WO2001012686A1 - Copolymere de cyclopolyene non conjugue, composition de caoutchouc et utilisation - Google Patents
Copolymere de cyclopolyene non conjugue, composition de caoutchouc et utilisation Download PDFInfo
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- WO2001012686A1 WO2001012686A1 PCT/JP2000/005330 JP0005330W WO0112686A1 WO 2001012686 A1 WO2001012686 A1 WO 2001012686A1 JP 0005330 W JP0005330 W JP 0005330W WO 0112686 A1 WO0112686 A1 WO 0112686A1
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- group
- conjugated
- structural unit
- unit derived
- conjugated cyclic
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Classifications
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
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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
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
- C08L23/0823—Copolymers of ethene with aliphatic cyclic olefins
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T152/00—Resilient tires and wheels
- Y10T152/10—Tires, resilient
- Y10T152/10495—Pneumatic tire or inner tube
Definitions
- the content of structural units derived from ⁇ -refin (A 1) is 97.9 to 55 mol 0 /.
- the content of the structural unit derived from the non-conjugated cyclic polyene ( ⁇ 2) is 2 to 30 mol%, and the content of the structural unit derived from the non-conjugated linear polyene (A 3) is 0.1 to 15 mol. %
- Intrinsic viscosity [ ⁇ ] measured in decalin at 135 ° C is 0.01 to 20 d 1 / g
- glass transition temperature (T g) is 40 ° C or less
- iodine value is 5 to 150 is a non-conjugated cyclic polyene copolymer.
- the structural unit derived from ⁇ -olefin (A 1) contains at least a structural unit derived from ethylene, and the structural unit derived from ethylene has at least 3 carbon atoms.
- the structural unit derived from ⁇ -olefin (A1) contains at least the structural unit derived from ethylene, and the molar ratio of the structural unit derived from ethylene and the structural unit derived from hyorefin having 3 or more carbon atoms is 1 00 0 ⁇ 50 50 above
- non-conjugated cyclic polyene-based copolymer according to any of (1) to (4) above, wherein the non-conjugated cyclic polyene ( ⁇ 2) is a non-conjugated cyclic polyene represented by the following formula (11-1): Polymer.
- R ', R 2, R 3, R 4, R 5, R e and R 7 are each independently a hydrogen atom or an alkyl group having a carbon number.
- a random copolymer comprising a structural unit derived from hyolefin (A1) and a structural unit derived from non-conjugated cyclic polyene (A2), wherein ⁇ -olefin (A1)
- the content of the structural unit derived from the non-conjugated cyclic polyene ( ⁇ 2) is 7 to 30 mol 0 /.
- T g transfer temperature
- the structural unit derived from ⁇ -olefin (A 1) contains at least a structural unit derived from ethylene, and the structural unit derived from ethylene is the mole of the structural unit derived from ⁇ -refin having 3 or more carbon atoms.
- the non-conjugated cyclic polyene-based copolymer of the present invention is a random copolymer containing a structural unit derived from ⁇ -amino olefin (A 1) and a structural unit derived from non-conjugated cyclic polyene ( ⁇ 2).
- the content of the structural unit derived from ⁇ -refin (A 1) is 93-70 moles 0 /.
- the content of the structural unit derived from the non-conjugated cyclic polyene ( ⁇ 2) is 7 to 30 mol 0 /.
- non-conjugated cyclic polyene-based copolymer of the present invention comprises a structural unit derived from ⁇ -olefin (A 1), a non-conjugated cyclic polyene ( ⁇ 2) and a non-conjugated chain-shaped polyene ( ⁇ 2).
- the intrinsic viscosity [ ⁇ ] measured in decalin (decahydronaphtalene) at 135 ° C. is 0.01 to 20 (11 ⁇ , preferably 0.5 to 0.5 mol%). . 1 to 1 0 d 1 Zg, more preferably 0.5 to 5 (1 1 8, the glass transition temperature (T g) 40 ° C or less, preferably one 3 0 ⁇ + 2 0 ° C, more preferably one 30 to 115 ° C, most preferably 130 to 110 ° C, and an iodine value of 5 to 150, preferably 10 to 130, more preferably 10 to 120. Is a non-conjugated cyclic polyene copolymer.
- the non-conjugated cyclic polyene copolymer of the present invention has an intrinsic viscosity [7]] within the above range. Therefore, it is excellent in mechanical strength and workability, and as the value falls within the above-mentioned preferable range or more preferable range, the performance becomes more excellent.
- non-conjugated cyclic polyene-based copolymer of the present invention is used as a raw material for a rubber material for a tire, the lower the crystallinity, the better.
- ⁇ -olefin (A1) constituting the non-conjugated cyclic polyene copolymer of the present invention
- ⁇ -olefin (A 1) can be used alone or in combination of two or more.
- the non-conjugated cyclic polyene-based copolymer of the present invention contains at least a structural unit derived from ethylene as a structural unit derived from ⁇ -olefin (A 1), and a structural unit derived from ethylene / 3 carbon atoms It is desirable that the molar ratio of the structural units derived from the above-mentioned ⁇ -refin is 100/0 to 1/99, preferably, ⁇ / ⁇ , and more preferably, 95/5 to 5050.
- a cyclic compound having two or more non-conjugated unsaturated bonds can be used without limitation, but a non-conjugated cyclic polyene represented by the above formula (1-1) is preferable.
- halogen atoms represented by ⁇ to 4 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
- examples of the hydrocarbon group represented by R ′ to R 4 include an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, and a carbon atom having 3 to 1 carbon atoms.
- examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group and an octadecyl group. I can do it.
- examples of the halogenated alkyl group include groups in which at least a part of the hydrogen atoms forming the above-mentioned alkyl group has been substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.
- Examples of the cycloalkyl group include a cyclohexyl group.
- Examples of the aromatic hydrocarbon group include a phenyl group and a naphthyl group.
- Examples of the unsaturated hydrocarbon group include a vinyl group and an aryl group.
- non-conjugated cyclic polyene (A 2) represented by the above formula (111) include an alkylidene group formed by R 1 and R 2 or by R 3 and R 4 .
- cyclic Poryen (A2- 2) both one least of R' ⁇ R 4 but double bond is a monovalent unsaturated hydrocarbon group which chromatic on one or more unsaturated hydrocarbon group-containing non-conjugated cyclic Polje emissions (a 2 ⁇ 3)
- the symmetric axis there is a ring-symmetric non-conjugated cyclic polyene (A2-4) in which the ring has left-right symmetry.
- alkylidene group represented by R 17 in the above formula (1-2) include an alkylidene group having 1 to 20 carbon atoms such as a methylene group, an ethylidene group, a propylidene group, and an isopropylidene group. .
- S in the above formula (1-2) is preferably 0.
- the halogen atom represented by R ′ 8 and R 19 are the same as those described above.
- the hydrocarbon group include an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon having 6 to 20 carbon atoms.
- specific examples include 5-methylene one 2-norbornene, such as the c the formula mentioned groups (1 2) alkylidene group containing represented by non-conjugated cyclic Poryen (A. 2-1), 5- Echiride Examples thereof include 1-norbornene (ENB), 5-isopropylidene-12-norbornene, and the following compounds. Of these, 5-ethylidene-12-norbornene is preferred.
- Non-conjugated cyclic polyene (A2-1) that is, an alkylidene group-containing non-conjugated cyclic polyene (A2-1) in which s is 0 in the above formula (1-2), or m is 0 in the above formula (1-1).
- Polycyclic non-conjugated cyclic polyenes (A2-2) are preferred.
- the non-conjugated chain polyene (A3) constituting the non-conjugated cyclic polyene-based copolymer of the present invention is a compound having two or more non-conjugated unsaturated bonds in one molecule, Trien or non-conjugated tetraethylen can be used.
- the non-conjugated chain polyene (A3) can be used alone or in combination of two or more.
- non-conjugated triene or tetraene (A3-1) represented by the formula (2-1) include the following compounds (provided that the compound contained in the formula (2-2) is Excluded).
- non-conjugated triene (A3-2) represented by the formula (2-2) include the following compounds.
- DMDT 4,8-dimethyl-1,4,8-decatriene
- the non-conjugated polyenes represented by the formulas (2-1) and (2-2) usually have a geometric isomer structure (trans-form, cis-form), but the non-conjugated polyene used as a monomer in the present invention.
- the conjugated polyene (A3) may be a mixture of a trans form and a cis form, or may be a trans form alone or a cis form alone.
- the non-conjugated triene or tetraene (A3-1) represented by the formula (2-1) can be produced by a known method.
- a vinyl group-containing halide eg, aryl halide, halogen halide
- the reaction of the conjugated gen structure-containing triene compound represented by the formula (2-5) with ethylene is usually carried out in the presence of a catalyst.
- a catalyst comprising a transition metal thiocyanate, an organic compound which can be a ligand of the transition metal of this salt, and an organic aluminum compound can be used.
- the non-conjugated cyclic polyene-based copolymer of the present invention comprises a non-conjugated cyclic polyene ( ⁇ 2) such as ⁇ -olefin (A 1) and a non-conjugated cyclic polyene represented by the above formula (111), or ⁇ —Non-conjugated cyclic polyene ( ⁇ 2) such as non-conjugated cyclic polyene represented by the formula (1-1), non-conjugated cyclic polyene represented by the formula (2-1)
- Non-conjugated chain polyene (A3) can be produced by co-polymerization in the presence of a catalyst.
- vanadium vanadium
- a vanadium-based catalyst comprising a soluble vanadium compound (c-1) and an organoaluminum compound (d-1);
- soluble vanadium compound (c-11) an electron donor adduct of a soluble vanadium compound obtained by contacting an electron donor can also be used.
- organoaluminum compound (d-1) forming a vanadium-based catalyst a compound having at least one A 1 -carbon bond in a molecule can be used.
- Such compounds include, for example, those represented by the formula (5)
- the group having a cyclopentagenenyl skeleton may be substituted with a halogen atom, a trialkylsilyl group, or the like.
- the organoaluminoxy compound (d-2) and the ionized ionic compound (e-1) used for forming the metallocene catalyst will be described.
- the organoaluminoxy compound (d-2) may be a known aluminoxane or a benzene-insoluble organoaluminoxy compound (d-2).
- Such a known aluminoxane is specifically represented by the following formula (11) or (12).
- meta-acene catalyst comprising a meta-acene compound (c-2) and an organoaluminoxy compound (d-2) or an ionized ionic compound (e-1)
- a polymer-based catalyst may be used.
- concentration of the meta-mouthed compound (c-2) is usually 0.
- ⁇ -olefin (A 1) and non-conjugated cyclic polyene ( ⁇ 2), or hy-olefin (A 1), non-conjugated cyclic polyene ( ⁇ 2) and non-conjugated cyclic polyene (A 3) The non-conjugated cyclic polyene copolymer having the composition is supplied to the polymerization system in such an amount as to obtain the copolymer.
- a molecular weight regulator such as hydrogen can be used.
- zeolite As the vulcanizing agent (F), zeolite, zeolite compounds, organic peroxides and the like can be used.
- thio compound examples include thio chloride, dichloride, polymer polysulfide, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, selenium dimethyldithiocarbamate, and the like. Is raised.
- vulcanization accelerator examples include N-cyclohexyl-2-benzothiazolsulfenamide (CBS), N-oxydiethylene-2-benzothiazolsulfenamide, N, N-diisopropyl-2 Sulfenamide-based compounds such as -benzothiazolesulfenamide; 2-mercaptobenzothiazole (MBT), 2- (2,4-dinitropenyl) mercaptobenzothiazole, 2- (2,6-ethyl) -4-morpholinothio) benzothiazole, 2- (4'-morpholinodithio) benzothiazol, thiazole compounds such as dibenzothiazyl disulfide; diphenyldananidin, triphenylphenylguanidine, diorsonitriluguanidine, orthonitrylbiguanide, Guanidine compounds such as diphenylguanidinephthalate; acetate aldehydes Reaction products, butyl alde
- the vulcanization aid is used in an amount of 0.5 to 2 mol, preferably approximately equimolar to 1 mol of the organic peroxide. It is preferable.
- the compounding amount of the reinforcing agent depends on the non-conjugated cyclic polyene copolymer (A) and the gen-based rubber. It is desirably 300 parts by weight or less, preferably 100 to 300 parts by weight, more preferably 10 to 200 parts by weight, based on 100 parts by weight in total with (B).
- a vulcanized rubber having improved mechanical properties such as tensile strength, tear strength and abrasion resistance can be obtained.
- the hardness can be increased without impairing other physical properties of the vulcanized rubber, and the cost can be further reduced.
- the rubber composition of the present invention may further contain, as other components, compounds constituting a foaming system such as a foaming agent, a foaming aid, an antioxidant (stabilizer), a processing aid, and a plasticizer.
- a foaming system such as a foaming agent, a foaming aid, an antioxidant (stabilizer), a processing aid, and a plasticizer.
- agents such as agents, coloring agents and other rubber compounding agents can be compounded.
- the type and content of other components are appropriately selected depending on the application.
- the foaming agent is used in an amount of 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, based on a total of 100 parts by weight of the non-conjugated cyclic polyene copolymer ( ⁇ ) and the gen-based rubber ( ⁇ ⁇ ). It can be used in parts amounts. From the rubber composition containing the foaming agent in such an amount, a foam having an apparent specific gravity of 0.03 to 0.8 g / cm 3 can be produced.
- a foaming aid can be used together with the foaming agent.
- the foaming agent has effects such as lowering the decomposition temperature, accelerating the decomposition, and homogenizing the bubbles.
- examples of such a foaming aid include organic acids such as salicylic acid, phthalic acid, stearic acid and oxalic acid, urea and derivatives thereof.
- the rubber composition of the present invention preferably contains an antioxidant because the material life can be extended.
- an antioxidant include phenylnaphthylamine, 4,4 '-(a, ⁇ -dimethylbenzyl) diphenylamine, N, N'-di-2-naphthyl- ⁇ -phenylenediamine and the like. 2,6-di-1-butyl-4-methyl-2-aromatic secondary amine stabilizer CT / JP
- a heating tank such as a hot air, a fluidized bed of glass beads, UHF (ultra-high frequency electromagnetic wave), steam or LCM (hot molten salt tank) is used. It is preferred to heat at a temperature of 150-270 ° C for 1-30 minutes.
- a mold may be used, or a mold may not be used.
- the rubber composition is usually continuously molded and vulcanized.
- the rubber composition of the present invention can achieve both the improvement of braking performance by improving the grip property with the road surface and the improvement of fuel economy by reducing the rolling resistance during stable running.
- the rubber composition of the present invention is excellent in weather resistance, ozone resistance, rubber elasticity, mechanical strength, hardness and the like.
- the rubber composition of the present invention can be widely used as a raw material for rubber products, It can be suitably used as a rubber material for tires.
- Specific examples of rubber materials for tires include materials such as tire treads and tire side walls. Of these, it is most preferable to use it as a material (raw material) for a tire tread. In this case, the characteristics of the rubber composition of the present invention are most effectively exhibited, and excellent damping performance, excellent fuel efficiency and And a tire with excellent weather resistance and ozone resistance can be obtained.
- the rubber material for a tire of the present invention contains the non-conjugated cyclic polyene-based copolymer (A) of the present invention, and may be composed of only the non-conjugated cyclic polyene-based copolymer (A). Rubber or additives may be included.
- the content of the non-conjugated cyclic polyene-based copolymer (A) in the rubber material for a tire of the present invention is 3% by weight or more, preferably 5 to 90% by weight.
- the rubber material for a tire of the present invention has both excellent braking performance and excellent fuel economy performance, and is also excellent in rubber elasticity, mechanical strength, weather resistance, ozone resistance, hardness and the like. Specific examples of the rubber material for a tire include the same as described above.
- the rubber material for a tire of the present invention contains the rubber composition of the present invention, and may be composed of only the rubber composition of the present invention, or may contain other rubbers and additives. Good.
- the content of the rubber composition of the present invention in the rubber material for a tire of the present invention is 3% by weight or more, and preferably 5 to 90% by weight.
- the rubber material for a tire of the present invention has both excellent braking performance and excellent fuel economy performance, and also has excellent rubber elasticity, mechanical strength, weather resistance, ozone resistance, hardness and the like. Specific examples of the rubber material for a tire include the same as described above.
- the tire tread of the present invention is obtained from the rubber material for a tire of the present invention.
- the tire tread may be obtained from only the rubber material for a tire of the present invention, or may include other rubbers and additives. May be.
- the content of the rubber material for tire of the present invention in the tire tread of the present invention is 3% by weight / 0 . Or more, preferably is desirably 5-9 0 weight 0/0.
- Ties obtained by vulcanizing the rubber composition or the rubber material for tires of the present invention PT / JP
- the jarred has both excellent braking performance and excellent fuel efficiency, and is also excellent in weather resistance and ozone resistance.
- the tire of the present invention is a tire provided with the tire tread of the present invention.
- the tire of the present invention has both excellent braking performance and excellent fuel economy performance, and is also excellent in weather resistance, ozone resistance and the like.
- the rubber composition of the present invention contains a non-conjugated cyclic polyene-based copolymer having specific physical properties and a gen-based rubber at a specific ratio, so that both excellent braking performance and excellent fuel efficiency are achieved. You can get tires.
- the rubber material for a tire of the present invention contains the above-mentioned non-conjugated cyclic polyene-based copolymer or rubber composition, the rubber material has both excellent braking performance and excellent fuel efficiency, rubber elasticity and mechanical properties. Excellent strength, weather resistance, ozone resistance, hardness, etc.
- the tire tread of the present invention is obtained from the rubber material for a tire, the tire tread has both excellent damping performance and excellent fuel economy performance, and also has excellent weather resistance and ozone resistance.
- the tire of the present invention Since the tire of the present invention is provided with the above-described tire tread, it has both excellent braking performance and excellent fuel economy performance, and also has excellent weather resistance, ozone resistance and the like.
- BEST MODE FOR CARRYING OUT THE INVENTION is provided with the above-described tire tread, it has both excellent braking performance and excellent fuel economy performance, and also has excellent weather resistance, ozone resistance and the like.
- the unvulcanized compounded rubber was heated by a press heated to 160 ° C. for 20 minutes to produce a vulcanized sheet, and the following tests were performed.
- Table 4 shows the results.
- Table 3 Units of compounding amount parts by weight
- Vulcanization accelerator C B Z * 5 0.5
- HAF carbon black HAF Asahi # 70 (trademark), manufactured by Asahi Carbon
- Vulcanization accelerator DPG Sansera I D (trademark), manufactured by Sanshin Chemical Co., Ltd.
- Example 7 was carried out in the same manner as in Example 7 except that the non-conjugated cyclic polyene-based copolymer was not used, and that 100 parts by weight of 38 shaku was used. Table 4 shows the results. Table 4 Example 7 Comparative Example 1
- ta ⁇ ⁇ (attenuation rate) of the rubber composition at 0 ° C was used as an index of tire damping. The greater the value of ta ⁇ ⁇ at 0 ° C, the better the braking performance.
- t a ⁇ ⁇ (attenuation rate) of the rubber composition at 50 ° C was used as an index of vehicle fuel efficiency. The smaller the value of ta ⁇ ⁇ at 50 ° C, the better the fuel economy.
- the tan S (attenuation rate) was determined from a rubber composition by molding a 10 mm-wide, 2 mm-thick, 30 mm-long strip-shaped sample from this rubber composition, and using this sample, a RD manufactured by Rheometrics Co., Ltd.
- the temperature dispersion of viscoelasticity was measured by S-II under the condition of 1 Hz (6.28 rad / sec).
- the unvulcanized compounded rubber was heated by a press heated to 160 ° C. for 20 minutes to prepare a vulcanized sheet, and the following tests were performed. Table 6 shows the results.
- HAF Ribon Black HAF Asahi # 70 (trademark), manufactured by Asahi Ribon * 4 Vulcanization accelerator CBZ: Suncellar CM (trademark), manufactured by Sanshin Chemical Co., Ltd.
- Example 8 was carried out in the same manner as in Example 8, except that 100 parts by weight of SBR was used without using the non-conjugated cyclic polyene copolymer. Table 6 shows the results.
- non-conjugated cyclic polyene-based copolymer and rubber composition of the present invention can be suitably used as raw materials for rubber materials for tires, tire treads and tires.
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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)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Tires In General (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE60024652T DE60024652T2 (de) | 1999-08-10 | 2000-08-09 | Unkonjugiertes cyklisches polyencopolymer, kautschukzusammensetzung und verwendung |
EP00951912A EP1217015B1 (en) | 1999-08-10 | 2000-08-09 | Unconjugated cyclopolyene copolymer, rubber composition, and use |
US09/787,890 US6787623B1 (en) | 1999-08-10 | 2000-08-09 | Unconjugated cyclopolyene copolymer, rubber composition, and use |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11/226917 | 1999-08-10 | ||
JP22691799 | 1999-08-10 |
Publications (1)
Publication Number | Publication Date |
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WO2001012686A1 true WO2001012686A1 (fr) | 2001-02-22 |
Family
ID=16852633
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2000/005330 WO2001012686A1 (fr) | 1999-08-10 | 2000-08-09 | Copolymere de cyclopolyene non conjugue, composition de caoutchouc et utilisation |
Country Status (7)
Country | Link |
---|---|
US (1) | US6787623B1 (ja) |
EP (1) | EP1217015B1 (ja) |
JP (1) | JP5287018B2 (ja) |
KR (1) | KR100632821B1 (ja) |
CN (1) | CN1191283C (ja) |
DE (1) | DE60024652T2 (ja) |
WO (1) | WO2001012686A1 (ja) |
Cited By (1)
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EP1152016A1 (en) * | 1999-11-22 | 2001-11-07 | Mitsui Chemicals, Inc. | Ethylene copolymer rubber, process for producing the same, and use |
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DE60137727D1 (de) * | 2001-12-21 | 2009-04-02 | Pirelli | Cycloolefinpolymer enthaltende reifen, lauffläche und elastomerische zusammensetzung |
WO2005105913A1 (ja) * | 2004-04-28 | 2005-11-10 | Mitsui Chemicals, Inc. | ゴム組成物およびその用途 |
KR20080092459A (ko) * | 2004-04-28 | 2008-10-15 | 미쓰이 가가쿠 가부시키가이샤 | 비공액 폴리엔계 공중합체 및 고무 조성물 |
EP1741746A4 (en) * | 2004-04-28 | 2010-10-20 | Mitsui Chemicals Inc | METHOD OF MANUFACTURING RUBBER COMPOSITION, RUBBER COMPOSITION AND USE THEREOF |
WO2007060723A1 (ja) * | 2005-11-24 | 2007-05-31 | Polyplastics Co., Ltd. | シクロオレフィン系共重合体 |
CN101346425B (zh) * | 2005-12-27 | 2011-07-20 | 住友橡胶工业株式会社 | 侧壁用橡胶组合物及其制造方法 |
KR100814161B1 (ko) * | 2006-12-05 | 2008-03-14 | 금호타이어 주식회사 | 타이어 트레드용 고무조성물 |
JP2009138046A (ja) * | 2007-12-04 | 2009-06-25 | Sumitomo Chemical Co Ltd | ゴム組成物および防振材 |
FR2975999B1 (fr) * | 2011-06-01 | 2014-07-04 | Michelin Soc Tech | Pneu dont la bande de roulement comporte une composition de caoutchouc thermo-expansible reduisant les bruits de roulage |
TWI522375B (zh) * | 2011-10-13 | 2016-02-21 | Mitsui Chemicals Inc | An ethylene-based copolymer, a composition containing the copolymer, and a molded product and a film or sheet made of a vinyl copolymer or a composition |
WO2015122415A1 (ja) | 2014-02-13 | 2015-08-20 | 三井化学株式会社 | エチレン・α-オレフィン・非共役ポリエン共重合体およびその用途、並びにその製造方法 |
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- 2000-08-09 WO PCT/JP2000/005330 patent/WO2001012686A1/ja active IP Right Grant
- 2000-08-09 KR KR1020017004281A patent/KR100632821B1/ko not_active IP Right Cessation
- 2000-08-09 US US09/787,890 patent/US6787623B1/en not_active Expired - Fee Related
- 2000-08-09 CN CNB008022089A patent/CN1191283C/zh not_active Expired - Fee Related
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EP1152016A1 (en) * | 1999-11-22 | 2001-11-07 | Mitsui Chemicals, Inc. | Ethylene copolymer rubber, process for producing the same, and use |
EP1152016A4 (en) * | 1999-11-22 | 2003-03-26 | Mitsui Chemicals Inc | RUBBER OF ETHYLENE POLYMER, METHOD FOR THE PRODUCTION THEREOF AND USE THEREOF |
US6635727B1 (en) | 1999-11-22 | 2003-10-21 | Mitsui Chemicals, Inc. | Ethylene copolymer rubber, process for producing the same, and use |
Also Published As
Publication number | Publication date |
---|---|
EP1217015A4 (en) | 2002-11-04 |
CN1327454A (zh) | 2001-12-19 |
CN1191283C (zh) | 2005-03-02 |
US6787623B1 (en) | 2004-09-07 |
JP2008308696A (ja) | 2008-12-25 |
DE60024652T2 (de) | 2006-06-22 |
DE60024652D1 (de) | 2006-01-12 |
KR100632821B1 (ko) | 2006-10-16 |
EP1217015B1 (en) | 2005-12-07 |
KR20010075584A (ko) | 2001-08-09 |
JP5287018B2 (ja) | 2013-09-11 |
EP1217015A1 (en) | 2002-06-26 |
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