KR100246140B1 - A composition of epdm rubber by using waste tires of vehicle - Google Patents
A composition of epdm rubber by using waste tires of vehicle Download PDFInfo
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- KR100246140B1 KR100246140B1 KR1019970064828A KR19970064828A KR100246140B1 KR 100246140 B1 KR100246140 B1 KR 100246140B1 KR 1019970064828 A KR1019970064828 A KR 1019970064828A KR 19970064828 A KR19970064828 A KR 19970064828A KR 100246140 B1 KR100246140 B1 KR 100246140B1
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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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
- C08K3/04—Carbon
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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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L17/00—Compositions of reclaimed rubber
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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
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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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
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/20—Recycled plastic
- C08L2207/24—Recycled plastic recycling of old tyres and caoutchouc and addition of caoutchouc particles
Abstract
본 발명은 자동차의 폐타이어를 이용한 에틸렌-프로필렌-디엔계(ethylene-propylene-diene-terpolymer; EPDM) 고무 조성물에 관한 것으로서, 주성분인 EPDM 고무에 자동차 폐타이어 분쇄물, 보강제로 EPDM-산 무수물 그래프트 공중합체, 충진제, 무기가황제, 가황촉진제, 가황촉진조제 및 노화방지제가 포함된 EPDM 고무 조성물에 관한 것이다. 본 발명의 EPDM 고무 조성물은 스코칭(scorching) 시간 및 최적 경화시간이 짧으면서, 열안정성, 내후성, 내노화성 및 내오존성 등의 물성 저하가 작은 우수한 EPDM 고무 조성물이다.The present invention relates to an ethylene-propylene-diene-terpolymer (EPDM) rubber composition using waste tires of automobiles. The present invention relates to an EPDM rubber composition comprising a copolymer, a filler, an inorganic vulcanizing agent, a vulcanization accelerator, a vulcanization accelerator and an anti-aging agent. The EPDM rubber composition of the present invention is an excellent EPDM rubber composition having a short scorching time and an optimum curing time, and having a small deterioration in physical properties such as thermal stability, weather resistance, aging resistance and ozone resistance.
Description
본 발명은 자동차의 폐타이어를 이용한 에틸렌-프로필렌-디엔계(ethylene-propylene-diene-terpolymer; 이하, "EPDM"이라 약칭한다) 고무 조성물에 관한 것으로서, 주성분인 EPDM 고무에 폐타이어의 분쇄물, 보강제 및 각종 첨가제가 포함된 EPDM 고무 조성물에 관한 것이다.The present invention relates to an ethylene-propylene-diene-terpolymer (hereinafter, simply referred to as "EPDM") rubber composition using waste tires of automobiles, comprising a pulverized product of waste tires in EPDM rubber as a main component, It relates to an EPDM rubber composition comprising a reinforcing agent and various additives.
자동차의 수가 급격히 증가하면서 폐자동차의 부품을 처리하는 것이 매우 중요한 문제로 대두되고 있다. 그 중에서도 플라스틱 부품은 재활용하기가 매우 어려운데, 이는 각종 자동차 부품에 사용되는 플라스틱 소재의 대부분이 공중합체, 복합체 및 폴리머 블렌드여서 재활용될 때 수지의 물성이 저하되는 등의 문제가 발생되기 때문이다.As the number of automobiles increases rapidly, the treatment of parts of scrapped vehicles is becoming an important issue. Among them, plastic parts are very difficult to recycle, because most of the plastic materials used in various automobile parts are copolymers, composites, and polymer blends, which causes problems such as deterioration of the physical properties of the resin.
종래의 자동차 폐타이어를 재활용하는 방법으로는 폐타이어 분쇄물과 EPDM을 용융·혼합하여 재생 수지를 제조하였다. 그러나, 분쇄고무에 포함된 가황제로 인해 EPDM 고무의 가교밀도가 감소하게 되며, EPDM과 분쇄고무 간의 낮은 접착력 때문에 재생수지의 인장강도, 신율 및 압축영구줄음율(ratio of permanent shrinkage by compression)이 크게 감소한다는 단점이 있다.In the conventional method of recycling automobile waste tires, recycled resins were prepared by melting and mixing waste tire pulverized products and EPDM. However, the vulcanizing agent contained in the crushed rubber decreases the crosslinking density of the EPDM rubber, and the tensile strength, elongation and the ratio of permanent shrinkage by compression of the recycled resin are greatly increased due to the low adhesion between the EPDM and the crushed rubber. The disadvantage is that it decreases.
또한, 폐타이어를 탈황시켜 재생수지를 생산하는 방법이 있는데, 이 방법은 탈황시 고무사슬의 절단이 발생되기 때문에 원료고무보다 인장강도 및 신율 등의 기계적 물성이 낮다는 문제점이 있다.In addition, there is a method of producing recycled resin by desulfurizing waste tires, and this method has a problem in that mechanical properties such as tensile strength and elongation are lower than raw rubbers because the rubber chain is cut during desulfurization.
이에 본 발명자는 상기와 같은 문제점을 해결하기 위하여 연구를 계속하여 오던 중, 자동차용 부품의 재료로 널리 사용되고 있는 내노화성, 내후성 및 내오존성이 우수한 EPDM 고무를 주성분으로 하고, 여기에 폐타이어 분쇄물, 보강제 및 각종 첨가제를 포함하는 짧은 스코칭 시간, 최적 경화시간 및 최대토크의 내오존성 등의 물성이 저하되지 않은 우수한 EPDM 고무 조성물을 개발하여 본 발명을 완성하였다.Accordingly, the present inventors have continued research to solve the above problems, the main component is EPDM rubber, which is widely used as a material for automobile parts, and has excellent aging resistance, weather resistance, and ozone resistance. The present invention has been completed by developing an excellent EPDM rubber composition that does not degrade physical properties such as short scouring time, optimal curing time and maximum torque ozone resistance including reinforcing agent and various additives.
본 발명의 목적은 자동차 폐타이어를 이용한 EPDM 고무 조성물을 제공하는 것이다.It is an object of the present invention to provide an EPDM rubber composition using automobile waste tires.
상기와 같은 목적을 달성하기 위하여, 본 발명에서는 주성분인 EPDM 고무에 폐타이어 분쇄물, EPDM-말레산 무수물 그래프트 중합체(이하, "EPDM-g-MAH"라 약칭한다), 카본블랙, 가공유, 무기가황제, 가황촉진제, 가황촉진조제 및 노화방지제 등이 포함된 EPDM 고무 조성물을 제공한다.In order to achieve the above object, in the present invention, waste tire ground product, EPDM-maleic anhydride graft polymer (hereinafter abbreviated as "EPDM-g-MAH") in the main component EPDM rubber, carbon black, processed oil, inorganic The present invention provides an EPDM rubber composition containing a vulcanizing agent, a vulcanization accelerator, a vulcanization accelerator, an anti-aging agent and the like.
이하, 본 발명을 상세히 설명하기로 한다.Hereinafter, the present invention will be described in detail.
본 발명의 조성물은 주성분인 EPDM 고무 100 중량%에 폐타이어 분쇄고무가 5∼40 중량%, 카본블랙이 5∼100 중량%, 보강제로서 EPDM-말레산 무수물 그래프트 중합체가 5∼40 중량%, 가공유가 10∼50 중량%, 무기가황제로서 황이 0.5∼5 중량%, 가황촉진제가 0.5∼5 중량%, 가황촉진조제가 5∼20 중량% 및 노화방지제가 0.1∼5 중량%로 포함된 EPDM 고무 조성물이다.The composition of the present invention is 100% by weight of EPDM rubber as a main component, 5 to 40% by weight of waste tire crushed rubber, 5 to 100% by weight of carbon black, 5 to 40% by weight of EPDM-maleic anhydride graft polymer as a reinforcing agent. EPDM rubber containing 10-50 wt% oil, 0.5-5 wt% sulfur as inorganic vulcanizing agent, 0.5-5 wt% vulcanization accelerator, 5-20 wt% vulcanization accelerator and 0.1-5 wt% anti-aging agent Composition.
본 발명의 조성물에는 열안정성, 내후성, 내노화성 및 내오존성이 우수하며, 각종 자동차용 부품의 재료로 널리 사용되는 합성고무인 EPDM 고무가 주성분으로 사용된다.In the composition of the present invention, EPDM rubber, which is a synthetic rubber that is excellent in thermal stability, weather resistance, aging resistance, and ozone resistance, is widely used as a material for various automotive parts, is used as a main component.
본 발명의 조성물에는수평균 분자량이 100,000∼500,000이고, 비중이 0.85∼0.87이며, 무늬점도가 35∼75ML1+4(100℃)인 EPDM 고무를 사용하는 것이 바람직하다.In the composition of the present invention, it is preferable to use EPDM rubber having a number average molecular weight of 100,000 to 500,000, a specific gravity of 0.85 to 0.87, and a pattern viscosity of 35 to 75 ML 1 + 4 (100 ° C).
본 발명의 조성물에는 폐타이어의 분쇄고무가 사용되는데, 평균입도가 300∼450㎛인 것을 5∼40 중량% 첨가하는 것이 바람직하다.Although the crushed rubber | gum of waste tire is used for the composition of this invention, it is preferable to add 5-40 weight% of things with an average particle size of 300-450 micrometers.
본 발명의 조성물에는 카본블랙이 사용되는데, 5∼40 중량%를 첨가하는 것이 바람직하다.Although carbon black is used for the composition of this invention, it is preferable to add 5-40 weight%.
본 발명의 조성물에는 보강성이 크고, 내마모성이 좋으며 입자경이 30∼40㎚ 인 HAF(high abrasion furnace) 또는 사출용 제품으로 평활한 면을 얻을 수 있고, 열전도성이 좋은 FEF(fast extrusion furnace) 등의 카본 블랙이 사용된다.The composition of the present invention has a high reinforcement property, good abrasion resistance, a high abrasion furnace (HAF) having a particle size of 30 to 40 nm, or a smooth surface can be obtained from an injection molding product, and a fast extrusion furnace (FEF) having good thermal conductivity. Carbon black is used.
본 발명의 조성물에는 EPDM-말레산 무수물 그래프트 중합체(EPDM-g-MAH)가 보강제로서 5∼40 중량%가 사용되는데, 10∼30 중량%를 첨가하는 것이 바람직하다.In the composition of the present invention, EPDM-maleic anhydride graft polymer (EPDM-g-MAH) is used as a reinforcing agent, 5 to 40% by weight, preferably 10 to 30% by weight.
또한, 본 발명의 조성물에는 가공유로서 나프텐계 오일이 10∼50 중량%로 첨가된다.In addition, naphthenic oil is added to the composition of the present invention at 10 to 50% by weight as a processing oil.
본 발명의 조성물에는 가황제로서 황이 0.5∼5 중량%로 첨가된다.To the composition of the present invention, sulfur is added at 0.5 to 5% by weight as a vulcanizing agent.
본 발명의 조성물에는 고무의 가황시간을 조절하고, 사용되는 가황제의 양을 감소시키며, 가황온도를 저하시키고, 고무제품의 품질을 향상시키기 위해 가황촉진제(vulcanization accelerator)가 사용되는데, 티우람계 가황촉진제가 0.5∼5 중량%로 첨가된다.In the composition of the present invention, a vulcanization accelerator is used to adjust the vulcanization time of the rubber, reduce the amount of vulcanizing agent used, lower the vulcanization temperature, and improve the quality of the rubber product. Vulcanization accelerator is added at 0.5 to 5% by weight.
본 발명의 조성물에는 가황촉진제와 작용하여 가황촉진효과를 증가시키기 위해 가황촉진조제(vulcanizing acceleration activator)가 사용되는데, 가황촉진조제로서 산화아연과 같은 염기성 금속 산화물과 스테아린 산이 5∼20 중량%로 첨가된다.In the composition of the present invention, a vulcanizing acceleration activator is used to increase the vulcanization accelerator effect by working with a vulcanization accelerator, and as a vulcanization accelerator, a basic metal oxide such as zinc oxide and stearic acid are added at 5 to 20% by weight. do.
본 발명의 조성물에는 가황된 고무가 열, 광 및 산소에 의해 노화되는 것을 방지하기 위하여 노화방지제가 첨가되는데, 벤조이미다졸류의 노방지지제가 0.1∼5 중량%로 첨가된다.An anti-aging agent is added to the composition of the present invention in order to prevent the vulcanized rubber from aging by heat, light and oxygen, and an anti-rusting agent of benzoimidazoles is added at 0.1 to 5% by weight.
이하, 실시예에 의하여 본 발명의 EPDM 고무 조성물에 관하여 상세히 설명한다. 단 이들 실시예는 본 발명을 예시하는 것일 뿐 본 발명이 실시예에 의하여 한정되는 것은 아니다.Hereinafter, the EPDM rubber composition of the present invention will be described in detail by examples. However, these Examples are only for illustrating the present invention and the present invention is not limited by the Examples.
〈실시예 1〉<Example 1>
EPDM 고무 100 중량%를 70℃에서 롤-밀(rolled-mill)을 이용하여 5분 동안 분쇄한 뒤 폐타이어 분쇄고무 30 중량%와 4분 동안 혼합하고, 여기에 카본블랙 20 중량%를 첨가하여 5분 동안 혼합하였다. 이 혼합물에 EPDM-g-MAH 25 중량%를 첨가하여 5분 동안 혼합하고, 여기에 가공유로서 나프텐계 오일 25 중량%를 첨가하여 혼합한 다음 무기가황제로서 황을 1.5 중량%, 가황촉진제로서 티우람계 화합물을 1.5 중량%, 가황촉진조제로서 산화아연과 스테아린 산을 5 중량%, 그리고 노화방지제로서 테트라부틸 티우람 디설파이드(t-butyl thiuram disulfide) 0.5 중량%를 첨가하여 5분 동안 골고루 섞어준 뒤 경화시켜 시편을 제조하였다.100% by weight of EPDM rubber was pulverized using a rolled mill at 70 ° C. for 5 minutes, mixed with 30% by weight of waste tire crushed rubber for 4 minutes, and 20% by weight of carbon black was added thereto. Mix for 5 minutes. 25% by weight of EPDM-g-MAH was added to the mixture and mixed for 5 minutes. 25% by weight of naphthenic oil was added thereto as a processing oil, followed by mixing. 1.5% by weight of the uranium compound, 5% by weight of zinc oxide and stearic acid as a vulcanization accelerator, and 0.5% by weight of t-butyl thiuram disulfide as an anti-aging agent were mixed evenly for 5 minutes. After curing, a specimen was prepared.
제조된 시편은 스코칭 시간, 최적 경화시간, 인장강도(ASTM D638), 신율(ASTM D638), 인장 모듈러스(신율 300%), 인열강도 및 내오존성(ASTM D256)을 측정하여 하기 표 2에 나타낸 바와 같은 결과를 얻었다.The prepared specimens were measured in scouring time, optimal hardening time, tensile strength (ASTM D638), elongation (ASTM D638), tensile modulus (elongation 300%), tear strength and ozone resistance (ASTM D256) The results as shown were obtained.
〈실시예 2 내지 5〉<Examples 2 to 5>
본 발명에서는 하기 표 1로 구성되는 실시예의 조성물을 상기 실시예 1의 방법과 동일한 방법으로 제조하였다.In the present invention, the composition of the Example consisting of Table 1 was prepared in the same manner as in Example 1.
제조된 시편은 스코칭 시간, 최적 경화시간, 인장강도(ASTM D638), 신율(ASTM D638), 인장모듈러스(신율 300%), 인열강도 및 내오존성(ASTM D256)을 측정하여 하기 표 2에 나타낸 바와 같은 결과를 얻었다.The prepared specimens were measured for scouring time, optimal hardening time, tensile strength (ASTM D638), elongation (ASTM D638), tensile modulus (300% elongation), tear strength and ozone resistance (ASTM D256). The results as shown were obtained.
상기한 실시예의 조성을 갖는 본 발명의 EPDM 고무 조성물과 비교하기 위하여 하기 비교실시예의 조성을 갖는 EPDM 고무 조성물을 제조하였다.An EPDM rubber composition having the composition of the following comparative example was prepared for comparison with the EPDM rubber composition of the present invention having the composition of the above-described example.
〈비교실시예〉<Comparative Example>
EPDM 고무 125 중량%를 70℃에서 롤-밀(rolled-mill)을 이용하여 5분 동안 분쇄한 뒤 폐타이어 분쇄고무 30 중량%와 4분 동안 혼합하고, 여기에 카본블랙 20 중량%를 첨가하여 5분 동안 혼합하였다. 이 혼합물에 가공유로서 나프텐계 오일 25 중량%를 첨가하여 혼합한 다음 무기 가황제로서 황을 1.5 중량%, 가황촉진제로서 티우람계 화합물을 1.5 중량%, 가황촉진조제로서 산화아연과 스테아린 산을 5 중량%, 그리고 노화방지제로서 테트라부틸 티우람 디설파이드(t-butyl thiuram disulfide) 0.5 중량%를 첨가하여 5분 동안 골고루 섞어준 뒤 경화시켜 시편을 제조하였다.125% by weight of EPDM rubber was pulverized using a rolled-mill at 70 ° C. for 5 minutes, mixed with 30% by weight of waste tire crushed rubber for 4 minutes, and 20% by weight of carbon black was added thereto. Mix for 5 minutes. To this mixture, 25 wt% of naphthenic oil was added as a processing oil and mixed, 1.5 wt% of sulfur as an inorganic vulcanizing agent, 1.5 wt% of thiuram compound as a vulcanization accelerator, and 5% of zinc oxide and stearic acid as a vulcanization accelerator. By weight, and 0.5% by weight of tetrabutyl thiuram disulfide (t-butyl thiuram disulfide) was added to the mixture by mixing for 5 minutes and then cured to prepare a specimen.
제조된 시편은 스코칭 시간, 최적 경화시간, 인장강도(ASTM D638), 신율(ASTM D638), 인장모듈러스(신율 300%), 인열강도 및 내오존성(ASTM D256)을 측정하여 하기 표 2에 나타낸 바와 같은 결과를 얻었다.The prepared specimens were measured for scouring time, optimal hardening time, tensile strength (ASTM D638), elongation (ASTM D638), tensile modulus (300% elongation), tear strength and ozone resistance (ASTM D256). The results as shown were obtained.
상기에서 살펴본 바와 같이, 본 발명의 폐타이어를 이용한 EPDM 고무 조성물은 주성분인 EPDM의 물성저하가 없으면서 스코칭 시간이 짧으면서, 최적 경화시간 및 최대 토크의 내오존성 등의 기타 물성이 저하되지 않은 우수한 EPDM 고무 조성물로서 각종 자동차용 부품에 유용하게 사용될 수 있다.As described above, the EPDM rubber composition using the waste tire of the present invention is excellent in that the scouring time is short without the physical property deterioration of the main component EPDM, and other physical properties such as optimum curing time and ozone resistance of the maximum torque are not deteriorated. The EPDM rubber composition can be usefully used in various automotive parts.
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| KR1019970064828A KR100246140B1 (en) | 1997-11-29 | 1997-11-29 | A composition of epdm rubber by using waste tires of vehicle |
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| KR1019970064828A KR100246140B1 (en) | 1997-11-29 | 1997-11-29 | A composition of epdm rubber by using waste tires of vehicle |
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| KR100246140B1 true KR100246140B1 (en) | 2000-03-15 |
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Cited By (4)
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|---|---|---|---|---|
| KR100867417B1 (en) * | 2006-12-22 | 2008-11-06 | (주)폴리싸이클 | Apparatus and Method for devulcanization and deodorization of Reclaimed Rubber Powder |
| KR101280838B1 (en) | 2011-05-11 | 2013-07-02 | 주식회사 대흥알앤티 | Rubber compound for car engine mount enhanced dynamic characteristics by mixing epdm with silica |
| KR101335962B1 (en) * | 2011-12-28 | 2013-12-03 | 한국타이어 주식회사 | Rubber composition for tire cord topping and tire manufactured by using the same |
| KR101338005B1 (en) * | 2011-05-11 | 2013-12-06 | 주식회사 대흥알앤티 | Rubber compound for car engine mount enhanced vds by mixing epdm with hybrid vulcanization system |
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| KR100392502B1 (en) * | 2000-10-27 | 2003-07-22 | 금호산업주식회사 | Rubber composition for tire |
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1997
- 1997-11-29 KR KR1019970064828A patent/KR100246140B1/en not_active IP Right Cessation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100867417B1 (en) * | 2006-12-22 | 2008-11-06 | (주)폴리싸이클 | Apparatus and Method for devulcanization and deodorization of Reclaimed Rubber Powder |
| KR101280838B1 (en) | 2011-05-11 | 2013-07-02 | 주식회사 대흥알앤티 | Rubber compound for car engine mount enhanced dynamic characteristics by mixing epdm with silica |
| KR101338005B1 (en) * | 2011-05-11 | 2013-12-06 | 주식회사 대흥알앤티 | Rubber compound for car engine mount enhanced vds by mixing epdm with hybrid vulcanization system |
| KR101335962B1 (en) * | 2011-12-28 | 2013-12-03 | 한국타이어 주식회사 | Rubber composition for tire cord topping and tire manufactured by using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR19990043786A (en) | 1999-06-15 |
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