えば、イソプレンゴム（ＩＲ）、ブタジエンゴム（ＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、ブチルゴム（ＩＩＲ）、およびアクリルニトリルブタジエンゴム（ＮＢＲ）などのジエン系合成ゴム；臭素化ブチルゴム（ＢＲ−ＩＩＲ）などのハロゲン化ブチルゴム；その他ポリウレタンゴム、アクリルゴム、フッ素ゴム、シリコンゴム、およびクロロスルホン化ポリエチレンなどを含めた合成ゴム類などを含有してもよい。 The rubber composition for anti-vibration rubber according to the present invention contains 60 parts by mass or more of natural rubber when the total amount of rubber components is 100 parts by mass. The rubber composition for vibration-proof rubber may contain a diene rubber other than natural rubber, and examples thereof include isoprene rubber (IR), butadiene rubber (BR), styrene-butadiene rubber (SBR), butyl rubber (IIR), And diene synthetic rubber such as acrylonitrile-butadiene rubber (NBR); halogenated butyl rubber such as brominated butyl rubber (BR-IIR); and other polyurethane rubber, acrylic rubber, fluororubber, silicone rubber, chlorosulfonated polyethylene, etc. Synthetic rubbers and the like may be contained.
本発明に係る防振ゴム用ゴム組成物は、カーボンブラックを含有することが好ましい。防振ゴムの低動倍率化を図る場合、一般には非汎用の大粒径カーボンブラックを配合する技術が用いられるが、かかる技術では、防振ゴムの耐久性が悪化する傾向がある。しかしながら、本発明においては、特定割合の天然ゴムに対し、前記式（Ｉ）に記載の化合物を０．１〜５質量部含有するため、汎用性のカーボンブラックを使用する場合であっても、防振ゴムの低動倍率化を実現し、かつ耐久性をも向上し得る。 The rubber composition for vibration-proof rubber according to the present invention preferably contains carbon black. In order to reduce the dynamic ratio of the anti-vibration rubber, generally, a technique of blending a non-general-use large particle size carbon black is used, but such a technique tends to deteriorate the durability of the anti-vibration rubber. However, in the present invention, since 0.1 to 5 parts by mass of the compound represented by the formula (I) is contained with respect to a specific ratio of natural rubber, even when general-purpose carbon black is used, It is possible to achieve a low dynamic magnification of the anti-vibration rubber and also improve durability.
カーボンブラックとしては、例えばＳＡＦ級（ＡＳＴＭナンバーでＮ１００番台）、ＩＳＡＦ級（同Ｎ２００番台）、ＨＡＦ級（同３００番台）、ＦＥＦ級（同Ｎ５００番台）、ＧＰＦ級（同Ｎ６００番台）、ＳＲＦ級（同７００番台）など、通常のゴム工業で使用されるカーボンブラックを使用することができる。カーボンブラックは、通常のゴム工業において、そのハンドリング性を考慮して造粒された、造粒カーボンブラックであってもよく、未造粒カーボンブラックであってもよい。 As carbon black, for example, SAF class (N100 series by ASTM number), ISAF class (N200 series), HAF class (300 series), FEF class (N500 series), GPF class (N600 series), SRF class Carbon black used in the usual rubber industry, such as the same 700 series, can be used. The carbon black may be a granulated carbon black or a non-granulated carbon black that has been granulated in consideration of its handling property in the usual rubber industry.
本発明においては、前記カーボンブラックの中でも汎用性のカーボンブラックである、ＨＡＦ級、ＦＥＦ級、およびＧＰＦ級からなる群より選択される少なくとも１種のカーボンブラックを使用することが好ましい。また、最終的に得られる加硫ゴムのゴム物性を考慮した場合、ゴム組成物中のカーボンブラックの含有量は、ゴム組成物中のゴム成分の全量を１００質量部としたとき、１０〜１００質量部とすることが好ましく、２０〜７０質量部とすることがより好ましい。 In the present invention, it is preferable to use at least one carbon black selected from the group consisting of HAF grade, FEF grade, and GPF grade, which is a versatile carbon black among the carbon blacks. When considering the rubber physical properties of the finally obtained vulcanized rubber, the content of carbon black in the rubber composition is 10 to 100 when the total amount of the rubber components in the rubber composition is 100 parts by mass. It is preferable to set it as a mass part, and it is more preferable to set it as 20 to 70 mass parts.
式（Ｉ）に記載の化合物は下記構造式：
なお、カーボンブラックへの親和性を高めるためには、式（Ｉ）中のＲ１およびＲ２が水素原子であり、Ｍ＋がナトリウムイオンである下記式（Ｉ’）に記載の化合物：
ゴム成分の全量を１００質量部としたとき、前記式（Ｉ）に記載の化合物の含有量は０．１〜５質量部であり、０．３〜３質量部であることが好ましく、０．５〜２質量部であることが特に好ましい。 When the total amount of the rubber component is 100 parts by mass, the content of the compound represented by the formula (I) is 0.1 to 5 parts by mass, preferably 0.3 to 3 parts by mass, and 0. It is particularly preferably 5 to 2 parts by mass.
本発明の防振ゴム用ゴム組成物は、上記ゴム成分、前記式（Ｉ）に記載の化合物およびカーボンブラックと共に、硫黄系加硫剤、加硫促進剤、シリカ、シランカップリング剤、ステアリン酸、加硫促進助剤、加硫遅延剤、老化防止剤、ワックスやオイルなどの軟化剤、加工助剤などの通常ゴム工業で使用される配合剤を、本発明の効果を損なわない範囲において適宜配合し用いることができる。 The rubber composition for a vibration-proof rubber of the present invention comprises a sulfur-based vulcanizing agent, a vulcanization accelerator, silica, a silane coupling agent, and stearic acid together with the rubber component, the compound represented by the formula (I) and carbon black. , Vulcanization accelerating aids, vulcanization retarders, antioxidants, softeners such as waxes and oils, compounding agents normally used in the rubber industry, such as processing aids, within the range that does not impair the effects of the present invention. It can be blended and used.
本発明に係る防振ゴム用ゴム組成物では、硫黄系加硫剤を含有することが好ましい。かかる硫黄系加硫剤としての硫黄は通常のゴム用硫黄であればよく、例えば粉末硫黄、沈降硫黄、不溶性硫黄、高分散性硫黄などを用いることができる。本発明に係る防振ゴム用ゴム組成物における硫黄の含有量は、製造される防振ゴムの動倍率および耐熱性を考慮した場合、ゴム成分１００重量部に対して０．２〜５質量部であることが好ましく、０．５〜３質量部であることがより好ましい。 The rubber composition for a vibration-proof rubber according to the present invention preferably contains a sulfur-based vulcanizing agent. Sulfur as the sulfur-based vulcanizing agent may be ordinary sulfur for rubber, and for example, powdered sulfur, precipitated sulfur, insoluble sulfur, highly dispersible sulfur and the like can be used. The content of sulfur in the rubber composition for a vibration-proof rubber according to the present invention is 0.2 to 5 parts by mass with respect to 100 parts by weight of the rubber component, in consideration of the dynamic ratio and heat resistance of the manufactured vibration-proof rubber. Is preferable, and more preferably 0.5 to 3 parts by mass.
加硫促進剤としては、ゴム加硫用として通常用いられる、スルフェンアミド系加硫促進剤、チウラム系加硫促進剤、チアゾール系加硫促進剤、チオウレア系加硫促進剤、グアニジン系加硫促進剤、ジチオカルバミン酸塩系加硫促進剤などの加硫促進剤を単独、または適宜混合して使用しても良い。製造される防振ゴムの低動倍率化の観点から、スルフェンアミド系加硫促進剤を使用することが好ましい。また、加硫促進剤の配合量は、ゴム成分１００重量部に対して０．１〜５質量部であることが好ましく、０．２〜３質量部であることがより好ましい。 As the vulcanization accelerator, usually used for rubber vulcanization, sulfenamide-based vulcanization accelerator, thiuram-based vulcanization accelerator, thiazole-based vulcanization accelerator, thiourea-based vulcanization accelerator, guanidine-based vulcanization A vulcanization accelerator such as an accelerator or a dithiocarbamate vulcanization accelerator may be used alone or in an appropriate mixture. It is preferable to use a sulfenamide-based vulcanization accelerator from the viewpoint of lowering the dynamic expansion ratio of the produced vibration-insulating rubber. Further, the compounding amount of the vulcanization accelerator is preferably 0.1 to 5 parts by mass, and more preferably 0.2 to 3 parts by mass with respect to 100 parts by mass of the rubber component.
老化防止剤としては、ゴム用として通常用いられる、芳香族アミン系老化防止剤、アミン−ケトン系老化防止剤、モノフェノール系老化防止剤、ビスフェノール系老化防止剤、ポリフェノール系老化防止剤、ジチオカルバミン酸塩系老化防止剤、チオウレア系老化防止剤などの老化防止剤を単独、または適宜混合して使用しても良い。 As the anti-aging agent, usually used for rubber, aromatic amine anti-aging agent, amine-ketone anti-aging agent, monophenol anti-aging agent, bisphenol anti-aging agent, polyphenol anti-aging agent, dithiocarbamic acid Antiaging agents such as salt antiaging agents and thiourea antiaging agents may be used alone or in admixture.
本発明の防振ゴム用ゴム組成物は、上記ゴム成分、前記式（Ｉ）に記載の化合物およびカーボンブラックと共に、硫黄系加硫剤、加硫促進剤、シリカ、シランカップリング剤、ステアリン酸、加硫促進助剤、加硫遅延剤、老化防止剤、ワックスやオイルなどの軟化剤、加工助剤などの通常ゴム工業で使用される配合剤などを、バンバリーミキサー、ニーダー、ロールなどの通常のゴム工業において使用される混練機を用いて混練りすることにより得られる。 The rubber composition for a vibration-proof rubber of the present invention comprises a sulfur-based vulcanizing agent, a vulcanization accelerator, silica, a silane coupling agent, and stearic acid together with the rubber component, the compound represented by the formula (I) and carbon black. , Vulcanization accelerating aids, vulcanization retardants, antioxidants, softeners such as waxes and oils, processing aids and other compounding agents normally used in the rubber industry, such as Banbury mixers, kneaders, rolls, etc. It is obtained by kneading using a kneader used in the rubber industry.
また、上記各成分の配合方法は特に限定されず、硫黄系加硫剤、および加硫促進剤などの加硫系成分以外の配合成分を予め混練してマスターバッチとし、残りの成分を添加してさらに混練する方法、各成分を任意の順序で添加し混練する方法、全成分を同時に添加して混練する方法などのいずれでもよい。 Further, the mixing method of each of the above components is not particularly limited, and a sulfur-based vulcanizing agent, and a compounding component other than the vulcanizing system component such as a vulcanization accelerator are kneaded in advance to form a master batch, and the remaining components are added. And further kneading, a method of adding each component in an arbitrary order and kneading, a method of simultaneously adding all components and kneading, and the like.
上記各成分を混練し、成形加工した後、加硫を行うことで、動倍率の低減と耐久性の向上とが両立された防振ゴムを製造することができる。加硫温度としては、例えば１２０〜２００℃が例示可能であり、１４０〜１８０℃が好ましい。 By kneading the above-mentioned components, molding and processing, and then performing vulcanization, it is possible to manufacture a vibration-proof rubber in which both reduction in dynamic ratio and improvement in durability are achieved. The vulcanization temperature may be, for example, 120 to 200 ° C, preferably 140 to 180 ° C.
本実施形態に係る防振ゴム用途の具体例としては、エンジンマウント、ストラットマウント、ボディマウント、キャブマウント、メンバーマウント、デフマウントなどのマウント、サスペンションブッシュ、アームブッシュ、トルクブッシュなどのブッシュ、トーショナ ルダンパー、マフラーハンガー、ダンパープーリ、ダイナミックダンパーなどの各種自動車用防振ゴムが挙げられる。また自動車用以外にも、鉄道車両用防振ゴム、産業機械用防振ゴム、建築用免震ゴム、免震ゴム支承等の防振、免震ゴムに好適に用いることができる。 Specific examples of anti-vibration rubber applications according to the present embodiment include mounts for engine mounts, strut mounts, body mounts, cab mounts, member mounts, differential mounts, etc., suspension bushes, arm bushes, bushings such as torque bushes, and torsional dampers. , Various muffler hangers, damper pulleys, dynamic dampers and other anti-vibration rubber for automobiles. Further, in addition to automobiles, it can be suitably used for anti-vibration rubber for railway vehicles, anti-vibration rubber for industrial machines, anti-vibration rubber for construction, anti-vibration rubber for anti-vibration rubber, etc.
以下に、この発明の実施例を記載してより具体的に説明する。 Hereinafter, the embodiments of the present invention will be described in more detail.
（ゴム組成物の調製）
ゴム成分１００重量部に対して、表１の配合処方に従い、実施例１〜５、比較例１〜２のゴム組成物を配合し、通常のバンバリーミキサーを用いて混練し、ゴム組成物を調整した。表１に記載の各配合剤を以下に示す。
(Preparation of rubber composition)
The rubber compositions of Examples 1 to 5 and Comparative Examples 1 and 2 were compounded with 100 parts by weight of the rubber component according to the compounding recipe of Table 1 and kneaded using a normal Banbury mixer to prepare the rubber composition. did. Each compounding agent shown in Table 1 is shown below.
・ＮＲ：天然ゴム、ＲＳＳ＃３
・ＢＲ：ブタジエンゴム、ランクセス社製「ＢＵＮＡ ＣＢ２２」
・式（Ｉ）記載の化合物（（２Ｚ）−４−［（４−アミノフェニル）アミノ］−４−オキソ−２−ブテン酸ナトリウム）：住友化学社製「スミリンク２００」
・カーボンブラックＦＥＦ（Ｎ５５０）：東海カーボン社製「シーストＳＯ」
・カーボンブラックＨＡＦ（Ｎ３３９）：東海カーボン社製「シーストＫＨ」
・酸化亜鉛：三井金属鉱業社製「酸化亜鉛１種」
・ステアリン酸：花王社製「ルナックＳ−２０」
・ワックス：日本精鑞社製「ＯＺＯＡＣＥ２７０１」
・老化防止剤６Ｃ：Ｆｌｅｘｓｙｓ社製「ＳＡＮＴＯＦＬＥＸ６ＰＰＤ」
・老化防止剤ＲＤ：大内新興化学工業社製「ノクラック２２４」
・硫黄：細井化学工業社製「ゴム用粉末硫黄１５０メッシュ」
・加硫促進剤ＣＺ：大内新興化学工業社製「ノクセラーＤＭ−Ｐ」
・加硫促進剤ＴＳ：三新化学工業社製「サンセラーＴＳ」
・ NR: Natural rubber, RSS # 3
BR: butadiene rubber, LANXESS "BUNA CB22"
-Compound of formula (I) ((2Z) -4-[(4-aminophenyl) amino] -4-oxo-2-butenoate sodium): "Sumilink 200" manufactured by Sumitomo Chemical Co., Ltd.
・ Carbon black FEF (N550): "Seast SO" manufactured by Tokai Carbon Co., Ltd.
・ Carbon black HAF (N339): "Seast KH" manufactured by Tokai Carbon Co., Ltd.
・ Zinc oxide: Mitsui Mining & Smelting Co., Ltd. "Zinc oxide type 1"
-Stearic acid: "Lunack S-20" manufactured by Kao Corporation
・ Wax: "OZOACE2701" manufactured by Nippon Seiro Co., Ltd.
・ Anti-aging agent 6C: "SANTOFLEX6PPD" manufactured by Flexsys
・ Anti-aging agent RD: "Nocrac 224" manufactured by Ouchi Shinko Chemical Co., Ltd.
・ Sulfur: Hosoi Chemical Co., Ltd. "Rubber powder sulfur 150 mesh"
・ Vulcanization accelerator CZ: "Nox Cellar DM-P" manufactured by Ouchi Shinko Chemical Industry Co., Ltd.
・ Vulcanization accelerator TS: Sansan Chemical Co., Ltd. "Suncellar TS"
実施例１〜６、比較例１〜２
バンバリーミキサーを使用し、下記表１に示す配合（質量部）に従い、まず、第一混合段階で、硫黄と加硫促進剤と加硫遅延剤を除く成分を添加混合し（混合時の排出温度は１６０℃）、次いで、得られた混合物に、最終混合段階で硫黄と加硫促進剤を添加混合して、防振ゴム用ゴム組成物を調製した。各ゴム組成物について、それぞれ加硫ゴムを作製して特性を評価した。
Examples 1-6, Comparative Examples 1-2
Using a Banbury mixer, according to the composition (parts by mass) shown in Table 1 below, first, in the first mixing step, the components other than sulfur, the vulcanization accelerator and the vulcanization retarder were added and mixed (the discharge temperature during mixing). Was 160 ° C.), and then sulfur and a vulcanization accelerator were added and mixed to the obtained mixture in the final mixing stage to prepare a rubber composition for a vibration-proof rubber. For each rubber composition, a vulcanized rubber was prepared and its properties were evaluated.
得られた加硫ゴムを下記評価基準により評価した。 The obtained vulcanized rubber was evaluated according to the following evaluation criteria.
［動倍率］
所定の金型を使用し、各ゴム組成物を１５０℃×２５分にて加硫して得られた加硫ゴムサンプル（５０ｍｍΦ×２５ｍｍ）について、静ばね定数Ｋｓと動ばね定数Ｋｄを下記方法により測定し、その比（Ｋｄ／Ｋｓ）を算出して動倍率を求めた。実施例１〜４および比較例１については、比較例１の結果を１００として指数評価を行い、実施例５〜６については、比較例２の結果を１００として指数評価を行った。指数が小さいほど、加硫ゴムの動倍率が低く、動特性に優れることを意味する。
[Moving ratio]
The static spring constant Ks and the dynamic spring constant Kd of the vulcanized rubber sample (50 mmΦ × 25 mm) obtained by vulcanizing each rubber composition at 150 ° C. for 25 minutes using a predetermined mold were measured by the following method. And the ratio (Kd / Ks) was calculated to obtain the dynamic magnification. For Examples 1 to 4 and Comparative Example 1, index evaluation was performed with the result of Comparative Example 1 as 100, and for Examples 5 to 6, index evaluation was performed with the result of Comparative Example 2 as 100. The smaller the index, the lower the dynamic ratio of the vulcanized rubber and the better the dynamic characteristics.
・静ばね定数（Ｋｓ）：オリエンテック（株）製テンシロンを測定機に用い、加硫ゴムサンプルについて、１０ｍｍ／分のクロスヘッドスピードで０〜５ｍｍ間の圧縮（２０％までの圧縮）を２回繰返し、２回目の荷重−たわみ線図を描き、次式に基づいて算出した。
静ばね定数（Ｎ／ｍｍ）＝（ｗ２−ｗ１）／（δ２−δ１）
（式中、ｗ１はたわみ量δ１が１．３ｍｍ時の荷重（Ｎ）、ｗ２はたわみ量δ２が３．８ ｍｍ時の荷重（Ｎ）である。）
-Static spring constant (Ks): Tensilon manufactured by Orientec Co., Ltd. was used as a measuring machine, and a vulcanized rubber sample was compressed at a crosshead speed of 10 mm / min between 0 and 5 mm (compression up to 20%) to 2. It was repeated twice, and a second load-deflection diagram was drawn and calculated based on the following formula.
Static spring constant (N / mm) = (w2-w1) / (δ2-δ1)
(In the formula, w1 is the load (N) when the deflection amount δ1 is 1.3 mm, and w2 is the load (N) when the deflection amount δ2 is 3.8 mm.)
・動ばね定数（Ｋｄ）：（株）鷺宮製作所製ダイナミックサーボを測定機に用い、初期歪（圧縮）１０％、周波数１００Ｈｚ、振幅±０．０５ｍｍ（±０．２％）で行い、ＪＩＳＫ６３９４に記載の計算方法によりを求めた（単位はＮ／ｍｍ）。 -Dynamic spring constant (Kd): Dynamic servo manufactured by Sagimiya Seisakusho Co., Ltd. is used as a measuring machine, and initial strain (compression) is 10%, frequency is 100 Hz, and amplitude is ± 0.05 mm (± 0.2%). Was calculated by the calculation method described (unit is N / mm).
［耐久性］
各ゴム組成物を所定の円柱構造（φ３０×Ｈ２０）となるようにトランスファー成型したものを、５５°傾けて上下定荷重加振（上方向０．９ｋＮ、下方向０．３ｋＮ）を３Ｈｚの周波数で与え、亀裂が成長しバネが初期より半分になった回数に基づき耐久性を評価した。評価は、実施例１〜４および比較例１については、比較例１の結果を１００として指数評価を行い、実施例５〜６については、比較例２の結果を１００として指数評価を行った。指数が大きいほど、加硫ゴムの耐久性に優れることを意味する。
[durability]
Transfer molding of each rubber composition into a predetermined columnar structure (φ30 × H20) was tilted at 55 ° and vertical constant load vibration (upward 0.9 kN, downward 0.3 kN) was applied at a frequency of 3 Hz. The durability was evaluated based on the number of times the crack grew and the spring became half the initial amount. Regarding the evaluation, for Examples 1 to 4 and Comparative Example 1, index evaluation was performed by setting the result of Comparative Example 1 to 100, and for Examples 5 to 6, the result of Comparative Example 2 was set to 100. The larger the index, the better the durability of the vulcanized rubber.
結果は表１に示す通りであり、コントロールである比較例１および比較例２に対し、式（Ｉ）記載の化合物を添加した実施例１〜６では加硫ゴムの動倍率は低減され、かつ耐久性が向上していることがわかる。 The results are shown in Table 1, and in Examples 1 to 6 in which the compound of the formula (I) was added, the dynamic ratio of the vulcanized rubber was reduced, as compared with the control of Comparative Example 1 and Comparative Example 2, and It can be seen that the durability is improved.
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