JPH0657767B2 - Modified rubber composition - Google Patents
Modified rubber compositionInfo
- Publication number
- JPH0657767B2 JPH0657767B2 JP1926387A JP1926387A JPH0657767B2 JP H0657767 B2 JPH0657767 B2 JP H0657767B2 JP 1926387 A JP1926387 A JP 1926387A JP 1926387 A JP1926387 A JP 1926387A JP H0657767 B2 JPH0657767 B2 JP H0657767B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- alkali metal
- polymer
- modified
- diene
- 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
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Description
【発明の詳細な説明】 〈産業上の利用分野〉 本発明は反撥弾性及び低温におけるＪＩＳ硬度の改良さ
れた加硫ゴムを与える変性ゴム組成物に関するものであ
り、より詳しくは活性なアルカリ金属末端を有するジエ
ン系重合体ゴム又はアルカリ金属が付加された共役ジエ
ン系重合体ゴムと 一般式 （式中Ｒ１、Ｒ２、Ｒ３はアルキル基又はアルコキシ
基、Ｒ４、Ｒ５はアルキル基、ｎは整数を表わす。）で
示されるアミノシラン化合物を反応させて得られる変性
ジエン系重合体ゴムをゴム成分として含有する変性ゴム
組成物に関するものである。TECHNICAL FIELD The present invention relates to a modified rubber composition which gives a vulcanized rubber having improved impact resilience and improved JIS hardness at low temperature, and more specifically to an active alkali metal terminal. And a conjugated diene polymer rubber having an alkali metal added thereto and a general formula (Wherein R 1 , R 2 , and R 3 are alkyl groups or alkoxy groups, R 4 and R 5 are alkyl groups, and n is an integer), and a modified diene polymer obtained by reacting the aminosilane compound The present invention relates to a modified rubber composition containing rubber as a rubber component.
〈従来の技術〉 従来からポリブタジエンやブタジエン−スチレン共重合
体ゴム等の共役ジエン系重合体ゴムは自動車タイヤトレ
ッド用ゴムとして使用されてきたが、近年自動車の低燃
費化の要求と雪上及び氷上での走行安全性の要求から自
動車タイヤトレッド用ゴムとして転動抵抗が小さく、雪
上及び氷上での路面グリップの大きいゴム材料が望まれ
てきている。<Prior Art> Conventionally, conjugated diene-based polymer rubbers such as polybutadiene and butadiene-styrene copolymer rubber have been used as rubbers for automobile tire treads, but in recent years, demand for low fuel consumption of automobiles and snow and ice Due to the requirement of driving safety, a rubber material having a small rolling resistance and a large road surface grip on snow and ice has been desired as a rubber for an automobile tire tread.
転動抵抗は重合体の反撥弾性と相関があり、反撥弾性が
高くなると転動抵抗は小さくなる。The rolling resistance correlates with the impact resilience of the polymer, and the higher the impact resilience, the smaller the rolling resistance.
一方、雪上及び氷上での路面グリップは低温におけるＪ
ＩＳ硬度と相関があり、低温におけるＪＩＳ硬度が低い
ほど雪上及び氷上での路面グリップは大きくなることが
知られている。然るに既存のゴム材料においては、これ
ら特性は、実用上不満足であった。On the other hand, the road grip on snow and ice is
It is known that there is a correlation with the IS hardness, and the lower the JIS hardness at low temperature, the greater the road surface grip on snow and ice. However, in the existing rubber material, these characteristics were not practically satisfactory.
〈発明が解決しようとする問題点〉 本発明の目的は、反撥弾性を高め、低温でのＪＩＳ硬度
を低減するジエン系重合体ゴムをゴム成分として含有す
る変性ゴム組成物を提供することにある。<Problems to be Solved by the Invention> An object of the present invention is to provide a modified rubber composition containing a diene polymer rubber as a rubber component, which enhances impact resilience and reduces JIS hardness at low temperatures. .
〈問題点を解決するための手段〉 本発明者らは共役ジエン系重合体ゴムをゴム成分として
含有するゴム組成物の反撥弾性を高く、かつ低温でのＪ
ＩＳ硬度を低くすべく鋭意研究を重ねた結果、アルカリ
金属含有ジエン系重合体と特定の化合物とを反応させ、
特定の原子団を重合体中に導入することにより得られた
変性ジエン系重合体ゴムをゴム成分として含有するゴム
組成物は前記の目的が達せられることを見い出し本発明
を完成するに到った。<Means for Solving Problems> The present inventors have found that a rubber composition containing a conjugated diene-based polymer rubber as a rubber component has high impact resilience and J at low temperature.
As a result of repeated intensive studies to lower the IS hardness, an alkali metal-containing diene polymer is reacted with a specific compound,
It was found that a rubber composition containing a modified diene polymer rubber obtained by introducing a specific atomic group into a polymer as a rubber component can achieve the above-mentioned object and completed the present invention. .
すなわち、本発明は、 ゴム成分及び配合剤から成るゴム組成物において活性な
アルカリ金属末端を有するジエン系重合体ゴム又はアル
カリ金属が付加された共役ジエン系ゴムと 一般式 （式中Ｒ１、Ｒ２、Ｒ３はアルキル基又はアルコキシ
基、Ｒ４、Ｒ５はアルキル基、ｎは整数を表わす。）で
示されるアミノシラン化合物を反応させて得られる変性
ジエン系重合体ゴムをゴム成分中に少なくとも１０重量
％含むことを特徴とする変性ゴム組成物に関するもので
ある。That is, the present invention relates to a diene-based polymer rubber having an active alkali metal terminal or a conjugated diene-based rubber to which an alkali metal is added in a rubber composition comprising a rubber component and a compounding agent and a general formula (Wherein R 1 , R 2 , and R 3 are alkyl groups or alkoxy groups, R 4 and R 5 are alkyl groups, and n is an integer), and a modified diene polymer obtained by reacting the aminosilane compound The present invention relates to a modified rubber composition characterized by containing at least 10% by weight of rubber in a rubber component.
本発明で使用するアルカリ金属含有ジエン系重合体と
は、ジエン系単量体あるいは該単量体及びこれと共重合
可能な他の単量体をアルカリ金属基材触媒を用いて重合
して得られるアルカリ金属がジエン系重合体末端に結合
したもの、及び重合方法（例えば溶液重合、乳化重合な
ど）の如何を問わず、重合体鎖中に共役ジエン単位を有
するジエン系重合体に後からの反応でアルカリ金属を付
加させたものをいう。The alkali metal-containing diene polymer used in the present invention is obtained by polymerizing a diene monomer or the monomer and another monomer copolymerizable therewith with an alkali metal-based catalyst. Which has a conjugated diene unit in the polymer chain, regardless of the polymerization method (eg solution polymerization, emulsion polymerization, etc.) It means that an alkali metal is added by the reaction.
ジエン系重合体ゴムとしては、１，３−ブタジエン、イ
ソプレン、１，３−ペンタジエン（ピペリレン）、２，
３−ジメチル−１，３−ブタジエン、１，３−ヘキサジ
エンなどの共役ジエンモノマーの重合体もしくは共重合
体ゴム、または共役ジエンモノマーと該モノマーと共重
合可能なスチレン、α−メチルスチレン、ビニルトルエ
ン、ビニルナフタレン、ジビニルベンゼン、トリビニル
ベンゼン、ジビニルナフタレンなどの芳香族ビニル化合
物、アクリロニトリルなどの不飽和ニトリル、（メタ）
アクリル酸のエステル類もしくはビニルピリジンなどと
の共重合体ゴムが挙げられるが、これらに限定されるも
のではない。Examples of the diene polymer rubber include 1,3-butadiene, isoprene, 1,3-pentadiene (piperylene), 2,
Polymer or copolymer rubber of conjugated diene monomer such as 3-dimethyl-1,3-butadiene and 1,3-hexadiene, or styrene, α-methylstyrene, vinyltoluene copolymerizable with the conjugated diene monomer and the monomer , Vinylnaphthalene, divinylbenzene, trivinylbenzene, divinylnaphthalene and other aromatic vinyl compounds, acrylonitrile and other unsaturated nitriles, (meth)
Examples thereof include, but are not limited to, a copolymer rubber with an ester of acrylic acid or vinyl pyridine.
具体的にはポリブタジエンゴム、ポリイソプレンゴム、
ブタジエン−イソプレン共重合体ゴム、ブタジエン−ス
チレン共重合体ゴムなどが例示できる。Specifically, polybutadiene rubber, polyisoprene rubber,
Examples thereof include butadiene-isoprene copolymer rubber and butadiene-styrene copolymer rubber.
ジエン系重合体ゴムの末端にアルカリ金属が結合したジ
エン系重合体ゴムとは、前述のとおり、ジエン系重合体
ゴムをアルカリ金属基材触媒で重合して得たもので、重
合体鎖の少なくとも一端にアルカリ金属が結合した、重
合停止前のリビング重合体である。アルカリ金属基材触
媒、重合溶剤、ランダマイザー、共役ジエン単位のミク
ロ構造調節剤など通常使用されているものを用いること
が可能であり、該重合体の製造方法は特に制約は受けな
い。The diene polymer rubber in which an alkali metal is bonded to the end of the diene polymer rubber is, as described above, obtained by polymerizing the diene polymer rubber with an alkali metal-based catalyst, and at least the polymer chain. It is a living polymer before the termination of polymerization, in which an alkali metal is bonded to one end. It is possible to use a commonly used one such as an alkali metal-based catalyst, a polymerization solvent, a randomizer, a microstructure modifier for conjugated diene units, and the method for producing the polymer is not particularly limited.
ジエン系重合体ゴムにアルカリ金属を付加させたジエン
系重合体ゴムとは、アルカリ金属基材触媒、アルカリ土
類金属基材触媒、Ziegler系触媒などを用いた溶液重
合、レドックス型触媒等を用いた乳化重合など通常の重
合方法によって前記した共役ジエンモノマーあるいは共
役ジエンモノマーおよびこれと共重合可能なモノマーと
を重合又は共重合させて得られるジエン系共重合体ゴム
（具体的にはポリブタジエンゴム、ポリイソプレンゴ
ム、ブタジエン−スチレン共重合体ゴム、ブタジエン−
イソプレン共重合体ゴム、ポリペンタジエンゴム、ブタ
ジエン−ピペリレン共重合体ゴム、ブタジエン−プロピ
レン交互共重合体ゴムなどが例示されるが）にアルカリ
金属を付加させたものである。Diene polymer rubbers obtained by adding an alkali metal to diene polymer rubbers include alkali metal base catalysts, alkaline earth metal base catalysts, solution polymerization using Ziegler catalysts, redox type catalysts, etc. Diene copolymer rubber obtained by polymerizing or copolymerizing the conjugated diene monomer or the conjugated diene monomer and a monomer copolymerizable therewith by a usual polymerization method such as emulsion polymerization (specifically, polybutadiene rubber, Polyisoprene rubber, butadiene-styrene copolymer rubber, butadiene-
Examples thereof include isoprene copolymer rubber, polypentadiene rubber, butadiene-piperylene copolymer rubber, and butadiene-propylene alternating copolymer rubber), but with an alkali metal added thereto.
ジエン系重合体ゴムへのアルカリ金属付加は通常実施さ
れている方法が用いられ、例えばジエン系重合体ゴムを
炭化水素溶媒中で、通常のアルカリ金属基材触媒とエー
テル化合物、アミン化合物、ホスフィン化合物等の極性
化合物の存在下に３０〜１００℃の温度で数十分乃至数
十時間の条件で付加反応が行われる。アルカリ金属基材
触媒の使用量はジエン系重合体ゴム１００ｇ当たり通
常、0.1〜10ミリモルの範囲でよく、0.1ミリモル未満で
は反撥弾性の向上は得られず、10ミリモルを超えると重
合体の架橋、切断等の副反応が生じ反撥弾性の向上に寄
与しない。Alkali metal addition to the diene polymer rubber may be carried out by a commonly used method. For example, a diene polymer rubber may be added to a hydrocarbon solvent in a conventional alkali metal base catalyst and an ether compound, an amine compound or a phosphine compound. The addition reaction is carried out in the presence of such a polar compound at a temperature of 30 to 100 ° C. for several tens of minutes to several ten hours. The amount of the alkali metal-based catalyst used may be usually in the range of 0.1 to 10 mmol per 100 g of the diene polymer rubber. If it is less than 0.1 mmol, the impact resilience cannot be improved, and if it exceeds 10 mmol, crosslinking of the polymer, Side reactions such as cutting occur and do not contribute to the improvement of impact resilience.
極性化合物はアルカリ金属基材触媒１モルに対して通常
0.1〜10モル、好ましくは0.5〜２モルである。重合およ
び付加反応に使用されるアルカリ金属基材触媒を例示す
るならば以下のとおりである。The polar compound is usually used for 1 mol of the alkali metal-based catalyst.
It is 0.1 to 10 mol, preferably 0.5 to 2 mol. An example of the alkali metal-based catalyst used in the polymerization and the addition reaction is as follows.
リチウム、ナトリウム、カリウム、ルビジウム、セシウ
ム金属またはこれらの炭化水素化合物又は極性化合物と
の錯体である。It is a complex with lithium, sodium, potassium, rubidium, cesium metal or their hydrocarbon compounds or polar compounds.
好ましくは、２〜２０個の炭素原子を有するリチウムま
たはナトリウム化合物である。Preferred are lithium or sodium compounds having 2 to 20 carbon atoms.
例えば、エチルリチウム、ｎ−プロピルリチウム、iso
−プロピルリチウム、ｎ−ブチルリチウム、sec−ブチ
ルリチウム、ｔ−オクテルリチウム、ｎ−デシルリチウ
ム、フェニルリチウム、２−ナフチルリチウム、２−ブ
チル−フェニルリチウム、４−フェニル−ブチルリチウ
ム、シクロヘキシルリチウム、４−シクロペンチルリチ
ウム、１，４−ジリチオ−ブテン−２、ナトリウムナフ
タレン、ナトリウムビフェニル、カリウム−テトラヒド
ロフラン錯体、カリウムジエトキシエタン錯体、α−メ
チルスチレンテトラマーのナトリウム塩等である。For example, ethyl lithium, n-propyl lithium, iso
-Propyl lithium, n-butyl lithium, sec-butyl lithium, t-octyl lithium, n-decyl lithium, phenyl lithium, 2-naphthyl lithium, 2-butyl-phenyl lithium, 4-phenyl-butyl lithium, cyclohexyl lithium, 4-cyclopentyl lithium, 1,4-dilithio-butene-2, sodium naphthalene, sodium biphenyl, potassium-tetrahydrofuran complex, potassium diethoxyethane complex, sodium salt of α-methylstyrene tetramer and the like.
重合反応およびアルカリ金属付加反応は炭化水素溶剤ま
たはテトロヒドロフラン、テトラヒドロピラン、ジオキ
サンなどのアルカリ金属基材触媒を破壊しない溶剤中で
行われる。The polymerization reaction and the alkali metal addition reaction are carried out in a hydrocarbon solvent or a solvent that does not destroy the alkali metal-based catalyst such as tetrohydrofuran, tetrahydropyran and dioxane.
適当な炭化水素溶剤としては、脂肪族炭化水素、芳香族
炭化水素、脂環族炭化水素から選ばれ、特に炭素数２〜
１２個を有するプロパン、ｎ−ブタン、iso−ブタン、
ｎ−ペンタン、iso−ペンタン、ｎ−ヘキサン、シクロ
ヘキサン、プロペン、１−ブテン、iso−ブテン、トラ
ンス−２−ブテン、シス−２−ブテン、１−ペンテン、
２−ペンテン、１−ヘキセン、２−ヘキセン、ベンゼ
ン、トルエン、キシレン、エチルベンゼンなどが好まし
い。またこれらの溶剤は２種以上を混合して使用するこ
とができる。The suitable hydrocarbon solvent is selected from aliphatic hydrocarbons, aromatic hydrocarbons and alicyclic hydrocarbons, and particularly has 2 to 2 carbon atoms.
Propane having twelve, n-butane, iso-butane,
n-pentane, iso-pentane, n-hexane, cyclohexane, propene, 1-butene, iso-butene, trans-2-butene, cis-2-butene, 1-pentene,
2-Pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene and the like are preferable. Further, these solvents can be used as a mixture of two or more kinds.
次に、本発明で使用する前記のアルカリ金属含有ジエン
系重合体ゴムと反応させる化合物は 一般式 （式中Ｒ１、Ｒ２、Ｒ３はアルキル基又はアルコキシ
基、Ｒ４、Ｒ５はアルキル基、ｎは整数を表わす。）で
示されるアミノシラン化合物である。Next, the compound to be reacted with the above-mentioned alkali metal-containing diene polymer rubber used in the present invention is represented by the general formula (Wherein R 1 , R 2 , and R 3 are alkyl groups or alkoxy groups, R 4 and R 5 are alkyl groups, and n is an integer).
このようなアミノシラン化合物の具体例を以下に示す。Specific examples of such aminosilane compounds are shown below.
３−ジメチルアミノメチルトリメトキシシラン、３−ジ
メチルアミノエチルトリメトキシシラン、３−ジメチル
アミノプロピルトリメトキシシラン、３−ジメチルアミ
ノブチルトリメトキシシラン、３−ジメチルアミノメチ
ルジメトキシメチルシラン、３−ジメチルアミノエチル
ジメトキシメチルシラン、３−ジメチルアミノプロピル
ジメトキシメチルシラン、３−ジメチルアミノブチルジ
メトキシメチルシラン、３−ジメチルアミノメチルトリ
エトキシシラン、３−ジメチルアミノエチルトリエトキ
シシラン、３−ジメチルアミノプロピルトリエトキシシ
ラン、３−ジメチルアミノブチルトリエトキシシラン、
３−ジメチルアミノメチルジエトキシメチルシラン、３
−ジメチルアミノエチルジエトキシメチルシラン、３−
ジメチルアミノプロピルジエトキシメチルシラン、３−
ジメチルアミノブチルジエトキシメチルシラン等があげ
られるが、特に好ましいのは３−ジメチルアミノプロピ
ルジエトキシメチルシランである。3-dimethylaminomethyltrimethoxysilane, 3-dimethylaminoethyltrimethoxysilane, 3-dimethylaminopropyltrimethoxysilane, 3-dimethylaminobutyltrimethoxysilane, 3-dimethylaminomethyldimethoxymethylsilane, 3-dimethylaminoethyl Dimethoxymethylsilane, 3-dimethylaminopropyldimethoxymethylsilane, 3-dimethylaminobutyldimethoxymethylsilane, 3-dimethylaminomethyltriethoxysilane, 3-dimethylaminoethyltriethoxysilane, 3-dimethylaminopropyltriethoxysilane, 3 -Dimethylaminobutyltriethoxysilane,
3-dimethylaminomethyldiethoxymethylsilane, 3
-Dimethylaminoethyldiethoxymethylsilane, 3-
Dimethylaminopropyldiethoxymethylsilane, 3-
Examples thereof include dimethylaminobutyldiethoxymethylsilane, and particularly preferred is 3-dimethylaminopropyldiethoxymethylsilane.
該アミノシラン化合物の使用量は、末端にアルカリ金属
が結合したジエン系重合体ゴムを製造する際に使用する
アルカリ金属基材触媒またはジエン系重合体ゴムに後か
らの反応でアルカリ金属を付加する際使用するアルカリ
金属基材触媒１モル当り、通常0.05〜10モルであり、好
ましくは0.2〜２モルである。The amount of the aminosilane compound used is such that when an alkali metal is added to an alkali metal-based catalyst or a diene polymer rubber used in the production of a diene polymer rubber in which an alkali metal is bonded to the terminal, in a subsequent reaction. The amount is usually 0.05 to 10 mol, preferably 0.2 to 2 mol, per mol of the alkali metal-based catalyst used.
該アミノシラン化合物とアルカリ金属末端を有する活性
共役ジエン系重合体ゴムまたはアルカリ金属が付加した
共役ジエン系重合体ゴムとの反応は迅速に起きるので、
反応温度および反応時間は広範囲に選択できるが、一般
的には室温乃至100℃、数秒乃至数時間である。Since the reaction between the aminosilane compound and the active conjugated diene-based polymer rubber having an alkali metal terminal or the conjugated diene-based polymer rubber to which an alkali metal is added occurs rapidly,
The reaction temperature and reaction time can be selected over a wide range, but are generally room temperature to 100 ° C. and several seconds to several hours.
反応は、アルカリ金属含有ジエン系重合体ゴムと該アミ
ノシラン化合物とを接触させればよく、例えばアルカリ
金属基材触媒を用いてジエン系重合体ゴムを重合し、該
重合体ゴム溶液中に該アミノシラン化合物を所定量添加
する方法、ジエン系重合体ゴム溶液中でのアルカリ金属
付加反応終了後、引き続いて該アミノシラン化合物を添
加して反応させる方法が、好ましい状態として例示でき
るが、この方法に限定されるものではない。The reaction may be carried out by contacting the alkali metal-containing diene polymer rubber with the aminosilane compound. For example, the diene polymer rubber is polymerized using an alkali metal base catalyst and the aminosilane is added to the polymer rubber solution. A method of adding a predetermined amount of a compound, a method of reacting by adding the aminosilane compound after the completion of the alkali metal addition reaction in a diene polymer rubber solution can be exemplified as a preferable state, but is not limited to this method. Not something.
得られた改質ジエン系重合体ゴムには分子末端あるいは
分子鎖中にアミノシラン化合物が導入されている。The resulting modified diene polymer rubber has an aminosilane compound introduced at the molecular end or in the molecular chain.
反応終了後、改質されたジエン系重合体ゴムは反応溶液
中からの凝固剤の添加あるいはスチーム凝固など通常の
溶液重合によるゴムの製造において使用される凝固方法
がそのまま用いられ、凝固温度も何等ら制限されていな
い。After completion of the reaction, the modified diene polymer rubber is used as it is in the coagulation method used in the production of rubber by ordinary solution polymerization such as addition of a coagulant from the reaction solution or steam coagulation, and the coagulation temperature is Is not restricted from
反応系から分離されたクラムの乾燥も通常の合成ゴムの
製造で用いられているバンドドライヤー、押し出し型の
ドライヤー等が使用でき、乾燥温度も何ら制限されな
い。The crumb separated from the reaction system can also be dried by using a band dryer, an extrusion type dryer or the like used in the usual production of synthetic rubber, and the drying temperature is not limited at all.
このようにして得られた改質ジエン系重合体ゴムは未改
質のゴムに比して反撥弾性及び低温でのＪＩＳ硬度が改
良されるので、特に自動車タイヤ用に好ましく用いられ
るが、それ以外にも靴底用、床材用、防振ゴム用などの
各種工業用原料ゴムとして使用することもできる。The modified diene-based polymer rubber thus obtained has improved impact resilience and JIS hardness at low temperatures as compared with unmodified rubber, and thus is preferably used especially for automobile tires. Also, it can be used as a raw material rubber for various industrial purposes such as shoe soles, floor materials, anti-vibration rubbers, etc.
本発明において、改質された変性ジエン系重合体ゴム
は、ゴム成分としてゴム組成物中に少なくとも１０重量
％、好ましくは２０重量％以上含まれることが必要であ
る。In the present invention, the modified modified diene polymer rubber is required to be contained as a rubber component in the rubber composition at least 10% by weight, preferably 20% by weight or more.
該ゴム成分の含量が１０重量％未満では反撥弾性の向上
は期待できない。If the content of the rubber component is less than 10% by weight, improvement in impact resilience cannot be expected.
該変性ジエン系重合体ゴムと他のゴムとを組み合わせて
使用する場合には、他のゴムとしては乳化重合スチレン
−ブタジエン共重合体ゴム、溶液重合（アニオン重合触
媒、Ziegler型触媒等）によるポリブタジエンゴム、ス
チレン−ブタジエン共重合体ゴム、ポリイソプレンゴ
ム、ブタジエン−イソプレン共重合体ゴム等及び天然ゴ
ムなどが含まれ、目的に応じて、これらのゴムの１種又
は２種以上が選択使用される。When the modified diene polymer rubber and other rubber are used in combination, the other rubber is emulsion-polymerized styrene-butadiene copolymer rubber, polybutadiene produced by solution polymerization (anionic polymerization catalyst, Ziegler type catalyst, etc.). Rubber, styrene-butadiene copolymer rubber, polyisoprene rubber, butadiene-isoprene copolymer rubber and the like and natural rubber are included, and one or more of these rubbers are selected and used according to the purpose. .
改質された変性ジエン系重合体ゴムのムーニー粘度（Ｍ
Ｌ1+4100℃）は通常１０〜200の範囲であり、好ましく
は２０〜150の範囲である。１０未満では引張強さ等の
機械的物性が劣り、200を越えると他のゴムと組合せて
使用する場合に混和性が悪く、加工操作性が困難とな
り、得られたゴム組成物の加硫物の機械的特性が低下す
るので好ましくない。Mooney viscosity of the modified modified diene polymer rubber (M
L 1 + 4 100 ° C.) is usually in the range of 10 to 200, preferably 20 to 150. If it is less than 10, mechanical properties such as tensile strength are inferior, and if it exceeds 200, miscibility is poor when it is used in combination with other rubber and processing operability becomes difficult, and a vulcanized product of the obtained rubber composition is obtained. It is not preferable because the mechanical properties of are deteriorated.
本発明で使用するゴム成分のすべて、あるいは一部を油
展ゴムとして使用することができる。All or part of the rubber component used in the present invention can be used as an oil-extended rubber.
本発明のゴム組成物はゴム成分と各種配合剤とをロール
・バンバリー等の混合機を用いて製造される。使用する
各種配合剤はゴム工業で常用されているものからゴム組
成物の使用目的に適したものを選べばよく、特に制限さ
れない。The rubber composition of the present invention is produced by mixing the rubber component and various compounding agents with a mixing machine such as a roll and Banbury. The various compounding agents to be used may be selected from those commonly used in the rubber industry, and those suitable for the purpose of use of the rubber composition may be selected, and are not particularly limited.
通常、加硫系としては硫黄、ステアリン酸、亜鉛華、各
種加硫促進剤（チアゾール系、チウラム系、スルフエン
アミド系等）あるいは有機過酸化物などが、補強剤とし
ては、ＨＡＦ、ＩＳＡＦ等の種々のグレードのカーボン
ブラック、シリカなど、充填剤としては炭酸カルシウ
ム、タルクなどが、その他の配合剤としてはプロセス
油、加工助剤、老化防止剤等が使用される。これらの配
合剤の種類及び使用量はゴム組成物の使用目的に応じて
選択されるものであり、本発明においては特に限定され
ない。Usually, the vulcanization type is sulfur, stearic acid, zinc white, various vulcanization accelerators (thiazole type, thiuram type, sulfenamide type, etc.) or organic peroxides, and the reinforcing agent is various types such as HAF and ISAF. Grades of carbon black, silica and the like, fillers such as calcium carbonate and talc, and other compounding agents such as process oils, processing aids and antiaging agents. The type and amount of these compounding agents are selected according to the purpose of use of the rubber composition, and are not particularly limited in the present invention.
本発明の変性ゴム組成物は反撥弾性及び低温でのＪＩＳ
硬度が改良されるので特に自動車タイヤ用に好ましく用
いられるが、それ以外にも靴底用、床材用、防振ゴム用
などの各種工業用原料ゴムとして使用することもでき
る。The modified rubber composition of the present invention has impact resilience and JIS at low temperature.
Since it has improved hardness, it is preferably used especially for automobile tires, but it can also be used as various industrial raw material rubbers for shoe soles, floor materials, anti-vibration rubbers, etc.
〈実施例〉 以下に実施例により本発明を具体的に説明するが、本発
明はこれら実施例に限定されるものではない。<Examples> The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples.
実施例１ 内容積１０のステンレス製重合反応器を洗浄、乾燥し
乾燥窒素で置換した後に、１，３−ブタジエン1000g、
ｎ−ヘキサン4300g、エチレングリコールジエチルエー
テル４０ミリモル、ｎ−ブチルリチウム（ｎ−ヘキサン
溶液）4.7ミリモルを添加し撹拌下に５０℃で１時間重
合を行った。Example 1 A polymerization reactor made of stainless steel having an internal volume of 10 was washed, dried and replaced with dry nitrogen, and then 1000 g of 1,3-butadiene,
4300 g of n-hexane, 40 mmol of ethylene glycol diethyl ether and 4.7 mmol of n-butyllithium (n-hexane solution) were added, and polymerization was carried out at 50 ° C. for 1 hour while stirring.
重合完了後３−ジメチルアミノプロピルジエトキシメチ
ルシランを4.1ミリモル添加し、撹拌下に３０分間反応
させたのち、１０ミリリッターのメタノールを加えて更
に５分間撹拌した。After the completion of the polymerization, 4.1 mmol of 3-dimethylaminopropyldiethoxymethylsilane was added, and the mixture was reacted for 30 minutes while stirring. Then, 10 milliliter of methanol was added and the mixture was further stirred for 5 minutes.
その後重合反応器の内容物を取り出し、５ｇの２，６−
ジ−ｔ−ブチル−ｐ−クレゾール（住友化学社製 スミ
ライザー ＢＨＴ）を加え、ｎ−ヘキサンの大部分を蒸
発させたのち、６０℃で２４時間減圧乾燥した。Then, the contents of the polymerization reactor were taken out, and 5 g of 2,6-
Di-t-butyl-p-cresol (Sumitomo Chemical Co., Ltd.
Riser BHT) and add most of the n-hexane to steam.
After emission, it was dried under reduced pressure at 60 ° C. for 24 hours.
生成重合体ゴムのムーニー粘度および１，２−結合単位
量（赤外分光分析法により）を測定した。The Mooney viscosity and 1,2-bond unit content (by infrared spectroscopy) of the resulting polymer rubber were measured.
生成重合体ゴムのムーニー粘度は８５で、ビニル含量は
７０％であった。The resulting polymer rubber had a Mooney viscosity of 85 and a vinyl content of 70%.
比較例１ ３−ジメチルアミノプロピルジエトキシメチルシランを
添加しないこと以外は実施例１と同じ方法で重合体を得
た。Comparative Example 1 A polymer was obtained by the same method as in Example 1 except that 3-dimethylaminopropyldiethoxymethylsilane was not added.
生成重合体ゴムのムーニー粘度は８５、ビニル含量は７
０％であった。The polymer rubber produced has a Mooney viscosity of 85 and a vinyl content of 7
It was 0%.
実施例２ 内容積１０のステンレス製重合反応器を洗浄、乾燥
し、乾燥窒素で置換した後に、１，３−ブタジエン750
ｇ、スチレン250ｇ、ｎ−ヘキサン4300g、テトラヒドロ
フラン２３ｇ、ｎ−ブチルリチウム（ｎ−ヘキサン溶
液）5.2ミリモルを添加し、撹拌下に５０℃で１時間重
合を行った。重合完了後３−ジメチルアミノプロピルジ
エトキシメチルシランを4.4ミリモル添加し、撹拌下に
３０分間反応させたのち、１０ミリリッターのメタノー
ルを加えて、更に５分間撹拌した。Example 2 A polymerization reactor made of stainless steel with an internal volume of 10 was washed, dried, and purged with dry nitrogen.
g, 250 g of styrene, 4300 g of n-hexane, 23 g of tetrahydrofuran and 5.2 mmol of n-butyllithium (n-hexane solution) were added, and polymerization was carried out at 50 ° C. for 1 hour while stirring. After the completion of the polymerization, 4.4 mmol of 3-dimethylaminopropyldiethoxymethylsilane was added, and the mixture was reacted for 30 minutes with stirring, then 10 milliliter of methanol was added, and the mixture was further stirred for 5 minutes.
その後重合反応器の内容物を取り出し、５ｇの２，６−
ジ−ｔ−ブチル−ｐ−クレゾール（スミライザー ＢＨ
Ｔ）を加え、ｎ−ヘキサンの大部分を蒸発させたのち、
６０℃で２４時間減圧乾燥した。Then, the contents of the polymerization reactor were taken out, and 5 g of 2,6-
Di-t-butyl-p-cresol (Sumilyzer BH
T) was added to evaporate most of the n-hexane,
It was dried under reduced pressure at 60 ° C. for 24 hours.
生成重合体ゴムのムーニー粘度、ビニル含量（赤外分光
分析法により）およびスチレン含量（屈折率法により）
を測定した。Mooney viscosity, vinyl content (by infrared spectroscopy) and styrene content (by refractive index method) of the resulting polymer rubber
Was measured.
生成重合体ゴムのムーニー粘度は８５、スチレン含量は
２５％、ビニル含量は４０％であった。The resulting polymer rubber had a Mooney viscosity of 85, a styrene content of 25% and a vinyl content of 40%.
比較例２ ３−ジメチルアミノプロピルジエトキシメチルシランを
添加しないこと以外は実施例２と同じ方法で重合体を得
た。Comparative Example 2 A polymer was obtained by the same method as in Example 2 except that 3-dimethylaminopropyldiethoxymethylsilane was not added.
生成重合体ゴムのムーニー粘度は８５、スチレン含量は
２５％、ビニル含量は４０％であった。The resulting polymer rubber had a Mooney viscosity of 85, a styrene content of 25% and a vinyl content of 40%.
実施例１〜２および比較例１〜２で得られた生成重合体
ゴムを第１表の配合処方に従い、ロール上で混練し配合
ゴムを得、これを１６０℃×３０ 分の条件でプレス加硫した。The produced polymer rubbers obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were kneaded on a roll according to the compounding recipe of Table 1 to obtain compounded rubber, which was 160 ° C. × 30. Press vulcanization was performed under the condition of minutes.
加硫ゴムの反撥弾性はリュプケレジリエンステスターを
用いて６０℃で測定した。ＪＩＳ硬度はＪＩＳ Ｋ６３
０１により−２０℃で測定した。The impact resilience of the vulcanized rubber was measured at 60 ° C. using a Lupkeresilien tester. JIS hardness is JIS K63
01 at -20 ° C.
これらの結果を第２表に示す。この結果から、本発明の
変性ゴム組成物は、アミノシラン化合物を添加しないこ
と以外は本発明の重合体と同一方法で得た重合体を含む
ゴム組成物及び本発明の重合体とムーニー粘度を同一に
したアミノシラン化合物を含有しない重合体を含むゴム
組成物に比べて反撥弾性が著しく高く、かつ低温でのＪ
ＩＳ硬度が著しく低いことがわかる。The results are shown in Table 2. From these results, the modified rubber composition of the present invention has the same Mooney viscosity as the rubber composition containing the polymer obtained by the same method as the polymer of the present invention and the polymer of the present invention except that the aminosilane compound is not added. The impact resilience is significantly higher than that of the rubber composition containing a polymer containing no aminosilane compound, and the J
It can be seen that the IS hardness is extremely low.
実施例３および比較例３ 内容積１０のステンレス製重合反応器を洗浄、乾燥
し、スチレン−ブタジエン共重合体（ムーニー粘度５
１、スチレン含量２５％、ビニル含量４０％）500ｇ、
ｎ−ヘキサン4300gを仕込み、撹拌溶解させた。次にｎ
−ブチルリチウム（ｎ−ヘキサン溶液）6.4ミリモル及
びテトラメチルエチレンジアミンを6.4ミリモルを添加
し、７０℃で１時間反応させた。Example 3 and Comparative Example 3 A stainless steel polymerization reactor having an internal volume of 10 was washed and dried to give a styrene-butadiene copolymer (Moonie viscosity 5
1, styrene content 25%, vinyl content 40%) 500g,
4300 g of n-hexane was charged and dissolved with stirring. Then n
-Butyl lithium (n-hexane solution) (6.4 mmol) and tetramethylethylenediamine (6.4 mmol) were added, and the mixture was reacted at 70 ° C for 1 hour.
次に３−ジメチルアミノプロピルジエトキシメチルシラ
ンを6.4ミリモル添加し、撹拌下に３０分間反応させた
のち、１０ミリリッターのメタノールを加えて更に５分
間撹拌した。Next, 6.4 mmol of 3-dimethylaminopropyldiethoxymethylsilane was added, and the mixture was reacted for 30 minutes while stirring. Then, 10 milliliter of methanol was added and the mixture was further stirred for 5 minutes.
その後重合反応器の内容物を取り出し、５ｇの２，６−
ジ−ｔ−ブチル−ｐ−クレゾール（スミライザー ＢＨ
Ｔ）を加え、ｎ−ヘキサンの大部分を蒸発させたのち、
６０℃で２４時間減圧乾燥した。得られた重合体のムー
ニー粘度は５１であった。Then, the contents of the polymerization reactor were taken out, and 5 g of 2,6-
Di-t-butyl-p-cresol (Sumilyzer BH
T) was added to evaporate most of the n-hexane,
It was dried under reduced pressure at 60 ° C. for 24 hours. The obtained polymer mu
The knee viscosity was 51.
得られた生成重合体ゴムについて実施例１と同様の方法
にて配合、加硫ゴム物性を測定した。The resulting polymer rubber was compounded in the same manner as in Example 1 and the vulcanized rubber physical properties were measured.
また比較のため、変性前の前記スチレン−ブタジエン共
重合体（ムーニー粘度５１、スチレン含量２５％、ビニ
ル含量４０％）について同様の方法にて配合、加硫ゴム
物性を測定し比較例３とした。For comparison, the styrene-butadiene copolymer (modified Mooney viscosity 51, styrene content 25%, vinyl content 40%) before modification was compounded by the same method and the physical properties of the vulcanized rubber were measured. .
これらの結果を第２表に示した。The results are shown in Table 2.
〈発明の効果〉 以上述べたように、本発明によれば反撥弾性を高め、低
温でＪＩＳ硬度を低減するジエン系重合体ゴムをゴム成
分として含有する変性ゴム組成物を提供することができ
る。<Effects of the Invention> As described above, according to the present invention, it is possible to provide a modified rubber composition containing, as a rubber component, a diene polymer rubber that enhances impact resilience and reduces JIS hardness at low temperatures.
Claims (1)
おいて活性なアルカリ金属末端を有するジエン系重合体
ゴム又はアルカリ金属が付加された共役ジエン系ゴムと 一般式 （式中Ｒ１、Ｒ２、Ｒ３はアルキル基又はアルコキシ
基、Ｒ４、Ｒ５はアルキル基、ｎは整数を表わす。）で
示されるアミノシラン化合物とを反応させて得られる変
性ジエン系重合体ゴムをゴム成分中に少なくとも１０重
量％含むことを特徴とする変性ゴム組成物。1. A rubber composition comprising a rubber component and a compounding agent, wherein a diene polymer rubber having an active alkali metal terminal or a conjugated diene rubber having an alkali metal added thereto and a general formula (Wherein R 1 , R 2 , and R 3 are alkyl groups or alkoxy groups, R 4 and R 5 are alkyl groups, and n is an integer), and a modified diene-based compound obtained by reacting the aminosilane compound A modified rubber composition, characterized in that the rubber component contains at least 10% by weight of a united rubber.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1926387A JPH0657767B2 (en) | 1987-01-28 | 1987-01-28 | Modified rubber composition |
| EP87117741A EP0270071B1 (en) | 1986-12-01 | 1987-12-01 | Process for preparing modified diene polymer rubbers |
| DE3789203T DE3789203T2 (en) | 1986-12-01 | 1987-12-01 | Process for the preparation of modified rubber-diene polymers. |
| CA000553234A CA1310787C (en) | 1986-12-01 | 1987-12-01 | Process for preparing modified diene polymer rubbers |
| US07/415,380 US4957976A (en) | 1986-12-01 | 1989-09-29 | Process for preparing diene polymer rubbers |
| US07/501,700 US5015692A (en) | 1986-12-01 | 1990-03-30 | Process for preparing modified diene polymer rubbers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1926387A JPH0657767B2 (en) | 1987-01-28 | 1987-01-28 | Modified rubber composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63186748A JPS63186748A (en) | 1988-08-02 |
| JPH0657767B2 true JPH0657767B2 (en) | 1994-08-03 |
Family
ID=11994552
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1926387A Expired - Lifetime JPH0657767B2 (en) | 1986-12-01 | 1987-01-28 | Modified rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0657767B2 (en) |
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