WO1993014160A1 - Composition de caoutchouc vulcanisable et caoutchouc vulcanise - Google Patents

Composition de caoutchouc vulcanisable et caoutchouc vulcanise Download PDF

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Publication number
WO1993014160A1
WO1993014160A1 PCT/JP1993/000004 JP9300004W WO9314160A1 WO 1993014160 A1 WO1993014160 A1 WO 1993014160A1 JP 9300004 W JP9300004 W JP 9300004W WO 9314160 A1 WO9314160 A1 WO 9314160A1
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WO
WIPO (PCT)
Prior art keywords
weight
parts
rubber composition
styrene
rubber
Prior art date
Application number
PCT/JP1993/000004
Other languages
English (en)
French (fr)
Japanese (ja)
Inventor
Masashi Aoshima
Hironobu Shigematsu
Takeru Wadaki
Toshikatsu Kanehara
Kazuya Watanabe
Toshiyuki Tanaka
Original Assignee
Sumitomo Chemical Company, Limited
Toyoda Gosei 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
Application filed by Sumitomo Chemical Company, Limited, Toyoda Gosei Co., Ltd. filed Critical Sumitomo Chemical Company, Limited
Publication of WO1993014160A1 publication Critical patent/WO1993014160A1/ja
Priority to US08/505,708 priority Critical patent/US5597860A/en

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Classifications

    • 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
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Ethene-propene or ethene-propene-diene copolymers
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • the present invention relates to a vulcanizable rubber composition containing an ethylene / polyolefin 'non-conjugated gen copolymer and a vulcanized rubber produced using the same.
  • a vulcanizable rubber composition and vulcanized rubber can be used in a wide range of fields such as vehicle parts, industrial parts, and building materials.
  • EPDM non-conjugated gen-copolymer
  • the following methods are known as methods for obtaining a vulcanized rubber having a hardness of 45 (Short D hardness according to ASTMD224) or more. Also have problems.
  • a vulcanized rubber having the above hardness can be obtained by increasing the amount of a vulcanizing agent. It has the drawback of poor weather resistance and heat resistance.
  • the degree of composition of the vulcanizable rubber composition is greatly increased, kneading with a Banbury mixer and processing with a roll are difficult, and the obtained vulcanized rubber is difficult to obtain.
  • the hardness is insufficient.
  • the processability in the production of the vulcanizable rubber composition is better than the former, but during vulcanization, the continuous vulcanization method uses the curing reaction of the alkylphenol resin.
  • the problem to be solved by the present invention is to provide a vulcanized rubber having characteristics of high strength and high hardness without impairing the features of EPDM such as excellent weather resistance, ozone resistance and heat resistance, and
  • the object is to provide a vulcanizable rubber composition that gives it.
  • the present inventors have conducted intensive studies to solve the above problems, and as a result, completed the present invention.
  • the present invention has a Mooney viscosity of 1 0 ⁇ 1 0 0 (ML doctor 4 1 0 0 D C), the weight ratio forces of ethylene Les N'nohi Ichio Le off fin 5 0/5 0-9 0/1 0, Ethylene with an iodine titer of 20 to 45 ⁇ Hyorefin 'non-conjugated gen copolymer 30 to 80 wt% and styrene / conjugated diolefin 100 to 100 parts by weight of a polymer component consisting of 20 to 70 wt% of a block copolymer, 20 to 150 parts by weight of a reinforcing filler, and A vulcanizable rubber composition containing 3 to 30 parts by weight, 0 to 50 parts by weight of a styrene resin and 0 to 100 parts by weight of an extender oil, and a continuous vulcanization method using the same.
  • This is a vulcanized rubber that has excellent weather
  • homorefin which is a constituent component of the copolymer
  • examples of the homorefin which is a constituent component of the copolymer include propylene, 1-butene, 41-methisolate 1-pentene, 1-hexene, 1-octene and the like. Of which proselenium and 1-butene are preferred.
  • the weight ratio of ethylene Z monoolefin in the copolymer is 50 Z 50 to 90 Z 10, preferably 65/35 to 90 Z 10. And more preferably 70 Z30 to 85/15. If the ethylene content is less than 50% of the total weight of ethylene and ⁇ -olefin, the strength after vulcanization will be low-and if it exceeds 90%, ordinary rubber molding will be performed. Neither of them is preferred because processing under conditions is difficult.
  • Non-conjugated genes which are constituents of the copolymer include 1,4-pentagen, 1,4-hexadiene, divinylbenzene, dicyclopentadiene, methylenno brebolene, and ethylideneno.
  • the content of the non-conjugated gen in the copolymer is such that the iodine value is 20 to 45, preferably 20 to 35. If the iodine value is less than 20, it is not preferable because the strength and elongation after vulcanization are low. Conversely, when the iodine value exceeds 45, problems such as a decrease in elongation after vulcanization and an increase in cost occur.
  • Mooney viscosity is less than 100, there is a problem that the performance after vulcanization, for example, tensile strength, is reduced, and if the Mooney viscosity is more than 100, the vulcanizable rubber composition has a problem. It is not preferable because the viscosity becomes too high and the processability during kneading by a Banbury mixer or the like deteriorates.
  • Conjugated diolefins include 1,3—butadiene, isoprene, 2,3—dimethyl-1,3—butadiene, 1,3,1-pentylbenzene, etc.
  • 1,3-butadiene power is particularly preferred.
  • the structure of the block copolymer is represented by the general formula (A-B) n , A- (B-A) n , B- (A-B) n (where A is mainly styrene).
  • B is a polymer block mainly composed of conjugated diolefins
  • B is a polymer block mainly composed of conjugated diolefins. It is not always necessary to clearly distinguish the boundary between the and the B block.
  • N is an integer of 1 or more.
  • the weight ratio of styrene Z conjugated diolefin in the block polymer is preferably 30/70 to 90/10 in order to increase the hardness of the vulcanized rubber. , More preferably 40/60 to 90 X 10, and more preferably 60 ⁇ 40 to 90/10.
  • the two-component polystyrene of the ethylene-hyrefin 'non-covalent gen copolymer and the styrene-conjugated diolefin composite used in the present invention In the mer component, the mixing ratio of ethylene ⁇ ⁇ : —olefin / non-conjugated gen copolymer is 30 to 80%. If the blending ratio of the ethylene / polyolefin / non-conjugated gen copolymer is less than 30% by weight, the elongation of the vulcanized rubber decreases, which is not preferable. If the content is more than 0 wt%, the hardness of the vulcanized rubber becomes low, and a problem such as that a desired hardness cannot be obtained occurs.
  • the vulcanizable rubber composition of the present invention contains a reinforcing filler, zeolite, and, if necessary, a styrene resin and an extension oil, together with one of the above-mentioned polymers.
  • a reinforcing filler include carbon black and sili- con, among which carbon black is preferred.
  • the compounding amount of the reinforcing filler is 20 to 150 parts by weight, preferably 30 to 120 parts by weight, based on 100 parts by weight of the polymer component. If the compounding amount of the reinforcing filler is in such a range, the processability is good, and a vulcanizable rubber composition which provides a high-strength and high-strength vulcanized rubber can be obtained.
  • the compounding amount in the present invention is 3 to 30 parts by weight, preferably 4 to 15 parts by weight, based on 100 parts by weight of the polymer component. If the blending amount is less than 3 parts by weight, the strength and hardness of the vulcanized rubber become low, which is not preferable. On the other hand, if the compounding amount exceeds 30 parts by weight, the elongation after vulcanization decreases, the excess iodide blooms, and the effect of improving the hardness of the vulcanized rubber becomes insignificant. I don't like it.
  • a styrene resin is not essential, but may be blended for the purpose of improving the hardness of the vulcanized rubber.
  • the blending amount is determined by mixing a styrene resin with a polystyrene / ethylene / non-conjugated gen copolymer and a styrene / conjugated diol / olefin block copolymer. 0 to 50 parts by weight, preferably 5 to 50 parts by weight, and particularly preferably 5 to 30 parts by weight per 100 parts by weight of the mer component. If the blending amount of the styrene resin exceeds 50 parts by weight, elongation after vulcanization and tensile strength are unfavorably reduced.
  • styrene resin As such a styrene resin, styrene alone can be used.
  • polystyrene which is a polymer, rubber-modified polystyrene
  • HIPS styrene-acrylonitrile copolymer
  • polystyrene which is a homopolymer of styrene, is preferred.
  • extender oil that the vulcanizable rubber composition of the present invention optionally contains include so-called process oils such as lipstick oil, naphthene oil and paraffin oil. Vegetable oils such as palm oil can be mentioned. Of these, process oils are preferred, especially paraffin oil or naphthenic oil.
  • the extender oil is blended in an amount of 0 to 100 parts by weight with respect to 100 parts by weight of the polymer component, so that the desired processability of the vulcanizable rubber composition and the hardness of the vulcanized rubber can be improved. It is arbitrarily selected from this range depending on the degree. By selecting the amount of the extender oil from the above range, it is possible to obtain a vulcanizable rubber composition having good processability and providing a vulcanized rubber having high strength and high hardness.
  • the vulcanizable rubber composition of the present invention can be blended with a polyethylene resin or a polypropylene resin as necessary for improving processability and the like.
  • the vulcanizable rubber composition of the present invention includes a filler, a softening agent, a vulcanization accelerator, a vulcanization aid, a processing aid, an antifoaming agent, zinc white, stearic acid, anti-aging.
  • a compounding agent commonly used for rubber applications, such as an agent, can be appropriately added.
  • a conventionally known vulcanizable composition is used.
  • Method can be applied. That is, the above-mentioned compounding agent is added to the polymer component, and the mixture is sufficiently mixed with an open roll mill, a Banbury mixer, a kneader, or the like to obtain a vulcanizable rubber composition of the present invention.
  • the rubber composition is molded into a desired shape by, for example, extrusion molding or force-rendering molding as required.
  • Vulcanize As the vulcanization method, press vulcanization, can vulcanization, hot air vulcanization, UHF vulcanization, LCM vulcanization, PCM vulcanization, etc., or a continuous vulcanization method combining these methods Can be done.
  • the continuous vulcanization method which can efficiently produce long products, is preferable as the method for producing the vulcanized rubber of the present invention.
  • EPDM is originally used. A vulcanized rubber having high strength and high hardness can be obtained without impairing the weather resistance, ozone resistance and ripening resistance.
  • Table 4 shows the combination of the polymer component and the polystyrene, the blending amount of the polymer, and the physical properties of the obtained vulcanized rubber.
  • the value of the vulcanized rubber was measured in accordance with ASTM D224.
  • the kneading agent was kneaded in the same manner as in the example with the combination of the polymer component and the polystyrene shown in Table 7 and the mixing amount thereof, and then vulcanized.
  • Table 7 shows the physical properties of the obtained vulcanized rubber.
  • the vulcanized rubbers of Examples 1 to 18 of the present invention all have high strength and high hardness.
  • the vulcanized rubber of Comparative Example 1 in which EPDM exceeds 80 wt% among the binary polymer components has lower hardness than the vulcanized rubbers of Examples 8 to 10.
  • the vulcanized rubber of Comparative Example 2 containing no styrene 'conjugated diolefin block copolymer as a polymer component has excellent hardness but low tensile strength.
  • the vulcanizable rubber composition of the present invention is used for the production of vulcanized rubber by itself, and can be used as a part of a rubber product, for example, as a surface layer, a lip portion, a core material portion, or the like, and other rubber compositions.
  • Object and resin composition Compounded and used for the production of rubber products.
  • the vulcanized rubber of the present invention has excellent weather resistance, ozone resistance and heat resistance, and has high strength and hardness, so that it can be used in a wide range of fields such as automotive parts, industrial parts, and building materials. It can be. Packings, hoses, drainage rubber, glass runners, weather strips, soft solids and hard solids Solid rubber part of solid rubber composite, solid rubber part of sponge rubber and solid rubber applied to trunk sealer for door rubber seal, mudguard For industrial parts, rubber ports, sealing materials, rubber, etc. are used for industrial parts, and for building materials, setting blocks, rubber tiles, etc. And gaskets.

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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)
PCT/JP1993/000004 1992-01-08 1993-01-06 Composition de caoutchouc vulcanisable et caoutchouc vulcanise WO1993014160A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US08/505,708 US5597860A (en) 1992-01-08 1995-07-21 Vulcanizable rubber compositions and vulcanized rubber

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP4/1397 1992-01-08
JP139792 1992-01-08

Publications (1)

Publication Number Publication Date
WO1993014160A1 true WO1993014160A1 (fr) 1993-07-22

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Application Number Title Priority Date Filing Date
PCT/JP1993/000004 WO1993014160A1 (fr) 1992-01-08 1993-01-06 Composition de caoutchouc vulcanisable et caoutchouc vulcanise

Country Status (6)

Country Link
US (1) US5597860A (en, 2012)
EP (1) EP0574591A4 (en, 2012)
JP (1) JPH05301998A (en, 2012)
CA (1) CA2104775A1 (en, 2012)
TW (1) TW256848B (en, 2012)
WO (1) WO1993014160A1 (en, 2012)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19512472A1 (de) * 1994-04-04 1995-10-05 Sumitomo Chemical Co Kautschukzusammensetzung mit hoher Härte
US5732436A (en) * 1995-08-21 1998-03-31 Feigenbaum; Jeffery J. Replacement wiper blade
MXPA02002512A (es) 1999-09-17 2002-07-30 Procter & Gamble Materiales elastomeros de baja relajacion de tensiones.
WO2001019916A1 (en) * 1999-09-17 2001-03-22 The Procter & Gamble Company Radiation crosslinked elastomeric materials
US8578046B2 (en) 2005-10-20 2013-11-05 Qualcomm Incorporated System and method for adaptive media bundling for voice over internet protocol applications
JP2008201973A (ja) * 2007-02-22 2008-09-04 Meiwa Rubber Kogyo Kk 工業用ゴムロール組成物

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4829870A (en, 2012) * 1971-08-20 1973-04-20
JPS60163944A (ja) * 1984-02-07 1985-08-26 Japan Synthetic Rubber Co Ltd ゴム組成物
JPS6160739A (ja) * 1984-09-03 1986-03-28 Asahi Chem Ind Co Ltd 熱可塑性高弾性エラストマ−の組成物
JPH01139634A (ja) * 1987-11-27 1989-06-01 Japan Synthetic Rubber Co Ltd 防振・防音・遮音材用ゴム組成物

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US3445543A (en) * 1965-12-13 1969-05-20 Phillips Petroleum Co Cured blend of diene block copolymer,olefin rubber and polystyrene
US3897405A (en) * 1973-01-02 1975-07-29 Goodrich Co B F EPDM polymers grafted with vulcanization accelerators
CA1078679A (en) * 1975-09-15 1980-06-03 Arthur A. Blaskiewicz Epdm copolymer rubber-highly unsaturated rubber (filled) blends
US4350795A (en) * 1977-06-13 1982-09-21 The Firestone Tire & Rubber Company Thermoplastic elastomer blends
JPS5423958A (en) * 1977-07-25 1979-02-22 Nippon Electric Co Laminated ceramic capacitor
JPS6357662A (ja) * 1986-08-28 1988-03-12 Asahi Chem Ind Co Ltd 耐熱性に優れたシリンジ用ガスケツト
US4778852A (en) * 1987-04-06 1988-10-18 The Firestone Tire & Rubber Company Roofing composition
EP0387436A1 (en) * 1989-03-16 1990-09-19 Sumitomo Chemical Company, Limited Rubber compositions
US5348994A (en) * 1992-03-05 1994-09-20 Exxon Research & Engineering Co. Polymer-modified functionalized asphalt compositions and methods of preparation (C-2747)

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4829870A (en, 2012) * 1971-08-20 1973-04-20
JPS60163944A (ja) * 1984-02-07 1985-08-26 Japan Synthetic Rubber Co Ltd ゴム組成物
JPS6160739A (ja) * 1984-09-03 1986-03-28 Asahi Chem Ind Co Ltd 熱可塑性高弾性エラストマ−の組成物
JPH01139634A (ja) * 1987-11-27 1989-06-01 Japan Synthetic Rubber Co Ltd 防振・防音・遮音材用ゴム組成物

Non-Patent Citations (1)

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Title
See also references of EP0574591A4 *

Also Published As

Publication number Publication date
US5597860A (en) 1997-01-28
JPH05301998A (ja) 1993-11-16
EP0574591A1 (en) 1993-12-22
TW256848B (en, 2012) 1995-09-11
CA2104775A1 (en) 1993-07-09
EP0574591A4 (en) 1995-07-26

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