KR20040001728A - Tire Sidewall Compound - Google Patents

Tire Sidewall Compound Download PDF

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KR20040001728A
KR20040001728A KR1020020037043A KR20020037043A KR20040001728A KR 20040001728 A KR20040001728 A KR 20040001728A KR 1020020037043 A KR1020020037043 A KR 1020020037043A KR 20020037043 A KR20020037043 A KR 20020037043A KR 20040001728 A KR20040001728 A KR 20040001728A
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phr
rubber
rubber composition
composition
epdm
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KR1020020037043A
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Korean (ko)
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조선이
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금호타이어 주식회사
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Publication of KR20040001728A publication Critical patent/KR20040001728A/en

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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
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • 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
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • 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

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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

PURPOSE: Provided is a rubber composition for tire side wall, which has improved anti-fatigue, anti-cracking, anti-ozone, adhesion and tensile properties without adding any conventional anti-aging agents. CONSTITUTION: The rubber composition for tire side wall comprises a blend formed of 15-80 phr of a natural rubber, 15-80 phr of a solid EPDM(ethylene propylene diene monomer) rubber and 5-40 phr of a liquid EPDM rubber as a base rubber. In particular, the solid and liquid EPDM rubbers comprise ethylene and propylene in the weight ratio of 45/55-80/20 and a diene in the amount of up to 13 wt%. Further, the rubber composition optionally further comprises a conventional additive, such as carbon black, zinc, steric acid, processing oil, a vulcanizing accelerator and sulfur.

Description

타이어 사이드월 고무조성물{Tire Sidewall Compound}Tire sidewall rubber composition {Tire Sidewall Compound}

본 발명은 타이어 사이드월용 고무 조성물로서, 보다 상세하게는 원료 고무의 성분으로 액상 이피디엠 고무를 적용하여 내오존 특성과 내피로 특성이 우수하면서도 접착성이 우수한 타이어 사이드월용 고무 조성물에 관한 것이다.The present invention relates to a rubber composition for a tire sidewall, and more particularly, to a rubber composition for a tire sidewall by applying liquid EPDM rubber as a component of a raw rubber, and having excellent ozone resistance and fatigue resistance and excellent adhesiveness.

사이드월 고무 조성물은 크게 두가지로 분류되며, 전통적인 천연고무/부타디엔고무, 천연고무/스티렌부타디엔공중합체/부타디엔고무의 블랜드 시스템에 PPD계의 노화방지제가 도입된 것과, 화학적 노화방지제를 전혀 적용하지 않는 천연고무/이피디엠 블랜드 시스템을 이용하는 것이 있다.There are two types of sidewall rubber compositions, PPD-based antioxidants are introduced in blend systems of traditional natural rubber / butadiene rubber, natural rubber / styrenebutadiene copolymer / butadiene rubber, and no chemical antioxidants are applied. Natural rubber / IPDM blend systems are used.

노화방지제를 사용하는 천연고무/부타디엔고무 블랜드 시스템은 대략 2년 정도의 크랙 방지효과가 있으며, 그 후에는 미세한 크랙이 다량 발생하는 문제가 있다. 또한 사용한 노화방지제가 제조공정 중에 열이력을 받아 소모되거나 다른 컴포넌트로 이동하여 감소되고, 표면으로 이동하여 외관오염을 발생시키기도 한다.Natural rubber / butadiene rubber blend system using an anti-aging agent has a crack prevention effect of about two years, after which there is a problem that a large amount of fine cracks occur. In addition, the used anti-aging agent is consumed by the heat history during the manufacturing process, or reduced by moving to other components, and may move to the surface to cause appearance contamination.

이피디엠 고무의 특징은 에틸렌과 프로필렌이 포화된 구조로서 폴리머 주쇄상에 가지 구조가 없어서 오존이 결합할 수 있는 약한 결합을 가지고 있지 않다.따라서 여기에 이중결합을 가진 디엔(diene monomer)을 소량 첨가하여 가교 결합을 형성하고 있다.The characteristic of EPDM rubber is that ethylene and propylene are saturated, and there is no branched structure on the polymer main chain, so it has no weak bond to which ozone can bind. Therefore, a small amount of diene monomer having double bond is added thereto. To form a crosslink.

상기와 같은 이피디엠 고무는 내피로 특성(DMFC, FTF 등) 및 내오존 특성에 있어서 탁월한 성능을 발휘할 수 있어 노화방지제를 사용하지 않아도 되는 장점을 가지고 있으나, 화합물의 구조가 거의 포화되어 있기 때문에 타 컴포넌트와의 접착성이 현저히 떨어져 현재까지 잘 적용되고 있지 않는 실정이다.The above EPDM rubber has the advantage of not having to use an anti-aging agent because it can exert excellent performance in fatigue resistance (DMFC, FTF, etc.) and ozone resistance, but since the structure of the compound is almost saturated, The adhesiveness with the component is remarkably poor, so it is not applied well until now.

본 발명자는 사이드월용 고무 조성물로서 노화방지제를 사용하지 않으면서, 내노화 특성이 우수한 이피디엠 고무를 사용하는 경우 단점으로 지적되던 접착성의 하락을 해결하기 위한 방안을 강구하여 오던 중, 액상 이피디엠 고무를 원료 고무로 적량 첨가하는 경우 위 조건을 충족할 수 있음을 알아내고서 본 발명을 완성하게 되었다.The present inventors have been devising a way to solve the deterioration of adhesiveness, which has been pointed out as a disadvantage when using EPDM rubber having excellent aging resistance without using an anti-aging agent as a rubber composition for sidewalls. The present invention has been completed by finding out that the above conditions can be met when adding a proper amount to the raw rubber.

따라서 본 발명의 목적은 내오존 특성과 내피로 특성이 우수하면서도 접착성이 우수한 타이어 사이드월용 고무조성물을 제공함에 있다.Accordingly, an object of the present invention is to provide a rubber composition for tire sidewalls having excellent ozone resistance and fatigue resistance and excellent adhesion.

본 발명은 타이어 사이드월용 고무 조성물로서,The present invention is a rubber composition for tire sidewalls,

천연 고무 20∼80phr과, 고상 이피디엠 고무 20∼80phr 및 액상 이피디엠 고무 5∼40 phr로 블랜드된 고무를 원료 고무로 하는 사이드월용 고무 조성물을 포함한다.The rubber composition for sidewall which uses as a raw material rubber the rubber blended with 20-80 phr of natural rubber, 20-80 phr of solid EPDM rubber, and 5-40 phr of liquid EPDM rubber is included.

액상 이피디엠 고무는 고상 이피디엠 고무가 지니는 다른 컴포넌트와의 접착성 저하의 단점을 극복하기 위해 첨가된다. 액상 이피디엠 고무는 바람직하기로는 원료고무 100phr 내에 5∼40phr로 첨가된다. 따라서 본 발명에 의한 사이드월 고무조성물에 적용되는 원료 고무는 기존의 천연 고무 15∼80phr, 고상 이피디엠 고무 15∼80phr과 함께 액상 이피디엠 고무 5∼40phr이 배합되어 원료 고무 100phr을 구성한다.Liquid IPDM rubber is added to overcome the disadvantages of poor adhesion with other components of the solid EPDM rubber. The liquid IPDM rubber is preferably added at 5 to 40 phr in 100 phr of the raw rubber. Therefore, the raw material rubber applied to the sidewall rubber composition according to the present invention is composed of 15 to 80 phr of conventional natural rubber and 15 to 80 phr of solid phase EPDM rubber to form 5 to 40 phr of liquid EPDM rubber to form 100 phr of raw rubber.

상기 액상 이피디엠 고무의 첨가량이 5phr 미만인 경우에는 요구되는 접착성을 얻기가 곤란하고, 40phr을 초과하는 경우에는 초과분에 따른 물성의 개선효과가 미미하여 상기 범위로 제한하는 것이 권장된다.If the added amount of the liquid EPDM rubber is less than 5 phr, it is difficult to obtain the required adhesiveness, and if it exceeds 40 phr, it is recommended to limit the above range because the improvement of physical properties due to the excess is insignificant.

상기 고상 및 액상 이피디엠 고무의 조성은 원하는 정도의 물성개선 및 접착성의 증진을 위해서는 바람직하기로는 에틸렌/프로필렌의 함량비가 45/55∼80/20(중량%/중량%)이며, 디엔(ENB 또는 DCPD) 함량이 13중량% 이하를 만족하는 고무로부터 선택된다.The composition of the solid and liquid EPDM rubber is preferably 45/55 to 80/20 (wt% / wt%) of ethylene / propylene in order to improve the properties and adhesion of the desired degree, and diene (ENB or DCPD) content is selected from rubbers that satisfy 13% by weight or less.

본 발명의 사이드월 고무 조성물은 통상의 첨가물로서 카본블랙, 아연화, 스테아린산, 공정오일, 가류촉진제 및 유황을 포함할 수 있다. 이 경우 각 성분의 바람직한 조성비는 카본블랙 20∼80phr, 아연화 1∼5phr, 스테아린산 1∼5phr, 공정오일 1∼20phr, 가류촉진제 1∼3phr 및 유황 1∼5phr로 배합될 수 있다.The sidewall rubber composition of the present invention may include carbon black, zincated, stearic acid, process oil, vulcanization accelerator, and sulfur as common additives. In this case, the preferred composition ratio of each component may be blended with 20 to 80 phr of carbon black, 1 to 5 phr of zincated, 1 to 5 phr of stearic acid, 1 to 20 phr of process oil, 1 to 3 phr of vulcanization accelerator, and 1 to 5 phr of sulfur.

이하 본 발명의 내용을 실시예에 의해 보다 상세하게 설명하기로 한다. 다만이들 실시예는 본 발명의 내용을 이해하기 위해 제시되는 것일 뿐 본 발명의 권리범위가 이들 실시예에 한정되어지는 것으로 해석되어져서는 아니된다.Hereinafter, the content of the present invention will be described in more detail with reference to Examples. However, these examples are only presented to understand the content of the present invention and should not be construed that the scope of the present invention is limited to these embodiments.

<비교예 1> 고무조성물의 제조Comparative Example 1 Preparation of Rubber Composition

하기 표 1에 나타난 바와 같이 천연고무 50phr, 부타디엔 고무 50phr로 구성되는 원료고무 100 phr을 기준으로 카본블랙 N660 50 phr, 노화방지제(HPPD) 2phr, 노화방지제(TMDQ) 2phr, 왁스 2phr, 점착제(Dyphene-8318) 4phr, 아연화 3phr, 스테아린산 2phr, 공정오일(aromatic) 10phr, 가류촉진제(TBBS) 1phr, 유황 2phr을 첨가하여 밴버리 믹서(Banbury mixer)에 배합하여 160℃의 온도에서 방출시켜 사이드월 고무조성물을 제조하였다. 생성된 고무조성물의 물성시험 결과는 표 2∼4에 나타내었다.As shown in Table 1, based on 100 phr of raw rubber consisting of 50 phr of natural rubber and 50 phr of butadiene rubber, carbon black N660 50 phr, anti-aging agent (HPPD) 2 phr, anti-aging agent (TMDQ) 2 phr, wax 2 phr, adhesive (Dyphene) -8318) Add 4 phr, 3 phr galvanized, 2 phr stearic acid, 10 phr process oil (aromatic), 1 phr vulcanization accelerator (TBBS), 2 phr sulfur and mix in Banbury mixer to release at 160 ℃ and release sidewall rubber composition Was prepared. The physical property test results of the resulting rubber composition are shown in Tables 2-4.

<비교예 2> 고무조성물의 제조Comparative Example 2 Preparation of Rubber Composition

하기 표 1에 나타난 바와 같이 천연고무 60phr, 고상 이피디엠 고무 40phr로 구성되는 원료고무 100 phr을 기준으로 카본블랙 N330 50 phr, 아연화 3phr, 스테아린산 2phr, 공정오일(aromatic) 10phr, 가류촉진제(CBS) 1phr, 유황 2phr을 첨가하여 밴버리 믹서(Banbury mixer)에 배합하여 160℃의 온도에서 방출시켜 사이드월 고무조성물을 제조하였다. 생성된 고무조성물의 물성시험 결과는 표 2∼4에 나타내었다.As shown in Table 1, based on 100 phr of raw rubber consisting of 60 phr of natural rubber and 40 phr of solid EPDM rubber, carbon black N330 50 phr, galvanized 3 phr, stearic acid 2 phr, process oil (aromatic) 10 phr, vulcanization accelerator (CBS) 1 phr, sulfur 2 phr was added to the Banbury mixer to release at a temperature of 160 ℃ to prepare a sidewall rubber composition. The physical property test results of the resulting rubber composition are shown in Tables 2-4.

<실시예 1> 고무조성물의 제조Example 1 Preparation of Rubber Composition

원료고무로 고상이피디엠고무 35phr, 액상이피디엠 고무 5phr을 배합하는 것을 제외하고는 비교예 2와 동일한 조성 및 과정으로 사이드월 고무조성물을 제조하였으며, 그 결과를 표 2∼4에 나타내었다.A sidewall rubber composition was prepared in the same composition and procedure as in Comparative Example 2, except that 35 phr of solid PDM rubber and 5 phr of liquid PDM rubber were mixed as raw materials, and the results are shown in Tables 2 to 4 below.

<표 1> 고무조성물(단위: phr)<Table 1> Rubber Composition (Unit: phr)

조성Furtherance 비교예 1Comparative Example 1 비교예 2Comparative Example 2 실시예 1Example 1 천연고무Natural rubber 5050 6060 6060 부타디엔고무Butadiene rubber 5050 -- -- 고상이피디엠고무* Solid phase DM rubber * -- 4040 3535 액상이피디엠고무** Liquid EPDM Rubber ** -- -- 55 카본블랙(N660)Carbon black (N660) 5050 -- -- 카본블랙(N330)Carbon black (N330) -- 5050 5050 노화방지제(HPPD)Anti Aging Agent (HPPD) 22 -- -- 노화방지제(TMDQ)Antioxidant (TMDQ) 22 -- -- 왁스Wax 22 -- -- 점착제(Dyphene-8318)Adhesive (Dyphene-8318) 44 -- -- 아연화Zincification 33 33 33 스테아린산Stearic acid 22 22 22 공정오일(aromatic)Process oil 1010 1010 1010 가류촉진제(TBBS)Vulcanization accelerator (TBBS) 1One -- -- 가류촉진제(CBS)Vulcanization accelerator (CBS) -- 1One 1One 유황brimstone 22 22 22

*,** 고상 및 액상 이피디엠의 조성*, ** Composition of solid and liquid EPDM

구분division 점도(ML1+4@125℃)Viscosity (ML1 + 4 @ 125 ℃) ENB 함량(중량%)ENB content (% by weight) 에틸렌(중량%)Ethylene (% by weight) 고상이피디엠고무Go Sang PDM Rubber 4848 9.09.0 6060 액상이피디엠고무Liquid PDM Rubber -(액상)-(Liquid) 9.59.5 4646

<표 2> 가류특성 및 기계적 물성<Table 2> Vulcanization Characteristics and Mechanical Properties

구분division 비교예 1Comparative Example 1 비교예 2Comparative Example 2 실시예 1Example 1 RHEO@160℃RHEO @ 160 ℃ 1212 1111 1111 End cure time(분)End cure time (minutes) 무늬점도@100℃Viscosity @ 100 ℃ 4848 7171 6464 무늬점도@125℃Viscosity @ 125 ℃ 3434 4848 4545 스코치타임(분)Scorch time (minutes) 4444 2424 2626 경도(shore A)Hardness (shore A) 5151 4949 4949 인장강도(kg/cm2)Tensile Strength (kg / cm 2 ) 174174 145145 155155 내크랙성(DMFC,mm)@297킬로사이클Crack resistance (DMFC, mm) @ 297 kilocycles 2525 1919 33 내피로특성(킬로사이클)Fatigue Resistance (Kilo Cycle) 330330 110110 760760

<표 3> 가류특성 및 기계적 물성<Table 3> Vulcanization and Mechanical Properties

구분division 비교예 1Comparative Example 1 비교예 2Comparative Example 2 실시예 1Example 1 점착성(TACK)TACK 1717 1One 88 카카스 부위와의 Peel-strength(kg.f/in)Peel-strength with carcass site (kg.f / in) 3535 1414 2525

<표 4> 오존노화특성<Table 4> Ozone Aging Characteristics

구분division 비교예 1Comparative Example 1 비교예 2Comparative Example 2 실시예 1Example 1 100시간 후After 100 hours 절단됨Cut 크랙 ×Crack × 크랙 ×Crack ×

본 발명에 의하면 상기 표 2∼4에서 볼 수 있는 바와 같이 기존의 노화방지제를 첨가하지 않은 상태에서도 내피로 특성, 내크랙 특성 및 내오존 노화 특성이 현저히 개선되는 것뿐만 아니라 인장물성 및 접착성도 개선된다.According to the present invention, as shown in Tables 2 to 4, fatigue resistance, crack resistance, and ozone aging characteristics are not only remarkably improved, but also tensile properties and adhesive properties are not added to the existing anti-aging agents. do.

Claims (3)

타이어 사이드월용 고무 조성물에 있어서,In the rubber composition for tire sidewalls, 천연 고무 15∼80phr과, 고상 이피디엠 고무 15∼80phr 및 액상 이피디엠 고무 5∼40 phr로 블랜드된 고무를 원료 고무로 함을 특징으로 하는 사이드월용 고무 조성물Rubber composition for sidewalls comprising a rubber blended with 15 to 80 phr of natural rubber, 15 to 80 phr of solid EPDM rubber and 5 to 40 phr of liquid EPDM rubber 제 1항에 있어서,The method of claim 1, 고상 및 액상 이피디엠의 조성은 에틸렌/프로필렌의 함량비가 45/55∼80/20(중량%/중량%)이며, 디엔 함량이 13중량% 이하임을 특징으로 하는 사이드월용 고무 조성물The composition of the solid and liquid EPDM is 45/55 to 80/20 (wt% / wt%), and the diene content is 13 wt% or less. 제 1항에 있어서,The method of claim 1, 상기 사이드월용 고무 조성물은 공지의 첨가물로서 카본블랙 20∼80phr, 아연화 1∼5phr, 스테아린산 1∼5phr, 공정오일 1∼20phr, 가류촉진제 1∼3phr 및 유황 1∼5phr의 조성비로 배합됨을 특징으로 하는 사이드월용 고무 조성물The rubber composition for the sidewall is a known additive, characterized in that it is blended in a composition ratio of 20 to 80 phr, zincated 1 to 5 phr, stearic acid 1 to 5 phr, process oil 1 to 20 phr, vulcanization accelerator 1 to 3 phr and sulfur 1 to 5 phr. Rubber composition for sidewall
KR1020020037043A 2002-06-28 2002-06-28 Tire Sidewall Compound KR20040001728A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100668634B1 (en) * 2005-03-28 2007-01-16 금호타이어 주식회사 Manufacturing method of tire rubber compound prevented blooming amd improved tack property

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05170989A (en) * 1991-12-12 1993-07-09 Yokohama Rubber Co Ltd:The Rubber composition for sidewall
KR19990032299A (en) * 1997-10-17 1999-05-15 신형인 Rubber composition containing liquid EPDM rubber
KR19990041200A (en) * 1997-11-21 1999-06-15 홍건희 Rubber composition for white sidewalls and black cover strips on tires
KR20010106731A (en) * 2000-05-23 2001-12-07 조충환 A rubber composition for tire sidewalls

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05170989A (en) * 1991-12-12 1993-07-09 Yokohama Rubber Co Ltd:The Rubber composition for sidewall
KR19990032299A (en) * 1997-10-17 1999-05-15 신형인 Rubber composition containing liquid EPDM rubber
KR19990041200A (en) * 1997-11-21 1999-06-15 홍건희 Rubber composition for white sidewalls and black cover strips on tires
KR20010106731A (en) * 2000-05-23 2001-12-07 조충환 A rubber composition for tire sidewalls

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100668634B1 (en) * 2005-03-28 2007-01-16 금호타이어 주식회사 Manufacturing method of tire rubber compound prevented blooming amd improved tack property

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