KR100351007B1 - Tire tread composition - Google Patents
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- KR100351007B1 KR100351007B1 KR1020000027689A KR20000027689A KR100351007B1 KR 100351007 B1 KR100351007 B1 KR 100351007B1 KR 1020000027689 A KR1020000027689 A KR 1020000027689A KR 20000027689 A KR20000027689 A KR 20000027689A KR 100351007 B1 KR100351007 B1 KR 100351007B1
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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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- 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
- C08K9/00—Use of pretreated ingredients
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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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
본 발명은 타이어 트레드용 고무 조성물에 관한 것으로서, 표면이 개질된 카본블랙을 보강제로 사용하고, 이를 비닐기를 다량 함유하는 용액중합 스타이렌-부타디엔 공중합체 및 폴리부타디엔 고무와 선혼합하고, 여기에 유리전이온도가 높은 고스타이렌 함량의 유화중합 스타이렌-부타디엔 공중합체를 혼합하여 얻어진 고무 조성물로서, 이는 흡장고무층(Bound rubber) 구조를 제어할 수 있게 되어 저온 및 고온에서의 점탄성 특성과 마모성능이 동시에 개선되어 요구되는 타이어 성능, 즉 젖은 노면에서의 제동성, 저회전저항 및 내구성을 동시에 개선할 수 있다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber tread rubber composition, which uses carbon black with a modified surface as a reinforcing agent, and premixes it with a solution-polymerized styrene-butadiene copolymer and a polybutadiene rubber containing a large amount of vinyl groups. A rubber composition obtained by mixing a high styrene-containing emulsion-polymerized styrene-butadiene copolymer with high transition temperature, which can control the structure of the boundary rubber layer, thereby improving the viscoelastic properties and wear performance at low and high temperatures. At the same time, it is possible to improve the required tire performance, i.e. braking on wet roads, low rolling resistance and durability at the same time.
Description
본 발명은 타이어 트레드용 고무 조성물에 관한 것으로서, 더욱 상세하게는 유리전이온도가 다른 고무를 순차적으로 혼합하고, 표면개질된 고보강성 카본블랙을 보강제로 첨가한 타이어 트레드용 고무 조성물에 관한 것이다.The present invention relates to a rubber tread rubber composition, and more particularly, to a rubber tread rubber composition in which rubbers having different glass transition temperatures are sequentially mixed and surface modified high reinforcement carbon black is added as a reinforcing agent.
최근들어, 경량의 트럭용 래디알 타이어에 있어서 그 요구성능이 종래 마모 및 내구성 중심에서 이제는 부가적으로 젖은 노면에서의 제동성 및 저연비성까지가 요구되고 있다.In recent years, the demand for performance in light truck radial tires has been demanded from the conventional wear and durability centers to braking and low fuel efficiency on wet roads.
이와같은 요구에 부합하기 위해 고무 조성물에 사용되는 배합제도 종래의 천연고무 중심에서 제동성능을 보강하기 위해 합성고무, 특히 스타이렌-부타디엔 공중합체 및 폴리부타디엔 등을 용도에 따라 단독으로 또는 블렌딩하여 사용하고 있으며, 점차로 그 사용 비중이 커지고 있다. 이에 따라서, 카본블랙도 천연고무계에서는 ISAF 또는 SAF급의 고보강성 카본블랙이 사용되고, 합성고무계에서는 발열측면 등을 고려하여 HAF-HS급 등이 사용되고 있다.In order to meet such demands, the compounding agent used in the rubber composition is used alone or blended with synthetic rubber, in particular, styrene-butadiene copolymer and polybutadiene, to reinforce braking performance in conventional natural rubber centers. It is increasingly being used. Accordingly, carbon black is also used in the natural rubber system, ISAF or SAF grade of high reinforcement carbon black, and synthetic rubber system is used HAF-HS grade in consideration of the heat generation side.
그러나, 마모-내구-제동-저연비의 성능은 상호간에 이율배반적인 특성을 지니고 있어 이러한 성능을 동시에 향상시키거나 균형을 맞추는 것은 여전히 난제로 남아 있다.However, the performance of wear-durability-braking-low fuel economy has mutually betrayal characteristics, so it is still difficult to improve or balance these performances simultaneously.
이를 해결하기 위한 종래의 기술로는 제동성 및 마모 향상을 위해 합성고무, 즉 스타이렌-부타디엔 공중합체 및 폴리부타디엔 고무를 혼합 사용하게 되는데, 저발열 및 저연비의 문제로 SAF급과 같은 고보강성 카본블랙은 적용하지 못하거나, 그 사용량을 줄이는 방법을 채택하고 있다. 이와같은 카본블랙 선택에 있어서의 제한이 결과적으로 고무의 강도를 저하시켜 마모 등에서는 불리하다.Conventional technology to solve this problem is to use a mixture of synthetic rubber, that is, styrene-butadiene copolymer and polybutadiene rubber to improve the braking properties and wear, high reinforcement carbon such as SAF grade due to low heat generation and low fuel consumption Black doesn't apply or adopts a method that reduces its usage. Such a limitation in the selection of carbon black consequently lowers the strength of the rubber and is disadvantageous in wear and the like.
또한, 종래의 혼합방법 상으로는 충진고무 조성물 내에 형성되는 보강고무 또는 흡장고무(bound rubber)의 구조를 제어할 수 없기 때문에 다양한 온도영역에서 발현되는 제반성능들의 균형있는 제어는 불가능하였다.In addition, in the conventional mixing method, it is not possible to control the structure of the reinforcement rubber or the bound rubber formed in the filling rubber composition, so that it is impossible to control the balanced performance of various performances expressed in various temperature ranges.
이에 본 발명자는 유리전이온도가 다른 고무를 순차적으로 혼합하고, 여기에 표면개질된 고보강성의 카본블랙을 첨가하여 고무조성물 내의 보강고무 구조를 제어할 경우, 저온 및 고온에서의 점탄성 특성과 동시에 마모성능이 개선되어 젖은 노면에서의 제동성, 저연비 및 내구성을 동시에 개선할 수 있음을 알게되어 본 발명을 완성하게 되었다.Accordingly, the present inventors sequentially mixed rubbers having different glass transition temperatures, and added the surface-modified high reinforcement carbon black to control the reinforcement rubber structure in the rubber composition, and at the same time wear and viscoelastic properties at low and high temperatures It has been found that the performance can be improved to simultaneously improve braking performance, low fuel consumption and durability on wet roads, thereby completing the present invention.
따라서, 본 발명의 목적은 저온 및 고온에서의 점탄성 특성과 동시에 마모성능이 개선되어 젖은 노면에서의 제동성, 저연비 및 내구성을 동시에 개선할 수 있는 타이어 트레드용 고무 조성물을 제공하는 데 있다.Accordingly, it is an object of the present invention to provide a rubber composition for tire treads which can improve the viscoelastic properties at low and high temperatures and at the same time improve braking performance, low fuel consumption and durability on wet road surfaces.
이와같은 목적을 달성하기 위한 본 발명의 타이어 트레드용 고무 조성물은 고정 스타이렌 함량이 40중량%인 유화중합 스타이렌-부타디엔 공중합체 30∼80중량부; 스타이렌 함량 23중량% 이하이고, 부타디엔부의 비닐결합 함량이 전체 부타디엔부 함량 중 60중량% 이상인 용액중합 스타이렌-부타디엔 공중합체 10∼40중량부; 및 폴리부타디엔 고무 10∼30중량부를 원료고무로 하고; 질소흡착 비표면적이 125∼150㎡/g이고 DBP 흡유량이 115∼135㎖/100g, 그리고 비착색력이 130이상인 표면개질된 카본블랙을 보강제로서 함유한 것임을 그 특징으로 한다.The rubber composition for tire treads of the present invention for achieving the above object comprises 30 to 80 parts by weight of an emulsion-polymerized styrene-butadiene copolymer having a fixed styrene content of 40% by weight; 10 to 40 parts by weight of a solution-polymerized styrene-butadiene copolymer having a styrene content of 23% by weight or less and a vinyl bond content of butadiene portion of 60% by weight or more of the total butadiene portion content; And 10 to 30 parts by weight of polybutadiene rubber as raw material rubber; The nitrogen adsorption specific surface area is 125 to 150 m 2 / g, DBP oil absorption is 115 to 135ml / 100g, and the surface-modified carbon black having a specific coloring power of 130 or more as a reinforcing agent.
이와같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
본 발명에 따른 타이어 트레드용 고무 조성물은 원료고무로서 유리전이온도가 서로 다른 것을 혼합하여 사용하는 바, 구체적으로는 고정 스타이렌 함량이 40중량%인 유화중합 스타이렌-부타디엔 공중합체 30∼80중량부; 스타이렌 함량 23중량% 이하이고, 부타디엔부의 비닐결합 함량이 전체 부타디엔부 함량 중 60중량% 이상인 용액중합 스타이렌-부타디엔 공중합체 10∼40중량부; 및 폴리부타디엔 고무 10∼30중량부를 원료고무로 한다.The rubber composition for tire treads according to the present invention uses a mixture of different glass transition temperatures as a raw material rubber, specifically, 30 to 80 weight of an emulsion polymerization styrene-butadiene copolymer having a fixed styrene content of 40% by weight. part; 10 to 40 parts by weight of a solution-polymerized styrene-butadiene copolymer having a styrene content of 23% by weight or less and a vinyl bond content of butadiene portion of 60% by weight or more of the total butadiene portion content; And 10 to 30 parts by weight of polybutadiene rubber as raw material rubber.
여기서, 비닐함량이 높은 용액중합 스타이렌-부타디엔 공중합체와 폴리부타디엔 고무는 상기 원료고무 성분 중 상대적으로 유리전이온도가 낮고 반응성이 높은 비닐기를 함유하는 것이며, 스타이렌 함량이 높은 유화중합 스타이렌-부타디엔 고무는 상대적으로 유리전이온도가 높은 것에 해당된다.Here, the solution-polymerized styrene-butadiene copolymer and polybutadiene rubber having a high vinyl content include vinyl groups having a relatively low glass transition temperature and high reactivity among the raw material rubber components, and emulsified polymerization styrene having a high styrene content. Butadiene rubber corresponds to a relatively high glass transition temperature.
이들 원료고무를 일시에 첨가하는 것이 아니고, 우선은 상대적으로 유리전이온도가 낮고 반응성이 높은 비닐기를 함유하는 용액중합 스타이렌-부타디엔 공중합체 및 폴리부타디엔 고무와 카본블랙을 선혼합함으로써 카본블랙 흡장 고무층(bound rubber)의 성분을 저유리전이온도 및 고온도의존화하도록 한다.Rather than adding these raw rubbers at one time, first of all, a solution-polymerized styrene-butadiene copolymer containing a vinyl group having a relatively low glass transition temperature and high reactivity, a polybutadiene rubber, and carbon black are premixed with a carbon black occluding rubber layer. Dependence of low rubber transition temperature and high temperature on components of bound rubber.
그 다음, 여기에 상대적으로 유리전이온도가 높은 고스타이렌 함량의 유화중합 스타이렌-부타디엔 공중합체를 혼합하여 상대적으로 운동성이 큰 자유고무상(rubber matrix phase)를 형성토록 하여 고무조성물 내의 보강고무구조(bound rubber structure)를 제어하도록 한다.Next, a high styrene-containing emulsion-polymerized styrene-butadiene copolymer having a relatively high glass transition temperature is mixed to form a rubber matrix phase having a relatively high mobility, thereby reinforcing rubber in the rubber composition. Take control of the bound rubber structure.
그런데, 일반적으로 스타이렌-부타디엔 공중합체나 폴리부타디엔 고무를 혼합사용하는 경우에는 저발열 및 저연비의 문제로 SAF급과 같은 고보강성 카본블랙을 적용할 수 없어 내마모성이 떨어지는 문제가 있었다.However, in general, when styrene-butadiene copolymer or polybutadiene rubber is mixed and used, high reinforcement carbon black such as SAF grade cannot be applied due to low heat generation and low fuel consumption, thereby resulting in poor wear resistance.
따라서, 본 발명에서는 표면이 개질된 고보강성의 카본블랙을 적용하는 바, 구체적으로는 질소흡착 비표면적이 125∼150㎡/g이고 DBP 흡유량이 115∼135㎖/100g, 그리고 비착색력이 130이상인 표면활성도를 높인 고보강성 카본블랙을 사용하는 것이 바람직하다.Therefore, in the present invention, the surface-modified high-reinforcement carbon black is applied. Specifically, the nitrogen adsorption specific surface area is 125 to 150 m 2 / g, the DBP oil absorption is 115 to 135 ml / 100 g, and the specific coloring power is 130 or more. It is preferable to use high reinforcing carbon black with high surface activity.
한편, 원료고무 중 고정스타이렌 함량이 40중량%인 유화중합 스타이렌-부타디엔 공중합체는 30∼80중량부로 사용하는 바, 만일 그 함량이 30중량부 미만이면 트랙션 성능 또는 그립력이 저하되는 문제가 있고, 80중량부를 초과 하면 발열이 높아지는 문제가 발생될 수 있다.Meanwhile, the emulsion-polymerized styrene-butadiene copolymer having a fixed styrene content of 40% by weight in the raw material rubber is used at 30 to 80 parts by weight. If the content is less than 30 parts by weight, the traction performance or the grip force is deteriorated. And, if more than 80 parts by weight may cause a problem that the heat generation increases.
그리고, 부타디엔부의 비닐결합 함량이 전체 부타디엔부 함량 중 60중량% 이상이고, 스타이렌 함량 23중량% 이하인 용액중합 스타이렌-부타디엔 공중합체를 10∼40중량부로 사용하는 바, 만일 그 함량이 10중량부 미만이면 저연비 성능이 불리하고, 40중량부를 초과하면 내마모 성능이 저하된다.In addition, if the vinyl bond content of the butadiene portion is not less than 60% by weight of the total butadiene portion, and the solution-polymerized styrene-butadiene copolymer having a styrene content of 23% by weight or less is used in an amount of 10 to 40 parts by weight. If it is less than a part, low fuel consumption performance is disadvantageous, and if it exceeds 40 weight part, abrasion resistance falls.
마지막으로 폴리부타디엔 고무의 함량은 10∼30중량부로 사용하는 것이 제동성능과 내마모 성능의 균형 및 가공성에 있어 바람직하다.Finally, the content of polybutadiene rubber is preferably 10 to 30 parts by weight in terms of balance and workability of braking performance and wear resistance.
한편, 상기와 같은 표면개질된 고보강성의 카본블랙은 45 ∼ 85 중량부로 첨가되는 것이 바람직하다.On the other hand, the surface-modified high reinforcement carbon black as described above is preferably added to 45 to 85 parts by weight.
그밖에 본 발명의 타이어 트레드용 고무 조성물에는 통상의 고무 배합제들, 예를들어 산화아연, 스테아린산, 유황, 촉진제 등을 첨가할 수 있음을 물론이다.In addition, the rubber composition for tire tread of the present invention can be added to the conventional rubber compounding agents, for example, zinc oxide, stearic acid, sulfur, accelerators and the like.
이하, 본 발명을 실시예에 의거 상세히 설명하면 다음과 같은 바, 본 발명이 실시예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.
실시예 1Example 1
다음 표 1에 나타낸 바와 같은 조성 및 함량으로 먼저, SBR3(비닐함량 63%인 용액중합 스타이렌-부타디엔 공중합체)와 BR(폴리부타디엔 고무)과 카본블랙C(표면개질된 고보강성 카본블랙)을 선혼합하고, 여기에 SBR2(스타이렌 함량 40%인 유화중합 스타이렌-부타디엔 고무)와 그밖의 첨가제를 배합하여 고무시편을 제조하였다.To the composition and content as shown in Table 1, SBR3 (solution polymerization styrene-butadiene copolymer of 63% vinyl content), BR (polybutadiene rubber) and carbon black C (surface modified high reinforcement carbon black) Premixed, rubber specimens were prepared by mixing SBR2 (emulsion polymerization styrene-butadiene rubber having 40% styrene content) and other additives.
비교예 1∼4Comparative Examples 1 to 4
다음 표 1에 나타낸 바와 같은 조성 및 함량으로 통상의 방법에 따라 동시에 모든 화합물을 투입하고, 배합하여 고무시편을 제조하였다.In the following compositions and contents as shown in Table 1, all compounds were simultaneously added and combined in a conventional manner to prepare rubber specimens.
실험예Experimental Example
상기 실시예 1 및 비교예 1∼4에 따라 얻어진 고무시편에 대하여 경도, 모듈러스, 인장강도, 동적손실계수, 람몬마모지수, 흡장고무층 함량을 측정하여 그 결과를 다음 표 2에 나타내었다.For the rubber specimens obtained according to Example 1 and Comparative Examples 1 to 4, the hardness, modulus, tensile strength, dynamic loss coefficient, Rammon abrasion index, and occlusive rubber layer content were measured, and the results are shown in Table 2 below.
상기 표 1의 결과로부터, 실시예 1에서와 같이 표면개질된 카본블랙을 사용하고, 유리전이온도가 서로 다른 원료고무를 혼합하여 이들을 순차적으로 혼합한 경우 저온 및 고온에서의 점탄성 특성과 동시에 마모성능이 개선되는 것을 알 수있다.From the results of Table 1, when using a surface-modified carbon black as in Example 1, by mixing the raw material rubbers having different glass transition temperatures and sequentially mixing them, the viscoelastic properties at the low temperature and high temperature at the same time wear performance It can be seen that this is improved.
이상에서 상세히 설명한 바와 같이, 본 발명에 따라 표면이 개질된 카본블랙을 보강제로 사용하고, 이를 비닐기를 다량 함유하는 용액중합 스타이렌-부타디엔 공중합체 및 폴리부타디엔 고무와 선혼합하고, 여기에 유리전이온도가 높은 고스타이렌 함량의 유화중합 스타이렌-부타디엔 공중합체를 혼합하여 얻어진 고무 조성물의 경우, 흡장고무층 구조를 제어할 수 있게 되어 저온 및 고온에서의 점탄성 특성과 동시에 마모성능이 개선되어 요구되는 타이어 성능, 즉 젖은 노면에서의 제동성, 저회전저항 및 내구성을 동시에 개선할 수 있다.As described in detail above, the surface-modified carbon black according to the present invention is used as a reinforcing agent, and it is premixed with a solution-polymerized styrene-butadiene copolymer and a polybutadiene rubber containing a large amount of vinyl groups, and the glass transition thereto. In the case of a rubber composition obtained by mixing a high-temperature, high-styrene emulsion-polymerized styrene-butadiene copolymer, it is possible to control the occluded rubber layer structure to improve the viscoelastic properties at low and high temperatures and at the same time improve the wear performance. Tire performance, i.e. braking on wet roads, low rolling resistance and durability can be improved simultaneously.
Claims (2)
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020000027689A KR100351007B1 (en) | 2000-05-23 | 2000-05-23 | Tire tread composition |
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| Application Number | Priority Date | Filing Date | Title |
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| KR1020000027689A KR100351007B1 (en) | 2000-05-23 | 2000-05-23 | Tire tread composition |
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| KR20010106747A KR20010106747A (en) | 2001-12-07 |
| KR100351007B1 true KR100351007B1 (en) | 2002-08-30 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100888135B1 (en) | 2007-10-31 | 2009-03-13 | 금호타이어 주식회사 | Tread rubber composition having improved abrasion resistance |
| KR101119601B1 (en) | 2009-12-01 | 2012-03-06 | 한국타이어 주식회사 | Tread Composition and a Tread comprising the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20030092376A (en) * | 2002-05-29 | 2003-12-06 | 금호타이어 주식회사 | Good dry and wet stop distance PCR Tread compound |
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2000
- 2000-05-23 KR KR1020000027689A patent/KR100351007B1/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100888135B1 (en) | 2007-10-31 | 2009-03-13 | 금호타이어 주식회사 | Tread rubber composition having improved abrasion resistance |
| KR101119601B1 (en) | 2009-12-01 | 2012-03-06 | 한국타이어 주식회사 | Tread Composition and a Tread comprising the same |
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| Publication number | Publication date |
|---|---|
| KR20010106747A (en) | 2001-12-07 |
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