KR101697928B1 - Antimicrobial composition for polyurethane - Google Patents
Antimicrobial composition for polyurethane Download PDFInfo
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- KR101697928B1 KR101697928B1 KR1020160038929A KR20160038929A KR101697928B1 KR 101697928 B1 KR101697928 B1 KR 101697928B1 KR 1020160038929 A KR1020160038929 A KR 1020160038929A KR 20160038929 A KR20160038929 A KR 20160038929A KR 101697928 B1 KR101697928 B1 KR 101697928B1
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Abstract
Description
본 발명은 폴리우레탄용 항균제 조성물에 관한 것으로, 더욱 상세하게는 폴리우레탄용 원료에 혼합되어 우수한 경시 안정성을 나타내는 비유독성 항균제 조성물에 관한 것이다.More particularly, the present invention relates to a non-toxic antimicrobial composition which is mixed with a raw material for polyurethane and exhibits excellent long-term stability.
종래에 제조되는 폴리우레탄 성형품은 사용 중에 세균이나 곰팡이 등에 의해 폴리우레탄 성형품이 오염되는 것을 방지하기 위해 다양한 방법이 적용되고 있는데, 한국특허등록 제10-0879756호 "항균 폴리우레탄 폼용 폴리올 조성물"에는 항균성이 우수하고, 항균제 투입으로 인한 침전발생없이 스프레이 발포성이 우수하며, 단열성능, 접착성, 기계적 강도 및 치수안정성이 탁월하고, 단열 및 결로방지 효과로 인해 에너지 절감 효과를 얻을 수 있어 경제성이 우수한 항균 폴리우레탄폼용 폴리올 조성물이 기재되어 있으며, 한국특허등록 제10-1321845호 "통기성이 향상된 항균 폴리우레탄 폼 제조용 이소시아네이트 조성물"에는 바이오 추출물을 이용하여 항균성을 부여하는 내용이 기재되어 있고, 한국특허등록 제10-0448091 "항균 폴리우레탄 폼의 제조방법" 및 한국특허등록 제10-1414434호 "항균기능을 갖는 폴리우레탄 폼의 제조방법"에는 무기항균제를 사용하는 기술이 개재되어 있습니다.Various methods have been applied to conventionally-produced polyurethane molded articles in order to prevent contamination of polyurethane molded articles by bacteria or molds during use. Korean Patent Registration No. 10-0879756 entitled "Polyol Composition for Antibacterial Polyurethane Foam & Excellent antimicrobial agent, excellent spraying foaming property without precipitation due to the injection of antimicrobial agent, excellent heat insulating performance, adhesiveness, mechanical strength and dimensional stability, and energy saving effect due to the effect of preventing adiabatic and condensation, Patent Document No. 10-1321845 entitled "Isocyanate Composition for Producing Antimicrobial Polyurethane Foam Having Improved Breathability" describes a content for imparting antimicrobial activity using a bio extract, 10-0448091 "Method for producing antibacterial polyurethane foam" and Korean Patent Registration No. 10-1414434 entitled "Method for producing polyurethane foam having antibacterial function ", there is a technique using inorganic antibacterial agent.
상기의 나열된 기술들에는 다양한 항균제 성분이 혼합되어 폴리우레탄 성형품에 항균성을 부여하는 방법이 기재되어 있으나, 상기의 기술들을 통해 제조된 폴리우레탄 성형품은 항균성능이 미미하거나, 항균성능이 오랜기간 동안 유지되지 못하며, 환경관련법에 의해 유독물질로 분류되는 성분 등이 혼합된 항균제가 사용되어 향후 사용에 제한을 받을 수 있는 문제점이 있었다.Although the above listed technologies disclose a method of imparting antimicrobial properties to a polyurethane molded article by mixing various antibacterial components, the polyurethane molded article produced by the above techniques has insufficient antibacterial performance, and the antibacterial performance is maintained for a long time And the antibacterial agent mixed with the ingredients classified as a toxic substance according to the environment-related law is used, and thus there is a problem that the use of the antibacterial agent may be restricted in future use.
따라서, 우수한 항균 및 항곰팡이 성능을 나타내면서도, 유독성분이 함유되지 않아 환경친화적인 폴리우레탄용 항균제의 개발이 요구되고 있다.Accordingly, development of an environmentally friendly antimicrobial agent for polyurethane which is excellent in antibacterial and antifungal properties, but which does not contain toxic components is desired.
특히 오랜 기간 사용하여도 황변 현상이 나타나지 않고 경시 안정성이 우수한 폴리우레탄용 항균제의 개발이 필요하다. In particular, it is necessary to develop an antimicrobial agent for polyurethane, which does not show yellowing even when used for a long period of time and has excellent stability over time.
본 발명의 목적은 폴리우레탄용 원료에 혼합되어 우수한 항균성 및 항곰팡이성을 나타내면서도, 유독성분이 함유되지 않아 환경친화적인 폴리우레탄용 항균제 조성물을 제공하는 것이다.An object of the present invention is to provide an environmentally friendly antimicrobial composition for polyurethane which is mixed with a raw material for polyurethane to exhibit excellent antimicrobial and antifungal properties but does not contain toxic components.
본 발명의 다른 목적은 폴리우레탄 성형품을 오랜 기간 사용하여도 황변 현상이 나타나지 않는 경시 안정성이 우수한 폴리우레탄용 항균제 조성물을 제공하는 것이다.Another object of the present invention is to provide a polyurethane antimicrobial composition having excellent stability over time without yellowing even when a polyurethane molded article is used for a long period of time.
본 발명자들은 다양한 항균제를 선별하여 무수히 반복실험한 결과 테부코나졸을 N-부틸-1,2-벤질이소치아졸린-3-온에 혼합하여 사용하는 경우 우수한 항균성능, 경시 안정성을 모두 얻을 수 있다는 것을 발견하고 본 발명을 완성하였다. The present inventors selected numerous antibacterial agents and repeatedly conducted numerous experiments. As a result, it was found that when antibacterial composition was mixed with N-butyl-1,2-benzylisothiazolin-3-one, excellent antibacterial performance and stability with time were obtained And completed the present invention.
본 발명의 바람직한 특징에 따르면, 상기 폴리우레탄용 항균제 조성물은 테부코나졸 5 내지 30중량% 및 N-부틸-1,2-벤질이소치아졸린-3-온 1 내지 3중량%를 포함하는 것을 특징으로 한다. According to a preferred feature of the present invention, the antimicrobial composition for polyurethane comprises 5 to 30% by weight of tebuconazole and 1 to 3% by weight of N-butyl-1,2-benzylisothiazolin-3-one .
용제는 벤질알코올, 에탄올 및 트리프로필렌글리콜모노메틸에테르로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것으로 한다.The solvent is one or more selected from the group consisting of benzyl alcohol, ethanol and tripropylene glycol monomethyl ether.
항균제 조성물은 용제 외에, 디옥틸말레이트에 디이소노닐프탈레이트, 폴리옥시프로필렌트리올 및 폴리에테르폴리올로 이루어진 그룹에서 선택된 하나 이상을 혼합하여 이루어지는 디옥틸말레이트 혼합물을 포함할 수 있다.The antimicrobial composition may contain, in addition to the solvent, a dioctylalate mixture in which dioctyl malate is mixed with at least one selected from the group consisting of diisononyl phthalate, polyoxypropylene triol and polyether polyol.
본 발명에 따른 폴리우레탄용 항균제 조성물은 폴리우레탄용 원료에 혼합되어 우수한 항균성 및 항곰팡이성을 나타내는 폴리우레탄 성형품을 제공하는 탁월한 효과를 나타낸다.INDUSTRIAL APPLICABILITY The antimicrobial agent composition for polyurethane according to the present invention exhibits an excellent effect of providing a polyurethane molded article which is mixed with raw materials for polyurethane and exhibits excellent antibacterial and antifungal properties.
또한, 폴리우레탄 성형품에 오랜기간 항균성능을 부여할 뿐만 아니라, 유독성분이 함유되지 않아 환경친화적인 탁월한 효과를 나타낸다.In addition, it not only imparts antimicrobial activity to polyurethane molded articles for a long period of time, but also exhibits an environmentally friendly excellent effect because no toxic components are contained therein.
도 1은 실시 예와 비교 예의 세균에 대한 항균 활성을 비교하여 나타낸 사진이다.
도 2는 실시 예와 비교 예의 곰팡이에 대한 저해활성을 비교하여 나타낸 사진이다.
도 3은 다양한 항균제를 사용한 우레탄의 황변 시험결과를 나타낸 사진
도 4는 테부코나졸 및 N-부틸-1,2-벤질이소치아졸린-3-온을 사용한 우레탄의 황변 시험결과를 나타낸 사진
도 5는 실시 예와 비교 예의 생물학적 가수분해 시험 결과를 나타낸 사진 Fig. 1 is a photograph showing antimicrobial activities against bacteria in Examples and Comparative Examples.
Fig. 2 is a photograph showing the inhibitory activity against molds in Examples and Comparative Examples.
3 is a photograph showing the results of the yellowing test of urethane using various antibacterial agents
4 is a photograph showing the result of yellowing test of urethane using tebuconazole and N-butyl-1,2-benzylisothiazolin-3-one
Figure 5 shows the results of biological hydrolysis Photograph showing test result
이하에는, 본 발명의 바람직한 실시예와 각 성분의 물성을 상세하게 설명하되, 이는 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자가 발명을 용이하게 실시할 수 있을 정도로 상세하게 설명하기 위한 것이지, 이로 인해 본 발명의 기술적인 사상 및 범주가 한정되는 것을 의미하지는 않는다.Hereinafter, preferred embodiments of the present invention and physical properties of the respective components will be described in detail with reference to the accompanying drawings. However, the present invention is not limited thereto, And this does not mean that the technical idea and scope of the present invention are limited.
본 발명에 따른 폴리우레탄용 항균제 조성물은 용제, 항균제 및 디옥틸말레이트 혼합물로 이루어지며, 테부코나졸 5 내지 30 중량% 및 N-부틸-1,2-벤질이소치아졸린-3-온 1 내지 3중량%를 포함하는 것을 특징으로 한다. The antimicrobial agent composition for polyurethane according to the present invention comprises a mixture of a solvent, an antibacterial agent and a dioctylmaleate, and comprises 5 to 30% by weight of tebuconazole and 1 to 3% by weight of N-butyl-1,2-benzylisothiazolin- By weight.
상기 용제는 본 발명에 따른 항균제 조성물을 구성하는 항균제를 용해시켜 균일한 물성을 나타내도록 하는 역할을 하는데, 벤질알코올, 에탄올 및 트리프로필렌글리콜모노메틸에테르로 이루어진 그룹에서 선택된 하나 이상으로 이루어지는 것이 바람직하며, 벤질알코올로 이루어지는 것이 가장 바람직하다.The solvent serves to dissolve the antimicrobial agent constituting the antimicrobial composition according to the present invention to exhibit uniform physical properties, and it is preferably composed of at least one selected from the group consisting of benzyl alcohol, ethanol and tripropylene glycol monomethyl ether , And benzyl alcohol are most preferable.
상기 벤질알코올은 일랑일랑유, 투베로즈 및 아카시아의 화정유 중에 유리 상태로 함유되어 있는 한편, 재스민 및 가데니아의 화정유, 페루 및 톨루 발삼, 클로브유 속에 에스테르로서 존재하는데, 벤즈알데히드를 수산화나트륨 수용액과 끓이고, 벤즈알데히드 냄새가 소실된 후 진한 탄산나트륨 수용액을 서서히 가하여 생성된 벤질알코올을 수증기 증류하여 분리하고 감압 증류하는 과정을 통해 제조하거나, 염화벤질을 탄산나트륨 수용액과 잘 저어 섞으면서 끓여, 얻어진 기름층을 세정 후, 감압 증류하고, 정제는 벤젠 용액으로서 분말상 염화칼슘을 반응시켜 생성되는 고형 첨가물을 벤젠으로 세정 후 물로 분해하여 건조 감압 증류하는 과정을 통해 제조된다.The benzyl alcohol is contained in the refined oil of ylang ylang oil, tuberose and acacia in a free state, while it exists as an ester in petroleum refinery oil of jasmine and gadenia, perl and tolus balsam and clove oil. The benzaldehyde is dissolved in an aqueous solution of sodium hydroxide After boiling, the benzaldehyde odor is removed, a concentrated aqueous solution of sodium carbonate is gradually added thereto, and the produced benzyl alcohol is separated by steam distillation and distilled under reduced pressure. Alternatively, benzyl chloride is boiled with an aqueous solution of sodium carbonate and boiled. And then purified by vacuum distillation. The refined product is prepared by reacting calcium chloride in powder form as a benzene solution, washing the resulting solid additive with benzene, decomposing the product into water, and drying and distillation under reduced pressure.
상기의 과정을 통해 제조되는 벤질알코올은 인체유해성이 낮을 뿐만 아니라, 상기 항균제에 대해 우수한 용해성을 나타낸다.The benzyl alcohol produced through the above process is low in human harmfulness and exhibits excellent solubility to the above-mentioned antibacterial agent.
테부코나졸은 곰팡이 균주(토양미생물 포함)에 항곰팡이 성능이 우수하며, N-부틸-1,2-벤질이소치아졸린-3-온은 곰팡이, 세균 등 토양미생물의 일종인 방선균 등에까지 항균-항곰팡이 성능을 보유한다. Tebuconazole has excellent antifungal properties against fungal strains (including soil microorganisms) and N-butyl-1,2-benzylisothiazolin-3-one has antibacterial activity against actinomycetes, which are a kind of soil microorganisms such as fungi and bacteria, Has antifungal performance.
상기 항균제는 테부코나졸 5 내지 30중량% 및 N-부틸-1,2-벤질이소치아졸린-3-온 1 내지 10중량%를 함유하며, 상기 항균제에 살균 효과를 부여하는 역할을 하는데, 상기 테부코나졸 혼합물의 함량이 5중량% 미만이거나 N-부틸-1,2-벤질이소치아졸린-3-온의 함량이 10중량%를 초과하게 되면 경시 안정성이 떨어져 황변 현상이 나타나고, N-부틸-1,2-벤질이소치아졸린-3-온의 함량이 지나치게 작으면 상기 항균제 조성물의 항곰팡이 효과가 저하될 수 있다. The antimicrobial agent contains 5 to 30% by weight of tebuconazole and 1 to 10% by weight of N-butyl-1,2-benzylisothiazolin-3-one and serves to impart a sterilizing effect to the antibacterial agent. When the content of the tebuconazole mixture is less than 5% by weight or when the content of N-butyl-1,2-benzylisothiazolin-3-one exceeds 10% by weight, -1,2-benzylisothiazolin-3-one is too small, the antifungal effect of the antimicrobial composition may be deteriorated.
상기 디옥틸말레이트 혼합물은 5 내지 20중량%가 함유되며, 본 발명에 따른 폴리우레탄용 항균제 조성물과 폴리우레탄 원료의 반응성을 향상시켜 폴리우레탄 원료가 성형품으로 성형된 후에도 오랜기간 동안 항균 및 항곰팡이 효과가 유지될 수 있도록 하는 역할을 한다.The dioctylmalate mixture contains 5 to 20% by weight, and the reactivity of the polyurethane raw material with the antimicrobial composition for polyurethane according to the present invention is improved so that even after the polyurethane raw material is molded into a molded article, the antibacterial and antifungal effect So that it can be maintained.
상기 디옥틸말레이트 혼합물의 함량이 5중량% 미만이면 상기의 효과가 미미하며, 상기 디옥틸말레이트 혼합물의 함량이 20중량%를 초과하게 되면 상대적으로 용제 및 항균제의 함량이 줄어들어 균질성, 항균 및 항곰팡이 효과가 저하될 수 있다.If the content of the dioctylmalate mixture is less than 5% by weight, the above effect is insignificant. When the content of the dioctylmalate mixture exceeds 20% by weight, the content of the solvent and the antibacterial agent is decreased and the homogeneity, The effect may be deteriorated.
이때, 상기 디옥틸말레이트 혼합물은 디옥틸말레이트에 디이소노닐프탈레이트, 폴리옥시프로필렌트리올 및 폴리에테르폴리올로 이루어진 그룹에서 선택된 하나 이상을 혼합하여 이루어지는 것이 바람직하다.At this time, it is preferable that the dioctylalate mixture is a mixture of diolefumarate with at least one selected from the group consisting of diisononyl phthalate, polyoxypropylene triol and polyether polyol.
상기의 성분으로 이루어지는 폴리우레탄용 항균제 조성물은 벤질알코올, 에탄올 및 트리프로필렌글리콜모노메틸에테르로 이루어진 그룹에서 선택된 하나 이상으로 이루어진 용제를 반응기에 투입하고 교반하여 균질화한 상태에서 테부코나졸 및 N-부틸-1,2-벤질이소치아졸린-3-온을 반응기에 투입하고 항균제가 상기 용제에 완전히 용해될 때까지 교반하고, 항균제가 용해된 용제에 디옥틸말레이트, 디이소노닐프탈레이트, 폴리옥시프로필렌트리올 및 폴리에테르폴리올 등으로 이루어지는 디옥틸말레이트 혼합물을 혼합하고 교반하여 제조된다.The antimicrobial composition for polyurethane comprising the above components is prepared by adding a solvent composed of at least one selected from the group consisting of benzyl alcohol, ethanol and tripropylene glycol monomethyl ether into a reactor, stirring the homogenized mixture, and dissolving tebuconazole and N-butyl -1,2-benzylisothiazolin-3-one is introduced into a reactor and stirred until the antimicrobial agent is completely dissolved in the solvent. To the solvent in which the antimicrobial agent is dissolved is added dioctylmalate, diisononylphthalate, polyoxypropylene tri Lt; / RTI > and a polyether polyol, and the like.
상기의 과정을 통해 제조된 폴리우레탄용 항균제 조성물은 폴리우레탄 원료에 0.1 내지 3중량% 혼합하여 사용하는 것이 바람직하다.The antimicrobial composition for polyurethane produced through the above process is preferably used in a mixing ratio of 0.1 to 3% by weight to the polyurethane raw material.
이하에서는, 본 발명에 따른 폴리우레탄용 항균제 조성물의 제조방법 및 물성을 실시예를 들어 설명하기로 한다.Hereinafter, the method for producing the antimicrobial composition for polyurethane and the physical properties according to the present invention will be described with reference to examples.
<실시예 1> 테부코나졸 30%+N-부틸-1,2-벤질이소치아졸린-3-온(BBIT)3% Example 1 Tebuconazole 30% + N-butyl-1,2-benzylisothiazolin-3-one (BBIT) 3%
벤질알코올 500g을 반응기에 투입하고 150rpm의 속도로 10분동안 교반하여 균질화한 상태에서 테부코나졸 300g N-부틸-1,2-벤질이소치아졸린-3-온 30g으로 이루어진 항균제를 반응기에 투입하고 항균제가 상기 용제에 완전히 용해될 때까지 교반하고, 항균제가 용해된 용제에 디옥틸말레이트 170g을 혼합하여 폴리우레탄용 항균제 조성물을 제조하였다.500 g of benzyl alcohol was charged into the reactor and stirred at a speed of 150 rpm for 10 minutes to homogenize. Then, an antibacterial agent consisting of 300 g of tebuconazole and 30 g of N-butyl-1,2-benzylisothiazolin-3-one was added to the reactor The mixture was stirred until the antimicrobial agent completely dissolved in the solvent, and 170 g of dioctylmalate was mixed with a solvent in which the antimicrobial agent was dissolved to prepare a polyimide antimicrobial composition.
<시험예 1> 항균 성능 ≪ Test Example 1 >
상기 실시예 1을 통해 제조된 폴리우레탄용 항균제 조성물을 폴리우레탄 원료에 함유한 후에 폴리우레탄을 폼으로 성형한 후에 항균성을 측정하여 아래 표 1및 도 1에 나타내었다.The antimicrobial composition for polyurethane prepared in Example 1 was contained in a polyurethane raw material, and polyurethane was molded into a foam, and the antimicrobial activity thereof was measured and shown in Table 1 and FIG. 1 below.
항균성 측정은 JIS L 1902 : 2008-Qualitative Test의 시험방법을 이용하였으며, 사용 배지는 Difco사의 Nutrient Agar Medium을 이용하였고, 사용 주는 황색포도상구균{Starphylococcus aureus(ATCC NO. 6538)}과 대장균{Escherichia coli (ATCC NO. 8739) 및 폐렴균}을 이용하였다.The antimicrobial activity was determined by the method of JIS L 1902: 2008-Qualitative Test. The medium used was Difco's Nutrient Agar Medium, and Starfylococcus aureus (ATCC No. 6538) and Escherichia coli (ATCC No. 8739) and pneumococci).
폴리우레탄 폼을 가로 28mm ×세로 28mm의 크기로 절단한 후에 상기 폴리우레탄용 항균제 조성물 2% 함유된 시료와 함유되지 않은 시료를 준비하고, 황색포도상구균과 대장균 및 폐렴균을 액체배지에서 배양한 후 1ml 당 107개 정도로 희석한 접종 균액을 준비하고 균액 1ml를 한천배지(Nutrient Agar Medium)에 접종하여 도말하고 건조시킨다. 상기의 과정을 통해 준비된 시료를 시험균이 도말 된 평판배지 가운데 올리고 배지와 접촉되도록 고정한 후에 37℃ 배양기에서 36시간 동안 배양하고, 배양이 완료된 후에는 시험균이 충분히 자란 것을 확인하고 주변에 형성된 Halo zone(Clear zone)의 크기를 측정하는 방법으로 항균성을 측정하였다.After the polyurethane foam was cut into a size of 28 mm x 28 mm in length, samples containing and not containing 2% of the antimicrobial composition for polyurethane were prepared, and staphylococcus aureus, E. coli and pneumococcus were cultured in a liquid medium, Prepare an inoculum diluted to about 10 7 per well, inoculate 1 ml of the bacterial solution into an agar medium (Nutrient Agar Medium), and then dry and dry. The prepared sample was fixed in a flat plate culture medium in which the test bacteria were plated and allowed to contact with the culture medium, and then cultured in a 37 ° C incubator for 36 hours. After the culture was completed, The antimicrobial activity was measured by measuring the size of the zone (clear zone).
division
위에 표 1 및 도 1에 나타낸 것처럼, 본 발명을 통해 제조된 폴리우레탄용 항균제 조성물은 폴리우레탄 원료에 적용된 후에 폴리우레탄 폼으로 성형되면 우수한 항균성을 나타내는 것을 알 수 있다.As shown in Table 1 and FIG. 1, it can be seen that the antimicrobial composition for polyurethane prepared through the present invention exhibits excellent antimicrobial activity when it is formed into a polyurethane foam after being applied to a polyurethane raw material.
<시험예 2> 항곰팡이 성능 ≪ Test Example 2 > Antifungal performance
또한, 상기 실시예 1을 통해 제조된 폴리우레탄용 항균제 조성물을 폴리우레탄 원료에 함유시켜 폴리우레탄을 폼으로 성형한 후에 항곰팡이성을 측정하여 아래 표 2에 나타내었다.The antibacterial composition for polyurethane prepared in Example 1 was contained in a polyurethane raw material to form a polyurethane foam, and antifungal property was measured and shown in Table 2 below.
항곰팡이성은 ASTM-G21(DISK)방법을 이용하였으며, 배지는 NSGA(Nutrient Salt Agar Medium (NSGA Medium)를 이용하였고, 시료는 폴리우레탄용 항균제 조성물이 2% 함유된 폴리우레탄 폼을 가로 직경이 5cm인 원으로 절단하여 사용하였으며, 4주 동안 저항성과 저지환의 크기를 측정하였으며, 상기 저항성은 곰팡이 혼합 포자액이 접종된 한천배지에 시료를 정착 시키고 28℃의 온도에서 85%의 습도 조건으로 조절된 배양기에서 배양한 후에, 배양기간 동안 시료 표면에 곰팡이의 생육 여부를 확인하는 방법을 이용하였다.The antifungal property was determined by ASTM-G21 (DISK) method. The medium was NSGA (Nutrient Salt Agar Medium (NSGA Medium), and the sample was a polyurethane foam containing 2% of the antimicrobial composition for polyurethane, The resistance was measured by incubating the agar medium inoculated with the mixed fungus spore solution at a temperature of 28 ° C and a humidity of 85% After culturing in an incubator, a method of confirming the growth of fungi on the surface of the sample during the incubation period was used.
또한, 저항성등급은 시료에 포자형성 및 균사의 발육 상태를 측정하여 구분된 것으로, 0 ; 성장없음, 1 ; 전체 면적의 10%이하, 2 ; 전체 면적의 11 내지 30%, 3 ; 전체 면적의 31 내지 60%, 4 ; 전체 면적의 61 내지 99%로 구분하였다.In addition, the resistance grade is classified by measuring spore formation and mycelial growth state in the sample, No growth, 1; Less than 10% of the total area, 2; 11 to 30% of the total area, 3; 31 to 60% of the total area, 4; And 61 to 99% of the total area.
위에 표 2에 나타낸 것처럼, 본 발명에 따른 폴리우레탄용 항균제 조성물은 곰팡이 혼합 포자액에 대한 저항성과 저지환이 크게 나타난 것으로 볼 때, 우수한 항곰팡이성을 나타내는 것을 알 수 있으며, 4주 경과 후에도 항곰팡이 성이 유지되는 것을 알 수 있다.As shown in Table 2 above, the antimicrobial composition for polyurethane according to the present invention shows excellent resistance to fungus by showing resistance and inhibition against fungus mixed spore solution, and even after 4 weeks, It can be seen that sex remains.
<시험예 3> 원료 선별을 위한 황변 시험 ≪ Test Example 3 > Yellowing test for sorting raw materials
항균제의 양을 하기 표 3에 기재된 대로 우레탄 수지 원액에 투입하고 80℃에서 10일간 보관한 후 황변 여부를 확인하였다. The amount of the antimicrobial agent was put into the urethane resin stock solution as shown in Table 3, and stored at 80 占 폚 for 10 days, and the yellowing was confirmed.
결과를 하기 표 3 및 도 3에 게시하였다.The results are shown in Table 3 and FIG.
(B/L)No additives
(B / L)
배합비Raw material
Mixing ratio
(원액)R solution
(Undiluted solution)
BBIT 5%TB 10% +
BBIT 5%
BBIT 5% + IPBC 5%TB 5% +
BBIT 5% + IPBC 5%
함량input
content
안정성Save
stability
방치 후80 ℃
After leaving
*TB:테부코나졸* TB: Tebuconazole
** IPBC: 아이오도프로피닐 부틸카바메이트** IPBC: Iodopropynyl butylcarbamate
*** OBPA: 바이나신(10, 10-oxybis-phenoxyarsin) *** OBPA: 10,10-oxybis-phenoxyarsin
상기 표 3 및 도 3에서 알 수 있는 바와 같이, BBIT 단독 및 테부코나졸과 BBIT 혼합물이 가장 양호한 저장 안정성을 나타낸다는 것을 알 수 있었다. OBPA의 경우 안정하나 이는 비소를 30% 포함하는 독성 화합물이다. As can be seen in Table 3 and FIG. 3, it was found that BBIT alone and the mixture of tebuconazole and BBIT exhibited the best storage stability. OBPA is stable, but it is a toxic compound containing 30% of arsenic.
<시험예 4> 적정 조성 선별을 위한 황변 시험 <Test Example 4> Yellowing test for selecting a proper composition
시험 예 3에서 선별된 테부코나졸(Tebuconazole)과 N-부틸-1,2-벤질이소치아졸린-3-온(BBIT)의 저장 안정성이 우수한 적정 비율을 찾기 위해 먼저, BBIT 5% 3종, Tebuconazole 5% 3종을 첨가하여 항균제 조성물을 만들고 우레탄 수지 원액 대비 1중량% 첨가하여 80℃에서 10일간 보관한 후 황변 여부를 확인하였다. 도 4a에 나타낸 바와 같이, BBIT 5%를 사용한 경우 황변 현상이 나타났다. In order to find a proper ratio of Tebuconazole and N-butyl-1,2-benzylisothiazolin-3-one (BBIT) selected in Test Example 3, Tebuconazole 5% 3 kinds were added to make an antimicrobial composition, and 1% by weight of the antimicrobial composition was added to the urethane resin solution. After storage at 80 ° C for 10 days, yellowing was confirmed. As shown in FIG. 4A, yellowing occurred when BBIT 5% was used.
또, 각각 BBIT 3%(좌측 사진), BBIT 5%(우측 사진)를 각각 첨가하여 항균제 조성물을 제조하고, 이것을 우레탄 수지 원액 대비 1중량% 첨가하여 80℃에서 10일간 보관한 후 황변 여부를 확인하였다. 도 4b의 우측 사진에 나타난 바와 같이, BBIT 5%를 사용한 경우 황변 현상이 나타났다. Further, antibacterial composition was prepared by adding
즉, BBIT 단독으로 일정 농도 이상 사용하는 경우 용이하게 황변이 일어나며, 테부코나졸을 혼합하는 경우 황변 현상이 억제된다는 것을 알 수 있었다. That is, when BBIT alone is used at a certain concentration or more, yellowing easily occurs, and it is found that yellowing is suppressed when tebuconazole is mixed.
<시험예 5> 적정 조성 선별을 위한 황변 시험 <Test Example 5> Yellowing test for selecting a proper composition
테부코나졸과 BBIT 하기 표 4에 게시된 비로 혼합하고, 다른 항균제와 저장안정성을 비교하였다. 항균제의 양을 하기 표 4에 기재된 대로 우레탄 수지 원액에 투입하고 80℃에서 15일간 보관한 후 황변 여부를 확인하였다. Tebuconazole and BBIT were mixed at the ratios listed in Table 4 below and compared with other antimicrobial agents for storage stability. The amount of the antimicrobial agent was put into the urethane resin stock solution as shown in Table 4, and stored at 80 캜 for 15 days, and the yellowing was confirmed.
결과를 하기 표 4 및 도 5에 게시하였다.The results are shown in Table 4 and FIG.
(원액)R solution
(Undiluted solution)
BBIT 1%TB * 30%
BBIT 3%TB 30%
BBIT 5%TB 30%
BBIT 5%
BBIT 10%TB 30%
BBIT 10%
* TB: 테부코나졸 * TB: Tebuconazole
** NPT: 소듐 피리티온 ** NPT: sodium pyrithione
*** OBPA: 바이나신(10, 10-oxybis-phenoxyarsin) *** OBPA: 10,10-oxybis-phenoxyarsin
테부코나졸과 BBIT를 혼합하는 경우 BBIT 함량 10%까지 황변이 없었다. 상기 표 3과 표 4에서 알 수 있는 바와 같이, 다른 항균제는 모두 우레탄 원액에 부가하여 장기 보관하는 경우 황변이나 침전 현상이 생기고 본 발명의 실시예의 제품을 제외하고 유일하게 황변이 생기지 않는 OBPA는 비소화합물로 독성이 크다. When tebuconazole and BBIT were mixed, there was no yellowing up to 10% of BBIT content. As can be seen from Tables 3 and 4, all of the other antimicrobial agents added to the urethane stock solution resulted in yellowing or precipitation when stored for a long period of time. OBPA, which is the only yellowing-free product except for the products of the examples of the present invention, High toxicity with compounds.
<시험예 6> 생물학적 가수분해 시험 ≪ Test Example 6 > Biological hydrolysis exam
시료 전처리 Sample preparation
실시예 1의 항균제 조성물, 항균제를 사용하지 않은 BLANK 조성물, 그리고 시판 항균제 조성물을 각각 1중량% 사용하여 제조한 PU FOAM시료(200X100X10T) 3종을 준비하였다. 시료에 대하여 동일한 압력을 가하여 굴절시키는 것이 중요하므로 부식이 일어나지 않는 PE재질의 케이블 타이를 이용하여 굴절된 시료를 고정하고 타이의 길이를 동일하게 유지하도록 하여 굴절된 힘이 동일해 지도록 하였다. Three kinds of PU FOAM samples (200X100X10T) prepared by using the antimicrobial composition of Example 1, the BLANK composition without using an antimicrobial agent, and the commercial antimicrobial composition at 1 wt% were prepared. Because it is important to refract by applying the same pressure to the specimen, the refracted specimen is fixed by using a cable tie of PE which does not cause corrosion, so that the length of the tie is kept the same so that the refracted force becomes equal.
Standard Practice for Evaluating Microbial Susceptibility of Nonmetallic Materials By Laboratory Soil Burial (ASTM G160 : 12)에 따라 시험하였다. 상기의 폴리우레탄 폼(Mid Sol.) 시료 3종을 외부 1.0 X 1.0 ㎡, Fill 30cm Soil Chamber에 매립하고 천연 조건에서 6개월 후에 평가하였다. 사진을 도 6에 게시하였다. Standard Practice for Evaluating Microbial Susceptibility of Nonmetallic Materials By Laboratory Soil Burial (ASTM G160: 12). Three samples of the above polyurethane foam (Mid Sol.) Were embedded in an external 1.0 X 1.0 m 2, Fill 30 cm Soil Chamber and evaluated after 6 months under natural conditions. A photograph is shown in Fig.
Claims (5)
5 to 30% by weight of tebuconazole and 1 to 10% by weight of N-butyl-1,2-benzylisothiazolin-3-one.
상기 폴리우레탄용 항균제 조성물은 벤질알코올 및 디옥틸말레이트로 이루어진 용제를 더 포함하는 것을 특징으로 하는 폴리우레탄용 항균제 조성물.
The method according to claim 1,
Wherein the antimicrobial composition for polyurethane further comprises a solvent consisting of benzyl alcohol and dioctyl malate.
디옥틸말레이트는 디이소노닐프탈레이트, 폴리옥시프로필렌트리올 및 폴리에테르폴리올로 이루어진 그룹에서 선택된 하나 이상을 혼합하여 이루어지는 디옥틸말레이트 혼합물인 것을 특징으로 하는 폴리우레탄용 항균제 조성물.
The method of claim 2,
Wherein the dioctyl malate is a mixture of at least one selected from the group consisting of diisononyl phthalate, polyoxypropylene triol and polyether polyol.
The antimicrobial composition for polyurethane according to claim 3, wherein the dioctyl malate mixture is contained in an amount of 5 to 20% by weight.
A polyurethane foam comprising 0.1 to 3% by weight of the antibacterial composition of claim 1.
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| KR102523278B1 (en) * | 2022-09-02 | 2023-04-25 | 주식회사 바른생활 | Manufacturing method of scrubber with excellent durability, anti-bacterial properties and biodegradability |
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| KR20070084373A (en) * | 2004-11-22 | 2007-08-24 | 헨켈 코만디트게젤샤프트 아우프 악티엔 | Mold-resistant construction materials |
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| KR20130100889A (en) * | 2010-04-13 | 2013-09-12 | 아치 팀버 프로텍션 리미티드 | Wood preservative formulations comprising isothiazolones which provide protectin against surface staining |
| JP5714101B2 (en) * | 2011-05-11 | 2015-05-07 | 日本曹達株式会社 | Building material preservative |
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| KR20080016852A (en) * | 2005-06-14 | 2008-02-22 | 신젠타 파티서페이션즈 아게 | Antifungal wallboards and building materials and methods for the production thereof |
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| KR102523278B1 (en) * | 2022-09-02 | 2023-04-25 | 주식회사 바른생활 | Manufacturing method of scrubber with excellent durability, anti-bacterial properties and biodegradability |
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