KR101247392B1 - A rubber composite - Google Patents
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- KR101247392B1 KR101247392B1 KR1020110047076A KR20110047076A KR101247392B1 KR 101247392 B1 KR101247392 B1 KR 101247392B1 KR 1020110047076 A KR1020110047076 A KR 1020110047076A KR 20110047076 A KR20110047076 A KR 20110047076A KR 101247392 B1 KR101247392 B1 KR 101247392B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
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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
- C08L9/06—Copolymers with styrene
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
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Abstract
본 발명은 승용차 타이어용 트레드 고무조성물을 개시한다.
본 발명에 따르는 승용차 타이어용 트레드 고무조성물에 의하면, 원료고무 100중량부에 대하여 CnHn+2O-C-O-N=N-R-Si-(OEt)3인 오가노실란(Organosilane) 1 내지 15 중량부를 포함하는 것을 특징으로 하는데, 이에 의할 때, 일반 승용차 타이어에 있어서 회전저항으로 나타나는 발열 및 연비저하를 줄이고 제동력과 마모 등의 제반특성을 향상시키게 된다.The present invention discloses a tread rubber composition for a passenger car tire.
According to the tread rubber composition for passenger car tires according to the present invention, it comprises 1 to 15 parts by weight of organosilane, which is C n H n + 2 OCON = NR-Si- (OEt) 3 , based on 100 parts by weight of the raw material rubber. In this case, it is possible to reduce heat generation and fuel economy, which are represented by rotational resistance, and improve various characteristics such as braking force and wear in general passenger car tires.
Description
본 발명은 승용차 타이어용 트레드 고무 조성물에 관한 것으로, 더욱 상세하게는 일반 승용차 타이어에 있어서 회전저항으로 나타나는 발열 및 연비저하를 줄이고 제동력과 마모 등의 제반특성을 향상시킨 승용차 타이어용 트레드 고무 조성물에 관한 것이다. The present invention relates to a tread rubber composition for passenger car tires, and more particularly, to a tread rubber composition for passenger car tires, which reduces heat and fuel efficiency, which are shown as rolling resistance, and improves various characteristics such as braking force and wear in general passenger car tires. will be.
최근 승용차 타이어의 트레드 부위의 회전저항을 감소시키기 위해 입자경이 크고 표면의 작용기가 발달한 카본블랙을 사용하거나 실리카 및 실란커플링제를 사용하여 회전저항을 낮추려는 연구가 꾸준히 진행되고 있다.Recently, in order to reduce the rolling resistance of the tread portion of a passenger car tire, studies are being made to reduce the rolling resistance by using carbon black having a large particle diameter and developing functional groups on the surface, or by using silica and a silane coupling agent.
일반적으로 타이어 트레드 부위에 사용되는 고무조성물은 카본블랙 및 실리카의 종류, 사용량에 따라 반발특성 및 발열특성은 개선이 되지만, 회전저항의 지표인 70℃ 탄델타(Tanδ) 값이 고무조성물의 특성에 따라 전이되는 경향이 있다.In general, the rubber composition used in the tire tread part is improved in the resilience and heat generation characteristics depending on the type and amount of carbon black and silica, but the 70 ° C tan delta (Tanδ), an index of rotational resistance, Therefore they tend to metastasize.
일반적으로 회전저항의 지표인 70℃ 탄델타(Tanδ)값이 향상되면 제동성의 지표인 0℃ 탄델타(Tanδ) 값이 저하되는 상반된 성능을 나타내며, 이때 주로 사용되는 고무조성물은 유화중합 스타이렌-부타디엔 고무 블렌드로 카본블랙 및 실리카 성분과의 친화도가 떨어짐에 따라 분산이 최대로 이루어지지 못해 고무조성물의 물성이 최대한 발휘되지 못하는 문제점이 있었다.In general, when the 70 ° C tan delta (Tanδ), an index of rotational resistance, is improved, the 0 ° C tan delta (Tanδ), which is an indicator of braking performance, decreases, and the main rubber composition is emulsion polymerization styrene. Butadiene rubber blend has a problem in that the physical properties of the rubber composition is not exhibited to the maximum as the affinity between the carbon black and the silica component is lowered.
이들의 문제점을 해소하기 위해서 각종 실란커플링제가 개발되었는데 실란커플링제를 보강제로 사용하는 것이 개발되어 있다. In order to solve these problems, various silane coupling agents have been developed, and the use of silane coupling agents as reinforcing agents has been developed.
그러나 이 실란커플링제 보강제에 의해서도 고무조성물의 파괴특성, 작업성 및 가공성을 고수준으로 하는데는 불충분하였다. 또한 이 실란 커플링제중 가장 널리 이용되는 실란 커플링제로 비스-(트리에톡시실릴-프로필)-테트라설파이드{Bis-(triethoxysilyl-propyl)-tetrasulfide ; 이하 TESPT라 한다)는 150℃이상의 고온에서 배합시 실란커플링제 내의 Sulfur가 분해되어 Free sulfur가 되며 이 Sulfur로 인해 고무배합물의 인장물성이 현저하게 하락하는 문제가 있으며 유동성이 현저하게 떨어지고 작업성 및 가공성의 저하를 초래한다는 결점이 있었다. However, this silane coupling agent reinforcing agent was also insufficient to bring high breaking properties, workability and workability of the rubber composition. As the most widely used silane coupling agent among these silane coupling agents, bis- (triethoxysilyl-propyl) -tetrasulfide {Bis- (triethoxysilyl-propyl) -tetrasulfide; When TESPT) is blended at a temperature higher than 150 ℃, sulfur in the silane coupling agent is decomposed to become free sulfur, and this sulfur causes a problem that the tensile property of the rubber compound is significantly decreased. There existed a fault which brought about the fall of workability.
본 발명이 해결하고자 하는 기술적 과제는 일반 승용차 타이어에 있어서 회전저항으로 나타나는 발열 및 연비저하를 줄이고 제동력과 마모 등의 제반특성을 향상시킨 승용차 타이어용 트레드 고무 조성물을 제공하는 것이다.The technical problem to be solved by the present invention is to provide a tread rubber composition for a passenger car tire, which reduces heat and fuel economy, which are represented by rotational resistance, and improves various characteristics such as braking force and wear in a general car tire.
본 발명은 상술한 기술적 과제를 해결하기 위하여, 승용차 타이어용 트레드 고무조성물에 있어서, 원료고무 100중량부에 대하여 아래 화학식 1에 의한 오가노실란(Organosilane) 1 내지 15 중량부를 포함하는 것을 특징으로 하는 승용차 타이어용 트레드 고무 조성물을 제공한다.The present invention, in order to solve the above technical problem, in the tread rubber composition for passenger car tires, characterized in that it comprises 1 to 15 parts by weight of organosilane (Organosilane) according to the formula (1) based on 100 parts by weight of the raw material rubber Provided is a tread rubber composition for a passenger car tire.
<화학식 1>≪ Formula 1 >
CnHn+2O-C-O-N=N-R-Si-(OEt)3 C n H n + 2 OCON = NR-Si- (OEt) 3
(n : 1 내지 5인 정수, R : C2 내지 C15인 알킬기)(n: integer of 1 to 5, R: C 2 To C 15 alkyl group)
본 발명의 일실시예에 의하면, 상기 원료고무는 스티렌 30∼50중량%, 비닐 10∼30중량% 및 아로마틱 오일 20~50중량%으로 이루어질 수 있다.According to one embodiment of the invention, the raw material rubber may be made of 30 to 50% by weight of styrene, 10 to 30% by weight of vinyl and 20 to 50% by weight of aromatic oils.
본 발명의 다른 실시예에 의하면, 상기 원료고무에는 그 전체 중량에 대하여 스티렌 15~40중량%를 더 포함할 수 있다.According to another embodiment of the present invention, the raw material rubber may further include 15 to 40% by weight of styrene relative to the total weight.
본 발명의 또 다른 실시예에 의하면, 상기 오가노실란는 pH가 6.5~8.5일 수 있다.According to another embodiment of the present invention, the organosilane may have a pH of 6.5 ~ 8.5.
본 발명에 따르면, 일반 승용차 타이어에 있어서 회전저항으로 나타나는 발열 및 연비저하를 줄이고 제동력과 마모 등의 제반특성을 향상시키는 효과가 있다.According to the present invention, there is an effect of reducing heat generation and fuel economy reduction, which are represented by rotational resistance, and improving various characteristics such as braking force and wear in a general passenger car tire.
이하에서는 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 원료고무 100중량부에 대하여 CnHn+2O-C-O-N=N-R-Si-(OEt)3로 표기되는 오가노실란(Organosilane) 1 내지 15 중량부를 포함하는 특징이 있다.The present invention is characterized by including 1 to 15 parts by weight of organosilane represented by C n H n + 2 OCON = NR-Si- (OEt) 3 based on 100 parts by weight of the raw material rubber.
여기서, n은 1, 2, 3, 4 또는 5인 정수이고, R은 C2 내지 C15인 알킬기로 탄소수가 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 또는 15인 알킬기를 의미한다.Where n is an integer equal to 1, 2, 3, 4 or 5, and R is C 2 To An alkyl group having C 15 means an alkyl group having 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15 carbon atoms.
상기 원료고무는 천연고무나 합성고무 또는 이들의 혼합으로 사용될 수 있는데, 특히 스티렌 30∼50중량%, 비닐 10∼30중량% 및 아로마틱 오일 20~50중량%으로 이루어진 유화중합 스티렌-부타디엔 고무를 사용할 수 있다.The raw material rubber may be used as natural rubber or synthetic rubber or a mixture thereof, in particular, emulsified polymerized styrene-butadiene rubber composed of 30 to 50% by weight of styrene, 10 to 30% by weight of vinyl and 20 to 50% by weight of aromatic oils. Can be.
여기에, 스티렌 15~40중량%을 더하여 유화중합 스티렌-부타디엔 고무의 혼합고무를 사용할 수 있음은 물론이다.Of course, by adding 15 to 40% by weight of styrene can be used a mixed rubber of the emulsion polymerization styrene-butadiene rubber.
또한, 상기 오가노실란는 pH가 6.5~8.5인데, 만일 pH가 6.5 미만이면, 가황속도가 느려 정상시간 내에 가교반응이 일어나지 않으며, 반대로 pH가 8.5를 초과하면 가교반응속도가 빨라지고, 가황고무 물성이 하락하여 오가노실란을 사용하여 나타날 수 있는 장점인 물성 개선 효과가 낮아질 수 있다 In addition, the organosilane has a pH of 6.5 to 8.5, if the pH is less than 6.5, the vulcanization rate is low, so that the crosslinking reaction does not occur in a normal time. On the contrary, if the pH exceeds 8.5, the crosslinking reaction rate is increased, and the vulcanized rubber property is May be lowered and the improvement of physical properties, which is an advantage of using organosilane, may be lowered.
아울러, 상기 원료고무 100중량부에 대하여 상기 오가노실란(Organosilane)이 1 내지 15 중량부가 사용되는데, 만일 1중량부 미만이면, 그 첨가량이 미미하여 효과가 없을 수 있으며, 반대로, 15중량부를 초과하면, 혼합, 압출 등의 공정성에 악영향을 미칠 수 있다.In addition, 1 to 15 parts by weight of the organosilane (Organosilane) is used with respect to 100 parts by weight of the raw material rubber, if less than 1 part by weight, the amount may be insignificant and ineffective, on the contrary, if more than 15 parts by weight It may adversely affect the processability of mixing, extrusion, and the like.
한편, 본 발명에 따르는 고무 조성물에는 스테아린산, 노화방지제, 왁스, 아로마틱 오일, 황, 촉진제 등과 같은 첨가제들이 사용될 수 있음은 물론이다.On the other hand, the rubber composition according to the present invention may be used additives such as stearic acid, antioxidants, waxes, aromatic oils, sulfur, accelerators and the like.
<실시예 1>≪ Example 1 >
스티렌 40중량%, 비닐 20중량% 및 아로마틱 오일 40중량%를 포함하는 유화중합 스티렌-부타디엔 고무와 여기 전체 중량에 대하여 스티렌 20중량%를 더한 유화중합 스티렌-부타디엔 고무의 혼합고무 100중량부에 대하여 카본블랙 3 중량부, 실리카(로디아사, 1165MP) 70중량부, C2H4O-C-O-N=N-R-Si-(OEt)3 2.2중량부, TESPT 4.4중량부, 산화아연(ZnO) 3중량부, 스테아린산(Stearic acid) 1중량부를 밴버리 믹서에 넣고 165℃에서 30분 동안 배합한 후 방출하였다. 다음으로, 가류제로서 유황 1.75중량부, 가류촉진제로서 N-t-부틸벤조티아졸 설펜아미드(N-t-butylbenzothiazole sulfenamide, NS) 1.0중량부를 상기 방출된 배합물에 첨가하고, 가류촉진제 Tetrabenzylthiuram disulfide를 0.05 중량부를 첨가하여 90℃에서 10분 동안 가류하여 본 발명에 따르는 고무 조성물을 제조하였다.100 parts by weight of a mixture of an emulsion-polymerized styrene-butadiene rubber comprising 40% by weight of styrene, 20% by weight of vinyl and 40% by weight of an aromatic oil and an emulsion-polymerized styrene-butadiene rubber plus 20% by weight of styrene 3 parts by weight of carbon black, 70 parts by weight of silica (Rhodia, 1165MP), 2.2 parts by weight of C 2 H 4 OCON = NR-Si- (OEt) 3 , 4.4 parts by weight of TESPT, 3 parts by weight of zinc oxide (ZnO), stearic acid (Stearic acid) 1 part by weight was placed in a Banbury mixer, blended at 165 ° C. for 30 minutes, and then released. Next, 1.75 parts by weight of sulfur as a vulcanizing agent, 1.0 part by weight of Nt-butylbenzothiazole sulfenamide (NS) as a vulcanization accelerator was added to the released formulation, and 0.05 parts by weight of vulcanization accelerator Tetrabenzylthiuram disulfide was added. And vulcanized at 90 ° C. for 10 minutes to prepare a rubber composition according to the present invention.
상기 카본블랙은 BET값이 120∼160m2/g, DBP흡착량이 110∼160ml/100g, 실리카는 BET값이 80~220m2/g인 실리카를 사용하였다. The carbon black used a silica having a BET value of 120 to 160 m 2 / g, a DBP adsorption amount of 110 to 160 ml / 100 g, and a silica having a BET value of 80 to 220 m 2 / g.
하기의 표 1에 실시예 1 고무의 성분을 정리하여 나타내었다.Table 1 below shows the components of the rubber of Example 1 together.
<실시예 2><Example 2>
C2H4O-C-O-N=N-R-Si-(OEt)3를 2.6중량부를 사용하고, 실리카(로디아사, ZPR-200MP) 70중량부, TESPT 5.3중량부를 사용하는 것을 제외하고는 상기 실시예 1과 동일한 방법으로 고무 조성물을 제조하였다.Except for using 2.6 parts by weight of C 2 H 4 OCON = NR-Si- (OEt) 3 , 70 parts by weight of silica (Rhodia, ZPR-200MP), 5.3 parts by weight of TESPT, the same as in Example 1 A rubber composition was prepared by the method.
<비교예><Comparative Example>
천연고무 70중량부 및 부타디엔 고무(BR) 30중량부로 이루어진 원료고무 100중량부에 대하여 카본블랙 5중량부, 실리카 70중량부, 실란커플링제(TESPT) 5.6중량부, 산화아연(ZnO) 3중량부, 스테아린산(Stearic acid) 1중량부를 밴버리 믹서에 넣고 150℃에서 30분 동안 배합한 후 방출하였다. 다음으로, 가류제로 유황 1.75중량부, 가류촉진제로서 N-t-부틸벤조티아졸 설펜아미드(NS) 1.0중량부를 상기 방출된 배합물에 첨가하고 110℃에서 10분 동안 가류하여 고무를 제조하였다.5 parts by weight of carbon black, 70 parts by weight of silica, 5.6 parts by weight of silane coupling agent (TESPT), and 3 parts of zinc oxide (ZnO) based on 100 parts by weight of the raw material rubber consisting of 70 parts by weight of natural rubber and 30 parts by weight of butadiene rubber (BR). Part, 1 part by weight of stearic acid (Stearic acid) was placed in a Banbury mixer, blended for 30 minutes at 150 ℃ and released. Next, 1.75 parts by weight of sulfur as a vulcanizing agent and 1.0 part by weight of N-t-butylbenzothiazole sulfenamide (NS) as a vulcanization accelerator were added to the released blend and vulcanized at 110 ° C. for 10 minutes to prepare a rubber.
상기 카본블랙은 BET값이 120∼160m2/g, DBP흡착량이 110∼160ml/100g, 실리카는 BET값이 100∼200m2/g, DBP흡착량이 240∼300ml/100g인 것을 사용하였다.The carbon black had a BET value of 120 to 160 m 2 / g, a DBP adsorption amount of 110 to 160 ml / 100 g, and a silica having a BET value of 100 to 200 m 2 / g and a DBP adsorption amount of 240 to 300 ml / 100 g.
<시험예 1>≪ Test Example 1 >
상기 실시예 1,2 및 비교예에서 제조한 고무 시편을 ASTM 관련 규정에 의해 경도, 300%모듈러스, 인장강도, 신장율, 리바운드, 발열, PICO마모, 웨트 스키드 저항 및 분산성을 측정하고 그 결과를 아래의 표 1에 나타내었다. Rubber specimens prepared in Examples 1 and 2 and Comparative Examples were measured for hardness, 300% modulus, tensile strength, elongation, rebound, heat generation, PICO wear, wet skid resistance, and dispersibility according to ASTM-related regulations. It is shown in Table 1 below.
*tand70℃: 회전저항을 나타내는 수치로 낮을수록 유리함.* tand70 ℃: The lower the value, the better the rotational resistance.
Claims (4)
<화학식 1>
CnHn+2O-C-O-N=N-R-Si-(OEt)3
(n : 1 내지 5인 정수, R : C2 내지 C15인 알킬기)
A tread rubber composition for a passenger car tire, comprising: 1 to 15 parts by weight of organosilane according to formula (1) based on 100 parts by weight of raw material rubber.
≪ Formula 1 >
C n H n + 2 OCON = NR-Si- (OEt) 3
(n: an integer of 1 to 5, R: C 2 to C 15 alkyl group)
상기 원료고무는 스티렌 30∼50중량%, 비닐 10∼30중량% 및 아로마틱 오일 20~50중량%으로 이루어진 것을 특징으로 하는 승용차 타이어용 트레드 고무 조성물.
The method of claim 1,
The raw material rubber is a tread rubber composition for a passenger car tire, characterized in that consisting of styrene 30 to 50% by weight, vinyl 10 to 30% by weight and aromatic oil 20 to 50% by weight.
상기 원료고무에는 그 전체 중량에 대하여 스티렌 15~40중량%를 더 포함하는 것을 특징으로 하는 승용차 타이어용 트레드 고무 조성물.
The method of claim 2,
Tread rubber composition for passenger car tires, characterized in that the raw material rubber further comprises 15 to 40% by weight based on the total weight.
상기 오가노실란는 pH가 6.5~8.5인 것을 특징으로 하는 승용차 타이어용 트레드 고무 조성물.The method of claim 1,
The organosilane is tread rubber composition for passenger car tires, characterized in that the pH is 6.5 ~ 8.5.
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|---|---|---|---|---|
| KR100462096B1 (en) | 1996-01-26 | 2005-04-19 | 꽁빠니 제네랄 드 에따블리세망 미쉘린-미쉘린 에 씨 | Rubber composition having a base of a diene polymer having a silanol function and comprising an or ganosilane derivative |
| KR100485202B1 (en) | 1996-01-11 | 2005-08-11 | 꽁빠니 제네랄 드 에따블리세망 미쉘린-미쉘린 에 씨 | Tire casings and tire treads comprising silica-based rubber compositions containing reinforcing additives based on functionalized polyorganosiloxanes and organosilane compounds, and methods for improving the rubber compositions |
| KR100569520B1 (en) | 1998-10-15 | 2006-04-07 | 더 굿이어 타이어 앤드 러버 캄파니 | Preparation of reinforced rubber and use in tires |
| KR100869256B1 (en) | 2007-11-07 | 2008-11-18 | 금호타이어 주식회사 | Tire Tread Rubber Composition |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100485202B1 (en) | 1996-01-11 | 2005-08-11 | 꽁빠니 제네랄 드 에따블리세망 미쉘린-미쉘린 에 씨 | Tire casings and tire treads comprising silica-based rubber compositions containing reinforcing additives based on functionalized polyorganosiloxanes and organosilane compounds, and methods for improving the rubber compositions |
| KR100462096B1 (en) | 1996-01-26 | 2005-04-19 | 꽁빠니 제네랄 드 에따블리세망 미쉘린-미쉘린 에 씨 | Rubber composition having a base of a diene polymer having a silanol function and comprising an or ganosilane derivative |
| KR100569520B1 (en) | 1998-10-15 | 2006-04-07 | 더 굿이어 타이어 앤드 러버 캄파니 | Preparation of reinforced rubber and use in tires |
| KR100869256B1 (en) | 2007-11-07 | 2008-11-18 | 금호타이어 주식회사 | Tire Tread Rubber Composition |
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