KR100360599B1 - Antimicrobial inorganic composite powder having excellent color stability and antimicrobial property and preparation thereof - Google Patents
Antimicrobial inorganic composite powder having excellent color stability and antimicrobial property and preparation thereof Download PDFInfo
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Abstract
Description
본 발명은 미생물의 번식억제 및 사멸시키기 위한 항균물질에 관한 것으로서, 보다 구체적으로는 색상 안정성 및 항균력이 우수한 새로운 항균성 무기 복합분체 및 그 제조방법에 관한 것이다.The present invention relates to an antimicrobial material for inhibiting and killing microorganisms, and more particularly, to a novel antimicrobial inorganic composite powder having excellent color stability and antimicrobial activity, and a method of manufacturing the same.
최근까지도 미생물의 번식억제 및 사멸시키기 위한 항균물질로써 생체피부 세포에 좋지못한 영향을 줄 뿐만아니라 피부 자극의 원인이 되는 메틸 파라벤, 프로필 파라벤류의 유기 방부제를 이용하고 있다.Until recently, organic preservatives such as methyl parabens and propyl parabens, which are used as antibacterial substances for inhibiting and killing microorganisms, not only adversely affect biological skin cells but also cause skin irritation.
이러한 유기 방부제의 문제점을 해결하기 위하여 은 및 일부 항균력을 갖고있는 금속을 함유하고 있는 무기계 항균분체를 제조하는 방법이 미국특허 제147686호, 미국특허 제2232723호, 일본특허공개 소60-100504호, 일본특허공개 평 5-179053호 등의 특허문헌과 기타 자료(참조: 미국 듀폰사에서 발간한 'Micro-Free Amp Antimicrobial powder'라는 제명하의 자료) 등에 제안되어 있다.In order to solve the problems of such organic preservatives, a method of preparing inorganic antimicrobial powders containing silver and metals having some antibacterial activity is disclosed in U.S. Patent No. 147686, U.S. Patent No. 22272323, Japanese Patent Application Publication No. 60-100504, Patent documents such as Japanese Patent Application Laid-open No. Hei 5-179053 and other data (see also: Data under the exclusion of 'Micro-Free Amp Antimicrobial powder' published by DuPont, USA).
이들 방법은 이산화티탄 수화물 분체 또는 이산화티탄 분체, 황산바륨 분체, 산화아연 분체 등의 표면위에 금속 은 및 금속 구리, 아연 등을 기체상에서 증착, 압착 혼합, 혼합후 환원, 고온에서의 열분해 방법 등으로 제조하는 방법이다. 이러한 방법으로 제조하는 무기계 항균분체는 유기계에 비해 저독성, 열안정성에서는 우수하나, 금속 특유의 색상을 띠며, 제품 적용시 회색으로의 색상전이, 항균력의 지속성, 분산성 등이 부족하여 적용 범위가 크지 않다. 특히 화장품에 적용시 사용감촉, 퍼짐성 등의 화장품 원료로서의 기능성 부족과 금속 특유의 금속성 색상과 변색 등의 문제점으로 메이컵 화장품에만 사용되거나 그 사용량에 제한을 받아 왔었다.These methods include deposition of metal silver, metal copper and zinc on the surface of titanium dioxide hydrate powder or titanium dioxide powder, barium sulfate powder, zinc oxide powder, etc. in the gas phase, compression mixing, reduction after mixing, and pyrolysis at high temperature. It is a method of manufacturing. Inorganic antimicrobial powders produced in this way are less toxic and superior in thermal stability than organic ones, but they have a distinctive color and are not suitable for application due to their lack of color transition to gray, persistence of antimicrobial activity, and dispersibility. not. In particular, it has been used only in cosmetics or has been limited in its amount due to problems such as lack of functionality as a raw material of cosmetics such as texture, spreadability, and metallic color and discoloration peculiar to metal when applied to cosmetics.
이에, 본 발명자들은 상기한 문제점들을 해결하기 위해서 연구를 거듭한 결과, 초미립자 상태의 산화아연 수화물을 0.5∼10 ㎛의 실리카(구상, 판상, 무정형)미립자 위에 피복하여 항균분체의 담체로 사용함으로써 이산화티탄 수화물 분체,이산화티탄 분체, 황산바륨 분체, 산화아연 분체 등이 주성분인 기존의 무기계 항균분체의 단점인 적용시의 상용성 부족을 해결할 수 있고, 특히 화장품에 적용시 사용감촉, 퍼짐성 등이 개선되고, 고온으로 열처리 하는 것에 의하여 아연 산화물과 금속 은이 초미립자 상태의 미세결정 복합물 형태를 형성케 함으로써, 기존의 무기 항균분체의 단점인 금속 특유의 금속성 색상과 적용시 회색계통으로의 색상전이를 완벽하게 억제할 수 있고, 초미립자 상태의 아연산화물과 금속 은의 항균활동에 대한 상승작용으로 우수한 항균력을 제공함을 발견할 수 있었다. 더욱이 규산소다 성분에 의한 보호 피복층의 피복량을 조절함에 따라 항균물질의 적절한 방출제어가 가능함을 발견하여 항균활동의 지속성의 문제를 해결함으로써 본 발명을 완성할 수 있었다.Accordingly, the present inventors have conducted research to solve the above problems, and as a result, the zinc oxide hydrate in ultrafine particles is coated on 0.5 to 10 μm silica (sphere, plate, amorphous) fine particles and used as a carrier for antimicrobial powder. Titanium hydrate powder, titanium dioxide powder, barium sulfate powder, zinc oxide powder, etc., can solve the lack of compatibility in application, which is a disadvantage of the conventional inorganic antibacterial powder, and improves the feeling of use and spreadability, especially when applied to cosmetics By heat treatment at high temperature, zinc oxide and metal silver form microcrystalline composites of ultra-fine particle state, so that metallic color, which is a disadvantage of conventional inorganic antimicrobial powder, and color transition to gray system when applied It can be suppressed, and synergistically against the antimicrobial activity of ultrafine zinc oxide and metal silver. It was found that it provides a lot of antibacterial activity. Moreover, the present invention was completed by solving the problem of the persistence of the antimicrobial activity by discovering that proper release control of the antimicrobial substance was possible by controlling the coating amount of the protective coating layer by the sodium silicate component.
따라서, 본 발명의 목적은 금속특유의 금속성 색상과 적용시 회색계통으로의 색상전이를 완벽하게 억제하고, 화장품에 이르기까지 광범위한 적용범위를 가지며, 또한 지속성이 우수한 무기계 항균분체 및 그 제조방법을 제공하는 것이다.Accordingly, an object of the present invention is to completely suppress the color transition to the gray system when applied to the metallic color and the metal unique to the metal, has a wide range of applications to cosmetics, and also provides an inorganic antimicrobial powder excellent in durability and a method of manufacturing the same. It is.
도 1은 본 발명에 의한 항균성 무기 복합분체를 0.2wt% 적용시 24시간 경과후 효모(검은곰팡이)의 100% 사멸을 보여주는 사진.1 is a photograph showing 100% killing of yeast (black mold) after 24 hours when applying 0.2 wt% of the antimicrobial inorganic composite powder according to the present invention.
도 2는 본 발명에 의한 항균성 무기 복합분체 미적용시 24시간 경과 후 효모(검은곰팡이)의 증식 상태를 보여주는 사진.Figure 2 is a photograph showing the growth state of the yeast (black mold) after 24 hours when the antimicrobial inorganic composite powder according to the present invention.
상기한 목적을 달성한 본 발명의 항균성 무기복합분체는 0.5∼10 ㎛의 실리카 미립자위에 상기 실리카 100중량부에 대하여 산화아연 15∼40중량부와 금속 은 1∼5중량부가 포함된 복합물이 초미립 결정입자 상태로 피복되고 그 위에 알카리금속규산염 성분이 2∼8중량부의 양으로 피복된 보호피복층이 형성된 것을 특징으로 한다.The antimicrobial inorganic composite powder of the present invention, which achieves the above object, is an ultrafine particle composite containing 15 to 40 parts by weight of zinc oxide and 1 to 5 parts by weight of silver on a silica particle of 0.5 to 10 μm with respect to 100 parts by weight of the silica. It is characterized in that the protective coating layer is coated in the form of crystal grains and on which the alkali metal silicate component is coated in an amount of 2 to 8 parts by weight.
본 발명의 바람직한 일 구현에 의하면 상기한 항균성 무기복합분체는 다음의 공정들을 포함하는 방법으로 제조할 수 있다.According to a preferred embodiment of the present invention, the antimicrobial inorganic composite powder may be prepared by a method including the following steps.
(ⅰ) 나노미터(㎚) 단위로 제어된 초미립자 형태의 산화아연 수화물을 0.5∼10 ㎛의 실리카 미립자위에 피복하는 공정,(Iii) coating zinc oxide hydrate in the form of ultrafine particles controlled in nanometer (nm) units on silica fine particles of 0.5 to 10 mu m;
(ⅱ) 상기 피복공정(ⅰ)의 생성물에 금속 은을 도핑하는 공정,(Ii) doping metal silver into the product of the coating step (iii),
(ⅲ) 상기 도핑공정(ⅱ)의 생성물에 알카리금속규산염을 흡착시키는 공정,(Iii) adsorbing an alkali metal silicate on the product of the doping step (ii);
(ⅳ) 상기 흡착공정(ⅲ)의 생성물을 그 아연산화물과 금속 은이 초미립자 상태의 미세 결정 복합물로 형성함과 동시에 규산염 성분의 보호 피복층을 형성하도록 열처리하는 공정, 및(Iii) heat-treating the product of the adsorption step (iii) to form the zinc oxide and the metal silver into a microcrystalline composite of ultrafine particles and to form a protective coating layer of a silicate component; and
(ⅴ) 상기 열처리공정(ⅳ)의 생성물을 평균 입경 0.5∼10 ㎛의 미립자로 분쇄하는 공정.(Iii) A step of grinding the product of the heat treatment step (iii) into fine particles having an average particle diameter of 0.5 to 10 m.
상기한 본 발명의 목적, 그 외의 목적, 특징 및 장점은 하기 발명의 상세한 설명으로부터 당업자에게 명백하게 드러날 것이다.The above and other objects, features and advantages of the present invention will become apparent to those skilled in the art from the following detailed description.
이하, 본 발명을 보다 상세히 설명하기로 한다.Hereinafter, the present invention will be described in more detail.
본 발명에 따르는 항균성 복합 분체는 광범위한 적용에 적합하도록 실리카를 담체로 사용한 것으로 실리카의 형태학적 특성을 그대로 유지하면서 제조할 수 있어서 구형도가 0.28 이하인 박편상, 구형도가 1.0에 가까운 구상, 그 중간단계인 무정형 형태로 제조할 수 있다. 따라서 실리카의 고유한 특성인 섬유, 플라스틱, 코팅, 건축자재, 비누, 화장품 원재료 등과 상용성이 본 무기계 항균 복합분체에서도 그대로 발현되며, 항균력, 열안정성 및 색상 안정성 등이 우수하다.The antimicrobial composite powder according to the present invention uses silica as a carrier to be suitable for a wide range of applications, and can be prepared while maintaining the morphological characteristics of silica as it is. It can be prepared in amorphous form, which is a step. Therefore, compatibility with fiber, plastics, coatings, building materials, soaps, and cosmetic raw materials, which are inherent to silica, is also expressed in this inorganic antimicrobial composite powder, and has excellent antibacterial activity, thermal stability, and color stability.
이러한 특성을 갖는 본 발명의 항균성 복합분체의 제조하는 방법을 바람직한 구현의 방법으로 예를 들어 설명하기로 한다.The method for producing the antimicrobial composite powder of the present invention having these characteristics will be described by way of example as a preferred embodiment.
우선 0.5∼10 ㎛의 입자크기를 갖는 구상, 판상 및/또는 무정형의 실리카 미립자를 담체로 하여 그 위에 나노미터 단위의 초미립자 상태로 산화아연 수화물을 피복한다 (공정 ⅰ). 예를 들어 이 산화아연 수화물 피복공정(ⅰ)은 실험실 규모에서 다음과 같은 방법으로 수행될 수 있다. 즉, 0.5∼10㎛의 실리카 미립자 분체를 실리카 분체의 5∼10배의 정제수가 담겨있는 사구 반응기내에 넣은 후 교반하여 수분산 시키면서, 반응기의 온도를 60∼90℃로 승온한 다음 산화아연 수화물 수용액을 투입하고, 온도를 60∼90℃로 유지하면서 반응을 2∼5 시간 진행한 후, 24시간 이상 정치시켜 40℃ 이하로 냉각시킨다. 수세 및 여과 과정을 거친 후, 건조하여 초미립자 상태의 산화아연 수화물이 피복된 실리카(구상, 판상, 무정형)미립자 분체를 제조한다. 이때 산화아연 수화물의 피복량은 20∼30 중량부 정도가 바람직하다.First, zinc oxide hydrate is coated in nanometer ultrafine particles with spherical, plate-like and / or amorphous silica fine particles having a particle size of 0.5 to 10 탆 as a carrier (step iii). For example, this zinc oxide hydrate coating process can be carried out on a laboratory scale in the following way. That is, 0.5 to 10 μm of silica fine particle powder is placed in a sand dune reactor containing 5 to 10 times the purified water of silica powder, followed by stirring and dispersing. The temperature of the reactor is raised to 60 to 90 ° C. The reaction was allowed to proceed for 2 to 5 hours while maintaining the temperature at 60 to 90 ° C, and then left to stand for at least 24 hours to cool down to 40 ° C or less. After washing with water and filtration, it is dried to prepare silica (spherical, plate-like, amorphous) fine powder coated with zinc oxide hydrate in ultrafine state. At this time, the coating amount of the zinc oxide hydrate is preferably about 20 to 30 parts by weight.
다음, 상기 피복 공정(ⅰ)의 생성물위에 금속 은을 도핑한다 (공정 ⅱ). 예를 들어 금속 은 도핑공정(ⅱ)은 다음과 같은 방법으로 수행될 수 있다. 즉, 상기 산화아연 수화물이 피복된 실리카 미립자 분체에 질산은 또는 황산은 수용액을 헨셀믹서를 이용하여 도포하는 것에 의해 금속 은을 도핑할 수 있다. 여기서 금속 은의 도핑량은 2∼5 중량부가 바람직하다.Next, metal silver is doped onto the product of the coating step (iii) (step ii). For example, the metal silver doping process (ii) may be performed in the following manner. That is, metal silver can be doped by applying silver nitrate or silver sulfate aqueous solution to the zinc fine particle powder coated with zinc oxide hydrate using a Henschel mixer. The doping amount of the metal silver is preferably 2 to 5 parts by weight.
다음, 상기 도핑공정(ⅱ)의 생성물 위에 규산소다 및/또는 규산칼륨과 같은 알카리금속 규산염을 흡착시킨다 (공정 ⅲ). 예를 들어 규산염 흡착공정(ⅲ)은 다음과 같은 방법으로 수행될 수 있다. 즉, 금속 은이 도핑된 분체에 규산소다액(SiO2/Na2O 몰비 1.62∼3.23)을 헨셀믹서를 이용하여 도포하는 것에 의해 규산염을 도포할 수 있다.Next, an alkali metal silicate such as sodium silicate and / or potassium silicate is adsorbed onto the product of the doping step (ii) (step iii). For example, the silicate adsorption process can be carried out in the following manner. That is, silicate can be applied by applying a silicate liquid (SiO 2 / Na 2 O molar ratio 1.62 to 3.23) to a metal silver-doped powder using a Henschel mixer.
다음, 상기 규산염 흡착공정(ⅲ)에서 얻은 무기 복합분체는 그 아연산화물과 금속 은이 초미립자 상태의 미세 결정 복합물로 형성함과 동시에 규산염 성분의 보호 피복층을 형성하도록 열처리한다 (공정 ⅳ). 상기 열처리는 고온의 전기로에서 수행하는 것이 바람직하며, 무기 복합분체를 전기로를 이용하여 열처리 할 때에는 단계별로 승온하여 먼저 수분을 제거하고, 바람직하게 800℃ 이상, 보다 바람직하게 800℃∼950℃의 온도에서 1∼4시간 열처리하여 질산은 또는 황산은 성분이 산화아연 수화물과 반응하여 금속 은 및 아연산화물 성분으로 이루어진 미세결정 복합물 형태를 생성시킴과 동시에 규산염 성분의 보호피복층을 형성시킨다. 이때의 생성물은 분체들이 서로 응집되어 거대 입자를 형성한다.Next, the inorganic composite powder obtained in the silicate adsorption step (iii) is heat-treated so that the zinc oxide and the metal silver are formed into a microcrystalline composite in an ultrafine state and at the same time form a protective coating layer of the silicate component. The heat treatment is preferably carried out in a high-temperature electric furnace, when the inorganic composite powder is heat-treated using an electric furnace to increase the temperature step by step to remove the water first, preferably 800 ℃ or more, more preferably 800 ℃ to 950 ℃ temperature The heat treatment at 1-4 hours at the silver nitrate or silver sulfate component reacts with the zinc oxide hydrate to form a microcrystalline complex consisting of metal silver and zinc oxide components, and simultaneously form a protective coating layer of the silicate component. The product at this time is the aggregate of the powders to form large particles.
마지막으로, 상기 열처리 공정(ⅳ)에서 얻어진 응집된 입자들을 분쇄 혹은 분리하여 평균 입경이 0.5∼10 ㎛의 미립자상 항균성 무기 복합분체를 제조한다. 이러한 미분쇄에는 예를 들어 햄머밀 등과 같은 통상의 분쇄장치를 사용할 수 있다.Finally, the agglomerated particles obtained in the heat treatment step (iii) are pulverized or separated to prepare a particulate antimicrobial inorganic composite powder having an average particle diameter of 0.5 to 10 m. For such grinding, a conventional grinding device such as a hammer mill can be used.
본 발명의 항균성 무기 복합분체는 항균력을 나타내고자하는 적용제품에 따라 적당량 선정될 수 있으며, 바람직하게는 적용제품의 0.1∼10 중량부, 바람직하게 0.5∼7중량부 적용시 우수한 항균활동을 보여 주었다. 특히 본 발명의 항균성 무기 복합분체는 색조화장료에 적용할 경우 기존의 항균성 무기 분체와는 달리 사용감촉, 퍼짐성 등의 화장품 원료로서의 기능성 부족과 금속 특유의 금속성 색상과 변색 등의 문제점을 일으키지 않아 효과적이다. 색조화장료에 적용할 경우 본 발명의 항균성 무기 복합분체의 바람직한 배합량은 화장료 총중량에 0.1∼10 중량부 정도이다.The antimicrobial inorganic composite powder of the present invention may be selected in an appropriate amount depending on the application product to exhibit antimicrobial activity, and preferably showed excellent antimicrobial activity when 0.1 to 10 parts by weight, preferably 0.5 to 7 parts by weight of the applied product is applied. . In particular, the antimicrobial inorganic composite powder of the present invention is effective when applied to color cosmetics, unlike the existing antimicrobial inorganic powder, it does not cause problems such as lack of functionality as a cosmetic raw material such as feel and spread, and metallic color and discoloration peculiar to metal. . When applied to color cosmetics, the preferred compounding amount of the antimicrobial inorganic composite powder of the present invention is about 0.1 to 10 parts by weight based on the total weight of the cosmetic.
이상 설명한 바와 같은 본발명의 특징 및 기타의 장점들은 후술되는 실시예의 설명으로부터 보다 명백하게 될 것이다. 물론, 본 발명이 이들 실시예에만 한정되는 것은 아님을 이해하여야 할 것이다.Features and other advantages of the present invention as described above will become more apparent from the following description of the embodiments. Of course, it should be understood that the present invention is not limited only to these examples.
복합분체의 제조Preparation of Composite Powder
[실시예 1]Example 1
3ℓ의 4구 반응기에 정제수 1ℓ를 투입후 평균 입경이 2 ㎛인 무정형의 실리카 미분체 200g을 반응기내에 넣은후 교반하여 수분산시키면서, 반응기의 온도를 60∼90℃로 승온시킨 다음 고형분 함량이 20% 되게 제조한 산화아연 수화물 200g을 1시간에 걸쳐 적가(滴加)하고, 온도를 75℃로 유지하면서 반응을 4시간 진행한 후, 반응물을 24시간 정치시켰다. 얻어진 슬러리 상태의 혼합물에 정제수 1ℓ를 가하여 수세한 후, 진공 탈수기를 이용하여 여과하였다. 얻어진 여과케이크를 140℃ 열풍 건조기에서 13시간 건조시켜 산화아연 수화물 피복 실리카 복합분체를 제조하였다.After adding 1 liter of purified water to a 3-liter four-necked reactor, 200 g of amorphous silica fine powder having an average particle diameter of 2 μm was placed in the reactor, stirred and dispersed, and the temperature of the reactor was raised to 60 to 90 ° C., followed by a solid content of 20 After 200 g of zinc oxide hydrate prepared in% was added dropwise over 1 hour, the reaction was allowed to proceed for 4 hours while maintaining the temperature at 75 ° C, and the reaction was allowed to stand for 24 hours. 1 L of purified water was added to the obtained slurry mixture, followed by washing with water, followed by filtration using a vacuum dehydrator. The obtained filter cake was dried in a 140 degreeC hot air dryer for 13 hours, and the zinc oxide hydrate coated silica composite powder was produced.
얻어진 산화아연 수화물 피복 실리카 복합분체에 증류수로 3배 희석된 질산은 수용액을 헨셀믹서를 이용하여 14.4g을 도포하여 금속 은을 도핑하고, 규산소다액 (SiO2/Na2O 몰비 3.23)를 10g을 도포하여 규산염을 피복하였다.To the obtained zinc oxide hydrate coated silica composite powder, 14.4 g of silver nitrate solution diluted three times with distilled water was applied using a Henschel mixer to dope metal silver, and 10 g of sodium silicate liquid (SiO2 / Na2O molar ratio 3.23) was applied to silicate. Was coated.
결과의 생성물을 전기로에서 단계별 승온 과정을 거쳐 850℃에서 2시간 열처리함으로써 잔여 수분제거와 산화아연 수화물과 질산은 성분이 아연산화물과 금속 은 복합 성분으로된 미세결정 입자가 실리카 표면위에 생성되고, 규산소다 성분의 보호피복층이 형성된 입자 응집체를 얻었다.The resultant product is heat-treated at 850 ° C. for 2 hours through a step-up process in an electric furnace to remove residual water, and to form zinc oxide hydrate and silver nitrate, and microcrystalline particles composed of zinc oxide and metal silver composite components on the surface of silica. A particle aggregate in which the protective coating layer of the component was formed was obtained.
얻어진 입자 응집체를 임팩트 밀을 이용하여 분쇄하여 목적하는 무기계 항균 복합분체를 제조하였다. 복합분체는 항균력을 보이는 무정형의 형태를 가진 평균입경 2.2 ㎛의 백색 미분체였다.The obtained particle aggregate was pulverized using an impact mill to prepare a desired inorganic antimicrobial composite powder. The composite powder was a white fine powder having an average particle diameter of 2.2 μm with an amorphous form showing antibacterial activity.
[실시예 2]Example 2
실시예 1에서 고형분 함량이 20% 되게 제조한 산화아연 수화물을 350g 적가한 것과, 질산은 수용액을 18.0g 투입한 것을 제외하고는 실시예 1과 동일한 방법으로 복합분체를 제조하였다. 복합분체는 항균력을 갖는 평균입경 2.3 ㎛의 무정형 백색 미분체였다.A composite powder was prepared in the same manner as in Example 1, except that 350 g of zinc oxide hydrate prepared in Example 1 was added dropwise to 20%, and 18.0 g of silver nitrate was added thereto. The composite powder was an amorphous white fine powder having an average particle diameter of 2.3 μm with antibacterial activity.
[실시예 3]Example 3
실시예 1에서 평균 입경이 5 ㎛인 무정형의 실리카 미분체를 사용한 것을 투입한 것을 제외하고는 실시예 1과 동일한 방법으로 복합분체를 제조하였다. 복합분체는 항균력을 갖는 평균입경 5.2 ㎛의 무정형 백색 미분체였다.A composite powder was prepared in the same manner as in Example 1, except that in Example 1, an amorphous silica fine powder having an average particle diameter of 5 μm was used. The composite powder was an amorphous white fine powder having an average particle size of 5.2 μm with antibacterial activity.
[실시예 4]Example 4
평균 입경이 5 ㎛인 무정형의 실리카 미분체를 사용한 것과, 산화아연 수화물을 350g을 적가한 것과, 질산은 수용액을 18.0g 투입한 것을 제외하고는 실시예 1과 동일한 방법으로 복합분체를 제조하였다. 복합분체는 항균력을 갖는 무정형의 백색 미분체(평균입경 5.3 ㎛)였다.A composite powder was prepared in the same manner as in Example 1, except that amorphous silica fine powder having an average particle diameter of 5 µm was used, 350 g of zinc oxide hydrate was added dropwise, and 18.0 g of silver nitrate aqueous solution was added. The composite powder was an amorphous white fine powder having an antimicrobial activity (average particle size 5.3 mu m).
상기 실시예 1∼4에 의해 제조된 본 발명의 항균성 무기 복합분체의 항균력 및 항균제품에 대한 적용시 이들의 항균 시험결과, 광변성, 화장품에의 적용시의 항균력, 변색 특성, 피부독성, 사용감 등과 섬유에의 적용시 특성 등을 측정 및 평가하였다.When the antimicrobial activity and antimicrobial products of the antimicrobial inorganic composite powders of the present invention prepared by Examples 1 to 4, their antimicrobial test results, photodegeneration, antibacterial activity, color change characteristics, skin toxicity, feeling of use when applied to cosmetics The properties and the like when applied to the fibers were measured and evaluated.
항균시험Antibacterial test
상기 실시예 1 내지 4에 의해 제조된 항균성 무기 복합분체를 증류수 150g이 들어있는 각각의 샤를레에 300㎎씩 주입한 다음, 여러종류의 미생물을 주입하고, 30℃에서 24시간 배양 후 감소율을 측정하였다. 그 결과는 하기 표 1에 제시된다.Injecting the antimicrobial inorganic composite powder prepared in Examples 1 to 4 by 300mg each charle containing 150g of distilled water, and then injecting a variety of microorganisms, the reduction rate after incubation at 30 ℃ for 24 hours was measured . The results are shown in Table 1 below.
복합분체의 색도변화 시험Chromaticity change test of composite powder
상기 실시예 1 내지 4에 의해 제조된 항균성 무기 복합분체를 자외선 램프를 사용하여 13mW/sec·㎠의 조사강도로 72시간 조사한 후 변색정도를 색차계를 이용하여 L값(백색도)를 측정하였다. 그 결과는 하기 표 2에 제시된다.The antimicrobial inorganic composite powders prepared in Examples 1 to 4 were irradiated for 72 hours with an irradiation intensity of 13 mW / sec · cm 2 using an ultraviolet lamp, and then the L value (whiteness) was measured using a color difference meter. The results are shown in Table 2 below.
제형예Formulation example
상기 실시예 4의 항균성 무기 복합분체를 각각 3%, 5%, 0% 적용하여 하기 표 3에 나타낸 제형예 1 내지 3의 색조화장품(트위케이크)를 제조하였다. 제조된 색조화장품의 항균성을 시험하기 위하여 대장균, 포도상구균, 칸다다균이 혼합된 박테리아 2.4×103개와 효모(검은곰팡이)1.4×102개 주입하여 30℃에서 배양하여 시간경과에 따라 미생물의 사멸정도를 측정하였다. 측정결과는 하기 표 4 및 5에 각각 제시된다. 또한, 제형예 1 및 2의 트윈케이크를 20∼30대의 여성 50명을 대상으로 사용성을 평가하여 그 결과를 하기 표 6에 나타내었다.3%, 5%, and 0% of the antimicrobial inorganic composite powder of Example 4 was applied to prepare color cosmetics (twicakes) of Formulation Examples 1 to 3 shown in Table 3 below. In order to test the antimicrobial activity of the manufactured color cosmetics, 2.4 × 10 3 bacteria mixed with E. coli, Staphylococcus aureus and Kanda bacteria were injected and 1.4 × 10 2 yeasts (black mold) were incubated at 30 ° C. to kill microorganisms over time. The degree was measured. The measurement results are shown in Tables 4 and 5, respectively. In addition, to evaluate the usability of the twin cakes of Formulation Examples 1 and 2 for 50 women in their 20s to 30s, the results are shown in Table 6 below.
단섬유 원사 적용시 색도 변화 및 항균성Color change and antimicrobial activity when short fiber
실시예 1의 항균성 복합분체를 각각 0%, 0.6%, 1% 및 3% 적용한 폴리에스터 단섬유(6 데니아)의 백색도 변화를 측정하여 그 결과를 하기 표 7에 나타내었으며, 또한 상기 단섬유를 30g씩 넣은 후 대장균, 포도상구균, 칸다다균이 혼합된 박테리아 균주 2.4×103개를 투입하고 30℃에서 배양하여 시간경과에 따른 미생물의 사멸정도를 측정하여 그 결과를 하기 표 8에 나타내었다.The whiteness of the polyester short fibers (6 denia) to which the antimicrobial composite powder of Example 1 was applied 0%, 0.6%, 1% and 3%, respectively, was measured and the results are shown in Table 7 below. After the 30g each put E. coli, Staphylococcus, Kanda bacteria mixed 2.4 × 10 3 bacteria strains were mixed and incubated at 30 ℃ measured the killing degree of microorganisms over time and the results are shown in Table 8 below.
기초화장품(크림) 적용시 색도변화 시험Chromaticity change test when applying basic cosmetics (cream)
상기 실시예 1 내지 4의 항균성 무기 복합분체를 각각 5% 적용하여 기초화장품을 제조한 후 처음 상태와 30일 동안 태양광에 방치한 후의 색도변화를 일본 미놀타사제 색차계 CR-200을 이용하여 측정하였다. 측정결과 기존의 무기계 항균분체와는 달리 금속특유의 금속성의 색상이 나타나지 않았으며 30일 후에도 변색이 되지 않아 기초화장품에 대한 적용이 가능하였다. 측정결과는 하기 표 9에 제시된다.5% of each of the antimicrobial inorganic composite powders of Examples 1 to 4 was used to prepare a basic cosmetic, and then chromaticity change after leaving in sunlight for the first time and for 30 days was measured using a color difference meter CR-200 manufactured by Minolta Japan. It was. As a result of the measurement, unlike the conventional inorganic antimicrobial powder, the metallic metallic color did not appear, and after 30 days, it was not discolored, and thus it was possible to apply to basic cosmetics. The measurement results are shown in Table 9 below.
상기 실시예 4의 항균성 무기분체의 안전성을 장치(Skintex UMA)를 사용하여 생체외 시험하였다. 블랭크(Blank)와 활성화된 쿠베트(Activated cuvette)에 시료를 각각 300㎎ 적용하여 25℃에서 24시간 배양후 시료를 제거하고 로우 챔버(low chamber)에 있는 용액의 OD값을 미국 베크만사제 DU7500 스펙트로미터로 470㎚에서 측정한 한 바, 결과치가 PDⅡ 0.23으로 자극정도가 낮은 안전한 물질임을 확인할 수 있었다.The safety of the antimicrobial inorganic powder of Example 4 was tested in vitro using a device (Skintex UMA). 300 mg of the sample was applied to the blank and the activated cuvette, and the samples were removed after incubation at 25 ° C. for 24 hours, and the OD value of the solution in the low chamber was measured using DU7500 Spectrometer manufactured by Beckman, USA. When measured at 470nm by meter, the result was PDII 0.23, and it was confirmed that it is a safe substance with low irritation degree.
이상의 실험으로부터 알 수 있는 바와 같이 기존의 무기계 항균분체의 화장품(기초화장품 및 색조화장품) 적용시 발생하는 문제점인 금속특유의 금속성 색상과 변색의 문제, 사용성의 부족, 피부안정성 등의 문제를 본 발명을 통한 항균성 무기 복합분체를 사용하여 해결할 수 있었다. 또한 단섬유 제조공정에서 폴리에스터 대비하여 각각 0.6중량%, 1중량%, 3중량% 투입하여 단섬유 원사를 제조한 후 백색도 변화측정결과로부터 알 수 있는 바와 같이 본발명에 따르는 항균성 무기 복합분체를 사용하면 적용시 항균력이 우수한 폴리에스터 원사를 제조할 수 있음을 알 수 있었다.As can be seen from the above experiments, problems such as problems of metallic color and discoloration, lack of usability, skin stability, and the like, which are problems occurring when applying cosmetics (base cosmetics and color cosmetics) of existing inorganic antimicrobial powders, have problems of the present invention. It could be solved using antimicrobial inorganic composite powder through. In addition, in the short fiber manufacturing process, 0.6 wt%, 1 wt%, and 3 wt% of polyester were prepared, respectively, to prepare a short fiber yarn, and then, as can be seen from the whiteness change measurement results, the antimicrobial inorganic composite powder according to the present invention was prepared. When used, it was found that the polyester yarn with excellent antimicrobial activity can be produced.
이와 같이 본 발명에 의하면 기존의 은계 무기 항균분체의 단점인 금속 특유의 금속성 색상이 없고 사용시 회색계통으로의 색상전이가 없으며, 열처리 과정에서 생성된 초미립자 상태의 아연산화물과 금속 은 복합물이 항균활동에 상승작용을 하여 우수한 항균력을 제공할 수 있으며, 또한 규산소다 성분에 의한 보호 피복층의 형성으로 항균 물질의 적절한 방출제어로 항균활동의 지속성을 제공할 수 있다.As described above, according to the present invention, there is no metallic color unique to the metal, which is a disadvantage of the conventional silver inorganic antimicrobial powder, and there is no color transition to the gray system when used, and the ultrafine zinc oxide and metal silver complexes generated during the heat treatment process are used for antibacterial activity. Synergistic action can provide excellent antimicrobial activity, and by forming the protective coating layer by the sodium silicate component can provide the sustainability of the antimicrobial activity by controlling the release of the antimicrobial material.
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