JPS6333436A - Rubber composition - Google Patents
Rubber compositionInfo
- Publication number
- JPS6333436A JPS6333436A JP17533186A JP17533186A JPS6333436A JP S6333436 A JPS6333436 A JP S6333436A JP 17533186 A JP17533186 A JP 17533186A JP 17533186 A JP17533186 A JP 17533186A JP S6333436 A JPS6333436 A JP S6333436A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- weight
- rubber
- molecular weight
- styrene
- 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.)
- Pending
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 63
- 239000005060 rubber Substances 0.000 title claims abstract description 63
- 239000000203 mixture Substances 0.000 title abstract description 29
- 229920001577 copolymer Polymers 0.000 claims abstract description 63
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 2
- 238000005299 abrasion Methods 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 7
- 238000013329 compounding Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 18
- 238000000034 method Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- 239000004606 Fillers/Extenders Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000004816 latex Substances 0.000 description 3
- 229920000126 latex Polymers 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 2
- 241001441571 Hiodontidae Species 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000010692 aromatic oil Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- OAQBFYNZVHHSCE-UHFFFAOYSA-N S(OC)OC.[Na] Chemical compound S(OC)OC.[Na] OAQBFYNZVHHSCE-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
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 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
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000006235 reinforcing carbon black Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、常温において固体状の乳化重合スチレン−ブ
タジエン共重合体ゴムと、低分子量の乳化重合スチレン
−ブタジエン共重合体とからなるゴム組成物に関し、そ
の加硫物の物理的性質においては、高抗張力であり、か
つ耐摩耗性に優れるという特徴を有するゴム組成物を提
供するものである。Detailed Description of the Invention [Field of Industrial Application] The present invention provides a rubber composition comprising an emulsion-polymerized styrene-butadiene copolymer rubber that is solid at room temperature and a low-molecular-weight emulsion-polymerized styrene-butadiene copolymer. In terms of the physical properties of the vulcanizate, the present invention provides a rubber composition that has high tensile strength and excellent abrasion resistance.
乳化重合スチレン−ブタジエン共重合体ゴム（以下、ｒ
ｓＢＲ」という）は、いわゆる汎用ゴムとして大量に生
産され１品質および価格の安定性に優れ、かつ天然ゴム
に比較して耐老化性、耐熱性、耐摩耗性に優れていると
いった特徴を有しているため、自動車用タイヤとくに乗
用車用ラジアルタイヤの素材として大量に使用されてい
る。そして、乗用車用ラジアルタイヤの部材のうち、と
くにＳＢＲが多く使用されるのはトレッド部分である。Emulsion polymerized styrene-butadiene copolymer rubber (hereinafter referred to as r
sBR) is produced in large quantities as a so-called general-purpose rubber, and has excellent quality and price stability, as well as superior aging resistance, heat resistance, and abrasion resistance compared to natural rubber. Therefore, it is used in large quantities as a material for automobile tires, especially radial tires for passenger cars. Among the components of radial tires for passenger cars, SBR is particularly often used in the tread portion.
自動車用タイヤ、とくに乗用車用ラジアルタイヤのトレ
ッドが具備すべき重要な性能の一つとして操縦安定性が
ある。操縦安定性を確保するためには、トレッド部分の
路面把握力（グリップ性）が高いことが必要であり、こ
のためにトレッド部材の改良検討がおこなわれているこ
とはいうまでもない。そのひとつの方法として、トレッ
ドパターンの改良によるアプローチがおこなわれている
。すなわち、この方法においては、トレッドに刻まれた
パターンのグループ（溝）を深くすることによって、路
面に直接触れるトレッド部分番路面から受ける圧力に対
して変形しやすくすることにより、路面からの圧力をト
レッド内部で熱エネルギーに変えてしまう能力、すなわ
ち路面からの圧力をある程度吸収してしまう能力を増加
させ、このことによりトレッドの路面把握性を向上させ
るわけである。One of the important performances that the tread of automobile tires, especially radial tires for passenger cars, should have is steering stability. In order to ensure steering stability, it is necessary for the tread portion to have a high road grip (grip), and it goes without saying that improvements to tread members are being considered for this purpose. One approach is to improve the tread pattern. In other words, in this method, by deepening the pattern groups (grooves) carved into the tread, the parts of the tread that directly touch the road surface are easily deformed in response to the pressure received from the road surface, thereby reducing the pressure from the road surface. This increases the ability of the tread to convert it into thermal energy, that is, to absorb a certain amount of pressure from the road surface, thereby improving the tread's ability to grip the road surface.
しかし、この方法においては、反面ではゴムの変形を容
易にすることから、トレッド部分の摩耗量が増大し、十
分な耐摩耗性を得ることができないという問題が生じる
。トレッド素材としてのゴムの耐摩耗性を向上させるた
めに従来から行なわれている方法としては、高補強性カ
ーボンブラックの充てん量を増加させる手段があるが、
この方法によると同時に硬度やモジュラスが上昇し、ト
レッド部材が変形しにくくなり、その結果路面把握性が
損こなわれるという問題をもたらす。However, in this method, on the other hand, since the rubber is easily deformed, the amount of wear on the tread portion increases, resulting in a problem that sufficient wear resistance cannot be obtained. A conventional method to improve the wear resistance of rubber as a tread material is to increase the amount of highly reinforcing carbon black.
This method simultaneously increases the hardness and modulus, making it difficult for the tread member to deform, resulting in a problem of impaired road grip.
また、トレッド素材としてのＳＢＲのムーニー粘度（平
均分子量のパラメータ）を大きくすることで、耐摩耗性
を向上させる方法があるが、この方法ではＳＢＨの加工
性を低下させるという問題を生じ、自ら限界がある。Additionally, there is a method to improve wear resistance by increasing the Mooney viscosity (parameter of average molecular weight) of SBR as a tread material, but this method has the problem of reducing the workability of SBH, and it has reached its own limit. There is.
このように、タイヤトレッドの路面把握性と耐摩耗性は
、これまでに知られているゴム素材を用いても、一方が
改良されれば他方が損なわれるという、いわゆる二律背
反の関係にあり、両者をともに改良することはきわめて
困難なことと考えられていた。In this way, the road grip and abrasion resistance of a tire tread are in a so-called trade-off relationship, meaning that if one is improved, the other will be impaired, even if conventional rubber materials are used. It was thought that it would be extremely difficult to improve both.
上記問題点は、
（ａ）ムーニー粘度（ＭＬ、＊、、１００℃）が８０〜
１４０、結合スチレンが４５重量％以下の乳化重合スチ
レン−ブタジエン共重合体ゴム（Ａ）と、（以下、「共
重合体ゴム（Ａ）」と表わす。）と、重量平均分子量が
５００〜１５゜０００、結合スチレンが５０〜９０重量
％の乳化重合スチレン−ブタジエン共重合体（Ｂ）（以
下、共重合体（Ｂ）」と表わす、）とを含み、（ｂ）前
記共重合体ゴム（Ａ）と前記共重合体ＣＢ）との配合比
が、共重合体ゴム（Ａ）１００重量部に対して共重合体
（Ｂ）１０〜６０重量部であり、
（ｃ）ムーニー粘度（ＭＬ、、４，１００℃）が３０以
上である、
ことを特徴とするゴム組成物によって解決される。The above problems are as follows: (a) Mooney viscosity (ML, *, 100℃) is 80~
140, an emulsion-polymerized styrene-butadiene copolymer rubber (A) containing 45% by weight or less of bound styrene (hereinafter referred to as "copolymer rubber (A)"), and a weight average molecular weight of 500 to 15°. 000, an emulsion-polymerized styrene-butadiene copolymer (B) containing 50 to 90% by weight of bound styrene (hereinafter referred to as "copolymer (B)"), (b) the copolymer rubber (A ) and the copolymer CB) are 10 to 60 parts by weight of the copolymer (B) to 100 parts by weight of the copolymer rubber (A), and (c) Mooney viscosity (ML, The problem is solved by a rubber composition characterized in that the temperature (4,100°C) is 30 or more.
本発明のゴム組成物において特に特徴となる点は、低分
子量かつ高結合スチレンの共重合体（Ｂ）を共重合体ゴ
ム（Ａ）と組み合せて用いることにより、たとえば高芳
香族系伸展油を共重合体ゴム（Ａ）の可塑剤として用い
たゴム組成物に比して、加硫物において適度な硬度なら
びにモジュラスなどを保有したまま、耐摩耗性において
著しい改善を達成することができることにある。その結
果、本発明によれば、たとえば路面把握性と耐摩耗性と
いう二律背反的な特性をともに満足するタイヤトレッド
部材用のゴム素材を提供することができる。A particular feature of the rubber composition of the present invention is that, by using a low molecular weight, highly bonded styrene copolymer (B) in combination with a copolymer rubber (A), for example, a highly aromatic extender oil can be used. Compared to the rubber composition used as a plasticizer for copolymer rubber (A), it is possible to achieve a significant improvement in abrasion resistance while maintaining appropriate hardness and modulus in the vulcanized product. . As a result, according to the present invention, it is possible to provide a rubber material for a tire tread member that satisfies the antinomic properties of road grip and wear resistance.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明における共重合体ゴム（Ａ）は、乳化重合によっ
て製造され、結合スチレンが４５重量％以下のスチレン
−ブタジエン共重合体ゴムであり、ムーニー粘度（ＭＬ
ｌ、４，１００℃）（以下、単に「ムーニー粘度」と表
わす。）が８０〜１４０である。The copolymer rubber (A) in the present invention is a styrene-butadiene copolymer rubber produced by emulsion polymerization, containing 45% by weight or less of bound styrene, and has a Mooney viscosity (ML
1, 4,100°C) (hereinafter simply referred to as "Mooney viscosity") is 80 to 140.
通常、実用的に用いられるスチレン−ブタジエン共重合
体ゴムは、結合スチレンが２０〜３０重量％であり、結
合スチレンは多くとも４５重量％を越えない、結合スチ
レンが４５重量％を越えると、最終的に得られるゴム組
成物の耐摩耗性が不十分となる。Usually, practically used styrene-butadiene copolymer rubber contains 20 to 30% by weight of bound styrene, and does not exceed 45% by weight at most. The abrasion resistance of the resulting rubber composition becomes insufficient.
このような結合スチレンが４５重量％以下の共重合体ゴ
ム（Ａ）において、ムーニー粘度が上記の範囲外にあっ
て８０未満であると、低分子量の共重合体（Ｂ）が伸展
油と同様に可塑剤としても機能するため、最終的に得ら
れるゴム組成物のムーニー粘度が低下し、その加硫物に
対して充分な物理的性質、特に耐摩耗性の改良を期待す
ることが困難となる。In such a copolymer rubber (A) containing 45% by weight or less of bound styrene, if the Mooney viscosity is outside the above range and is less than 80, the low molecular weight copolymer (B) will be similar to extender oil. Because it also functions as a plasticizer, the Mooney viscosity of the final rubber composition decreases, making it difficult to expect sufficient improvements in the physical properties, especially abrasion resistance, of the vulcanizate. Become.
一方、共重合体ゴム（Ａ）のムーニー粘度が］−４０を
越えるものを、たとえば、高芳香族系油を３７．５部混
合しても、最終的に得られるゴム組成物のムーニー粘度
がおよそ８０程度以上と大きくなり、混練り時あるいは
押し出し成形時の発熱が大きく、またゲル化やスコーチ
が発生するなど、加工上のトラブルを起すことになり好
ましくない。On the other hand, even if a copolymer rubber (A) with a Mooney viscosity exceeding -40 is mixed with, for example, 37.5 parts of highly aromatic oil, the Mooney viscosity of the final rubber composition will be This is not preferable since it becomes large, about 80 or more, and generates a large amount of heat during kneading or extrusion molding, and also causes processing problems such as gelation and scorch.
共重合体ゴム（Ａ）に混合される共重合体（Ｂ）は、乳
化重合法で製造され、低分子量かつ高結合スチレンのス
チレン−ブタジエン共重合体である。The copolymer (B) to be mixed into the copolymer rubber (A) is produced by an emulsion polymerization method and is a styrene-butadiene copolymer of low molecular weight and highly bonded styrene.
共重合体（Ｂ）の重量平均分子量は、５００〜１５，０
００、好ましくは２，０００〜１２゜ＯｏＯである。共
重合体ＣＢ）として重合平均分子量が５００未満のもの
を用いた場合は、その加硫物が充分が物理的性質、特に
破断応力を維持することが困難となり、かつ耐摩耗性の
改良効果はほとんど期待できない。The weight average molecular weight of the copolymer (B) is 500 to 15,0
00, preferably 2,000 to 12°OoO. If a copolymer CB) with a polymerization average molecular weight of less than 500 is used, it will be difficult to maintain the physical properties, especially the breaking stress, even if the vulcanizate is sufficient, and the effect of improving wear resistance will be poor. I can hardly expect it.
また、共重合体（Ｂ）として重量平均分子量が１５，０
００を越えるものを用いた場合は。In addition, the copolymer (B) has a weight average molecular weight of 15.0
If you use more than 00.
加硫物は破断応力を高いレベルで維持し、かつ耐摩耗性
の改良効果も充分期待できるが、硬度およびモジュラス
が高くなって変形しにくい加硫物となるため、路面把握
性能が不十分となる。Vulcanized products maintain a high level of breaking stress and can be expected to have a sufficient effect of improving wear resistance, but the hardness and modulus of the vulcanized product increases, making it difficult to deform, resulting in insufficient road grip performance. Become.
また、共重合体（Ｂｌ）の結合スチレンは、５０〜９０
重量％であることが必要である。共重合体（Ｂ）の結合
スチレンが５０重量％未満であると、耐摩耗性の改良効
果が小さく、また、結合スチレンが９０重量％を越える
と、加硫物の硬度およびモジュラスが高くなって変形し
にくい加硫物となるため、路面把握力の低下を招くこと
となる。In addition, the bound styrene content of the copolymer (Bl) is 50 to 90
It is necessary that the amount is % by weight. If the amount of bound styrene in the copolymer (B) is less than 50% by weight, the effect of improving wear resistance will be small, and if the amount of bound styrene exceeds 90% by weight, the hardness and modulus of the vulcanizate will increase. This results in a vulcanized product that is difficult to deform, resulting in a decrease in road grip.
共重合体（Ｂ）の重量平均分子量の範囲および結合スチ
レンの範囲は上述の通りであるが、これらの条件におい
て、特に耐摩耗性と路面把握性とのバランスが優れるも
のは、以下の条件を満足するものである。The weight average molecular weight range and bound styrene range of the copolymer (B) are as described above, but under these conditions, those with a particularly excellent balance between abrasion resistance and road grip properties should meet the following conditions. It's satisfying.
９０〉ｘ＞５０
４．１）ｙ
Ｏ，６ｘ＋１７ｙ＞１００
ただし、ここにおいて、又は重量％で表現した結合スチ
レン、ｙは重量平均分子量の常用対数である。90>x>50 4.1) y O,6x+17y>100 where bound styrene or expressed in weight percent, y is the common logarithm of the weight average molecular weight.
本発明において、共重合体ゴム（Ａ）に混合される共重
合体（Ｂ）の量は、共重合体ゴム（Ａ）１００重量部に
対して１０〜６０重量部、より好ましくは２０〜４５重
量部の範囲で選び、最終的に得られるゴム組成物のムー
ニー粘度が３０以上になることが必要である。共重合体
（Ｂ）の混合量が１０重量部未満では、ゴム組成物の混
練り性、成形性といった加工性が低下し、結果として耐
摩耗性の改良がはかれない。In the present invention, the amount of the copolymer (B) mixed into the copolymer rubber (A) is 10 to 60 parts by weight, more preferably 20 to 45 parts by weight, based on 100 parts by weight of the copolymer rubber (A). It is necessary that the Mooney viscosity of the rubber composition finally obtained is 30 or more. If the amount of copolymer (B) mixed is less than 10 parts by weight, the processability of the rubber composition, such as kneading properties and moldability, will deteriorate, and as a result, the abrasion resistance will not be improved.
このような場合、たとえ高芳香族油などの可塑剤を添加
したとしても耐摩耗性の改良は期待できない。また、共
重合体（Ｂ）の混合量が６０重量部を越えると、ゴム組
成物のムーニー粘度が３０より小さくなるので、硬度、
モジュラス。In such cases, even if a plasticizer such as a highly aromatic oil is added, no improvement in wear resistance can be expected. Furthermore, if the amount of copolymer (B) mixed exceeds 60 parts by weight, the Mooney viscosity of the rubber composition will be lower than 30, so that the hardness
modulus.
破断応力が低くなり、その結果、路面把握力は充分であ
っても耐摩耗性が低下してしまい、両特性のバランスを
良好なものとすることができない。The breaking stress decreases, and as a result, even if the road surface gripping force is sufficient, the wear resistance decreases, making it impossible to achieve a good balance between both properties.
本発明の共重合体ゴム（Ａ）および共重合体（Ｂ）は、
いずれも通常の乳化重合技術によって製造することがで
きる。共重合体（Ｂ）は、通常のゴム状高分子量重合体
を得るにの用いられる重合処方において、ｔｅｒｔ−ド
デシルメルカプタンのような分子量調節剤を増量して反
応させることで容易に得られる。一方、ムーニー粘度が
８０〜１４０の共重合体ゴム（Ａ）は、共重合体（Ｂ）
と同様の乳化重合処方で製造することができ、重合体の
ムーニー粘度は分子量調節剤の使用量を設定することに
より目的の値に調整される。The copolymer rubber (A) and copolymer (B) of the present invention are:
Both can be produced by conventional emulsion polymerization techniques. The copolymer (B) can be easily obtained by adding a molecular weight regulator such as tert-dodecyl mercaptan to the polymerization recipe used to obtain ordinary rubbery high molecular weight polymers and reacting the same. On the other hand, the copolymer rubber (A) having a Mooney viscosity of 80 to 140 is the copolymer rubber (B)
It can be produced using the same emulsion polymerization recipe as above, and the Mooney viscosity of the polymer is adjusted to the desired value by setting the amount of the molecular weight regulator.
本発明のゴム組成物を調整する方法としては、共重合体
ゴム（Ａ）と共重合体（Ｂ）をラテックス状態で混合し
た後固形化する方法、あるいは固形状の共重合体ゴム（
Ａ）と共重合体（Ｂ）を混合する方法を用いることがで
きる。さらには、分子量調節剤およびスチレンモノマー
とブタジェンモノマーの仕込比を変量させながら行う多
段重合法により、高分子量の共重合体ゴム（Ａ）と低分
子量の共重合体（Ｂ）の混合物を一挙に得ることのでき
る特殊な重合法によっても、前記混合法によるのと同様
なゴム組成物が得られる。 このようにして得た本発明
のゴム組成物は、カーボンブラック等の補強剤、加硫剤
、加硫促進剤等の配合剤を添加してタイヤ等のゴム製品
の製造に使用される。The rubber composition of the present invention can be prepared by mixing the copolymer rubber (A) and the copolymer (B) in a latex state and then solidifying the mixture, or by solidifying the copolymer rubber (
A method of mixing A) and copolymer (B) can be used. Furthermore, a mixture of high molecular weight copolymer rubber (A) and low molecular weight copolymer rubber (B) can be prepared at once by a multi-stage polymerization method that is carried out while varying the molecular weight regulator and the charging ratio of styrene monomer and butadiene monomer. Rubber compositions similar to those obtained by the above-mentioned mixing method can also be obtained by special polymerization methods that can be obtained. The rubber composition of the present invention thus obtained is used for manufacturing rubber products such as tires by adding compounding agents such as a reinforcing agent such as carbon black, a vulcanizing agent, and a vulcanization accelerator.
次に実施例を挙げて本発明をさらに具体的に説明する。 Next, the present invention will be explained in more detail with reference to Examples.
実施例１〜３、比較例１〜６
（１）共重合体ゴム（Ａ）の製造
重合処方 （重量部）
ブタジェン ７１．０
スチレン ２９．０
重合用処理水 ２００．０
樹脂酸石けん Ｓ、Ｏ硫
酸第一鉄７含水物 ０．０２ア
ルキルナフタレン
スルフオン酸ナトリウム ０．１５エ
チレンジアミンテトラアセテート ０．１０ナ
トリウムジメチルスルホキシレート ０．１０ク
メンハイドロパーオキサイド ０．１０第
３Ｒドデシルメルカプタン ０．２７以上
の重合処方により、反応温度５℃で重合し、重合転化率
６０％の時点で重合停止剤を添加したあと、未反応のス
チレンおよびブタジェンを回収し、ムーニー粘度１１０
のゴム状共重合体（結合スチレン約２３重量％）を固形
分で約２３重量％を含むラテックスを得た。Examples 1 to 3, Comparative Examples 1 to 6 (1) Production of copolymer rubber (A) Polymerization recipe (parts by weight) Butadiene 71.0
Styrene 29.0
Treated water for polymerization 200.0
Resin acid soap S, O ferrous sulfate 7-hydrate 0.02 Sodium alkylnaphthalene sulfonate 0.15 Ethylenediaminetetraacetate 0.10 Sodium dimethyl sulfoxylate 0.10 Cumene hydroperoxide 0.10 3R dodecyl mercaptan Polymerization was carried out at a reaction temperature of 5°C using a polymerization recipe of 0.27 or higher, and after adding a polymerization terminator at a polymerization conversion rate of 60%, unreacted styrene and butadiene were recovered, and the Mooney viscosity was 110.
A latex containing about 23% by weight of a rubbery copolymer (about 23% by weight of bound styrene) in solids was obtained.
（２）共重合体（Ｂ）の製造
スチレンとブタジェンの仕込み量を変え、かつ分子量調
節剤である第３級ドデシルメルカプタンのみを適宜大幅
に増量したほかは共重合体ゴム（Ａ）の場合と同様に重
合し、種々の分子量および結合スチレンをもつ８種の共
重合体を得た。これらサンプルの分子量および結合スチ
レンを第１表に示す。なお、共重合体の結合スチレンは
１００ＭＨｚのＮＭＲで測定した。また、重量平均分子
量はＧＰＣ（ゲルパーミェーションクロマトグラフィ）
で測定したポリスチレン換算の重量平均分子量である。(2) Production of copolymer (B) Same as in the case of copolymer rubber (A) except that the amounts of styrene and butadiene were changed and only the amount of tertiary dodecyl mercaptan, which is a molecular weight regulator, was increased appropriately. Eight types of copolymers having various molecular weights and bound styrene were obtained by polymerization in the same manner. The molecular weights and bound styrene of these samples are shown in Table 1. Note that the bound styrene of the copolymer was measured by NMR at 100 MHz. In addition, the weight average molecular weight is determined by GPC (gel permeation chromatography).
It is the weight average molecular weight measured in terms of polystyrene.
なお、ＧＰＣはＷａｔｅｒｓ社製ｒＡＬＣ−ＧＰＣＪを
使用し、カラムは東洋曹達社製のｒＧＭＨ３Ｊ、ｒＧＭ
Ｈ６」およびｒＧ６０００Ｈ６Ｊを直列に結合して使用
した。For GPC, rALC-GPCJ manufactured by Waters was used, and the columns were rGMH3J and rGM manufactured by Toyo Soda.
H6'' and rG6000H6J were used in combination in series.
第１表
（３）ゴム組成物の調製およびその評価（１）で得られ
た共重合体ゴム（Ａ）のラテックスと（２）で得られた
各種ラテックスとを第２表に示す所定量で混合したあと
、通常の酸−塩凝固法により凝固させ、水洗、乾燥を行
ない、実施例につき３種、比較例につき６種のゴム組成
物を得た。なお、比較例１においては、（２）で得られ
たラテックスの代りに高芳香族系伸展油「アロマ」 （
日本合成ゴム１ＩＩｙｓ＞を用いた。Table 1 (3) Preparation and evaluation of rubber compositions The copolymer rubber (A) latex obtained in (1) and the various latexes obtained in (2) were mixed in the prescribed amounts shown in Table 2. After mixing, the mixture was coagulated by a conventional acid-salt coagulation method, washed with water, and dried to obtain three types of rubber compositions for Examples and six types for Comparative Examples. In addition, in Comparative Example 1, highly aromatic extender oil "Aroma" (
Japan Synthetic Rubber 1IIys> was used.
これらのゴム組成物を下記の配合処方によりバンバリー
ミキサ−およびロールにより混練し。These rubber compositions were kneaded using a Banbury mixer and rolls according to the following formulation.
下記の加硫条件によりプレス加硫により加硫ゴム試料を
作成した。Vulcanized rubber samples were prepared by press vulcanization under the following vulcanization conditions.
（配合処方） 重量部
共重合体ゴム（Ａ）１００
共重合体（Ｂ ） ３７．５亜鉛華
３
ステアリン酸 ２
カーボンブラック ７５
加硫促進剤 １．５
硫黄 ２．０
（加硫条件）１５５℃、３０分
このようにして得られた加硫ゴム試料について下記の特
性試験を行なった。(Blending recipe) Parts by weight Copolymer rubber (A) 100 Copolymer (B) 37.5 Zinc white
3 Stearic acid 2 Carbon black 75 Vulcanization accelerator 1.5 Sulfur 2.0 (Vulcanization conditions) 155° C., 30 minutes The following characteristic tests were conducted on the vulcanized rubber samples thus obtained.
■ 常態物性（ＪＩＳ Ｋ−６３０１に準じて測定）
３００％モジュラス（ｋｇ／ｄ）
引張強度 （ｋｇ／Ｊ）
硬度 （ＪＩＳ−Ａ形）
■ 耐摩耗性
ピコ摩耗試験法（ＡＳＴＭ Ｄ２２２８）によって測
定した。■ Normal state physical properties (measured according to JIS K-6301) 300% modulus (kg/d) Tensile strength (kg/J) Hardness (JIS-A type) ■ Abrasion resistance Measured by Pico abrasion test method (ASTM D2228) .
■ 路面把握性
英国道路研究所ポータプルスキッドテスターを使用して
ウェットスキッドを測定した。■ Road grip Wet skid was measured using a British Road Research Institute portable skid tester.
このとき、試験路面としては７スフアルトを用い、路面
を水で十分にぬらした状態で測定を行なった。At this time, 7 Sfalto was used as the test road surface, and the measurement was performed with the road surface sufficiently wet with water.
以上の特性試験の結果を第２表に示す。The results of the above characteristic tests are shown in Table 2.
第２表の結果より、以下のことが理解される。From the results in Table 2, the following can be understood.
比較例１に示されているように、低分子量の共重合体（
Ｂ）の代わりに高芳香族系伸展油を使用すると、耐摩耗
性
に劣る。比較例３に示されているように、共重合体（Ｂ
）として、結合スチレンが適当であっても重量平均分子
量が過大である場合には、モジュラスおよび硬度が大幅
に上昇し、耐摩耗性、ウェットスキッドともに劣る。比
較例４に示されているように、共重合体（Ｂ）として重
量平均分子量が大きい場合には、やはりモジュラスおよ
び硬度がともに上昇し、さらにウェットスキッドが劣り
、耐摩耗性も改良されない。比較例５．６に示されてい
るように、共重合体（Ｂ）として結合スチレンが低い場
合には、モジュラスおよび硬度が低下し、比較例５にお
いては耐摩耗性が劣る。比較例２に示されるように、共
重合体（Ｂ）として結合スチレンが低くかつ重量平均分
子量が過大である場合には、耐摩耗性は改良されるがウ
ェットスキッドが劣る。As shown in Comparative Example 1, a low molecular weight copolymer (
If a highly aromatic extender oil is used instead of B), the wear resistance will be poor. As shown in Comparative Example 3, copolymer (B
), even if the bonded styrene is appropriate, if the weight average molecular weight is excessive, the modulus and hardness will increase significantly, and both wear resistance and wet skid will be poor. As shown in Comparative Example 4, when the weight average molecular weight of the copolymer (B) is large, both the modulus and hardness increase, the wet skid is poor, and the abrasion resistance is not improved. As shown in Comparative Example 5.6, when the copolymer (B) has a low amount of bound styrene, the modulus and hardness decrease, and Comparative Example 5 has poor wear resistance. As shown in Comparative Example 2, when the copolymer (B) has a low bound styrene content and an excessive weight average molecular weight, the abrasion resistance is improved but the wet skid is poor.
一方、本発明の実施例においては、いずれも加硫ゴムの
常態物性に優れ、さらにウェットスキツド性を損するこ
となく、耐摩耗性を改良できることがわかる。On the other hand, in all the examples of the present invention, it can be seen that the vulcanized rubber has excellent normal physical properties, and furthermore, the abrasion resistance can be improved without impairing the wet skid property.
比較例７．８
実施例１〜３、比較例１〜６の項（１）において述べた
共重合体ゴム（Ａ）の製造において、重合処方における
第３級ドデシルメルカプタンのみを変量したほかは同様
に重合を行ない、ムーニー粘度が１４５および７０のゴ
ム状共重合体を含む比較用ラテックスを得た。Comparative Example 7.8 In the production of the copolymer rubber (A) described in Section (1) of Examples 1 to 3 and Comparative Examples 1 to 6, the same procedure was carried out except that only the tertiary dodecyl mercaptan in the polymerization recipe was varied. Comparative latexes containing rubbery copolymers having Mooney viscosities of 145 and 70 were obtained.
実施例１〜３、比較例１〜６の項（２）において述べた
低分子量の共重合体（Ｂ）のサンプルのうち、スチレン
含有量が８３．３重量％、重量平均分子量が６，５００
のもの（サンプル２）を、上述の各比較用ラテックスに
混合した後、凝固、乾燥し、ムーニー粘度が各々８８お
よび２６のゴム組成物を得た。このゴム組成物を実施例
１〜３、比較例１〜６の項（３）において述べたと同じ
処方および混練り方法で混練りし、さらにピコ摩耗およ
びウェットスキッドを測定した。結果を第３表に示す。Among the samples of the low molecular weight copolymer (B) described in Section (2) of Examples 1 to 3 and Comparative Examples 1 to 6, the styrene content was 83.3% by weight and the weight average molecular weight was 6,500.
(Sample 2) was mixed with each of the above-mentioned comparative latexes, coagulated and dried to obtain rubber compositions having Mooney viscosities of 88 and 26, respectively. This rubber composition was kneaded using the same formulation and kneading method as described in Section (3) of Examples 1 to 3 and Comparative Examples 1 to 6, and further, pico wear and wet skid were measured. The results are shown in Table 3.
第３表より、比較例７に示されるように、高分子量の共
重合体ゴム（Ａ）のムーニー粘度が過大の場合には、耐
摩耗性の改良効果はあるが、ウェットスキッドが劣る。From Table 3, as shown in Comparative Example 7, when the Mooney viscosity of the high molecular weight copolymer rubber (A) is excessive, there is an effect of improving the abrasion resistance, but the wet skid is poor.
この比較例７で耐摩耗性の改良効果が小さいのは、ゴム
組成物のムーニー粘度の高さかられかるように加工性が
きわめて悪く、混練り性が良くないため、カーボンなど
の分散が良好でなくなったためと考えらる。また、比較
例８に示されるように、共重合体ゴム（Ａ）のムーニー
粘度が過小の場合には、耐摩耗性が劣る。The reason why the abrasion resistance improvement effect in Comparative Example 7 is small is because the rubber composition has extremely poor processability and poor kneading properties, as evidenced by the high Mooney viscosity, and the dispersion of carbon, etc. is not good. I think it's because it's gone. Moreover, as shown in Comparative Example 8, when the Mooney viscosity of the copolymer rubber (A) is too small, the abrasion resistance is poor.
なお、第３表には比較のため実施例２の結果もあわせて
記載する。Note that Table 3 also shows the results of Example 2 for comparison.
本発明のゴム組成物は、低分子量かつ高結合スチレンの
共重合体（Ｂ）を含有しており、その加硫物において適
度な硬度、モジュラスなどの物性値を保有した状態で優
れた耐摩耗性を有し、特に、路面把握性と耐摩耗性とい
う二律背反的な特性を要求されるタイヤトレッド部材、
その他耐摩耗性の要求されるベルトなどの各種部材の素
材として好適である。The rubber composition of the present invention contains a copolymer (B) of low molecular weight and highly bonded styrene, and the vulcanized product thereof has excellent wear resistance while maintaining appropriate physical properties such as hardness and modulus. In particular, tire tread components that require contradictory characteristics such as road grip and wear resistance.
It is also suitable as a material for various other members such as belts that require wear resistance.
Claims (1)
℃）が８０〜１４０、結合スチレンが４５重量％以下 の乳化重合スチレン−ブタジエン共重合体 ゴム（Ａ）と、重量平均分子量が５００〜 １５，０００、結合スチレンが５０〜９０ 重量％の乳化重合スチレン−ブタジエン共 重合体（Ｂ）とを含み、 （ｂ）前記共重合体ゴム（Ａ）と前記共重合体（Ｂ）と
の配合比が、共重合体ゴム（Ａ） １００重量部に対して共重合体（Ｂ）１０ 〜６０重量部であり、 （ｃ）ムーニー粘度（ＭＬ＿１＿＋＿４、１００℃）が
３０以上である、 ことを特徴とするゴム組成物。(1) (a) Mooney viscosity (ML_1_+_4, 100
Emulsion polymerized styrene-butadiene copolymer rubber (A) with a weight average molecular weight of 500 to 15,000 and 50 to 90 weight % of bound styrene and a weight average molecular weight of 500 to 15,000 and 50 to 90 weight % of bound styrene. styrene-butadiene copolymer (B), and (b) the blending ratio of the copolymer rubber (A) and the copolymer (B) is based on 100 parts by weight of the copolymer rubber (A). 10 to 60 parts by weight of copolymer (B), and (c) a Mooney viscosity (ML_1_+_4, 100°C) of 30 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17533186A JPS6333436A (en) | 1986-07-25 | 1986-07-25 | Rubber composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17533186A JPS6333436A (en) | 1986-07-25 | 1986-07-25 | Rubber composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6333436A true JPS6333436A (en) | 1988-02-13 |
Family
ID=15994202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17533186A Pending JPS6333436A (en) | 1986-07-25 | 1986-07-25 | Rubber composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6333436A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5153255A (en) * | 1989-06-26 | 1992-10-06 | Japan Synthetic Rubber Co., Ltd. | Process for preparing a rubber composition having two different molecular weights |
| US5232987A (en) * | 1988-02-01 | 1993-08-03 | Japan Synthetic Rubber Co., Ltd. | Rubber compositions |
| US7594528B2 (en) | 2007-03-08 | 2009-09-29 | The Goodyear Tire & Rubber Company | Tire with sidewall comprised of emulsion styrene/butadiene rubber, cis 1,4-polyisoprene rubber and cis 1,4-polybutadiene rubber |
| CN104769030A (en) * | 2012-10-24 | 2015-07-08 | 米其林集团总公司 | High-styrene content SBR in rubber compositions |
| JP2018177909A (en) * | 2017-04-07 | 2018-11-15 | 住友ゴム工業株式会社 | Tire |
-
1986
- 1986-07-25 JP JP17533186A patent/JPS6333436A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5232987A (en) * | 1988-02-01 | 1993-08-03 | Japan Synthetic Rubber Co., Ltd. | Rubber compositions |
| US5153255A (en) * | 1989-06-26 | 1992-10-06 | Japan Synthetic Rubber Co., Ltd. | Process for preparing a rubber composition having two different molecular weights |
| US7594528B2 (en) | 2007-03-08 | 2009-09-29 | The Goodyear Tire & Rubber Company | Tire with sidewall comprised of emulsion styrene/butadiene rubber, cis 1,4-polyisoprene rubber and cis 1,4-polybutadiene rubber |
| CN104769030A (en) * | 2012-10-24 | 2015-07-08 | 米其林集团总公司 | High-styrene content SBR in rubber compositions |
| US20150259517A1 (en) * | 2012-10-24 | 2015-09-17 | Compagnie Generale Des Establissments Michhein | High-styrene content sbr in rubber compositions |
| JP2018177909A (en) * | 2017-04-07 | 2018-11-15 | 住友ゴム工業株式会社 | Tire |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4487892A (en) | Rubber compositions for use in tires | |
| US6114432A (en) | Diene rubber composition | |
| JP5291858B2 (en) | Rubber composition and pneumatic tire using the same | |
| JPH05255459A (en) | Core/shell polymer for use in tire tread | |
| US5753761A (en) | Method of preparing trans polybutadiene blend for use in tires | |
| US5232987A (en) | Rubber compositions | |
| JPS63101440A (en) | Rubber composition | |
| EP0328284B1 (en) | Rubber compositions | |
| US5880206A (en) | Rubber composition and process for producing the same | |
| US2657190A (en) | Blends of polybutadiene and butadiene-acrylonitrile copolymer | |
| JP2682148B2 (en) | Rubber composition | |
| JPS6399252A (en) | Improved rubber composition | |
| JPS6333436A (en) | Rubber composition | |
| JPH11315167A (en) | Elastomer blend and its use in tire | |
| JP4278340B2 (en) | Rubber composition, method for producing the same, rubber molded article and fuel hose | |
| JPS6227442A (en) | Improved rubber composition for tire | |
| JP5121300B2 (en) | Rubber composition and pneumatic tire using the same | |
| JPS61120839A (en) | Vulcanized rubber composition for tire tread | |
| JPS60197749A (en) | Rubber composition | |
| JPH07103270B2 (en) | Abrasion resistance high hysteresis loss rubber composition | |
| JP3918692B2 (en) | Modified diene polymer rubber, method for producing the same, and rubber composition | |
| JPH06220256A (en) | Rubber composition | |
| JPS63234045A (en) | Rubber composition for tire | |
| JPS6134741B2 (en) | ||
| JP4670132B2 (en) | Conjugated diene polymer and process for producing the same |