KR20020078722A - Rubber composition for tire - Google Patents

Rubber composition for tire Download PDF

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Publication number
KR20020078722A
KR20020078722A KR1020010018850A KR20010018850A KR20020078722A KR 20020078722 A KR20020078722 A KR 20020078722A KR 1020010018850 A KR1020010018850 A KR 1020010018850A KR 20010018850 A KR20010018850 A KR 20010018850A KR 20020078722 A KR20020078722 A KR 20020078722A
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South Korea
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rubber
tire
rubber composition
polybutadiene
toughness
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KR1020010018850A
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Korean (ko)
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KR100407859B1 (en
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이경남
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한국타이어 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0025—Compositions of the sidewalls
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PURPOSE: Provided is a rubber composition for tire hump strip, which keeps hardness, abrasion-resistance, rigidity, permanent compression set rate, and toughness and improves heat age resistance. CONSTITUTION: The rubber composition contains a natural rubber and a cis 1,4-polybutadiene rubber as raw rubber and conventional additives such as zinc oxide, stearic acid, carbon black, aromatic oil, sulfur, TBBS(N-t-butyl-2-benzothiazole sulfenamide), and etc, wherein the raw rubber contains 10-40pts.wt. of a syndiotactic 1,2-polybutadiene rubber.

Description

내열노화성을 향상시킨 타이어 험프스트립용 고무조성물{Rubber composition for tire}Rubber composition for tire hump strip with improved aging resistance

본 발명은 내열노화성을 향상시킨 타이어 험프스트립용 고무조성물에 관한 것으로서, 더욱 상세하게는 천연고무와 부타디엔 고무 블렌드 중 부타디엔 고무의 일정량을 내열노화성이 우수한 신디오택틱 1,2-부타디엔 고무로 대체함으로써 내열노화성을 향상시킬 수 있는 타이어 험프스트립용 고무조성물에 관한 것이다.The present invention relates to a rubber composition for tire hump strips having improved heat aging resistance, and more particularly, to a syndiotactic 1,2-butadiene rubber having a predetermined amount of butadiene rubber in a blend of natural rubber and butadiene rubber. The present invention relates to a rubber composition for a tire hump strip, which can improve heat aging resistance by replacing it.

최근 환경보호와 자원절약면에서 타이어의 재생성 향상 요구가 높아지고 있다. 타이어를 재생하여 사용하기 위해서는 비드부의 내구성이 가장 중요하다.Recently, in terms of environmental protection and resource saving, there is an increasing demand for tire regeneration. The durability of the bead part is the most important to regenerate and use the tire.

비드부의 내구성 향상에 가장 큰 영향을 미치는 것 중의 하나는 험프스트립으로, 이는 높은 터프니스와 경도, 내마멸성, 상대적으로 낮은 영구압축변형률, 내열노화성 등이 요구되는 고무조성물로 이루어져 있다. 특히 험프스트립용 고무조성물에 있어서 터프니스와 내열노화성은 내구성 향상을 위하여 가장 중요한 물성으로 평가되고 있다.One of the biggest influences on the durability improvement of the bead part is the hump strip, which is composed of a rubber composition requiring high toughness, hardness, abrasion resistance, relatively low permanent compressive strain, and heat aging resistance. Especially in hump strip rubber compositions, toughness and heat aging resistance are evaluated as the most important physical properties for improving durability.

험프스트립용 고무조성물의 터프니스와 내열노화성을 유지하기 위한 종래의방법으로는 카본블랙, 유황, 가류촉진제와 같은 첨가제를 다량 투입하는 방법을 사용하고 있으나, 다량의 유황 첨가는 압출된 고무에서 다량의 유황이 표면에 석출되어 생산성 및 물성의 저하, 특히 내열노화성의 저하를 유발하게 되며, 다량의 카본블랙을 사용하는 경우 경도는 증가하지만 신장율이 감소하므로 터프니스의 향상을 기대할 수 없다.Conventional methods for maintaining the toughness and heat aging resistance of rubber compositions for hump strips include the addition of large amounts of additives such as carbon black, sulfur and vulcanization accelerators. A large amount of sulfur precipitates on the surface, leading to deterioration in productivity and physical properties, in particular, deterioration of heat aging resistance. In the case of using a large amount of carbon black, the hardness is increased but the elongation is decreased, so the toughness cannot be expected to be improved.

또다른 방법으로, 상기와 같은 험프스트립용 고무조성물의 특성을 만족시키기 위하여 천연고무와 시스 1,4-폴리부타디엔 고무를 혼용하고, 그 혼용비율을 조정하거나 카본블랙의 등급을 조정하는 등의 여러 가지 기술들이 사용되고 있다. 특히 최근에는 내마멸성 향상을 위해 천연고무와 합성고무의 혼용 비율에서 시스 1,4-폴리부타디엔 고무의 혼용 비율을 크게 증가시키고 있는 추세로, 이와같이 하면 내마멸성은 어느 정도 향상시킬 수 있었으나 열노화에 의한 터프니스 저하로 인하여 타이어 비드 토우 부분이 떨어져 나가거나 크랙이 발생하여 타이어의 내구성이 크게 저하되는 문제가 있다.As another method, in order to satisfy the characteristics of the hump strip rubber composition as described above, natural rubber and cis 1,4-polybutadiene rubber may be mixed, and the mixing ratio may be adjusted or the grade of carbon black may be adjusted. Several techniques are used. In particular, in recent years, the mixing ratio of cis 1,4-polybutadiene rubber is greatly increased in the mixing ratio of natural rubber and synthetic rubber in order to improve abrasion resistance, but this can improve the wear resistance to some extent but it is tough due to thermal aging. Due to the varnish deterioration, the tire bead toe part is separated or cracks are generated, and thus the durability of the tire is greatly reduced.

반면에, 터프니스를 올리기 위해 천연고무 혼용 비율을 높이면 내마멸성이 불리하게 되고, 내열노화성을 개선하기 위하여 유황량을 줄이면 경도 저하와 영구압축변형율이 불리하게 된다. 따라서, 험프스트립용 고무조성물의 요구 물성을 만족시키면서 터프니스 및 내열노화성을 향상시키는 것은 현재까지 커다란 난제로 여겨져 왔다.On the other hand, increasing the mixing ratio of natural rubber to increase toughness is disadvantageous to wear resistance, reducing the amount of sulfur in order to improve the heat aging resistance is disadvantageous in hardness decrease and permanent compression strain. Therefore, improving toughness and heat aging resistance while satisfying the required physical properties of the hump strip rubber composition has been considered as a great challenge until now.

이에, 본 발명자는 상기한 바와 같은 문제점을 유발하지 않고 타이어의 험프스트립용 고무조성물의 내열노화성을 향상시키기 위한 연구를 수행하던 중, 통상적으로 사용하는 천연고무, 시스 1,4-폴리부타디엔 고무에 신디오택틱 1,2-폴리부타디엔 고무를 혼용한 결과, 열노화로 인한 주쇄의 절단을 감소시켜 험프스트립용 고무조성물의 내열노화성을 향상시킬 수 있음을 알게 되어 본 발명을 완성하게 되었다.Thus, the inventors of the present invention while conducting research to improve the heat aging resistance of the rubber hump strip rubber composition without causing the problems described above, commonly used natural rubber, sheath 1,4-polybutadiene rubber As a result of mixing syndiotactic 1,2-polybutadiene rubber in the present invention, the present invention has been found to reduce the cutting of the main chain due to thermal aging, thereby improving the heat aging resistance of the rubber composition for hump strips.

따라서, 본 발명의 목적은 험프스트립의 요구 물성인 경도, 내마멸성, 강성 및 영구압축변형율, 터프니스 등을 유지시키면서 내열노화성을 크게 향상시킨 타이어 험프스트립용 고무조성물을 제공하는 데 있다.Accordingly, an object of the present invention is to provide a rubber hump strip rubber composition which greatly improves heat aging resistance while maintaining hardness, abrasion resistance, rigidity and permanent compression strain, toughness, etc., which are required properties of hump strips.

이와같은 목적을 달성하기 위한 본 발명의 타이어 험프스트립용 고무조성물은 천연고무, 시스 1,4-폴리부타디엔 고무를 원료고무로 하는 것으로서, 이 원료고무는 신디오택틱 1,2-폴리부타디엔 고무를 10∼40중량부로 함유하는 것임을 그 특징으로 한다.The rubber composition for tire hump strips of the present invention for achieving the above object is made of natural rubber, cis 1,4-polybutadiene rubber as raw material rubber, and this raw material rubber is made of syndiotactic 1,2-polybutadiene rubber. It is characterized by containing in 10-40 weight part.

본 발명은 천연고무, 시스 1,4-폴리부타디엔 고무, 신디오택틱 1,2-폴리부타디엔 고무를 혼용함으로써 터프니스를 유지하면서 내열노화성을 향상시킨 것을 특징으로 하는 타이어 험프스트립용 고무조성물에 관한 것이다.The present invention is a rubber composition for a tire hump strip, characterized by improving the heat aging resistance while maintaining toughness by using a combination of natural rubber, cis 1,4-polybutadiene rubber, syndiotactic 1,2-polybutadiene rubber. It is about.

터프니스(toughness)라 함은 외부의 파괴 스트레스(stress)에 대응하는 재료의 저항 능력을 말하며, 터프니스의 척도는 신장율과 인장강도로서 신장율과 인장강도가 크다는 것은 터프니스가 크다는 것을 의미한다.Toughness refers to the ability of a material to respond to external fracture stresses. The toughness scale is elongation and tensile strength, which means that elongation and tensile strength are large.

또한, 내열노화성은 열적 분위기 하에서 일정시간 노화 후의 물성 저하에 대한 저항능력을 말하며, 내열노화성을 평가하는 항목은 노화후의 경도, 터프니스, 인열강도, 영구압축변형율 등 여러 가지가 있으나, 통상적으로 노화 후의 터프니스를 측정함으로써 내열노화성을 평가하고 있다.In addition, the heat aging resistance refers to the ability to resist the degradation of physical properties after a certain time aging in a thermal atmosphere, and there are various items for evaluating the heat aging resistance, such as hardness, toughness, tear strength, and permanent compressive strain after aging. By measuring the toughness after aging, heat aging resistance was evaluated.

통상적으로 고무의 열노화는 열적 분위기 하에서 산소가 주쇄의 이중결합과 반응하여 고무의 주쇄를 절단함으로써 고무조성물의 물성 저하를 유발시키는 것을 의미한다.In general, thermal aging of rubber means that oxygen reacts with a double bond of a main chain in a thermal atmosphere to cut the main chain of the rubber, thereby causing deterioration of physical properties of the rubber composition.

타이어의 험프스트립용 고무조성물에 통상적으로 사용되는 시스 1,4-폴리부타디엔 고무는 다음 화학식 1로부터 알 수 있듯이 주쇄에 이중결합이 많이 존재하므로 노화에 의한 주쇄 절단이 크고 내열노화성이 떨어진다.Cis 1,4-polybutadiene rubber, which is commonly used in the hump strip rubber composition of the tire, as can be seen from the following formula (1), since there are many double bonds in the main chain, the main chain breakage due to aging is large and heat aging resistance is poor.

반면에 본 발명에서 사용된 신디오택틱 1,2-폴리부타디엔 고무는 다음 화학식 2로부터 알 수 있듯이 주쇄에 이중결합이 존재하지 않으므로 산소와의 반응에 의한 주쇄 절단이 발생하지 않게 되어 내열노화성이 크게 증가한다.On the other hand, the syndiotactic 1,2-polybutadiene rubber used in the present invention does not have a double bond in the main chain, as can be seen from the following Chemical Formula 2, so that the main chain cleavage by the reaction with oxygen does not occur and thus the heat aging resistance Greatly increases.

따라서, 본 발명에서는 상기와 같은 구조를 갖는 신디오택틱 1,2-폴리부타디엔 고무를 시스 1,4-폴리부타디엔의 일부를 대체하여 첨가하는 바, 그 함량은 전체 원료고무 중 10∼40중량부, 더욱 좋게는 15∼35중량부가 적당하다. 만일, 신디오택틱 1,2-폴리부타디엔 고무의 함량이 10중량부 미만이면 내열노화성의 향상을 기대할 수 없고, 40중량부를 초과하면 신장율의 급격한 감소로 터프니스가 떨어지게 되어 내마멸성이 저하되며 노화 후의 터프니스도 감소하게 된다.Therefore, in the present invention, the syndiotactic 1,2-polybutadiene rubber having the structure as described above is added to replace a part of the cis 1,4-polybutadiene, the content of which is 10 to 40 parts by weight of the total raw rubber More preferably, 15-35 weight part is suitable. If the content of syndiotactic 1,2-polybutadiene rubber is less than 10 parts by weight, the improvement of heat aging resistance cannot be expected. Toughness will also decrease.

이와같은 신디오택틱 1,2-폴리부타디엔 고무와 함께 통상적으로 타이어의 험프스트립용 고무조성물에 사용되는 원료고무, 즉 천연고무와 시스 1,4-폴리부타디엔을 원료고무로 사용한다.Along with such syndiotactic 1,2-polybutadiene rubber, raw material rubber, ie, natural rubber and cis 1,4-polybutadiene, which are commonly used in the hump strip rubber composition of a tire, are used as the raw material rubber.

그리고, 통상의 타이어용 배합제를 첨가할 수 있는 바, 일예로 산화아연, 스테아린산, 카본블랙, 아로마틱 오일, 유황부, TBBS(N-t-buty1-2-benzothiazole sulfenamide) 등을 첨가할 수 있다.And a conventional compound for tires can be added, for example, zinc oxide, stearic acid, carbon black, aromatic oils, sulfur parts, TBBS (N-t-buty1-2-benzothiazole sulfenamide) and the like can be added.

이하, 본 발명을 실시예의 의하여 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail by way of Examples, but the present invention is not limited by the Examples.

실시예 1∼4 및 비교예 1∼3Examples 1-4 and Comparative Examples 1-3

가류 전 고무 시트는 다음 표 1에 기재된 배합비율로 고무와 첨가제를 통상적인 혼합방법에 의하여 혼합하였으며, 혼합된 고무를 150℃에서 30분 동안 가류하여 측정시편을 준비하였다. 상기 방법에 의하여 준비된 고무조성물의 물성 결과를 다음 표 1에 기재하였다.The rubber sheet before vulcanization was mixed with a rubber and an additive by the conventional mixing method in the mixing ratio shown in Table 1 below, and the mixed rubber was vulcanized at 150 ° C. for 30 minutes to prepare a test specimen. Physical properties of the rubber composition prepared by the above method are shown in Table 1 below.

실 시 예Example 비 교 예Comparative Example 1One 22 33 44 1One 22 33 배합제(1) Compounding (1) 천연고무Natural rubber 3030 3030 3030 3030 3030 3030 3030 시스 1,4-폴리부타디엔 고무Cis 1,4-polybutadiene rubber 6060 5050 4040 3030 7070 6565 2020 신디오택틱 1,2-폴리부타디엔 고무(2) Syndiotactic 1,2-Polybutadiene Rubber (2) 1010 2020 3030 4040 -- 55 5050 경도(Shore A)Shore A 7272 7373 7474 7474 7070 7171 7676 인장강도(㎏/㎠)Tensile Strength (㎏ / ㎠) 노화전Before aging 194194 200200 208208 205205 182182 185185 190190 노화후After aging 141141 144144 150150 147147 130130 132132 135135 신장율(%)Elongation (%) 노화전Before aging 405405 403403 400400 401401 400400 395395 350350 노화후(3) After Aging (3) 165165 172172 185185 175175 150150 151151 138138 인열강도(㎏/㎠)Tear strength (㎏ / ㎠) 노화전Before aging 4949 4848 5050 4848 5050 5151 4545 노화후After aging 2525 3434 4040 3535 1818 2020 1515 영구압축 변형율(4)(%)Permanent compression set (4) (%) 4848 4747 4545 4747 5252 5252 5050 마멸량(5)(㏄)Abrasion (5) (㏄) 0.2190.219 0.2170.217 0.2180.218 0.2200.220 0.2230.223 0.2220.222 0.2250.225 (주)1. 상기한 고무성분 외에 통상적으로 타이어 험프스트립용 고무조성물에 사용되는 산화아연 5중량부, 스테아린산 2중량부, 카본블랙 60중량부, 아로마틱 오일 4중량부, 유황 3중량부, TBBS(N-t-buty1-2-benzothiazole sulfenamide)1중량부를 사용하였다.2. 일본합성고무의 JSR RB를 사용하였다.3. 노화조건은 100℃, 96시간이다.4. 영구압축변형율은 100℃에서 24시간 동안 12㎜ 두께의 시편을 9.5㎜로 압축시켰을 때, 압축길이(2.5㎜)에 대한 줄어든 길이의 비를 지수로 나타낸 것이며, 수치가 작을수록 변형율이 적다.5. 마멸량이 적을수록 성능이 우수하다.Note 1. 5 parts by weight of zinc oxide, 2 parts by weight of stearic acid, 60 parts by weight of carbon black, 4 parts by weight of aromatic oil, 3 parts by weight of sulfur, TBBS (Nt-buty1-) in addition to the above-mentioned rubber components 1 part by weight of 2-benzothiazole sulfenamide) was used. JSR RB of Japanese synthetic rubber was used. Aging conditions are 100 ° C. and 96 hours. Permanent compression strain is an exponential representation of the ratio of reduced length to compression length (2.5 mm) when a 12 mm thick specimen is compressed to 9.5 mm for 24 hours at 100 ° C. 5 The smaller the value, the lower the strain. . The lower the amount of abrasion, the better the performance.

상기 표 1에 나타낸 바와 같이, 본 발명에 따른 타이어의 험프스트립용 고무조성물로 만들어진 실시예 1 내지 4의 가류시편은 노화 후의 터프니스, 즉 신장율과 인장강도가 우수하고 영구압축변형율과 마멸량도 비교적 적은 반면, 시스 1,4-폴리부타디엔 고무만을 사용한 비교예 1은 노화 후의 신장율과 인장강도가 크게 떨어질 뿐 아니라 영구압축변형율 및 마멸량도 높다. 그리고, 신디오택틱 1,2-폴리부타디엔 고무의 함량이 본 발명의 범위보다 적은 비교예 2는 신디오택틱 1,2-폴리부타디엔 고무를 사용하지 않은 비교예 1에 비하여 노화 후의 터프니스 향상을 기대할 수 없고 영구압축변형율과 마멸량도 그다지 차이를 보이지 않는다. 또한, 신디오택틱 1,2-폴리부타디엔 고무의 함량이 본 발명의 범위보다 많은 비교예 3은 노화 전의 신장율이 크게 떨어지고 인장강도도 그다지 크게 증가하지 않으므로 비교예 1에 비하여 노화 후의 터프니스가 감소, 즉 내열노화성이 감소하게 된다.As shown in Table 1, the vulcanization specimens of Examples 1 to 4 made of the rubber composition for the hump strip of the tire according to the present invention have excellent toughness after aging, that is, excellent elongation and tensile strength, and permanent compression strain and abrasion amount. On the other hand, Comparative Example 1, which uses only cis 1,4-polybutadiene rubber, not only significantly reduces elongation and tensile strength after aging but also high permanent compression set and wear rate. In addition, Comparative Example 2 in which the content of syndiotactic 1,2-polybutadiene rubber is less than the range of the present invention improves toughness after aging compared to Comparative Example 1 which does not use syndiotactic 1,2-polybutadiene rubber. Unexpectedly, the permanent compressive strain and the amount of wear do not show much difference. In addition, Comparative Example 3, in which the content of syndiotactic 1,2-polybutadiene rubber is greater than the range of the present invention, the elongation before aging decreases significantly and the tensile strength does not increase so much that the toughness after aging is reduced compared to Comparative Example 1. In other words, the heat aging resistance is reduced.

이상에서 상세히 설명한 바와 같이, 본 발명에 따라 원료고무로서 천연고무와 시스 1,4-폴리부타디엔과 더불어 신디오택틱 1,2-폴리부타디엔 고무를 사용한 경우 통상의 타이어 험프스트립용 고무에서 요구되는 경도, 내마멸성, 강성 및 영구압축변형율, 터프니스 등은 유지되면서 내열노화성을 크게 향상시킬 수 있게 되었다.As described in detail above, in the case of using syndiotactic 1,2-polybutadiene rubber together with natural rubber and cis 1,4-polybutadiene as raw material rubbers according to the present invention, the hardness required for the rubber of a typical tire hump strip In addition, the wear resistance, stiffness and permanent compression set, toughness, etc. can be maintained while greatly improving the heat aging resistance.

Claims (1)

천연고무와 시스 1,4-폴리부타디엔 고무를 원료고무로 하고, 여기에 통상의첨가제를 첨가하여 이루어진 타이어의 험프스트립용 고무조성물에 있어서,In the rubber composition for hump strips of a tire formed by using natural rubber and cis 1,4-polybutadiene rubber as a raw material rubber and adding a conventional additive thereto, 상기 원료고무는 신디오택틱 1,2-폴리부타디엔 고무를 10∼40중량부 되도록 함유하는 것임을 특징으로 하는 타이어의 험프스트립용 고무조성물.The rubber material for the hump strip of the tire, characterized in that it contains 10 to 40 parts by weight of syndiotactic 1,2-polybutadiene rubber.
KR10-2001-0018850A 2001-04-10 2001-04-10 Rubber composition for tire KR100407859B1 (en)

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CN106543487A (en) * 2015-09-16 2017-03-29 上海中冶环境工程科技有限公司 A kind of rubber using slag micro powder as rubber filler

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JPS54132646A (en) * 1978-04-06 1979-10-15 Bridgestone Corp Rubber composition for tire cord coating
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JPS6250350A (en) * 1985-08-29 1987-03-05 Ube Ind Ltd Rubber composition
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106543487A (en) * 2015-09-16 2017-03-29 上海中冶环境工程科技有限公司 A kind of rubber using slag micro powder as rubber filler

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