KR100205480B1 - Tire tread rubber composition containing silica - Google Patents

Tire tread rubber composition containing silica Download PDF

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KR100205480B1
KR100205480B1 KR1019960035767A KR19960035767A KR100205480B1 KR 100205480 B1 KR100205480 B1 KR 100205480B1 KR 1019960035767 A KR1019960035767 A KR 1019960035767A KR 19960035767 A KR19960035767 A KR 19960035767A KR 100205480 B1 KR100205480 B1 KR 100205480B1
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rubber composition
rubber
carbon black
silica
butadiene rubber
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KR19980016232A (en
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이석
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신형인
금호산업주식회사
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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
    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • 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
    • 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
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • C08L9/02—Copolymers with acrylonitrile
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof
    • C08L2666/08—Homopolymers or copolymers according to C08L7/00 - C08L21/00; Derivatives thereof

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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)
  • Tires In General (AREA)

Abstract

본 발명은 흡수성이 우수한 용액중합 SBR에 NBR을 블랜드한 고무성분에 카본블랙, 실란함유 실리카 및 디에틸렌 글리콜을 적용하여 제조되는 타이어 트래드용 고무조성물에 관한 것으로서, 본 발명의 고무 조성물은 인장특성, 내마모성이 우수하고, 특히 제동성(0℃ Tan δ)과 회전저항(60℃ Tan δ)이 대폭 개선된 고무조성물이다.The present invention relates to a rubber composition for tire treads prepared by applying carbon black, silane-containing silica and diethylene glycol to a rubber component blended with NBR in a solution-polymerized SBR having excellent water absorption. It is a rubber composition which is excellent in wear resistance and especially improved in braking resistance (0 ° C Tan δ) and rotational resistance (60 ° C Tan δ).

Description

실리카함유 타이어 트래드용 고무조성물Rubber composition for silica tread

본 발명은 승용차용 타이어 트래드에 적합한 고무조성물에 관한 것으로서, 보다 상세하게는 자동차의 연비특성 개선에 유효할 뿐만 아니라 재동성을 대폭 개선할 수 있는 타이어 트래드용 고무조성물에 관한 것이다.The present invention relates to a rubber composition suitable for tire treads for passenger cars, and more particularly, to a rubber tread composition for tire treads, which is not only effective for improving fuel efficiency characteristics of automobiles but also for significantly improving reworkability.

최근 환경규제 관련 자동차의 연비특성 개선은 자동차의 경량화, 연료효율증대 및 타이어의 노면과의 마찰저항감소이다. 이의 개선을 위해 타이어의 회전저항성능 개선 연구활동은 주로 트래드 부위에 집중되어 있다. 이는 노면과의 회전저항에 가장 영향을 미치는 부위가 타이어 트래드이며, 타이어 전체 회전저항손실중 트래드 부위가 약 45~50% 정도를 점유하기 때문이다.Recently, the improvement of fuel efficiency characteristics of automobiles related to environmental regulations is to reduce the weight of automobiles, increase fuel efficiency, and reduce the frictional resistance with the road surface of tires. In order to improve this, research activities to improve the rolling resistance of tires are mainly focused on the tread area. This is because the tire tread has the most influence on the rolling resistance with the road surface, and the tread portion occupies about 45-50% of the total tire rolling resistance loss.

이와 관련하여 타이어 트래드의 회전저항을 감소시키기 위해 입자경이 크고 표면특성이 우수한 카본블랙을 적용하거나 실리카 및 실란커플링제를 전량 또는 부분적으로 적용하여 회전저항 지표인 60℃ Tan δ값을 낮추려는 연구가 꾸준히 시도되고 있다. 일반적으로 회전저항 개선을 위해 적합한 카본블랙으로는 입자경이 크고 응집체특성중 웅집체크기가 크고 분포가 좁거나, 응집체크기가 작고 분포가 넓은 제품이 주로 사용되고 있다. 그러나 상기와 같은 카본블랙을 사용할 경우 동적특성중 반발탄성 및 발열특성은 개선된다 할지라도 Tan δ그라프가 제품특성에 따라 전이(shift)되는 특성이 있다. 즉, 회전저항 지표인 60℃ Tan δ값을 개선하기 위해 고보강성 카본블랙보다 입자경이 크고 표면특성(표면활성도)이 우수한 카본블랙을 적용할 경우 트랙션 지표인 0℃ Tan δ 값이 하락하는 문제점이 있다. 한편 실리카를 사용하는 경우는 제동성 및 회전저항 특성은 개선가능하나 기계적 특성 및 내마모성이 하락하는 문제점이 있다. 또한, 타이어 트래드 고무조성물에 주로 적용되는 고무성분은 래디칼 반응을 이용한 유화중합 스티렌부타디엔고무(SBR)와 부타디엔고무(BR)의 블랜드인 관계로 카본블랙 및 실리카성분과 친화도가 떨어져 분산불량 등으로 고무조성물의 물성이 최대한 발휘되지 못하는 문제점이 있다.In order to reduce the rolling resistance of the tire tread, a study to reduce the rolling resistance index of 60 ℃ Tan δ by applying carbon black with large particle size and excellent surface properties or by applying all or part of silica and silane coupling agent has been studied. It is constantly being tried. In general, suitable carbon blacks for improving rotational resistance are mainly used in products with large particle diameters, large lump size and narrow distribution, or small aggregate sizes and wide distribution. However, when using the carbon black as described above, even though the resilience and exothermic properties of the dynamic properties are improved, the Tan δ graph is shifted according to product characteristics. In other words, in order to improve the 60 ° C Tan δ value, which is a rolling resistance index, when the carbon black having a larger particle diameter and superior surface characteristics (surface activity) is applied than the high-reinforced carbon black, the traction index 0 ° C Tan δ value decreases. have. On the other hand, in the case of using silica, the braking property and the rolling resistance can be improved, but there is a problem in that the mechanical properties and the wear resistance decrease. In addition, the rubber component mainly applied to the tire tread rubber composition is a blend of emulsion polymerization styrene butadiene rubber (SBR) and butadiene rubber (BR) using a radical reaction, resulting in poor dispersion with carbon black and silica components. There is a problem that the physical properties of the rubber composition is not exhibited to the maximum.

따라서 본 발명에서는 0℃ Tan δ값 모두를 개선하여 타이어트래드 고무조성물의 제물성중 기계적 특성은 물론 제동성 및 회전저항이 개선된 고무조성물을 제공함을 목적으로 한다.Accordingly, an object of the present invention is to provide a rubber composition having improved braking property and rotational resistance, as well as mechanical properties, among the product properties of the tire tread rubber composition by improving all values of 0 ° C Tan δ.

상기의 목적을 달성하기 위한 본 발명에 따른 고무조성물은 용액중합 SBR과 아크릴로니트릴부타디엔 고무의 블랜드에 특정 물성의 카본블랙과 실란함유실리카(결합실리카) 및 디에틸렌글리콜을 적용하여 제조됨을 특징으로 한다.The rubber composition according to the present invention for achieving the above object is prepared by applying carbon black, silane-containing silica (bonded silica) and diethylene glycol of a specific physical property to a blend of solution polymerization SBR and acrylonitrile butadiene rubber do.

본 발명을 상세하게 설명하면 다음과 같다.The present invention will be described in detail as follows.

본 발명에서는 음이온 중합에 의한 용액중합 SBR(S-SBR)에 카본블랙 및 실리카 등의 충진제와 친화도가 높고 기계적 강도가 우수한 아크릴로니트릴부타디엔고무(NBR)를 1.5 : 0.1~3 : 1의 비율로 블랜드한 고무성분 100 중량부에 대하여 카본블랙 10~20phr 및 결합실리카 60~70phr을 적용하여 타이어 트래드 고무조성물의 동적성질( 0℃ 및 60℃ Tan δ)을 개선하였다.In the present invention, acrylonitrile butadiene rubber (NBR) having high affinity and excellent mechanical strength with fillers such as carbon black and silica in solution polymerization SBR (S-SBR) by anionic polymerization is in a ratio of 1.5: 0.1-3: 1. 10 to 20 phr of carbon black and 60 to 70 phr of bonded silica were applied to 100 parts by weight of the rubber component blended to improve the dynamic properties (0 ° C. and 60 ° C. Tan δ) of the tire tread rubber composition.

본 발명에서는 고무분자간 상호작용을 최대한으로 하기 위해 유기관능기로서 에톡시기를 갖는 실란커플링제(예, Si-69)를 미리 반응시킨 결합실리카를 사용하며, 가류시 실리카 입자의 응집특성에 의한 가류제류의 손실을 방지하기 위하여 디에틸렌글리콜(DEG)을 결합실리카 100 중량부에 대해 5~10 중량부로 가류전에 첨가한다.In the present invention, in order to maximize the interaction between rubber molecules, as the organic functional group, a silane coupling agent (eg, Si-69) having an ethoxy group is reacted in advance, and a vulcanizing agent due to the coagulation characteristics of silica particles during vulcanization is used. Diethylene glycol (DEG) is added to 5 to 10 parts by weight before vulcanization with respect to 100 parts by weight of bound silica to prevent the loss of.

본 발명에서 사용되는 용액중합 SBR의 바람직한 예로는 미세구조(Microstructure)중 시스(Cis) 함량이 35%이고 트랜스(Trans) 함량이 52%이며 비닐(Vinyl) 함량이 13%이며 유리전이온도(glass transition temperature)가 -78℃인 음이온 용액중합 SBR을 들 수 있다. 한편 아크릴로니트릴부타디엔고무의 바람직한 예로는 유리전이온도가 -22℃이며 아크릴로니트릴함량이 34%인 고무를 들 수 있다. 카본블랙은 요오드 흡착량 120~140mg/g, 디부틸프탈레이트 흡수가 110~130cc/100g, 착색도 110~120% 범위에 있는 것이 바람직하고, 결합 실리카는 BET 측정에 의한 표면적이 160~180m2/g, 디옥틸프탈레이트 흡수가 240~260cc/100g 범위이고 실란커플링제가 6~10% 함유된 것이 바람직하다.Preferred examples of the solution polymerization SBR used in the present invention include a cis content in the microstructure of 35%, a trans content of 52%, a vinyl content of 13%, and a glass transition temperature (glass). anion solution polymerization SBR having a transition temperature of -78 ° C. On the other hand, preferred examples of acrylonitrile butadiene rubber include a rubber having a glass transition temperature of -22 ° C and an acrylonitrile content of 34%. Carbon black preferably has an iodine adsorption amount of 120 to 140 mg / g, dibutyl phthalate absorption of 110 to 130 cc / 100 g, and a coloring degree of 110 to 120%, and the bonded silica has a surface area of 160 to 180 m 2 / g by BET measurement. It is preferable that the dioctyl phthalate absorption ranges from 240 to 260 cc / 100 g and contains 6 to 10% of the silane coupling agent.

이하 실시예 및 비교예를 통하여 본 발명을 상세하게 설명한다.Hereinafter, the present invention will be described in detail through Examples and Comparative Examples.

[실시예 1~3 및 비교예 1~3][Examples 1-3 and Comparative Examples 1-3]

하기 표 1에 나타낸 조성으로 통상의 방법에 따라 고무조성물을 제조한 후, 그 물성을 표준방법에 따라 측정하였고, 결과는 표 2와 같다.To prepare a rubber composition according to the conventional method with the composition shown in Table 1, the physical properties were measured according to the standard method, the results are shown in Table 2.

상기 표 2의 결과로부터 알 수 있는 바와 같이, 용액중합 SBR/NBR 블랜드에 특정 물성의 카본블랙 및 결합실리카를 적정량 적용한 본 발명의 고무조성물은 유화중합 SBR/BR 블랜드로 된 비교예의 조성물에 비해 인장특성개선은 물론 내마모성을 나타내는 피코 손실량도 양호하게 개선되었으며, 결합실리카 및 NBR 영향으로 발열특성은 비교예의 조성물과 동등수준으로 유지되면서, 제동성(Traction) 및 회전저항(Rolling resistance) 지표인 0℃와 60℃ Tan δ값이 대폭 개선되었다.As can be seen from the results of Table 2, the rubber composition of the present invention, in which a suitable amount of carbon black and bonded silica of a specific physical property is applied to the solution-polymerized SBR / NBR blend, the tensile composition is compared to the composition of the comparative example of the emulsion-polymerized SBR / BR blend. Pico loss, which shows not only improved properties but also wear resistance, has been improved. The exothermic properties are maintained at the same level as the composition of the comparative example due to the effect of bonding silica and NBR, and the braking and rolling resistance index is 0 ° C. And Tan δ value of 60 ℃ were greatly improved.

Claims (4)

용액중합 스티렌 부타디엔고무(SBR)와 아크릴로니트릴부타디엔고무(NBR)로 된 고무성분 100 중량부에 대하여 카본블랙 10~20phr, 실란커플링제가 결합된 결합실리카 60~70phr과, 상기 결합실리카 100 중량부에 대하여 디에틸렌글리콜 5~10 중량부를 포함하는 것을 특징으로 하는 타이어 트래드용 고무조성물.10 to 20 phr of carbon black, 60 to 70 phr of bonded silica combined with a silane coupling agent, and 100 weight of the bonded silica based on 100 parts by weight of a rubber component composed of solution-polymerized styrene butadiene rubber (SBR) and acrylonitrile butadiene rubber (NBR). A rubber composition for tire treads, comprising 5 to 10 parts by weight of diethylene glycol based on parts. 제1항에 있어서, 상기 용액중합 스티렌 부타디엔 고무는 시스함량 35%, 트랜스함량 52%, 비닐함량 13%, 유리전이온도 -78℃인 음이온 용액중합 스티렌 부타디엔고무이고, 상기 아크릴로니트릴부타디엔고무는 아크릴로니트릴 함량 34%, 유리전이온도 -22℃인 것임을 특징으로 하는 타이어 트래드용 고무조성물.The method of claim 1, wherein the solution-polymerized styrene butadiene rubber is an anionic solution-polymerized styrene butadiene rubber having a cis content of 35%, trans content 52%, vinyl content 13%, glass transition temperature -78 ℃, the acrylonitrile butadiene rubber A rubber composition for tire treads, characterized in that the acrylonitrile content is 34%, the glass transition temperature is -22 ℃. 제1항에 있어서, 상기 카본블랙은 요오드흡착량 120~140mg/g, 디부틸프탈레이트 흡수가 110~130cc/100g, 착색도 110~120%인 카본블랙임을 특징으로 하는 타이어 트래드용 고무조성물.The rubber composition for tire treads according to claim 1, wherein the carbon black is carbon black having an iodine adsorption amount of 120 to 140 mg / g, a dibutyl phthalate absorption of 110 to 130 cc / 100 g, and a coloring degree of 110 to 120%. 제1항에 있어서, 상기 실란함유 실리카는 BET 측정에 의한 표면적이 160~180m2/g, 디옥틸프탈레이트 흡수가 240~260cc/100g이며, 유기관능기로서 에톡시기를 갖는 실란커플링제를 6~10% 함유한 결합실리카임을 특징으로 하는 타이어 트래드용 고무조성물.The silane-containing silica according to claim 1, wherein the silane-containing silica has a surface area of 160 to 180 m 2 / g, dioctylphthalate absorption of 240 to 260 cc / 100 g by BET measurement, and 6 to 10 silane coupling agent having an ethoxy group as an organic functional group. A rubber composition for tire treads, characterized in that the binding silica containing 20%.
KR1019960035767A 1996-08-27 1996-08-27 Tire tread rubber composition containing silica KR100205480B1 (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000001234A (en) * 1998-06-10 2000-01-15 강한규 Rheological quality improved band-plylubricant
KR100437687B1 (en) * 2001-03-27 2004-06-26 금호타이어 주식회사 Dispersion-Improved Silica-filled SBR compounds Containing NSBR for Tire

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100464985B1 (en) * 2001-12-17 2005-01-05 한국타이어 주식회사 Rubber composition for tire hump strip improved thermal aging property

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20000001234A (en) * 1998-06-10 2000-01-15 강한규 Rheological quality improved band-plylubricant
KR100437687B1 (en) * 2001-03-27 2004-06-26 금호타이어 주식회사 Dispersion-Improved Silica-filled SBR compounds Containing NSBR for Tire

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