WO2020196272A1 - Cross-linked rubber composition and rubber product using same - Google Patents

Cross-linked rubber composition and rubber product using same Download PDF

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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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rubber composition
crosslinked rubber
mass
content
composition according
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PCT/JP2020/012316
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French (fr)
Japanese (ja)
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莉恵 森本
尚 松田
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バンドー化学株式会社
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Priority to JP2020516948A priority Critical patent/JP6804010B1/en
Publication of WO2020196272A1 publication Critical patent/WO2020196272A1/en

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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

This cross-linked rubber composition contains, as the main constituent of rubber components, an acid-modified EPDM obtained by performing carbonic acid-modification on an ethylene/propylene/non-conjugated diene copolymer having an ethylene content of 40-70 mass% and a non-conjugated diene content of 0.5-8.5 mass%.

Description

架橋ゴム組成物及びそれを用いたゴム製品Crosslinked rubber composition and rubber products using it
　本発明は、架橋ゴム組成物及びそれを用いたゴム製品に関する。 The present invention relates to a crosslinked rubber composition and a rubber product using the crosslinked rubber composition.
　ゴム製品に用いられる架橋ゴム組成物として、カルボン酸変性されたエチレン－α－オレフィンエラストマーをゴム成分とするものが知られている。例えば、特許文献１には、エチレン含量が１０～６０モル％であり且つカルボン酸で変性されたエチレン・プロピレン共重合体をゴム成分とする架橋ゴム組成物が開示されている。特許文献２には、エチレン含量が４０～９９モル％であり且つ不飽和カルボン酸で変性されたエチレン・プロピレン・ジエン三元共重合体をゴム成分とする架橋ゴム組成物が開示されている。特許文献３には、エチレン：プロピレンのモル比＝３０：７０である無水マレイン酸変性エチレン・プロピレン共重合体をゴム成分とする架橋ゴム組成物が開示されている。 As a crosslinked rubber composition used for rubber products, one containing a carboxylic acid-modified ethylene-α-olefin elastomer as a rubber component is known. For example, 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. Patent Document 3 discloses a crosslinked rubber composition containing a maleic anhydride-modified ethylene / propylene copolymer having a molar ratio of ethylene: propylene = 30:70 as a rubber component.
特許第５０４９４２２号公報Japanese Patent No. 50494422 国際公開第２００９／１２３２２８号International Publication No. 2009/123228 特開２０１０－２０２７８４号公報JP-A-2010-202784
　本発明は、エチレン含量が４０質量％以上７０質量％以下で且つ非共役ジエン含量が０．５質量％以上８．５質量％以下であるエチレン・プロピレン・非共役ジエン共重合体をカルボン酸変性させた酸変性ＥＰＤＭをゴム成分の主体とする架橋ゴム組成物である。 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.
　本発明は、本発明の架橋ゴム組成物で製品本体が形成されたゴム製品である。 The present invention is a rubber product in which the product body is formed of the crosslinked rubber composition of the present invention.
　以下、実施形態について詳細に説明する。 Hereinafter, the embodiment will be described in detail.
　実施形態に係る架橋ゴム組成物は、エチレン含量が４０質量％以上７０質量％以下で且つ非共役ジエン含量が０．５質量％以上８．５質量％以下であるエチレン・プロピレン・非共役ジエン共重合体（以下、「ベースＥＰＤＭ-Ａ」という。）をカルボン酸変性させた酸変性ＥＰＤＭ（以下「酸変性ＥＰＤＭ-Ａ」という。）をゴム成分の主体とする。 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.
　実施形態に係る架橋ゴム組成物によれば、エチレン含量が４０質量％以上７０質量％以下で且つ非共役ジエン含量が０．５質量％以上８．５質量％以下であるベースＥＰＤＭ-Ａをカルボン酸変性させた酸変性ＥＰＤＭ-Ａをゴム成分の主体とすることにより、充填材による効果を有効に得ることができる。これは、ゴム成分の主体が酸変性ＥＰＤＭ-Ａであることにより、充填材の高い分散性が得られるためであると推測される。 According to the crosslinked rubber composition according to the embodiment, 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. By using 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.
　ここで、ゴム成分は、酸変性ＥＰＤＭ-Ａを主体として含むので、その含有量が５０質量％よりも多い。ゴム成分における酸変性ＥＰＤＭ-Ａの含有量は、好ましくは８０質量％以上、より好ましくは９０質量％以上、最も好ましくは１００質量％である。なお、ゴム成分は、酸変性ＥＰＤＭ-Ａ以外のエチレン－α－オレフィンエラストマーを含んでいてもよく、また、その他のクロロプレンゴム（ＣＲ）、クロロスルホン化ポリエチレンゴム（ＣＳＭ）、水素添加アクリロニトリルゴム（Ｈ－ＮＢＲ）等を含んでいてもよい。 Here, since 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-α-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.
　カルボン酸変性前のベースＥＰＤＭ-Ａにおけるエチレン含量は、４０質量％以上７０質量％以下であって、エチレン成分の結晶化による加工性低下を抑制するとともに、充填材による効果を有効に得る観点から、好ましくは５１質量％以上６６質量％以下、より好ましくは５３質量％以上５７質量％以下である。ベースＥＰＤＭ-Ａにおけるプロピレン含量は、充填材による効果を有効に得る観点から、好ましくは３０質量％以上５０質量％以下、より好ましくは３５質量％以上４５質量％以下である。ベースＥＰＤＭ-Ａにおけるエチレン含量のプロピレン含量に対する比（エチレン含量／プロピレン含量）は、充填材による効果を有効に得る観点から、好ましくは０．６０以上２．４以下、より好ましくは１．０以上１．５以下である。 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 (ethylene content / propylene content) 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.
　ベースＥＰＤＭ-Ａの非共役ジエン成分としては、例えば、エチリデンノボルネン（ＥＮＢ）、ジシクロペンタジエン、１，４－ヘキサジエン等が挙げられる。非共役ジエン成分は、これらのうちのエチリデンノボルネン（ＥＮＢ）が好ましい。ベースＥＰＤＭ-Ａの非共役ジエン含量は、０．５質量％以上８．５質量％以下であって、変性時に副反応によりポリマー間が架橋してゲル化することによる加工性低下を抑制するとともに、充填材による効果を有効に得る観点から、好ましくは１．９質量％以上７．４質量％以下、より好ましくは４．５質量％以上５．５質量％以下である。ベースＥＰＤＭ-Ａにおけるエチレン含量の非共役ジエン含量に対する比（エチレン含量／非共役ジエン含量）は、充填材による効果を有効に得る観点から、好ましくは５．０以上１４０以下、より好ましくは１０以上１２以下である。 Examples of the non-conjugated diene component of the base EPDM-A include ethylidene nobornene (ENB), dicyclopentadiene, 1,4-hexadiene and the like. Of these, the non-conjugated diene component is preferably ethylidene norbornene (ENB). 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. From the viewpoint of effectively obtaining the effect of the filler, it is preferably 1.9% by mass or more and 7.4% by mass or less, and more preferably 4.5% by mass or more and 5.5% by mass or less. 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.
　酸変性ＥＰＤＭ-Ａのカルボン酸変性としては、例えば、無水マレイン酸変性、マレイン酸変性、無水イタコン酸変性、イタコン酸変性、フマル酸変性、メタクリル酸変性、アクリル酸変性等が挙げられる。酸変性ＥＰＤＭ-Ａのカルボン酸変性は、これらのうちの１種又は２種以上を含むことが好ましく、充填材による効果を有効に得る観点から、無水マレイン酸変性を含むことがより好ましい。 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.
　酸変性ＥＰＤＭ-Ａは、ベースＥＰＤＭ-Ａ、カルボン酸、及び反応開始剤を、ニーダー、バンバリーミキサー等の密閉型混練機に投入し、反応開始剤が分解する所定の温度下で所定時間混練してベースＥＰＤＭ-Ａにカルボン酸をグラフト反応させることにより得ることができる。反応開始剤としては、例えば、ジクミルパーオキサイドなどのジアルキルパーオキサイド類；ｔ－ブチルパーオキシアセテートなどのパーオキシエステル類；ジシクロヘキサノンパーオキサイドなどのケトンパーオキサイド類；ジ（４－ｔｅｒｔ－ブチルシクロヘキシル）パーオキシジカーボネート等の有機過酸化物が挙げられる。また、酸変性ＥＰＤＭ-Ａは、紫外線照射等の変性手段によっても得ることができる。 In the acid-modified EPDM-A, 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. Examples of 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.
　ゴム成分は、分子間が架橋しているが、架橋剤として有機過酸化物が用いられて架橋していてもよく、また、架橋剤として硫黄が用いられて架橋していてもよく、さらに、それらが併用されて架橋していてもよい。また、ゴム成分は、電子線等が用いられて架橋していてもよい。 Although 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.
　実施形態に係る架橋ゴム組成物に配合される充填材としては、例えば、シリカ、カーボンブラック、酸化チタン、酸化アルミニウム、炭酸カルシウム、炭酸マグネシウム、炭酸亜鉛、硫酸バリウム、珪藻土、クレー、タルク等が挙げられる。充填材は、これらのうちの１種又は２種以上を含むことが好ましく、充填材の補強効果を有効に得る観点から、シリカを含むことがより好ましい。 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.
　充填材として配合されているシリカとしては、例えば、沈降法シリカやゲル法シリカなどの湿式シリカ；焼成法シリカやアーク法シリカなどの乾式シリカ等の合成シリカが挙げられる。シリカは、これらのうちの１種又は２種以上を含むことが好ましく、シリカの補強効果を有効に得る観点から、沈降法シリカを含むことがより好ましい。ＩＳＯ９２７７に基づいて測定されるシリカのＢＥＴ比表面積は、例えば１５０ｍ２／ｇ以上２００ｍ２／ｇ以下である。シリカの一次粒子径は、例えば１０ｎｍ以上５０ｎｍ以下であり、シリカの凝集体の二次粒子径は、例えば１μｍ以上４０μｍ以下である。実施形態に係る架橋ゴム組成物における充填材のシリカの含有量は、シリカの補強効果を有効に得る観点から、ゴム成分１００質量部に対して、好ましくは２０質量部以上６０質量部以下、より好ましくは３０質量部以上５０質量部以下である。 Examples of the silica blended as the filler 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 μm or more and 40 μm 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.
　実施形態に係る架橋ゴム組成物は、その他に、ゴム配合剤として、加工助剤、加硫促進剤、加硫促進助剤、可塑剤、老化防止剤等を含有していてもよい。 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.
　実施形態に係る架橋ゴム組成物の歪量１％及び１００℃での貯蔵弾性係数Ｇ’（１００℃）は、好ましくは１．０ＭＰａ以上５．０ＭＰａ以下、より好ましくは２．０ＭＰａ以上４．０ＭＰａ以下である。この貯蔵弾性係数Ｇ’（１００℃）は、ＪＩＳ Ｋ６３９４：２００７に基づいて測定されるものである。 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.
　実施形態に係る架橋ゴム組成物の２５℃での１００％伸び時における引張応力Ｍ１００は、好ましくは２．０ＭＰａ以上、より好ましくは３．０ＭＰａ以上である。この２５℃での１００％伸び時における引張応力Ｍ１００は、ＪＩＳ Ｋ６２５１：２０１０に基づいて測定されるものである。 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.
　実施形態に係る架橋ゴム組成物の２５℃での引張強さＴＢは、好ましくは１２．６ＭＰａ以上、より好ましくは１３．０以上である。この２５℃での引張強さＴＢは、ＪＩＳ Ｋ６２５１：２０１０に基づいて測定されるものである。 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.
　以上の実施形態に係る架橋ゴム組成物は、ニーダー、バンバリーミキサー、オープンロール等のゴム混練機を用い、ゴム成分及び充填材、並びにその他のゴム配合剤を混練して未架橋ゴム組成物を調製し、その未架橋ゴム組成物を所定温度及び所定圧力で架橋させることにより得ることができる。 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.
　また、実施形態に係る架橋ゴム組成物は、ゴム製品の製品本体を形成するのに好適であり、具体的には、例えば伝動ベルトのベルト本体を形成するのに適しており、ゴム製品において、充填材による効果を有効に得ることができる。 Further, 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.
　（架橋ゴム組成物）
　以下の実施例１及び２並びに比較例のシート状の架橋ゴム組成物を作製した。それぞれの構成は表１にも示す。 (Crosslinked rubber composition)
Sheet-shaped crosslinked rubber compositions of Examples 1 and 2 and Comparative Examples below were prepared. Each configuration is also shown in Table 1.
　＜実施例１＞
　密閉型混練機に、ＥＰＤＭ（Nordel IP 4640 Dow Chemical社製　エチレン含量：５５質量％、プロピレン含量：４０質量％、非共役ジエン含量（ＥＮＢ含量）:４．９質量％、エチレン含量／プロピレン含量＝１．４、エチレン含量／非共役ジエン含量（ＥＮＢ含量）＝１１）とともに、このＥＰＤＭ１００質量部に対して、１質量部の無水マレイン酸及び０．１質量部の反応開始剤の有機過酸化物（パークミルＤ　日本油脂社製、ジクミルパーオキサイド）を投入し、それらを１７０℃の温度下で１０分間混練して無水マレイン酸変性ＥＰＤＭ１を調製した。次いで、この無水マレイン酸変性ＥＰＤＭ１をゴム成分とし、これに、ゴム成分１００質量部に対して、４０質量部の充填材としての沈降法シリカ（ウルトラジルＶＮ３  エボニック社製）、１質量部の加工助剤のステアリン酸（ステアリン酸Ｓ５０  新日本理化社製）、５質量部の加硫促進助剤の酸化亜鉛（酸化亜鉛３種  白水化学社製）、及び３．２質量部の架橋剤の有機過酸化物（パークミルＤ　日本油脂社製、ジクミルパーオキサイド）を配合して混練することにより未架橋ゴム組成物を調製した。そして、この未架橋ゴム組成物をプレス成形することによりシート状の架橋ゴム組成物を得た。得られたシート状の架橋ゴム組成物を実施例１とした。 <Example 1>
In a closed kneader, EPDM (Nordel IP 4640 Dow Chemical ethylene content: 55% by mass, propylene content: 40% by mass, non-conjugated diene content (ENB content): 4.9% by mass, ethylene content / propylene content = 1.4, ethylene content / non-conjugated diene content (ENB content) = 11), 1 part by mass of maleic anhydride and 0.1 part by mass of organic peroxide of the reaction initiator with respect to 100 parts by mass of this EPDM. (Parkmill D manufactured by Nippon Yushi Co., Ltd., dicumyl peroxide) was added, and they were kneaded at a temperature of 170 ° C. for 10 minutes to prepare maleic anhydride-modified EPDM1. Next, this 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.
　＜実施例２＞
　密閉型混練機に、ＥＰＤＭとともに、このＥＰＤＭ１００質量部に対して、１質量部の無水マレイン酸及び０．８質量部の反応開始剤の有機過酸化物（パーカドックス１６　化薬アクゾ社製、ジ（４－ｔｅｒｔ－ブチルシクロヘキシル）パーオキシジカーボネート）を投入し、それらを１３０℃の温度下で１０分間混練して無水マレイン酸変性ＥＰＤＭ２を調製した。無水マレイン酸変性ＥＰＤＭ１に代えて、ゴム成分として、この無水マレイン酸変性ＥＰＤＭ２を用いたことを除いて、実施例１と同一構成のシート状の架橋ゴム組成物を得た。得られたシート状の架橋ゴム組成物を実施例２とした。 <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.
　＜比較例＞
　無水マレイン酸変性ＥＰＤＭ１に代えて、ゴム成分として酸変性していないＥＰＤＭ（Nordel IP 4640 Dow Chemical社製）を用いたことを除いて、実施例１と同一構成のシート状の架橋ゴム組成物を得た。これを比較例とした。 <Comparison example>
A sheet-shaped crosslinked rubber composition having the same composition as that of Example 1 was used, except that EPDM (manufactured by Nordel IP 4640 Dow Chemical) which was not acid-modified was used as the rubber component instead of maleic anhydride-modified EPDM1. Obtained. This was used as a comparative example.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　（試験方法）
　＜貯蔵弾性係数Ｇ’（１００℃）＞
　実施例１及び２並びに比較例のそれぞれについて、ＪＩＳ Ｋ６３９４：２００７に基づいて、歪量１％及び１００℃での貯蔵弾性係数Ｇ’（１００℃）を測定した。 (Test method)
<Storage modulus G'(100 ° C)>
For each of Examples 1 and 2 and Comparative Example, the storage elastic modulus G'(100 ° C.) at a strain amount of 1% and 100 ° C. was measured based on JIS K6394: 2007.
　＜引張特性＞
　実施例１及び２並びに比較例のそれぞれについて、ＪＩＳ Ｋ６２５１：２０１０に基づいて、２５℃での１００％伸び時における引張応力Ｍ１００及び引張強さＴＢを測定した。 <Tensile characteristics>
For each of Examples 1 and 2 and Comparative Example, the tensile stress M 100 and the tensile strength TB at 100% elongation at 25 ° C. were measured based on JIS K6251: 2010.
　（試験結果）
　試験結果を表１に示す。これによれば、ゴム成分として無水マレイン酸変性ＥＰＤＭ１又は２を用いた実施例１及び２は、ゴム成分として酸変性していないＥＰＤＭを用いた比較例と比べると、１００℃での貯蔵弾性係数Ｇ’（１００℃）が低い一方、２５℃での１００％伸び時における引張応力Ｍ１００及び引張強さＴＢが高いことが分かる。これは、ゴム成分の主体が無水マレイン酸変性ＥＰＤＭ１又は２であることにより、充填材の沈降法シリカの高い分散性が得られたためであると推測される。 (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.
　本発明は、架橋ゴム組成物及びそれを用いたゴム製品の技術分野について有用である。 The present invention is useful in the technical fields of crosslinked rubber compositions and rubber products using them.

Claims (12)

  1. 　エチレン含量が４０質量％以上７０質量％以下で且つ非共役ジエン含量が０．５質量％以上８．５質量％以下であるエチレン・プロピレン・非共役ジエン共重合体をカルボン酸変性させた酸変性ＥＰＤＭをゴム成分の主体とする架橋ゴム組成物。 Acid modification by carboxylic acid modification of ethylene / propylene / non-conjugated diene copolymer having ethylene content of 40% by mass or more and 70% by mass or less and non-conjugated diene content of 0.5% by mass or more and 8.5% by mass or less. A crosslinked rubber composition containing EPDM as a main component of rubber.
  2. 　請求項１に記載された架橋ゴム組成物において、
    　前記エチレン・プロピレン・非共役ジエン共重合体におけるプロピレン含量が３０質量％以上５０質量％以下である架橋ゴム組成物。     In the crosslinked rubber composition according to claim 1,
    A crosslinked rubber composition having a propylene content of 30% by mass or more and 50% by mass or less in the ethylene / propylene / non-conjugated diene copolymer.
  3. 　請求項１又は２に記載された架橋ゴム組成物において、
    　前記エチレン・プロピレン・非共役ジエン共重合体におけるエチレン含量のプロピレン含量に対する比が０．６０以上２．４以下である架橋ゴム組成物。     In the crosslinked rubber composition according to claim 1 or 2.
    A crosslinked rubber composition in which the ratio of the ethylene content to the propylene content in the ethylene / propylene / non-conjugated diene copolymer is 0.60 or more and 2.4 or less.
  4. 　請求項１乃至３のいずれかに記載された架橋ゴム組成物において、
    　前記エチレン・プロピレン・非共役ジエン共重合体におけるエチレン含量の非共役ジエン含量に対する比が５．０以上１４０以下である架橋ゴム組成物。     In the crosslinked rubber composition according to any one of claims 1 to 3.
    A crosslinked rubber composition in which the ratio of the ethylene content to the non-conjugated diene content in the ethylene / propylene / non-conjugated diene copolymer is 5.0 or more and 140 or less.
  5. 　請求項１乃至４のいずれかに記載された架橋ゴム組成物において、
    　前記カルボン酸変性が無水マレイン酸変性を含む架橋ゴム組成物。     In the crosslinked rubber composition according to any one of claims 1 to 4.
    A crosslinked rubber composition in which the carboxylic acid modification includes maleic anhydride modification.
  6. 　請求項１乃至５のいずれかに記載された架橋ゴム組成物において、
    　充填材としてシリカが配合されている架橋ゴム組成物。     In the crosslinked rubber composition according to any one of claims 1 to 5.
    A crosslinked rubber composition containing silica as a filler.
  7. 　請求項６に記載された架橋ゴム組成物において、
    　前記シリカが沈降法シリカを含む架橋ゴム組成物。     In the crosslinked rubber composition according to claim 6,
    A crosslinked rubber composition in which the silica contains an immunoprecipitated silica.
  8. 　請求項６又は７に記載された架橋ゴム組成物において、
    　前記シリカの含有量が、前記ゴム成分１００質量部に対して２０質量部以上６０質量部以下である架橋ゴム組成物。     In the crosslinked rubber composition according to claim 6 or 7.
    A crosslinked rubber composition having a silica content of 20 parts by mass or more and 60 parts by mass or less with respect to 100 parts by mass of the rubber component.
  9. 　請求項１乃至８のいずれかに記載された架橋ゴム組成物において、
    　ＪＩＳ Ｋ６３９４：２００７に基づいて測定される歪量１％及び１００℃での貯蔵弾性係数が１．０ＭＰａ以上５．０ＭＰａ以下である架橋ゴム組成物。     In the crosslinked rubber composition according to any one of claims 1 to 8.
    A crosslinked rubber composition having a strain amount of 1% measured based on JIS K6394: 2007 and a storage elastic modulus at 100 ° C. of 1.0 MPa or more and 5.0 MPa or less.
  10. 　請求項１乃至９のいずれかに記載された架橋ゴム組成物において、
    　ＪＩＳ Ｋ６２５１：２０１０に基づいて測定される２５℃での１００％伸び時における引張応力が２．０ＭＰａ以上である架橋ゴム組成物。     In the crosslinked rubber composition according to any one of claims 1 to 9.
    A crosslinked rubber composition having a tensile stress of 2.0 MPa or more at 100% elongation at 25 ° C. measured based on JIS K6251: 2010.
  11. 　請求項１乃至１０のいずれかに記載された架橋ゴム組成物において、
    　ＪＩＳ Ｋ６２５１：２０１０に基づいて測定される２５℃での引張強さが１２．６ＭＰａ以上である架橋ゴム組成物。     In the crosslinked rubber composition according to any one of claims 1 to 10.
    A crosslinked rubber composition having a tensile strength of 12.6 MPa or more at 25 ° C. measured based on JIS K6251: 2010.
  12. 　請求項１乃至１１のいずれかに記載された架橋ゴム組成物で製品本体が形成されたゴム製品。 A rubber product in which the product body is formed of the crosslinked rubber composition according to any one of claims 1 to 11.
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