JPH021179B2 - - Google Patents
Info
- Publication number
- JPH021179B2 JPH021179B2 JP546282A JP546282A JPH021179B2 JP H021179 B2 JPH021179 B2 JP H021179B2 JP 546282 A JP546282 A JP 546282A JP 546282 A JP546282 A JP 546282A JP H021179 B2 JPH021179 B2 JP H021179B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polybutadiene
- styrene
- rubber composition
- properties
- 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
Links
- 229920001971 elastomer Polymers 0.000 claims description 20
- 239000005060 rubber Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 229920002857 polybutadiene Polymers 0.000 claims description 19
- 239000005062 Polybutadiene Substances 0.000 claims description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 11
- 229920000642 polymer Polymers 0.000 claims description 10
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- 229910052732 germanium Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 244000043261 Hevea brasiliensis Species 0.000 claims description 3
- 229920003052 natural elastomer Polymers 0.000 claims description 3
- 229920001194 natural rubber Polymers 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims 1
- 150000002900 organolithium compounds Chemical class 0.000 claims 1
- 238000005096 rolling process Methods 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- -1 amyllithium Chemical compound 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- 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
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 125000001979 organolithium group Chemical group 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 239000005063 High cis polybutadiene Substances 0.000 description 1
- 239000005064 Low cis polybutadiene 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
- 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
- 229910021623 Tin(IV) bromide Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 1
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 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
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000002994 raw material Substances 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
- IEXRMSFAVATTJX-UHFFFAOYSA-N tetrachlorogermane Chemical compound Cl[Ge](Cl)(Cl)Cl IEXRMSFAVATTJX-UHFFFAOYSA-N 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Description
本発明は転がり摩擦抵抗が小さくウエツトスキ
ツド抵抗が大きくてタイヤトレツドに適するゴム
組成物に関する。
自動車の低燃費化、走行安全性の要求からタイ
ヤトレツド用ゴムとして転がり摩擦抵抗が小さ
く、かつ湿れた路面でのすべり抵抗（ウエツトス
キツド抵抗）の大きいゴム材料が強く望まれてい
る。しかしこれら特性は相反する特性で、従来こ
れら特性を同時に満足するゴムはなかつた。そこ
でこれら特性の調和をとるため異種ゴムのブレン
ド組成物が用いられてきた。
乗用車用タイヤトレツドゴムとしては乳化重合
スチレンブタジエン共重合体、溶液重合スチレン
ブタジエン共重合体などのスチレンブタジエン共
重合体と高シスポリブタジエン、低シスポリブタ
ジエンなどのポリブタジエンとのブレンドゴム組
成物が広く用いられてきた。
しかしこれらブレンド組成物は転がり摩擦抵
抗、ウエツトスキツド特性の点で必らずしも十分
でない。
本発明の目的は破壊特性を損なうことなく転が
り摩擦抵抗が小さくウエツトスキツド抵抗が大き
いゴム組成物を提供することにある。
本発明に従つて、
ａ） スズ、ケイ素及びゲルマニウムから選ばれ
る少なくとも一種の金属と炭素との結合を分子
鎖に含む重合体を少なくとも20重量％含有し、
ビニル結合含有量が20％以上で60％未満である
ポリブタジエン20〜80重量％
ｂ） 結合スチレンが10〜40重量％でかつポリブ
タジエン部分のビニル含量が50％以下であるス
チレンブタジエン共重合体20〜80重量％及び
ｃ） 天然ゴム、シスポリイソプレン、シスポリ
ブタジエンから選ばれる一種以上のゴム０〜40
重量％からなるゴム組成物
が提供される。
本発明のゴム組成物の特徴は金属−炭素結合を
分子鎖中に含有する重合体を少なくとも20重量％
含有し、ビニル結合含有量が20〜60％、好ましく
は30〜50％であるポリブタジエン(a)を用いること
である。ポリブタジエン(a)の金属−炭素結合鎖含
有量が20％未満であれば転がり摩擦抵抗及び破壊
特性が改良されない。
またビニル結合含有量が20％未満であればウエ
ツトスキツド抵抗が向上しない、一方ビニル結合
含有量が60％をこえると本発明の(b)成分のスチレ
ンブタジエン共重合体との相溶性が悪くなり転が
り抵抗及び破壊特性が向上しない。
更にポリブタジエン(a)のムーニー粘度は好まし
くは20〜150、より好ましくは30〜80である。ム
ーニー粘度が20未満では破壊特性、転がり摩擦特
性が劣り、一方150をこえると加工性が劣る。
本発明のポリブタジエン(a)は、好ましくは、不
活性炭化水素溶媒中で有機リチウム開始剤を用い
てエーテル、第３級アミンなどの極性化合物の存
在下で１，３−ブタジエンを重合させ、ついで分
子鎖中に金属−炭素結合を導入することにより製
造される。
ここで有機リチウム開始剤としてたとえばメチ
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、アミルリチウム、
フエニルリチウムなどが用いられる。エーテル、
第３級アミンなどはミクロ構造のコントロール剤
として用いられ、たとえばジオキサン、テトラヒ
ドロフラン、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などが示される。重合
溶媒としてベンゼン、トルエンの如き芳香族炭化
水素、シクロヘキサン、メチルシクロペンタンの
如き脂還式炭化水素、プロパン、ペンタン、ｎ−
ヘキサンの如き脂肪族炭化水素が用いられる。
上記の重合反応の方法及び条件については例え
ば特願昭55年12月16日付出願の特願昭55−177831
号（特開昭57−100108号）に詳細に記載されてい
る。
かくして得られた重合体の分子鎖にケイ素、ゲ
ルマニウム、スズから選ばれる少なくとも一種の
金属を導入する方法として例えばカツプリング反
応を利用することができる。
カツプリング剤としてはハロゲン化ケイ素、ハ
ロゲン化ゲルマニウムあるいはハロゲン化スズ等
が用いられるが、工業的原材料の入手性から二塩
化スズ、四塩化ケイ素、四臭化ケイ素、四塩化ス
ズ、四臭化スズ、四塩化ゲルマニウム等が好適に
用いられる。
本発明のゴム組成物に於いてポリブタジエンの
割合は20−80重量％であり、20重量％未満では転
がり摩擦抵抗の点で不十分であり、80重量％をこ
えるとウエツトスキツド抵抗及び破壊特性の点で
不十分である。
本発明のスチレンブタジエン共重合体(b)は結合
スチレンが10−40重量％好ましくは15−35重量％
であり、かつポリブタジエン部分のビニル含量が
50％以下、ムーニー粘度ML100℃
１＋４が20−150の
重合体で乳化重合又は溶液重合で得られる非油展
又は油展のランダムなスチレンブタジエン共重合
体が用いられる。
結合スチレンが10重量％未満ではウエツトスキ
ツド抵抗特性が悪くなり、又結合スチレンが40重
量％を越えたりポリブタジエン部分のビニル含量
が50重量％を越えると前述のポリブタジエン(a)と
の相溶性が悪くなり、又転がり摩擦抵抗特性が悪
くなる。
尚、スチレン−ブタジエン共重合体(b)としてス
ズ、ケイ素、ゲルマニウム等の金属と炭素結合鎖
を含むスチレン−ブタジエン共重合体であつても
よい。
本発明のゴム組成物のスチレン−ブタジエン共
重合体(b)の割合は20−80重量％であり、20重量％
未満ではウエツトスキツド抵抗及び破壊特性の点
では不十分であり、80重量％をこえると転がり摩
擦抵抗の点で不十分である。
本発明の他のゴム成分(c)として天燃ゴム、シス
１，４−ポリイソプレン、シス１，４−ポリブタ
ジエンから選ばれた一種又は二種以上のゴムが40
重量％以下の割合で用いられる。
本発明によつて得られるゴム組成物はウエツト
スキツド特性、転がり摩擦特性の点で改善され、
破壊特性の点でも調和がとれているため、タイヤ
トレツド用ゴム素材として好適に使用できる。そ
の場合、配合剤として、通常使用される各種配合
剤、例えばカーボンブラツク、プロセスオイル、
充填剤、加硫促進剤、加硫剤などを使用すること
ができる。
以下に実施例を挙げて本発明をさらに具体的に
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。
各実施例において結合スチレンは赤外法（699
cm-1の吸収に基く検量線から）により、ポリブタ
ジエンのミクロ構造はD.Moreroらの方法
〔Chim.e Ind.41 758（1959）〕によつて求めた。
ウエツトスキツド特性の指標としてはスキツド
テスターによるウエツトスキツド抵抗を用いた。
転がり摩擦抵抗の指標としては70℃でのダンロ
ツプ反撥弾性を用いた。
金属−炭素結合鎖を含有する重合体の含有量は
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られ
た。
実施例１〜４，比較例１〜５
実施例１〜４及び比較例１〜４で用いられるポ
リブタジエンは表１の処方に従つて作つた。比較
例５は市販のポリブタジエンを用いた。
５のスチレン製反応器にシクロヘキサン2.25
Kg、１，３−ブタジエン500ｇ、所定量のテトラ
ヒドロフラン（THF）を仕込み、これら混合物
を50℃に調節した後、所定量のｎ−ブチルリチウ
ムを添加して50℃等温下で60分間重合を行なつ
た。重合体溶液に所定量のテトラクロロスズを添
加し、50℃30分間カツプリング反応を行つた。但
しポリブタジエン−２はカツプリング反応を行な
わなかつた。重合体は重合体溶液に２，６−ジタ
−シヤリ−ブチル−Ｐ−クレゾールを添加後、ス
チームストリツピングで脱溶媒を行ない、100℃
熱ロール乾燥を行なうことにより得られた。重合
体の特性値を第１表に示す。
The present invention relates to a rubber composition that has low rolling friction resistance and high wet skid resistance and is suitable for tire tread. Due to the demands for lower fuel consumption and driving safety for automobiles, there is a strong demand for rubber materials for tire treads that have low rolling friction resistance and high slip resistance on wet road surfaces (wet skid resistance). However, these properties are contradictory, and until now there has been no rubber that satisfies all of these properties at the same time. Therefore, in order to balance these properties, blend compositions of different rubbers have been used. Blend rubber compositions of styrene-butadiene copolymers, such as emulsion-polymerized styrene-butadiene copolymers and solution-polymerized styrene-butadiene copolymers, and polybutadienes, such as high-cis polybutadiene and low-cis polybutadiene, are widely used as tire tread rubber for passenger cars. I've been exposed to it. However, these blend compositions are not necessarily sufficient in terms of rolling friction resistance and wet skid properties. An object of the present invention is to provide a rubber composition that has low rolling friction resistance and high wet skid resistance without impairing fracture properties. According to the present invention, a) contains at least 20% by weight of a polymer containing in its molecular chain a bond between at least one metal selected from tin, silicon and germanium and carbon;
20-80% by weight of polybutadiene with a vinyl bond content of 20% or more and less than 60% b) 20-80% by weight of a styrene-butadiene copolymer with 10-40% by weight of bound styrene and a vinyl content in the polybutadiene portion of 50% or less 80% by weight and c) one or more rubbers selected from natural rubber, cis-polyisoprene, and cis-polybutadiene 0-40
A rubber composition is provided consisting of % by weight. The rubber composition of the present invention is characterized by containing at least 20% by weight of a polymer containing metal-carbon bonds in its molecular chain.
polybutadiene (a) having a vinyl bond content of 20 to 60%, preferably 30 to 50%. If the metal-carbon bond chain content of polybutadiene (a) is less than 20%, rolling friction resistance and fracture properties will not be improved. In addition, if the vinyl bond content is less than 20%, the wet skid resistance will not improve, while if the vinyl bond content exceeds 60%, the compatibility with the styrene-butadiene copolymer of component (b) of the present invention will deteriorate, resulting in poor rolling resistance. Resistance and fracture properties are not improved. Furthermore, the Mooney viscosity of polybutadiene (a) is preferably 20-150, more preferably 30-80. If the Mooney viscosity is less than 20, the fracture properties and rolling friction properties will be poor, while if it exceeds 150, the workability will be poor. The polybutadiene (a) of the present invention is preferably produced by polymerizing 1,3-butadiene in the presence of a polar compound such as an ether, a tertiary amine, etc. using an organolithium initiator in an inert hydrocarbon solvent; Manufactured by introducing metal-carbon bonds into the molecular chain. Examples of organolithium initiators include methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, amyllithium,
Phenyllithium and the like are used. ether,
Tertiary amines are used as microstructure control agents, such as dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, triethylamine, and N,N,N',N'-tetramethylethylenediamine. As a polymerization solvent, aromatic hydrocarbons such as benzene and toluene, fatty cyclic hydrocarbons such as cyclohexane and methylcyclopentane, propane, pentane, n-
Aliphatic hydrocarbons such as hexane are used. Regarding the method and conditions of the above polymerization reaction, for example, Japanese Patent Application No. 55-177831 filed on December 16, 1982.
(Japanese Patent Application Laid-Open No. 57-100108). For example, a coupling reaction can be used as a method for introducing at least one metal selected from silicon, germanium, and tin into the molecular chain of the polymer thus obtained. Silicon halides, germanium halides, tin halides, etc. are used as coupling agents, but due to the availability of industrial raw materials, tin dichloride, silicon tetrachloride, silicon tetrabromide, tin tetrachloride, tin tetrabromide, Germanium tetrachloride and the like are preferably used. The proportion of polybutadiene in the rubber composition of the present invention is 20-80% by weight; less than 20% by weight is insufficient in terms of rolling friction resistance, and more than 80% by weight is poor in wet skid resistance and fracture properties. is insufficient. The styrene-butadiene copolymer (b) of the present invention contains 10-40% by weight of bound styrene, preferably 15-35% by weight.
and the vinyl content of the polybutadiene part is
A non-oil-extended or oil-extended random styrene-butadiene copolymer obtained by emulsion polymerization or solution polymerization with a Mooney viscosity of 50% or less and a Mooney viscosity of ML100°C 1+4 of 20-150 is used. If the bound styrene content is less than 10% by weight, the wet skid resistance properties will deteriorate, and if the bound styrene content exceeds 40% by weight or the vinyl content in the polybutadiene portion exceeds 50% by weight, the compatibility with the polybutadiene (a) described above will deteriorate. , and the rolling friction resistance characteristics deteriorate. Incidentally, the styrene-butadiene copolymer (b) may be a styrene-butadiene copolymer containing a metal such as tin, silicon, or germanium and a carbon bond chain. The proportion of styrene-butadiene copolymer (b) in the rubber composition of the present invention is 20-80% by weight, and 20% by weight.
If it is less than 80% by weight, it is insufficient in terms of wet skid resistance and fracture properties, and if it exceeds 80% by weight, it is insufficient in terms of rolling friction resistance. As the other rubber component (c) of the present invention, one or more rubbers selected from natural rubber, cis-1,4-polyisoprene, and cis-1,4-polybutadiene are used.
It is used in a proportion of less than % by weight. The rubber composition obtained by the present invention has improved wet skid properties and rolling friction properties,
Since it has well-balanced fracture properties, it can be suitably used as a rubber material for tire treads. In that case, various commonly used compounding agents such as carbon black, process oil,
Fillers, vulcanization accelerators, vulcanizing agents, etc. can be used. The present invention will be described in more detail with reference to Examples below, but the present invention does not exceed the gist thereof.
The present invention is not limited to these examples. In each example, bonded styrene was measured by infrared method (699
The microstructure of polybutadiene was determined by the method of D.Morero et al. [Chim.e Ind. 41 758 (1959)]. Wet skid resistance measured by a skid tester was used as an index of wet skid characteristics. Dunlop rebound resilience at 70°C was used as an index of rolling friction resistance. The content of polymers containing metal-carbon bond chains is determined using gel permeation chromatography (GPC method).
It was determined from the proportion of high molecular weight components measured in . Examples 1 to 4, Comparative Examples 1 to 5 The polybutadiene used in Examples 1 to 4 and Comparative Examples 1 to 4 was produced according to the recipe in Table 1. Comparative Example 5 used commercially available polybutadiene. Cyclohexane 2.25 in the styrene reactor No. 5
Kg, 500 g of 1,3-butadiene, and a predetermined amount of tetrahydrofuran (THF) were charged, and the mixture was adjusted to 50°C. Then, a predetermined amount of n-butyllithium was added and polymerization was carried out for 60 minutes at 50°C isothermally. Summer. A predetermined amount of tetrachlorotin was added to the polymer solution, and a coupling reaction was performed at 50°C for 30 minutes. However, polybutadiene-2 did not undergo the coupling reaction. The polymer was prepared by adding 2,6-di-tert-butyl-P-cresol to the polymer solution, removing the solvent by steam stripping, and heating at 100°C.
Obtained by hot roll drying. The property values of the polymer are shown in Table 1.
【表】
第２及び３表に示す配合処方に従つてブラベン
ダープラストミル及びロールで混練り配合して、
145℃35分間加硫を行なつた。
加硫物の性質を第３表に示す。
第２表
重量部
重合体 100
HAF 50
ステアリン酸 １
亜鉛華 ３
イオウ 1.75
加硫促進剤TBBS（NS）* 1.0
＊Ｎ−tert−ブチル−２−ベンゾチアジルス
ルフエンアミド
第３表から本発明の実施例は転がり摩擦抵抗が
小さく（反撥弾性大）ウエツトスキツド抵抗が大
きくて（ウエツトスキツド指数大）バランスがと
れたすぐれた特性を示し、破壊特性（モジユラ
ス、引張強さ）を損わないことを示している。[Table] Knead and blend using a Brabender plasto mill and roll according to the formulation shown in Tables 2 and 3.
Vulcanization was performed at 145°C for 35 minutes. The properties of the vulcanizate are shown in Table 3. Table 2 Weight parts Polymer 100 HAF 50 Stearic acid 1 Zinc white 3 Sulfur 1.75 Vulcanization accelerator TBBS (NS) * 1.0 *N-tert-butyl-2-benzothiazyl sulfenamide From Table 3, the compounds of the present invention The examples show excellent, well-balanced properties with low rolling friction resistance (high rebound resilience) and high wet skid resistance (high wet skid index), and show that the fracture properties (modulus, tensile strength) are not impaired. There is.
Claims (1)
ばれる少なくとも一種の金属と炭素との結合を
分子鎖に含む重合体を少なくとも20重量％含有
し、ビニル結合含有量が20％以上で60％未満で
あるポリブタジエン20〜80重量％ ｂ） 結合スチレンが10〜40重量％でかつポリブ
タジエン部分のビニル含量が50％以下であるス
チレンブタジエン共重合体20〜80重量％及び ｃ） 天然ゴム、シスポリイソプレン、シスポリ
ブタジエンから選ぱれる一種以上のゴム０〜40
重量％からなるゴム組成物。 ２ 上記金属−炭素結合がスズ−炭素結合である
特許請求の範囲第１項記載のゴム組成物。 ３ 上記ポリブタジエンが炭化水素溶媒中で有機
リチウム化合物触媒を用いて１，３−ブタジエン
を重合させて得られるものである特許請求の範囲
第１項記載のゴム組成物。[Claims] 1 a) Contains at least 20% by weight of a polymer whose molecular chain contains a bond between at least one metal selected from tin, silicon, and germanium and carbon, and has a vinyl bond content of 20% or more. b) 20-80% by weight of polybutadiene with less than 60% b) 20-80% by weight of a styrene-butadiene copolymer with 10-40% by weight of bound styrene and a vinyl content in the polybutadiene portion of not more than 50%; and c) natural rubber; One or more rubbers selected from cis-polyisoprene and cis-polybutadiene 0-40
A rubber composition consisting of % by weight. 2. The rubber composition according to claim 1, wherein the metal-carbon bond is a tin-carbon bond. 3. The rubber composition according to claim 1, wherein the polybutadiene is obtained by polymerizing 1,3-butadiene in a hydrocarbon solvent using an organolithium compound catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP546282A JPS58122939A (en) | 1982-01-19 | 1982-01-19 | Rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP546282A JPS58122939A (en) | 1982-01-19 | 1982-01-19 | Rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58122939A JPS58122939A (en) | 1983-07-21 |
| JPH021179B2 true JPH021179B2 (en) | 1990-01-10 |
Family
ID=11611889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP546282A Granted JPS58122939A (en) | 1982-01-19 | 1982-01-19 | Rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58122939A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0480566U (en) * | 1990-11-28 | 1992-07-14 |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4530959A (en) * | 1984-03-08 | 1985-07-23 | The Goodyear Tire & Rubber Company | Pneumatic tire with tread of medium vinyl polybutadiene/rubber blend |
| JPH0649800B2 (en) * | 1985-11-21 | 1994-06-29 | 日本合成ゴム株式会社 | Butadiene polymer rubber composition |
| JPH0721090B2 (en) * | 1985-12-28 | 1995-03-08 | 旭化成工業株式会社 | Rubber composition for tire |
| JPH0627219B2 (en) * | 1986-09-08 | 1994-04-13 | 日本合成ゴム株式会社 | Polybutadiene rubber composition |
-
1982
- 1982-01-19 JP JP546282A patent/JPS58122939A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0480566U (en) * | 1990-11-28 | 1992-07-14 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58122939A (en) | 1983-07-21 |
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