KR100425663B1 - Rubber composition for tire tread - Google Patents

Rubber composition for tire tread Download PDF

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KR100425663B1
KR100425663B1 KR10-2001-0073254A KR20010073254A KR100425663B1 KR 100425663 B1 KR100425663 B1 KR 100425663B1 KR 20010073254 A KR20010073254 A KR 20010073254A KR 100425663 B1 KR100425663 B1 KR 100425663B1
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rubber
rubber composition
weight
parts
resistance
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KR10-2001-0073254A
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KR20030042557A (en
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임성수
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한국타이어 주식회사
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00Compositions of natural rubber
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B60VEHICLES IN GENERAL
    • B60CVEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016Compositions of the tread
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/20Carboxylic acid amides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

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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 타이어 트레드용 고무조성물에 관한 것으로서, 더욱 상세하게는 천연고무 또는 디엔계 합성고무 단독, 또는 천연고무와 디엔계 합성고무를 블렌드한 고무 100 중량부에 다음 화학식 1로 표시되는 n-탈로우 1,3-프로판디아민 디스테아레이트를 0.2∼15 중량부 첨가하여 카본 블랙의 표면을 효과적으로 개질시킴으로써, 발열은 증가시키지 않으면서 내마모 성능이 우수하여, 결과적으로 내칩컷성과 청킹성을 향상시킨 타이어 트레드용 고무조성물에 관한 것이다.The present invention relates to a rubber composition for tire tread, and more particularly, n-deal represented by the following general formula (1) to 100 parts by weight of natural rubber or diene synthetic rubber alone, or a blend of natural rubber and diene synthetic rubber. By adding 0.2-15 parts by weight of raw 1,3-propanediamine distearate to effectively modify the surface of the carbon black, the wear resistance is excellent without increasing heat generation, resulting in improved chip cut resistance and chunking resistance. A rubber composition for tire treads.

(화학식 1)(Formula 1)

[RH2N(CH2)3NH3]2+ 2{C17H35COO}- [RH 2 N (CH 2 ) 3 NH 3 ] 2+ 2 {C 17 H 35 COO} -

상기 식에서 R은 탄소수 10∼40 사이의 지방족 알킬기이다.In the above formula, R is an aliphatic alkyl group having 10 to 40 carbon atoms.

Description

타이어 트레드용 고무조성물 {Rubber composition for tire tread}Rubber composition for tire treads {Rubber composition for tire tread}

본 발명은 타이어 트레드용 고무조성물에 관한 것으로서, 더욱 상세하게는 카본블랙을 함유한 고무조성물에 다중작용 첨가제(multi-functional additive)로서 양이온 계면활성제를 첨가함으로써 인장강도와 내티어링(tearing resistance)을 개선하여 내마모성, 내칩컷성과 청킹성을 향상시킨 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to rubber compositions for tire treads, and more particularly to tensile strength and tearing resistance by adding cationic surfactants as multi-functional additives to rubber compositions containing carbon black. Improved wear resistance, chip cut resistance and chunking resistance.

타이어는 여러 부품으로 이루어져 있지만 그 중에서도 특히 트레드 고무는 타이어의 마모성능에 가장 중요한 영향을 미친다. 타이어의 마모는 타이어의 회전시 노면과 타이어의 마찰로 인해 트레드 고무가 미세하게 계속적으로 떨어져 나가면서 발생한다.Tires consist of several parts, but tread rubber, among other things, has the most important influence on the wear performance of tires. Tire wear occurs when the tread rubber drops off continuously due to the friction between the road surface and the tires when the tire rotates.

하지만, 트레드 고무가 외부의 충격에 의해 상당한 크기의 덩어리로 떨어져 나가는 현상, 즉 칩컷(chip-cut)과 청킹(chunking) 등이 트레드 고무의 마모성능을 떨어뜨리는 데 치명적인 영향을 미치는 경우가 많다.However, the phenomenon in which the tread rubber falls to a large sized mass by external impact, that is, chip-cut and chunking, etc., often have a fatal effect on the wear performance of the tread rubber.

따라서, 트레드 고무의 내마모 성능을 향상시키기 위해서는 마찰에 의한 내마모성 뿐만 아니라, 외부 충격에 견딜 수 있는 내칩컷과 내청킹 성능을 동시에 향상시키는 것이 매우 중요하다.Therefore, in order to improve the abrasion resistance of the tread rubber, it is very important to simultaneously improve the abrasion resistance due to friction as well as the chip cut and the anti-chunking performance that can withstand external impacts.

일반적으로 타이어의 마모성능은 카본 블랙의 영향을 많이 받지만, 현재의 기술로써 여러 카본블랙이 개발되어 좋은 성능을 나타내고 있고 또한 새로운 카본블랙들이 개발되고 있는 실정이다.In general, the wear performance of the tire is greatly affected by carbon black, but as the current technology, various carbon blacks have been developed to show good performance and new carbon blacks are being developed.

그러나, 현재 제품들 대비 향상된 카본블랙 특성을 얻기 위해서는 새로운 제조공법과 방법들이 추가되므로, 가격면에서 상대적으로 상승될 가능성이 높다. 따라서 기존의 카본블랙들을 그대로 사용하면서 보다 향상된 내마모성을 얻기 위한 방법들이 개발되고 있는데, 이러한 방법들은 마모성능은 물론 가격 면에서도 유리한 장점을 갖고 있는 경우가 많다.However, as new manufacturing methods and methods are added to obtain improved carbon black properties compared to current products, the price is likely to increase relatively. Therefore, methods for obtaining improved wear resistance while using existing carbon blacks are being developed. These methods often have advantages in terms of wear performance and price.

이러한 방법들의 예를 들면, 카본블랙의 표면을 개질하는 방법들이 많이 사용되고 있는데, 개질 방법에는 제조과정에서 새로운 공정을 추가하여 화학적으로 표면을 개질하는 방법과 고무조성물에 첨가제를 추가하여 고무조성물 내에서 가공 중에 카본 블랙의 표면을 개질하는 방법이 있다.For example, many methods for modifying the surface of carbon black are used. The method includes chemically modifying the surface by adding a new process in the manufacturing process and adding an additive to the rubber composition in the rubber composition. There is a method of modifying the surface of carbon black during processing.

또한, 내칩컷성과 내청킹 성능을 개선하기 위해서는 파단시의 강도와 신장율을 크게 증가시켜 파단에너지를 향상시키고 티어링 에너지를 높이면 효과가 있는 것으로 알려져 왔다.In addition, in order to improve the chip cut resistance and the anti-chunking performance, it has been known to increase the strength and elongation at break, thereby improving the breaking energy and increasing the tearing energy.

종래에는 파단시의 강도와 신장율을 향상시키기 위하여 수지를 사용하거나 가교구조를 변경하는 등의 방법을 이용하여 이들 물성에 유리하도록 선택하여 사용하였지만, 효과면에서 만족할만한 결과를 얻을 수 없었다.Conventionally, in order to improve the strength and elongation at break, a resin was used or a method such as changing the crosslinking structure was used to favor these properties, but the results were not satisfactory.

따라서, 내마모성을 떨어뜨리지 않으면서 내칩컷성과 내청킹 성능을 개선시킬 수 있는 트레드 고무의 개발이 시급한 실정이다.Therefore, it is urgent to develop a tread rubber that can improve chip cut resistance and chunking performance without deteriorating wear resistance.

이에, 본 발명자들은 종래 타이어 트레드용 고무의 마모성능을 개선시키고 내칩컷성과 내청킹성을 개선시키기 위해 연구 노력하던 중, 종래의 고무조성물에 다중작용 첨가제로서 양이온 계면활성제를 첨가함으로써 카본블랙의 표면을 개질시켜 발열은 증가시키지 않으면서 종합적인 내마모성이 개선되는 것을 알게 되어 본 발명을 완성하게 되었다.Accordingly, the present inventors have been researching to improve the wear performance of the tire tread rubber and improve the chip cut resistance and the anti-chunking resistance, and by adding a cationic surfactant as a multifunctional additive to the conventional rubber composition, the surface of the carbon black has been improved. The present invention was completed by finding that the overall wear resistance was improved without modifying the exotherm.

따라서, 본 발명의 목적은 내마모 성능이 우수하고, 내칩컷성과 청킹성을 개선시킬 수 있을 뿐만 아니라, 발열을 증가시키지 않는 타이어 트레드용 고무 조성물을 제공하는 데 있다.Accordingly, it is an object of the present invention to provide a rubber tread rubber composition which is excellent in wear resistance, can improve chip cut resistance and chunking, and does not increase heat generation.

상기와 같은 목적을 달성하기 위한 본 발명의 타이어 트레드용 고무 조성물은 천연고무 또는 디엔계 합성고무 단독 또는 이들의 블렌드물 100 중량부에 양이온 계면 활성제인 n-탈로우 1,3-프로판디아민 디스테아레이트를 0.2∼15 중량부 첨가하여 이루어진 것임을 그 특징으로 한다.The rubber composition for tire treads of the present invention for achieving the above object is n-tallow 1,3-propanediamine distea which is a cationic surfactant in 100 parts by weight of natural rubber or diene synthetic rubber alone or blends thereof. It is characterized by the fact that it is made by adding 0.2-15 weight part of rates.

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

본 발명은 카본블랙을 함유한 타이어 트레드용 고무 조성물에 다중작용 첨가제인 양이온 계면활성제를 첨가한 것이다.The present invention adds a cationic surfactant as a multifunctional additive to a rubber tread rubber composition containing carbon black.

본 발명에서 사용되는 고무는 통상의 타이어 트레드 고무 조성에서와 같이 천연고무 또는 디엔계 합성고무를 단독으로 사용하거나, 또는 상기 천연고무와 디엔계 합성고무를 일정비율로 블렌드한 고무를 주성분으로 사용한다.As the rubber used in the present invention, natural rubber or diene-based synthetic rubber is used alone as in a conventional tire tread rubber composition, or a rubber obtained by blending the natural rubber and diene-based synthetic rubber at a predetermined ratio is used as a main component. .

그리고, 통상인 보강제로서 카본 블랙을 사용한다. 카본 블랙은 통상 상기 고무 100 중량부에 대해 카본블랙의 특성에 따라서 40∼60 중량부로 첨가되어 오고 있다.And carbon black is used as a normal reinforcing agent. Carbon black is usually added in an amount of 40 to 60 parts by weight based on the characteristics of carbon black with respect to 100 parts by weight of the rubber.

한편, 본 발명에서는 고무조성물 내의 카본블랙의 표면을 개질시키고, 발열을 증가시키지 않으면서 종합적인 내마모 성능을 향상시킬 수 있도록 다중작용 첨가제인 양이온 계면활성제를 사용한다.On the other hand, the present invention uses a cationic surfactant as a multifunctional additive to modify the surface of the carbon black in the rubber composition, and improve the overall wear resistance without increasing the heat generation.

이러한 양이온 계면활성제는 하기 화학식 1과 같은 n-탈로우 1,3-프로판디아민 디스테아레이트로서, 상기 고무 100 중량부에 대하여 0.2∼15 중량부로 첨가될 수 있으며, 바람직하기로는 1∼4 중량부이다.Such cationic surfactants are n-tallow 1,3-propanediamine distearate, such as the following Chemical Formula 1, and may be added in an amount of 0.2 to 15 parts by weight, preferably 1 to 4 parts by weight, based on 100 parts by weight of the rubber. to be.

만일 그 함량이 0.2 중량부 미만일 경우에는 카본 블랙의 표면개질 효과가 미흡하며, 또한 15 중량부를 초과할 경우에는 내마모 성능에는 오히려 불리할 뿐만 아니라 경제적인 측면에서도 바람직하지 못하다.If the content is less than 0.2 parts by weight, the surface modification effect of carbon black is insufficient, and if it exceeds 15 parts by weight, it is not only disadvantageous to wear resistance but also economically unfavorable.

화학식 1Formula 1

[RH2N(CH2)3NH3]2+ 2{C17H35COO}- [RH 2 N (CH 2 ) 3 NH 3 ] 2+ 2 {C 17 H 35 COO} -

상기 식에서 R은 탄소수 10∼40 사이의 지방족 알킬기이다.In the above formula, R is an aliphatic alkyl group having 10 to 40 carbon atoms.

또한, 본 발명에서는 본 발명의 조성물 이외에 통상의 고무배합제로 사용되는 노화방지제, 연화제, 가황제, 가황촉진제 등을 적정 수준으로 배합하는 것은 물론이다.In addition, in the present invention, of course, in addition to the composition of the present invention, an antioxidant, a softener, a vulcanizing agent, a vulcanization accelerator, and the like used as a general rubber compounding agent may be blended at an appropriate level.

한편, 이와같은 본 발명의 조성에 따라 타이어 트레드 고무를 제조하는 과정은 통상의 과정에 따른다.On the other hand, the manufacturing process of the tire tread rubber according to the composition of the present invention follows a conventional process.

이하, 본 발명을 실시예에 의거하여 상세하게 설명하면 다음과 같은 바, 본 발명이 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following Examples, but the present invention is not limited thereto.

실시예 1 ∼ 3Examples 1-3

다음 표 1에 나타낸 바와 같이 각 성분을 배합하여 고무 조성물을 제조하였다.As shown in Table 1 below, each component was combined to prepare a rubber composition.

얻어진 고무를 이용하여 인장강도, 인장탄성률, 신장률, 티어링 강도, 람본마모량 및 동적 손실 계수(tan δ)를 측정하였으며, 그 결과를 다음 표 2에 나타내었다.The obtained rubber was used to measure tensile strength, tensile modulus, elongation, tearing strength, amount of rambon wear and dynamic loss factor (tan δ), and the results are shown in Table 2 below.

조성(중량부)Composition (part by weight) 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 비교예 1Comparative Example 1 천연고무Natural rubber 100100 100100 100100 100100 양이온 계면활성제(1) Cationic Surfactants (1) 1One 33 66 -- 카본블랙Carbon black 5050 5050 5050 5050 산화아연Zinc oxide 33 33 33 33 스테아린산Stearic acid 22 22 22 22 노화방지제Anti-aging 22 22 22 22 유황brimstone 1.51.5 1.51.5 1.51.5 1.51.5 촉진제(2) Accelerators (2) 1.01.0 1.01.0 1.01.0 1.01.0 (주)(1) : n-탈로우 1,3-프로판디아민 디스테아레이트(2) : N-t-부틸-2-벤조디아질-설펜아미드(1) (n): n- tallow 1, 3- propanediamine distearate (2): N-t- butyl- 2-benzodiazyl- sulfenamide

물성Properties 실시예 1Example 1 실시예 2Example 2 실시예 3Example 3 비교예 1Comparative Example 1 인장강도(kg/㎠)Tensile Strength (kg / ㎠) 310310 330330 320320 290290 인장탄성율 (kg/㎠)Tensile Modulus (kg / ㎠) 145145 140140 130130 145145 신장율(%)Elongation (%) 550550 570570 580580 530530 티어링 강도(kg/㎠)Tearing Strength (kg / ㎠) 9090 110110 102102 8585 람본마모량(cc)(1) Rambon Wear (cc) (1) 0.4660.466 0.4160.416 0.4420.442 0.5190.519 동적손실계수(tan δ, 60℃)Dynamic loss factor (tan δ, 60 ℃) 0.09410.0941 0.09450.0945 0.09880.0988 0.09440.0944 (주) (1) : 고무산업에서 통상 사용하는 마모시험(상온, 슬립율 25%에서 측정). 동적손실계수 온도를 변화시키면서 트위스트 타입 점탄성시험기를 사용하여 0.5% 변형률에 10Hz 주파수로 측정함.(1) (1): Abrasion test normally used in the rubber industry (measured at room temperature and slip ratio of 25%). Dynamic Loss Coefficient Measured at 10Hz frequency at 0.5% strain using a twisted type viscoelastic tester with varying temperature.

상기 표 2의 결과로부터, 종래의 타이어 트레드용 고무조성물에 본 발명의 양이온 계면활성제인 n-탈로우 1,3-프로판디아민 디스테아레이트를 첨가함으로써, 내마모성능이 우수하고, 인장강도, 신장률, 티어링 강도 등의 기계적 물성이 우수한 것을 확인할 수 있다.From the results in Table 2, by adding n-tallow 1,3-propanediamine distearate, which is a cationic surfactant of the present invention, to a conventional rubber tread rubber composition, excellent wear resistance, tensile strength, elongation, tearing It can be confirmed that the mechanical properties such as strength is excellent.

이상의 상세히 설명한 바와 같이, 본 발명의 타이어 트레드용 고무조성물에 양이온 계면활성제인 n-탈로우 1,3-프로판디아민 디스테아레이트를 사용한 결과 카본 블랙의 표면을 효과적으로 개질시킴으로써, 발열은 증가시키지 않으면서 내마모 성능이 우수하여, 결과적으로 내칩컷성과 청킹성을 향상시킴을 보인다.As described in detail above, as a result of using n-tallow 1,3-propanediamine distearate as a cationic surfactant in the rubber composition for tire treads of the present invention, by effectively modifying the surface of the carbon black, the heat generation is not increased. It has excellent wear resistance, which results in improved chip cut resistance and chunking resistance.

Claims (1)

천연고무 또는 디엔계 합성고무 단독, 또는 이들의 블렌드물에 보강제로서 카본블랙을 포함하는 타이어 트레드용 고무조성물에 있어서,In a rubber composition for tire treads comprising carbon black as a reinforcing agent in natural rubber or diene-based synthetic rubber alone or in blends thereof, 상기 조성물은 다음 화학식 1로 표시되는 n-탈로우 1,3-프로판디아민 디스테아레이트를 상기 고무 100 중량부에 대하여 0.2∼15 중량부 포함하는 것임을 특징으로 하는 타이어 트레드용 고무조성물.The composition is a tire composition for a tire tread, characterized in that it comprises 0.2 to 15 parts by weight of n- tallow 1,3-propanediamine distearate represented by the following formula (1) based on 100 parts by weight of the rubber. 화학식 1Formula 1 [RH2N(CH2)3NH3]2+ 2{C17H35COO}- [RH 2 N (CH 2 ) 3 NH 3 ] 2+ 2 {C 17 H 35 COO} - 상기 식에서 R은 탄소수 10∼40 사이의 지방족 알킬기이다.In the above formula, R is an aliphatic alkyl group having 10 to 40 carbon atoms.
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Citations (4)

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Publication number Priority date Publication date Assignee Title
US4853146A (en) * 1987-01-24 1989-08-01 Akzo N.V. Thickening compositions and thickened aqueous acid solutions
US5182035A (en) * 1991-01-16 1993-01-26 Ecolab Inc. Antimicrobial lubricant composition containing a diamine acetate
US5244028A (en) * 1992-05-20 1993-09-14 The Goodyear Tire & Rubber Company Tire sidewall composition containing silica having low pH
US5569690A (en) * 1994-04-20 1996-10-29 Sumitomo Rubber Industries Limited Rubber composition for tire

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4853146A (en) * 1987-01-24 1989-08-01 Akzo N.V. Thickening compositions and thickened aqueous acid solutions
US5182035A (en) * 1991-01-16 1993-01-26 Ecolab Inc. Antimicrobial lubricant composition containing a diamine acetate
US5244028A (en) * 1992-05-20 1993-09-14 The Goodyear Tire & Rubber Company Tire sidewall composition containing silica having low pH
US5569690A (en) * 1994-04-20 1996-10-29 Sumitomo Rubber Industries Limited Rubber composition for tire

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