KR100853400B1 - Method for preparing silver contained black rubber - Google Patents

Method for preparing silver contained black rubber Download PDF

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KR100853400B1
KR100853400B1 KR1020070025666A KR20070025666A KR100853400B1 KR 100853400 B1 KR100853400 B1 KR 100853400B1 KR 1020070025666 A KR1020070025666 A KR 1020070025666A KR 20070025666 A KR20070025666 A KR 20070025666A KR 100853400 B1 KR100853400 B1 KR 100853400B1
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silver
activated carbon
rubber
weight
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박영철
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경상대학교산학협력단
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/02Ingredients treated with inorganic substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00Compositions of natural rubber
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

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Abstract

A method for producing silver-containing black rubber is provided to improve dispersibility of silver, uniform distribution of silver and excellent antibacterial activity, and to enable rapid compounding. A method for producing silver-containing black rubber comprises the steps of: adding 1-100 phr of silver-deposited active carbon containing at least 0.001 wt% of silver based on the weight of the active carbon, alone or in combination with carbon black mixed in a ratio of 10-80 wt% to a conventional rubber material blend containing 100 phr of natural rubber or synthetic rubber, 1-100 phr of carbon black, 0-100 phr of petroleum oil, 3-10 phr of zinc oxide, 1-10 phr of stearic acid, 1-10 phr of sulfur and 0.1-10 phr of a vulcanization accelerator, wherein the silver-deposited active carbon substituting form the carbon black; and vulcanizing the resultant blend.

Description

은 함유 흑색 고무의 제조방법{Method for preparing silver contained black rubber}Method for preparing silver contained black rubber

도 1은 천연 고무원료에서 은 첨착 활성탄 첨가에 따른 고무의 물성 변화 결과치이다.1 is a result of changing the physical properties of the rubber according to the addition of silver impregnated activated carbon in the natural rubber raw material.

도 2는 합성 고무(EPDM)원료에서 은 첨착 활성탄 첨가에 따른 고무의 물성 변화 결과치이다.Figure 2 is a result of the physical property change of the rubber according to the addition of silver impregnated activated carbon in the synthetic rubber (EPDM) raw material.

본 발명은 고무에 금속 은을 함유시켜 항균성이 우수한 은 함유 흑색고무를 제조하는 방법에 관한 것이다. 더욱 상세하게는 통상적인 고무 원재료 배합물에 표면적이 넓은 활성탄을 첨가하되 은 함유량이 활성탄 무게 기준 0.001 중량% 이상 함유된 은 첨착 활성탄을 단독으로 또는 카본블랙과 일정 비율로 섞어 혼합하여서 되는 금속 은의 분산성이 우수한 은 함유 흑색 고무를 제조하는 방법에 관한 것이다.The present invention relates to a method for producing silver-containing black rubber having excellent antibacterial properties by containing metal silver in rubber. More specifically, the dispersibility of metallic silver obtained by adding activated carbon having a large surface area to a conventional rubber raw material compound, or by adding a silver impregnated activated carbon containing 0.001% by weight or more based on the weight of activated carbon alone or by mixing it with carbon black in a certain ratio. It is related with the method of manufacturing this excellent silver containing black rubber | gum.

일반적으로 범용고무는 천연고무(NR)나 합성고무 소재에 물성을 향상시키기 위하여 산화아연, 스테아릭산, 황, 촉진제, 산화방지제, 충전제, 가소제 등을 배합하여 최종 고무 제품을 제조한다. 범용 제품의 경우 생산비가 싼 국가에서 수입되고, 국내 생활 여건이 향상됨에 따라 소비자는 고부가 가치 제품을 선호하는 경향이다. 이에 따라 국내 기업들도 소비자 기호에 맞는 맞춤식 제품 생산이 필요하다. 국내 주거 문화가 아파트 등의 다가구 시설로 변화됨에 따라 실내 온도 변화가 크지 않으므로 실내 미생물 서식 밀도도 높아지고 있다. 특히 생물 알레르기와 연관된 여러 가지 질병이 야기되므로 항균성이 우수한 제품을 선호하게 된다. 은의 경우 친환경적인 항균 물질이지만 고가이므로 은 함유 고무를 사용한 다양한 고무 제품은 경제성이 있는 은 함유 제품으로서 가능성이 있다. In general, general purpose rubbers are prepared by mixing zinc oxide, stearic acid, sulfur, accelerators, antioxidants, fillers, plasticizers, etc. in order to improve physical properties of natural rubber (NR) or synthetic rubber materials. As general-purpose products are imported from countries where production costs are low and domestic living conditions improve, consumers tend to prefer high-value products. Accordingly, domestic companies also need to produce customized products that meet consumer preferences. As the domestic residential culture is changed to multi-family facilities such as apartments, indoor microbial density is also increasing due to the small change in indoor temperature. In particular, various diseases associated with biological allergies are caused, and thus, a product having excellent antibacterial property is preferred. Silver is an environmentally friendly antibacterial substance, but since it is expensive, various rubber products using silver-containing rubber have potential as silver-containing products with economical efficiency.

은 함유 제품 제조에 관하여는 나노 입자 파우더를 에탄올이나 에칠렌글리콜에 분산시켜 합성수지에 혼합하여 합성 수지 마스터 배치를 만드는 방법 [한국공개특허 제10-2004-0023455호 참조], 에칠렌글리콜이나 비이온성 고분자가 녹아 있는 용액에 은염을 첨가하여 은 이온을 만들고 이것을 고온에서 합성수지에 분산시켜 나노 은 입자가 생성된 합성수지를 제조하는 방법 [한국공개특허 제10-2004-0094262호 참조], 나노 실버나 콜로이드성 은 용액을 천연고무에 혼합 또는 침적이나 코팅하는 방법 [한국공개특허 제10-2004-0096930호 참조]이 소개된 바 있으나, 나노 은의 지속성에 문제가 있고, 미량의 은을 고무나 합성수지 전체에 균질하게 배합하기 위하여는 원료 비가 높게 되고, 혼합 시간이 장시간이 소요되며, 혼합에 필요한 동력 비용도 높다는 문제가 있다.       Regarding the production of silver-containing products, a method of preparing a synthetic resin master batch by dispersing nanoparticle powder in ethanol or ethylene glycol and mixing with synthetic resin [see Korean Patent Publication No. 10-2004-0023455], ethylene glycol or a nonionic polymer A method of preparing a synthetic resin in which nano silver particles are produced by adding silver salt to a dissolved solution and dispersing it in a synthetic resin at a high temperature [refer to Korean Patent Publication No. 10-2004-0094262], nano silver or colloidal silver A method of mixing or depositing or coating a solution in natural rubber has been introduced [see Korean Patent Publication No. 10-2004-0096930], but there is a problem in the persistence of nano silver, and a small amount of silver is uniformly dispersed in rubber or synthetic resin. In order to mix, there is a problem that the raw material ratio is high, the mixing time takes a long time, and the power cost required for mixing is also high. .

이에 본 발명은 종래의 이와 같은 문제점을 해소하기 위하여 예의 연구를 거듭한 결과, 통상적인 고무 원재료 배합물에 은 함유량이 활성탄 무게 기준 0.001 중량% 이상 함유된 은 첨착 활성탄을 단독 또는 카본블랙과 일정 비율로 섞어 혼합할 경우 금속 은의 분산성을 높일 수 있고, 단시간에 배합도 가능하며, 은 분포도 매우 균질할 뿐 아니라 항균력도 우수한 은 함유 흑색고무를 제조할 수 있음을 알게 되어 본 발명을 완성하게 되었다.Accordingly, the present invention has been conducted in order to solve such a conventional problem, as a result, the silver impregnated activated carbon containing silver content of 0.001% by weight or more based on the weight of activated carbon in a conventional rubber raw material blend alone or in a certain ratio with carbon black When mixing to increase the dispersibility of the metal silver, it can be blended in a short time, it was found that not only the silver distribution is very homogeneous but also excellent antibacterial silver-containing black rubber to complete the present invention.

즉, 본 고안은 고무에 금속 은을 함유시켜 항균성이 우수한 은 함유 흑색 고무를 제조하는 방법을 제공하는데 그 목적이 있는 것이다. That is, the present invention is to provide a method for producing a silver-containing black rubber excellent in antimicrobial properties by containing metal silver in the rubber.

보통 은은 범용적인 항균제로 잘 알려진 물질로서 미세 입자의 은은 세균을 비롯한 균류 및 바이러스 등에도 탁월한 효과가 있으면서도 부작용이 없다. 그러나 은은 고가이므로 사용이 제한적이다. 따라서 본 발명의 방법에 의해서 제조된 은 함유 흑색고무는 경제적인 항균성 고무 소재로 활용이 가능하다.      Usually, silver is a material well known as a general-purpose antimicrobial agent, and fine particles of silver have excellent effects on bacteria, fungi and viruses, but also have no side effects. However, silver is expensive and its use is limited. Therefore, the silver-containing black rubber produced by the method of the present invention can be utilized as an economical antimicrobial rubber material.

본 발명의 은 함유 흑색고무는, 천연고무 또는 합성고무 100 PHR, 카본블랙 1 ~ 100 PHR, 석유오일 0 ~ 100 PHR, 산화아연 3 ~ 10 PHR, 스테아릭산 1 ~ 10 PHR, 황 1 ~ 10 PHR, 가황촉진제 0.1 ~ 10 PHR으로 이루어진 통상적인 고무 원재료 배합물에서 카본블랙을 대신하여 은 함유량이 활성탄 무게 기준으로 0.001중량% 이상 함유된 은 첨착 활성탄을 단독으로 1 ~ 100 PHR 첨가하거나, 또는 카본블랙이 10~80 중량% 비율로 혼합된 혼합 은 첨착 활성탄을 1 ~ 100 PHR 첨가 혼합하고 가류시켜서 제조하는 것을 특징으로 한다. Silver-containing black rubber of the present invention is natural rubber or synthetic rubber 100 PHR, carbon black 1-100 PHR, petroleum oil 0-100 PHR, zinc oxide 3-10 PHR, stearic acid 1-10 PHR, sulfur 1-10 PHR In a conventional rubber raw material blend consisting of 0.1 to 10 PHR of vulcanization accelerator, 1 to 100 PHR of silver impregnated activated carbon containing 0.001% by weight or more by weight of activated carbon in place of carbon black is added alone, or carbon black is The mixed mixture at a ratio of 10 to 80% by weight is prepared by mixing and vulcanizing the impregnated activated carbon by adding 1 to 100 PHR.

본 발명에서 통상적인 고무 원재료 배합물에 첨가되는 활성탄 무게 기준 0.001중량% 이상 함유된 은 첨착 활성탄은 표면적이 넓은 활성탄을 질산은 수용액이나 금속 은을 질산에 용해시킨 은 수용액에 함침시킨 후, 여과 · 수세 후 건조과정을 거쳐서 제조를 한다. The silver impregnated activated carbon containing 0.001% by weight or more based on the weight of activated carbon added to a conventional rubber raw material blend in the present invention is impregnated with activated carbon having a large surface area in an aqueous solution of silver nitrate or silver silver dissolved in nitric acid, followed by filtration and washing with water. Manufacture through drying process.

이와 같은 본 발명을 다음에서 더욱 상세히 설명하기로 한다. 하기에서 본 발명을 설명함에 있어 관련된 공지 기능 또는 구성에 대한 구체적인 설명이 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 경우에는 그 상세한 설명을 생략할 것이다. 그리고 후술하는 용어들은 본 발명에서의 기능을 고려하여 정의된 용어들로서, 이는 사용자, 운용자의 의도 또는 관례 등에 따라 달라질 수 있으며, 이에 따라 각 용어의 의미는 본 명세서 전반에 걸친 내용을 토대로 해석되어야 할 것이다. This invention will be described in more detail below. In the following description of the present invention, detailed descriptions of well-known functions or configurations will be omitted if it is determined that the detailed description of the present invention may unnecessarily obscure the subject matter of the present invention. And the following terms are terms defined in consideration of functions in the present invention, which may vary according to the intention or custom of the user, operator, etc. Accordingly, the meaning of each term should be interpreted based on the contents throughout the present specification. will be.

본 발명에서 상기 통상적인 고무 원재료 배합물은 천연고무 또는 합성고무 100 PHR에 카본블랙 1 ~ 100 PHR, 석유오일 0 ~ 100 PHR, 산화아연 3 ~ 10 PHR, 스테아릭산 1 ~ 10 PHR, 황 1 ~ 10 PHR, 가황촉진제 0.1 ~ 10 PHR을 함께 배합하여서 이루어진 것이다.In the present invention, the conventional rubber raw material blend is carbon black 1-100 PHR, petroleum oil 0-100 PHR, zinc oxide 3-10 PHR, stearic acid 1-10 PHR, sulfur 1-10 in natural rubber or synthetic rubber 100 PHR. PHR, the vulcanization accelerator is made by combining 0.1 ~ 10 PHR together.

본 발명의 은 함유 흑색고무의 제조는 상기한 바와 같은 통상적인 고무 원재료 배합물에 은 함유량이 활성탄 무게 기준으로 0.001중량% 이상 함유된 은 첨착 활성탄을 단독 또는 카본블랙이 10~80 중량% 비율로 혼합된 혼합 은 첨착 활성탄을 배합하고 가류시켜서 제조한다. In the production of silver-containing black rubber of the present invention, a silver-containing activated carbon containing 0.001% by weight or more based on the weight of activated carbon in a conventional rubber raw material blend as described above is mixed alone or in a ratio of 10 to 80% by weight of carbon black. The mixed mixture is prepared by blending and vulcanizing impregnated activated carbon.

상기한 본 발명의 방법에서, 은 첨착 활성탄으로는 시중에서 판매되는 은 첨착 활성탄을 사용할 수 있으나 이 경우 은의 함량이 1000 ppm 정도로 낮으므로 이 보다 높은 농도의 것을 얻기 위하여 활성탄을 원료로 하여 다음과 같은 방법으로 제조하여 사용할 수 있다. 즉, 200 mesh 이하로 미분쇄한 활성탄을 활성탄 투입 양의 0.001중량% 이상의 질산은 수용액이나, 활성탄 투입 양의 0.001중량% 이상의 금속 은과 질산 수용액을 가열 교반 용해 시켜 제조한 질산은 수용액이 담겨있는 침적조에서 먼저 상온에서 2시간 이상 침적시킨다.In the above-described method of the present invention, commercially available silver impregnated activated carbon may be used as silver impregnated activated carbon, but in this case, since the content of silver is low as about 1000 ppm, activated carbon is used as a raw material to obtain a higher concentration. It can be manufactured and used by the method. That is, a deposition tank containing an aqueous solution of silver nitrate prepared by heating and stirring an activated carbon finely pulverized to 200 mesh or less in an amount of 0.001% by weight or more of silver activated carbon or an aqueous solution of metal silver and nitric acid of 0.001% or more by weight of activated carbon. At first, immerse at least 2 hours at room temperature.

상기 침적이 완료된 후 생성된 은 첨착 활성탄을 필터여과기나 원심여과기를 이용한 여과공정을 통하여 수용액을 분리 시킨 후 4~5회 세척수로 세척을 한다. After the deposition is completed, the silver-impregnated activated carbon produced is separated by an aqueous solution through a filtration process using a filter filter or a centrifugal filter, and then washed with 4 to 5 wash water.

상기 세척이 완료 된 후에는 약 100 ~ 120 ℃ 정도의 온도에서 24시간 건조 후 다시 130 ~ 150℃ 온도에서 24시간 건조하면, 활성탄에 은 함유량이 활성탄 무게 기준 0.001 중량% 이상 함유된 첨착 활성탄을 얻을 수 있다. After the washing is completed, and after drying for 24 hours at a temperature of about 100 ~ 120 ℃ and then again for 24 hours at 130 ~ 150 ℃ temperature, to obtain impregnated activated carbon containing a silver content of 0.001% by weight or more based on the weight of activated carbon Can be.

이와 같은 본 발명을 실시예에 의거하여 더욱 상세하게 설명하면 다음과 같다. The present invention will be described in more detail based on the following examples.

실험예Experimental Example 1 One

천연고무100 PHR, 카본블랙 50 PHR, 산화아연 5 PHR, 스테아릭산 3 PHR을 사용하여 고무 혼합체를 만들어 Mooney 점도계에서 125 ℃로 가온하여 점도를 측정하고 Mooney Scorch 값(t5)을 구하였다. A rubber mixture was prepared using natural rubber 100 PHR, carbon black 50 PHR, zinc oxide 5 PHR, stearic acid 3 PHR, and heated to 125 ° C. in a Mooney viscometer to measure viscosity and obtain Mooney Scorch value (t5).

천연고무100 PHR, 카본블랙 50 PHR, 산화아연 5 PHR, 스테아릭산 3 PHR, 가황촉진제 1.7 PHR, 황 2.5 PHR을 혼합하여 시료를 제조하고 진동디스크 경화계(ODR)에서 180 ℃로 가온하여 가류 특성을 분석하였다. Natural rubber 100 PHR, carbon black 50 PHR, zinc oxide 5 PHR, stearic acid 3 PHR, vulcanization accelerator 1.7 PHR, sulfur 2.5 PHR were prepared to prepare a sample and heated to 180 ° C. in a vibrating disc curing system (ODR) Was analyzed.

천연고무100 PHR, 카본블랙 50 PHR, 산화아연 5 PHR, 스테아릭산 3 PHR, 가황촉진제 1.7 PHR, 황 2.5 PHR을 혼합하여 시료를 제조하고 시편 금형에서 160 ℃로 가류 경화 시켜 시편을 제조하고 물성치를 측정하였다. Prepare a sample by mixing natural rubber 100 PHR, carbon black 50 PHR, zinc oxide 5 PHR, stearic acid 3 PHR, vulcanization accelerator 1.7 PHR, sulfur 2.5 PHR and vulcanizing and curing at 160 ℃ Measured.

이에 따른 결과를 도 1에 나타내었다. The results are shown in FIG. 1.

실시예Example 1 One

증류수 1000 에 질산은 500 g을 넣어 잘 교반시키며 용해를 완료한 뒤, 증류수로 희석하여 150 L로 만들었다. 200 mesh 이하의 미분 대나무활성탄 10 kg을 투입하고 잘 교반시키면서 2시간동안 침적을 시켜 수용액상의 은 이온이 활성탄 세공 내부까지 잘 흡착 되도록 하였다. 흡착이 완료 된 후 여지가 있는 깔때기에서 여과를 완료한 후 온수를 가하여 4~5 차례 수세하였다. 수세가 완료 된 후 100 ℃의 온풍건조기에서 24시간 건조하고, 다시 온풍건조기 온도를 130 ℃까지 높인 후 24시간 건조를 완료하여 3.23 중량% 은 첨착 활성탄을 제조하였다.500 g of nitric acid was added to distilled water and stirred well. After dissolving, the solution was diluted with distilled water to 150 L. 10 kg of finely divided bamboo activated carbon of 200 mesh or less was added thereto, and the mixture was deposited for 2 hours while stirring well so that silver ions in the aqueous solution were well adsorbed to the inside of the activated carbon pores. After the adsorption was completed, the filtration was completed in a funnel, then washed with warm water 4-5 times. After washing with water was completed 24 hours in a hot air dryer of 100 ℃, again to increase the temperature of the hot air dryer to 130 ℃ 24 hours to complete the drying to prepare 3.23% by weight of silver-impregnated activated carbon.

상기 실험예 1에서 카본블랙 50 PHR 대신에 상기에서 제조한 은 첨착활성탄 15 PHR와 카본블랙 35 PHR을 혼합 첨가하여 0.28중량% 은 함유 흑색 고무를 제조하였다. Instead of carbon black 50 PHR in Experimental Example 1, 0.28% by weight of silver-containing black rubber was prepared by mixing 15 PHR of silver-impregnated activated carbon and 35 PHR.

이에 대한 물성 변화 결과값을 도 1에 나타내었다. Physical property change results for this are shown in FIG. 1.

실시예Example 2 2

실시예 1과 동일하게 하되 카본블랙 50 PHR 대신에 은 첨착활성탄 35 PHR와 카본블랙 15 PHR을 혼합 첨가하여 0.65중량% 은 함유 흑색 고무를 제조하였다.In the same manner as in Example 1, but instead of carbon black 50 PHR, silver impregnated activated carbon 35 PHR and carbon black 15 PHR were added and mixed to prepare 0.65 wt% silver-containing black rubber.

이에 대한 물성 변화 결과값을 도 1에 나타내었다.Physical property change results for this are shown in FIG. 1.

실시예Example 3 3

실시예 1과 동일하게 하되, 카본블랙 50 PHR 대신에 은 첨착활성탄 50 PHR을 혼합 첨가하여 0.93중량% 은 함유 흑색 고무를 제조하였다.In the same manner as in Example 1, instead of carbon black 50 PHR, silver impregnated activated carbon 50 PHR was added and mixed to prepare 0.93 wt% silver-containing black rubber.

이에 대한 물성 변화 결과값을 도 1에 나타내었다. Physical property change results for this are shown in FIG. 1.

비교예Comparative example 1 One

실시예 1과 동일하게 하되, 카본블랙 50 PHR외에 5 중량% 은나노 에틸렌글리콜 10 PHR을 더 혼합 첨가하여 0.29중량% 은 함유 흑색 고무를 제조하였다. In the same manner as in Example 1, in addition to 50 PHR of carbon black, 5 wt% silver nano ethylene glycol 10 PHR was further added to prepare 0.29 wt% silver-containing black rubber.

이에 대한 물성 변화 결과값을 도 1에 나타내었다. Physical property change results for this are shown in FIG. 1.

실험예Experimental Example 2 2

합성고무 EPDM 100 PHR, 스테아릭산 1 PHR, 산화아연 5 PHR, 석유오일 50 PHR, 카본블랙 80 PHR을 사용하여 고무 혼합체를 만들어 Mooney 점도계에서 125 ℃로 가온하여 점도를 측정하고 Mooney Scorch 값(t5)을 구하였다. Synthetic rubber EPDM 100 PHR, stearic acid 1 PHR, zinc oxide 5 PHR, petroleum oil 50 PHR, carbon black 80 PHR were used to make a rubber mixture and heated to 125 ° C on Mooney viscometer to measure the viscosity and Mooney Scorch value (t5) Was obtained.

합성고무 EPDM 100 PHR, 스테아릭산 1 PHR, 산화아연 5 PHR, 석유오일 50 PHR, 카본블랙 80 PHR, 가황촉진제 2.5 PHR, 황 1.5 PHR을 혼합하여 시료를 제조하고 진동디스크 경화계(ODR)에서 180 ℃로 가온하여 가류 특성을 분석하였다. Samples were prepared by mixing synthetic rubber EPDM 100 PHR, stearic acid 1 PHR, zinc oxide 5 PHR, petroleum oil 50 PHR, carbon black 80 PHR, vulcanization accelerator 2.5 PHR, sulfur 1.5 PHR, and 180 on an vibration disc hardening system (ODR). Warming up to < RTI ID = 0.0 >

합성고무 EPDM 100 PHR, 스테아릭산 1 PHR, 산화아연 5 PHR, 석유오일 50 PHR, 카본블랙 80 PHR, 가황촉진제 2.5 PHR, 황 1.5 PHR을 혼합하여 시료를 제조하고 시편 금형에서 160 ℃로 가류 경화 시켜 시편을 제조하고 물성치를 측정하였다. Prepare a sample by mixing synthetic rubber EPDM 100 PHR, stearic acid 1 PHR, zinc oxide 5 PHR, petroleum oil 50 PHR, carbon black 80 PHR, vulcanization accelerator 2.5 PHR, sulfur 1.5 PHR. Specimens were prepared and measured.

그 결과를 도 2에 나타내었다.The results are shown in FIG.

실시예Example 4 4

증류수 1000 에 질산은 500 g을 넣어 잘 교반시키며 용해를 완료한 뒤, 증류수로 희석하여 150 L로 만들었다. 200 mesh 이하의 미분 대나무활성탄 10 kg을 투입하고 잘 교반시키면서 2시간동안 침적을 시켜 수용액상의 은 이온이 활성탄 세공 내부까지 잘 흡착 되도록 하였다. 흡착이 완료 된 후 여지가 있는 깔때기에서 여과를 완료한 후 온수를 가하여 4~5 차례 수세하였다. 수세가 완료 된 후 100 ℃의 온풍건조기에서 24시간 건조하고, 다시 온풍건조기 온도를 130 ℃까지 높인 후 24시간 건조를 완료하여 3.23 중량% 은 첨착 활성탄을 제조하였다.500 g of nitric acid was added to distilled water and stirred well. After dissolving, the solution was diluted with distilled water to 150 L. 10 kg of finely divided bamboo activated carbon of 200 mesh or less was added thereto, and the mixture was deposited for 2 hours while stirring well so that silver ions in the aqueous solution were well adsorbed to the inside of the activated carbon pores. After the adsorption was completed, the filtration was completed in a funnel, then washed with warm water 4-5 times. After washing with water was completed 24 hours in a hot air dryer of 100 ℃, again to increase the temperature of the hot air dryer to 130 ℃ 24 hours to complete the drying to prepare 3.23% by weight of silver-impregnated activated carbon.

상기 실험예 2에서 카본블랙 80 PHR 대신에 상기에서 제조한 은 첨착활성탄 30 PHR와 카본블랙 50 PHR을 혼합 첨가하여 0.38중량% 은 함유 흑색 고무를 제조하였다. 0.38 wt% silver-containing black rubber was prepared by mixing 30 PHR of the silver-impregnated activated carbon and 50 PHR prepared above instead of the carbon black 80 PHR in Experimental Example 2.

이에 대한 물성 변화 결과값을 도 2에 나타내었다. The result change of the physical properties is shown in FIG. 2.

실시예Example 5 5

실시예 2와 동일하게 하되, 카본블랙 80 PHR 대신에 은 첨착 활성탄 50 PHR와 카본블랙 30 PHR을 혼합 첨가하여 0.63중량% 은 함유 흑색 고무를 제조하였다.In the same manner as in Example 2, instead of carbon black 80 PHR, silver-impregnated activated carbon 50 PHR and carbon black 30 PHR were mixed and added to prepare 0.63 wt% silver-containing black rubber.

이에 대한 물성 변화 결과값을 도 2에 나타내었다. The result change of the physical properties is shown in FIG. 2.

실시 예 6Example 6

실시예 2와 동일하게 하되, 카본블랙 80 PHR 대신에 은 첨착 활성탄 80 PHR 혼합 첨가하여 1.00중량% 은 함유 흑색 고무를 제조하였다.In the same manner as in Example 2, 1.00 wt% silver-containing black rubber was prepared by adding 80 PHR of silver-impregnated activated carbon instead of 80 PHR of carbon black.

이에 대한 물성 변화 결과값을 도 2에 나타내었다. The result change of the physical properties is shown in FIG. 2.

비교예Comparative example 2 2

실시예 2와 동일하게 하되, 카본블랙 80 PHR 외에 5 중량% 은나노 에틸렌글리콜 20 PHR을 더 혼합 첨가하여 0.39중량% 은 함유 흑색 고무를 제조하였다.In the same manner as in Example 2, in addition to carbon black 80 PHR, 5 wt% silver nano ethylene glycol 20 PHR was further added to prepare a 0.39 wt% silver-containing black rubber.

이에 대한 물성 변화 결과값을 도 2에 나타내었다. The result change of the physical properties is shown in FIG. 2.

이상에서 본 발명의 바람직한 구현 예를 한정하여 설명하였으나, 본 발명은 이에 한정되지 않고, 다양한 변화와 변경 및 균등물을 사용할 수 있다. 따라서, 본 발명은 상기 구현예를 적절히 변형하여 응용할 수 있고, 이러한 응용도 하기 특허청구범위에 기재된 기술적 사상을 바탕으로 하는 한 본 발명의 권리범위에 속하게 됨은 당연하다 할 것이다. Although limited embodiments of the present invention have been described in detail, the present invention is not limited thereto, and various changes, modifications, and equivalents may be used. Therefore, the present invention can be applied by appropriately modifying the above embodiments, it will be natural that such applications also fall within the scope of the present invention based on the technical idea described in the claims.

본 발명의 은 첨착활성탄을 이용한 은 함유 흑색 고무 제조방법은 기존의 금속 은이나 나노 은 함유 에틸렌글리콜을 이용한 혼합법에 비하여 고무 내에 은 분 포가 매우 균일하며 혼합 시간도 매우 단축할 수 있다는 장점을 가지고 있다. Silver-containing black rubber manufacturing method using the silver-impregnated activated carbon of the present invention has the advantage that the silver distribution in the rubber is very uniform and the mixing time can be very short compared to the conventional mixing method using the metal silver or nano silver-containing ethylene glycol. have.

또한 은 나노 에틸렌글리콜 혼합 시 발생되는 외부에 잔여 액이 남고 혼합성도 매우 좋지 않은 점을 개선 할수 있다. 도 1, 2의 결과에서도 은첨착활성탄 함유비가 증가 할수록 Mooney Scorch 값이 증가하여 복잡한 제품 금형 사용 시에도 충분한 체움 시간을 확보 할 수 있다. 은 함유량 0.28 중량%인 은 함유 흑색고무를 JIS Z 2801 항균성 제품-항균 작용 및 효과 시험법에 의하여 실험한 결과 대장균과 황색포도상 구균에 대한 항균성을 확인할 수 있다.In addition, it is possible to remedy that the remaining solution left in the outside of silver nano ethylene glycol mixed and very poor mixing. In the results of Figures 1 and 2, as the content of silver-impregnated activated carbon increases, Mooney Scorch value increases to ensure sufficient stay time even when using a complex product mold. Silver-containing black rubber having a silver content of 0.28% by weight was tested by JIS Z 2801 antimicrobial product-antibacterial action and effect test method, and antimicrobial activity against Escherichia coli and Staphylococcus aureus can be confirmed.

Claims (2)

천연고무 또는 합성고무 100 PHR, 카본블랙 1 ~ 100 PHR, 석유오일 0 ~ 100 PHR, 산화아연 3 ~ 10 PHR, 스테아릭산 1 ~ 10 PHR, 황 1 ~ 10 PHR, 가황촉진제 0.1 ~ 10 PHR으로 이루어진 통상적인 고무 원재료 배합물에서 카본블랙을 대신하여 은 함유량이 활성탄 무게 기준으로 0.001중량% 이상 함유된 은 첨착 활성탄을 단독으로 1 ~ 100 PHR 첨가하는 단계 또는 카본블랙이 10~80 중량% 비율로 혼합된 혼합 은 첨착 활성탄을 1 ~ 100 PHR 첨가 혼합하는 단계; 상기 혼합물을 가류시키는 단계로 이루어지는 것을 특징으로 하는 은 함유 흑색 고무의 제조방법.Natural or synthetic rubber 100 PHR, carbon black 1 ~ 100 PHR, petroleum oil 0 ~ 100 PHR, zinc oxide 3 ~ 10 PHR, stearic acid 1 ~ 10 PHR, sulfur 1 ~ 10 PHR, vulcanization accelerator 0.1 ~ 10 PHR In the conventional rubber raw material blend, 1 to 100 PHR of silver-impregnated activated carbon containing 0.001% by weight or more based on the weight of activated carbon in place of carbon black is added or carbon black is mixed in a ratio of 10 to 80% by weight. Mixing is adding 1 ~ 100 PHR of the impregnated activated carbon; A method for producing a silver-containing black rubber, characterized by comprising the step of vulcanizing the mixture. 제 1항에 있어서, 상기 은 첨착 활성탄은 200 mesh 이하로 미분쇄한 활성탄을 활성탄 투입 양의 0.001중량% 이상의 질산은 수용액이나, 활성탄 투입 양의 0.001중량% 이상의 금속 은과 질산 수용액을 가열 교반 용해 시켜 제조한 질산은 수용액이 담겨있는 침적조에서 상온에서 2시간 이상 침적하는 단계; The method of claim 1, wherein the silver impregnated activated carbon is dissolved in activated carbon, which is pulverized to 200 mesh or less, by dissolving at least 0.001% by weight of silver nitrate in aqueous solution of activated carbon or 0.001% by weight or more of metal silver and nitric acid in activated carbon. Immersing the prepared silver nitrate at room temperature for 2 hours or more in an immersion tank containing an aqueous solution; 상기 침적이 완료된 후 생성된 은 첨착 활성탄을 필터여과기나 원심여과기를 이용한 여과공정을 통하여 수용액을 분리 시킨 후 4~5회 세척수로 세척하는 단계; 및Separating the aqueous solution through the filtration process using a filter filter or a centrifugal filter of the silver-impregnated activated carbon produced after the deposition is completed, and washing with 4 to 5 wash water; And 상기 세척이 완료 된 후 약 100~120 ℃의 온도에서 24시간 건조 후 다시 130~150℃ 온도에서 24시간 건조하여 활성탄에 은 함유량이 활성탄 무게 기준 0.001중량% 이상 함유된 은 첨착 활성탄을 제조하는 단계로 이루어지는 것을 특징으로 하는 은 함유 흑색 고무를 제조하는 방법. After the washing is completed and dried for 24 hours at a temperature of about 100 ~ 120 ℃ and again for 24 hours at a temperature of 130 ~ 150 ℃ to prepare a silver impregnated activated carbon containing a silver content in the activated carbon containing more than 0.001% by weight based on the weight of activated carbon A method for producing a silver-containing black rubber, characterized in that consisting of.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4961950A (en) 1972-10-14 1974-06-15
KR100308880B1 (en) 1999-05-14 2001-09-28 신형인 Tread Rubber Composition for Snow Tire
KR100369615B1 (en) 2000-06-09 2003-01-29 금호산업 주식회사 Undertread rubber composition for bias
JP2005155695A (en) 2003-11-21 2005-06-16 Tomoe Tech Res Co Antibacterial butterfly valve and its constituent material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4961950A (en) 1972-10-14 1974-06-15
KR100308880B1 (en) 1999-05-14 2001-09-28 신형인 Tread Rubber Composition for Snow Tire
KR100369615B1 (en) 2000-06-09 2003-01-29 금호산업 주식회사 Undertread rubber composition for bias
JP2005155695A (en) 2003-11-21 2005-06-16 Tomoe Tech Res Co Antibacterial butterfly valve and its constituent material

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