KR100379037B1 - Rubber Compound which has little change in spring rate for Suspension Bush - Google Patents
Rubber Compound which has little change in spring rate for Suspension Bush Download PDFInfo
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- 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
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- 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
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- 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
- C08K5/39—Thiocarbamic acids; Derivatives thereof, e.g. dithiocarbamates
- C08K5/40—Thiurams, i.e. compounds containing groups
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- C08L7/00—Compositions of natural rubber
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
- F16F1/00—Springs
- F16F1/36—Springs made of rubber or other material having high internal friction, e.g. thermoplastic elastomers
- F16F1/3605—Springs made of rubber or other material having high internal friction, e.g. thermoplastic elastomers characterised by their material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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Abstract
본 발명은 특성변화 저감 서스펜션 부시(suspension bush)용 고무 조성물에 관한 것으로서, 더욱 상세하게는 황과 가류제를 사용하는 세미-이.브이 큐어 시스템(semi-E.V cure system)에 하이브리드(hybrid) 가교 형성을 위해 듀라링크 에이치티에스(Duralink-HTS)를 첨가함으로써 내열성 및 내구성을 향상시킨 특성변화 저감서스펜션 부시용 고무 조성물에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber composition for reducing characteristic suspension suspension bushes, and more particularly to hybrid crosslinking to a semi-EV cure system using sulfur and vulcanizing agents. The present invention relates to a rubber composition for reducing characteristic suspension suspensions having improved heat resistance and durability by adding Duralink-HTS to form.
Description
본 발명은 특성변화 저감 서스펜션 부시(suspension bush)용 고무 조성물에 관한 것으로서, 더욱 상세하게는 황과 가류제를 사용하는 세미-이.브이 큐어 시스템(semi-E.V cure system)에 하이브리드(hybrid) 가교 형성을 위해 듀라링크 에이치티에스(Duralink-HTS)를 첨가함으로써 내열성 및 내구성을 향상시킨 특성변화 저감 서스펜션 부시용 고무 조성물에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber composition for reducing characteristic suspension suspension bushes, and more particularly to hybrid crosslinking to a semi-EV cure system using sulfur and vulcanizing agents. The present invention relates to a rubber composition for reducing characteristic suspension bushes having improved heat resistance and durability by adding Duralink-HTS to form.
일반적으로 서스펜션 부시류들은 차량의 하부구조를 구성하는 각종 링크(link)류들에 부속되어 차체와 서스펜젼 부품 연결부에서 불규칙한 노면으로부터 전달되는 진동과 충격을 완화시켜 승차감을 향상시키는 역할을 한다. 이러한 고무 부시류들은 차량 1대당 10개 이상이 사용되며 고급차종의 경우 그 수량이 증가되어 차량의 승차감 향상을 위해 사용되어 진다.In general, the suspension bushes are attached to various links that form the undercarriage of the vehicle, and serve to improve ride comfort by mitigating vibrations and shocks transmitted from irregular road surfaces at the vehicle body and suspension component connections. These rubber bushes are used more than 10 per vehicle, and the number of luxury cars is used to increase the ride comfort of the vehicle.
특히, 서스펜션에 사용되는 고무류는 외부에서 가해지는 큰 외력에 대해 충분한 내구성능을 만족해야 하며 진동절연 효과가 뛰어나야 하는 상반된 특성을 만족시켜야 한다. 부시의 스프링 특성이 클 경우 핸들링(handling)이 좋아지는 반면 N.V.H(Noise, Vibration, Harshness) 성능이 저하되며, 스프링 특성이 낮은 부시를 사용할 경우에는 N.V.H 성능이 향상되어 승차감이 좋아지는 반면 핸들링 및 라이드(ride) 성능이 저하되어 이를 적절히 튜닝(tunning)해서 사용되고 있다.In particular, the rubbers used in the suspension must satisfy sufficient durability against large external forces applied from the outside and satisfy the opposing characteristics of excellent vibration insulation effect. Higher spring characteristics of the bush provide better handling, while NVH (Noise, Vibration, Harshness) performance is reduced, while lower spring characteristics of the bush improve NVH performance, resulting in better ride comfort, while handling and ride. The performance is degraded and it is being used by tuning it properly.
기존의 고무 부시(rubber bush)류는 생산 직후의 초기 내구성능만을 중시하여 고무가 사용되는 환경에 따른 노화현상에 의한 재료의 경시변화를 무시한 개발을 진행하여 왔다. 이에 따라 차량의 사용년수 증가에 따른 고무의 경화현상 발생으로 스프링 특성이 초기 튜닝값에 비해 증가되어져 노면으로부터의 진동을 바로 승차자에게 전달시키는데 이는 노화에 따른 가교 절단으로 인한 고무의 크랙(crack)발생으로 안락감을 저하시키는 문제가 발생되어 왔다. 이는 고무의 경시변화에 따른 열산화노화 현상에 의한 것으로 고무의 가교방식에 따른 요인이 지배적인 것으로 폴리-설파이드(poly-sulfide) 가교 구조 형성이 지배적인 씨.브이 큐어(C.V Cure)의 경우에 해당된다. 그러나 이를 방지하기 위해 내열산화성능이 우수한 이.브이 큐어(E.V Cure)를 사용하면 내구성능이 저하되어 자동차에서 요구되는 피로성능을 만족시키지 못하는 문제가 있다.Existing rubber bush (rubber bush) has been in development to ignore the aging change of the material due to the aging phenomena according to the environment in which the rubber is used, focusing only on the initial durability performance immediately after production. As a result of the hardening of rubber due to the increase in the number of years of use of the vehicle, the spring characteristics are increased compared to the initial tuning value, and the vibration from the road surface is immediately transmitted to the passenger, which causes cracking of the rubber due to cross-linking due to aging. There has been a problem of lowering comfort. This is due to thermal aging due to the change of rubber over time, and the factor of rubber crosslinking method is dominant. In the case of CV Cure, poly-sulfide crosslinking structure is dominant Yes. However, if the use of E.V Cure (excellent thermal oxidation resistance) to prevent this, there is a problem that the durability performance is reduced to satisfy the fatigue performance required in the car.
이에, 본 발명자는 상기 문제점들을 해결하기 위하여 연구 노력하였다. 그 결과, 배합시 첨가하는 가교제(sulfur)의 양을 감소시킨 세미 이.브이 큐어 시스템에 하이브리드 가교제를 첨가함으로써 본 발명을 완성하였다.Accordingly, the present inventors have made efforts to solve the above problems. As a result, the present invention was completed by adding a hybrid crosslinking agent to a semi E. Cure system in which the amount of the crosslinking agent added during the compounding was reduced.
따라서, 본 발명은 서스펜젼계에 사용되는 고무의 장기사용에 따른 노화로 인한 특성값 변화를 억제하여 차량의 장기 사용 후 초기와 같은 승차감을 유지시키는 서스펜젼 부시 고무 조성물을 제공하는데 그 목적이 있다.Accordingly, an object of the present invention is to provide a suspension bush rubber composition which suppresses the change in characteristic values due to aging according to long-term use of the rubber used in the suspension system to maintain the riding comfort as in the beginning after long-term use of the vehicle. have.
본 발명은 부시용 고무 조성물에 있어서, 황, 가류제를 사용하는 세미 이.브이 큐어 시스템에 하이브리드 가교 형성을 위해 듀라링크 에이치티에스(Duralink-HTS)를 첨가한 특성변화 저감 서스펜션 부시 고무 조성물에 그 특징이 있다.The present invention is a rubber composition for the bush, sulfur, vulcanizing agent semi-V curing system using a Duralink HTS (Duralink-HTS) for the hybrid cross-linking to reduce the characteristic change suspension bush rubber composition There is a characteristic.
이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
본 발명은 기존의 서스펜션 고무 부시가 경화되어 차량의 N.V.H가 악화되는 현상을 방지하기 위해 배합시 첨가하는 가교제(sulfur)의 양을 감소시킨 세미 이.브이 큐어 시스템을 사용한다. 또한, 세미 이.브이 큐어 시스템은 모노(mono), 디-설파이드(di-sulfide) 구조를 지배적으로 형성시키기 때문에 고무분자간의 가교길이가 감소되므로 외부에서 가해지는 하중에 대한 충격 흡수성능이 감소하여 내구성능이 저하되는 문제점을 해결하기 위해 가교구조 내에 하이브리드(hybrid) 가교를 형성시켜 내열성과 내구성능을 동시에 만족시킨다.The present invention uses a semi E. Vcure system that reduces the amount of sulfur added during formulation to prevent the existing suspension rubber bush from hardening and deteriorating the N.V.H of the vehicle. In addition, since the semi-V cured system predominantly forms a mono and di-sulfide structure, the crosslinking length between rubber molecules is reduced, thereby reducing the impact absorption performance against externally applied loads. In order to solve the problem of deterioration in durability, a hybrid crosslink is formed in the crosslinking structure to satisfy both heat resistance and durability.
고무의 열노화에 의한 경화현상은 고무재료 내의 가교구조의 변화(가교도 저하, 각 평균 길이의 감소, 단일황 결합 증가, 사이클릭 설파이드(cyclic sulfide), 콘쥬게이티드 트리엔(conjugated triene) 등의 증가)에 의한 가교 구조 변화로 고무는 경화되거나 연화되어 초기의 특성을 상실하게 된다. 이러한 고무 가교 구조의 변화에 의해 고무의 모둘러스(modulus)가 증가되고 인장강도가 저하되며 내부발열이 증가되어 피로수명이 저하된다. 특히, 경화현상에 의하여 고무가 초기에 갖고 있던 특성을 잃어 버리게 된다.Curing phenomena due to thermal aging of rubbers may be caused by changes in the crosslinked structure in the rubber material (reduced crosslinking, decreasing average length, increasing monosulfur bonds, cyclic sulfides, conjugated trienes, etc.). Change in the crosslinking structure causes the rubber to harden or soften, resulting in loss of initial properties. Due to the change in the rubber crosslinking structure, modulus of rubber is increased, tensile strength is decreased, and internal heat is increased, thereby reducing fatigue life. In particular, hardening causes the rubber to lose its initial characteristics.
고무의 내열노화성능을 향상시키기 위해 황을 1.0 ∼ 2.0 phr(parts per hundred parts of rubber)을 사용하며 설펜아미드(sulfenamide)계 가류촉진제와 티우람(thiuram)계 가류촉진제를 사용하는 세미 이.브이 큐어 시스템을 사용한다. 이때 사용되는 황의 첨가량은 2.0 phr 이상일 때에는 폴리-설파이드(poly-sulfide) 구조가 주로 형성되어 고무의 내열성을 악화시키며 1.0 phr 이하로 첨가되면 고무의 피로성능을 악화시켜 자동차에서 사용되는 조건을 만족시키지 못하게 된다.Semi-E. V using sulfur of 1.0 to 2.0 phr (parts per hundred parts of rubber) to improve the heat aging performance of rubber, and sulfenamide based thiuram vulcanization accelerator Use a cure system. In this case, when the amount of sulfur used is 2.0 phr or more, a poly-sulfide structure is mainly formed to deteriorate the heat resistance of the rubber, and when it is added below 1.0 phr, the fatigue performance of the rubber deteriorates to satisfy the conditions used in automobiles. I can't.
또한, 설펜아미드계 가류촉진제를 1.5 ∼ 3.0 phr로, 티우람계 가류촉진제를 0.1 ∼ 0.5 phr로 첨가한다. 가류제의 양을 과량 첨가시에는 고무의 스코치(schorch)가 발생되어 제품의 가공시 스크류(screw) 내에서 가교가 발생되어 제품의 성형이 곤란하며 그 첨가량이 부족할 때는 적정가황도에 이르는 시간이 길어져 생산성이 떨어지는 문제가 생기며 가교도에도 영향을 미치므로 적정의 배합량을 선택하는 것이 필수적이다.In addition, sulfenamide vulcanization accelerators are added at 1.5 to 3.0 phr, and thiuram vulcanization accelerators are added at 0.1 to 0.5 phr. When the amount of vulcanizing agent is added excessively, rubber scorch is generated and cross-linking occurs in the screw during processing of the product, which makes it difficult to mold the product. It is essential to select a proper blending amount because there is a problem of low productivity and affects the degree of crosslinking.
하이브리드 가교 형성을 위해 듀라링크 에이치티에스(Duralink-HTS, Hexamethlylene-1,6 bisthiosulphate disodium salt dihydrate)를 사용하며 그의 첨가량은 1.0 ∼ 3,0 phr이 바람직하다. 그 첨가량이 3.0 phr이상일 때는 과량으로 첨가된 HTS가 고무의 노화에 의해 생성된 디엔(diene) 또는 트리엔(triene) 구조와 반응하여 가교를 형성하므로 고무의 물성 저하를 발생시키며 1.0 phr이하로첨가할 때는 충분한 가교형성이 불가하여 고무의 피로성능이 저하되는 현상이 나타난다. 이러한 하이브리드 가교는 고온에서도 길고 유연한 가교 구조를 형성시켜 고무의 특성을 유지시킨다.Duralink-HTS (Hexamethlylene-1,6 bisthiosulphate disodium salt dihydrate) is used to form the hybrid crosslink, and the amount thereof is preferably 1.0 to 3,0 phr. When the added amount is more than 3.0 phr, the excessively added HTS reacts with the diene or triene structure formed by aging of the rubber to form crosslinks, resulting in the deterioration of the physical properties of the rubber and being added below 1.0 phr. In this case, sufficient cross-linking is impossible and the fatigue performance of rubber appears. Such hybrid crosslinking maintains the rubber properties by forming a long and flexible crosslinked structure even at high temperatures.
이하. 본 발명을 실시예에 의거하여 더욱 상세하게 설명하겠는바, 본 발명이 실시예에 한정되는 것은 아니다.Below. The present invention will be described in more detail based on Examples, but the present invention is not limited to Examples.
실시예 1∼3 및 비교예 1∼3Examples 1-3 and Comparative Examples 1-3
특성변화가 적은 부시 재료를 제조하기 위해 다음 표 1과 같은 조성과 배합량에 따라 고무 및 약품을 계량하여 밴버리 혼합기(Banbury Mixer[Kobe Steel co. Ltd])에서 가황계를 제외한 모든 약품을 넣고 4분간 혼련한 후 롤 제분기(Roll Mill[Toyo Seiki co. Ltd])에서 황과 가류촉진제를 고르게 분산 혼합하여 고무 조성물을 제조하였다.In order to manufacture a bush material with little change in properties, rubber and chemicals were weighed according to the composition and blending amount as shown in the following Table 1, and all the chemicals except the vulcanization system were added in a Banbury Mixer (Kobe Steel co. Ltd). After kneading, a rubber composition was prepared by uniformly dispersing sulfur and a vulcanization accelerator in a roll mill (Roll Mill [Toyo Seiki co. Ltd]).
이렇게 만들어진 고무 조성물을 레오미터(Rheometer[Monsanto R100])를 사용하여 적정가류시간을 측정한 뒤 프레스(Press[Toyo Seiki co. Ltd])를 이용하여 165 ℃에서 210 kgf/cm2으로 가열 가압하여 가황시편을 제조하였다. 또한, 고무사출기를 이용하여 부시 제품을 제조하였다.The rubber composition thus prepared was measured using a rheometer (Rheometer [Monsanto R100]) to measure the appropriate holding time, and then heated and pressurized to 210 kgf / cm 2 at 165 ° C. using a press (Press [Toyo Seiki co. Ltd]). Vulcanized specimens were prepared. In addition, a bush product was manufactured using a rubber injection machine.
경도는 KS M 6784에 따라 측정하며, 인장강도, 신율 및 모둘러스는 KS M6782에 따라 아령형 3호로 측정하였다. 또한, 70 ℃에서 72시간 노화 후 물성변화를 평가하고, 압축영구 줄음율은 KS M 6783에 따라 측정하였다.Hardness was measured in accordance with KS M 6784, tensile strength, elongation and modulus were measured in dumbbell type 3 according to KS M6782. In addition, the change in physical properties after 72 hours of aging at 70 ℃, the compression set was measured in accordance with KS M 6783.
제품평가는 당사의 유압식 동특성 시험기[Saginomiya]를 이용하여 부시의Product evaluation was conducted using our hydraulic dynamic testing machine [Saginomiya].
스프링상수(spr'g rate)를 측정하였으며, 기어오븐(Gear oven[Toyo seiki])으로 70℃에서 1000 시간 노화시키면서 각 시간대별로 특성의 변화량을 측정하였다.The spring constant (spr'g rate) was measured, and the amount of change in characteristics was measured at each time period by aging the gear oven (Gear oven [Toyo seiki]) for 1000 hours at 70 ° C.
또한, 유압식 방진고주 피로시험기[Saginomiya]를 이용하여 제품의 내구성능을 측정하였으며 노화품(70 ℃, 1000 h)에 대해서도 내구성능 측정을 수행하였다.In addition, the durability performance of the product was measured using a hydraulic dustproof fatigue tester [Saginomiya], and the durability performance was also measured for aging products (70 ℃, 1000 h).
상기 표 1을 기준으로 시편 및 제품의 결과를 다음 표 2에 나타내었다.The results of the specimens and products based on Table 1 are shown in Table 2 below.
본 발명에 의한 고무 조성물들은 노화에 의해 재료 물성의 저하를 억제하고특성 값의 변화를 최대한 억제하면서 제품의 내구성능을 만족시키는 효과를 나타내었다. 단, 상온상태에서의 내구성능이 약간 저하되는 현상이 나타났으나 이는 형상적인 요인에 의한 보완이 가능하며 노화 후 내구성능을 향상되어지는 현상을 나타내었다. 이는 차량의 사용기간에 따라 고무의 노화가 발생되어지는 현상을 고려할 때 노화 후의 내구성능이 실사용 조선을 반영하는 것으로 판단되어지므로 실제 필드(field)상에서의 내구성능은 향상되어질 것으로 판단된다.Rubber compositions according to the present invention exhibited the effect of satisfying the durability performance of the product while suppressing the degradation of material properties by aging and the maximum change of the characteristic value. However, a slight degradation of the durability at room temperature appeared, but this can be compensated for by geometric factors and improved durability after aging. In consideration of the phenomenon that the aging of the rubber occurs according to the service life of the vehicle, it is determined that the durability after aging reflects the actual shipbuilding, so the durability on the actual field is expected to be improved.
상술한 바와 같이, 본 발명은 황, 가류촉진제를 사용하는 세미 이.브이 큐어 시스템에 하이브리드 가교를 도입한 고무 조성물로 노화에 의한 특성변화를 억제하여 차량 사용년수 증가에 따른 N.V.H 악화를 억제하며 내구성능도 향상되어 차량을 장기 사용해도 초기의 승차감을 유지시키는데 효과가 있다.As described above, the present invention is a rubber composition incorporating hybrid crosslinking in a semi E. Cure system using sulfur and a vulcanization accelerator to suppress NVH deterioration due to the increase in the number of years of use by suppressing changes in characteristics due to aging. Performance is also improved, which is effective in maintaining the initial ride comfort even after long-term use of the vehicle.
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| KR10-2000-0078598A KR100379037B1 (en) | 2000-12-19 | 2000-12-19 | Rubber Compound which has little change in spring rate for Suspension Bush |
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| KR10-2000-0078598A KR100379037B1 (en) | 2000-12-19 | 2000-12-19 | Rubber Compound which has little change in spring rate for Suspension Bush |
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| KR100379037B1 true KR100379037B1 (en) | 2003-04-08 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03227335A (en) * | 1990-01-31 | 1991-10-08 | Kinugawa Rubber Ind Co Ltd | Vibration-damping rubber composition |
| JPH07278355A (en) * | 1994-04-11 | 1995-10-24 | Toyoda Gosei Co Ltd | Rubber composition for sliding member |
| JPH09176395A (en) * | 1995-11-22 | 1997-07-08 | Union Carbide Chem & Plast Technol Corp | Vulcanizable ethylene-alpha-olefin-diene elastomer composition |
| JPH10287750A (en) * | 1997-04-14 | 1998-10-27 | Sanwa Frontier:Kk | Blend rubber composition and production thereof |
| KR20000055350A (en) * | 1999-02-05 | 2000-09-05 | 정몽규 | Stabilizer bar-bush for automobile |
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- 2000-12-19 KR KR10-2000-0078598A patent/KR100379037B1/en active IP Right Grant
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03227335A (en) * | 1990-01-31 | 1991-10-08 | Kinugawa Rubber Ind Co Ltd | Vibration-damping rubber composition |
| JPH07278355A (en) * | 1994-04-11 | 1995-10-24 | Toyoda Gosei Co Ltd | Rubber composition for sliding member |
| JPH09176395A (en) * | 1995-11-22 | 1997-07-08 | Union Carbide Chem & Plast Technol Corp | Vulcanizable ethylene-alpha-olefin-diene elastomer composition |
| JPH10287750A (en) * | 1997-04-14 | 1998-10-27 | Sanwa Frontier:Kk | Blend rubber composition and production thereof |
| KR20000055350A (en) * | 1999-02-05 | 2000-09-05 | 정몽규 | Stabilizer bar-bush for automobile |
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