KR100360938B1 - Rubber composition for sidewall of radial tire for truck and bus - Google Patents

Rubber composition for sidewall of radial tire for truck and bus Download PDF

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KR100360938B1
KR100360938B1 KR1020000067607A KR20000067607A KR100360938B1 KR 100360938 B1 KR100360938 B1 KR 100360938B1 KR 1020000067607 A KR1020000067607 A KR 1020000067607A KR 20000067607 A KR20000067607 A KR 20000067607A KR 100360938 B1 KR100360938 B1 KR 100360938B1
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resistance
weight
rubber
parts
truck
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KR20020037589A (en
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김석윤
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한국타이어 주식회사
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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
    • C08K5/0008—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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • 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
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
    • 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
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3432—Six-membered rings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • 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

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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)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Tires In General (AREA)

Abstract

본 발명은 오염성 노화방지제에 폴리-2,2,4-트리메틸-1,2-디하이드로 퀴놀린, 1,1-디에톡시에탄 및 왁스를 적절한 비로 혼합하여 첨가한 고무 조성물에 관한 것으로서, 통상적으로 오염성 노화방지제만을 사용한 것에 비해 동등 이상의 내열노화성, 내피로성, 내크랙성장성을 유지하면서 외관 및 내오존성을 월등히 개선할 수 있게 되어 이를 트럭버스용 래디알 공기압 타이어의 사이드월 고무로 적용할 경우 재생시에도 동일한 외관을 유지할 수 있다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to rubber compositions in which poly-2,2,4-trimethyl-1,2-dihydroquinoline, 1,1-diethoxyethane and wax are mixed and added to a contaminant anti-aging agent, and are generally contaminant. Compared with the use of only anti-aging agents, it is possible to improve the appearance and ozone resistance significantly while maintaining the heat aging resistance, fatigue resistance, and crack growth resistance equal to or higher than that of the anti-aging agent, and when applied to the sidewall rubber of radial pneumatic tires for truck buses, The same appearance can be maintained.

Description

트럭버스용 래디알 공기압 타이어의 사이드월 고무 조성물{Rubber composition for sidewall of radial tire for truck and bus}Rubber composition for sidewall of radial tire for truck and bus}

본 발명은 트럭버스용 래디알 공기압 타이어의 사이드월 고무 조성물에 관한 것으로서, 더욱 상세하게는 공기압 타이어의 사이드월 부분에 동적내오존성이나 내피로성질을 개선하기 위해 사용되는 오염성 노화방지제와 더불어 새로운 노화방지제를 첨가함으로써 내오존성이 향상되고 공기압 타이어 사이드월 부분의 외관을 개선시킬 수 있는 조성물에 관한 것이다.The present invention relates to a sidewall rubber composition of a radial pneumatic tire for truck buses, and more particularly to a new aging with contaminant antioxidants used to improve dynamic ozone resistance or fatigue resistance in the sidewall portion of pneumatic tires. It is related with the composition which can improve ozone resistance and improve the appearance of a pneumatic tire sidewall part by adding an inhibitor.

일반적으로 N-1,2-디메틸부틸-N'-p-페닐렌디아민 등과 같은 노화방지제는 분자량이 260∼300g/mol로 비교적 동적내오존성이나 내피로성질을 개선하기 위해 사용되고 있다. 그러나, 이와같은 노화방지제는 다른 계열의 노화방지제에 비하여 고무 표면을 황색으로 오염시키는 성질이 강한 문제가 있다. 특히, 요즈음에는 트럭버스용 래디알 타이어의 경우 재생이 일반화되어 가고 있으며, 따라서 재생 후에도 새 타이어와 같은 외관을 유지할 것이 요구되고 있다. 이러한 측면에서 고무 표면을 황색으로 오염시키는 노화방지제의 사용은 바람직하지 못하다.Generally, anti-aging agents such as N-1,2-dimethylbutyl-N'-p-phenylenediamine have a molecular weight of 260-300 g / mol and are used to improve relatively dynamic ozone resistance and fatigue resistance. However, such an anti-aging agent has a strong problem of contaminating the rubber surface with yellow as compared to other anti-aging agents. In particular, in recent years, the regeneration of truck tires for tires for truck buses is becoming more common, and therefore, it is required to maintain the same appearance as new tires even after regeneration. In this respect, the use of anti-aging agents that contaminate the rubber surface yellow is undesirable.

이러한 오염성 노화방지제의 사용에 따른 문제점을 해결하기 위해 다양한 연구노력이 수행되었던 바, 첫 번째 방법은 2,4,6-트리스-(N-1,4-디메틸펜틸-p-페닐렌디아민)-1,3,5-트리아진 등과 같은 분자량이 약 690∼800g/mol 정도의 비오염성 노화방지제를 사용하는 방법이 있다. 그런데, 이 새로운 노화방지제의 경우 N-1,3-디메틸부틸-N'-p-페닐렌디아민 노화방지제와 거의 동등수준의 내후성을 나타내기는 하나, 가격면에서 현재 사용되고 있는 노화방지제에 비하여 5배 정도 비싸다.Various research efforts have been carried out to solve the problems caused by the use of contaminating antioxidants. The first method is 2,4,6-tris- (N-1,4-dimethylpentyl-p-phenylenediamine)-. There is a method of using a non-polluting antioxidant having a molecular weight of about 690-800 g / mol such as 1,3,5-triazine. By the way, this new anti-aging agent has almost the same level of weather resistance as N-1,3-dimethylbutyl-N'-p-phenylenediamine anti-oxidant, but it is 5 times higher than the anti-oxidants currently used in terms of price. About expensive

두 번째 방법으로는 에틸렌-프로필렌-디엔 고무, 브로모 치환 부틸고무, 이소부틸렌-p-메틸스티렌 공중합 고무 등과 같은 포화고무를 천연고무 및 부타디엔 고무와 같은 디엔계 고무와 혼용함으로써 오염성 노화방지제를 사용하지 않도록 하는 방법이 있다. 그런데, 이 방법은 가공 중에 포화고무와 디엔계 고무와의 혼용성이 문제가 되며 전반적으로 내피로성, 내크랙성장성 등의 물성이 떨어지는 경향을 나타낸다.The second method is to use contaminated antioxidants by mixing saturated rubbers such as ethylene-propylene-diene rubber, bromo substituted butyl rubber, and isobutylene-p-methylstyrene copolymer rubber with diene-based rubber such as natural rubber and butadiene rubber. There is a way to disable it. However, this method has a problem of miscibility between saturated rubber and diene rubber during processing, and exhibits a general tendency of poor physical properties such as fatigue resistance and crack growth resistance.

이에, 본 발명자는 동적내오존성이나 내피로성이 우수한 종래의 오염성 노화방지제를 사용하였을 때 나타나는 외관문제를 개선하기 위해 연구노력하던 중, 비오염성 노화방지제를 혼합사용한 결과, 외관이 우수하면서도 동적내오존성이나 내피로성이 우수한 트럭버스용 래디알 공기압 타이어의 사이드월을 제조할 수 있음을 알게되어 본 발명을 완성하게 되었다.Therefore, the present inventors have been trying to improve the appearance problems when using conventional anti-fouling antioxidants excellent in dynamic ozone resistance or fatigue resistance, as a result of using a non-polluting anti-oxidant mixed, excellent appearance and dynamic ozone resistance The present invention was completed by knowing that a sidewall of a radial pneumatic tire for truck buses having excellent fatigue resistance can be manufactured.

따라서, 본 발명의 목적은 동적내오존성이나 내피로성질의 개선 효과 뿐만아니라 고무표면을 황색으로 오염시키는 등의 외관문제를 개선할 수 있는 트럭버스용 래디알 공기압 타이어의 사이드월 고무 조성물을 제공하는 데 있다.Accordingly, it is an object of the present invention to provide a sidewall rubber composition of a radial pneumatic tire for truck buses that can improve not only the effect of improving the dynamic ozone resistance and fatigue resistance, but also the appearance problems such as contaminating the rubber surface with yellow. There is.

이와같은 목적을 달성하기 위한 본 발명의 트럭버스용 래디알 공기압 타이어의 사이드월 고무 조성물은 천연고무와 부타디엔 고무를 주성분으로 하고, 여기에 N-1,3-디메틸부틸-N'-p-페닐렌디아민 0.5∼4중량부, 폴리-2,2,4-트리메틸-1,2-디하이드로 퀴놀린 0.5∼4중량부, 1,1-디에톡시에탄 1∼3중량부 및 왁스 1∼4 중량부로 이루어진 노화방지제를 첨가하여 이루어진데 그 특징이 있다.The sidewall rubber composition of the radial pneumatic tire for truck buses of the present invention for achieving the above object is based on natural rubber and butadiene rubber, and N-1,3-dimethylbutyl-N'-p-phenyl 0.5 to 4 parts by weight of rendiamine, 0.5 to 4 parts by weight of poly-2,2,4-trimethyl-1,2-dihydroquinoline, 1 to 3 parts by weight of 1,1-diethoxyethane and 1 to 4 parts by weight of wax It is made by adding an anti-aging agent that is characterized by.

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

본 발명은 종래의 오염성 노화방지제를 첨가하여 나타나는 외관문제를 개선할 수 있도록 새롭게 노화방지제 시스템을 도입한 트럭버스용 래디알 공기압 타이어의 사이드월 고무 조성물에 관한 것이다.The present invention relates to a sidewall rubber composition of a radial pneumatic tire for truck buses, in which a new anti-aging system is introduced to improve the appearance problem caused by adding a conventional anti-fouling agent.

본 발명의 고무 조성물에 있어서 노화방지제는 1,1-디에톡시에탄을 더 첨가하여 이루어진 것으로, 구체적으로는 N-1,3-디메틸부틸-N'-p-페닐렌디아민, 폴리-2,2,4-트리메틸-1,2-디하이드로 퀴놀린, 1,1-디에톡시에탄 및 왁스로 이루어진다.In the rubber composition of the present invention, the anti-aging agent is formed by further adding 1,1-diethoxyethane, and specifically N-1,3-dimethylbutyl-N'-p-phenylenediamine, poly-2,2 , 4-trimethyl-1,2-dihydro quinoline, 1,1-diethoxyethane and wax.

왁스를 첨가하지 않은 상태에서 종래의 오염성 노화방지제인 N-1,3-디메틸부틸-N'-p-페닐렌 디아민을 1,1-디에톡시에탄으로 대체할 경우, 내오존성이 떨어진다.When no conventional wax is added and N-1,3-dimethylbutyl-N'-p-phenylene diamine, which is a conventional antifouling antioxidant, is replaced with 1,1-diethoxyethane, ozone resistance is poor.

따라서, 왁스를 첨가하는 것이 바람직하며, 왁스가 첨가된 상태에서 1,1-디에톡시에탄을 종래의 오염성 노화방지제와 함께 사용하는 것이 N-1,3-디메틸부틸-N'-p-페닐렌 디아민과 왁스만을 사용한 것에 비하여 외관이 많이 개선되고 내오존성이 더 우수하다. 그러나, 내열노화성은 저하되며, 내피로성 및 내크랙성장성은 약간 떨어진다.Therefore, it is preferable to add a wax, and it is preferable to use 1,1-diethoxyethane with a conventional antifouling anti-aging agent in the state where the wax is added. N-1,3-dimethylbutyl-N'-p-phenylene Compared to using only diamine and wax, the appearance is much improved and ozone resistance is better. However, heat aging resistance is lowered, and fatigue resistance and crack growth resistance are slightly inferior.

이러한 점을 감안하여 노화방지제를 조성한 결과, N-1,3-디메틸부틸-N'-p-페닐렌디아민/폴리-2,2,4-트리메틸-1,2-디하이드로 퀴놀린/1,1-디에톡시에탄/왁스를 1/1/2/2로 하였을 때, 외관과 내오존성이 개선되고, 내피로성, 내크랙성장성, 내열노화성은 동등 수준으로 유지되는 최적의 고무 조성물을 얻을 수 있게 되었다.In view of this, the anti-aging agent was formed, and as a result, N-1,3-dimethylbutyl-N'-p-phenylenediamine / poly-2,2,4-trimethyl-1,2-dihydro quinoline / 1,1 When the diethoxyethane / wax is 1/1/2/2, the appearance and the ozone resistance are improved, and the optimum rubber composition can be obtained in which fatigue resistance, crack growth resistance, and heat aging resistance are maintained at the same level. .

구체적인 조성은 N-1,3-디메틸부틸-N'-p-페닐렌디아민 0.5∼4중량부, 폴리-2,2,4-트리메틸-1,2-디하이드로 퀴놀린 0.5∼4중량부, 1,1-디에톡시에탄 1∼3중량부 및 왁스 1∼4 중량부이다. 이와같은 조성범위가 노화방지제의 비용측면에서 경제적이면서도 외관개선의 효과가 우수하다.Specific compositions include 0.5 to 4 parts by weight of N-1,3-dimethylbutyl-N'-p-phenylenediamine, 0.5 to 4 parts by weight of poly-2,2,4-trimethyl-1,2-dihydroquinoline, 1 1 to 3 parts by weight of 1-diethoxyethane and 1 to 4 parts by weight of wax. Such a composition range is economical in terms of cost of the anti-aging agent, and the effect of appearance improvement is excellent.

이와같은 노화방지제는 주고무 성분 100중량부에 대하여 3중량부 이내로 첨가되는 것이 바람직하다.Such an anti-aging agent is preferably added within 3 parts by weight with respect to 100 parts by weight of the high-rubber component.

본 발명에 따른 고무 조성물에 있어서 고무는 천연고무와 부타디엔 고무를 혼합한 것으로서, 천연고무 40∼50중량부와 부타디엔 고무 50∼60중량부로 이루어진다.In the rubber composition according to the present invention, the rubber is a mixture of natural rubber and butadiene rubber, and is composed of 40 to 50 parts by weight of natural rubber and 50 to 60 parts by weight of butadiene rubber.

여기에 카본블랙, 상기의 노화방지제, 기타의 배합제를 첨가하는 바, 카본블랙으로는 질소흡착 비표면적이 70∼100㎡/g이고, DBP 흡유량이 60∼100㎖/100g인 카본블랙을 47∼57중량부 되도록 첨가한다.Carbon black, the above-mentioned anti-aging agent, and other compounding agents are added thereto. As carbon black, carbon black having a nitrogen adsorption specific surface area of 70 to 100 m 2 / g and a DBP oil absorption of 60 to 100 ml / 100 g is obtained. Add so that it is -57 weight part.

기타 배합제로는 통상의 배합제, 가류촉진제, 가류제, 스테아린산, 산화아연, 점착제, 아로마틱 오일 등을 들 수 있으며, 구체적인 함량은 가류촉진제인 N-tert-부틸-2-벤조 설펜아미드 1중량부, 가류제인 황 1.7중량부, 스테아린산 3중량부, 산화아연 4중량부, 점착제로 쿠마론인덴 레진 3중량부, 아로마틱 오일 6중량부로 이루어진다. 그러나, 이에 한정되는 것은 아니다.Other compounding agents include conventional compounding agents, vulcanization accelerators, vulcanizing agents, stearic acid, zinc oxide, pressure-sensitive adhesives, aromatic oils, etc., the specific content is 1 part by weight of N-tert-butyl-2-benzo sulfenamide as a vulcanization accelerator , 1.7 parts by weight of sulfur as a vulcanizing agent, 3 parts by weight of stearic acid, 4 parts by weight of zinc oxide, 3 parts by weight of coumarone-indene resin as an adhesive, and 6 parts by weight of aromatic oil. However, it is not limited to this.

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 1 및 비교예 1∼5Example 1 and Comparative Examples 1-5

다음 표 1에 나타낸 바와 같은 조성비 및 조성으로 배합제를 반바리 믹서를 이용하여 고무 시트를 제조하였다. 얻어진 고무 시트를 150℃의 가류프레스에서 30분간 가류하여 시험시편을 준비한 뒤, 모듈러스, 점탄성, 내열노화성, 내크랙성장성, 내피로성, 내오존성, 외관변화양상을 측정하였으며, 무니점도는 가류하지 않은 고무시트에 대하여 MV2000(Monsanto사 제작)으로 측정하였다. 측정결과는 다음 표 2에 나타낸 바와 같다.Next, a rubber sheet was prepared using a half-barrier mixer at a composition ratio and composition as shown in Table 1 below. After preparing the test specimens by vulcanizing the obtained rubber sheet for 30 minutes in a vulcanization press at 150 ° C., modulus, viscoelasticity, heat aging resistance, crack growth resistance, fatigue resistance, ozone resistance, and appearance change were measured. The rubber sheet was measured using MV2000 (manufactured by Monsanto). The measurement results are shown in Table 2 below.

여기서, 내피로성은 118% 스트레인 조건에서 6개의 샘플을 fatigue to failure 테스터로 측정하여 6개 샘플의 50% 잔존율로 횟수를 구하였다.Here, fatigue resistance was measured by a fatigue to failure tester with six samples at 118% strain, and the number of times with 50% residual ratio of six samples was obtained.

내크랙 성장성은 샘플에 구멍을 뚫어놓고 굴곡피로운동을 하는 과정에서 구멍의 성장정도를 측정하였다.Crack growth resistance was measured by measuring the growth rate of the hole in the process of bending fatigue movement by drilling a hole in the sample.

동적 내오존성은 오존 50ppm, 40℃ 조건에서 굴곡피로운동을 하는 과정에서 오존크랙의 발생정도를 관찰하여 내오존성 등급을 1∼10등급으로 나누었는 바, 구체적으로 1등급은 크랙이 전혀 없는 상태이고, 점차적으로 크랙이 증가하여 10등급은 시편이 끊어지는 상태로 하였다.Dynamic ozone resistance was divided into 1 to 10 grades by observing the occurrence of ozone cracks during bending fatigue movement at 50ppm and 40 ℃ ozone. The cracks gradually increased and the grade 10 was made to break the specimen.

그리고, 외관은 밖에 약 6개월 정도 방치한 상태에서 황변현상이 일어나는 정도를 1∼10등급으로 나누었다.In addition, the appearance was divided into 1 to 10 grades in which the yellowing phenomenon occurred while left for about 6 months.

(단위: 중량부)(Unit: parts by weight) 실시예 1Example 1 비교예Comparative example 1One 22 33 44 55 디엔계 천연고무Diene Natural Rubber 5555 5555 5555 5555 5555 5555 부타디엔 고무Butadiene rubber 4545 4545 4545 4545 4545 4545 카본블랙Carbon black 5252 5252 5252 5252 5252 5252 산화아연Zinc oxide 44 44 44 44 44 44 스테아린산Stearic acid 33 33 33 33 33 33 노화방지제Anti-aging N-1,3-디메틸부틸-N'-p-페닐렌디아민N-1,3-dimethylbutyl-N'-p-phenylenediamine 1One -- -- 22 33 33 폴리-2,2,4-트리메틸-1,2-디하이드로 퀴놀린Poly-2,2,4-trimethyl-1,2-dihydroquinoline 1One 1One 1One 1One 1One 1One 1,1-디에톡시에탄1,1-diethoxyethane 22 33 33 1One -- -- 왁스Wax 22 -- 22 22 22 -- 쿠마론인덴 수지Coumaroneindene resin 33 33 33 33 33 33 아로마틱 오일Aromatic oils 66 66 66 66 66 66 N-tert-부틸-2-벤조 설펜아미드N-tert-butyl-2-benzo sulfenamide 1One 1One 1One 1One 1One 1One 유황brimstone 1.71.7 1.71.7 1.71.7 1.71.7 1.71.7 1.71.7 카본블랙: 질소흡착 비표면적이 70∼100㎡/g이고, DBP 흡유량이 60∼100㎖인 카본블랙Carbon black: carbon black having a nitrogen adsorption specific surface area of 70 to 100 m 2 / g and a DBP oil absorption of 60 to 100 ml

실시예 1Example 1 비 교 예Comparative Example 1One 22 33 44 55 인장초기물성Tensile Initial Properties 300% 모듈러스300% modulus 6969 6767 6868 6868 6767 6868 파단시 신장율(%)Elongation at Break (%) 617617 626626 620620 621621 629629 623623 인장강도(kgf/㎠)Tensile strength (kgf / ㎠) 205205 202202 200200 204204 203203 205205 파단에너지(kgf/㎟)Breaking energy (kgf / ㎡) 632632 632632 620620 633633 638638 639639 인장(70℃×1주)Tensile (70 degrees * 1 week) 300% 모듈러스300% modulus 7777 7979 7979 7878 7777 7878 파단시 신장율(%)Elongation at Break (%) 578578 540540 545545 576576 580580 569569 인장강도(kgf/㎠)Tensile strength (kgf / ㎠) 197197 190190 195195 198198 198198 196196 파단에너지(kgf/㎟)Breaking energy (kgf / ㎡) 569569 513513 531531 570570 574574 558558 인장(70℃×2주)Tensile (70 ℃ x 2 weeks) 300% 모듈러스300% modulus 8787 8989 8989 8787 8787 8888 파단시 신장율(%)Elongation at Break (%) 536536 472472 492492 537537 538538 525525 인장강도(kgf/㎠)Tensile strength (kgf / ㎠) 190190 180180 186186 190190 191191 188188 파단에너지(kgf/㎟)Breaking energy (kgf / ㎡) 509509 425425 458458 510510 514514 494494 노화율Aging rate 1주당 파단에너지 감소율(kgf/㎟/1주)Breakage energy reduction rate per week (kgf / ㎡ / 1 week) 6262 104104 8181 6262 6262 7373 내피로성(Kcycle)Fatigue Resistance (Kcycle) 실온Room temperature 8282 7070 7676 8585 8080 7575 70℃×1주70 degrees Celsius * 1 week 5555 4848 5050 5757 5353 5050 70℃×2주70 degrees Celsius * 2 week 4444 4040 4141 4848 4343 4040 내크랙성장성(mm)Crack growth resistance (mm) 실온Room temperature 2121 2424 2323 1919 2020 2222 70℃×1주70 degrees Celsius * 1 week 2424 2828 2626 2323 2424 2626 70℃×2주70 degrees Celsius * 2 week 2626 3030 2828 2525 2727 2929 동적 내오존성Dynamic ozone resistance 2등급Grade 2 6등급Grade 6 2등급Grade 2 3등급Grade 3 3등급Grade 3 5등급Grade 5 외관Exterior 2등급Grade 2 1등급Grade 1 2등급Grade 2 4등급Grade 4 7등급Grade 7 6등급Grade 6

상기 표 2의 결과로부터, 본 발명에 따라 N-1,3-디메틸부틸-N'-p-페닐렌디아민, 폴리-2,2,4-트리메틸-1,2-디하이드로 퀴놀린, 1,1-디에톡시에탄 및 왁스를 1/1/2/2로 혼합하여 노화방지제로 첨가한 경우 내피로성, 내크랙성, 내열노화성 등은 동등 이상이면서도 내오존성 및 외관이 우수한 반면, N-1,3-디메틸부틸-N'-p-페닐렌디아민과 왁스 모두를 첨가하지 않고 과량의 1,1-에톡시에탄을 첨가한 비교예 1의 경우는 외관은 향상되나 내오존성이 특히 떨어지고, 왁스는 첨가하되 N-1,3-디메틸부틸-N'-p-페닐렌디아민을 첨가하지 않은 경우는 내오존성은 보다 향상되나 실시예에 비하여 노화율에서 차이를 보였다. 그리고, 과량의 N-1,3-디메틸부틸-N'-p-페닐렌디아민을 첨가하는 경우(비교예 3) 내오존성이나 외관이 떨어지고 1,1-디에톡시에탄을 첨가하지 않을 경우는 외관이 가장 떨어지며 왁스와 1,1-디에톡시에탄을 모두 첨가하지 않는 경우는 동적 내오존성이나 외관이 모두 나빠짐을 알 수 있다.From the results in Table 2 above, N-1,3-dimethylbutyl-N'-p-phenylenediamine, poly-2,2,4-trimethyl-1,2-dihydroquinoline, 1,1 according to the present invention -When mixed with diethoxyethane and wax in 1/1/2/2 and added as an anti-aging agent, fatigue resistance, crack resistance, heat aging resistance, etc. are equal to or higher but excellent in ozone resistance and appearance, whereas N-1, In Comparative Example 1, in which an excess of 1,1-ethoxyethane was added without adding both 3-dimethylbutyl-N'-p-phenylenediamine and wax, the appearance was improved, but the ozone resistance was particularly poor. When the addition of N-1,3-dimethylbutyl-N'-p-phenylenediamine was not added, the ozone resistance was more improved, but there was a difference in aging rate compared to the example. In addition, when an excessive amount of N-1,3-dimethylbutyl-N'-p-phenylenediamine is added (Comparative Example 3), when ozone resistance or appearance is deteriorated and 1,1-diethoxyethane is not added, the appearance It was found that the most inferior and the wax and 1,1-diethoxyethane were not added, both the dynamic ozone resistance and appearance deteriorated.

이상에서 상세히 설명한 바와 같이, 본 발명에 따라 오염성 노화방지제에 왁스, 폴리-2,2,4-트리메틸-1,2-디하이드로 퀴놀린, 1,1-디에톡시에탄 및 왁스를 적절한 비로 혼합사용하는 경우 통상 오염성 노화방지제만을 사용한 것에 비해 동등 이상의 내열노화성, 내피로성, 내크랙성장성을 유지하면서 외관 및 내오존성을 월등히 개선할 수 있게 되어 이를 트럭버스용 래디알 공기압 타이어의 사이드월 고무로 적용할 경우 재생시에도 동일한 외관을 유지할 수 있다.As described in detail above, according to the present invention, a mixture of wax, poly-2,2,4-trimethyl-1,2-dihydroquinoline, 1,1-diethoxyethane and wax in a contaminant anti-aging agent is used in an appropriate ratio. In this case, it is possible to improve the appearance and ozone resistance significantly while maintaining the heat aging resistance, fatigue resistance, and crack growth resistance equal to or higher than that used only with a contaminant anti-aging agent. In the case of regeneration, the same appearance can be maintained.

Claims (2)

천연고무와 부타디엔 고무를 주성분으로 하고, 여기에 카본블랙, 노화방지제 및 기타의 배합제를 첨가하여 이루어진 고무 조성물에 있어서,In a rubber composition comprising natural rubber and butadiene rubber as a main component, and carbon black, anti-aging agent and other compounding agents are added thereto, 상기 노화방지제는 N-1,3-디메틸부틸-N'-p-페닐렌디아민 0.5∼4중량부, 폴리-2,2,4-트리메틸-1,2-디하이드로 퀴놀린 0.5∼4중량부, 1,1-디에톡시에탄 1∼3중량부 및 왁스 1∼4 중량부로 이루어진 것임을 특징으로 하는 트럭버스용 래디알 공기압 타이어의 사이드월 고무 조성물.The anti-aging agent is 0.5 to 4 parts by weight of N-1,3-dimethylbutyl-N'-p-phenylenediamine, 0.5 to 4 parts by weight of poly-2,2,4-trimethyl-1,2-dihydroquinoline, A sidewall rubber composition of a radial pneumatic tire for truck buses, comprising 1 to 3 parts by weight of 1,1-diethoxyethane and 1 to 4 parts by weight of wax. 제 1 항에 있어서,The method of claim 1, N-1,3-디메틸부틸-N'-p-페닐렌디아민, 폴리-2,2,4-트리메틸-1,2-디하이드로 퀴놀린, 1,1-디에톡시에탄 및 왁스는 1:1:2:2 중량비로 첨가되는 것임을 특징으로 하는 트럭버스용 래디알 공기압 타이어의 사이드월 고무 조성물.N-1,3-dimethylbutyl-N'-p-phenylenediamine, poly-2,2,4-trimethyl-1,2-dihydro quinoline, 1,1-diethoxyethane and waxes are 1: 1: Radial pneumatic tire side truck rubber composition for truck bus, characterized in that added in a 2: 2 weight ratio.
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KR100803318B1 (en) * 2007-02-23 2008-02-13 금호타이어 주식회사 Rubber composition for tire comprising chain type carbon black
US11059958B2 (en) * 2017-05-12 2021-07-13 Hankook Tire Co., Ltd. Rubber composition for protecting sidewall of tire from ozone and tire manufactured using the same
EP3403851B1 (en) * 2017-05-18 2020-03-11 Hankook Tire Co., Ltd. Rubber composition for protecting sidewall of tire from ozone and tire manufactured using the same

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