KR20010081361A - Rubber composition for tier rim flange with good thermal aging and abrasion resistance properties - Google Patents

Rubber composition for tier rim flange with good thermal aging and abrasion resistance properties Download PDF

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KR20010081361A
KR20010081361A KR1020000006744A KR20000006744A KR20010081361A KR 20010081361 A KR20010081361 A KR 20010081361A KR 1020000006744 A KR1020000006744 A KR 1020000006744A KR 20000006744 A KR20000006744 A KR 20000006744A KR 20010081361 A KR20010081361 A KR 20010081361A
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rubber
weight
parts
sulfur
rubber composition
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KR1020000006744A
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KR100356591B1 (en
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박병호
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신형인
금호산업 주식회사
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C18/00—Disintegrating by knives or other cutting or tearing members which chop material into fragments
    • B02C18/06—Disintegrating by knives or other cutting or tearing members which chop material into fragments with rotating knives
    • B02C18/16—Details
    • B02C18/18—Knives; Mountings thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C18/00—Disintegrating by knives or other cutting or tearing members which chop material into fragments
    • B02C18/06—Disintegrating by knives or other cutting or tearing members which chop material into fragments with rotating knives
    • B02C18/16—Details
    • B02C18/24—Drives

Abstract

PURPOSE: Provided is a rubber composition for tire rim flange of high hardness with improved properties of anti-abrasion, anti-aging by heat and resistance and compression set against atmospheric factor and ozone. Rim flange contacts tire rim and gets abrasion and wears out easily by friction and heat according to continuous use of vehicle. . CONSTITUTION: The composition comprises 100wt.% of rubber raw material, namely 50-10wt.% natural rubber, 50-90wt.% polybutadiene rubber, 0.5-4.0wt.% heat stabilizer 1,6-bis(N,N-dibenzylthiocarbamoyl)hexane with mol. wt. of 693, 1.0-2.5wt.% free sulfur or oil treated sulfur for vulcanization, activators such as stearic acid, zinc oxidizer, carbon black as a filler, an accelerator, a plasticizer and a cross linking agent.

Description

열노화 및 내마멸 특성이 우수한 타이어 림 플렌지용 고무 조성물{RUBBER COMPOSITION FOR TIER RIM FLANGE WITH GOOD THERMAL AGING AND ABRASION RESISTANCE PROPERTIES}RUBBER COMPOSITION FOR TIER RIM FLANGE WITH GOOD THERMAL AGING AND ABRASION RESISTANCE PROPERTIES}

본 발명은 내마멸성 및 내열노화특성이 우수한 고경도의 타이어 림 플렌지(rim-flange)용 고무 조성물에 관한 것이다.The present invention relates to a rubber composition for high hardness tire rim flanges having excellent abrasion resistance and heat aging characteristics.

림 플렌지는 타이어의 림과 직접 접촉하는 부위로서 주행중 림과 반복적으로 마찰되어 마멸되기 쉽고, 고온 발열에 의해 비드부위의 고무가 열 노화되어 물성이 하락되어 조기 탈착되는 경우가 발생한다. 따라서, 림 플렌지용 고무에는 내열노화특성, 고경도, 내마멸성, 오존 및 환경인자에 대한 내저항성 및 내압축율(compression set)과 같은 특성들이 요구된다.The rim flange is a part in direct contact with the rim of the tire, which is easily rubbed with the rim while driving, and the rubber of the bead portion is thermally aged due to high temperature heat, resulting in a drop in physical properties and early detachment. Accordingly, the rubber for rim flanges requires properties such as heat aging characteristics, high hardness, abrasion resistance, resistance to ozone and environmental factors, and a compression set.

상기와 같은 요구조건들을 만족시키기 위해서는 카본블랙을 과량 사용하고, 가교결합의 형태가 단황결합(mono-sulfide)이 많은 것이 유리하나, 다른 요구성능들을 동시에 만족시키기 위하여 일반적으로 가류계는 다량의 황과 촉진제를 사용하는 통상적인 가류계를 사용하고 있다. 예로서, 천연고무(natural rubber) 10~50중량부와 폴리부타디엔 고무를 90~50중량부를 혼용 사용하므로써 내마멸성을 개선시킬 수 있고, 표면적이 큰 카본블랙을 70중량부, 그리고 황을 최소 2.0중량부 이상으로 과량 사용하므로써 고경도의 고무를 얻을 수 있으며, 단황(mono-sulfide) 결합을 유도하는 황 공여체 화합물을 함께 사용하므로써 내열 노화특성을 향상시킬 수 있다. 그러나, 상기 배합비로 제조된 조성물의 경우 일반적으로 부타디엔 고무의 사용량의 증가로 인해 배합공정에서 분산 및 과부하가 일어나게 된다는 단점이 있다. 또한, 과량의 카본블랙 및 황을 사용하므로써 고경도의 고무화합물을 얻을 수 있으나 높은 점도와 빠른 스코치 타임으로 인한 공정문제 발생 및 높은 히스테리시스(hysteresis)에 의한 발열과 열노화에 의해 물성이 하락될 수 있다. 그리고, 단황 결합을 유도하는 황 공여체로서 디모포린디설파이드 (Dimorpholine disulfide, 상품명: Sulfasan-R)가 주로 사용되고 있으나, 이는 환경규제물질로서 대체가 요구되고 있는 실정이다.In order to satisfy the above requirements, it is advantageous to use excessive amount of carbon black, and the form of crosslinking is more mono-sulfide, but in order to satisfy other requirements simultaneously, the vulcanization system generally has a large amount of sulfur. And a conventional vulcanization system using an accelerator. For example, by using 10-50 parts by weight of natural rubber and 90-50 parts by weight of polybutadiene rubber, abrasion resistance can be improved, 70 parts by weight of carbon black having a large surface area, and at least 2.0 parts by weight of sulfur. It is possible to obtain high hardness rubber by using excessive amount in excess of parts, and to improve heat aging resistance by using sulfur donor compound which induces mono-sulfide bond. However, in the case of the composition prepared at the above compounding ratio, there is a disadvantage in that dispersion and overload occur in the compounding process due to the increase in the amount of butadiene rubber. In addition, by using excess carbon black and sulfur, a rubber compound of high hardness can be obtained, but due to high viscosity and fast scorch time, process problems may occur, and physical properties may be degraded due to heat generation and heat aging due to high hysteresis. have. In addition, although a dimorpholine disulfide (trade name: Sulfasan-R) is mainly used as a sulfur donor to induce monsoon binding, this is a situation that requires replacement as an environmental regulator.

본 발명은 상기와 같은 문제점을 개선하기 위한 것으로, 본 발명에서는 내마멸성이 우수하고 경도가 높으며, 환경규제물질인 디모포린디설파이드(Dimorpholine disulfide)를 사용하지 않으면서 내열 노화특성이 개선된 승용차 및 트럭ㆍ버스용 타이어 림 플렌지용 고무 조성물을 제공하므로써 타이어의 내구력 향상 및 재생횟수를 증가시킬 수 있는 장점이 있다.The present invention is to improve the problems as described above, in the present invention is excellent in wear resistance, high hardness, car and truck with improved heat aging characteristics without using the environmental regulatory material Dimorpholine disulfide (Dimorpholine disulfide) By providing a rubber composition for tire rim flanges for buses, there is an advantage in that the tires have improved durability and increase the number of regenerations.

본 발명은 원료고무에 열안정성이 좋은 1,6-비스(N,N'-디벤질티오카바모일디티오)-헥산과 함께 가황제로서 유리 황이나 오일처리된 황을 적용시키므로써 내마멸성 및 내열노화특성이 현저히 개선된 고경도의 타이어 림 플렌지용 고무 조성물에 관한 것이다.The present invention is abrasion resistance and heat resistance by applying free sulfur or oil-treated sulfur as a vulcanizing agent with 1,6-bis (N, N'-dibenzylthiocarbamoyldithio) -hexane having good thermal stability to raw rubber The present invention relates to a rubber composition for high hardness tire rim flanges with remarkably improved aging characteristics.

상세하게는, 본 발명의 조성물은 천연고무(NR) 50~10중량%와 부타디엔 고무(PBR) 50~90중량%로 이루어진 원료고무 100중량부에 대하여, 열안정성이 좋은 1,6-비스(N,N'-디벤질티오카바모일디티오)-헥산 (1,6-bis(N,N'-dibenzylthiocarbam oyldithio)-hexane; 분자량=693; 이하 KA-9188로 명명) 0.5~4.0중량부와, 가황제로서 유리 황(이하 S) 혹은 오일이 처리된 황 1.0~4.0중량부를 함께 적용시킴으로써 내마멸성 및 내열노화특성을 개선시키는 효과가 있는 타이어 림 플렌지용 고무 조성물이다. 본 발명의 고무 조성물에는 필요에 따라 스테아르산과 같은 활성제, 보강충진제, 촉진제 및 기타 가소제, 연화제, 수지 가교용 수지제 및 노방제 등 다른 성분들이 적용될 수 있다.Specifically, the composition of the present invention has good thermal stability of 1,6-bis (100) by weight of the raw material rubber consisting of 50 to 10% by weight of natural rubber (NR) and 50 to 90% by weight of butadiene rubber (PBR). 0.5 to 4.0 parts by weight of N, N'-dibenzylthiocarbamoyldithio) -hexane (1,6-bis (N, N'-dibenzylthiocarbam oyldithio) -hexane; molecular weight = 693; hereinafter referred to as KA-9188) It is a rubber composition for tire rim flanges which has an effect of improving abrasion resistance and heat aging characteristics by applying together with 1.0 to 4.0 parts by weight of free sulfur (hereinafter referred to as S) or oil-treated sulfur as a vulcanizing agent. If necessary, other components such as active agents such as stearic acid, reinforcing fillers, accelerators and other plasticizers, softeners, resins for resin crosslinking and preservatives may be applied to the rubber composition of the present invention.

본 발명의 고무 조성물에서 원료 고무는 천연고무와 폴리부타디엔 고무의 블렌드가 적합하며, 특히 천연고무 50~10중량%와 부타디엔 고무(PBR) 50~90중량%의 범위로 배합된 것이 내마멸성을 개선시키는데 바람직하다.In the rubber composition of the present invention, the raw rubber is suitably a blend of natural rubber and polybutadiene rubber, and in particular, 50 to 10% by weight of natural rubber and 50 to 90% by weight of butadiene rubber (PBR) are used to improve abrasion resistance. desirable.

본 발명의 조성물에 사용되는 KA-9188은 1,6-비스(N,N'-디벤질티오카바모일디티오)-헥산으로서, 타이어의 내열노화특성을 개선시키기 위하여 본 발명의 조성물에 가황제와 함께 사용된다. KA-9188은 열안정성이 좋으며, 본 발명의 조성물에 원료고무 100중량부에 대하여 0.5~4.0중량부, 특히 0.5~2.5중량부 사용되는 것이 바람직하다. 0.5중량부 미만으로 적용하는 경우 물성을 개선시키는 효과가 적으며, 4.0중량부를 초과하여 적용시 더이상의 물성개선효과가 나타나지 않는다.KA-9188 used in the composition of the present invention is 1,6-bis (N, N'-dibenzylthiocarbamoyldithio) -hexane, which is a vulcanizing agent in the composition of the present invention to improve the heat aging characteristics of a tire. Used with KA-9188 has good thermal stability and is preferably used in the composition of the present invention in an amount of 0.5 to 4.0 parts by weight, particularly 0.5 to 2.5 parts by weight, based on 100 parts by weight of the raw material rubber. When applied in less than 0.5 parts by weight is less effective to improve the physical properties, when applied in excess of 4.0 parts by weight does not appear any more physical properties improvement effect.

본 발명에서 사용되는 가황제는 유리 황(S) 또는 오일이 처리된 황으로, 상기 조성물에 원료고무 100중량부에 대하여 1.0~2.5중량부 적용되는 것이 바람직하다. 상기 가황제를 1.0중량부 미만 사용시에는 KA-9188의 가류특성 및 물성개선에 도움이 되지 않으며, 2.5중량부 초과시 과도한 다중황 결합으로 인해 내열특성이 하락된다. 상기와 같은 이유로 최적물성의 결과를 얻기 위하여 KA-9188과 S의 비는 KA-9188:S = 0.02~4의 범위가 적합하다.The vulcanizing agent used in the present invention is free sulfur (S) or sulfur treated with oil, it is preferable that 1.0 to 2.5 parts by weight based on 100 parts by weight of the raw material rubber to the composition. When the vulcanizing agent is used in less than 1.0 parts by weight, it does not help the improvement of vulcanization and physical properties of KA-9188, and when it exceeds 2.5 parts by weight, the heat resistance is reduced due to excessive multi-sulfur bonding. For the same reason as above, the ratio of KA-9188 and S is preferably in the range of KA-9188: S = 0.02 to 4 in order to obtain optimal properties.

본 발명의 조성물에는 필요에 따라 다른 성분들이 추가될 수 있으며, 예로서, 활성제로서 스테아린산 1~3중량부, 아연화(ZnO) 3~6중량부, 보강충진제로 카본블랙 40~65중량부, 촉진제 0.5~1.8중량부 및 기타 가소제, 연화제, 수지 가교용 수지제와 노방제 등을 포함할 수 있다.Other components may be added to the composition of the present invention as needed. For example, 1 to 3 parts by weight of stearic acid, 3 to 6 parts by weight of zinc (ZnO), 40 to 65 parts by weight of carbon black as a reinforcing filler, accelerator 0.5 to 1.8 parts by weight and other plasticizers, softeners, resins for crosslinking resins and preservatives may be included.

이하 본 발명을 실시예를 통하여 더욱 자세히 설명한다.Hereinafter, the present invention will be described in more detail with reference to Examples.

실시예 1~4Examples 1-4

아래 표 1의 조성비에 따라 고무시편을 제조하였으며, 물성시험을 실시하여 그 결과를 표 1에 나타내었다.Rubber specimens were prepared according to the composition ratios of Table 1 below, and the results were shown in Table 1 by performing physical property tests.

또한, 비교예 1과 실시예 2를 선택하여 실차 시험에 적용하였으며, 이들을 트럭ㆍ버스용 타이어(11R22.5 953 패턴)에 적용하여 비드 부위의 내구력 시험 및재생회수율 결과를 비교하여 표 2에 나타내었다.In addition, Comparative Example 1 and Example 2 were selected and applied to the actual vehicle test, and these were applied to truck and bus tires (11R22.5 953 pattern) to compare the results of the durability test and the recovery rate of the bead region, and are shown in Table 2 below. It was.

1) BR-01: 폴리부타디엔 고무1) BR-01: Polybutadiene Rubber

2) 기타 화학물질: 노방제, 왁스, 수지 및 공정조제2) Other chemicals: preservatives, waxes, resins and process aids

3) 촉진제(NS): N-tert-Butyl-2-Benzothiazolsulfenamide3) Accelerator (NS): N-tert-Butyl-2-Benzothiazolsulfenamide

4) 300% 모듈러스: 300% 신장시의 응력값4) 300% Modulus: Stress value at 300% elongation

5) 리버전(Reversion)(%): 고온가류시 가교 결합률의 파괴율을 측정한 값으로, MDR 기기를 이용하여 180℃에서 토르크(Torque)를 측정하고, 다음 식을 이용하여 계산한 값. --> (최대 토르크 - 30분에서의 토르크)×100/(최대 토르크 - 최소 토르크)5) Reversion (%): A measure of the breaking rate of the crosslinking rate during high temperature vulcanization. Torque was measured at 180 ° C. using an MDR apparatus and calculated using the following equation. -> (Maximum torque-torque at 30 minutes) × 100 / (maximum torque-minimum torque)

6) 마모(abrasion): PICO 시험기기를 이용하여 내마모 정도를 평가한 것으로 80회 회전후 손실된 분량(g)을 나타냄.6) Abrasion: The degree of abrasion resistance was assessed using the PICO tester. It shows the amount lost (g) after 80 revolutions.

상기 표 1에서 알 수 있는 바와 같이, KA-9188과 황을 본 발명의 조성비에 따라 함께 사용한 실시예 1~3의 경우 비교예들에 비해 경도는 Sulfasan-R을 사용한 경우와 같은 수준을 유지하면서, 고온가류시 내열노화특성, 내발열특성, 파열특성(blow-out) 및 내마모특성들이 현저히 개선됨을 알 수 있다. KA-9188과 황의 혼합량 조절에 의하여 물성을 원하는대로 비교적 용이하게 조절할 수 있으며, 고온가류시 가교 결합률의 파괴율(reversion ration)도 비교예들에 비하여 현저히 우수함을 알 수 있다. 비교예 2와 같이 황을 사용하지 않고 KA-9188을 단독으로 사용하는 경우, 가류도가 매우 낮아 모듈러스 값도 낮으며, 내발열 및 내마모 특성이취약함을 알 수 있다.As can be seen in Table 1, in the case of Examples 1 to 3 using KA-9188 and sulfur according to the composition ratio of the present invention, compared to the comparative examples, the hardness is maintained at the same level as when using Sulfasan-R. In addition, it can be seen that the heat aging characteristics, the heat generation characteristics, the blow-out characteristics, and the wear resistance characteristics are significantly improved at high temperatures. By controlling the amount of KA-9188 and sulfur can be adjusted relatively easily as desired, it can be seen that the reversion ratio of the crosslinking rate at high temperature vulcanization is significantly superior to the comparative examples. When using KA-9188 alone without sulfur as in Comparative Example 2, it is found that the vulcanization rate is very low, the modulus value is low, and the heat generation and wear resistance properties are weak.

1) BAB(Bead above Burst) 시험: 공기압 80에서 40km/시의 속도로 주행시간에 따라 부하정도(Load index)를 변화시켜 사고시까지 걸리는 시간을 측정.1) BAB (Bead above Burst) test: Measures the time it takes for an accident by changing the load index according to the driving time at a speed of 80 to 40km / hr.

2) 재생 회수율: 시내버스에 100본을 취부하여 타이어 마모를 90%이상 진행시킨 후에 재생가능한 타이어의 비를 나타낸 것.2) Regeneration Recovery Rate: The ratio of recyclable tires after 100 tires were installed on a city bus and the tire wear progressed more than 90%.

상기 표 2로부터 알 수 있듯이, 비교예의 조성물에 비하여 본 발명에 따른 내열노화특성 및 내마멸성이 우수한 실시예의 조성물이 비드부 관련 내구력 특성이 상대적으로 우수하며, 특히 재생가능 타이어의 회수율이 현저히 우수함을 확인할 수 있다.As can be seen from Table 2, compared to the composition of the comparative example, the composition of the embodiment excellent heat aging characteristics and abrasion resistance according to the present invention is relatively excellent bead-related durability characteristics, in particular, it is confirmed that the recovery of the recyclable tire is significantly superior Can be.

이상의 비교예 및 실시예에서 알 수 있듯이, 본 발명의 배합비에 따라 1,6-비스(N,N'-디벤질티오카바모일디티오)-헥산과 가황제로서 유리 황이나 오일처리된 황을 적정비율로 함께 적용하므로써 타이어 림 플렌지용 고무의 경도와 내마멸성 및 내열노화 특성을 현저히 개선시킬 수 있다.As can be seen from the above Comparative Examples and Examples, 1,6-bis (N, N'-dibenzylthiocarbamoyldithio) -hexane and free sulfur or oil-treated sulfur as a vulcanizing agent according to the blending ratio of the present invention By applying them together at an appropriate ratio, the hardness, abrasion resistance and heat aging characteristics of the rubber for tire rim flanges can be significantly improved.

Claims (2)

천연고무 50~10중량%와 폴리부타디엔 고무 50~90중량%의 블렌드로 이루어진 원료고무 100중량부에 대하여, 1,6-비스(N,N'-디벤질티오카바모일디티오)-헥산(분자량=693)가 0.5~4.0중량부, 가황제로서 유리 황 또는 오일이 처리된 황이 1.0~2.5중량부로 함께 적용되는 것을 특징으로 하는 타이어 림 플렌지용 고무 조성물.1,6-bis (N, N'-dibenzylthiocarbamoyldithio) -hexane (100 parts by weight of the raw material rubber consisting of a blend of 50 to 10% by weight of natural rubber and 50 to 90% by weight of polybutadiene rubber) Molecular weight = 693) is 0.5 to 4.0 parts by weight, free sulfur or sulfur treated with oil as a vulcanizing agent is applied together with 1.0 to 2.5 parts by weight of the rubber composition for tire rim flanges. 제 1항에 있어서, 활성제로서 스테아린산, 아연화, 보강충진제로서 카본블랙, 촉진제, 가소제, 연화제, 수지 가교용 수지제 및 노방제를 더 포함하는 것을 특징으로 하는 타이어 림 플렌지용 고무 조성물.The rubber composition for tire rim flanges according to claim 1, further comprising stearic acid as an active agent, zincation, carbon black, accelerator, plasticizer, softener, resin crosslinking agent, and preservative as reinforcing filler.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020037600A (en) * 2000-11-15 2002-05-22 조충환 Tire rubber composition for truck and bus
KR20020042110A (en) * 2000-11-30 2002-06-05 신형인 Composition for tire hard apex with excellent thermal ageing resistance
CN102746536A (en) * 2012-06-29 2012-10-24 中橡集团曙光橡胶工业研究设计院 Formula of low-heat generation aircraft tire tread rubber

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Publication number Priority date Publication date Assignee Title
KR100426069B1 (en) * 2001-10-15 2004-04-06 금호타이어 주식회사 Rim flanger compound for high temperature curing
KR20040005286A (en) * 2002-07-09 2004-01-16 금호타이어 주식회사 Tire tread rubber composition
KR100529247B1 (en) * 2002-07-31 2005-11-17 금호타이어 주식회사 A reclaimed rubber composition of truck-tire
KR100641046B1 (en) 2005-06-23 2006-11-01 금호타이어 주식회사 Rubber composition for truck and bus tire for high temperature curing

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20020037600A (en) * 2000-11-15 2002-05-22 조충환 Tire rubber composition for truck and bus
KR20020042110A (en) * 2000-11-30 2002-06-05 신형인 Composition for tire hard apex with excellent thermal ageing resistance
CN102746536A (en) * 2012-06-29 2012-10-24 中橡集团曙光橡胶工业研究设计院 Formula of low-heat generation aircraft tire tread rubber

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