KR20130007765A - A composite for non-asbestos sheet and gasket - Google Patents
A composite for non-asbestos sheet and gasket Download PDFInfo
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- KR20130007765A KR20130007765A KR1020110068289A KR20110068289A KR20130007765A KR 20130007765 A KR20130007765 A KR 20130007765A KR 1020110068289 A KR1020110068289 A KR 1020110068289A KR 20110068289 A KR20110068289 A KR 20110068289A KR 20130007765 A KR20130007765 A KR 20130007765A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/02—Copolymers with acrylonitrile
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- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- 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
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- C08K5/14—Peroxides
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- 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
- C08K7/00—Use of ingredients characterised by shape
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- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L7/00—Compositions of natural rubber
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
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Abstract
Description
본 발명은 비석면 시트 및 가스켓의 조성물에 관한 것으로, 더욱 상세하게는 유기용매를 사용하지 않도록 조성함으로써 인체에 무해하여 보다 친환경적인 제품을 생산할 수 있고, 제조시간과 제조단계를 50%이상 단축하여 생산성을 현저히 높일 수 있는 비석면 시트 및 가스켓의 조성물에 관한 것이다.The present invention relates to a composition of non-asbestos sheets and gaskets, and more specifically, by not using an organic solvent, it is possible to produce a more environmentally friendly product harmless to the human body, and to reduce the manufacturing time and manufacturing steps by more than 50% It relates to a composition of non-asbestos sheets and gaskets that can significantly increase productivity.
종래 비석면 시트 및 가스켓의 조성물은 유기용제로 팽윤시킨 니트릴고무와 비석면계 무기물 섬유, 고무 첨가제, 가황제, 무기필러를 혼련하고, 이를 다시 열롤과 냉각롤 사이에서 가열 압연하여 가스켓으로 제조하였다.Conventional non-asbestos sheets and gaskets are prepared by mixing a nitrile rubber swelled with an organic solvent, a non-asbestos-based inorganic fiber, a rubber additive, a vulcanizing agent, and an inorganic filler and heat rolling between a heat roll and a cooling roll.
또한, 일본공개특허 제2008-0274053호)에 기재된 비석면계 시트가스켓은 섬유, 흑연, 고무를 물과 함께 교반한 후, 열프레스에서 적층 일체화시켜 제조하도록 구성되어 있다.In addition, the non-asbestos-based sheet gasket described in Japanese Patent Laid-Open No. 2008-0274053) is configured to stir fibers, graphite, and rubber together with water, and then to laminate and fabricate them in a heat press.
일본공개특허 제2005-0281463호에 기재된 석면 이외의 섬유를 사용한 조인트시트 및 그 제조방법은 섬유, 용제로 팽창시킨 고무, 고무약품, 활성백토, 또는 산성배토를 혼련한 후, 이를 가열 압연하여 조인트시트를 제조하도록 구성되어 있다.Joint sheet using a fiber other than asbestos described in Japanese Patent Application Laid-Open No. 2005-0281463 and a method for producing the same are kneaded with fibers, rubber expanded with a solvent, rubber chemicals, activated clay, or acidic clay, and then heated and rolled to form a joint It is configured to manufacture a sheet.
또한, 일본공개특허 제2000-0034467호에 기재된 조인트시트 형성용 조성물, 조인트시트 및 그 제조방법은 비석면계 무기물 섬유, 니트릴고무, 유기용제로 톨루엔을 이용한 조성물을 열롤과 냉각롤 사이에서 가열 압연하여 조인트시트를 제조하도록 구성되어 있다. In addition, the composition for forming a joint sheet, the joint sheet, and a method of manufacturing the same are described in JP 2000-0034467 A by using a non-asbestos-based inorganic fiber, nitrile rubber, and a composition using toluene as an organic solvent by heat rolling between a heat roll and a cooling roll. It is configured to manufacture a joint sheet.
일본공개특허 제1993-0162157호에 기재된 조인트시트의 제조방법은 유리섬유, 폴리아미드계 섬유, 유기용제에 용해시킨 천연고무 또는 합성고무와 충전제를 혼합하여 얻은 혼합물을 냉롤과 열롤 사이에 투입하여 조인트시트를 제조하도록 구성되어 있다.The method for producing a joint sheet described in Japanese Patent Application Laid-Open No. 1993-0162157 includes a mixture obtained by mixing a natural or synthetic rubber dissolved in a glass fiber, a polyamide fiber, an organic solvent, and a filler between a cold roll and a hot roll, and then It is configured to manufacture a sheet.
그러나, 상기한 비석면 가스켓은 과량의 충전제 및 섬유를 혼합하기 위하여 유기용제에 고무를 팽윤시켜 혼합하게 되고, 이처럼 비석면 가스켓의 조성물중 유기용제로 팽윤된 고무조성물을 사용하게 되면 과량의 충진제를 혼합할 수 있는 장점이 있지만, 팽윤에 따른 고무의 기계적 강도의 저하와 유기용제의 사용에 따른 작업환경오염 등 여러 문제가 발생된다. However, the non-asbestos gasket is swelled and mixed with an organic solvent in order to mix the excess filler and fiber, and when the rubber composition swelled with the organic solvent in the composition of the non-asbestos gasket is used, Although there is an advantage that can be mixed, there are various problems such as a decrease in the mechanical strength of the rubber due to swelling and pollution of the working environment due to the use of organic solvents.
또한, 비석면 가스켓의 조성물중 유기용제를 포함하는 경우 최소 2~3일 정도의 제조기간이 소요되는 등 제조의 생산성 및 경제성이 매우 떨어지면서 제조원가의 상승을 초래하게 되고, 궁극적으로 가격경쟁력이 현저히 저하되는 등의 문제를 초래하게 된다.In addition, when the non-asbestos gasket composition contains an organic solvent, a manufacturing period of at least 2 to 3 days is required, leading to an increase in manufacturing cost due to a very low productivity and economical efficiency, and ultimately a price competitiveness. It may cause problems such as deterioration.
본 발명은 상기한 종래 기술의 문제를 개선하기 위하여 안출된 것으로, 유기용매를 사용하지 않도록 조성함으로써 인체에 무해하여 보다 친환경적인 제품을 생산할 수 있고, 제조시간과 제조단계를 50%이상 단축하여 생산성을 현저히 높일 수 있는 비석면 시트 및 가스켓의 조성물을 제공함에 그 목적이 있다.The present invention has been made in order to improve the above problems of the prior art, it is possible to produce a more environmentally friendly product harmless to the human body by formulating not to use an organic solvent, the production time and manufacturing steps by reducing the productivity by more than 50% The purpose is to provide a composition of non-asbestos sheets and gaskets that can significantly increase the.
상기한 목적을 달성하기 위하여 본 발명은 아크릴니트릴부타디엔 고무 60~80 중량부, 저밀도 폴리에틸렌 수지 10~20 중량부, 천연고무 10~20 중량부로 혼합기재를 조성하고, 상기 혼합기재 100중량부에 대해서 무기 충전제 200~600중량부, 보강섬유 20~100 중량부, 실리카 10~50 중량부, 실란커플링제 2~5 중량부, 과산화물 가교제 2~5 중량부, 금속산화물 2~5중량부, 스테아린산 1~2중량부로 조성되는 것을 특징으로 하는 비석면 시트 및 가스켓의 조성물을 제공하게 된다.In order to achieve the above object, the present invention provides a mixed base with 60 to 80 parts by weight of acrylonitrile butadiene rubber, 10 to 20 parts by weight of low density polyethylene resin, and 10 to 20 parts by weight of natural rubber, and with respect to 100 parts by weight of the mixed base. Inorganic filler 200 to 600 parts by weight, reinforcing fibers 20 to 100 parts by weight, silica 10 to 50 parts by weight, silane coupling agent 2 to 5 parts by weight, peroxide crosslinking agent 2 to 5 parts by weight, metal oxides 2 to 5 parts by weight, stearic acid 1 It is to provide a composition of non-asbestos sheet and gasket, characterized in that the composition is ˜2 parts by weight.
이상과 같이 구성되는 본 발명은 친환경적이면서 생산성 및 효율성을 현저히 높일 수 있고, 이로부터 제조원가를 현격하게 낮출 수 있어 가격경쟁력을 높일 수 있는 등의 효과를 제공하게 된다.The present invention constituted as described above can significantly increase productivity and efficiency, and can significantly lower manufacturing costs therefrom, thereby providing an effect of increasing price competitiveness.
이하에서는 본 발명의 바람직한 실시예를 상세히 설명하기로 한다.Hereinafter, a preferred embodiment of the present invention will be described in detail.
본 발명에서는 혼합기재 100 중량부에 대해서, 아크릴니트릴부타디엔 고무는 60~80 중량부를 사용하는 것이 바람직한데, 아크릴니트릴부타디엔 고무 60 중량부 미만으로 사용할 경우 가스켓의 내유특성이 저하되는 문제가 있으며, 80중량부를 초과하는 경우 내열성 및 가공성이 떨어지는 문제가 있다. In the present invention, it is preferable to use 60 to 80 parts by weight of acrylonitrile butadiene rubber with respect to 100 parts by weight of the mixed substrate, but when using less than 60 parts by weight of acrylonitrile butadiene rubber, there is a problem that the oil resistance of the gasket is reduced, 80 When it exceeds the weight part, there exists a problem that heat resistance and workability are inferior.
또한, 본 발명에서 사용하는 아크릴니트릴부타디엔 고무는 가스켓의 내유성을 고려하여 아크릴나트릴의 함량이 30~40중량%, 가스켓의 가공성을 고려하여 무늬점도(ML1 +4, 100℃)가 40~80 범위의 기재를 사용하는 것이 바람직하다.In addition, the acrylonitrile butadiene rubber used in the present invention is 30 ~ 40% by weight of acryl natryl in consideration of oil resistance of the gasket, the pattern viscosity (ML 1 +4 , 100 ℃) 40 ~ in consideration of the workability of the gasket Preference is given to using substrates in the 80 range.
저밀도 폴리에틸렌 수지는 혼합기재 100 중량부에 대해서 10~20 중량부를 사용하는 것이 내열성 및 기계적강도 개선을 위해 바람직한데, 10중량부 미만으로 사용할 경우 가스켓의 내열성이 저하되며, 20중량부를 초과하는 경우 내유성이 저하되면서 가공성이 떨어지는 문제가 있다. The low density polyethylene resin is preferably used in an amount of 10 to 20 parts by weight based on 100 parts by weight of the mixed base material to improve heat resistance and mechanical strength. When it is used below 10 parts by weight, the heat resistance of the gasket is lowered. There is a problem in that workability is inferior while being lowered.
특히, 본 발명에서 사용하는 저밀도 폴리에틸렌 수지는 조성물의 가공성 개선을 위해 그 용융점도(MI, g/10min)가 20~30 범위의 수지를 적용하는 것이 바람직하다. In particular, in the low density polyethylene resin used in the present invention, it is preferable to apply a resin having a melt viscosity (MI, g / 10 min) of 20 to 30 in order to improve processability of the composition.
천연고무는 혼합기재 100중량부에 대해서 10~20 중량부를 사용하는 것이 조성물의 가공성 및 기계적 강도 개선을 위해 바람직한데, 10중량부 미만으로 사용할 경우 조성물의 가공성이 떨어지고, 20중량부를 초과하는 경우 내유성이 저하되는 문제가 있다.It is preferable to use 10-20 parts by weight based on 100 parts by weight of natural rubber for improving the processability and mechanical strength of the composition. When using less than 10 parts by weight, the processability of the composition is lowered, and oil resistance is greater than 20 parts by weight. This has a problem of deterioration.
이처럼, 본 발명의 혼합기재는 아크릴니트릴부타디엔 고무 60~80 중량부, 저밀도 폴리에틸렌 수지 10~20 중량부, 천연고무 10~20 중량부로 조성된다.As such, the mixed base of the present invention is composed of 60 to 80 parts by weight of acrylonitrile butadiene rubber, 10 to 20 parts by weight of low density polyethylene resin, and 10 to 20 parts by weight of natural rubber.
그리고, 본 발명에서 사용되는 무기 충전제는 혼합기재 100중량부에 대해서 200~600중량부 범위에서 사용하는 것이 바람직 하지만, 200중량부 미만에서는 가스켓의 내열성이 떨어지는 문제가 있으며, 600중량부를 초과하는 경우 조성물의 작업성이 저하되는 문제가 있다. In addition, the inorganic filler used in the present invention is preferably used in the range of 200 to 600 parts by weight with respect to 100 parts by weight of the mixed base, but if less than 200 parts by weight, there is a problem that the heat resistance of the gasket is inferior and exceeds 600 parts by weight. There exists a problem that the workability of a composition falls.
본 발명에서는 무기충전제로서 고령토와 황산바륨을 단독 또는 혼합하여 사용하도록 구성되어 있다. In the present invention, the inorganic filler is configured to use kaolin and barium sulfate alone or in combination.
또한, 본 발명에서 사용되는 보강섬유는 혼합기재 100중량부에 대해서 20~100 중량부를 사용하는 것이 바람직한데, 20중량부 미만에서는 보강효과가 떨어지며, 100 중량부를 초과하는 경우 조성물의 분산성 불량에 따른 기계적 강도의 개선 효과가 떨어진다. In addition, the reinforcing fibers used in the present invention is preferably used 20 to 100 parts by weight with respect to 100 parts by weight of the mixed base, less than 20 parts by weight of the reinforcing effect is poor, if the content exceeds 100 parts by weight to the poor dispersibility of the composition The improvement effect of mechanical strength is inferior.
본 발명에서의 보강섬유는 아라미드 섬유, 셀롤로오즈 섬유, 유리섬유, 폴리에스터 섬유, 나일론 섬유, 폴리프로필렌 섬유를 단독 또는 혼합하여 사용하도록 구성되어 있다.Reinforcing fibers in the present invention is configured to use aramid fibers, cellulose fibers, glass fibers, polyester fibers, nylon fibers, polypropylene fibers alone or in combination.
본 발명에서의 실리카는 혼합기재 100중량부에 대해서 10~50 중량부를 사용하는 것이 바람직한데, 10 중량부 미만에서는 보강효과와 보강섬유의 분산성을 개선하는 효과가 떨어지며, 50 중량부를 초과하는 경우 복원율이 떨어지는 문제가 있다. In the present invention, it is preferable to use 10 to 50 parts by weight with respect to 100 parts by weight of the mixed substrate, but less than 10 parts by weight of the reinforcing effect and the effect of improving the dispersibility of the reinforcing fibers is less than, if more than 50 parts by weight There is a problem that the recovery rate falls.
본 발명에서의 실란커플링제는 혼합기재 100중량부에 대해서 2~5 중량부를 사용하는 것이 바람직한데, 2중량부 미만에서는 보강효과와 실리카의 분산성을 개선하는 효과가 떨어지며, 5 중량부를 초과하는 경우 조성물의 스코치(scotch)에 대한 위험성이 커지게 된다.In the present invention, the silane coupling agent is preferably used in an amount of 2 to 5 parts by weight based on 100 parts by weight of the mixed base material. When the silane coupling agent is less than 2 parts by weight, the reinforcing effect and the effect of improving the dispersibility of silica are inferior. The risk for scotch of the composition is increased.
이때, 본 발명에서는 실란커플링제로서 비닐계 실란(비닐트리클로로 실란, 비닐트리메톡시실란, 비닐트리에톡시 실란), 에폭시계 실란(γ-글리시독시프로필메틸디에폭시 실란, γ-글리시독시프로필트리메톡시 실란, γ-글리시독시프로필트리에톡시 실란), 아미노계실란(γ-아미노프로필트리메톡시 실란, γ-아미노프로필트리에톡시 실란), 메타크리록시계 실란(γ-메타아크릴옥시프로필트리에톡시 실란, γ-메타아크릴옥시프로필트리메톡시 실란), 클로로프로필 실란(γ-클로로프로필트리에톡시 실란), 메르카프토 실란(γ-메르카프토프로필트리메톡시 실란) 등으로 이루어진 군에서 선택되는 어느 하나를 사용하도록 구성되어 있다. At this time, in the present invention, a vinyl silane (vinyl trichloro silane, vinyl trimethoxy silane, vinyl triethoxy silane), an epoxy silane (γ-glycidoxypropylmethyldiepoxy silane, γ-glycis) as a silane coupling agent Doxypropyltrimethoxy silane, γ-glycidoxypropyltriethoxy silane), amino silane (γ-aminopropyltrimethoxy silane, γ-aminopropyltriethoxy silane), methacryloxy silane (γ-meta Acryloxypropyltriethoxy silane, γ-methacryloxypropyltrimethoxy silane), chloropropyl silane (γ-chloropropyltriethoxy silane), mercapto silane (γ-mercaptopropyltrimethoxy silane) It is configured to use any one selected from the group consisting of.
한편, 본 발명에서는 조성물의 가교를 위해 과산화물 가교제를 사용하였고, 과산화물 가교제는 아크릴로니트릴부타디엔 고무 100 중량부에 대해서 2~5 중량부를 사용하는 것이 바람직한데, 2 중량부 미만에서는 가교효율이 떨어져 기계적 강도가 저하되며, 5 중량부를 초과하는 경우 과대한 가교로 인해 강도가 오히려 떨어지는 우려가 있다.Meanwhile, in the present invention, a peroxide crosslinking agent was used for crosslinking the composition, and the peroxide crosslinking agent is preferably used in an amount of 2 to 5 parts by weight based on 100 parts by weight of acrylonitrile butadiene rubber. If the strength is lowered and exceeds 5 parts by weight, there is a fear that the strength is rather lower due to excessive crosslinking.
본 발명에서의 가교제는 유기과산화물계 화합물이 바람직하며, 유기과산화물계 가교제로는 2,5-비스(터트부틸퍼옥시)-2,5-디메틸-3-헥엔, 디터트부틸퍼옥사이드, 2,5-비스(터트부틸퍼옥시)-2,5-디메틸-헥엔, 디벤조일퍼옥사이드, 비스(터트부틸퍼옥시이소프로필)벤젠, 부틸 4,4-비스(터트부틸퍼옥시)발러레이트, 1,1-비스(터트부틸퍼옥시)3,3,5-트리메틸클로로헥산, 터트부틸퍼옥시벤조에이트, 라우릴퍼옥사이드, 디큐밀퍼옥사이드 등을 사용하였다. The crosslinking agent in the present invention is preferably an organic peroxide compound, and as the organic peroxide crosslinking agent, 2,5-bis (tertbutylperoxy) -2,5-dimethyl-3-hexene, ditertbutyl peroxide, 2, 5-bis (tertbutylperoxy) -2,5-dimethyl-hexene, dibenzoylperoxide, bis (tertbutylperoxyisopropyl) benzene, butyl 4,4-bis (tertbutylperoxy) valorate, 1 , 1-bis (tertbutylperoxy) 3,3,5-trimethylchlorohexane, tertbutylperoxybenzoate, lauryl peroxide, dicumyl peroxide and the like were used.
본 발명에서 사용되는 첨가제는 아크릴로니트릴부타디엔 고무 100중량부에 대해서 금속산화물 2~5중량부, 스테아린산 1~2중량부를 사용하는 것이 바람직하며, 이는 통상적으로 고무용 조성물에서 사용되는 범위라 할 수 있다.As the additive used in the present invention, it is preferable to use 2 to 5 parts by weight of a metal oxide and 1 to 2 parts by weight of stearic acid based on 100 parts by weight of acrylonitrile butadiene rubber, which can be referred to as a range generally used in rubber compositions. have.
이상과 같은 조성물로 이루어지는 비석면 시트 및 가스켓의 제조공정을 설명하면 다음과 같다. Referring to the manufacturing process of the non-asbestos sheet and gasket composed of the composition as described above are as follows.
먼저, 기재인 아크릴로니트릴부타디엔 고무와 저밀도 폴리에틸렌 수지, 천연고무로 구성된 기재 100중량부에 대하여, 무기 충전제, 보강섬유, 실리카, 실란커플링제, 금속산화물, 스테아린산 등을 니이더(kneader)를 이용하여 혼련한 후, 오픈 롤밀에서 가교제를 혼합하여 조성물을 조성하며, 이 조성물을 고온/고압의 열프레스를 통해서 시트 및 가스켓을 성형하게 된다.First, an inorganic filler, a reinforcing fiber, silica, a silane coupling agent, a metal oxide, stearic acid, and the like are used for 100 parts by weight of a base material composed of acrylonitrile butadiene rubber, a low density polyethylene resin, and natural rubber. After kneading and kneading, a crosslinking agent is mixed in an open roll mill to form a composition, and the composition forms a sheet and a gasket through a high temperature / high pressure heat press.
더욱 상세하게 설명하면, 아크릴로니트릴부타디엔 고무 60~80 중량부와 저밀도 폴리에틸렌 수지 10~20 중량부, 천연고무 10~20중량부로 조성된 혼합기재 100 중량부에 대해서 보강섬유 20~100중량부, 실리카 10~50중량부, 실란커플링제 1~5 중량부, 금속산화물 2~5중량부, 스테아린산 1~2 중량부, 무기충진제 200~600중량부를 100~120℃의 니이더(kneader) 믹서에서 10~15분간 혼련한 후, 다시 60~80℃의 오픈롤에서 가교제 2~5 중량부를 추가 배합하여 가스켓의 조성물을 완성하고, 이 조성물을 시트상으로 성형하게 된다. More specifically, the reinforcing fiber 20 to 100 parts by weight based on 60 to 80 parts by weight of acrylonitrile butadiene rubber, 10 to 20 parts by weight of low density polyethylene resin, and 100 parts by weight of the mixed base material composed of 10 to 20 parts by weight of natural rubber, 10 to 50 parts by weight of silica, 1 to 5 parts by weight of silane coupling agent, 2 to 5 parts by weight of metal oxide, 1 to 2 parts by weight of stearic acid, and 200 to 600 parts by weight of inorganic filler in a kneader mixer at 100 to 120 ° C. After kneading for 10 to 15 minutes, 2 to 5 parts by weight of the crosslinking agent is further blended in an open roll at 60 to 80 ° C to complete the composition of the gasket, and the composition is molded into a sheet.
그리고, 성형된 상기 시트를 열 프레스에서 150~170℃, 100~150kg/cm2의 고온고압으로 5~10분간 다시 성형하여 가스켓으로 제조하게 된다.Then, the molded sheet is re-molded at a high temperature and high pressure of 150 to 170 ° C. and 100 to 150 kg / cm 2 in a hot press for 5 to 10 minutes to prepare a gasket.
이하에서는 본 발명을 실시예에 의거하여 더욱 구체적으로 설명하도록 한다.Hereinafter, the present invention will be described in more detail with reference to Examples.
아크릴로니트릴부타디엔 고무 70 중량부와 저밀도 폴리에틸렌 수지 20 중량부, 천연고무 10중량부로 조성된 혼합기재 100 중량부에 대해서 아라미드섬유 20중량부, 유리섬유 40 중량부, 실리카 20 중량부, 실란커플링제 1중량부, 금속산화물 5중량부, 스테아린산 1 중량부, 고령토 300중량부로 구성된 조성물을 니이더(kneader) 믹서에서 100~120℃, 약 12분동안 혼련하였다.20 parts by weight of aramid fibers, 40 parts by weight of glass fibers, 20 parts by weight of silica, and a silane coupling agent based on 70 parts by weight of acrylonitrile butadiene rubber, 20 parts by weight of a low density polyethylene resin, and 100 parts by weight of a mixed base composed of 10 parts by weight of natural rubber. The composition consisting of 1 part by weight, 5 parts by weight of metal oxide, 1 part by weight of stearic acid, and 300 parts by weight of kaolin was kneaded in a kneader mixer for 100 to 120 ° C. for about 12 minutes.
니이더 혼련작업을 끝난 조성물은 오픈 롤밀에서 기재 100 중량부에 대해서 유기과산화물 3중량부 투입하여 균일하게 혼합시킨 후, 2mm두께의 시트로 성형된다.After kneading kneading, the composition is added to 3 parts by weight of organic peroxide with respect to 100 parts by weight of the substrate in an open roll mill and uniformly mixed, and then molded into a sheet having a thickness of 2 mm.
그리고, 2mm두께로 성형된 시트를 2mm두께의 금형에 투입한 후, 155℃, 150kg/cm2의 프레스 조건에서 약 5분간 프레스 성형하여 비석면 가스켓으로 제조 완성하였다. Then, the sheet molded to a thickness of 2mm was put into a mold of 2mm thickness, and then press-molded for about 5 minutes under a press condition of 155 ° C and 150kg / cm 2 to manufacture and complete a non-asbestos gasket.
아크릴로니트릴부타디엔 고무 70 중량부와 저밀도 폴리에틸렌 수지 20 중량부, 천연고무 10중량부로 구성된 혼합기재 100 중량부에 대해서 셀롤로오즈 섬유 40중량부, 유리섬유 40 중량부, 실리카 10 중량부, 실란커플링제 1중량부, 금속산화물 5중량부, 스테아린산 1 중량부, 고령토 400중량부로 구성된 조성물을 니이더(kneader)에서 100~120℃, 약 12분동안 혼련하였다.40 parts by weight of cellulose fiber, 40 parts by weight of glass fiber, 10 parts by weight of silica, silane coupler based on 100 parts by weight of a mixed base composed of 70 parts by weight of acrylonitrile butadiene rubber, 20 parts by weight of low density polyethylene resin, and 10 parts by weight of natural rubber. The composition consisting of 1 part by weight of the ring agent, 5 parts by weight of metal oxide, 1 part by weight of stearic acid, and 400 parts by weight of kaolin was kneaded in a kneader at 100 to 120 ° C. for about 12 minutes.
그리고, 상기 조성물은 오픈 롤밀에서 기재 100 중량부에 대해서 유기과산화물 3중량부 투입하여 균일하게 혼합시킨 후, 2mm두께의 시트로 제조하였다.In addition, the composition was prepared by mixing 3 parts by weight of organic peroxide with respect to 100 parts by weight of the substrate in an open roll mill, and then uniformly mixing the sheet with a thickness of 2 mm.
이때, 2mm두께로 성형된 시트를 2mm두께의 금형에 투입한 후, 155℃, 150kg/cm2의 프레스 조건에서 약 5분간 프레스 성형하여 비석면 가스켓으로 제조 완성하였다. At this time, the sheet formed to a thickness of 2mm was put into a mold of 2mm thickness, and then press-molded for about 5 minutes at a press condition of 155 ° C. and 150kg / cm 2 to produce a non-asbestos gasket.
아크릴로니트릴부타디엔 고무 80 중량부와 저밀도 폴리에틸렌 수지 10 중량부, 천연고무 10중량부로 구성된 혼합기재 100 중량부에 대해서 아라미드 섬유 50중량부, 유리섬유 50 중량부, 실리카 20 중량부, 실란커플링제 1중량부, 금속산화물 5중량부, 스테아린산 1 중량부, 황산바륨 500중량부로 구성된 조성물을 니이더(kneader)에서 100~120℃, 약 15분동안 혼련하였다.50 parts by weight of aramid fiber, 50 parts by weight of glass fiber, 20 parts by weight of silica, silane coupling agent 1 with respect to 100 parts by weight of a mixed base composed of 80 parts by weight of acrylonitrile butadiene rubber, 10 parts by weight of low density polyethylene resin, and 10 parts by weight of natural rubber. The composition consisting of parts by weight, 5 parts by weight of metal oxide, 1 part by weight of stearic acid, and 500 parts by weight of barium sulfate was kneaded in a kneader at 100 to 120 ° C. for about 15 minutes.
그리고, 상기 조성물은 오픈 롤밀에서 기재 100 중량부에 대해서 유기과산화물 3중량부 투입하여 균일하게 혼합시킨 후, 2mm두께의 시트로 제조하였다.In addition, the composition was prepared by mixing 3 parts by weight of organic peroxide with respect to 100 parts by weight of the substrate in an open roll mill, and then uniformly mixing the sheet with a thickness of 2 mm.
이때, 2mm두께로 성형된 시트를 2mm두께의 금형에 투입한 후, 155℃, 150kg/cm2의 프레스 조건에서 약 5분간 프레스 성형하여 비석면 가스켓으로 제조 완성하였다. At this time, the sheet formed to a thickness of 2mm was put into a mold of 2mm thickness, and then press-molded for about 5 minutes at a press condition of 155 ° C. and 150kg / cm 2 to produce a non-asbestos gasket.
비교예Comparative example 1 One
아크릴로니트릴부타디엔 고무 50 중량부와 저밀도 폴리에틸렌 수지 30 중량부, 천연고무 20중량부로 구성된 혼합기재 100 중량부에 대해서 아라미드 섬유 40중량부, 유리섬유 40 중량부, 실리카 10 중량부, 실란커플링제 1중량부, 금속산화물 5중량부, 스테아린산 1 중량부, 고령토 300중량부로 구성된 조성물을 니이더(kneader)에서 100~120℃, 약 15분동안 혼련하였다.40 parts by weight of aramid fiber, 40 parts by weight of glass fiber, 10 parts by weight of silica, silane coupling agent 1 with respect to 100 parts by weight of a mixed substrate composed of 50 parts by weight of acrylonitrile butadiene rubber, 30 parts by weight of low density polyethylene resin, and 20 parts by weight of natural rubber. The composition consisting of parts by weight, 5 parts by weight of metal oxide, 1 part by weight of stearic acid, and 300 parts by weight of kaolin was kneaded in a kneader at 100 to 120 ° C. for about 15 minutes.
그리고, 상기 조성물은 오픈 롤밀에서 기재 100 중량부에 대해서 유기과산화물 3중량부 투입하여 균일하게 혼합시킨 후, 2mm두께의 시트로 제조하였다.In addition, the composition was prepared by mixing 3 parts by weight of organic peroxide with respect to 100 parts by weight of the substrate in an open roll mill, and then uniformly mixing the sheet with a thickness of 2 mm.
이때, 2mm두께로 성형된 시트를 2mm두께의 금형에 투입한 후, 155℃, 150kg/cm2의 프레스 조건에서 약 5분간 프레스 성형하여 비석면 가스켓으로 제조 완성하였다. At this time, the sheet formed to a thickness of 2mm was put into a mold of 2mm thickness, and then press-molded for about 5 minutes at a press condition of 155 ° C. and 150kg / cm 2 to produce a non-asbestos gasket.
비교예Comparative example 2 2
아크릴로니트릴부타디엔 고무 80 중량부와 저밀도 폴리에틸렌 수지 10 중량부, 천연고무 10중량부로 구성된 혼합기재 100 중량부에 대해서 셀롤로오즈 섬유 40중량부, 유리섬유 40 중량부, 실리카 10 중량부, 실란커플링제 1중량부, 금속산화물 5중량부, 스테아린산 1 중량부, 고령토 150중량부로 구성된 조성물을 니이더(kneader)에서 100~120℃, 약 12분동안 혼련하였다.40 parts by weight of cellulose fiber, 40 parts by weight of glass fiber, 10 parts by weight of silica, silane coupler based on 100 parts by weight of a mixed base composed of 80 parts by weight of acrylonitrile butadiene rubber, 10 parts by weight of low density polyethylene resin, and 10 parts by weight of natural rubber. A composition consisting of 1 part by weight of a ring agent, 5 parts by weight of a metal oxide, 1 part by weight of stearic acid, and 150 parts by weight of kaolin was kneaded in a kneader at 100 to 120 ° C. for about 12 minutes.
이때, 상기 조성물은 오픈 롤밀에서 기재 100 중량부에 대해서 유기과산화물 3중량부 투입하여 균일하게 혼합시킨 후, 2mm두께의 시트로 제조하였다.At this time, the composition was prepared by mixing 3 parts by weight of organic peroxide with respect to 100 parts by weight of the substrate in an open roll mill, and then uniformly mixing the sheet with a thickness of 2 mm.
그리고, 2mm두께로 성형된 시트를 2mm두께의 금형에 투입한 후 155℃, 150kg/cm2의 프레스 조건에서 약 5분간 프레스 성형하여 비석면 가스켓으로 제조 완성하였다. Then, the sheet formed to a thickness of 2mm was put into a mold of 2mm thickness, and then press-molded for about 5 minutes under a press condition of 155 ° C. and 150kg / cm 2 to produce a non-asbestos gasket.
비교예Comparative example 3 3
아크릴로니트릴부타디엔 고무 70 중량부와 저밀도 폴리에틸렌 수지 20 중량부, 천연고무 10 중량부로 구성된 혼합기재 100 중량부에 대해서 아라미드 섬유 40중량부, 유리섬유 40 중량부, 실리카 20 중량부, 실란커플링제 1중량부, 금속산화물 5중량부, 스테아린산 1 중량부, 고령토 700중량부로 구성된 조성물을 니이더(kneader)에서 100~120℃, 약 15분동안 혼련하였다.40 parts by weight of aramid fiber, 40 parts by weight of glass fiber, 20 parts by weight of silica, silane coupling agent 1 with respect to 100 parts by weight of a mixed substrate composed of 70 parts by weight of acrylonitrile butadiene rubber, 20 parts by weight of low density polyethylene resin, and 10 parts by weight of natural rubber. The composition consisting of parts by weight, 5 parts by weight of metal oxide, 1 part by weight of stearic acid, and 700 parts by weight of kaolin was kneaded in a kneader at 100 to 120 ° C. for about 15 minutes.
이때, 상기 조성물은 오픈 롤밀에서 기재 100 중량부에 대해서 유기과산화물 3중량부 투입하여 균일하게 혼합시킨 후, 2mm두께의 시트로 제조하였다.At this time, the composition was prepared by mixing 3 parts by weight of organic peroxide with respect to 100 parts by weight of the substrate in an open roll mill, and then uniformly mixing the sheet with a thickness of 2 mm.
그리고, 2mm두께로 성형된 시트를 금형두께가 2mm의 금형에 투입한 후 155℃, 150kg/cm2의 프레스 조건에서 약 5분간 프레스 성형하여 비석면 가스켓으로 제조 완성하였다. Then, the sheet molded to a thickness of 2mm was put into a mold having a mold thickness of 2mm, and then press-molded for about 5 minutes under a press condition of 155 ° C and 150 kg / cm 2 to manufacture a non-asbestos gasket.
고무
Rubber
1) NBR(내유성)
2) NR(천연고무)
3) Zinc oxide(산화아연)
4) Stearic acid(스테아린산)
5) Kaolin(고령토)
6) Aramid fiber(아라미드 섬유)
7) Glass fiber(유리섬유)
8) Trigonox(가교제)week)
1) NBR (oil resistance)
2) NR (natural rubber)
3) Zinc oxide
4) Stearic acid
5) Kaolin
6) Aramid fiber
7) Glass fiber
8) Trigonox
상기 실시예1 내지 실시예3 그리고 비교예1 내지 비교예3에 의해 제조된 가스켓의 조성물에 대하여 아래의 시험방법에 준하여 특성을 평가하였고, 그 시험결과를 하기의 표2에 나타내었다Properties of the gaskets prepared according to Examples 1 to 3 and Comparative Examples 1 to 3 were evaluated according to the following test methods, and the test results are shown in Table 2 below.
성형성 : ○(양호), △(보통), ×(불량)Moldability: ○ (good), △ (normal), × (bad)
1)압축율 : ASTM F36J 방법을 사용하여 측정하였다.1) Compression rate: measured using ASTM F36J method.
2)복원율 : ASTM F36J 방법을 사용하여 측정하였다.2) Recovery rate: measured using ASTM F36J method.
3)인장강도 : ASTM F152 방법을 사용하여 측정하였다.3) Tensile strength: measured using ASTM F152 method.
4)내유성 두께증가율 : ASTM F146 방법을 사용하여 측정하였다.4) Oil resistance thickness increase rate: measured using ASTM F146 method.
5)내유성 인장감소율 : ASTM F146 방법을 사용하여 측정하였다.5) Oil resistance tensile reduction rate: measured using ASTM F146 method.
6)강열감량 : ASTM F495 방법을 사용하여 측정하였다.6) Loss on ignition: measured using ASTM F495 method.
7)가공성 : 컴파운드 가공성 및 분산성을 평가하였다.7) Processability: Compound processability and dispersibility were evaluated.
상기 표1 및 표2에 나타난 바와 같이, 실시예1 내지 실시예3에 따른 비석면 시트 및 가스켓의 조성물은 종래 비석면 시트 및 가스켓의 조성물보다 물리적 특성에서 현저히 우수한 것으로 나타났고, 유기용매를 사용하지 않기 때문에 인체에 전혀 유해하지 않는 환경친화적인 조성물이라 할 수 있다. As shown in Table 1 and Table 2, the composition of the non-asbestos sheets and gaskets according to Examples 1 to 3 was found to be significantly superior in physical properties than the composition of the conventional non-asbestos sheets and gaskets, using an organic solvent It is not an environmentally friendly composition that is not harmful to the human body at all.
그러나, 비교예1의 경우에는 아크릴로니트릴고무의 조성비가 50 중량부로써 본 발명에서의 60 중량부에 미치지 못하고, 저밀도 폴리에틸렌 함량은 30중량부로써 본 발명에서의 20중량부를 초과하여 사용함으로써 내유성과 가공성이 떨어짐을 알 수 있었다.However, in the case of Comparative Example 1, the composition ratio of acrylonitrile rubber is less than 60 parts by weight in the present invention at 50 parts by weight, and the low density polyethylene content is 30 parts by weight in excess of 20 parts by weight in the present invention. And workability was inferior.
또한, 비교예2의 경우에는 무기충전제인 고령토의 함량이 150 중량부로써 본 발명에서의 200 중량부에 미치지 못하도록 사용함으로써 내열성을 요구하는 시트 및 가스켓의 제품으로 사용하기에 적합하지 않는 것으로 나타났다.In addition, in the case of Comparative Example 2, it was found that the content of kaolin, an inorganic filler, is 150 parts by weight so that it is not suitable for use in products of sheets and gaskets requiring heat resistance.
그리고, 비교예3은 무기충전제의 함량이 본 발명에서의 상한치인 600중량부를 초과하여 사용함으로써 내열성은 우수하나 조성물의 가공성이 떨어지는 문제가 있어 상용화 제품으로 활용하기에 부적합한 것으로 나타났다. In Comparative Example 3, the inorganic filler was used in an amount exceeding 600 parts by weight, which is the upper limit of the present invention.
본 발명은 상기의 실시예를 통해 기계적 강도 및 가공성, 두께 균일성의 우수성이 입증되었지만 상기의 구성에 의해서만 반드시 한정되는 것이 아니고, 본 발명의 기술적 사상을 벗어나지 않는 범위 내에서 여러 가지 치환, 변형 및 변경이 가능하다.Although the present invention has demonstrated excellent mechanical strength, workability and thickness uniformity through the above embodiments, it is not necessarily limited only to the above configuration, and various substitutions, modifications, and changes without departing from the technical spirit of the present invention. This is possible.
Claims (5)
상기 아크릴니트릴부타디엔 고무는 아크릴나트릴이 30~40중량부를 포함하고, 40~80의 무늬점도(ML1 +4, 100℃)를 갖도록 구성되는 것을 특징으로 하는 비석면 시트 및 가스켓의 조성물.The method according to claim 1,
The acrylonitrile butadiene rubber is 30 to 40 parts by weight of acrylnatrile , the composition of the non-asbestos sheet and gasket, characterized in that it is configured to have a pattern viscosity (ML 1 +4 , 100 ℃) of 40 ~ 80.
상기 저밀도 폴리에틸렌 수지는 20~30 용융점도(MI, g/10min)를 갖도록 구성되는 것을 특징으로 하는 비석면 시트 및 가스켓의 조성물.The method according to claim 1,
The low density polyethylene resin composition of the non-asbestos sheet and gasket, characterized in that it is configured to have a 20 to 30 melt viscosity (MI, g / 10min).
상기 실란커플링제는 비닐계 실란(비닐트리클로로 실란, 비닐트리메톡시실란, 비닐트리에톡시 실란), 에폭시계 실란(γ-글리시독시프로필메틸디에폭시 실란, γ-글리시독시프로필트리메톡시 실란, γ-글리시독시프로필트리에톡시 실란), 아미노계실란(γ-아미노프로필트리메톡시 실란, γ-아미노프로필트리에톡시 실란), 메타크리록시계 실란(γ-메타아크릴옥시프로필트리에톡시 실란, γ-메타아크릴옥시프로필트리메톡시 실란), 클로로프로필 실란(γ-클로로프로필트리에톡시 실란), 메르카프토 실란(γ-메르카프토프로필트리메톡시 실란)으로 이루어진 군에서 선택되는 어느 하나를 사용하도록 구성되는 것을 특징으로 하는 비석면 시트 및 가스켓의 조성물.The method according to claim 1,
The silane coupling agent is a vinyl silane (vinyl trichloro silane, vinyl trimethoxy silane, vinyl triethoxy silane), epoxy silane (γ-glycidoxypropylmethyldiepoxy silane, γ-glycidoxypropyltrime Methoxy silane, γ-glycidoxypropyltriethoxy silane), amino silane (γ-aminopropyltrimethoxy silane, γ-aminopropyltriethoxy silane), methacryloxy silane (γ-methacryloxypropyltri Ethoxy silane, γ-methacryloxypropyltrimethoxy silane), chloropropyl silane (γ-chloropropyltriethoxy silane) and mercapto silane (γ-mercaptopropyltrimethoxy silane) A composition of non-asbestos sheets and gaskets, characterized in that it is configured to use any one selected.
상기 가교제는 2,5-비스(터트부틸퍼옥시)-2,5-디메틸-3-헥엔, 디터트부틸퍼옥사이드, 2,5-비스(터트부틸퍼옥시)-2,5-디메틸-헥엔, 디벤조일퍼옥사이드, 비스(터트부틸퍼옥시이소프로필)벤젠, 부틸 4,4-비스(터트부틸퍼옥시)발러레이트, 1,1-비스(터트부틸퍼옥시)3,3,5-트리메틸클로로헥산, 터트부틸퍼옥시벤조에이트, 라우릴퍼옥사이드, 디큐밀퍼옥사이드로 이루어진 군에서 선택되는 어느 하나를 사용하도록 구성되는 것을 특징으로 하는 비석면 시트 및 가스켓의 조성물.The method according to claim 1,
The crosslinking agent is 2,5-bis (tertbutylperoxy) -2,5-dimethyl-3-hexene, ditertbutyl peroxide, 2,5-bis (tertbutylperoxy) -2,5-dimethyl-hexene , Dibenzoyl peroxide, bis (tertbutylperoxyisopropyl) benzene, butyl 4,4-bis (tertbutylperoxy) valerate, 1,1-bis (tertbutylperoxy) 3,3,5-trimethyl A composition of non-asbestos sheet and gasket, characterized in that it is configured to use any one selected from the group consisting of chlorohexane, tertbutyl peroxybenzoate, lauryl peroxide, dicumyl peroxide.
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| WO2016199993A1 (en) * | 2015-06-06 | 2016-12-15 | 김빛추리 | Heat-resistant joint sheet using waste fiber |
| KR20220120753A (en) * | 2021-02-22 | 2022-08-31 | 제일 이엔에스 주식회사 | Non-asbestos gasket composition having high heat resistant and gasket structure using the same |
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| KR101676864B1 (en) | 2015-08-26 | 2016-11-17 | 한국신발피혁연구원 | Composition for non-asbestos gasket with high heat resistance |
| KR101635723B1 (en) * | 2015-12-21 | 2016-07-04 | 제일이엔에스(주) | Gasket and manufacturing method thereof |
| KR102010040B1 (en) * | 2018-12-30 | 2019-08-12 | 제일이엔에스(주) | Manufacturing method for a gasket of low specific gravity |
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| KR20220120753A (en) * | 2021-02-22 | 2022-08-31 | 제일 이엔에스 주식회사 | Non-asbestos gasket composition having high heat resistant and gasket structure using the same |
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