JPH0231731B2 - SHINKINAGO MUZAIRYO - Google Patents
SHINKINAGO MUZAIRYOInfo
- Publication number
- JPH0231731B2 JPH0231731B2 JP8548181A JP8548181A JPH0231731B2 JP H0231731 B2 JPH0231731 B2 JP H0231731B2 JP 8548181 A JP8548181 A JP 8548181A JP 8548181 A JP8548181 A JP 8548181A JP H0231731 B2 JPH0231731 B2 JP H0231731B2
- Authority
- JP
- Japan
- Prior art keywords
- block
- polymer
- aromatic hydrocarbon
- weight
- monovinyl aromatic
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired - Lifetime
Links
- 229920000642 polymer Polymers 0.000 claims description 33
- 229920001400 block copolymer Polymers 0.000 claims description 27
- 238000005096 rolling process Methods 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 8
- 150000001993 dienes Chemical class 0.000 claims description 8
- 229920001971 elastomer Polymers 0.000 claims description 8
- 239000005060 rubber Substances 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 229920005604 random copolymer Polymers 0.000 claims description 7
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005299 abrasion Methods 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 229920003048 styrene butadiene rubber Polymers 0.000 description 14
- 239000002174 Styrene-butadiene Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 229920002857 polybutadiene Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003999 initiator Substances 0.000 description 5
- 125000001979 organolithium group Chemical group 0.000 description 5
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 101100228469 Caenorhabditis elegans exp-1 gene Proteins 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 230000020169 heat generation Effects 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 1
- APCLRHPWFCQIMG-UHFFFAOYSA-N 4-(5,6-dimethoxy-1-benzothiophen-2-yl)-4-oxobutanoic acid Chemical compound C1=C(OC)C(OC)=CC2=C1SC(C(=O)CCC(O)=O)=C2 APCLRHPWFCQIMG-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- QWFRFVPEFDDMQD-UHFFFAOYSA-N [Li]CCCCCCCCCC[Li] Chemical compound [Li]CCCCCCCCCC[Li] QWFRFVPEFDDMQD-UHFFFAOYSA-N 0.000 description 1
- QQDSVXYDUMVTSQ-UHFFFAOYSA-N [Li]CCCCC[Li] Chemical compound [Li]CCCCC[Li] QQDSVXYDUMVTSQ-UHFFFAOYSA-N 0.000 description 1
- BZEZSORUWZUMNU-UHFFFAOYSA-N [Li]CCCC[Li] Chemical compound [Li]CCCC[Li] BZEZSORUWZUMNU-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011630 iodine Chemical group 0.000 description 1
- 229910052740 iodine Chemical group 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- VJHDVMPJLLGYBL-UHFFFAOYSA-N tetrabromogermane Chemical compound Br[Ge](Br)(Br)Br VJHDVMPJLLGYBL-UHFFFAOYSA-N 0.000 description 1
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Description
本発明は共役ジオレフインとモノビニル芳香族
炭化水素を原料とし、モノビニル芳香族炭化水素
結合含有量の異る二つの重合体ブロツク部を有
し、かつ金属と炭素の結合を分子鎖にもつ重合体
を含有するブロツク共重合体に関する。
近年ウエツトスキツド抵抗性、転がり摩擦抵抗
性の改良を図るべく、主として有機リチウム開始
剤を用いて得られるSBR（スチレンブタジエンゴ
ム）、BR（ブタジエンゴム）の改質が試みられて
いる。最近ビニル結合の多いBRを含むゴム組成
物（英国特許第1166832号）が上記目的に合致す
るものとして提案されている。ビニル結合の多い
BRはウエツトスキツド抵抗性と転がり摩擦抵抗
性のバランスを取る上で優れているが、破壊特
性、摩耗特性が著しく劣つているため、単独で使
用するのは困難である。破壊特性、摩耗特性を改
良するため、NR（天然ゴム）、高シスBR、乳化
重合SBRなどのジエンゴムとのブレンド組成物
が提案されている。しかしNRまたは高シスBR
とのブレンド組成物ではウエツトスキツド抵抗性
と破壊特性、摩耗特性のバランスに劣り、SBR
とのブレンド組成物では転がり摩擦抵抗性に劣る
といつた欠点があつた。
また特開昭54−62248では結合スチレン含有量
が20〜40重量％でブタジエン部のビニル結合含有
率が比較的高いランダムSBRを用いることによ
りウエツトスキツド抵抗性と転がり摩擦抵抗性の
改良が試みられている。従来の乳化重合SBR、
有機リチウム開始剤により得られたSBRに比べ
確かにウエツトスキツド抵抗性、転がり摩擦抵抗
性、摩耗特性などのバランスは良くなつている
が、実用に供するには未だ不満足であり、他のジ
エンゴムとブレンドして使用せざるを得ない。し
かしどのゴムとのブレンド系においても高ビニル
BR同様ウエツトスキツド抵抗性、転がり摩擦抵
抗性、破壊特性、摩耗特性のバランスが不満足で
ある。
以上のように、SBRのビニル結合含有率を高
くすることにより比較的良好な物性のバランスが
得られるということ、およびポリマーブレンドに
おいてブレンドするポリマーの特性を活かしきれ
ていないという知見に基ずき、本発明者らは特願
昭55−178226、特願昭55−186194、特願昭55−
186195で提案したように、結合スチレン含有率、
ビニル結合含有率の異なるランダム共重合体のブ
ロツクからなるスチレン−ブタジエンブロツク共
重合体に於いて、各ブロツク部の結合スチレン、
ビニル結合を特定の範囲から選ぶことによりウエ
ツトスキツド抵抗性、転がり摩擦抵抗性、摩耗特
性、破壊特性のバランスに優れ、さらに従来の
SBRに比べて加工性をも改良されることを見出
した。これらのブタジエンブロツク共重合体は、
異つた特性を持ち、異つたソリユビリテイー・パ
ラメーター（Solubility Parameter）を持つた二
つ以上のブロツク部が加硫工程を通して相溶化さ
れるため、動力学的測定法による温度−tanδの分
散曲線のピークが単一なものとなりかつブロード
化されており、低温特性的に特徴のあるポリマー
になつている。しかしながら昨今のこれらブタジ
エンブロツク共重合体に対する社会的あるいは工
業的要求を考慮すると、該ブロツク共重合体は摩
耗特性、破壊特性の点で未だ不満足である。
本発明者らは、さらに有機リチウム開始剤を用
いて得られる共重合ゴムの物性改良に鋭意努力し
た結果、ムーニー粘度が20〜150でモノビニル芳
香族炭化水素の含有率の異なる２種類の特定のラ
ンダム共重合体のブロツクからなり、重合体の一
部が分子鎖中に金属と炭素との結合を有するブロ
ツク共重合体が、ウエツトスキツド抵抗性、転が
り摩擦抵抗性および破壊特性、摩耗特性に優れて
いることを見出し本発明に至つた。
すなわち本発明は、共役ジオレフイン、モノビ
ニル芳香族炭化水素を原料としており、モノビニ
ル芳香族炭化水素結合含有量を10重量％以下含む
（共）重合体ブロツク(A)およびモノビニル芳香族
炭化水素結合含有量を15〜50重量％含む共重合体
ブロツク(B)よりなるブロツク共重合体であつて、
(i) ブロツク(A)とブロツク(B)のそれぞれのブロツ
クを少なくとも10重量％以上含み、
(ii) 該ブロツク共重合体の全モノビニル芳香族炭
化水素結合含有量が10〜40重量％であり、
(iii) 該ブロツク共重合体の共役ジオレフイン部の
平均全ビニル結合含有量が20〜70％であり、
(iv) 該ブロツク共重合体が金属と炭素との結合を
分子鎖中に有する重合体を少なくとも20％含有
する
ことを特徴とするブロツク共重合体を提供するも
のである。
従来の有機リチウム開始剤使用して得られた
SBRはウエツトスキツド抵抗性、破壊特性、加
工性に劣つており、また乳化重合で得られた
SBRはウエツトスキツド抵抗性、転がり摩擦抵
抗性に不満足であつた。本発明のブロツクポリマ
ーは上記SBRの欠点を改良した極めて有用なポ
リマーである。
このような優れた諸物性は、異つたモノマー組
成、異つたガラス転移温度を持つ(A)、(B)２つの共
重合体ブロツク部が加硫工程を通して相溶化され
ることと、分子鎖中に金属−炭素結合を有する重
合体を含有することで加工性等が改良されること
で発現されているものと推測できる。本発明のブ
ロツクポリマーは、動力学的測定法による温度−
tanδの分散曲線のピークもブロード化されてお
り、低温特性も良好となつている。
本発明の重合体ブロツク(A)に相当するランダム
（共）重合体と、重合体ブロツク(B)に相当するラ
ンダム共重合体と他のゴムを単純にブレンドして
も本発明の優れた物性は得られない。分子鎖中に
金属−炭素結合をもつ重合体を含有していなけれ
ばならない。分子鎖中に金属−炭素結合を持つ重
合体を含有していないブロツク共重合体は本発明
のブロツク共重合体に比べて引張り強さなどに代
表される破壊特性などに劣つている。
本発明において用いられる共役オレフインは、
ブタジエン、イソプレンなどである。
ブロツク共重合体中のモノビニル芳香族炭化水
素としては通常、スチレン、α−メチルスチレ
ン、ｐ−メチルスチレン、ビニルトルエンなどが
用いられ特にスチレンが好ましい。モノビニル芳
香族炭化水素結合含有量は重合体ブロツク(A)が10
重量％以下、重合体ブロツク(B)が15〜50重量％、
好ましくは20〜45重量％でブロツク共重合体の全
モノビニル芳香族炭化水素結合含有量は10〜40重
量％好ましくは15〜35重量％である。重合体ブロ
ツク(A)のモノビニル芳香族炭化水素結合含有量が
10重量％をこえると転がり摩擦抵抗性に劣つてい
る。(B)重合体ブロツク(B)のモノビニル芳香族炭化
水素結合含有量が15重量％未満であると破壊特
性、ウエツトスキツド抵抗性に劣り50重量％をこ
えると転がり摩擦抵抗性に劣つてくる。
(A)、(B)各ブロツク部の共役ジオレフインの結合
様式は特に限定されないが、ウエツトスキツド抵
抗性、転がり摩擦抵抗性のバランスから見てブロ
ツク共重合体中の平均のビニル結合含有率は20〜
70％の範囲にあることが必要である。
ブロツク共重合体中に重合体ブロツク(A)、重合
体ブロツク(B)は各々少なくとも10重量％、好まし
くは20重量％以上含まれていることが必要であ
る。(A)、(B)どちらかの重合体ブロツクが10重量％
より小さくなるとウエツトスキツド特性、転がり
摩擦抵抗性のバランスが不満足なものとなりかつ
tanδの温度分散曲線のブロード化も図れない。ま
た各ブロツク部の結合様式がＡ−Ｂ−Ａ、Ｂ−Ａ
−Ｂ、Ａ−Ｂ−Ａ−Ｂ−Ａのようなマルチブロツ
クタイプになつていても、本発明の物性は損われ
ない。
本発明ブロツク共重合体の大きな特徴は、分子
鎖中に金属−炭素結合を持つ重合体を含有してい
ることにある。分子鎖中に金属−炭素結合を有す
る重合体はブロツク共重合体中に20重量％以上含
まれている必要がある。20重量％未満では破壊特
性および加工性が劣つてくる。炭素を結合する金
属としてケイ素、ゲルマニウム、錫、鉛などがあ
げられ、特に錫が好ましい。金属−炭素の結合様
式はブタジエニル−金属、イソプレニル−金属結
合を取ることが好ましい。また本発明のブロツク
共重合体において金属と炭素の結合を分子鎖中に
有する重合体の分子末端部はブロツク(A)である方
が転がり摩擦抵抗性等に優れ好ましい。
ブロツク共重合体のムーニー粘度（ML100℃1+4）
は20〜150が好ましく、20未満では破壊特性、転
がり摩擦抵抗性の点で劣り、150をこえると加工
性に劣つている。
本発明のブロツク共重合体は、炭化水素溶媒中
でエーテルまたは第３級アミンの存在下で有機リ
チウム化合物を用いて所望する(A)または(B)ブロツ
クのモノマー組成比でモノビニル芳香族炭化水素
と共役ジエンを共重合した後、更にもう一方のブ
ロツクのモノマー組成比でポリマーを添加して重
合し、その後ケイ素、ゲルマニウム、錫、鉛など
から選ばれた１種の金属ハライドを添加し、カツ
プリング反応せしめることによつて得られる。
各ブロツク部のミクロ構造コントロール剤、モ
ノビニル芳香族炭化水素のランダム化剤として使
用されるエーテル、第３級アミンとしては、エチ
ルエーテル、チオエーテル、アミルエーテル、テ
トラヒドロフラン、ジオキサン、エチレングリコ
ールジメチルエーテル、トリエチルアミン、Ｎ，
Ｎ，N′，N′−テトラメチルエチレンジアミン、
トリエチレンジアミン、Ｎ−メチルモルホリンな
どがある。
有機リチウム開始剤としてメチルリチウム、エ
チルリチウム、ｎ−ブチルリチウム、sec−ブチ
ルリチウム、フエニルリチウム、テトラメチレン
ジリチウム、ペンタメチレンジリチウム、デカメ
チレンジリチウムなどが用いられる。
重合溶媒としてはベンゼン、トルエン、キシレ
ン、シクロヘキサン、ヘキサン、ヘプタンなどが
使用される。
重合温度は通常０℃〜150℃の範囲にすること
が好ましい。
カツプリング剤としては、通常金属ハライドが
用いられ、一般式(1)、(2)、(3)で示される化合物が
あげられる。
(1) RuMX4-o
(2) M′X2
(3) X3M−R′−MX3又はX2RM−R′−MRX2
但しＭはSi、Ge、Sn，Pb；M′はSn又はPb；
Ｘは塩素、臭素又はヨウ素；
Ｒはアルキル基、アリル基、アリール基
R′はアルキレン基、アリール基、
ｎは０〜２の整数を示す。
具体的に例をあげれば、四塩化ケイ素、四臭化
ケイ素、四塩化ゲルマニウム、四臭化ゲルマニウ
ム、四塩化スズ、二塩化スズ、二塩化鉛、ジメチ
ルジクロロシランなどがある。
本発明のブロツク共重合体は優れた諸特性を活
かして単独でまたは天然ゴムや合成ゴムとブレン
ドし、通常の加硫ゴム用配合剤を加え加硫して、
履物底およびコンベアベルト、パツキン、ホー
ス、窓枠などの各種の工業用品用途に利用でき
る。
以下に本発明を実施例をあげてさらに詳細に説
明するが本発明はその要旨を越えない限りこれら
実施例によつて制限されるものではない。なおウ
エツトスキツド抵抗性の指標としてスキツドテス
ターによるウエツトスキツド抵抗を用い、転がり
摩擦抵抗性の指標として70℃での反撥弾性、グツ
ドリツチフレクソメーターによる発熱温度を用い
た。
実施例１〜10 比較例１〜７
表−１のサンプル（Exp−１〜18）を表−２の
重合処方により得た。溶媒としてシクロヘキサン
を用い、重合開始剤にはｎ−ブチルリチウムを使
用してまず重合体ブロツク(A)の重合条件下で重合
を実施した。重合転化率が95〜100％に達した後、
さらに所望のポリマー、エーテルを仕込み重合体
ブロツク(B)重合条件下で重合した。重合が終了し
た後、少量のブタジエンを添加し、重合体末端を
ブタジエニル−リチウムにした後、所定量のカツ
プリング剤を添加した。
重合体中のスチレン含有量、ビニル結合含有率
は赤外分光光度計により求めた。金属−炭素結合
鎖の含有率はゲルパーミエーシヨンクロマトグラ
フ（GPC）法で測定される高分子量成分の割合
から求めた。
Exp−１〜18の各種サンプルを使用して表−３
に示した配合処方により配合物を調整した。加硫
条件は145℃−30分とした。表−４に得られた加
硫物の性質を示した。
実施例１〜10は引張強さ、ダンロツプ反撥弾
性、グツドリツチ発熱、ウエツトスキツド特性、
ランボーン摩耗特性に優れ、かつバランスが取れ
ており、また加工性も良好である。
比較例１、２、５、６はビニル結合含有量また
はスチレン含有量のいずれかが本特許請求範囲か
ら外れており、実施例１〜10に比べて諸特性のバ
ランスに劣つている。ランダムタイプのSBRを
SnCl4でカツプリングしたサンプルの比較例３は
ウエツトスキツド特性、引張り強さに於いて実施
例１〜10に劣つている。金属−炭素結合鎖を含ま
ないブロツクポリマー（比較例４）は引張り強さ
等に於いて実施例１〜10に劣つている。重合体ブ
ロツク(A)に相当するランダム（共）重合体と重合
体ブロツク(B)に相当するランダム共重合体とを単
純にブレンドしても（比較例７）本発明のラジア
ルブロツク共重合体の物性を発現することはでき
ない。
The present invention uses a conjugated diolefin and a monovinyl aromatic hydrocarbon as raw materials, has two polymer block parts with different monovinyl aromatic hydrocarbon bond contents, and has a metal-carbon bond in the molecular chain. The present invention relates to a block copolymer containing In recent years, attempts have been made to modify SBR (styrene butadiene rubber) and BR (butadiene rubber), which are obtained mainly by using organolithium initiators, in order to improve wet skid resistance and rolling friction resistance. Recently, a rubber composition containing BR with many vinyl bonds (British Patent No. 1166832) has been proposed as meeting the above objective. Many vinyl bonds
BR has an excellent balance between wet skid resistance and rolling friction resistance, but it is difficult to use alone because its fracture and wear characteristics are significantly inferior. Blend compositions with diene rubbers such as NR (natural rubber), high-cis BR, and emulsion polymerized SBR have been proposed to improve fracture and wear characteristics. But NR or high cis BR
Blend compositions with SBR have a poor balance of wet skid resistance, fracture properties, and wear properties;
Blend compositions with 100% had the disadvantage of poor rolling friction resistance. Furthermore, in JP-A-54-62248, an attempt was made to improve wet skid resistance and rolling friction resistance by using random SBR with a bound styrene content of 20 to 40% by weight and a relatively high vinyl bond content in the butadiene moiety. There is. Conventional emulsion polymerization SBR,
Although it certainly has a better balance of wet skid resistance, rolling friction resistance, and abrasion characteristics than SBR obtained using organolithium initiators, it is still unsatisfactory for practical use, and it is difficult to blend it with other diene rubbers. I have no choice but to use it. However, in any blend system with rubber, high vinyl
Like BR, it has an unsatisfactory balance of wet skid resistance, rolling friction resistance, fracture properties, and wear properties. As mentioned above, based on the knowledge that a relatively good balance of physical properties can be obtained by increasing the vinyl bond content of SBR, and that the properties of the blended polymers are not fully utilized in polymer blends, The present inventors have applied for Japanese Patent Applications 178226-1982, 186194-1980,
As proposed in 186195, the bound styrene content,
In a styrene-butadiene block copolymer consisting of blocks of random copolymers with different vinyl bond contents, the bound styrene in each block,
By selecting the vinyl bond from a specific range, it achieves an excellent balance of wet skid resistance, rolling friction resistance, abrasion characteristics, and fracture characteristics.
It was also found that processability was improved compared to SBR. These butadiene block copolymers are
Because two or more block parts with different properties and different solubility parameters are made compatibilized through the vulcanization process, the peak of the temperature-tanδ dispersion curve determined by the kinetic measurement method is It is single and broad, making it a polymer with distinctive low-temperature properties. However, considering the recent social and industrial demands for these butadiene block copolymers, these block copolymers are still unsatisfactory in terms of wear and tear properties. As a result of further efforts to improve the physical properties of copolymer rubber obtained using an organolithium initiator, the present inventors have developed two specific types of rubber with a Mooney viscosity of 20 to 150 and different monovinyl aromatic hydrocarbon contents. Consisting of random copolymer blocks, some of which have metal and carbon bonds in their molecular chains, these block copolymers have excellent wet skid resistance, rolling friction resistance, fracture properties, and wear properties. This discovery led to the present invention. That is, the present invention uses a conjugated diolefin and a monovinyl aromatic hydrocarbon as raw materials, and a (co)polymer block (A) containing a monovinyl aromatic hydrocarbon bond content of 10% by weight or less and a monovinyl aromatic hydrocarbon bond content A block copolymer consisting of a copolymer block (B) containing 15 to 50% by weight, (i) containing at least 10% by weight or more of each of block (A) and block (B), (ii) ) the total monovinyl aromatic hydrocarbon bond content of the block copolymer is 10 to 40% by weight; (iii) the average total vinyl bond content of the conjugated diolefin moiety of the block copolymer is 20 to 70%; and (iv) the block copolymer contains at least 20% of a polymer having a metal-carbon bond in its molecular chain. obtained using conventional organolithium initiators
SBR has poor wet skid resistance, fracture properties, and processability, and is inferior to those obtained by emulsion polymerization.
SBR was unsatisfactory in wet skid resistance and rolling friction resistance. The block polymer of the present invention is an extremely useful polymer that has improved the above-mentioned drawbacks of SBR. These excellent physical properties are due to the fact that the two copolymer blocks (A) and (B), which have different monomer compositions and different glass transition temperatures, are made compatibilized through the vulcanization process, and that the molecular chains are It can be inferred that this is achieved by improving processability etc. by containing a polymer having a metal-carbon bond. The block polymer of the present invention has a temperature -
The peak of the tan δ dispersion curve is also broadened, and the low-temperature properties are also good. Even if a random (co)polymer corresponding to the polymer block (A) of the present invention, a random copolymer corresponding to the polymer block (B), and another rubber are simply blended, the excellent physical properties of the present invention can be achieved. cannot be obtained. It must contain a polymer with metal-carbon bonds in its molecular chain. A block copolymer that does not contain a polymer having a metal-carbon bond in its molecular chain is inferior to the block copolymer of the present invention in fracture properties such as tensile strength. The conjugated olefin used in the present invention is
Butadiene, isoprene, etc. As the monovinyl aromatic hydrocarbon in the block copolymer, styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, etc. are usually used, with styrene being particularly preferred. Monovinyl aromatic hydrocarbon bond content is 10 for polymer block (A).
% by weight or less, polymer block (B) is 15-50% by weight,
The total monovinyl aromatic hydrocarbon bond content of the block copolymer is preferably 10-40% by weight, preferably 15-35% by weight. The monovinyl aromatic hydrocarbon bond content of the polymer block (A) is
If it exceeds 10% by weight, rolling friction resistance is poor. (B) If the monovinyl aromatic hydrocarbon bond content of the polymer block (B) is less than 15% by weight, the fracture properties and wet skid resistance will be poor, and if it exceeds 50% by weight, the rolling friction resistance will be poor. (A) and (B) The bonding mode of the conjugated diolefin in each block part is not particularly limited, but considering the balance between wet skid resistance and rolling friction resistance, the average vinyl bond content in the block copolymer is 20 to 20%.
It needs to be in the 70% range. It is necessary that the polymer block (A) and the polymer block (B) each be contained in the block copolymer in an amount of at least 10% by weight, preferably 20% by weight or more. 10% by weight of either (A) or (B) polymer block
If it becomes smaller, the balance between wet skid characteristics and rolling friction resistance becomes unsatisfactory.
It is also impossible to make the temperature dispersion curve of tan δ broader. Also, the connection style of each block part is A-B-A, B-A.
-B, A-B-A-B-A, etc., the physical properties of the present invention are not impaired. A major feature of the block copolymer of the present invention is that it contains a polymer having metal-carbon bonds in its molecular chain. The polymer having a metal-carbon bond in its molecular chain must be contained in the block copolymer in an amount of 20% by weight or more. If it is less than 20% by weight, fracture properties and processability will be poor. Examples of metals that bind carbon include silicon, germanium, tin, and lead, with tin being particularly preferred. The metal-carbon bond mode is preferably butadienyl-metal or isoprenyl-metal bond. Further, in the block copolymer of the present invention, it is preferable that the molecule end portion of the polymer having a metal-carbon bond in the molecular chain be a block (A) because of excellent rolling friction resistance and the like. Mooney viscosity of block copolymer (ML 100 ℃ 1+4 )
is preferably from 20 to 150; if it is less than 20, it will be poor in fracture properties and rolling friction resistance, and if it exceeds 150, it will be poor in workability. The block copolymer of the present invention can be produced by using an organolithium compound in a hydrocarbon solvent in the presence of an ether or a tertiary amine to form a monovinyl aromatic hydrocarbon at a desired monomer composition ratio of (A) or (B) block. After copolymerizing the conjugated diene and the other block, a polymer is further added and polymerized in the monomer composition ratio of the other block, and then one type of metal halide selected from silicon, germanium, tin, lead, etc. is added, and coupling is performed. Obtained by reaction. Ethers and tertiary amines used as microstructure control agents for each block and randomizing agents for monovinyl aromatic hydrocarbons include ethyl ether, thioether, amyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, triethylamine, N ，
N,N',N'-tetramethylethylenediamine,
Examples include triethylenediamine and N-methylmorpholine. As the organolithium initiator, methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, phenyllithium, tetramethylene dilithium, pentamethylene dilithium, decamethylene dilithium, etc. are used. Benzene, toluene, xylene, cyclohexane, hexane, heptane, etc. are used as the polymerization solvent. The polymerization temperature is usually preferably in the range of 0°C to 150°C. As the coupling agent, metal halides are usually used, and examples thereof include compounds represented by general formulas (1), (2), and (3). (1) RuMX 4-o (2) M′X 2 (3) X 3 M−R′−MX 3 or X 2 RM−R′−MRX 2 where M is Si, Ge, Sn, Pb; M′ is Sn or Pb; X is chlorine, bromine or iodine; R is an alkyl group, allyl group, or aryl group; R' is an alkylene group or aryl group; Specific examples include silicon tetrachloride, silicon tetrabromide, germanium tetrachloride, germanium tetrabromide, tin tetrachloride, tin dichloride, lead dichloride, and dimethyldichlorosilane. Taking advantage of its excellent properties, the block copolymer of the present invention is used alone or blended with natural rubber or synthetic rubber, and is vulcanized with the addition of ordinary compounding agents for vulcanized rubber.
It can be used in various industrial applications such as footwear soles, conveyor belts, packing materials, hoses, and window frames. The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples unless the gist of the invention is exceeded. Wet skid resistance measured by a skid tester was used as an index of wet skid resistance, and rebound elasticity at 70°C and heat generation temperature measured by a wet skid flexometer were used as indicators of rolling friction resistance. Examples 1 to 10 Comparative Examples 1 to 7 Samples (Exp-1 to Exp-18) shown in Table-1 were obtained using the polymerization recipe shown in Table-2. Polymerization was first carried out under the polymerization conditions of polymer block (A) using cyclohexane as a solvent and n-butyllithium as a polymerization initiator. After the polymerization conversion rate reaches 95-100%,
Further, a desired polymer and ether were charged and polymerized under the polymerization conditions of polymer block (B). After the polymerization was completed, a small amount of butadiene was added to convert the polymer terminal to butadienyl-lithium, and then a predetermined amount of a coupling agent was added. The styrene content and vinyl bond content in the polymer were determined using an infrared spectrophotometer. The content of metal-carbon bond chains was determined from the proportion of high molecular weight components measured by gel permeation chromatography (GPC). Table-3 using various samples of Exp-1 to Exp-18
The formulation was prepared according to the formulation shown in . The vulcanization conditions were 145°C for 30 minutes. Table 4 shows the properties of the vulcanizate obtained. Examples 1 to 10 are tensile strength, Dunlop repulsion, stiffness heat generation, wet skid properties,
It has excellent Lambourn wear characteristics, is well balanced, and has good workability. In Comparative Examples 1, 2, 5, and 6, either the vinyl bond content or the styrene content is out of the scope of the present invention, and the balance of various properties is inferior to Examples 1 to 10. Random type SBR
Comparative Example 3, a sample coupled with SnCl4 , is inferior to Examples 1 to 10 in wet skid properties and tensile strength. The block polymer containing no metal-carbon bond chains (Comparative Example 4) is inferior to Examples 1 to 10 in terms of tensile strength and the like. Even if a random (co)polymer corresponding to polymer block (A) and a random copolymer corresponding to polymer block (B) are simply blended (Comparative Example 7), the radial block copolymer of the present invention It is not possible to express the physical properties of
【表】【table】
【表】【table】
【表】【table】
【表】
表 − ３
重量部
ブロツク共重合ゴム 100
ISAFタイプカーボン 50
芳香族プロセス油1) 10
亜鉛華 ４
ステアリン酸 ２
促進剤MSA2) 0.54
DM 3) 0.86
イオウ 2.0
１） 日本合成ゴム社製高芳香族系プロセス油
２） Ｎ−オキシジエチレン−２−ベンゾチアジ
ルスルフエンアミド（大内新興化学工業製）
３） ジベンゾチアジルジスルフイド（大内新興
化学工業製）[Table] Table - 3 Parts by weight Block copolymer rubber 100 ISAF type carbon 50 Aromatic process oil 1) 10 Zinc white 4 Stearic acid 2 Accelerator MSA 2) 0.54 DM 3) 0.86 Sulfur 2.0 1) Made by Japan Synthetic Rubber Co., Ltd. Aromatic process oil 2) N-oxydiethylene-2-benzothiazylsulfenamide (manufactured by Ouchi Shinko Kagaku Kogyo) 3) Dibenzothiazyl disulfide (manufactured by Ouchi Shinko Kagaku Kogyo)
【表】【table】
Claims (1)
ビニル芳香族炭化水素と共重合して得られた、モ
ノビニル芳香族炭化水素結合含有量が10重量％以
下の（共）重合体ブロツク(A)および、共役ジオレ
フインとモノビニル芳香族炭化水素を共重合して
得られたモノビニル芳香族炭化水素結合含有量が
15〜50重量％のランダム共重合体ブロツク(B)より
なるブロツク共重合体であつて、 (i) ブロツク(A)とブロツク(B)のそれぞれのブロツ
クを少なくとも10重量％以上含み、 (ii) 該ブロツク共重合体の全モノビニル芳香族炭
化水素結合含有量が10〜40重量％であり、 (iii) 該ブロツク共重合体の共役ジオレフイン部の
平均全ビニル結合含有量が20〜70％であり、 (iv) 該ブロツク共重合体が、ケイ素、ゲルマニウ
ム、錫、および鉛から選ばれた金属と炭素との
ブタジエニル−金属結合および／またはイソプ
レニル−金属結合を分子鎖中に有する重合体を
少なくとも20％含有している、 ことを特徴とするウエツトスキツド抵抗性、転が
り摩擦抵抗性、破壊特性および摩耗特性に優れた
ゴム材料。 ２ 金属と炭素の結合を分子鎖に有する重合体末
端部がブロツク(A)である特許請求の範囲第１項記
載のゴム材料。[Scope of Claims] 1. A (co)polymer block (A) having a monovinyl aromatic hydrocarbon bond content of 10% by weight or less, obtained by homopolymerizing a conjugated diolefin or copolymerizing it with a monovinyl aromatic hydrocarbon. ) and the monovinyl aromatic hydrocarbon bond content obtained by copolymerizing conjugated diolefin and monovinyl aromatic hydrocarbon.
A block copolymer consisting of 15 to 50% by weight of random copolymer block (B), (i) containing at least 10% by weight or more of each of block (A) and block (B), (ii) ) the total monovinyl aromatic hydrocarbon bond content of the block copolymer is 10 to 40% by weight; (iii) the average total vinyl bond content of the conjugated diolefin moiety of the block copolymer is 20 to 70%; (iv) the block copolymer contains at least a polymer having in its molecular chain a butadienyl-metal bond and/or an isoprenyl-metal bond between a metal selected from silicon, germanium, tin, and lead and carbon; A rubber material with excellent wet skid resistance, rolling friction resistance, fracture properties, and abrasion properties. 2. The rubber material according to claim 1, wherein the terminal portion of the polymer having a metal-carbon bond in the molecular chain is a block (A).
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8548181A JPH0231731B2 (en) | 1981-06-03 | 1981-06-03 | SHINKINAGO MUZAIRYO |
| EP19810305931 EP0054440B1 (en) | 1980-12-17 | 1981-12-17 | Styrene-butadiene block copolymer |
| EP19840106266 EP0134909B1 (en) | 1980-12-17 | 1981-12-17 | Styrene-butadiene block copolymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8548181A JPH0231731B2 (en) | 1981-06-03 | 1981-06-03 | SHINKINAGO MUZAIRYO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57200413A JPS57200413A (en) | 1982-12-08 |
| JPH0231731B2 true JPH0231731B2 (en) | 1990-07-16 |
Family
ID=13860097
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8548181A Expired - Lifetime JPH0231731B2 (en) | 1980-12-17 | 1981-06-03 | SHINKINAGO MUZAIRYO |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0231731B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0629284B2 (en) * | 1985-01-16 | 1994-04-20 | 日本エラストマ−株式会社 | Rubber composition for tires |
| JPS61291610A (en) * | 1985-06-18 | 1986-12-22 | Japan Synthetic Rubber Co Ltd | Block copolymer and its composition |
| JPH0755998B2 (en) * | 1985-12-18 | 1995-06-14 | 日本合成ゴム株式会社 | Oil-extended butadiene block copolymer rubber composition |
| JPH0660274B2 (en) * | 1986-03-24 | 1994-08-10 | 日本合成ゴム株式会社 | Diene rubber composition |
| CN100516103C (en) * | 2001-10-31 | 2009-07-22 | 米其林技术公司 | Preparation process for block copolymers for tire tread compositions, and such copolymers |
| FR2967681B1 (en) * | 2010-11-23 | 2012-11-30 | Michelin Soc Tech | DIAMOND ELASTOMER WITH LOW-FUNCTIONAL IP BLOCKS WITH IMPROVED COLD-FLOWING AND RUBBER COMPOSITION CONTAINING SAME |
-
1981
- 1981-06-03 JP JP8548181A patent/JPH0231731B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57200413A (en) | 1982-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3493461B2 (en) | Rubber composition | |
| US4397994A (en) | High vinyl polybutadiene or styrene-butadiene copolymer | |
| JPS60255838A (en) | Tire rubber composition | |
| JPH0129802B2 (en) | ||
| JPS6245895B2 (en) | ||
| JPH0380165B2 (en) | ||
| US20030119966A1 (en) | Modified rubber, process for producing the same, and composition | |
| US6846873B2 (en) | End-modified diene copolymer and rubber composition for tire tread including the same | |
| JPH0421702B2 (en) | ||
| EP0134909B1 (en) | Styrene-butadiene block copolymer | |
| EP0470693A2 (en) | Pneumatic tires | |
| JPS6250346A (en) | Rubber composition | |
| JPH0231731B2 (en) | SHINKINAGO MUZAIRYO | |
| JPS6360769B2 (en) | ||
| JPS62101638A (en) | Rubber composition | |
| JPH0791323B2 (en) | Novel random styrene-butadiene copolymer and composition thereof | |
| US5164450A (en) | Butadiene copolymer rubber composition | |
| JPS6181445A (en) | Rubber composition | |
| JPH0322413B2 (en) | ||
| JPH0689183B2 (en) | Rubber composition for sidewall | |
| JP3972656B2 (en) | Modified diene polymer rubber, method for producing the same, and rubber composition | |
| JPS6360770B2 (en) | ||
| JPS58122939A (en) | Rubber composition | |
| JPS60240746A (en) | Butadiene copolymer rubber composition | |
| JP3972672B2 (en) | Modified diene polymer rubber, method for producing the same, and rubber composition |