JP6234172B2 - Rubber composition for anti-vibration rubber and anti-vibration rubber - Google Patents
Rubber composition for anti-vibration rubber and anti-vibration rubber Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims description 114
- 239000005060 rubber Substances 0.000 title claims description 114
- 239000000203 mixture Substances 0.000 title claims description 36
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 62
- 239000011787 zinc oxide Substances 0.000 claims description 54
- 235000014692 zinc oxide Nutrition 0.000 claims description 54
- 239000002131 composite material Substances 0.000 claims description 35
- 238000004073 vulcanization Methods 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 21
- 239000011593 sulfur Substances 0.000 claims description 21
- 229910052717 sulfur Inorganic materials 0.000 claims description 21
- 229920001194 natural rubber Polymers 0.000 claims description 16
- 244000043261 Hevea brasiliensis Species 0.000 claims description 11
- 229920003052 natural elastomer Polymers 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000001179 sorption measurement Methods 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 description 20
- 239000003921 oil Substances 0.000 description 13
- 230000003712 anti-aging effect Effects 0.000 description 12
- 239000006229 carbon black Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 6
- 230000003068 static effect Effects 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 239000004636 vulcanized rubber Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- -1 CaCO 3 Substances 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 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
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-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
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 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 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 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
- 230000000704 physical effect Effects 0.000 description 1
- 150000008442 polyphenolic compounds Chemical class 0.000 description 1
- 235000013824 polyphenols Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 238000013040 rubber vulcanization Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Vibration Prevention Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、防振ゴム用ゴム組成物および防振ゴムに関し、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これを用いた防振ゴムに関するものである。 The present invention relates to a rubber composition for vibration proof rubber and vibration proof rubber, and more particularly to a rubber composition for vibration proof rubber that can be suitably used as a vibration proof member for an engine mount for automobiles, and a vibration proof rubber using the same. Is.
従来から天然ゴムに補強材としてのカーボンブラックを配合したものが防振ゴムとして使用されている。近年の市場においては、防振ゴム、特に自動車用防振ゴムとして、動倍率（動的バネ定数／静的バネ定数）の低減が要求されている。 Conventionally, natural rubber blended with carbon black as a reinforcing material has been used as an anti-vibration rubber. In recent years, a reduction in dynamic magnification (dynamic spring constant / static spring constant) is required as an anti-vibration rubber, particularly an anti-vibration rubber for automobiles.
防振ゴムの低動倍率化を図るためには、天然ゴム中のカーボンブラックの分散性を高めることが重要となる。従来は、カーボンブラックとして大粒径のものを使用することで、天然ゴム中のカーボンブラックの分散性を高める方法が採用されてきたが、この方法では防振ゴムの耐久性が損なわれる傾向があった。 In order to reduce the dynamic magnification of the vibration-proof rubber, it is important to improve the dispersibility of carbon black in natural rubber. Conventionally, a method of increasing the dispersibility of carbon black in natural rubber by using carbon black having a large particle size has been adopted, but this method tends to impair the durability of the vibration-proof rubber. there were.
ところで、一般にゴム組成物においては、硫黄を含む加硫剤と併用して、加硫時間の短縮、加硫温度の低下、加硫剤の減量を目的として加硫促進剤が配合される。かかる加硫促進剤を活性化し、促進効果をさらに高めるものとして、酸化亜鉛（亜鉛華）を代表とする金属酸化物が挙げられる。下記特許文献１では、天然ゴム１００重量部に対し、微粒子化された亜鉛華を特定量配合したゴム組成物を加硫することにより、動倍率が低減された防振ゴムが得られる点が記載されている。しかしながら、本発明者が鋭意検討した結果、防振ゴムの低動倍率化の観点から、かかる特許文献に記載の技術において、さらなる改良の余地があることが判明した。 By the way, in general, in a rubber composition, a vulcanization accelerator is blended in combination with a vulcanizing agent containing sulfur for the purpose of shortening the vulcanization time, lowering the vulcanization temperature, and reducing the amount of the vulcanizing agent. A metal oxide typified by zinc oxide (zinc white) is exemplified as one that activates the vulcanization accelerator and further enhances the acceleration effect. In the following Patent Document 1, it is described that an anti-vibration rubber with reduced dynamic ratio can be obtained by vulcanizing a rubber composition containing a specific amount of finely divided zinc white with respect to 100 parts by weight of natural rubber. Has been. However, as a result of intensive studies by the inventor, it has been found that there is room for further improvement in the technique described in the patent document from the viewpoint of reducing the dynamic magnification of the vibration-proof rubber.
下記特許文献２では、熱老化を抑制しつつ空気入りタイヤとしたときの諸物性（操縦性や乗り心地性、耐摩耗性など）を向上するために、空気入りタイヤの原料として、ＳＢＲに複合亜鉛華を添加したゴム組成物が記載されている。しかしながら、これらの文献に記載のゴム組成物は防振ゴム用として使用することが意図されているわけではなく、ましてやかかるゴム組成物を用いた場合、動倍率の低減に有効であるなどの記載や示唆があるわけではない。 In Patent Document 2 below, in order to improve various physical properties (maneuverability, ride comfort, wear resistance, etc.) of a pneumatic tire while suppressing heat aging, it is combined with SBR as a raw material for the pneumatic tire. A rubber composition to which zinc white is added is described. However, the rubber compositions described in these documents are not intended to be used as anti-vibration rubbers. Furthermore, when such a rubber composition is used, it is effective to reduce dynamic magnification. There is no suggestion.
なお、下記特許文献３および４には、複合亜鉛華粒子の製造方法が記載され、得られた複合亜鉛華をゴム組成物に配合する技術が記載されている。 Patent Documents 3 and 4 listed below describe a method for producing composite zinc white particles, and a technique for blending the obtained composite zinc white into a rubber composition.
しかしながら、本発明者らが鋭意検討した結果、上記特許文献３および４に記載の製造方法により得られた複合亜鉛華を使用した場合、特に近年要求されている、防振ゴムの高耐久化および低動倍率化の両立を図ることが困難であることが判明した。さらに、特許文献３および４に記載の技術は、防振ゴム用に開発されたものではなく、ましてや得られた複合亜鉛華を用いた場合、動倍率の低減に有効であるなどの記載や示唆があるわけではない。 However, as a result of intensive studies by the present inventors, when the composite zinc white obtained by the production methods described in Patent Documents 3 and 4 above is used, the durability of the vibration-proof rubber, which has been particularly required recently, and It was found that it was difficult to achieve both low dynamic magnification. In addition, the techniques described in Patent Documents 3 and 4 are not developed for vibration-proof rubber, and if the obtained composite zinc white is used, it is effective to reduce dynamic magnification. There is no reason.
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、高耐久性および低動倍率性の両立が可能な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 of the present invention is to provide a rubber composition for vibration-proof rubber and a vibration-proof rubber capable of achieving both high durability and low dynamic magnification.
本発明者らは、上記課題を解決すべく、防振ゴム用ゴム組成物に配合する複合亜鉛華の「窒素吸着比表面積」、「ＤＢＰ吸油量」および「亜鉛華濃度」に着目し、これらを最適化した複合亜鉛華をゴム組成物に配合し、これを原料として防振ゴムを製造することにより、高耐久性および低動倍率性の両立が可能な防振ゴムが得られることを見出した。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 problems, the present inventors pay attention to “nitrogen adsorption specific surface area”, “DBP oil absorption amount” and “zinc flower concentration” of the composite zinc white to be blended in the rubber composition for vibration-proof rubber, We have found that anti-vibration rubbers that are compatible with both high durability and low dynamic magnification can be obtained by blending composite zinc white with optimized rubber composition into rubber compositions and using them as raw materials. It was. The present invention has been made as a result of the above-described studies, and achieves the above-described object with the following configuration.
すなわち、本発明は、少なくとも天然ゴムおよびポリイソプレンゴムからなる群より選択される少なくとも１種８０重量部を含むゴム成分１００重量部に対し、複合亜鉛華を２〜１０重量部含有し、前記複合亜鉛華は、窒素吸着比表面積が１５〜１１０ｍ２／ｇ、ＤＢＰ吸油量が５０〜１００ｍｌ／１００ｇ、かつ亜鉛華濃度が３８〜６４重量％であることを特徴とする防振ゴム用ゴム組成物、に関する。本発明に係る防振ゴム用ゴム組成物は、少なくとも天然ゴムおよびポリイソプレンゴムからなる群より選択される少なくとも１種８０重量部を含むゴム成分１００重量部に対し、比表面積が大きく小粒径であって、分散性能に優れる特定の複合亜鉛華を特定部数配合するため、最終的に得られる加硫ゴムの高耐久性および低動倍率性の両立が可能となる。 That is, the present invention contains 2 to 10 parts by weight of composite zinc white with respect to 100 parts by weight of a rubber component containing at least 80 parts by weight of at least one selected from the group consisting of natural rubber and polyisoprene rubber. Zinc flower has a nitrogen adsorption specific surface area of 15 to 110 m 2 / g, a DBP oil absorption of 50 to 100 ml / 100 g, and a zinc flower concentration of 38 to 64% by weight. , Regarding. The rubber composition for vibration-proof rubber according to the present invention has a large specific surface area and a small particle size with respect to 100 parts by weight of a rubber component containing at least 80 parts by weight selected from the group consisting of at least natural rubber and polyisoprene rubber. In addition, since the specific composite zinc white having excellent dispersion performance is blended in a specific number of parts, it is possible to achieve both high durability and low dynamic magnification of the finally obtained vulcanized rubber.
上記防振ゴム用ゴム組成物において、前記ゴム成分１００重量部に対し、硫黄を０．１〜３重量部含有することが好ましい。かかるゴム組成物を原料として得られる防振ゴムでは、耐熱性やゴム強度などを維持しつつ、動倍率を低減することができる。 In the rubber composition for vibration-proof rubber, it is preferable to contain 0.1 to 3 parts by weight of sulfur with respect to 100 parts by weight of the rubber component. In the vibration-proof rubber obtained by using such a rubber composition as a raw material, the dynamic magnification can be reduced while maintaining heat resistance, rubber strength, and the like.
本発明に係る防振ゴムは、前記いずれかに記載の防振ゴム用ゴム組成物を使用し、加硫、成形して得られる。かかる防振ゴムは、動倍率が著しく低減されている。 The anti-vibration rubber according to the present invention is obtained by vulcanization and molding using any of the rubber compositions for anti-vibration rubber described above. Such an anti-vibration rubber has a significantly reduced dynamic magnification.
本発明に係る防振ゴム用ゴム組成物は、ゴム成分１００重量部に対し、少なくとも天然ゴムおよびポリイソプレンゴムからなる群より選択される少なくとも１種８０重量部を含む。加硫後に得られる防振ゴムの耐疲労性などを維持しつつ、動倍率を低減するためには、ゴム成分１００重量部に対し、天然ゴムおよびポリイソプレンゴムからなる群より選択される少なくとも１種を９０重量部以上含有することが好ましく、９５重量部以上含有することが好ましく、略１００重量部含有することが特に好ましい。 The rubber composition for vibration-proof rubber according to the present invention contains at least one 80 parts by weight selected from the group consisting of natural rubber and polyisoprene rubber with respect to 100 parts by weight of the rubber component. In order to reduce the dynamic magnification while maintaining the fatigue resistance of the vibration-proof rubber obtained after vulcanization, at least one selected from the group consisting of natural rubber and polyisoprene rubber with respect to 100 parts by weight of the rubber component It is preferable to contain 90 parts by weight or more of seeds, preferably 95 parts by weight or more, and particularly preferably about 100 parts by weight.
本発明に係る防振ゴム用ゴム組成物では、複合亜鉛華を２〜１０重量部含有する。複合亜鉛華は、ゴム中へのキャリアーとしてのｃｏｒｅに、ＣａＣＯ３、Ｃａ（ＯＨ）２、ＣａＳＯ４、ＺｎＯ、ＭｇＯ、Ｍｇ（ＯＨ）２、ＭｇＣＯ３などを有し、そのｃｏｒｅの表面に一般の亜鉛華よりもさらに活性度の高い亜鉛華を被覆した構造を有する。かかるｃｏｒｅの大きさと亜鉛華の被覆層の厚み比率などは任意に設定可能である。防振ゴム用ゴム組成物中の複合亜鉛華の配合量は、ゴム成分１００重量部に対して２〜１０重量部であり、防振ゴムの耐久性を向上しつつ動倍率をさらに低減するためには、３〜７重量部であることが好ましく、４〜６重量部であることがより好ましい。 The rubber composition for vibration-proof rubber according to the present invention contains 2 to 10 parts by weight of composite zinc white. Composite zinc white has cores as carriers in rubber, such as CaCO 3 , Ca (OH) 2 , CaSO 4 , ZnO, MgO, Mg (OH) 2 , MgCO 3, etc. It has a structure in which zinc oxide having a higher activity than that of zinc oxide is coated. The size of the core and the thickness ratio of the zinc oxide coating layer can be arbitrarily set. The compounding amount of the composite zinc white in the rubber composition for vibration-proof rubber is 2 to 10 parts by weight with respect to 100 parts by weight of the rubber component, in order to further reduce the dynamic magnification while improving the durability of the vibration-proof rubber. Is preferably 3 to 7 parts by weight, and more preferably 4 to 6 parts by weight.
本発明において使用する複合亜鉛華は、窒素吸着比表面積が１５〜１１０ｍ２／ｇ、ＤＢＰ吸油量が５０〜１００ｍｌ／１００ｇ、かつ亜鉛華濃度が３８〜６４重量％である点が特徴である。かかる複合亜鉛華は、例えば特開昭５４−７２７９号公報および特開昭６０−２６２８４１号公報などを参考に、ＣａＣｏ３などの前記ｃｏｒｅの中でも、できるだけ小さなｃｏｒｅ径を有するものを使用し、これに対し、亜鉛華濃度が３８〜６４重量％となるように亜鉛華の被覆量を調整することで製造することができる。所望の窒素吸着比表面積およびＤＢＰ吸油量の複合亜鉛華を得るためには、ｃｏｒｅとして、ｃｏｒｅ径が０．０６〜０．２２μｍ、好ましくは０．０８〜０．１２μｍのＣａＣＯ３、Ｃａ（ＯＨ）２、ＣａＳＯ４、ＺｎＯ、ＭｇＯ、Ｍｇ（ＯＨ）２、またはＭｇＣＯ３を使用することが好ましく、ＣａＣＯ３を使用することがより好ましい。 The composite zinc white used in the present invention is characterized by a nitrogen adsorption specific surface area of 15 to 110 m 2 / g, a DBP oil absorption of 50 to 100 ml / 100 g, and a zinc white concentration of 38 to 64% by weight. As such a composite zinc white, reference is made to, for example, JP-A-54-7279 and JP-A-60-262841, and among the cores such as CaCo 3 , one having the smallest possible core diameter is used. On the other hand, it can manufacture by adjusting the coating amount of zinc white so that zinc white density | concentration may be 38 to 64 weight%. In order to obtain a composite zinc white having a desired nitrogen adsorption specific surface area and DBP oil absorption, the core diameter is 0.06-0.22 μm, preferably 0.08-0.12 μm of CaCO 3 , Ca (OH ) 2 , CaSO 4 , ZnO, MgO, Mg (OH) 2 , or MgCO 3 are preferably used, and CaCO 3 is more preferably used.
複合亜鉛華の窒素吸着比表面積は、複合亜鉛華の粒子径の尺度となり、複合亜鉛華の粒子径が小さくなると、窒素吸着比表面積が大きくなる関係がある。得られる防振ゴムの低動倍率化および高耐久化を図るためには、使用する複合亜鉛華の窒素吸着比表面積は１５〜１１０ｍ２／ｇである必要があり、３１〜１０６ｍ２／ｇであることが好ましく、４８〜６９ｍ２／ｇであることがより好ましい。 The nitrogen adsorption specific surface area of the composite zinc white is a measure of the particle diameter of the composite zinc white, and there is a relationship that the nitrogen adsorption specific surface area increases as the particle diameter of the composite zinc white decreases. To achieve low dynamic magnification and high durability of the vibration damping rubber resulting nitrogen adsorption specific surface area of the composite zinc oxide to be used must be 15~110m 2 / g, in 31~106m 2 / g It is preferably 48 to 69 m 2 / g.
複合亜鉛華のＤＢＰ吸油量は、複合亜鉛華の凝集構造（ストラクチャーの発達度合）の尺度となり、凝集構造が発達するほど、ＤＢＰ吸油量が大きくなる傾向がある。得られる防振ゴムの低動倍率化および高耐久化を図るためには、使用する複合亜鉛華のＤＢＰ吸油量は５０〜１００ｍｌ／１００ｇである必要があり、６０〜８０ｍｌ／１００ｇであることが好ましい。 The DBP oil absorption amount of the composite zinc white is a scale of the aggregate structure (structure development degree) of the composite zinc white, and the DBP oil absorption amount tends to increase as the aggregate structure develops. In order to achieve low dynamic magnification and high durability of the vibration-proof rubber obtained, the DBP oil absorption amount of the composite zinc white used must be 50 to 100 ml / 100 g, and should be 60 to 80 ml / 100 g. preferable.
複合亜鉛華の亜鉛華濃度は、ゴム組成物中に配合する加硫促進剤を活性化するために、使用する複合亜鉛華の亜鉛華濃度は３８〜６４重量％である必要があり、５０〜６０重量％であることが好ましい。 The zinc white concentration of the composite zinc white needs to be 38 to 64% by weight in order to activate the vulcanization accelerator compounded in the rubber composition. 60% by weight is preferred.
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、ゴム成分１００重量部に対して０．１〜３重量部であることが好ましい。硫黄の含有量が０．１重量部未満であると、加硫ゴムの架橋密度が不足してゴム強度などが低下し、３重量部を超えると、特に耐熱性が悪化する。加硫ゴムのゴム強度を良好に確保し、動倍率および耐熱性をより向上するためには、硫黄の含有量がゴム成分１００重量部に対して０．７〜２．０重量部であることがより好ましく、０．９〜１．５重量部であることがさらに好ましい。 The rubber composition for vibration-proof rubber according to the present invention preferably contains a sulfur vulcanizing agent. Sulfur as the sulfur-based vulcanizing agent may be normal sulfur for rubber. For example, powdered sulfur, precipitated sulfur, insoluble sulfur, highly dispersible sulfur and the like can be used. The sulfur content in the rubber composition for vibration-proof rubber according to the present invention is preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the rubber component. When the sulfur content is less than 0.1 parts by weight, the crosslinking density of the vulcanized rubber is insufficient and the rubber strength and the like are reduced, and when it exceeds 3 parts by weight, the heat resistance is particularly deteriorated. In order to ensure good rubber strength of the vulcanized rubber and to further improve the dynamic magnification and heat resistance, the sulfur content is 0.7 to 2.0 parts by weight with respect to 100 parts by weight of the rubber component. Is more preferably 0.9 to 1.5 parts by weight.
本発明の防振ゴム用ゴム組成物は、上記ゴム成分、複合亜鉛華、硫黄系加硫剤と共に、加硫促進剤、カーボンブラック、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 vibration-proof rubber of the present invention comprises the above rubber component, composite zinc white, sulfur vulcanizing agent, vulcanization accelerator, carbon black, silica, silane coupling agent, stearic acid, and vulcanization acceleration aid. Additives usually used in the rubber industry, such as vulcanization retarders, anti-aging agents, softeners such as waxes and oils, processing aids, etc., can be appropriately mixed and used within a range not impairing the effects of the present invention. .
カーボンブラックとしては、例えばＳＡＦ、ＩＳＡＦ、ＨＡＦ、ＦＥＦ、ＧＰＦなどが用いられる。カーボンブラックは、加硫後のゴムの硬度、補強性、低発熱性などのゴム特性を調整し得る範囲で使用することができる。カーボンブラックの配合量はゴム成分１００重量部に対して、２０〜１２０重量部の範囲であることが好ましく、より好ましくは３０〜１００重量部であり、さらに好ましくは３０〜６０重量部である。この配合量が２０重量部未満では、カーボンブラックの補強効果が充分に得られず、１２０重量部を超えると、発熱性、ゴム混合性および加工時の作業性などが悪化する。 Examples of carbon black include SAF, ISAF, HAF, FEF, and GPF. Carbon black can be used within a range in which rubber properties such as hardness, reinforcement and low heat build-up of the rubber after vulcanization can be adjusted. The compounding amount of carbon black is preferably in the range of 20 to 120 parts by weight, more preferably 30 to 100 parts by weight, and further preferably 30 to 60 parts by weight with respect to 100 parts by weight of the rubber component. If the blending amount is less than 20 parts by weight, the reinforcing effect of carbon black cannot be sufficiently obtained. If the blending amount exceeds 120 parts by weight, exothermic properties, rubber mixing properties, workability during processing, and the like are deteriorated.
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。加硫促進剤の含有量は、ゴム成分１００重量部に対し、１〜５重量部であることが好ましい。なお、加硫促進剤の含有量は、併用する硫黄の含有量に応じて調節することが好ましく、具体的には、ゴム成分１００重量部に対し、硫黄の含有量が０．１５〜０．６重量部である場合、加硫促進剤の含有量は２．５〜５重量部であることが好ましく、硫黄の含有量が０．７〜３重量部である場合、加硫促進剤の含有量は２．５〜５重量部であることが好ましい。 As the vulcanization accelerator, sulfenamide vulcanization accelerator, thiuram vulcanization accelerator, thiazole vulcanization accelerator, thiourea vulcanization accelerator, guanidine vulcanization, which are usually used for rubber vulcanization. Vulcanization accelerators such as accelerators and dithiocarbamate vulcanization accelerators may be used alone or in admixture as appropriate. The content of the vulcanization accelerator is preferably 1 to 5 parts by weight with respect to 100 parts by weight of the rubber component. The content of the vulcanization accelerator is preferably adjusted according to the content of sulfur to be used in combination. Specifically, the sulfur content is 0.15 to 0.005 per 100 parts by weight of the rubber component. When the content is 6 parts by weight, the content of the vulcanization accelerator is preferably 2.5 to 5 parts by weight. When the content of sulfur is 0.7 to 3 parts by weight, the content of the vulcanization accelerator is included. The amount is preferably 2.5 to 5 parts by weight.
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 an anti-aging agent, an aromatic amine-based anti-aging agent, an amine-ketone anti-aging agent, a monophenol anti-aging agent, a bisphenol anti-aging agent, a polyphenol anti-aging agent, dithiocarbamic acid, which are usually used for rubber Anti-aging agents such as a salt-based anti-aging agent and a thiourea-based anti-aging agent may be used alone or in an appropriate mixture.
本発明の防振ゴム用ゴム組成物は、上記ゴム成分、複合亜鉛華、硫黄系加硫剤、必要に応じて、カーボンブラック、ステアリン酸、加硫促進剤、老化防止剤、ワックスなどを、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 vibration-proof rubber of the present invention comprises the above rubber component, composite zinc white, sulfur vulcanizing agent, and if necessary, carbon black, stearic acid, vulcanization accelerator, anti-aging agent, wax, etc. It can be obtained by kneading using a kneader such as a Banbury mixer, a kneader, or a roll, which is used in a normal 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。 In addition, the blending method of each of the above components is not particularly limited, and a blending component other than a vulcanizing component such as a sulfur vulcanizing agent and a vulcanization accelerator is previously kneaded to obtain a master batch, and the remaining components are added. Any of a method of further kneading, a method of adding and kneading each component in an arbitrary order, a method of adding all components simultaneously and kneading may be used.
上記各成分を混練し、成形加工した後、加硫を行うことで、低動倍率である防振ゴムを製造することができる。かかる防振ゴムは、エンジンマウント、トーショナルダンパー、ボディマウント、メンバーマウント、ストラットマウント、マフラーマウントなどの自動車用防振ゴムを始めとして、鉄道車両用防振ゴム、産業機械用防振ゴムに好適に用いることができ、特にエンジンマウントなどの低動倍率を必要とする自動車用防振ゴムの構成部材として有用である。 Anti-vibration rubber having a low dynamic magnification can be produced by kneading and molding each of the above components, followed by vulcanization. Such anti-vibration rubber is suitable for anti-vibration rubber for automobiles such as engine mount, torsional damper, body mount, member mount, strut mount, muffler mount, etc. In particular, it is useful as a component of a vibration-proof rubber for automobiles that require a low dynamic magnification such as an engine mount.
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 present invention will be described in more detail with reference to examples.
（ゴム組成物の調製）
ゴム成分１００重量部に対して、表２の配合処方に従い、実施例１〜２、比較例１〜５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２に記載の各配合剤を以下に示す。
(Preparation of rubber composition)
The rubber compositions of Examples 1 and 2 and Comparative Examples 1 to 5 are blended with 100 parts by weight of the rubber component according to the formulation of Table 2, and kneaded using a normal Banbury mixer to adjust the rubber composition. did. Each compounding agent described in Table 2 is shown below.
ａ）ゴム成分
天然ゴム（ＮＲ） 「ＲＳＳ＃３」
ｂ）カーボンブラック（ＧＰＦ） 「シーストＶ」 （東海カーボン社製）
ｃ）アロマオイル 「ＪＯＭＯ ＮＣ１４０」 （ＪＸ日鉱日石エネルギー社製）
ｄ）亜鉛華 「３種ＺｎＯ」
ｅ）複合亜鉛華
複合亜鉛華（Ａ）〜複合亜鉛華（Ｄ）
表１に記載のｃｏｒｅ径を有する炭酸カルシウムからなるｃｏｒｅに対し、当業者に公知の手法に基づき、亜鉛華を被覆することにより、複合亜鉛華（Ａ）〜（Ｄ）を製造した。製造した複合亜鉛華の窒素吸着比表面積（ｍ２／ｇ）、平均粒径（μｍ）、ＤＢＰ吸油量（ｍｌ／１００ｇ）および亜鉛華濃度（重量％）を表１に示す。なお、製造した複合亜鉛華の窒素吸着比表面積はＡＳＴＭ Ｄ６５５６に基づき測定し、複合亜鉛華の平均粒径は、窒素吸着比表面積の測定結果に基づき、複合亜鉛華を球状物と仮定して計算により算出した。ＤＢＰ吸油量は、ＡＳＴＭ Ｄ２４１４に基づき測定し、亜鉛華濃度はＩＣＰ−ＡＥＳを使用した元素分析に基づき測定した。なお炭酸カルシウムのｃｏｒｅ径は、算出した複合亜鉛華の平均粒径および亜鉛華濃度から、計算により算出可能である。
a) Rubber component
Natural rubber (NR) "RSS # 3"
b) Carbon Black (GPF) “Seast V” (Tokai Carbon Co., Ltd.)
c) Aroma oil “JOMO NC140” (manufactured by JX Nippon Oil & Energy Corporation)
d) Zinc Hana “3 types of ZnO”
e) Composite zinc white
Composite zinc white (A) to composite zinc white (D)
A composite zinc white (A) to (D) was produced by coating a core made of calcium carbonate having the core diameter shown in Table 1 with a zinc white based on a method known to those skilled in the art. Table 1 shows the nitrogen adsorption specific surface area (m 2 / g), average particle diameter (μm), DBP oil absorption (ml / 100 g), and zinc white concentration (% by weight) of the produced composite zinc white. In addition, the nitrogen adsorption specific surface area of the manufactured composite zinc white was measured based on ASTM D6556, and the average particle size of the composite zinc white was calculated based on the measurement result of the nitrogen adsorption specific surface area, assuming that the composite zinc white was a spherical object. Calculated by The DBP oil absorption was measured based on ASTM D2414, and the zinc white concentration was measured based on elemental analysis using ICP-AES. The core diameter of calcium carbonate can be calculated from the calculated average particle diameter and zinc white concentration of the composite zinc white.
ｆ）ステアリン酸 （日油社製）
ｇ）ワックス 「ＯＺＯＡＣＥ−２７０１」（日本精蝋社製）
ｈ）老化防止剤 Ｎ−（１，３−ジメチルブチル）−Ｎ’−フェニル−ｐ−フェニレンジアミン 「アンテージ６Ｃ」 （川口化学工業社製）
ｉ）硫黄 ５％オイル処理硫黄
ｊ）加硫促進剤
（Ａ）チウラム化合物 テトラメチルチウラムモノスルフィド 「ノクセラーＴＳ（ＴＳ−Ｐ）」 （大内新興化学工業社製）
（Ｂ）スルフェンアミド系加硫促進剤 Ｎ−シクロヘキシル−２−ベンゾチアゾリルスルフェンアミド 「ノクセラー ＣＺ−Ｇ（ＣＺ）」 （大内新興化学工業社製）
（Ｃ）チアゾール系加硫促進剤 ジ−２−ベンゾチアゾリルジスルフィド 「ノクセラー ＤＭ−Ｐ（ＤＭ）」 （大内新興化学工業社製）
f) Stearic acid (manufactured by NOF Corporation)
g) Wax “OZOACE-2701” (manufactured by Nippon Seiwa Co., Ltd.)
h) Anti-aging agent N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine “ANTAGE 6C” (manufactured by Kawaguchi Chemical Co., Ltd.)
i) Sulfur 5% oil-treated sulfur j) Vulcanization accelerator (A) Thiuram compound Tetramethylthiuram monosulfide “Noxeller TS (TS-P)” (manufactured by Ouchi Shinsei Chemical Co., Ltd.)
(B) Sulfenamide vulcanization accelerator N-cyclohexyl-2-benzothiazolylsulfenamide “Noxeller CZ-G (CZ)” (manufactured by Ouchi Shinsei Chemical Co., Ltd.)
(C) Thiazole-based vulcanization accelerator di-2-benzothiazolyl disulfide “Noxeller DM-P (DM)” (manufactured by Ouchi Shinsei Chemical Co., Ltd.)
（評価）
評価は、各ゴム組成物を所定の金型を使用して、１６０℃で２０分間加熱、加硫して得られたゴムについて行った。
(Evaluation)
The evaluation was performed on rubbers obtained by heating and vulcanizing each rubber composition at 160 ° C. for 20 minutes using a predetermined mold.
＜動倍率（動的バネ定数／静的バネ定数）＞
動倍率は、動的バネ定数および静的バネ定数を測定することにより算出した。
<Dynamic magnification (dynamic spring constant / static spring constant)>
The dynamic magnification was calculated by measuring the dynamic spring constant and the static spring constant.
（１）動的バネ定数（Ｋｄ）
測定機として、島津製作所社製「サーボパルサーＥＨＦ−Ｅシリーズ」を使用し、初期歪１０％、周波数１００Ｈｚ、振幅±０．０５ｍｍとして、ＪＩＳ Ｋ ６３９４に記載の計算方法により算出した。
(1) Dynamic spring constant (Kd)
A “servo pulser EHF-E series” manufactured by Shimadzu Corporation was used as a measuring machine, and the calculation was performed according to the calculation method described in JIS K 6394 with an initial strain of 10%, a frequency of 100 Hz, and an amplitude of ± 0.05 mm.
（２）静的バネ定数（Ｋｓ）
測定機として、島津製作所社製「サーボパルサーＥＨＦ−Ｅシリーズ」を使用し、φ５０ｍｍ×２５ｍｍの加硫ゴムテストピースに、０．７ｍｍ／ｓｅｃのクロスヘッドスピードで０〜５ｍｍ間の予備圧縮を２回繰り返し、次に０．１６７ｍｍ／ｓｅｃのクロスヘッドスピードで０〜５ｍｍ間の本圧縮を１回行った。３回目の荷重−たわみ線図を描き、下記式（１）に基づいて算出した。
(2) Static spring constant (Ks)
Use a “Servo Pulsar EHF-E Series” manufactured by Shimadzu Corporation as a measuring machine, and apply 2 pre-compression between 0 and 5 mm at a crosshead speed of 0.7 mm / sec to a vulcanized rubber test piece of φ50 mm × 25 mm. Then, the main compression of 0 to 5 mm was performed once at a crosshead speed of 0.167 mm / sec. A third load-deflection diagram was drawn and calculated based on the following formula (1).
（静的バネ定数（Ｎ／ｍｍ））＝（ｗ２−ｗ１）／（δ２−δ１） （１）
（上記式（１）において、ｗ１；たわみ量δ１が１．３ｍｍ時の荷重（Ｎ）、ｗ２；たわみ量δ２が３．８ｍｍ時の荷重（Ｎ））
算出した動的バネ定数（Ｋｄ）と静的バネ定数（Ｋｓ）とに基づき、動倍率（Ｋｄ／Ｋｓ）を算出した。評価結果を表２に示す。
(Static spring constant (N / mm)) = (w2-w1) / (δ2-δ1) (1)
(In the above formula (1), w1; load (N) when the deflection amount δ1 is 1.3 mm, w2; load (N) when the deflection amount δ2 is 3.8 mm)
Based on the calculated dynamic spring constant (Kd) and static spring constant (Ks), the dynamic magnification (Kd / Ks) was calculated. The evaluation results are shown in Table 2.
＜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、比較例１を１００とした指数評価で行い、数値が高いほど耐久性に優れることを意味する。結果を表２に示す。
<Durability>
Each rubber composition is transfer-molded so as to have a predetermined cylindrical structure (φ30 × H20), tilted by 55 °, and subjected to constant vertical load excitation (upward 0.9 kN, downward 0.3 kN) at a frequency of 3 Hz. The durability was evaluated based on the number of times the crack grew and the spring was halved from the initial stage. Evaluation is performed by index evaluation with Comparative Example 1 being 100, and the higher the value, the better the durability. The results are shown in Table 2.
＜ゴム硬度および引張特性＞
ＪＩＳ−Ｋ ６２５３に準拠し、タイプＡデュロメーターにてゴム硬度を測定した、さらに、ＪＩＳ３号ダンベルを使用して作製したサンプルをＪＩＳ−Ｋ ６２５１に準拠して、引張強さ（ＴＢ（ＭＰａ））および伸び（ＥＢ（％））を測定した。結果を表２に示す。
<Rubber hardness and tensile properties>
According to JIS-K 6253, rubber hardness was measured with a type A durometer. Further, a sample produced using a JIS No. 3 dumbbell was subjected to tensile strength (TB (MPa)) in accordance with JIS-K 6251. And elongation (EB (%)) was measured. The results are shown in Table 2.
表２の結果から、実施例１〜２に係る防振ゴム用ゴム組成物の加硫ゴムは、低動倍率化され、かつ高耐久化されていることがわかる。
From the results of Table 2, it can be seen that the vulcanized rubber of the rubber composition for vibration-proof rubber according to Examples 1 and 2 has a low dynamic magnification and high durability.
Claims (3)
前記複合亜鉛華は、窒素吸着比表面積が４８〜６９ｍ２／ｇ、ＤＢＰ吸油量が６０〜８０ｍｌ／１００ｇ、かつ亜鉛華濃度が３８〜６４重量％であることを特徴とする防振ゴム用ゴム組成物。 2-10 parts by weight of composite zinc white is contained with respect to 100 parts by weight of a rubber component containing at least 80 parts by weight selected from the group consisting of at least natural rubber and polyisoprene rubber,
The composite zinc white has a nitrogen adsorption specific surface area of 48 to 69 m 2 / g, a DBP oil absorption of 60 to 80 ml / 100 g, and a zinc white concentration of 38 to 64% by weight. Rubber composition.
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