KR20040003995A - Tire tread rubber composition for truck and bus - Google Patents

Tire tread rubber composition for truck and bus Download PDF

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Publication number
KR20040003995A
KR20040003995A KR1020020039031A KR20020039031A KR20040003995A KR 20040003995 A KR20040003995 A KR 20040003995A KR 1020020039031 A KR1020020039031 A KR 1020020039031A KR 20020039031 A KR20020039031 A KR 20020039031A KR 20040003995 A KR20040003995 A KR 20040003995A
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weight
parts
heat
tire tread
rubber composition
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KR1020020039031A
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KR100513232B1 (en
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김명선
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금호타이어 주식회사
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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
    • 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
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3462—Six-membered rings
    • C08K5/3465—Six-membered rings condensed with carbocyclic rings
    • 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
    • B60C2200/00—Tyres specially adapted for particular applications
    • B60C2200/06—Tyres specially adapted for particular applications for heavy duty vehicles
    • B60C2200/065—Tyres specially adapted for particular applications for heavy duty vehicles for construction vehicles

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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)
  • Tires In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PURPOSE: A tire tread rubber composition for a truck and a bus is provided, to prevent the rapid deterioration of the abrasion resistance in aging and to improve heat resistance and antiaging property. CONSTITUTION: The tire tread rubber composition comprises 100 parts by weight of a base rubber; and 1-3 parts by weight of a heat-resistant antiaging agent whose ratio of monomers to dimers and trimers is 1:9 to 1.5:8.5. Preferably the heat-resistant antiaging agent is 2,2,4-trimethyl-1,2-dihydroquinoline.

Description

트럭 및 버스용 타이어 트레드 고무조성물{Tire tread rubber composition for truck and bus}Tire tread rubber composition for truck and bus

본 발명은 트럭 및 버스용 타이어 트레드 고무조성물에 관한 것으로 보다 상세하게는 원료고무 100 중량부에 대하여 내열성 노화방지제로서 단량체(monomer)와 다량체(dimer and trimer)의 비율이 1:9∼1.5:8.5인 2,2,4-트리메틸-1,2-디하이드로퀴놀린(2,2,4-trimethyl-1,2-dihydroquinoline) 1∼3 중량부 포함하는 트럭 및 버스용 타이어 트레드 고무조성물에 관한 것이다.The present invention relates to a tire tread rubber composition for trucks and buses. More specifically, the ratio of monomers and dimers and trimers as heat-resistant anti-aging agents based on 100 parts by weight of raw material rubber is 1: 9 to 1.5: It relates to a tire tread rubber composition for trucks and buses comprising 1 to 3 parts by weight of 2,2,4-trimethyl-1,2-dihydroquinoline (8.5). .

공기압 타이어의 트레드 고무는 천연고무를 주원료로 하여 기타 공정조제로서 카본블랙, 노화방지제, 연화제, 가류제 및 가류촉진제를 사용하여 제조되며 타이어의 여러부위중 지면과 직접적으로 접촉하기 때문에 내열성능, 내마모성능 및 노화물성이 우수하게 설계되어야 한다.Tread rubber of pneumatic tires is manufactured using carbon black, anti-aging agent, softening agent, vulcanizing agent and vulcanization accelerator as other process aids using natural rubber as the main raw material, and because it is in direct contact with the ground in various parts of the tire, it has heat resistance and wear resistance. It should be designed with excellent performance and aging capability.

천연고무를 주원료로 사용하는 트럭 및 버스용 트레드 고무의 경우 노화방지제는 일반적으로 산화방지 기능 및 내열성이 우수한 내열성 노화방지제로서 퀴놀린(Quinoline)계인 2,2,4-트리메틸-1,2-디하이드로퀴놀린을 사용하여 지속적인용출(migration)작용을 통해 내산화 및 내열기능을 유지하도록 하는데 타이어의 계속적인 사용으로 지면과의 마찰에 의한 열노화가 진행됨에 따라 내열성 노화방지제의 용출이 급격히 진행되어 트레드 고무의 마모성능이 급격히 하락하는 문제가 있다.In the case of tread rubber for trucks and buses using natural rubber as the main raw material, the anti-aging agent is generally a heat-resistant anti-aging agent having excellent anti-oxidation function and heat resistance, and is quinoline-based 2,2,4-trimethyl-1,2-dihydro. The quinoline is used to maintain oxidation and heat-resistance function through continuous dissolution (migration) action. The continuous use of tires leads to rapid aging of the heat-resistant anti-oxidant due to friction with the ground. There is a problem that the wear performance of the sharp drop.

본 발명은 상기의 문제점을 해결하기 위해 노력하던중 2,2,4-트리메틸-1,2-디하이드로퀴놀린의 구성성분에 있어서 단량체의 함량을 줄이고 다량체의 함량을 증가시킨 것을 내열성 노화방지제로 사용하면 내열성 및 노화방지 성능은 동일하게 유지하면서 노화시의 마모성능이 급격히 하락하는 문제를 해결할 수 있음을 알게 되었다.The present invention is to reduce the monomer content and increase the multimer content in the components of 2,2,4-trimethyl-1,2-dihydroquinoline while trying to solve the above problems as a heat resistant antioxidant It has been found that the use can solve the problem of a sharp drop in wear performance during aging while maintaining the same heat resistance and anti-aging performance.

따라서 본 발명은 종래 내열성 노화방지제로 사용하던 2,2,4-트리메틸-1,2-디하이드로퀴놀린에 있어서 단량체의 함량을 감소시키고 다량체의 함량을 증가시킨 것을 트레드 고무조성물의 내열성 노화방지제로 사용하여 내열성 및 노화방지 성능이 우수하면서 노화시 마모성능이 급격히 하락하는 것을 방지할 수 있는 트럭 및 버스용 타이어 트레드 고무조성물의 제공을 목적으로 한다.Therefore, in the present invention, 2,2,4-trimethyl-1,2-dihydroquinoline, which has been used as a heat-resistant anti-aging agent, has reduced monomer content and increased multimer content as a heat-resistant anti-aging agent of a tread rubber composition. The purpose of the present invention is to provide a tire and tread rubber composition for trucks and buses, which is excellent in heat resistance and anti-aging performance and can prevent a sharp drop in wear performance during aging.

본 발명의 트럭 및 버스용 타이어 트레드 고무조성물은 공지의 트럭 및 버스용 타이어 트레드 고무조성물에 있어서, 원료고무 100 중량부에 대하여단량체(monomer)와 다량체(dimer and trimer)의 비율이 1:9∼1.5:8.5인 내열성 노화방지제로서 퀴놀린계인 2,2,4-트리메틸-1,2-디하이드로퀴놀린 1∼3 중량부 포함하는 것을 특징으로 한다.The tire tread rubber composition for trucks and buses of the present invention is a known truck and bus tire tread rubber composition, in which a ratio of monomer and dimer is 1: 9 with respect to 100 parts by weight of raw material rubber. It is characterized by including 1-3 weight parts of quinoline type 2,2,4-trimethyl- 1,2- dihydroquinoline as a heat resistant antioxidant which is -1.5: 8.5.

상기에서 원료고무는 천연고무를 단독으로 사용하거나 천연고무와 합성고무가 1:1로 혼합된 혼합고무를 사용할 수 있다.In the above raw material rubber may be used alone or mixed rubber mixed with natural rubber and 1: 1 synthetic rubber.

상기 내열성 노화방지제의 단량체(monomer)와 다량체(dimer and trimer) 비율에 있어서 단량체 비율이 1 미만이면 고무의 초기 내열성능, 내마모성능 및 노화물성이 하락하는 문제가 있고, 단량체 비율이 1.5 초과하면 열노화가 진행됨에 따라 노화방지제의 용출이 급격히 진행되어 트레드 고무의 마모성능이 급격히 하락하는 문제가 있어 본 발명에서 내열성 노화방지제는 단량체와 다량체의 비율이 1:9∼1.5:8.5인 퀴놀린계 노화방지제를 사용하는 것이 좋다.When the monomer ratio is less than 1 in the monomer and monomer and trimer ratio of the heat resistant antioxidant, there is a problem that the initial heat resistance, abrasion resistance, and aging resistance of the rubber are deteriorated. As the heat aging progresses, the elution of the anti-aging agent rapidly progresses and the wear performance of the tread rubber decreases rapidly. In the present invention, the heat-resistant anti-aging agent is a quinoline-based monomer having a ratio of 1: 9 to 1.5: 8.5. It's a good idea to use anti-aging agents.

한편 상기의 노화방지제를 원료고무 100 중량부에 대하여 1 중량부 미만 사용하면 내열성 노화방지제의 역할을 하지 못하는 문제가 있고, 3 중량부 초과 사용하면 과사용된 내열성 노화방지제가 도리어 고무의 물성을 감소시킬 수 있기 때문에 본 발명에서 내열성 노화방지제는 원료고무 100 중량부에 대하여 1∼3 중량부 포함하는 것이 바람직하다.On the other hand, if the antioxidant is less than 1 part by weight based on 100 parts by weight of the raw material rubber, there is a problem that does not act as a heat-resistant antioxidant, when used over 3 parts by weight overused heat-resistant antioxidants will reduce the physical properties of the rubber Since the heat-resistant anti-aging agent in the present invention can be included 1 to 3 parts by weight based on 100 parts by weight of the raw material rubber.

이하 본 발명을 다음의 비교예, 실시예 및 시험예에 의하여 설명하고자 한다. 이들은 본 발명의 일예로서 이들이 본 발명의 권리범위를 한정하는 것은 아니다.Hereinafter, the present invention will be described by the following comparative examples, examples and test examples. These are examples of the present invention and they do not limit the scope of the present invention.

<비교예>Comparative Example

하기의 표 1과 같이 원료고무인 천연고무 100 중량부에 대하여 보강충진제로서 카본블랙(N330) 48 중량부, 아연화 5 중량부, 스테아린산 3 중량부, 내열성 노화방지제로서 2,2,4-트리메틸-1,2-디하이드로퀴놀린(S-RD, 남경화공창, 중국 남경시) 1 중량부, 공지의 노화방지제 4 중량부, 프로세스 오일 6 중량부, 유황 1.7 중량부, 가황촉진제 0.7 중량부를 밴부릭 믹서에서 혼합한 후 160℃에서 30분 동안 가류하여 타이어 트레드 고무를 제조하였다.As shown in Table 1, 48 parts by weight of carbon black (N330), 5 parts by weight of zinc, 5 parts by weight of stearic acid, and 2,2,4-trimethyl-1 as heat-resistant antioxidants, as a reinforcing filler, based on 100 parts by weight of natural rubber, which is a raw material rubber. , 2-dihydroquinoline (S-RD, Nanjing Chemical Industry, Nanjing, China) 1 part by weight, 4 parts by weight of known anti-aging agent, 6 parts by weight of process oil, 1.7 parts by weight of sulfur, 0.7 parts by weight of vulcanization accelerator in a Banburic mixer After mixing, the mixture was vulcanized at 160 ° C. for 30 minutes to prepare a tire tread rubber.

상기에서 노화방지제인 2,2,4-트리메틸-1,2-디하이드로퀴놀린(S-RD, 남경화공창, 중국 남경시)은 단량체 함량이 30 중량%, 다이머(dimer) 이상의 다량체 함량이 70 중량% 이고, 연화점이 87.8℃인 것이다.The anti-aging agent 2,2,4-trimethyl-1,2-dihydroquinoline (S-RD, Nanjing Chemical Industry, Nanjing, China) has a monomer content of 30% by weight, a multimer content of dimer or more 70 Weight% and a softening point of 87.8 ° C.

<실시예><Example>

하기의 표 1과 같이 원료고무인 천연고무 100 중량부에 대하여 보강충진제로서 카본블랙(N330) 48 중량부, 아연화 5 중량부, 스테아린산 3 중량부, 내열성 노화방지제로서 2,2,4-트리메틸-1,2-디하이드로퀴놀린(Kumanox-RD, 금호몬산토, 대한민국) 1 중량부, 공지의 노화방지제 4 중량부, 프로세스 오일 6 중량부, 유황 1.7 중량부, 가황촉진제 0.7 중량부 혼합한 후 밴부릭 믹서에서 160℃에서 30분 동안 가류하여 타이어 트레드 고무를 제조하였다.As shown in Table 1, 48 parts by weight of carbon black (N330), 5 parts by weight of zinc, 5 parts by weight of stearic acid, and 2,2,4-trimethyl-1 as heat-resistant antioxidants, as a reinforcing filler, based on 100 parts by weight of natural rubber, which is a raw material rubber. Banburic mixer after mixing 1 part by weight of 2-, 2-dihydroquinoline (Kumanox-RD, Kumhomonsanto, Korea), 4 parts by weight of known antioxidant, 6 parts by weight of process oil, 1.7 parts by weight of sulfur, 0.7 parts by weight of vulcanization accelerator Tire tread rubber was prepared by quenching at 160 DEG C for 30 minutes.

상기에서 노화방지제인 2,2,4-트리메틸-1,2-디하이드로퀴놀린(Kumanox-RD, 금호몬산토, 대한민국)은 단량체 함량이 15 중량%, 다이머(dimer) 이상의 다량체함량이 85 중량%이고, 연화점이 89.1℃인 것이다.The anti-aging agent 2,2,4-trimethyl-1,2-dihydroquinoline (Kumanox-RD, Kumho Monsanto, South Korea) has a monomer content of 15% by weight, 85% by weight of a multimer of a dimer or more The softening point is 89.1 ° C.

표 1. 비교예 및 실시예의 고무조성물(단위 : 중량부)Table 1. Rubber compositions of Comparative Examples and Examples (unit: parts by weight)

항목Item 비교예Comparative example 실시예Example 천연고무Natural rubber 100100 100100 카본블랙Carbon black 4848 4848 아연화Zincification 55 55 스테아린산Stearic acid 33 33 내열성 노화방지제*Heat resistant antioxidants * 1One -- 내열성 노화방지제**Heat Resistant Antioxidant ** -- 1One 기타 노화방지제Other Anti Aging Agents 44 44 프로세스 오일Process oil 66 66 유황brimstone 1.71.7 1.71.7 가류촉진제Vulcanization accelerator 0.70.7 0.70.7

* 내열성 노화방지제 : S-RD* Heat resistant anti-aging agent: S-RD

** 내열성 노화방지제 : Kumanox-RD** Heat resistant anti-aging agent: Kumanox-RD

<시험예 1><Test Example 1>

상기 비교예 및 실시예에 의해 제조한 트레드 고무중의 일부시편을 ASTM 관련 규정에 의해 내오존성능, 인장물성 및 마모성능을 측정하고 그 결과를 아래의 표 2에 정리하여 나타내었다.Some specimens of the tread rubbers prepared according to Comparative Examples and Examples were measured for ozone resistance, tensile properties, and abrasion performance according to ASTM-related regulations, and the results are summarized in Table 2 below.

표 2. 비교예 및 실시예의 트레드 고무의 물성 측정결과Table 2. Measurement results of physical properties of tread rubbers of comparative examples and examples

항목Item 비교예Comparative example 실시예Example 내오존성능(오존챔버)Ozone Performance (Ozone Chamber) 정적 평가Static evaluation 양호Good 양호Good 동적 평가Dynamic evaluation 양호Good 양호Good 인장물성(초기/노화*)Tensile Properties (Initial / Aging *) 경도(Shore A)Shore A 60/6160/61 60/6160/61 300% 모듈러스(kg/cm2)300% modulus (kg / cm 2 ) 102/108102/108 99/11299/112 인장강도(kg/cm2)Tensile Strength (kg / cm 2 ) 294/175294/175 301/188301/188 신율(%)% Elongation 611/401611/401 629/468629/468 마모성능(초기/노화*)Wear performance (initial / aging *) 피코(pico, g)Pico (g) 0.029/0.0760.029 / 0.076 0.029/0.0570.029 / 0.057 딘(din, g)Din (g) 0.228/0.4430.228 / 0.443 0.222/0.4030.222 / 0.403

*노화는 105℃에서 120hr 동안 방치* Aging is allowed to stand at 105 ℃ for 120hrs

<시험예 2><Test Example 2>

상기 비교예 및 실시예에 의해 제조한 트레드 고무를 11.00-20 규격 타이어의 실차시험을 실시하여 내마모성능을 측정하고 그 결과를 아래의 표 3에 정리하여 나타내었다.The tread rubbers prepared according to Comparative Examples and Examples were subjected to a real vehicle test of a 11.00-20 standard tire to measure abrasion resistance, and the results are shown in Table 3 below.

표 3. 비교예 및 실시예의 트레드 고무의 내마모성능 측정결과Table 3. Measurement Results of Wear Resistance of Tread Rubbers of Comparative Examples and Examples

항목Item 비교예Comparative example 실시예Example 10000km 주행시점의 마모지수(km/mm)Wear index (km / mm) at 10000km driving 4820(100%)4820 (100%) 4910(100%)4910 (100%) 20000km 주행시점의 마모지수(km/mm)Wear index (km / mm) at 20000km 5598(116%)5598 (116%) 6118(125%)6118 (125%) 30000km 주행시점의 마모지수(km/mm)Wear index (km / mm) at 30000km 6088(126%)6088 (126%) 6835(139%)6835 (139%) 40000km 주행시점의 마모지수(km/mm)Wear index (km / mm) at 40000km 7261(151%)7261 (151%) 8254(168%)8254 (168%)

* 마모지수는 높을수록 성능이 우수함을 나타냄* Higher wear index indicates better performance

** 주행거리가 늘어남에 따라 실시예의 초기 마모지수 대비 노화 마모지수 향상율이 크게 나타남** The aging wear index improved significantly compared to the initial wear index of the embodiment as the mileage increased.

상기 시험예의 결과에서처럼 내열성 노화방지제인 2,2,4-트리메틸-1,2-디하이드로퀴놀린에 있어서, 단량체의 함량이 감소(다량체의 함량 증가)한 실시예의 고무가 실시예의 고무보다 단량체의 함량이 많은 비교예의 고무와 비교시 물성이 동등 수준을 유지하면서 급격한 내마모특성의 하락을 감소시켜 결과적으로 내마모성능이 향상됨을 알 수 있다.In the 2,2,4-trimethyl-1,2-dihydroquinoline, which is a heat-resistant anti-aging agent, as in the results of the test example, the rubber of the example in which the monomer content was reduced (increase in the amount of the multimer) was higher than that of the rubber in the example. It can be seen that the wear resistance is improved as a result of reducing the sharp drop in wear resistance while maintaining the same physical properties as compared to the rubber of the comparative example with a lot of content.

Claims (2)

공지의 트럭 및 버스용 타이어 트레드 고무조성물에 있어서,In known tire tread rubber compositions for trucks and buses, 원료고무 100 중량부에 대하여 단량체와 다량체의 비율이 1:9∼1.5:8.5인 내열성 노화방지제 1∼3 중량부 포함하는 것을 특징으로 하는 트럭 및 버스용 타이어 트레드 고무조성물Tire tread rubber composition for trucks and buses, comprising 1 to 3 parts by weight of a heat resistant antioxidant having a ratio of monomers and multimers of 1: 9 to 1.5: 8.5 based on 100 parts by weight of the raw material rubber. 제 1 항에 있어서, 내열성 노화방지제는 2,2,4-트리메틸-1,2-디하이드로퀴놀린(2,2,4-trimethyl-1,2-dihydroquinoline) 임을 특징으로 하는 트럭 및 버스용 타이어 트레드 고무조성물The tire tread for trucks and buses according to claim 1, wherein the heat resistant anti-aging agent is 2,2,4-trimethyl-1,2-dihydroquinoline (2,2,4-trimethyl-1,2-dihydroquinoline). Rubber composition
KR10-2002-0039031A 2002-07-05 2002-07-05 Tire tread rubber composition for truck and bus KR100513232B1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5318651A (en) * 1976-08-05 1978-02-21 Sumitomo Chem Co Ltd Antioxidizing agent for rubber
JPS53145854A (en) * 1977-05-25 1978-12-19 Sumitomo Chem Co Ltd Deterioration of inhibitor for rubber
JPS6050213B2 (en) * 1978-01-21 1985-11-07 住友化学工業株式会社 Anti-deterioration agent for rubber
CA2113743C (en) * 1993-02-03 2005-06-28 Naoki Inui Reinforced rubber article, production thereof and rubber composition suitable therefor
JP3373040B2 (en) * 1994-05-13 2003-02-04 横浜ゴム株式会社 Pneumatic tires with improved wear resistance

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