KR100656260B1 - Rubber composition for tire tread having improved abrasion resistance - Google Patents

Rubber composition for tire tread having improved abrasion resistance Download PDF

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KR100656260B1
KR100656260B1 KR1020050048280A KR20050048280A KR100656260B1 KR 100656260 B1 KR100656260 B1 KR 100656260B1 KR 1020050048280 A KR1020050048280 A KR 1020050048280A KR 20050048280 A KR20050048280 A KR 20050048280A KR 100656260 B1 KR100656260 B1 KR 100656260B1
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rubber
rubber composition
weight
neodymium
butadiene rubber
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KR1020050048280A
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Korean (ko)
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최희성
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금호타이어 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
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B60C1/0016—Compositions of the tread
    • 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
    • C08L9/06—Copolymers with styrene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
    • B01J2523/37—Lanthanides
    • B01J2523/3725—Neodymium
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • 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

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

Abstract

Provided is a rubber composition for a tire tread which is remarkably improved in abrasion resistance, heat resistance and durability without the deterioration of basic physical properties. The rubber composition comprises 100 parts by weight of a rubber material which comprises a neodymium-butadiene rubber prepared by using neodymium as a catalyst; and 3-10 parts by weight of an engineering elastomer which comprises a styrene-butadiene rubber or a mixture of a styrene-butadiene rubber and pulp. The content of pulp in the engineering elastomer is 20-30 wt%. Preferably the content of cis of the neodymium-butadiene rubber is 98 % or more.

Description

내마모성이 향상된 타이어 트레드용 고무 조성물{RUBBER COMPOSITION FOR TIRE TREAD HAVING IMPROVED ABRASION RESISTANCE}Rubber composition for tire treads with improved wear resistance {RUBBER COMPOSITION FOR TIRE TREAD HAVING IMPROVED ABRASION RESISTANCE}

본 발명은 내마모성이 향상된 타이어 트레드용 고무 조성물에 관한 것으로, 보다 상세하게는, 네오디뮴(neodimium, Nd)을 촉매로 하여 폴리머의 시스(cis) 함량을 향상시킨 네오디뮴-부타디엔 고무(Nd-BR)와 엔지니어링 엘라스토머를 포함하므로써, 발열 특성 및 내마모성을 향상시킨 타이어 트레드용 고무 조성물에 관한 것이다.The present invention relates to a rubber tread rubber composition having improved abrasion resistance, and more particularly, to neodymium-butadiene rubber (Nd-BR) having improved cis content of a polymer by using neodymium (neodimium, Nd) as a catalyst. It is related with the rubber composition for tire treads which improved an exothermic property and abrasion resistance by including an engineering elastomer.

자동차 산업의 발전과 더불어 자동차 운행 도로환경 조건의 개선에 따라 소비자들의 타이어에 대한 요구 조건도 다양해지고 있다. With the development of the automobile industry, the demands on the tires of consumers are also diversified as the road conditions of automobiles are improved.

최근 환경친화적인 관점에서, 실리카를 타이어용 고무 조성물의 보강재로서 많이 사용하고 있다. 그러나, 일반적으로, 타이어용 고무 조성물에서 보강재로 실리카를 사용하게 되면, 카본블랙 대비 내마모성이 하락하게 된다. 따라서, 타이어용 고무 조성물의 내마모성을 향상시키기 위해 상업적 공정에서는, 주로 구조가 발달하고 입자크기가 작은 카본블랙을 실리카와 함께 사용하고 있다. 또한, 마모 성능을 향상시키고자, 원료고무로서, 폴리머 상에서 마모특성이 좋은 부타디엔 고무 (BR)를 스티렌-부타디엔 고무(SBR)와 함께 사용하는 방법이 시도되기도 하였으나, 이들 보강재의 혼용 및 원료고무의 혼용과 같은 방법만으로는 내마모성을 향상시키는 데에 한계가 있으며, 그러한 혼용으로 인하여 다른 물성이 하락하게 되는 부작용도 있는 것이 문제이다. In recent years, from an environmentally friendly point of view, silica is widely used as a reinforcing material for rubber compositions for tires. In general, however, when silica is used as a reinforcing material in a rubber composition for a tire, wear resistance is lower than that of carbon black. Therefore, in order to improve abrasion resistance of the rubber composition for tires, carbon black, which is mainly developed in structure and small in particle size, is used together with silica. In addition, in order to improve wear performance, a method of using butadiene rubber (BR) with good wear characteristics on a polymer together with styrene-butadiene rubber (SBR) as a raw material rubber has been attempted. There is a limit to improving wear resistance by the same method as the mixed use, and there is a side effect that other physical properties decrease due to the mixed use.

따라서, 내마모성을 향상시킬 수 있을 뿐만 아니라, 다른 물성의 유지 내지 향상도 가능하게 하는, 보다 개선된 타이어 트레드용 고무 조성물의 개발이 요청되고 있는 실정이다.Accordingly, there is a demand for development of a rubber composition for tire treads, which can not only improve wear resistance but also maintain or improve other physical properties.

본 발명은 상기한 바와 같은 종래 기술의 문제점을 해결하고자 한 것으로서, 본 발명의 목적은, 향상된 내마모성을 가질 뿐만 아니라, 발열 특성과 같은 다른 물성도 유지 내지 향상된 타이어 트레드용 고무 조성물을 제공하는 것이다.The present invention is to solve the problems of the prior art as described above, it is an object of the present invention to provide a rubber composition for tire treads not only having improved wear resistance, but also maintaining other physical properties such as exothermic properties.

본 발명에 따르면, 네오디뮴(neodimium, Nd)을 촉매로 하여 제조된 네오디뮴-부타디엔 고무(Nd-BR)를 포함하는 원료고무 100중량부 및 엔지니어링 엘라스토머 3~10중량부를 포함하여 이루어지는 것을 특징으로 하는 타이어 트레드용 고무 조성물이 제공된다.According to the present invention, a tire comprising: 100 parts by weight of raw rubber including neodymium-butadiene rubber (Nd-BR) prepared by using neodymium (Nd) as a catalyst and 3 to 10 parts by weight of engineering elastomer A rubber composition for tread is provided.

본 발명에 따른 타이어 트레드용 고무 조성물에 있어서, 상기 원료고무에 포함되는 상기 네오디뮴-부타디엔 고무는, 고무 내의 시스(cis) 함량을 높이고자 네오디뮴(neodimium, Nd)을 촉매로 하여 제조된 것으로서, 그 시스함량은 98% 이상인 것이 바람직하다. 이 시스함량이 98% 미만이면, 고무 조성물의 내마모성의 향상이 충분하지 않게 된다. 또한, 상기 원료고무 중의 상기 네오디뮴-부타디엔 고무의 함량은 10~30중량%인 것이 바람직한데, 이 함량이 10중량% 미만이면, 고무 조성물의 내마모성의 향상이 충분하지 않게 되고, 30중량%를 초과하면, 내마모성 이외의 물성의 하락이 우려된다.In the rubber composition for tire treads according to the present invention, the neodymium-butadiene rubber included in the raw material rubber is manufactured by using neodymium (Nd) as a catalyst to increase the cis content in the rubber. It is preferable that sheath content is 98% or more. If this sheath content is less than 98%, the improvement of abrasion resistance of a rubber composition will not become enough. In addition, the content of the neodymium-butadiene rubber in the raw material rubber is preferably 10 to 30% by weight, when the content is less than 10% by weight, the improvement of wear resistance of the rubber composition is not sufficient, and exceeds 30% by weight If it does, the fall of physical properties other than abrasion resistance is feared.

본 발명에 따른 타이어 트레드용 고무 조성물에 있어서, 상기 원료고무에는 상기 네오디뮴-부타디엔 고무 이외에, 스티렌-부타디엔 고무(SBR), 이소프렌 고무(IR), 부타디엔 고무(BR), 천연고무(NR) 등이 단독으로, 또는 둘 이상 더 혼합되어 사용될 수 있으며, 바람직하게는 스티렌-부타디엔 고무(SBR) 단독, 또는 스티렌-부타디엔 고무(SBR)와 다른 고무와의 혼합물이 더 사용된다. 상기 스티렌-부타디엔 고무(SBR) 내의 스티렌 함량은 23.5~40중량%인 것이 바람직하다.In the rubber composition for tire tread according to the present invention, the raw material rubber, in addition to the neodymium-butadiene rubber, styrene-butadiene rubber (SBR), isoprene rubber (IR), butadiene rubber (BR), natural rubber (NR) and the like It may be used alone or in admixture of two or more, preferably a styrene-butadiene rubber (SBR) alone or a mixture of styrene-butadiene rubber (SBR) with other rubbers is further used. The styrene content in the styrene-butadiene rubber (SBR) is preferably 23.5 to 40% by weight.

본 발명에 따른 타이어 트레드용 고무 조성물에 포함되는 상기 엔지니어링 엘라스토머는, 스티렌-부타디엔 고무 단독 또는 그 혼합고무에 펄프를 혼입하여 제조한 것으로서, 펄프의 함량이 바람직하게는 20~30중량%인 복합재료이다. 상기 혼합고무로는, 예컨대, 천연고무:스티렌-부타디엔 고무가 중량비로 6:4~5:5의 비율로 혼합된 고무를 사용할 수 있다. 상기 엔지니어링 엘라스토머는 내마모성의 향상시 초래될 수 있는 다른 물성들의 저하를 막기 위해 사용되는 것으로서, 본 발명의 고무 조성물에는 원료고무 100중량부에 대하여 3~10중량부가 포함된다. 상기 엔지니어링 엘라스토머의 함량이 2중량부 미만이면, 목적하는 사용효과를 기대할 수 없으며, 10중량부를 초과하면, 고무 조성물의 가공성이 나빠지는 문제가 있다.The engineering elastomer included in the tire tread rubber composition according to the present invention is manufactured by mixing pulp with styrene-butadiene rubber alone or a mixture of rubbers thereof, and the pulp content is preferably 20 to 30% by weight. to be. As the mixed rubber, for example, a rubber in which a natural rubber: styrene-butadiene rubber is mixed in a weight ratio of 6: 4 to 5: 5 may be used. The engineering elastomer is used to prevent the deterioration of other physical properties that may be caused when the wear resistance is improved, the rubber composition of the present invention includes 3 to 10 parts by weight based on 100 parts by weight of the raw material rubber. If the content of the engineering elastomer is less than 2 parts by weight, the desired use effect can not be expected, if it exceeds 10 parts by weight, there is a problem that the workability of the rubber composition is deteriorated.

본 발명에 따른 타이어 트레드용 고무 조성물에는, 상기한 성분들 이외에도, 타이어 트레드용 고무 조성물에 통상적으로 사용되는 첨가제들이 더 포함될 수 있는데, 예컨대 활성제로서 스테아린산, 산화아연(ZnO), 보강 충전재로서 카본블랙 및/또는 실리카, 촉진제 및 기타 가소제, 연화제, 노방제 등이 적절하게 더 포함될 수 있다.In addition to the above components, the rubber composition for tire treads according to the present invention may further include additives commonly used in the rubber composition for tire treads, for example, stearic acid, zinc oxide (ZnO) as an active agent, and carbon black as a reinforcing filler. And / or silica, promoters and other plasticizers, emollients, preservatives and the like may suitably be further included.

이하에서, 실시예 및 비교예를 통하여 본 발명을 보다 상세히 설명하나, 본 발명의 범위가 이하의 실시예에 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited to the following Examples.

<실시예 1~2 및 비교예 1~2><Examples 1 and 2 and Comparative Examples 1 and 2>

다음 표 1에 나타난 조성에 따라 실시예 1~3 및 비교예 1~2의 고무 조성물을 제조하고, 그로부터 고무시편을 제조한 후, 물성을 측정하여 그 결과를 표 1에 기재하였다. The rubber compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were prepared according to the compositions shown in Table 1 below, rubber samples were prepared therefrom, and then the physical properties thereof were measured.

[표 1]TABLE 1

항목 Item 실시예Example 비교예Comparative example 1One 22 1One 22 조성비 (단위: 중량부)  Composition ratio (unit: parts by weight) 원료고무(SBR/Nd-BR)Raw material rubber (SBR / Nd-BR) 90/1090/10 90/1090/10 100/0100/0 90/1090/10 보강재(CB/SIL)Reinforcement material (CB / SIL) 45/2045/20 45/2045/20 45/2045/20 45/2045/20 분산제Dispersant 33 33 33 33 활성제Active agent 44 44 44 44 공정유Process oil 88 88 88 88 유황brimstone 33 33 33 33 가황촉진제Vulcanization accelerator 33 33 33 33 E.EE.E 55 1010 00 00 기본 물성 Basic properties 경도Hardness 7373 7373 7272 7272 300% MOD300% MOD 151151 162162 145145 142142 TSTS 205205 215215 195195 193193 EBEB 445445 455455 430430 425425 내마모성Wear resistance PICO(%)PICO (%) 108108 110110 100100 105105 발열특성Exothermic characteristics H-BUH-BU 21.221.2 22.022.0 30.830.8 26.226.2 내구성능Durability 주행거리/세퍼레이션Mileage / separation 401km/무401km / nothing 407km/무407km / nothing 372km/유372km / existence 385km/무385km / nothing

상기 표 1에서 사용된 약어 및 용어에 대한 설명은 다음과 같다.Descriptions of abbreviations and terms used in Table 1 are as follows.

SBR: 스티렌-부타디엔 고무SBR: styrene-butadiene rubber

Nd-BR: 네오디뮴-부타디엔 고무(시스함량 98.5%)Nd-BR: neodymium-butadiene rubber (cis content 98.5%)

C/B: 카본블랙(N330)C / B: carbon black (N330)

SIL: 실리카(제품명 Zeosil)SIL: Silica (product name Zeosil)

공정유: 아로마틱 오일Process Oil: Aromatic Oil

유황: 유리 황(free sulfur)Sulfur: free sulfur

가황촉진제: 디페닐렌 구아니딘Vulcanization Accelerator: Diphenylene Guanidine

E.E: 엔지니어링 엘라스토머(NR:SBR=5:5, 펄프함량 25중량%, 비중 1.05g/cc, 분해온도 200℃ 이상)E.E: Engineering elastomer (NR: SBR = 5: 5, pulp content 25% by weight, specific gravity 1.05 g / cc, decomposition temperature over 200 ℃)

경도: 고무 경도(JIS)Hardness: Rubber Hardness (JIS)

300% MOD: 300% 신장시 단위면적당 받는 힘(kgf/㎠)300% MOD: Force per unit area at 300% elongation (kgf / ㎠)

TS: 파괴시 인장강도(kgf/㎠)TS: Tensile strength at break (kgf / ㎠)

EB: 파단연신율(%)EB: Elongation at Break (%)

PICO(%): 마모성에 관련한 피코 어브레이젼 테스트(Pico abrasion test)로서, 비.에프. 굿리치 어브레이젼 테스트(B.F. Goodrich Abrasion Test)를 이용하여 80회 회전하여 마모된 후 남은 비교예 1의 시편무게를 100으로 했을 때의 상대적인 무게. 값이 클수록 내마모성이 우수함을 나타낸다.PICO (%): Pico abrasion test related to abrasion. Relative weight when the specimen weight of Comparative Example 1 is 100 after wear by rotating 80 times using B.F. Goodrich Abrasion Test. The larger the value, the better the wear resistance.

H-BU: 발열성(Heat Build-Up)에 관련한 테스트로서, 페리(Ferry) 발열테스트기를 이용하여 측정한 온도(℃). 온도가 낮을수록 내발열성이 우수함을 나타낸다.H-BU: A test related to heat build-up, measured by a Ferry heat tester (° C.). Lower temperature indicates better heat resistance.

내구성능: 주행한 거리/해당 주행거리에서의 세퍼레이션 유무Durability: Separation at distance traveled / distance covered

상기 표 1을 살펴보면, 네오디뮴-부타디엔 고무(Nd-BR)를 포함하는 원료고무 와 엔지니어링 엘라스토머를 사용하여 제조된 본 발명의 실시예 1~2에 따른 고무 조성물은, 이를 모두 포함하지 않거나(비교예 1), 네오디뮴-부타디엔 고무만을 포함하는(비교예 2) 고무 조성물에 비하여, 내마모성, 내발열성 및 내구성능이 현저히 개선되었음을 알 수 있으며, 기본 물성의 하락도 없음을 알 수 있었다. Looking at Table 1, the rubber composition according to Examples 1 to 2 of the present invention manufactured using a raw material rubber and an engineering elastomer including neodymium-butadiene rubber (Nd-BR), or does not include all (comparative examples 1), compared with a rubber composition containing only neodymium-butadiene rubber (Comparative Example 2), it can be seen that the wear resistance, heat resistance and durability improved significantly, and there was no decrease in basic physical properties.

이상 설명한 바와 같이, 본 발명에 따르면, 기본 물성의 하락없이, 내마모성, 내발열성 및 내구성능이 현저히 향상된 타이어 트레드용 고무 조성물을 얻을 수 있다.As described above, according to the present invention, a rubber composition for tire treads with remarkably improved wear resistance, heat resistance, and durability can be obtained without deterioration of basic physical properties.

Claims (3)

네오디뮴을 촉매로 하여 제조된 네오디뮴-부타디엔 고무를 포함하는 원료고무 100중량부 및 스티렌-부타디엔 고무 단독 또는 그 혼합고무와 펄프의 복합재료로 이루어진, 펄프의 함량이 20~30중량%인 엔지니어링 엘라스토머 3~10중량부를 포함하여 이루어지는 것을 특징으로 하는 타이어 트레드용 고무 조성물.Engineering Elastomer 3 with pulp content of 20 to 30% by weight, consisting of 100 parts by weight of raw material rubber containing neodymium-butadiene rubber prepared by neodymium, and styrene-butadiene rubber alone or a composite of rubber and pulp A rubber composition for tire treads, comprising ˜10 parts by weight. 제1항에 있어서, 상기 네오디뮴-부타디엔 고무의 시스함량은 98% 이상인 것을 특징으로 하는 타이어 트레드용 고무 조성물.The rubber tread rubber composition according to claim 1, wherein the cis content of the neodymium-butadiene rubber is 98% or more. 삭제delete
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100760825B1 (en) * 2006-10-23 2007-10-04 한국타이어 주식회사 Rubber composition for truck/bus tire tread
KR100760824B1 (en) * 2006-10-23 2007-10-04 한국타이어 주식회사 Rubber composition for truck/bus tire tread
EP2368918A1 (en) * 2010-03-24 2011-09-28 LANXESS Deutschland GmbH Process for the production of water and solvent-free polymers

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JPH03210345A (en) * 1990-01-11 1991-09-13 Toyo Tire & Rubber Co Ltd Studless tire
US5798416A (en) 1995-07-18 1998-08-25 Toyo Tire & Rubber Co., Ltd. Automobile vibration-isolating rubber composition and automobile vibration-isolating device
KR19990026211A (en) * 1997-09-23 1999-04-15 신형인 Tread Silica Rubber Composition
KR20040001729A (en) * 2002-06-28 2004-01-07 금호타이어 주식회사 Tire tread Compound with Low Rolling Resistance
KR20040090239A (en) * 2003-04-17 2004-10-22 금호타이어 주식회사 Tread compound for tire

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JPH03210345A (en) * 1990-01-11 1991-09-13 Toyo Tire & Rubber Co Ltd Studless tire
US5798416A (en) 1995-07-18 1998-08-25 Toyo Tire & Rubber Co., Ltd. Automobile vibration-isolating rubber composition and automobile vibration-isolating device
KR19990026211A (en) * 1997-09-23 1999-04-15 신형인 Tread Silica Rubber Composition
KR20040001729A (en) * 2002-06-28 2004-01-07 금호타이어 주식회사 Tire tread Compound with Low Rolling Resistance
KR20040090239A (en) * 2003-04-17 2004-10-22 금호타이어 주식회사 Tread compound for tire

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100760825B1 (en) * 2006-10-23 2007-10-04 한국타이어 주식회사 Rubber composition for truck/bus tire tread
KR100760824B1 (en) * 2006-10-23 2007-10-04 한국타이어 주식회사 Rubber composition for truck/bus tire tread
EP2368918A1 (en) * 2010-03-24 2011-09-28 LANXESS Deutschland GmbH Process for the production of water and solvent-free polymers
WO2011117302A1 (en) * 2010-03-24 2011-09-29 Lanxess Deutschland Gmbh Process for the production of water and solvent-free polymers
KR101486638B1 (en) * 2010-03-24 2015-01-26 란세스 도이치란트 게엠베하 Process for the production of water and solvent-free polymers
US8975361B2 (en) 2010-03-24 2015-03-10 Lanxess Deutschland Gmbh Process for the production of water and solvent-free polymers

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