WO2002085978A1 - Melanges caoutchoutes destines a du caoutchouc moule et stable vis-a-vis de l'eau sterilisee au chlore - Google Patents

Melanges caoutchoutes destines a du caoutchouc moule et stable vis-a-vis de l'eau sterilisee au chlore Download PDF

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Publication number
WO2002085978A1
WO2002085978A1 PCT/JP2002/003776 JP0203776W WO02085978A1 WO 2002085978 A1 WO2002085978 A1 WO 2002085978A1 JP 0203776 W JP0203776 W JP 0203776W WO 02085978 A1 WO02085978 A1 WO 02085978A1
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Prior art keywords
rubber
component
composition according
rubber composition
ethylene
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PCT/JP2002/003776
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English (en)
Japanese (ja)
Inventor
Hachiro Hisada
Original Assignee
Three Bond Co., Ltd.
Threebond Rubber Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2001120512A external-priority patent/JP2002317084A/ja
Priority claimed from JP2001286666A external-priority patent/JP2003096253A/ja
Application filed by Three Bond Co., Ltd., Threebond Rubber Co., Ltd. filed Critical Three Bond Co., Ltd.
Publication of WO2002085978A1 publication Critical patent/WO2002085978A1/fr

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    • 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

Definitions

  • the present invention is chlorine (C 1 2), hypochlorous acid (HC 1 0), relates to a stable rubber composition in water containing chlorine-based substances such as hypochlorite ion (C 1 ⁇ I), in particular
  • the present invention relates to a chlorine-resistant rubber composition used for equipment that comes into contact with tap water containing a chlorine-based germicide. Background technology>
  • Sterilizing tap water in Japan is C 1 2 (chlorine) or N a C 1 O chlorine pasteurization due to (sodium hypochlorite) is mainly.
  • the concentration of available chlorine in the water supply is generally in the range of 0.5 to 1.0 PPM, but there are some areas with a high concentration of about 1.5 PPM.
  • the pollution of rivers, lakes, etc., which are water sources has progressed, and the amount of chlorine-based disinfectants used for sterilization has tended to increase.
  • various types of hot water supply equipment, dishwashing equipment, and solar systems have become widespread, and these equipments are used in various places.
  • pressure-reducing valve equipment and pumping equipment used in high-rise houses have become widespread, and as a result, the use of connecting equipment for connecting water distribution pipes in various places has increased.
  • ethylene-propylene-gen-terpolymer, phenol-formaldehyde resin and phthalic acid-based prepolymer Water-resistant rubber (JP-A-9-1249778), a chlorine-resistant water-resistant rubber blended with ethylene-propylene rubber and hydrogenated phthalonitrile 'butadiene rubber (JP-A-9-157464), and ethylene-propylene rubber.
  • Chlorinated water-resistant rubber obtained by adding dipheninoleamine and menolecaptobenzimidazole to butadiene rubber and butadiene rubber (Japanese Patent Laid-Open No. 10-60 / 198), and fluororesin fine powder to ethylene propylene rubber.
  • the above-mentioned conventional chlorine-resistant rubber has not yet reached sufficient chlorine resistance.
  • fluorine-based rubber that has excellent weather resistance such as chemical resistance.
  • This fluorine-based rubber is expensive and may have poor physical properties other than chemical resistance.
  • the present invention has durability against water containing a chlorine-based disinfectant, and more specifically, even if it has been in contact with or immersed in cold, hot, or hot water for a long time, the chlorine-based disinfection
  • An object of the present invention is to provide a rubber composition which is extremely resistant to deterioration by a chemical agent, has durability comparable to that of a fluororubber, has excellent physical properties, is inexpensive and has high chlorine resistance.
  • the present inventor has conducted intensive studies on the mechanism by which chlorine-based sterilizing water deteriorates rubber, and as a result, has found that the above-mentioned object can be achieved by providing the following rubber composition.
  • (b) rubber material having a double bond in the main chain and / or a double bond in the main chain (C) a filler;
  • the rubber composition (the first embodiment of the present invention);
  • A a saturated synthetic rubber having substantially no double bond in the main chain; (c) a filler; (d) a vulcanizing agent; (e) a vulcanization accelerator; ( f) A rubber composition containing a divalent or higher valent metal fatty acid salt; and (g) an organotin compound (the second embodiment of the present invention).
  • the component (a) “saturated synthetic rubber having substantially no double bond in the main chain” that constitutes the present invention is a basic material for vulcanized rubber such as elongation and tensile strength of rubber after vulcanization. It is responsible for the physical properties, and it is effective to use a rubber material containing as few unsaturated groups as possible so as not to be deteriorated by chlorine contained in tap water and the like.
  • E PDM ethylene-propylene-one rubber
  • EPM ethylene-propylene rubber
  • H-NBR hydrogenated-tolylbutadiene rubber
  • CSM chlorosulfonated polyethylene
  • CPE chlorinated polyethylene
  • CHR epichlorohydrin rubber
  • ACM acrylic rubber
  • the component (b) a rubber material having a double bond in a main chain; // Synthetic resin having a double bond in the main chain ”1S It seems that the chlorine resistance of the rubber product after vulcanization is improved.
  • the double bond in the (b) component contained in the rubber product after vulcanization binds preferentially to chlorine, and the chlorine-substituted site is close to hydrogen and dehydrochlorinated. It is thought that repeating the reaction does not make it possible to incorporate a large amount of chlorine into the molecule. For this reason, the attack of chlorine on the saturated rubber described in (a) above is reduced, and the polymer chain is less likely to be broken. Therefore, it is considered that the rubber does not deteriorate and the chlorine resistance is remarkably improved.
  • the rubber composition of the second embodiment of the present invention may be similarly blended with the component (b).
  • any rubber material or resin having an unsaturated bond in the molecule can be used, but the degree of unsaturation is suitably 5% or more.
  • the degree of unsaturation used here will be described using styrene rubber (SBR styrene-butadiene copolymer rubber) as an example.
  • SBR styrene rubber
  • 5% of unsaturation as used herein can be expressed as X / X + y 5 ° / 0 , in other words, the copolymer contains 5% or more of butadiene segments It can be styrene rubber.
  • the benzene ring (P h) also has a double bond in the styrene segment, but the double bond in this case is not present in the main chain of the molecule but in the side chain, and therefore is not present in the present invention. It is not considered in saturation. Also, (one CH 2 — C
  • Specific examples of rubber materials having a double bond in the main chain include natural rubber (NR), isoprene rubber (IR), styrene rubber (SBR), butadiene rubber (BR), petroleum rubber (NBR), and chloroprene rubber (CR ) Etc. are raised.
  • the butyl rubber (IIR) obtained by copolymerizing an isoprene segment having no double bond in the main chain and an isoprene segment having a double bond in the main chain is mostly commercially available. Is not more than a few% (unsaturation degree is less than 5%), and thus is not often suitable for the first embodiment of the present invention.
  • synthetic resins having a double bond in the main chain include styrene-butadiene-styrene block copolymer (SB S), styrene-isoprene-styrene block copolymer (SIS), polymethyl methacrylate (PMMA), and polyacetic acid.
  • SB S styrene-butadiene-styrene block copolymer
  • SIS styrene-isoprene-styrene block copolymer
  • PMMA polymethyl methacrylate
  • PVA c acrylonitrile-butadiene-styrene copolymer
  • ABS unsaturated polyester
  • the amount of the component (b) is preferably 5 to 50 parts by weight, more preferably 10 to 35 parts by weight, per 100 parts by weight of the component (a). If the amount of component (b) is less than 5 parts by weight, effective chlorine resistance may not be obtained, and if it exceeds 50 parts by weight, rubber properties after vulcanization may be reduced.
  • filler (c) used in the present invention conventionally known fillers can be used. Specifically, inorganic materials such as carbon black, silicic acid, silicates, calcium carbonate, magnesium carbonate, clay, talc, bentonite, sericite, myriki, Ryosubest, calcium silicate, alumina hydrate, barium sulfate, etc.
  • examples of the filler include organic fillers such as polyethylene resin, polypropylene resin, styrene resin, coumarone-indene resin, melamine resin, phenol resin, and cork powder.
  • the amount of the filler is 0.1 to 200 parts by weight based on 100 parts by weight of the component (a), but the amount is outside the above range depending on the type of the filler. May also be blended. These fillers may be arbitrarily determined in kind and amount in accordance with the purpose.
  • vulcanizing agent crosslinking agent
  • vulcanization accelerator used in the present invention
  • conventionally known ones can be used.
  • the vulcanizing agent include sulfur compounds such as sulfur, powdered sulfur, sulfur white, precipitated sulfur, colloidal sulfur, sulfur chloride, inorganic compounds such as selenium, tellurium, zinc oxide, magnesium oxide, and lead monoxide, and morpholine disulfide.
  • organic vulcanizing agents such as organic sulfur compounds such as phenols, alkylphenol disulfides and thiuram disulfides, dithiolbamates, oximes, dinitroso compounds, polyamines and organic peroxides.
  • the vulcanization accelerator examples include metal oxides such as zinc oxide and magnesium oxide, metal hydroxides such as hydroxylic acid, fatty acids such as stearic acid, oleic acid, and lauric acid, and fatty acids such as zinc stearate. Derivatives, amines such as diethanolamine, triethanolamine and dihexylhexylamine, and various organic compounds such as thiazoles, sulfinamides, thiurams and dithioates are listed. These vulcanizing agents and vulcanization accelerators can be used as a mixture of two or more kinds, and if necessary, a conventionally known vulcanization aid may be used in combination. The amount of the vulcanizing agent or vulcanization accelerator added may be within the range of conventionally known amounts, and is appropriately determined depending on the type of the rubber material and other compounds.
  • Examples of the (f) divalent or higher valent metal fatty acid salt used in the second embodiment of the present invention include, for example, metals of higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid and oleic acid.
  • Examples of the metal element include salts of divalent or more metals such as zinc, calcium, tin, barium, lead, cadmium, and strontium that can form a salt with the fatty acid.
  • stearic acid-based metal salts are preferred as fatty acids. Particularly preferred are calcium stearate, zinc stearate and tin stearate.
  • the (g) organotin compound used in the second embodiment of the present invention particularly, octyltin mercapto, octyltin malate, monooctyltin mercapto, dibutyltin mercapto, dibutyltin malate, Diptyl tin lauray Examples of each compound can be exemplified.
  • the amount of the component (f) added to the rubber composition of the present invention is preferably 0.3 to 10 parts by weight, particularly preferably 1 to 5 parts by weight, based on 100 parts by weight of the rubber material. If the amount is less than 0.3 part by weight, the improvement of chlorine resistance may be insufficient.If the amount is more than 10 parts by weight, it is difficult to uniformly disperse in the composition, and the physical properties of the rubber after vulcanization deteriorate. May be.
  • the amount of the component (g) is preferably from 0.2 to 8 parts by weight, more preferably from 0.5 to 5 parts by weight, based on 100 parts by weight of the rubber material.
  • the amount is less than 0.5 part by weight, the improvement of chlorine resistance may be insufficient. If the amount is more than 8 parts by weight, it is applied to the rubber surface after vulcanization to impair the appearance of the product or the physical properties of the rubber. May be reduced.
  • various additives can be used according to the intended use of the rubber product after vulcanization.
  • Epoxylated vegetable oils such as tin lalate compounds, hydrotalcites, epoxidized soybean oil, epoxy linseed oil, and epoxidized cotton oil may be added.
  • the hydrotalcites as used herein are natural hydrotalcite or synthetic hydrated talcite, and the added amount thereof is 0.2 to 10 parts by weight based on 100 parts by weight of the component (a). And more preferably 0.5 to 3 parts by weight. If the amount is less than 0.2 part by weight, the effect may not be confirmed. If the amount exceeds 10 parts by weight, the rubber properties after vulcanization may be deteriorated.
  • epoxidized vegetable oil examples include epoxidized soybean oil, epoxidized linseed oil, epoxidized cotton oil, and the like.
  • the amount of the epoxidized vegetable oil is 1.0 with respect to 100 parts by weight of the component (a). It is preferably from 10 to 10 parts by weight, more preferably from 1 to 7 parts by weight. If the amount is less than 1.0 part by weight, the effect may not be confirmed. If the amount is more than 10 parts by weight, mold contamination during the vulcanization step and bleeding from the vulcanized rubber tend to occur.
  • the present invention further includes a known vulcanization aid added to an ordinary rubber composition, a processing aid.
  • Agents, antioxidants, sequestering agents, softeners, coloring agents, fillers and the like may be added.
  • the rubber composition of the present invention is usually produced as a product by kneading the above-described components, forming the mixture into a desired shape, and then vulcanizing the mixture.
  • a specific molding and vulcanizing method conventionally known methods such as injection molding, pressure (press) molding, extrusion molding, calendar molding, and the like can be used. Pressing at 80 ° C to 50 to 300 kgf / cm 2 and vulcanizing for 2 to 30 minutes enable molding. Other methods can be easily formed by appropriately selecting the conditions. Also, secondary vulcanization may be performed if necessary. Examples>
  • the components were kneaded at the mixing ratios shown in Tables 1A to 6A to obtain a uniform vulcanized rubber composition.
  • the vulcanized rubber composition is subjected to any conditions (temperature: 160 to 175 ° C, time: 7 to: about 0 minutes, pressurization: 180 kgf / cm 2 : Is arbitrarily set according to the type of rubber material and the type of crosslinking agent, the amount added, etc.) to obtain a rubber sheet of t 2 (thickness 2 mm) and 250 ⁇ (250 mm x 250 mm).
  • Magnesium oxide and calcium hydroxide are vulcanization accelerators for fluoro rubber.
  • Example 1 IngredientsExample 1 A Example 2 A Example 3 A Example 4 A Example 5 A Example 6 A Example 7 A Example 8 A Example 9 A Example 10 A Rubber material Esplene 524 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0
  • Example 11 A Example 12A Example 13 A Example 14 A Example 1 A Example lb A ⁇ ⁇ 1 J 1 / AM lo A ⁇ ⁇ ReiUA Rubber material Esplene 5 24 ⁇ 0 ⁇ 0 100.0 100.0 100.0 100.0 100 .o 100.0 100.0 100.0
  • Magnesium oxide and calcium hydroxide are vulcanization accelerators for fluoro rubber.
  • Esprene 524 Sumitomo Chemical Industries Ethylene Propylene Gen Rubber (E PDM)
  • -Zetpol 1 020 Hydrogenated nitrile butadiene rubber (H-NBR) manufactured by Zeon Corporation
  • IR 2200 Polyisoprene rubber (IR) manufactured by Zeon Corporation
  • NBR Zeon Etoryl Butadiene Rubber
  • Viton E 60 C Fluoro rubber manufactured by Dupont 'Dow' Elastomer Co., Ltd. The vulcanizing agent is already contained in the system.
  • Vulcanization type 1 (sulfur type)
  • -Noxeller CZ Vulcanization accelerator manufactured by Ouchi Shinko Chemical Co., Ltd. (main component: N-cyclohexinoleyl 2-benzothiazolyl snoride)
  • Noxeller II Vulcanization accelerator manufactured by Ouchi Shinko Chemical Co., Ltd. (main component: 2-mercaptobenzothiazolone)
  • Acting S L Vulcanization accelerator manufactured by Yoshitomi Pharmaceutical Co., Ltd. (main component: adduct of dicyclohexylamine and ethylene glycol)
  • Vulcanization system 2 (peroxide system)
  • Perhexa 25B Organic peroxide manufactured by NOF Corporation (main component: 2,5-dimethyl-2,5-di (t-butylperoxy) hexane)
  • -Peroximon F40 Organic peroxide manufactured by NOF Corporation (main component: ⁇ , ⁇ -bis (t-butynolezoleoxy-m-isopropyl) benzene)
  • NOCRAC CD Ouchi Shinko Chemical Co., Ltd. Antioxidant (main component: 4, 4 '_ bis (alpha, alpha _ dimethylcarbamoyl Honoré benzyl) Jifue - / Reamin)
  • Nocrack MB Antioxidant manufactured by Ouchi Shinko Chemical Co., Ltd. (main component: 2-mercaptobenzimidazole)
  • TP-955 Plasticizer manufactured by Sanyo Trading Co., Ltd. (dibutoxetoxetil adipate)
  • (b) a rubber material having a double bond in the main chain and Z or a synthetic resin having a double bond in the main chain it is about 500 hours by weight.
  • the carbon powder of the filler does not fall off, there is a case where the carbon powder does not fall off even if it exceeds 100 hours when more than 10 parts by weight is blended.
  • the rubber material alone having a double bond in the main chain has no chlorine resistance at all.
  • the rubber composition of the present invention has rubber properties equal to or higher than that of the fluorine-based rubber even after immersion in chlorine-containing water for more than 100 hours, It turns out that it has sufficient durability.
  • Rubber that has not dropped carbon powder for more than 100 hours has comparable durability in general rubber physical properties to fluorocarbon rubber, or has sufficient durability. It is easy to manufacture a product for the purpose by arbitrarily selecting and blending the components of (e), and a rubber product with low cost can be obtained.
  • Examples 1B to 18B, Comparative Examples 1B to 41B The components were kneaded at the mixing ratios shown in Tables 1B to 8B to obtain a uniform vulcanized rubber composition.
  • the vulcanized rubber composition is vulcanized by applying a pressure (180 kgi / cm 2 ) at 160 to 180 ° C for about 10 minutes, and t 2 (thickness 2 mm), 250 ⁇ (250 mm x 250 mm) of a rubber sheet.
  • Zinc oxide 0.V 0. ⁇ 0.n 5 0 5.0 5.0
  • Example 15B Example 6B
  • Example 7B Example 8B
  • Example 9B Example 10B Comparative fe 16B Comparative car father 17B Comparative car father 18B Esplen 20 1 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Stearic acid 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0
  • DHT-4 A one 0.5 0.5 one Ade forcer 0 — 1 30 P — two —. 4,0 Sulfur 2.0 2.0 2.0 2.0 1.0 2.0 t Axel CZ 2.0 2.0 2.0 2.0 2.0 2.0 en en Axel DM 0.8 0.8 0.8 0, 8 0.8 0.8 Axel TMT 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
  • DHT-4A one — 0.5 0.5 — Ade force sizer 0 — 1 30 P two 4.0
  • ESPREN 606 40 PHR oil-extended ethylene propylene gen rubber (EPDM) manufactured by Sumitomo Chemical Co., Ltd.
  • Esplen 201 Ethylene propylene rubber (EPM)-Sumpol 1041 manufactured by Sumitomo Chemical Co., Ltd.
  • Mistron Trooper White reinforcement made by Nippon Mistron (main component: magnesium silicate)
  • P—21OA—5 A mixture of zinc and calcium fatty acid salts and hydrotalcite manufactured by Kyodo Yakuhin.
  • KS-43D-2 Dioctyltin mercapto compound manufactured by Kyodo Yakuhin
  • Adeiki Saiser O—130P Epoxidized soybean oil manufactured by Adeka Gas Chemical Co., Ltd.
  • Axel CZ Vulcanization accelerator manufactured by Kawaguchi Chemical Industry Co., Ltd. (Main component: N-cyclohexyl-2-benzothiazonolacenolefenamide)
  • Axel TMT Vulcanization accelerator manufactured by Kawaguchi Chemical Co., Ltd. (main component: tetramethylthiuramidine sulfide)
  • Axel DM Vulcanization accelerator manufactured by Kawaguchi Chemical Industry Co., Ltd. (Main ingredient: 2-benzothiazoyl) Do,)
  • TMP T Trimethylolpropane triatarylate
  • TA IC Nippon Kasei's organic peroxide vulcanization aid (main component: triallyl isocyanate)
  • Peroximon F40 Organic peroxide manufactured by NOF Corporation
  • Antage MB Anti-aging agent manufactured by Kawaguchi Chemical Co., Ltd. (Main ingredient 2
  • Antage RD Anti-aging agent manufactured by Kawaguchi Chemical Co., Ltd. (main component 2,2,4-trimethyl-1,1,2-dihydroquinoline)
  • T P-95 Plasticizer manufactured by Sanyo Trading Co., Ltd.
  • the rubber after vulcanization of the rubber composition of the present invention has sufficient chlorine resistance up to 168 hours. That is, in a system to which only one of (f) a divalent or higher valent metal fatty acid salt and (g) an organotin compound is added, almost no improvement in chlorine resistance is observed. Also, from Tables 1B and 2B, when EPDM is used, there is no difference in performance when using either vulcanization system 1 (sulfur system) or vulcanization system 2 (peroxide system). I could't see it.
  • the present invention has durability against water containing a chlorine-based disinfectant. It is possible to provide a rubber composition which receives extremely little and has extremely improved durability and high chlorine resistance.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un mélange caoutchouté sensiblement exempt de fluor et comprenant comme ingrédients principaux (a) un caoutchouc synthétique saturé sensiblement exempt de liaison double dans la chaîne principale, (b) un matériau caoutchouc et/ou une résine synthétique ayant respectivement des liaisons doubles dans la chaîne principale, (c) une charge, (d) un agent de vulcanisation, et (e) un accélérateur de vulcanisation, sachant que l'ingrédient (b) a un degré de non saturation de minimum 5 % ; ou un mélange cacoutchouté sensiblement exempt de fluor et comprenant comme ingrédients principaux (a) un caoutchouc synthétique saturé sensiblement exempt de liaison double dans la chaîne principale, (c) une charge, (d) un agent de vulcanisation, (e) un accélérateur de vulcanisation, (f) un sel d'acide gras d'un métal ayant une valence d'au moins 2, et (g) un composé organostannique. Les mélanges caoutchoutés permettent d'obtenir un caoutchouc moulé ayant une résistance à l'eau contenant un bactéricide à base de chlore. De manière plus spécifique, même en contact avec ou immergé dans de l'eau froide, tiède ou chaude pendant longtemps, le caoutchouc est beaucoup altéré par le bactéricide à base de chlore. Le caoutchouc a une durabilité nettement améliorée et une grande résistance au chlore.
PCT/JP2002/003776 2001-04-19 2002-04-16 Melanges caoutchoutes destines a du caoutchouc moule et stable vis-a-vis de l'eau sterilisee au chlore WO2002085978A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2001120512A JP2002317084A (ja) 2001-04-19 2001-04-19 塩素系殺菌水に安定な加硫ゴム組成物及びゴム成形体
JP2001-120512 2001-04-19
JP2001-286666 2001-09-20
JP2001286666A JP2003096253A (ja) 2001-09-20 2001-09-20 塩素系殺菌水に安定なゴム組成物

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007100064A1 (fr) * 2006-03-01 2007-09-07 Jsr Corporation Composition de caoutchouc, caoutchouc reticule et article moule
CN102153788A (zh) * 2011-02-21 2011-08-17 江苏荣昌机械制造集团有限公司 压路机减震块的注射成型工艺

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JPS6234925A (ja) * 1985-08-08 1987-02-14 Osaka Soda Co Ltd ブレンドゴムホ−ス
JPH01299848A (ja) * 1988-05-27 1989-12-04 Showa Denko Kk ゴム組成物
JPH01306439A (ja) * 1988-06-04 1989-12-11 Showa Denko Kk ゴム組成物
JPH04353543A (ja) * 1991-05-31 1992-12-08 Hitachi Metals Ltd 耐塩素水性ゴム組成物及び耐塩素水性ゴム製品
JPH05140334A (ja) * 1991-11-15 1993-06-08 Nippon Valqua Ind Ltd 代替フロン用ゴム成形体およびその製造方法
JPH05230300A (ja) * 1992-02-24 1993-09-07 Hitachi Metals Ltd 耐塩素水性ゴム組成物及びそのゴム製品
JPH08291242A (ja) * 1995-02-22 1996-11-05 Nitto Kasei Co Ltd 高温加工に適したハロゲン含有樹脂組成物
JPH08336935A (ja) * 1995-06-14 1996-12-24 Daiso Co Ltd ゴム積層体
JPH09157464A (ja) * 1995-12-05 1997-06-17 Fujikura Rubber Ltd シール材用のゴム組成物
JP2001206987A (ja) * 2000-01-26 2001-07-31 Tokai Rubber Ind Ltd ゴム組成物、積層体及びホース

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS53125456A (en) * 1977-04-09 1978-11-01 Osaka Soda Co Ltd Crosslinked rubber blend composition
JPS6234925A (ja) * 1985-08-08 1987-02-14 Osaka Soda Co Ltd ブレンドゴムホ−ス
JPH01299848A (ja) * 1988-05-27 1989-12-04 Showa Denko Kk ゴム組成物
JPH01306439A (ja) * 1988-06-04 1989-12-11 Showa Denko Kk ゴム組成物
JPH04353543A (ja) * 1991-05-31 1992-12-08 Hitachi Metals Ltd 耐塩素水性ゴム組成物及び耐塩素水性ゴム製品
JPH05140334A (ja) * 1991-11-15 1993-06-08 Nippon Valqua Ind Ltd 代替フロン用ゴム成形体およびその製造方法
JPH05230300A (ja) * 1992-02-24 1993-09-07 Hitachi Metals Ltd 耐塩素水性ゴム組成物及びそのゴム製品
JPH08291242A (ja) * 1995-02-22 1996-11-05 Nitto Kasei Co Ltd 高温加工に適したハロゲン含有樹脂組成物
JPH08336935A (ja) * 1995-06-14 1996-12-24 Daiso Co Ltd ゴム積層体
JPH09157464A (ja) * 1995-12-05 1997-06-17 Fujikura Rubber Ltd シール材用のゴム組成物
JP2001206987A (ja) * 2000-01-26 2001-07-31 Tokai Rubber Ind Ltd ゴム組成物、積層体及びホース

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007100064A1 (fr) * 2006-03-01 2007-09-07 Jsr Corporation Composition de caoutchouc, caoutchouc reticule et article moule
JPWO2007100064A1 (ja) * 2006-03-01 2009-07-23 Jsr株式会社 ゴム組成物、架橋ゴム、及び成形品
CN102153788A (zh) * 2011-02-21 2011-08-17 江苏荣昌机械制造集团有限公司 压路机减震块的注射成型工艺
CN102153788B (zh) * 2011-02-21 2012-03-14 江苏荣昌机械制造集团有限公司 压路机减震块的注射成型工艺

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