KR100703848B1 - Bead filler rubber composition for truck and bus radial tires - Google Patents

Bead filler rubber composition for truck and bus radial tires Download PDF

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KR100703848B1
KR100703848B1 KR1020050053936A KR20050053936A KR100703848B1 KR 100703848 B1 KR100703848 B1 KR 100703848B1 KR 1020050053936 A KR1020050053936 A KR 1020050053936A KR 20050053936 A KR20050053936 A KR 20050053936A KR 100703848 B1 KR100703848 B1 KR 100703848B1
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bead filler
rubber composition
rubber
radial tire
weight
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KR1020050053936A
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Korean (ko)
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KR20060134335A (en
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강성일
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금호타이어 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
    • 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
    • C08K3/06—Sulfur
    • 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
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • 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
    • C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
    • C08K5/31—Guanidine; Derivatives thereof
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/43—Compounds containing sulfur bound to nitrogen
    • C08K5/44—Sulfenamides
    • 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
    • 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
    • B60C2001/005—Compositions of the bead portions, e.g. clinch or chafer rubber or cushion rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant

Abstract

본 발명은 트럭·버스용 래디얼 타이어 비드필러 고무 조성물에 관한 것이며, 더욱 상세하게는 천연 고무를 포함하는 종래의 비드필러용 고무 조성물의 블로우 아웃(Blow Out) 성능을 현저하게 개량한 트럭·버스용 래디얼 타이어 비드필러 고무 조성물에 관한 것이다. BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a radial tire bead filler rubber composition for trucks and buses, and more particularly for trucks and buses, which has remarkably improved the blow out performance of conventional bead filler rubber compositions containing natural rubber. A radial tire bead filler rubber composition.

본 발명에 따르면, 경도, 발열특성이 개선되고, 특히 블로우 아웃(Blow Out) 시간이 현저하게 개선된 트럭·버스용 래디얼 타이어 비드필러용 고무조성물을 제공할 수 있다.According to the present invention, it is possible to provide a rubber composition for a radial tire bead filler for trucks and buses, in which hardness and heat generation characteristics are improved, and in particular, blow out time is remarkably improved.

래디얼 타이어, 비드필러, 고무 조성물, 가황촉진제, 블로우 아웃 Radial Tire, Bead Filler, Rubber Composition, Vulcanization Accelerator, Blow Out

Description

트럭·버스용 래디얼 타이어 비드필러 고무 조성물{BEAD FILLER RUBBER COMPOSITION FOR TRUCK AND BUS RADIAL TIRES}Radial tire bead filler rubber composition for truck bus {BEAD FILLER RUBBER COMPOSITION FOR TRUCK AND BUS RADIAL TIRES}

본 발명은 트럭·버스용 래디얼 타이어 비드필러 고무 조성물에 관한 것이며, 더욱 상세하게는 천연 고무를 포함하는 종래의 비드필러용 고무 조성물의 블로우 아웃(Blow Out) 성능을 현저하게 개량한 트럭·버스용 래디얼 타이어 비드필러 고무 조성물에 관한 것이다. BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a radial tire bead filler rubber composition for trucks and buses, and more particularly for trucks and buses, which has remarkably improved the blow out performance of conventional bead filler rubber compositions containing natural rubber. A radial tire bead filler rubber composition.

트럭·버스 래디얼 타이어 비드필러용 고무 조성물은 비드필러 부위에서 카카스(Carcass)를 지지하는 역할 및 특히 노면으로부터 유입되는 충격을 완화 하는 역할을 한다. 최근 트럭·버스 차량의 고성능화 및 고속도로 발달로 인하여 고속 주행 성능이 현저하게 향상되었을 뿐 아니라, 이차적으로 차량 성능의 향상으로 인한 적재 중량의 증가 등으로 인하여 트럭·버스 래디얼 타이어에 가해지는 가혹도는 점차 커지고 있는 상황이다. 따라서 트럭·버스용 래디얼 타이어의 비드필러부는, 특별히 경도, 내열성 및 블로우 아웃(Blow Out) 성능이 탁월할 것이 요구되고 있다.The rubber composition for truck bus radial tire bead fillers serves to support Carcass at the bead filler site and, in particular, to mitigate the impact from the road surface. Recently, due to the high performance of trucks and buses and the development of expressways, not only the high-speed driving performance has been remarkably improved, but also the severity applied to truck and bus radial tires is gradually increased due to the increase in loading weight due to the improvement of vehicle performance. The situation is growing. Therefore, the bead filler part of the radial tire for trucks and buses is especially required to be excellent in hardness, heat resistance, and blow out performance.

종래에는 일반적으로 이러한 비드필러부의 물성 개선을 위하여 충전제의 종 류 혹은 첨가량을 조정하여 제반 성능을 개선시키고자 하였다. 그러나 물성 개선, 특히 경도향상을 위하여 충전제 첨가량을 증가시킬 경우, 오히려 내열성 및 블로우 아웃(Blow Out) 성능은 저하하여 비드필러부의 온도가 상승하게 되고, 궁극적으로는 트럭·버스 래디얼 타이어를 취부하는 버스차량 혹은 카고차량에서 림과의 마찰로 인한 발열로 인하여 비드부의 파열을 야기시키는 일이 있었다.Conventionally, in order to improve the physical properties of the bead filler, it was intended to improve overall performance by adjusting the type or amount of filler. However, when the amount of filler is increased to improve physical properties, especially hardness, the heat resistance and blow out performance is lowered, thereby increasing the temperature of the bead filler unit, and ultimately, a bus for mounting a truck / bus radial tire In a vehicle or a cargo vehicle, the bead ruptures due to heat generated by friction with the rim.

이와 같이 트럭·버스 래디얼용 타이어의 비드 필러부의 물성 개선을 위하여 다양한 고무 조성물의 개발이 행하여지고 있다. 예를 들면, 대한민국 특허 공개공보 1996-0000996에서는 마모 및 발열 저항을 개선한 공기압 타이어용 고무조성물로서, 비드부의 골심역할과 충격 완화를 위해 고무 100중량부에 대하여 헥사메틸렌-1,6-비스티오설페이트 0.5~3.5중량부를 배합함으로써 경도 상승 및 마모량의 감소, 영구 변형 성능의 상승, 및 내 발열 성능의 상승을 유도하여, 높은 경도를 요구하는 에이펙스부분에 적용하는 고무 조성물을 개발하였다. 또한, 대한민국 특허 공개공보 1995-25063에서는 고 보강성 에이펙스 고무조성물로서 공기압 타이어의 비드부 고무조성물에 결합제로서 접착제인 레졸시놀 포름알데히드 수지 및 헥사 메톡시 메틸렌아민을 첨가하여 타이어의 내굴곡성 및 저 발열의 성능을 유지하는 고경도 고무 조성물을 개발한 바 있다.In this way, various rubber compositions have been developed for improving the physical properties of the bead pillar of the tire for truck bus radials. For example, Korean Patent Laid-Open Publication No. 1996-0000996 discloses a rubber composition for pneumatic tires with improved wear and heat resistance, and is based on hexamethylene-1,6-bisthio with respect to 100 parts by weight of rubber in order to relieve the core role and impact of the bead portion. By blending 0.5 to 3.5 parts by weight of sulfate, a rubber composition is applied to an apex part requiring high hardness by inducing a rise in hardness and a decrease in wear, an increase in permanent deformation performance, and an increase in heat resistance. In addition, Korean Patent Laid-Open Publication No. 1995-25063 discloses a high reinforcement apex rubber composition, which adds resorcinol formaldehyde resin and hexamethoxy methyleneamine as an adhesive to the bead portion rubber composition of a pneumatic tire, thereby providing flexibility and low tire resistance. It has been developed a high hardness rubber composition that maintains the performance of heat generation.

그러나, 상기 특허출원의 기술들은 트럭·버스 래디얼 타이어의 비드필러부의 고무 조성물의 전체적인 조성을 크게 변경시키지 않으면서도, 보다 간단하고 효과적으로 블로우 아웃 성능을 현저하게 개량시키기에는 미흡한 점이 있었다. However, the above-described patented techniques have been insufficient to significantly improve blowout performance more simply and effectively without significantly changing the overall composition of the rubber composition of the bead filler portion of the truck / bus radial tire.

본 발명은 트럭·버스 래디어용 타이어에 있어서 비드필러부의 차량의 림과의 마찰로 인한 발열로 인한 파열을 일으키는 것을 방지하기 위하여, 다른 물성은 동등 수준으로 유지하면서, 특히 블로우 아웃 성능을 향상시킨 비드필러부 고무 조성물을 제공하는 것을 그 목적으로 한다.The present invention is a bead that improves blow-out performance, while maintaining other physical properties at the same level, in order to prevent the rupture due to the heat generated by friction with the rim of the bead filler unit in the tire for truck and bus radiator It aims at providing the filler part rubber composition.

본 발명은 원료고무 100중량부에 대하여, 가교제로서 황 0.5~4.0중량부, 가황촉진제로서 N,N-디페닐구아니딘과 N-tert-부틸벤조티아졸설펜아미드를 합계량으로서 1~10중량부 포함하고, N,N-디페닐구아니딘:N-tert-부틸벤조티아졸설펜아미드의 혼합비를 1:1~1:5로 하는 트럭·버스용 래디얼 타이어 비드필러 고무 조성물에 관한 것이다.The present invention contains 0.5 to 4.0 parts by weight of sulfur as a crosslinking agent and 1 to 10 parts by weight of N, N-diphenylguanidine and N- tert -butylbenzothiazolesulfenamide as a vulcanization accelerator based on 100 parts by weight of the raw material rubber. The present invention relates to a radial tire bead filler rubber composition for truck buses, wherein the mixing ratio of N, N-diphenylguanidine: N- tert -butylbenzothiazolesulfenamide is 1: 1 to 1: 5.

본 발명의 트럭·버스용 래디얼 타이어 비드필러 고무 조성물에 사용되는 원료고무로는, 그 종류에 특별한 제한이 없으며, 천연고무, 합성고무, 천연고무와 합성고무의 혼합고무를 사용할 수 있다. 천연고무와 합성고무의 혼합고무를 사용하는 경우에는 천연 고무 80~100중량부와 합성 고무로서 1,4-폴리부타디엔 고무 0~20중량부를 혼용한 것을 사용하는 것이 바람직하다.As a raw material rubber used for the radial tire bead filler rubber composition for trucks and buses of this invention, there is no restriction | limiting in particular in the kind, The natural rubber, synthetic rubber, the mixed rubber of natural rubber and synthetic rubber can be used. When using the mixed rubber of natural rubber and synthetic rubber, it is preferable to use the thing which mixed 80-100 weight part of natural rubber and 0-20 weight part of 1, 4- polybutadiene rubbers as a synthetic rubber.

또한 본 발명의 트럭·버스용 래디얼 타이어 비드필러 고무 조성물에 사용되는 가교제로서는 유리 황 및/또는 오일 처리된 황을 사용할 수 있다. 그 사용량은 0.5~4.0중량부인 것이 바람직한데, 가교제가 0.5중량부 미만이면, 가황고무 물성이 낮고, 4.0중량부를 초과하면, 내노화 물성이 하락하여 바람직하지 않다.Moreover, free sulfur and / or oil-treated sulfur can be used as a crosslinking agent used for the radial tire bead filler rubber composition for trucks and buses of this invention. The amount of the crosslinking agent is preferably 0.5 to 4.0 parts by weight, but if the crosslinking agent is less than 0.5 parts by weight, the vulcanized rubber properties are low.

본 발명의 고무조성물에 사용되는 가황촉진제는, 원료고무 100중량부에 대하 여 N,N-디페닐구아니딘과 N-tert-부틸벤조티아졸설펜아미드를 합계량으로서 1~10중량부 포함하고, N,N-디페닐구아니딘:N-tert-부틸벤조티아졸설펜아미드의 혼합비는 1:1~1:5인 것이 바람직하다. 상기 가황촉진제의 사용량이 1중량부 미만이면, 가황 속도가 느리고, 10중량부를 초과하면, 스코치 발생으로 인하여 바람직하지 않다. 또한 상기 가황촉진제 중 N,N-디페닐구아니딘:N-tert-부틸벤조티아졸설펜아미드의 혼합비가 상기 범위를 벗어나면, 가황속도 및 스코치 발생의 측면에서 바람직하지 않다. The vulcanization accelerator used in the rubber composition of the present invention contains 1 to 10 parts by weight of N, N-diphenylguanidine and N- tert -butylbenzothiazolesulfenamide relative to 100 parts by weight of the raw material rubber, and N The mixing ratio of, N-diphenylguanidine: N- tert -butylbenzothiazolesulfenamide is preferably 1: 1 to 1: 5. If the amount of the vulcanization accelerator is less than 1 part by weight, the vulcanization rate is slow, and if it exceeds 10 parts by weight, it is not preferable due to the scorch generation. In addition, when the mixing ratio of N, N-diphenylguanidine: N- tert -butylbenzothiazolesulfenamide in the vulcanization accelerator is out of the above range, it is not preferable in view of vulcanization rate and scorch generation.

또한, 트럭·버스용 래디얼 타이어 비드필러 고무 조성물에는 통상의 타이어 비드필러 고무 조성물에 사용되는 기타 첨가제 및 배합제를 통상의 함량 범위로 포함할 수 있다.In addition, the radial tire bead filler rubber composition for trucks and buses may include other additives and compounding agents used in conventional tire bead filler rubber compositions in a conventional content range.

이하, 본 발명을 실시예를 통하여 더욱 상세히 설명한다. 그러나 이들 실시예가 본 발명의 범위를 제한하는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. However, these examples do not limit the scope of the present invention.

실시예Example

표 1의 고무조성물 혼합비에 따라 실시예 1~2 및 비교예 1~2의 원료를 반바리 믹서로 배합하고, 105℃의 온도에서 방출하여 비드필러 고무조성물을 제조하고 시편을 제작한 후 타이어의 제반 물성에 대한 표준시험법에 따라 공정성, 인장물성 등의 시험을 실시하여, 그 결과를 표 2에 나타내었다.According to the mixing ratio of the rubber composition of Table 1, the raw materials of Examples 1 and 2 and Comparative Examples 1 and 2 were blended with a half-barrier mixer, discharged at a temperature of 105 ° C. to prepare a bead filler rubber composition, and a specimen was prepared. In accordance with the standard test method for the overall physical properties, tests such as fairness, tensile properties and the like are shown in Table 2.

표 1 트럭·버스 래디얼 타이어용 비드필러 고무조성물 (단위:중량부) Table 1 Bead filler rubber composition for truck and bus radial tires (unit: parts by weight)

조성Furtherance 실시예1Example 1 실시예2Example 2 비교예1Comparative Example 1 비교예2Comparative Example 2 천연고무 카본블랙 공정오일 산화아연 스테아린산 유황 가황촉진제(DPG)1) 가황촉진제(TBBS)2) Natural Rubber Carbon Black Process Oil Zinc Oxide Stearic Acid Sulfur Vulcanization Accelerator (DPG) 1) Vulcanization Accelerator (TBBS) 2) 100 50 3 5 1 3 0.5 1.4100 50 3 5 1 3 0.5 1.4 100 50 3 5 1 3 0.5 1.0100 50 3 5 1 3 0.5 1.0 100 50 3 5 1 3 0 0.8100 50 3 5 1 3 0 0.8 100 50 3 5 1 3 0.5 0.4100 50 3 5 1 3 0.5 0.4

가황촉진제(DPG)1) : N,N-디페닐구아니딘Vulcanization Accelerator (DPG) 1) : N, N-diphenylguanidine

가황촉진제(TBBS)2) : N-tert-부틸벤조티아졸설펜아미드Vulcanization accelerator (TBBS) 2) : N- tert -butylbenzothiazolesulfenamide

표 2 트럭·버스 래디얼 타이어용 비드필러 고무조성물의 물성 Table 2 Properties of Bead Filler Rubber Compositions for Truck and Bus Radial Tires

물성Properties 실시예1Example 1 실시예2Example 2 비교예1Comparative Example 1 비교예2Comparative Example 2 공정성 100℃ 점도 스코치타임(t5) 가류시간(t90)   Processability 100 ℃ Viscosity Scotch Time (t5) Curing Time (t90) 62 13 962 13 9 62 12 862 12 8 65 20 1565 20 15 62 13 1162 13 11 인장물성 경도 300%모듈러스(kg/㎠) 인장강도(kg/㎠) 신율(%)  Tensile Properties Hardness 300% Modulus (kg / ㎠) Tensile Strength (kg / ㎠) Elongation (%) 63 141 285 50963 141 285 509 64 162 277 46064 162 277 460 61 138 290 53061 138 290 530 63 120 812 57563 120 812 575 발열(온도차℃)Exothermic (temperature difference ℃) 1414 1313 1515 1414 내블로우 아웃성(시간)Blow-out resistance (time) 60.060.0 46.646.6 28.728.7 26.526.5

상기 표 2에서 알 수 있는 바와 같이, 본 발명에 의한 트럭·버스용 래디얼 타이어 비드필러용 고무조성물은, 가황촉진제를 한가지 성분만 단독으로 사용한 경우(비교예 1), 및 혼합사용하였으나 그 혼합비가 본 발명에서 한정한 범위 외에 있는 경우(비교예 2)에 비하여, 경도, 발열특성 등의 물성은 동등 수준이거나 또는 그 이상으로 개선되고, 특히 블로우 아웃(Blow Out) 성능이 현저하게 개선된 것을 알 수 있다.As can be seen in Table 2, the rubber composition for truck tire radial filler bead filler according to the present invention, when only one component of the vulcanization accelerator is used alone (Comparative Example 1), and the mixed ratio was used Compared with the case outside the range defined by the present invention (Comparative Example 2), the physical properties such as hardness and heat generation characteristics are improved to the same level or more, and in particular, the blow out performance is remarkably improved. Can be.

본 발명에 따르면, 블로우 아웃(Blow Out) 성능이 현저하게 개선된 트럭·버스용 래디얼 타이어 비드필러용 고무조성물을 제공할 수 있다.According to the present invention, it is possible to provide a rubber composition for a radial tire bead filler for trucks and buses, in which blow out performance is remarkably improved.

Claims (3)

원료고무 100중량부에 대하여, 가교제로서 황 0.5~4.0중량부, 가황촉진제로서 N,N-디페닐구아니딘과 N-tert-부틸벤조티아졸설펜아미드를 합계량으로서 1~10중량부 포함하고, N,N-디페닐구아니딘:N-tert-부틸벤조티아졸설펜아미드의 혼합비가 1:1~1:5인 트럭·버스용 래디얼 타이어 비드필러 고무 조성물.To 100 parts by weight of raw material rubber, 0.5 to 4.0 parts by weight of sulfur as a crosslinking agent, 1 to 10 parts by weight of N, N-diphenylguanidine and N- tert -butylbenzothiazolesulfenamide as a vulcanization accelerator are included, Radial tire bead filler rubber composition for trucks and buses whose mixing ratio of, N-diphenylguanidine: N- tert -butylbenzothiazolesulfenamide is 1: 1-1: 5. 제1항에 있어서, 상기 원료고무는 천연고무 80~100중량부와 1,4-폴리부타디엔 고무 0~20중량부로 이루어진 것을 특징으로 하는 트럭·버스용 래디얼 타이어 비드필러 고무 조성물.The radial tire bead filler rubber composition according to claim 1, wherein the raw material rubber comprises 80 to 100 parts by weight of natural rubber and 0 to 20 parts by weight of 1,4-polybutadiene rubber. 제1항에 있어서, 상기 가교제는 오일 처리된 황인 것을 특징으로 하는 트럭·버스용 래디얼 타이어 비드필러 고무 조성물.The radial tire bead filler rubber composition according to claim 1, wherein the crosslinking agent is oil-treated sulfur.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR0142300B1 (en) * 1993-01-07 1998-06-01 윤양중 Tire tread
KR20010081360A (en) * 2000-02-14 2001-08-29 신형인 Rubber compositions containing silica master batch
US20020036043A1 (en) 2000-08-03 2002-03-28 Georges Marcel Victor Thielen Runflat tire having a rubberized insert containing 1,6-bis(N,N'-dibenzylthiocarbamoyldithio)-hexane
KR100449890B1 (en) 2001-09-10 2004-09-22 금호타이어 주식회사 Tire tread rubber composition for bus

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR0142300B1 (en) * 1993-01-07 1998-06-01 윤양중 Tire tread
KR20010081360A (en) * 2000-02-14 2001-08-29 신형인 Rubber compositions containing silica master batch
US20020036043A1 (en) 2000-08-03 2002-03-28 Georges Marcel Victor Thielen Runflat tire having a rubberized insert containing 1,6-bis(N,N'-dibenzylthiocarbamoyldithio)-hexane
KR100449890B1 (en) 2001-09-10 2004-09-22 금호타이어 주식회사 Tire tread rubber composition for bus

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