WO2020196272A1 - Composition de caoutchouc réticulé et produit en caoutchouc l'utilisant - Google Patents

Composition de caoutchouc réticulé et produit en caoutchouc l'utilisant Download PDF

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Publication number
WO2020196272A1
WO2020196272A1 PCT/JP2020/012316 JP2020012316W WO2020196272A1 WO 2020196272 A1 WO2020196272 A1 WO 2020196272A1 JP 2020012316 W JP2020012316 W JP 2020012316W WO 2020196272 A1 WO2020196272 A1 WO 2020196272A1
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WIPO (PCT)
Prior art keywords
rubber composition
crosslinked rubber
mass
content
composition according
Prior art date
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PCT/JP2020/012316
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English (en)
Japanese (ja)
Inventor
莉恵 森本
尚 松田
Original Assignee
バンドー化学株式会社
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.)
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Application filed by バンドー化学株式会社 filed Critical バンドー化学株式会社
Priority to JP2020516948A priority Critical patent/JP6804010B1/ja
Publication of WO2020196272A1 publication Critical patent/WO2020196272A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment

Definitions

  • the present invention relates to a crosslinked rubber composition and a rubber product using the crosslinked rubber composition.
  • Patent Document 1 discloses a crosslinked rubber composition containing an ethylene / propylene copolymer modified with a carboxylic acid and having an ethylene content of 10 to 60 mol% as a rubber component.
  • Patent Document 2 discloses a crosslinked rubber composition containing an ethylene-propylene-diene ternary copolymer modified with an unsaturated carboxylic acid and having an ethylene content of 40 to 99 mol% as a rubber component.
  • the present invention carboxylic acid-modified an ethylene / propylene / non-conjugated diene copolymer having an ethylene content of 40% by mass or more and 70% by mass or less and a non-conjugated diene content of 0.5% by mass or more and 8.5% by mass or less. It is a crosslinked rubber composition containing the subjected acid-modified EPDM as a main component of the rubber component.
  • the present invention is a rubber product in which the product body is formed of the crosslinked rubber composition of the present invention.
  • the crosslinked rubber composition according to the embodiment contains ethylene, propylene, and non-conjugated diene having an ethylene content of 40% by mass or more and 70% by mass or less and a non-conjugated diene content of 0.5% by mass or more and 8.5% by mass or less.
  • the main component of the rubber component is acid-modified EPDM (hereinafter referred to as "acid-modified EPDM-A”) obtained by modifying a polymer (hereinafter referred to as "base EPDM-A”) with carboxylic acid.
  • the base EPDM-A having an ethylene content of 40% by mass or more and 70% by mass or less and a non-conjugated diene content of 0.5% by mass or more and 8.5% by mass or less is carboxylic.
  • the acid-modified acid-modified EPDM-A as the main component of the rubber component, the effect of the filler can be effectively obtained. It is presumed that this is because the main component of the rubber component is acid-modified EPDM-A, so that high dispersibility of the filler can be obtained.
  • the rubber component mainly contains acid-modified EPDM-A, its content is more than 50% by mass.
  • the content of the acid-modified EPDM-A in the rubber component is preferably 80% by mass or more, more preferably 90% by mass or more, and most preferably 100% by mass.
  • the rubber component may contain an ethylene- ⁇ -olefin elastomer other than acid-modified EPDM-A, and other chloroprene rubber (CR), chlorosulfonated polyethylene rubber (CSM), hydrogenated acrylonitrile rubber ( H-NBR) and the like may be included.
  • CR chloroprene rubber
  • CSM chlorosulfonated polyethylene rubber
  • H-NBR hydrogenated acrylonitrile rubber
  • the ethylene content in the base EPDM-A before carboxylic acid modification is 40% by mass or more and 70% by mass or less, from the viewpoint of suppressing deterioration of processability due to crystallization of the ethylene component and effectively obtaining the effect of the filler. It is preferably 51% by mass or more and 66% by mass or less, and more preferably 53% by mass or more and 57% by mass or less.
  • the propylene content in the base EPDM-A is preferably 30% by mass or more and 50% by mass or less, and more preferably 35% by mass or more and 45% by mass or less from the viewpoint of effectively obtaining the effect of the filler.
  • the ratio of the ethylene content to the propylene content in the base EPDM-A is preferably 0.60 or more and 2.4 or less, more preferably 1.0 or more, from the viewpoint of effectively obtaining the effect of the filler. It is 1.5 or less.
  • non-conjugated diene component of the base EPDM-A examples include ethylidene nobornene (ENB), dicyclopentadiene, 1,4-hexadiene and the like. Of these, the non-conjugated diene component is preferably ethylidene norbornene (ENB).
  • ENB ethylidene norbornene
  • the non-conjugated diene content of the base EPDM-A is 0.5% by mass or more and 8.5% by mass or less, and suppresses a decrease in processability due to cross-linking and gelation between the polymers due to a side reaction during modification.
  • the ratio of the ethylene content to the non-conjugated diene content (ethylene content / non-conjugated diene content) in the base EPDM-A is preferably 5.0 or more and 140 or less, more preferably 10 or more, from the viewpoint of effectively obtaining the effect of the filler. It is 12 or less.
  • Examples of the carboxylic acid modification of the acid-modified EPDM-A include maleic anhydride modification, maleic acid modification, itaconic anhydride modification, itaconic acid modification, fumaric acid modification, methacrylic acid modification, acrylic acid modification and the like.
  • the carboxylic acid modification of the acid-modified EPDM-A preferably contains one or more of these, and more preferably contains maleic anhydride modification from the viewpoint of effectively obtaining the effect of the filler.
  • the base EPDM-A, the carboxylic acid, and the reaction initiator are put into a closed kneader such as a kneader or a Banbury mixer, and kneaded for a predetermined time at a predetermined temperature at which the reaction initiator decomposes. It can be obtained by grafting a carboxylic acid to the base EPDM-A.
  • the reaction initiator include dialkyl peroxides such as dicumyl peroxide; peroxyesters such as t-butylperoxyacetate; ketone peroxides such as dicyclohexanone peroxide; and di (4-tert-butyl). Includes organic peroxides such as cyclohexan) peroxydicarbonate.
  • the acid-modified EPDM-A can also be obtained by a modification means such as ultraviolet irradiation.
  • the rubber component is cross-linked between molecules, it may be cross-linked by using an organic peroxide as a cross-linking agent, or may be cross-linked by using sulfur as a cross-linking agent. They may be used together and crosslinked. Further, the rubber component may be crosslinked by using an electron beam or the like.
  • Examples of the filler compounded in the crosslinked rubber composition according to the embodiment include silica, carbon black, titanium oxide, aluminum oxide, calcium carbonate, magnesium carbonate, zinc carbonate, barium sulfate, diatomaceous earth, clay, talc and the like. Be done.
  • the filler preferably contains one or more of these, and more preferably contains silica from the viewpoint of effectively obtaining the reinforcing effect of the filler.
  • silica blended as the filler examples include wet silica such as sedimentation silica and gel silica; and synthetic silica such as dry silica such as calcining silica and arc silica.
  • the silica preferably contains one or more of these, and more preferably contains an immunoprecipitated silica from the viewpoint of effectively obtaining the reinforcing effect of silica.
  • the BET specific surface area of silica measured based on ISO9277 is, for example, 150 m 2 / g or more and 200 m 2 / g or less.
  • the primary particle size of silica is, for example, 10 nm or more and 50 nm or less, and the secondary particle size of the silica aggregate is, for example, 1 ⁇ m or more and 40 ⁇ m or less.
  • the silica content of the filler in the crosslinked rubber composition according to the embodiment is preferably 20 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the rubber component from the viewpoint of effectively obtaining the reinforcing effect of silica. It is preferably 30 parts by mass or more and 50 parts by mass or less.
  • the crosslinked rubber composition according to the embodiment may also contain a processing aid, a vulcanization accelerator, a vulcanization accelerator, a plasticizer, an antiaging agent and the like as a rubber compounding agent.
  • the strain amount of the crosslinked rubber composition according to the embodiment is 1%, and the storage elastic modulus G'(100 ° C.) at 100 ° C. is preferably 1.0 MPa or more and 5.0 MPa or less, more preferably 2.0 MPa or more and 4.0 MPa. It is as follows. This storage elastic modulus G'(100 ° C.) is measured based on JIS K6394: 2007.
  • the tensile stress M 100 at 100% elongation of the crosslinked rubber composition according to the embodiment at 25 ° C. is preferably 2.0 MPa or more, more preferably 3.0 MPa or more.
  • the tensile stress M 100 at 100% elongation at 25 ° C. is measured based on JIS K6251: 2010.
  • the tensile strength TB of the crosslinked rubber composition according to the embodiment at 25 ° C. is preferably 12.6 MPa or more, more preferably 13.0 or more.
  • the tensile strength TB at 25 ° C. is measured based on JIS K6251: 2010.
  • the crosslinked rubber composition according to the above embodiment is prepared by kneading a rubber component, a filler, and other rubber compounding agents using a rubber kneader such as a kneader, a Banbury mixer, or an open roll to prepare an uncrosslinked rubber composition.
  • the uncrosslinked rubber composition can be obtained by crosslinking the uncrosslinked rubber composition at a predetermined temperature and a predetermined pressure.
  • the crosslinked rubber composition according to the embodiment is suitable for forming a product body of a rubber product, and specifically, for example, is suitable for forming a belt body of a transmission belt.
  • the effect of the filler can be effectively obtained.
  • Sheet-shaped crosslinked rubber compositions of Examples 1 and 2 and Comparative Examples below were prepared. Each configuration is also shown in Table 1.
  • maleic anhydride-modified EPDM1 was used as a rubber component, and 1 part by mass of precipitated silica (manufactured by Ultrazil VN3 Ebonic) as a filler for 40 parts by mass of the rubber component was processed.
  • Auxiliary agent stearic acid (Stearate S50 manufactured by Shin Nihon Rika Co., Ltd.), 5 parts by mass of vulcanization accelerator auxiliary agent zinc oxide (zinc oxide type 3 manufactured by Shiramizu Chemical Co., Ltd.), and 3.2 parts by mass of cross-linking agent organic
  • An uncrosslinked rubber composition was prepared by blending and kneading a peroxide (Parkmill D, manufactured by Nippon Oil & Fats Co., Ltd., dicumyl peroxide). Then, this uncrosslinked rubber composition was press-molded to obtain a sheet-shaped crosslinked rubber composition.
  • the obtained sheet-shaped crosslinked rubber composition was designated as Example 1.
  • Example 2 In a closed kneader, together with EPDM, 1 part by mass of maleic anhydride and 0.8 parts by mass of reaction initiator organic peroxide (manufactured by Percadox 16 Chemical Axo) with respect to 100 parts by mass of EPDM. (4-tert-Butylcyclohexyl) peroxydicarbonate) was added, and they were kneaded at a temperature of 130 ° C. for 10 minutes to prepare maleic anhydride-modified EPDM2.
  • a sheet-shaped crosslinked rubber composition having the same composition as that of Example 1 was obtained except that the maleic anhydride-modified EPDM2 was used as the rubber component instead of the maleic anhydride-modified EPDM1.
  • the obtained sheet-shaped crosslinked rubber composition was designated as Example 2.
  • Test results The test results are shown in Table 1. According to this, Examples 1 and 2 using maleic anhydride-modified EPDM 1 or 2 as the rubber component have a storage elastic modulus at 100 ° C. as compared with a comparative example using EPDM not acid-modified as the rubber component. It can be seen that while G'(100 ° C.) is low, the tensile stress M 100 and the tensile strength TB at 100% elongation at 25 ° C. are high. It is presumed that this is because the main component of the rubber component is maleic anhydride-modified EPDM1 or 2, which provides high dispersibility of the precipitation silica of the filler.
  • the present invention is useful in the technical fields of crosslinked rubber compositions and rubber products using them.

Abstract

Cette composition de caoutchouc réticulé contient, en tant que constituant principal de composants de caoutchouc, un EPDM modifié par un acide obtenu par la réalisation d'une modification par acide carbonique sur un copolymère d'éthylène/propylène/diène non conjugué ayant une teneur en éthylène de 40 à 70 % en masse et une teneur en diène non conjugué de 0,5 à 8,5 % en masse.
PCT/JP2020/012316 2019-03-26 2020-03-19 Composition de caoutchouc réticulé et produit en caoutchouc l'utilisant WO2020196272A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022145493A1 (fr) * 2020-12-31 2022-07-07 Bridgestone Corporation Utilisation d'epdm à fonction thiol dans des compositions de caoutchouc

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60248746A (ja) * 1984-05-24 1985-12-09 Sumitomo Chem Co Ltd 表面処理剤組成物
JPS6241245A (ja) * 1985-08-19 1987-02-23 Sumitomo Chem Co Ltd 加硫ゴム組成物
JPH03162437A (ja) * 1989-11-22 1991-07-12 Japan Synthetic Rubber Co Ltd 吸水性ポリマー複合体
JPH05112681A (ja) * 1991-02-22 1993-05-07 Arco Chem Technol Lp 結晶質プロピレンポリマーとスチレンコポリマーを含む樹脂ブレンド
JP2008050615A (ja) * 2007-10-10 2008-03-06 Riken Technos Corp 非ハロゲン系熱可塑性樹脂組成物
JP2012172692A (ja) * 2011-02-17 2012-09-10 Nsk Ltd 自動二輪車の車輪用回転速度検出装置
JP2012215248A (ja) * 2011-03-31 2012-11-08 Nitta Corp 歯付ベルト
WO2014133105A1 (fr) * 2013-02-28 2014-09-04 株式会社ブリヂストン Pneumatique
JP2016030810A (ja) * 2014-07-30 2016-03-07 三井化学株式会社 組成物、架橋体および用途

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60248746A (ja) * 1984-05-24 1985-12-09 Sumitomo Chem Co Ltd 表面処理剤組成物
JPS6241245A (ja) * 1985-08-19 1987-02-23 Sumitomo Chem Co Ltd 加硫ゴム組成物
JPH03162437A (ja) * 1989-11-22 1991-07-12 Japan Synthetic Rubber Co Ltd 吸水性ポリマー複合体
JPH05112681A (ja) * 1991-02-22 1993-05-07 Arco Chem Technol Lp 結晶質プロピレンポリマーとスチレンコポリマーを含む樹脂ブレンド
JP2008050615A (ja) * 2007-10-10 2008-03-06 Riken Technos Corp 非ハロゲン系熱可塑性樹脂組成物
JP2012172692A (ja) * 2011-02-17 2012-09-10 Nsk Ltd 自動二輪車の車輪用回転速度検出装置
JP2012215248A (ja) * 2011-03-31 2012-11-08 Nitta Corp 歯付ベルト
WO2014133105A1 (fr) * 2013-02-28 2014-09-04 株式会社ブリヂストン Pneumatique
JP2016030810A (ja) * 2014-07-30 2016-03-07 三井化学株式会社 組成物、架橋体および用途

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022145493A1 (fr) * 2020-12-31 2022-07-07 Bridgestone Corporation Utilisation d'epdm à fonction thiol dans des compositions de caoutchouc

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JPWO2020196272A1 (ja) 2021-04-08

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