JPH0967469A - Production of rubber composition - Google Patents
Production of rubber compositionInfo
- Publication number
- JPH0967469A JPH0967469A JP8159926A JP15992696A JPH0967469A JP H0967469 A JPH0967469 A JP H0967469A JP 8159926 A JP8159926 A JP 8159926A JP 15992696 A JP15992696 A JP 15992696A JP H0967469 A JPH0967469 A JP H0967469A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- weight
- diene
- raw
- parts
- 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.)
- Granted
Links
Classifications
-
- Y02T10/862—
Landscapes
- Tires In General (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は加硫物のtanδの
バランスに優れたゴム組成物の製造方法、特に空気入り
タイヤ用ゴム組成物の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing a rubber composition having an excellent tan δ balance of a vulcanized product, and more particularly to a method for producing a rubber composition for a pneumatic tire.
【0002】[0002]
【従来の技術】自動車の低燃費化のためにタイヤトレッ
ドゴムのtanδのバランスを改良することが提案され
ており、具体的には配合成分の分割混合や末端変性ゴム
の使用などが提案されている。2. Description of the Related Art It has been proposed to improve the balance of tan δ of tire tread rubber in order to reduce fuel consumption of automobiles. Specifically, split mixing of compounding components and use of terminal modified rubber have been proposed. There is.
【0003】例えば、特公平5−1298号公報には、
共役ジエン系重合体の末端部分に芳香族第3級アミノ基
を有する共役ジエン系重合体を含む加硫物の反撥弾性及
び引張強度を一層改良したゴム組成物が記載されてい
る。一方、特開昭55−10434号公報には無定形の
1,2−ポリブタジエンと天然ゴム及び/もしくはポリ
イソプレンゴム(又は一部共役ジエン系ゴムを含んでい
てもよい)とからなる原料ゴムにカーボンブラックを配
合してタイヤトレッド用ゴム組成物を製造するに際し、
先ず少なくとも25重量%の1,2−ポリブタジエンを
含む原料ゴム成分とカーボンブラックを特定の割合で混
合した後、残りの原料ゴム成分を添加混合して低燃費性
と安全性を改善することが記載されている。For example, Japanese Patent Publication No. 5-1298 discloses that
A rubber composition in which the vulcanizate and the tensile strength of a vulcanizate containing a conjugated diene-based polymer having an aromatic tertiary amino group at the terminal portion of the conjugated diene-based polymer are further improved is described. On the other hand, JP-A-55-10434 discloses a raw material rubber composed of amorphous 1,2-polybutadiene and natural rubber and / or polyisoprene rubber (or a conjugated diene rubber may be partially contained). When manufacturing a rubber composition for a tire tread by blending carbon black,
First, it is described that a raw material rubber component containing at least 25% by weight of 1,2-polybutadiene and carbon black are mixed in a specific ratio, and then the remaining raw material rubber component is added and mixed to improve fuel economy and safety. Has been done.
【0004】更に特開平2−129241号公報には末
端変性共役ジエン系重合体を有機溶媒中でカーボンブラ
ックと配合して加硫物の引張強度及び耐摩耗性を改良す
ることが提案されている。Further, JP-A-2-129241 proposes to blend a terminal-modified conjugated diene polymer with carbon black in an organic solvent to improve the tensile strength and abrasion resistance of a vulcanized product. .
【0005】[0005]
【発明が解決しようとする課題】しかしながら、前記し
た配合成分の分割混合法や末端変性ゴムの使用などの技
術は例えばオイル及びカーボンブラックの高配合系にお
いては効果がうすいなどの問題があり、依然としてその
改善が求められている。従って、本発明は加硫物のta
nδのバランスに優れたゴム組成物の製造方法を提供す
ることを目的とする。However, the above-mentioned techniques such as the divided mixing method of the compounding components and the use of the terminal modified rubber have the problems that the effect is thin in a high compounding system of oil and carbon black, and still remain. The improvement is required. Accordingly, the present invention is directed to the vulcanizate ta
It is an object to provide a method for producing a rubber composition having an excellent balance of nδ.
【0006】[0006]
【課題を解決するための手段】本発明に従えば、末端変
性及び/もしくはカップリングされたジエン系ゴム20
〜80重量%を含む原料ゴム混合物(A)50〜90重
量部と、末端変性されていない少なくとも1種のジエン
系ゴムからなる原料ゴム(B)50〜10重量部とから
なる原料ゴム100重量部に対し、補強剤50〜120
重量部と軟化剤20〜80重量部を混合してゴム組成物
を製造するに際し、原料ゴム(A)の平均ガラス転移温
度TgA(℃)と原料ゴム(B)の平均ガラス転移温度
TgB(℃)とが以下の関係にあり、TgA+20>T
gB>TgA−20、そして原料ゴム(A)と補強剤総
量の80重量%以上を135℃以上の温度で混合した
後、原料ゴム(B)と残りの補強剤及び軟化剤を添加混
合することを特徴とする空気入りタイヤ用ゴム組成物の
製造方法が提供される。According to the present invention, a terminal-modified and / or coupled diene rubber 20 is used.
100 to 50 parts by weight of a raw material rubber mixture (A) containing 50 to 90 parts by weight and 50 to 10 parts by weight of a raw material rubber (B) composed of at least one diene rubber which is not end-modified. Reinforcing agent 50 to 120
When the rubber composition is produced by mixing 20 parts by weight of the softening agent and 20 parts by weight of the softening agent, the average glass transition temperature TgA (° C) of the raw material rubber (A) and the average glass transition temperature TgB (° C of the raw material rubber (B) are measured. ) Has the following relationship, and TgA + 20> T
gB> TgA-20, and mixing 80% by weight or more of the raw material rubber (A) and the total amount of the reinforcing agent at a temperature of 135 ° C. or higher, and then adding and mixing the raw material rubber (B) and the remaining reinforcing agent and softening agent. A method for producing a rubber composition for a pneumatic tire is provided.
【0007】本発明に従えば、また、10万〜120万
の範囲の重量平均分子量Mw(A′)を有するジエン系
原料ゴム(A′)と、40万以上の重量平均分子量Mw
(B′)を有するジエン系原料ゴム(B′)とを混合し
てゴム組成物を製造するに際し、重量平均分子量が以下
の関係にあり、 0.08≦Mw(A′)/Mw(B′)<1…(III) 原料ゴム(A′)の平均ガラス転移温度TgA′(℃)
と原料ゴム(B′)の平均ガラス転移温度TgB′
(℃)とが以下の関係にある TgA′+20>TgB′>TgA′−20…(I′) ジエン系原料ゴム(A′)20〜90重量部と補強剤5
0〜120重量部とを最初に混合し、その後ジエン系原
料ゴム(B′)80〜10重量部とジエン系原料ゴム
(A′)及び(B′)の合計量100重量部に対して2
0〜80重量部の軟化剤を添加することを特徴とするゴ
ム組成物の製造方法が提供される。According to the present invention, a diene raw material rubber (A ') having a weight average molecular weight Mw (A') in the range of 100,000 to 1.2 million and a weight average molecular weight Mw of 400,000 or more are also used.
When the rubber composition is produced by mixing with the diene raw rubber (B ') having (B'), the weight average molecular weight has the following relationship: 0.08≤Mw (A ') / Mw (B ′) <1 (III) Average glass transition temperature TgA ′ (° C.) of raw rubber (A ′)
And the average glass transition temperature TgB 'of the raw rubber (B')
(° C.) has the following relationship: TgA ′ + 20> TgB ′> TgA′-20 (I ′) 20 to 90 parts by weight of diene raw rubber (A ′) and reinforcing agent 5
0 to 120 parts by weight are mixed first, and then 2 to 80 parts by weight of the diene-based raw material rubber (B ') and 100 parts by weight of the total amount of the diene-based raw material rubbers (A') and (B ').
Provided is a method for producing a rubber composition, which comprises adding 0 to 80 parts by weight of a softening agent.
【0008】[0008]
【発明の実施の形態】本発明者らはゴム組成物のtan
δが、カーボンブラックなどの充填剤近辺のゴム吸着相
とはほとんど無関係であり、マトリックス相によるもの
であることを見出しカーボンブラック表面とマトリック
ス相を出来るだけ隔離することによりtanδのバラン
スを改良することに成功したものである。そのために、
本発明の第一の態様によれば、カーボンブラックなどの
補強剤の表面との反応性が高い末端変性ジエン系ゴム
(例えばSBR)とカーボンブラックなどの補強剤とを
あらかじめ混合することにより、カーボン表面を末端変
性ジエン系ゴムで覆い、続いて反応性が低いジエン系ゴ
ム(例えば乳化重合SBR)を添加混合することによ
り、加硫物のtanδのバランスが改良されたゴム組成
物が得られる。BEST MODE FOR CARRYING OUT THE INVENTION
To find that δ is almost unrelated to the rubber adsorption phase near the filler such as carbon black and to be due to the matrix phase, and improve the tan δ balance by separating the carbon black surface and the matrix phase as much as possible. Is a successful one. for that reason,
According to the first aspect of the present invention, carbon is obtained by preliminarily mixing a terminal-modified diene rubber (for example, SBR) having high reactivity with the surface of a reinforcing agent such as carbon black and a reinforcing agent such as carbon black. By covering the surface with a terminal-modified diene-based rubber and then adding and mixing a diene-based rubber having low reactivity (for example, emulsion polymerization SBR), a rubber composition having an improved tan δ balance of the vulcanized product can be obtained.
【0009】本発明の第二の態様では、前記した特定の
関係(III)を満足する2種類のジエン系原料ゴムを用い
ジエン系原料ゴム(A′)と補強剤とを混合し、次にこ
れにジエン系原料ゴム(B′)と軟化剤を混合すること
により、加硫物のtanδのバランスが改良されたゴム
組成物が得られる。なお、Mw(A′)/Mw(B′)
の比が0.08未満では補強剤による補強性が低下する
ために破断物性や耐摩耗性が低下するので好ましくな
く、逆に1を超えるとマトリックス相に補強剤の効果が
およびtanδのバランスが低下するので好ましくな
い。In the second embodiment of the present invention, two kinds of diene raw rubbers satisfying the above-mentioned specific relation (III) are used, the diene raw rubber (A ') and the reinforcing agent are mixed, and then, A rubber composition having an improved tan δ balance of the vulcanized product can be obtained by mixing the diene-based raw material rubber (B ′) and the softening agent therein. Note that Mw (A ') / Mw (B')
If the ratio is less than 0.08, the reinforcing property by the reinforcing agent is deteriorated, and the fracture properties and wear resistance are deteriorated, which is not preferable. On the contrary, if the ratio exceeds 1, the effect of the reinforcing agent on the matrix phase and the balance of tan δ are balanced. It is not preferable because it decreases.
【0010】本発明の第一の態様に従えば、溶液重合に
より合成されかつ末端変性された、そして/又はカップ
リングされたジエン系ゴム(例えばポリブタジエンゴム
(BR)、スチレン−ブタジエン共重合ゴム(SB
R)、スチレン−イソプレン−ブタジエン共重合ゴム
(SIBR))を20〜80重量%、好ましくは50〜
80重量%含む原料ゴム混合物(A)50〜90重量
部、好ましくは50〜80重量部と、末端変性されてい
ないジエン系ゴム(B)(例えば乳化重合もしくは溶液
重合されたBR,SBR,SIBR)50〜10重量
部、好ましくは50〜20重量部とから成る原料ゴム
に、原料ゴム100重量部当り補強剤(例えばカーボン
ブラック、シリカなど)50〜120重量部、好ましく
は60〜100重量部及び軟化剤(例えば芳香族プロセ
ス油、ナフテン系プロセス油など)20〜80重量部、
好ましくは35〜70重量部を配合して成るゴム組成物
を製造するにあたり、原料ゴム(A)の平均ガラス転移
温度TgA(℃)と原料ゴム(B)の平均ガラス転移温
度TgB(℃)とが以下の関係: TgA+20>TgB>TgA−20、好ましくは20
>TgA>−45でかつ、TgA+20>TgB>Tg
A−10にあり、更に、原料ゴム(A)と補強剤総量の
80重量%以上、好ましくは85〜100重量%を先ず
135℃以上、好ましくは130〜150℃の温度で、
例えばバンバリーミキサーなどの密閉型ミキサーで混合
し、次に原料ゴム(B)と残りの補強剤及び軟化剤と
を、好ましくは135℃以上の温度で混合することによ
って所望のゴム組成物を得ることができる。According to the first aspect of the present invention, a diene rubber synthesized by solution polymerization and end-modified and / or coupled (for example, polybutadiene rubber (BR), styrene-butadiene copolymer rubber ( SB
R) and styrene-isoprene-butadiene copolymer rubber (SIBR)) in an amount of 20 to 80% by weight, preferably 50 to 50% by weight.
50 to 90 parts by weight, preferably 50 to 80 parts by weight, of a raw rubber mixture (A) containing 80% by weight, and a diene rubber (B) not end-modified (for example, emulsion-polymerized or solution-polymerized BR, SBR, SIBR ) 50 to 10 parts by weight, preferably 50 to 20 parts by weight of the raw material rubber, and 50 to 120 parts by weight, preferably 60 to 100 parts by weight of a reinforcing agent (for example, carbon black, silica, etc.) per 100 parts by weight of the raw material rubber. And 20 to 80 parts by weight of a softening agent (eg, aromatic process oil, naphthenic process oil, etc.),
Preferably, in producing a rubber composition containing 35 to 70 parts by weight, the average glass transition temperature TgA (° C) of the raw rubber (A) and the average glass transition temperature TgB (° C) of the raw rubber (B) are Has the following relationship: TgA + 20>TgB> TgA-20, preferably 20
>TgA> -45 and TgA + 20>TgB> Tg
A-10, and further 80% by weight or more, preferably 85 to 100% by weight of the total amount of the raw material rubber (A) and the reinforcing agent, at a temperature of 135 ° C. or more, preferably 130 to 150 ° C.,
For example, a desired rubber composition is obtained by mixing with a closed type mixer such as a Banbury mixer, and then mixing the raw rubber (B) and the remaining reinforcing agent and softening agent at a temperature of preferably 135 ° C. or higher. You can
【0011】本発明の第一の態様において使用される末
端変性ジエン系ゴムは、特開昭64−60604号公報
に記載のように常法に従って、溶液重合SBR,BRな
どのゴム分子の合成末端のアルカリ金属(例えばLi)
やアルカリ土類金属(例えばMg)を分子中に−CO−
N<もしくは−CS−N<結合を有する化合物(例えば
N,N−ジエチルホルムアミド、N,N−ジメチルアセ
トアミド、N,N−ジメチルベンズアミドなどのアミド
類、N,N′−ジメチル尿素、N,N′−ジメチルエチ
レン尿素などの尿素類、ε−カプロラクタム、N−メチ
ル−ε−カプロラクタム、N−メチル−2−ピロリド
ン、N−ビニル−2−ピロリドンなどのラクタム類など
特開昭61−103904号公報に記載の化合物、1,
3−ジメチル−2−イミダゾリジノン、1,3−ジメチ
ルエチレンチオウレアなど特開昭61−268702号
公報に記載の化合物などが挙げられる)と反応させて得
ることができる。この時合成末端の変性率が高い程効果
があり、通常20%以上の変性率のものが使用される。The terminal-modified diene rubber used in the first embodiment of the present invention is a synthetic terminal of rubber molecules such as solution-polymerized SBR and BR according to a conventional method as described in JP-A-64-60604. Alkali metal (eg Li)
Or alkaline earth metal (eg Mg) in the molecule -CO-
Compounds having N <or -CS-N <bond (for example, amides such as N, N-diethylformamide, N, N-dimethylacetamide, N, N-dimethylbenzamide, N, N'-dimethylurea, N, N Urea such as'-dimethylethyleneurea, lactams such as ε-caprolactam, N-methyl-ε-caprolactam, N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone. JP-A-61-103904 The compound described in 1,
3-dimethyl-2-imidazolidinone, 1,3-dimethylethylene thiourea and the like, such as the compounds described in JP-A-61-268702 and the like) can be obtained. At this time, the higher the modification rate of the synthetic terminal, the more effective it is. Usually, the modification rate of 20% or more is used.
【0012】本発明の第一の態様において使用されるカ
ップリングされたジエン系ゴムは、常法に従って、例え
ば、溶液重合されたジエン系ゴム(SBR,BRなど)
のゴム分子末端のアルカリ金属もしくはアルカリ土類金
属(又は上記方法で末端変性されたジエン系ゴムの残存
末端アルカリ金属もしくはアルカリ土類金属の20%以
上、好ましくは30〜50%を例えばハロゲン化スズも
しくはハロゲン化珪素と常法に従って反応させて得るこ
とができる。The coupled diene rubber used in the first embodiment of the present invention can be prepared by, for example, a solution-polymerized diene rubber (SBR, BR, etc.) according to a conventional method.
Alkali metal or alkaline earth metal at the terminal of the rubber molecule (or 20% or more, preferably 30 to 50%, of the remaining terminal alkali metal or alkaline earth metal of the diene rubber end-modified by the above-mentioned method is used, for example, tin halide. Alternatively, it can be obtained by reacting with silicon halide according to a conventional method.
【0013】前述の如く、本発明の第一の態様に従え
ば、第1工程で特定のジエン系原料ゴム(A)と例えば
カーボンブラックを先ず温度135℃以上で混合するこ
とによりカーボンブラック粒子の周囲に末端変性SBR
などのゴム吸着相を設け、それにマトリックス相となる
原料ゴム(B)を配合するので所望の加硫物を得ること
ができる。上記混合温度が135℃未満では補強剤粒子
と末端変性(及び/又はカップリング化)ジエン系ゴム
(A)との反応が不充分で所望の効果は得られない。As described above, according to the first aspect of the present invention, in the first step, the specific diene raw rubber (A) and carbon black, for example, are first mixed at a temperature of 135 ° C. or higher to form carbon black particles. Terminal modified SBR around
A rubber-adsorbed phase such as that described above is provided, and the raw material rubber (B) serving as the matrix phase is mixed therein, so that a desired vulcanized product can be obtained. If the mixing temperature is less than 135 ° C., the reaction between the reinforcing agent particles and the terminal-modified (and / or coupled) diene rubber (A) is insufficient and the desired effect cannot be obtained.
【0014】本発明の第二の態様に従えば、分子量の範
囲が10万〜120万、好ましくは12万〜90万のジ
エン系原料ゴム(A′)の重量平均分子量Mw(A′)
と、分子量の範囲が40万以上、好ましくは50万〜1
50万のジエン系原料ゴム(B′)の重量平均分子量M
w(B′)が以下の関係にあり、 0.08≦Mw(A′)/Mw(B′)<1…(III) 好ましくは0.1≦Mw(A′)/Mw(B′)≦0.
8 原料ゴム(A′)の平均ガラス転移温度TgA′(℃)
と原料ゴム(B′)の平均ガラス転移温度TgB′
(℃)とが以下の関係にある TgA′+20>TgB′>TgA′−20…(I′) 好ましくはTgA′+20>TgA′−10 20>TgA′>−45…(II′) ジエン系原料ゴム(A)20〜90重量部、好ましくは
50〜80重量部と補強剤(例えばカーボンブラック、
シリカなど)50〜120重量部、好ましくは60〜1
00重量部とを最初に接触させて、その後ジエン系原料
ゴム(B′)80〜10重量部、好ましくは50〜20
重量部とジエン系原料ゴム(A′)及び(B′)の合計
量100重量部に対して20〜80重量部、好ましくは
35〜70重量部の軟化剤(例えば芳香族プロセス油、
ナフテン系プロセス油など)を添加することによって加
硫物のtanδがバランスしたゴム組成物が製造され
る。上記原料ゴムとしては有機溶剤に溶解した原料ゴム
又は水系エマルジョンにした原料ゴムを用いることがで
きる。According to the second embodiment of the present invention, the weight average molecular weight Mw (A ') of the diene raw rubber (A') having a molecular weight range of 100,000 to 1,200,000, preferably 120,000 to 900,000.
And a molecular weight range of 400,000 or more, preferably 500,000 to 1
Weight average molecular weight M of 500,000 diene raw rubber (B ')
w (B ') has the following relationship: 0.08≤Mw (A') / Mw (B ') <1 (III) Preferably 0.1≤Mw (A') / Mw (B ') ≤0.
8 Raw material rubber (A ') average glass transition temperature TgA' (° C)
And the average glass transition temperature TgB 'of the raw rubber (B')
(C) has the following relationship: TgA '+ 20>TgB'>TgA'-20 ... (I ') Preferably TgA' + 20>TgA'-1020> TgA '>-45 ... (II') Diene system 20 to 90 parts by weight, preferably 50 to 80 parts by weight of the raw material rubber (A) and a reinforcing agent (for example, carbon black,
50 to 120 parts by weight, preferably 60 to 1
00 parts by weight is first contacted, and then 80 to 10 parts by weight of the diene raw rubber (B '), preferably 50 to 20 parts.
20 to 80 parts by weight, preferably 35 to 70 parts by weight, of a softening agent (for example, aromatic process oil, based on 100 parts by weight of the total amount of parts by weight and the diene raw rubbers (A ') and (B')).
A rubber composition in which the tan δ of the vulcanized product is balanced is manufactured by adding a naphthenic process oil or the like). As the raw material rubber, a raw material rubber dissolved in an organic solvent or a raw material rubber in an aqueous emulsion can be used.
【0015】本発明のゴム組成物には前記ポリマー分、
補強剤及び軟化剤に加えて、硫黄、加硫促進剤、老化防
止剤、その他の充填剤、可塑剤などの自動車タイヤ用そ
の他のゴム組成物に一般に配合されている各種添加剤を
配合することができ、かかる配合物は一般的な方法で加
硫することができる。これらの添加剤の配合量も一般的
な量とすることができる。例えば、硫黄の配合量はゴム
成分100重量部当り0.5重量部以上、更に好ましく
は1.0〜2.5重量部とするのが好ましい。加硫条件
も一般的な範囲である。これらの添加剤は前記第1工程
及び第2工程の完了後に配合するのが一般であるが、こ
れに限定されるものではない。The rubber composition of the present invention contains the above polymer component,
In addition to the reinforcing agent and the softening agent, blending various additives generally blended in other rubber compositions for automobile tires such as sulfur, vulcanization accelerator, antioxidant, other fillers, plasticizers, etc. And such formulations can be vulcanized by conventional methods. The amount of these additives may be a general amount. For example, the content of sulfur is preferably 0.5 parts by weight or more, more preferably 1.0 to 2.5 parts by weight, per 100 parts by weight of the rubber component. Vulcanization conditions are also in a general range. These additives are generally added after the completion of the first step and the second step, but the present invention is not limited thereto.
【0016】[0016]
【実施例】以下、実施例によって本発明を更に説明する
が、本発明の範囲をこれらの実施例に限定するものでな
いことは言うまでもない。EXAMPLES The present invention will be further described below with reference to examples, but it goes without saying that the scope of the present invention is not limited to these examples.
【0017】実施例1〜2及び比較例1〜4 実施例1及び比較例1〜2はSBR−1(ガラス転移点
温度−30℃、結合スチレン量20%、ビニル結合量6
5%、重量平均分子量35万の末端変性/カップリング
処理溶液重合スチレン−ブタジエン共重合体)と、SB
R−2(ガラス転移点温度−21℃、結合スチレン量4
5%、ビニル結合量12%、重量平均分子量120万の
50%油展の乳化重合スチレン−ブタジエン共重合体)
とを原料ゴムとして使用し、表Iに示すように、他の成
分を配合して加硫物性を評価した。結果も表Iに示す。 Examples 1 and 2 and Comparative Examples 1 to 4 Examples 1 and 2 are SBR-1 (glass transition temperature -30 ° C., bound styrene amount 20%, vinyl bond amount 6).
5%, end-modified / coupling solution-polymerized styrene-butadiene copolymer having a weight average molecular weight of 350,000) and SB
R-2 (glass transition temperature -21 ° C, amount of bound styrene 4
5%, vinyl bond amount 12%, 50% oil-extended emulsion-polymerized styrene-butadiene copolymer having a weight average molecular weight of 1.2 million)
And were used as raw rubbers, and as shown in Table I, other components were blended and vulcanized physical properties were evaluated. The results are also shown in Table I.
【0018】加硫物性(tanδ)は以下のようにして
測定した。東洋精機製作所製レオログラフソリッドを用
い、初期歪み=10%、動的歪み=2%、周波数=20
Hzで粘弾性を測定した(試料幅5mm、温度0℃及び40
℃)The vulcanized physical properties (tan δ) were measured as follows. Using Toyo Seiki Seisakusho's Rheological solid, initial strain = 10%, dynamic strain = 2%, frequency = 20
Viscoelasticity was measured in Hz (sample width 5 mm, temperature 0 ° C and 40
℃)
【0019】なお、加硫物性において0℃のtanδは
高いほど湿潤路面での摩擦力が大きく(タイヤのグリッ
プ力が高い)40℃のtanδは低いほど定エネルギー
変形におけるエネルギー損失が小さい(タイヤのころが
り抵抗が小さい)ことを示す。本発明ではtanδ(0
℃)/tanδ(40℃)(表において(a)/(b)
で表示)の値で評価し、この値が大きいほどtanδの
バランスが良好(即ちタイヤのグリップ力が高くころが
り抵抗が小さい)であることを示している。Regarding the vulcanization properties, the higher the tan δ at 0 ° C., the greater the frictional force on the wet road surface (higher the grip force of the tire), and the lower the tan δ at 40 ° C., the smaller the energy loss in constant energy deformation (the tire Rolling resistance is small). In the present invention, tan δ (0
℃) / tan δ (40 ℃) ((a) / (b) in the table
Value), the larger the value, the better the balance of tan δ (that is, the higher the grip force of the tire and the smaller the rolling resistance).
【0020】比較例1(標準例)は両方の工程のゴム組
成が同一になるようにしたものであり、実施例1は油展
乳化重合SBRをすべて第2工程にて投入したものであ
り、40℃のtanδが約10%低下し、かつtanδ
の温度勾配が大きく、タイヤのグリップ力を保持しつつ
低燃費化が達成出来ることを示している。一方比較例2
は変性溶液重合SBRのうち30重量部を第2工程で投
入したものであり、実施例1とは対照的にtanδの温
度勾配は悪化している。In Comparative Example 1 (standard example), the rubber compositions in both steps were made the same, and in Example 1, all the oil-extended emulsion-polymerized SBR was added in the second step. Tan δ at 40 ° C is reduced by about 10%, and tan δ
It shows that the temperature gradient is large and the fuel consumption can be reduced while maintaining the grip of the tire. Comparative example 2
Indicates that 30 parts by weight of the modified solution-polymerized SBR was added in the second step, and in contrast to Example 1, the temperature gradient of tan δ deteriorates.
【0021】実施例2及び比較例3〜4はSBR−1
(ガラス転移点温度−30℃、結合スチレン量20%、
ビニル結合量65%、重量平均分子量35万の末端変性
/カップリング処理溶液重合スチレン−ブタジエン共重
合体)70重量部と、SBR−2(ガラス転移点温度−
36℃、結合スチレン量33%、ビニル結合量13%、
重量平均分子量72万の50%油展の乳化重合スチレン
−ブタジエン共重合体を原料ゴムとして30重量部使用
した例である。これらの例でも前記例と同様に本発明に
係る実施例2は比較例3(標準例)や比較例4に比較し
てtanδ改善の効果が認められた。In Example 2 and Comparative Examples 3 to 4, SBR-1 was used.
(Glass transition temperature -30 ° C, amount of bound styrene 20%,
70 parts by weight of a terminal-modified / coupling solution-polymerized styrene-butadiene copolymer having a vinyl bond content of 65% and a weight average molecular weight of 350,000, and SBR-2 (glass transition temperature-
36 ° C, bound styrene content 33%, vinyl bond content 13%,
This is an example of using 30 parts by weight of a 50% oil-extended emulsion-polymerized styrene-butadiene copolymer having a weight average molecular weight of 720,000 as a raw material rubber. In these examples as well, the effect of improving tan δ was confirmed in Example 2 according to the present invention as compared with Comparative Example 3 (standard example) and Comparative Example 4 similarly to the above examples.
【0022】[0022]
【表1】 [Table 1]
【0023】実施例3〜4及び比較例5〜8 比較例5(標準例)及び比較例6は前記SBR−1 7
0重量部とBR−1(シス結合量30%、ビニル結合量
13%、重量平均分子量30万の溶液重合ブタジエン重
合体)30重量部とを使用して表IIに示すようにして配
分した例である。これらの原料ゴムのTgの相違は60
℃であり、本発明の条件を満たしておらず、前記非変性
油展乳化重合SBRを第2工程で投入してもtanδの
改善効果は認められなかった。 Examples 3 to 4 and Comparative Examples 5 to 8 Comparative Example 5 (standard example) and Comparative Example 6 are the same as the SBR-17.
Example in which 0 parts by weight and 30 parts by weight of BR-1 (solution-polymerized butadiene polymer having a cis bond content of 30%, a vinyl bond content of 13% and a weight average molecular weight of 300,000) were used as shown in Table II. Is. The difference in Tg of these raw rubbers is 60
C., which does not satisfy the conditions of the present invention, and the effect of improving tan δ was not observed even when the non-modified oil-extended emulsion-polymerized SBR was added in the second step.
【0024】実施例3〜4並びに比較例7(標準例)及
び比較例8は、SBR−4(ガラス転移温度−25℃、
結合スチレン量15%、ビニル結合量80%、重量平均
分子量35万の末端変性/カップリング処理溶液重合ス
チレン−ブタジエン重合体)60重量部と前記SBR−
2 40重量部を原料ゴムとして使用して表IIを示すよ
うにして配合した例である。Examples 3 to 4 and Comparative Example 7 (standard example) and Comparative Example 8 are SBR-4 (glass transition temperature -25 ° C.,
60% by weight of a terminally modified / coupling solution-polymerized styrene-butadiene polymer having a bound styrene content of 15%, a vinyl bond content of 80% and a weight average molecular weight of 350,000 and the SBR-
In this example, 240 parts by weight was used as a raw rubber and compounded as shown in Table II.
【0025】比較例7(標準例)はすべての原料ゴムを
第1工程で投入したものであり、比較例8(標準例)は
第1及び第2工程のゴム組成が同一になるようにしたも
のである。これらを混合方法の相違の効果を見ると、表
IIに示すように、第2工程で原料ゴムを追加添加する方
法では40℃のtanδの低下効果が生じるが、0℃の
tanδも低下してしまいtanδの温度勾配の改善は
認められない。In Comparative Example 7 (standard example), all the raw material rubbers were added in the first step, and in Comparative Example 8 (standard example), the rubber compositions in the first and second steps were the same. It is a thing. To see the effect of the difference in the mixing method,
As shown in II, the method of additionally adding the raw material rubber in the second step has the effect of lowering the tan δ at 40 ° C., but the tan δ at 0 ° C. also lowers, and no improvement in the temperature gradient of tan δ is observed.
【0026】一方、本発明の実施例3及び4では表IIに
示すように40℃のtanδが低下し、またtanδの
温度勾配が改良されていることが明らかである。On the other hand, in Examples 3 and 4 of the present invention, as shown in Table II, it is clear that tan δ at 40 ° C. is lowered and the temperature gradient of tan δ is improved.
【0027】[0027]
【表2】 [Table 2]
【0028】表III はSBR−1(ガラス転移点温度−
30℃、結合スチレン量20%、ビニル結合量65%、
重量平均分子量35万の末端変性/カップリング処理溶
液重合スチレン−ブタジエン共重合体)及びSBR−2
(ガラス転移点温度−21℃、結合スチレン量45%、
ビニル結合量12%、重量平均分子量120万の乳化重
合スチレン−ブタジエン重合体)及びSBR−5(ガラ
ス転移点温度−36℃、結合スチレン量35%、ビニル
結合量14%、重量平均分子量82万の乳化重合スチレ
ン−ブタジエン重合体)での例である。比較例9は加硫
系以外の全ての配合剤を第一工程で加えたものであり、
比較例10及び11は本発明とは逆に変性溶液重合SB
Rを第2工程で加えた場合の例である。表III に示すよ
うに、本発明である実施例5は比較例9に対して、0℃
のtanδが上昇し、40℃のtanδが低下してお
り、tanδ勾配も大きく、タイヤのグリップ力を保持
しつつ低燃費化が達成できることを示している。また、
逆に変性溶液重合SBRを第2工程で加えた場合の比較
例10に対して、比較例9に対して、0℃のtanδが
低下し、40℃のtanδが上昇しており悪化傾向にあ
る。実施例6及び比較例11も同様である。Table III shows SBR-1 (glass transition temperature-
30 ° C, bound styrene amount 20%, vinyl bond amount 65%,
Terminal-modified / coupling solution-polymerized styrene-butadiene copolymer having a weight average molecular weight of 350,000) and SBR-2
(Glass transition temperature -21 ° C, amount of bound styrene 45%,
Emulsion-polymerized styrene-butadiene polymer having a vinyl bond amount of 12% and a weight average molecular weight of 1,200,000 and SBR-5 (glass transition temperature -36 ° C, bound styrene amount of 35%, vinyl bond amount of 14%, weight average molecular weight of 820,000). Is an emulsion-polymerized styrene-butadiene polymer). Comparative Example 9 is one in which all compounding agents other than the vulcanizing system were added in the first step,
Contrary to the present invention, Comparative Examples 10 and 11 were modified solution polymerization SB.
This is an example when R is added in the second step. As shown in Table III, Example 5 of the present invention was compared with Comparative Example 9 at 0 ° C.
Tan δ of tan δ is increased and tan δ at 40 ° C. is decreased, and the tan δ gradient is large, which shows that fuel economy can be achieved while maintaining the grip force of the tire. Also,
On the contrary, in comparison with Comparative Example 10 in which the modified solution-polymerized SBR was added in the second step, tan δ at 0 ° C. was lower and tan δ at 40 ° C. was higher than that of Comparative Example 9. . The same applies to Example 6 and Comparative Example 11.
【0029】[0029]
【表3】 [Table 3]
【0030】なお、表I〜表III に示した配合成分は以
下の通りである。 SBR−1:ガラス転移点温度−30℃、結合スチレン
量20%、ビニル結合量65%、重量平均分子量35万
の末端変性及びカップリング処理を併用した溶液重合ス
チレン−ブタジエン共重合体 SBR−2:ガラス転移点温度−21℃、結合スチレン
量45%、ビニル結合量12%、重量平均分子量120
万の50%油展乳化重合スチレン−ブタジエン重合体 SBR−3:ガラス転移点温度−36℃、結合スチレン
量33%、ビニル結合量13%、重量平均分子量72万
の50%油展乳化重合スチレン−ブタジエン重合体 SBR−4:ガラス転移点温度−25℃、結合スチレン
量15%、ビニル結合量80%、重量平均分子量35万
の末端変性及びカップリング処理を併用した溶液重合ス
チレン−ブタジエン共重合体 SBR−5:ガラス転移点温度−36℃、結合スチレン
量35%、ビニル結合量14%、重量平均分子量82万
の50%油展乳化重合スチレン−ブタジエン重合体 BR−1:ガラス転移点温度−90℃、シス結合量30
%、ビニル結合量13%、重量平均分子量30万の溶液
重合ブタジエン重合体 カーボンブラック−1:窒素吸着比表面積117m2 /
g、DBP吸油量112ml/100g カーボンブラック−2:窒素吸着比表面積150m2 /
g、DBP吸油量127ml/100g 酸化亜鉛:亜鉛華3号 ステアリン酸:工業用ステアリン酸 老化防止剤6C:N−フェニル−N′−(1,3−ジメ
チルブチル)−p−フェニレンジアミン アロマオイル:芳香族プロセスオイル 粉末硫黄:5%油処理の粉末硫黄 加硫促進剤CZ:N−シクロヘキシル−2−ベンゾチア
ジルスルフェンアミド 加硫促進剤DPG:ジフェニルグアニジンThe blending components shown in Tables I to III are as follows. SBR-1: Glass transition temperature -30 ° C, bound styrene content 20%, vinyl bond content 65%, weight average molecular weight 350,000 solution-modified styrene-butadiene copolymer SBR-2 combined with terminal modification and coupling treatment : Glass transition temperature -21 ° C, bound styrene amount 45%, vinyl bond amount 12%, weight average molecular weight 120
50% oil-extended emulsion-polymerized styrene-butadiene polymer SBR-3: glass transition temperature -36 ° C, bound styrene amount 33%, vinyl bond amount 13%, weight-average molecular weight 720,000 50% oil-extended emulsion polymerized styrene -Butadiene polymer SBR-4: Glass transition temperature -25 ° C, bound styrene amount 15%, vinyl bond amount 80%, weight average molecular weight 350,000 solution-modified styrene-butadiene copolymerization using terminal modification and coupling treatment in combination. Combined SBR-5: Glass transition temperature -36 ° C, bound styrene amount 35%, vinyl bond amount 14%, 50% oil-extended emulsion-polymerized styrene-butadiene polymer BR-1: glass transition temperature -90 ° C, cis bond amount 30
%, Vinyl bond amount 13%, weight average molecular weight 300,000 solution-polymerized butadiene polymer carbon black-1: nitrogen adsorption specific surface area 117 m 2 /
g, DBP oil absorption 112 ml / 100 g Carbon black-2: Nitrogen adsorption specific surface area 150 m 2 /
g, DBP oil absorption 127 ml / 100 g Zinc oxide: Zinc white No. 3 Stearic acid: Industrial stearic acid Anti-aging agent 6C: N-phenyl-N '-(1,3-dimethylbutyl) -p-phenylenediamine Aroma oil: Aromatic process oil Sulfur powder: Sulfur powder treated with 5% oil Vulcanization accelerator CZ: N-cyclohexyl-2-benzothiazylsulfenamide Vulcanization accelerator DPG: Diphenylguanidine
【0031】[0031]
【発明の効果】以上説明したように、本発明に従えば、
tanδのバランスが改良され、従来の末端変性SBR
では使用効果が十分でなかった汎用・HPT系タイヤト
レッドの低燃費化が可能となり、また廉価な乳化重合S
BRを使用して溶液重合なみのtanδ低減効果を得る
ことができる。As described above, according to the present invention,
Improved tan δ balance, conventional end-modified SBR
It was possible to reduce the fuel consumption of general-purpose HPT-type tire treads that were not sufficiently used in the
BR can be used to obtain a tan δ reduction effect similar to solution polymerization.
Claims (8)
れたジエン系ゴム20〜80重量%を含む原料ゴム混合
物(A)50〜90重量部と、末端変性されていない少
なくとも1種のジエン系ゴムからなる原料ゴム(B)5
0〜10重量部とからなる原料ゴム100重量部に対
し、補強剤50〜120重量部と軟化剤20〜80重量
部を混合してゴム組成物を製造するに際し、原料ゴム
(A)の平均ガラス転移温度TgA(℃)と原料ゴム
(B)の平均ガラス転移温度TgB(℃)とが以下の関
係にあり、 TgA+20>TgB>TgA−20…(I) かつ、原料ゴム(A)と補強剤総量の80重量%以上を
135℃以上の温度で混合した後、原料ゴム(B)と残
りの補強剤及び軟化剤を添加混合することを特徴とする
ゴム組成物の製造方法。1. From 50 to 90 parts by weight of a raw rubber mixture (A) containing 20 to 80% by weight of a diene rubber end-modified and / or coupled, and at least one diene rubber not end-modified. Raw material rubber (B) 5
When a rubber composition is manufactured by mixing 50 to 120 parts by weight of a reinforcing agent and 20 to 80 parts by weight of a softening agent to 100 parts by weight of a raw material rubber composed of 0 to 10 parts by weight, the average of the raw material rubber (A) is The glass transition temperature TgA (° C.) and the average glass transition temperature TgB (° C.) of the raw rubber (B) have the following relationship: TgA + 20>TgB> TgA-20 (I) and the raw rubber (A) and reinforcement A method for producing a rubber composition, which comprises mixing 80% by weight or more of the total amount of the agent at a temperature of 135 ° C. or more and then adding and mixing the raw rubber (B) and the remaining reinforcing agent and softening agent.
gA(℃)が以下の範囲にある請求項1に記載のゴム組
成物の製造方法。 20 > TgA > −45…(II)2. The average glass transition temperature T of the raw rubber (A)
The method for producing a rubber composition according to claim 1, wherein gA (° C) is in the following range. 20>TgA> -45 ... (II)
系ゴムが、溶液重合されたジエン系原料ゴムのゴム分子
の合成末端のアルカリ金属またはアルカリ土類金属の2
0%以上を分子中に−CO−N<もしくは−CS−N<
結合を有する化合物と反応させて得られたスチレン−ブ
タジエン共重合体ゴム及び/またはポリブタジエンゴム
である請求項1又は2に記載のゴム組成物の製造方法。3. The end-modified diene rubber of the raw rubber (A) is a solution-polymerized diene-based rubber having a synthetic molecule end of a rubber molecule of the diene-based rubber.
0% or more is -CO-N <or -CS-N <in the molecule.
The method for producing a rubber composition according to claim 1 or 2, which is a styrene-butadiene copolymer rubber and / or a polybutadiene rubber obtained by reacting with a compound having a bond.
エン系ゴムが、溶液重合された原料ジエン系ゴムのゴム
分子の合成末端のアルカリ金属またはアルカリ土類金属
の20%以上をハロゲン化錫もしくはハロゲン化珪素と
反応させて得られたスチレン−ブタジエン共重合体ゴム
及び/またはポリブタジエンゴムである請求項1〜3の
いずれか1項に記載のゴム組成物の製造方法。4. The coupled diene rubber of the raw rubber (A) is a tin halide containing 20% or more of the alkali metal or alkaline earth metal at the synthetic end of the rubber molecule of the raw diene rubber solution-polymerized. Alternatively, the method for producing the rubber composition according to any one of claims 1 to 3, which is a styrene-butadiene copolymer rubber and / or a polybutadiene rubber obtained by reacting with silicon halide.
ン−ブタジエン共重合体ゴムからなり、原料ゴム(B)
が乳化重合により合成されたスチレン−ブタジエン共重
合体ゴムからなる請求項1〜4のいずれか1項に記載の
ゴム組成物の製造方法。5. The raw material rubber (A) comprises a solution-polymerized styrene-butadiene copolymer rubber, and the raw material rubber (B) is used.
5. The method for producing a rubber composition according to claim 1, wherein the rubber composition is a styrene-butadiene copolymer rubber synthesized by emulsion polymerization.
量Mw(A′)を有するジエン系原料ゴム(A′)と、
40万以上の重量平均分子量Mw(B′)を有するジエ
ン系原料ゴム(B′)とを混合してゴム組成物を製造す
るに際し、重量平均分子量が以下の関係にあり、 0.08≦Mw(A′)/Mw(B′)<1…(III) 原料ゴム(A′)の平均ガラス転移温度TgA′(℃)
と原料ゴム(B′)の平均ガラス転移温度TgB′
(℃)とが以下の関係にある TgA′+20>TgB′>TgA′−20…(I′) ジエン系原料ゴム(A′)20〜90重量部と補強剤5
0〜120重量部とを最初に混合し、その後ジエン系原
料ゴム(B′)80〜10重量部とジエン系原料ゴム
(A′)及び(B′)の合計量100重量部に対して2
0〜80重量部の軟化剤を添加することを特徴とするゴ
ム組成物の製造方法。6. A diene raw material rubber (A ′) having a weight average molecular weight Mw (A ′) in the range of 100,000 to 1,200,000,
When a rubber composition is produced by mixing with a diene raw rubber (B ') having a weight average molecular weight Mw (B') of 400,000 or more, the weight average molecular weight has the following relationship: 0.08≤Mw (A ') / Mw (B') <1 ... (III) Average glass transition temperature TgA '(° C) of raw rubber (A')
And the average glass transition temperature TgB 'of the raw rubber (B')
(° C.) has the following relationship: TgA ′ + 20> TgB ′> TgA′-20 (I ′) 20 to 90 parts by weight of diene raw rubber (A ′) and reinforcing agent 5
0 to 120 parts by weight are mixed first, and then 2 to 80 parts by weight of the diene-based raw material rubber (B ') and 100 parts by weight of the total amount of the diene-based raw material rubbers (A') and (B ').
A method for producing a rubber composition, which comprises adding 0 to 80 parts by weight of a softening agent.
TgA′(℃)が以下の範囲にある請求項6に記載のゴ
ム組成物の製造方法。 20>TgA′>−45…(II′)7. The method for producing a rubber composition according to claim 6, wherein the raw material rubber (A ′) has an average glass transition temperature TgA ′ (° C.) in the following range. 20> TgA '>-45 ... (II')
造方法で得られる、タイヤ用ゴム組成物。8. A rubber composition for a tire, which is obtained by the method according to any one of claims 1 to 7.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8159926A JP2918495B2 (en) | 1995-06-21 | 1996-06-20 | Method for producing rubber composition |
EP02022400A EP1277797B1 (en) | 1996-06-20 | 1996-12-12 | Process for production of rubber composition |
DE69634617T DE69634617T2 (en) | 1996-06-20 | 1996-12-12 | Process for the preparation of a rubber composition |
PCT/JP1996/003635 WO1997048766A1 (en) | 1996-06-20 | 1996-12-12 | Processes for producing rubber composition |
DE69626526T DE69626526T2 (en) | 1996-06-20 | 1996-12-12 | METHOD FOR PRODUCING A RUBBER COMPOSITION |
US08/952,486 US6077899A (en) | 1996-06-20 | 1996-12-12 | Process for production of rubber composition |
EP96941853A EP0850989B1 (en) | 1996-06-20 | 1996-12-12 | Processes for producing rubber composition |
Applications Claiming Priority (3)
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JP7-154378 | 1995-06-21 | ||
JP15437895 | 1995-06-21 | ||
JP8159926A JP2918495B2 (en) | 1995-06-21 | 1996-06-20 | Method for producing rubber composition |
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JPH0967469A true JPH0967469A (en) | 1997-03-11 |
JP2918495B2 JP2918495B2 (en) | 1999-07-12 |
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JP8159926A Expired - Fee Related JP2918495B2 (en) | 1995-06-21 | 1996-06-20 | Method for producing rubber composition |
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JP (1) | JP2918495B2 (en) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2000225805A (en) * | 1999-02-02 | 2000-08-15 | Bridgestone Corp | Pneumatic tire for heavy load |
JP2001081239A (en) * | 1999-09-16 | 2001-03-27 | Sumitomo Rubber Ind Ltd | Tread rubber composition for high-performance tire and its manufacture |
JP2003292675A (en) * | 2002-03-29 | 2003-10-15 | Yokohama Rubber Co Ltd:The | Rubber composition |
JPWO2002059193A1 (en) * | 2001-01-25 | 2004-05-27 | 横浜ゴム株式会社 | Rubber composition |
JP2006241355A (en) * | 2005-03-04 | 2006-09-14 | Bridgestone Corp | Rubber composition and pneumatic tire using the same |
WO2011148965A1 (en) * | 2010-05-26 | 2011-12-01 | 横浜ゴム株式会社 | Rubber composition for tyre treads |
WO2014002706A1 (en) * | 2012-06-30 | 2014-01-03 | 株式会社ブリヂストン | Rubber composition for tire treads |
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