KR20220092038A - Stability Enhanced Low Concentration Peracetic Acid Disinfectant Compositions - Google Patents

Stability Enhanced Low Concentration Peracetic Acid Disinfectant Compositions Download PDF

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KR20220092038A
KR20220092038A KR1020200183395A KR20200183395A KR20220092038A KR 20220092038 A KR20220092038 A KR 20220092038A KR 1020200183395 A KR1020200183395 A KR 1020200183395A KR 20200183395 A KR20200183395 A KR 20200183395A KR 20220092038 A KR20220092038 A KR 20220092038A
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peracetic acid
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composition
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김석준
주남진
주성연
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주식회사앤제이컴퍼니
군산대학교산학협력단
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/16Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group; Thio analogues thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/22Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing ingredients stabilising the active ingredients
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/02Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
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  • Toxicology (AREA)
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  • Inorganic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention relates to an eco-friendly low-concentration peracetic acid disinfectant composition with an improved stability that significantly increases a period for which sterilization effectiveness is maintained by stabilizing peracetic acid, which rapidly decomposes in summer or in a high-temperature environment, and that transforms to water and vinegar when decomposed naturally. The disinfectant composition comprises: a low-concentration peracetic acid composition including peracetic acid, hydrogen peroxide, acetic acid and water; a phosphate; and an ethanol extract of Ixeridium dentatum.

Description

안정성이 향상된 저농도 과초산계 소독제조성물{Stability Enhanced Low Concentration Peracetic Acid Disinfectant Compositions}Stability Enhanced Low Concentration Peracetic Acid Disinfectant Compositions

본 발명은 안정성이 향상된 저농도 과초산계 소독제조성물에 관한 것으로서, 특히 여름철이나 고온 환경에서 분해가 빨리 일어나는 과초산(peracetic acid)을 안정화시켜 살균력의 유효기간을 현저히 증가시킬 수 있는 안정성이 향상된 저농도 과초산계 소독제조성물에 관한 것이다.The present invention relates to a low-concentration peracetic acid-based disinfectant composition with improved stability, particularly in summer or in a high-temperature environment, by stabilizing peracetic acid, which rapidly decomposes, thereby significantly increasing the effective period of sterilization. It relates to an acetic acid-based disinfectant composition.

과초산의 살균기전은 두 가지로 첫째는 활성산소의 방출로 세포막의 단백질 및 효소의 씨올(-SH) 및 황 결합(-S-)을 파괴하여 세포막의 전달 과정을 막는 것이고 둘째는 하이드록실 라디칼(·OH)을 발생시켜 미생물을 비활성화시키는 것이다.The sterilization mechanism of peracetic acid is twofold. First, it blocks the cell membrane transfer process by breaking the thiol (-SH) and sulfur bonds (-S-) of proteins and enzymes in the cell membrane by releasing active oxygen, and second, the hydroxyl radical (·OH) is generated to inactivate microorganisms.

실제 항균시험에서는 과초산이 아주 낮은 농도(100ppm)에서 5분 이하의 접촉에도 박테리아, 효모 및 곰팡이를 비활성화시키나 유기물 존재하에서는 200 내지 500ppm이 요구된다. In the actual antibacterial test, peracetic acid inactivates bacteria, yeast and mold at a very low concentration (100ppm) even in contact for less than 5 minutes, but 200 to 500ppm is required in the presence of organic matter.

기존 식품살균용 식품 첨가물 6종(차아염소산 나트륨 등)은 유기물이 존재하면 살균력이 급격하게 저하되어 축산물에는 살균효과가 거의 없으나 과초산은 유기물 존재하에서도 살모넬라 균과 같은 식중독 균에 대해서 차아염소산 나트륨과 비교하여 기온에 따라 10 내지 1000배 이상을 나타내어 소고기, 돼지고기, 닭고기, 오리고기 등의 축산물 가공 시설이나 도구 등의 살균에 매우 효과적이다. Existing 6 types of food additives for food sterilization (sodium hypochlorite, etc.) have almost no sterilization effect on livestock products because their sterilization power decreases rapidly when organic substances are present. In comparison, it shows 10 to 1000 times or more depending on the temperature, so it is very effective in sterilizing livestock products processing facilities or tools such as beef, pork, chicken, and duck meat.

또한, 과초산계 소독제는 사용자 및 환자의 안전도가 높고 바이오필름의 생성을 억제하며 유기물 존재 시에도 탁월한 소독 효과가 있어 반복 재사용하는 내시경에서도 환자간 교차감염을 막기 위해 최근 많이 사용되고 있다. In addition, peracetic acid-based disinfectants have high safety for users and patients, suppress the formation of biofilms, and have an excellent disinfecting effect even in the presence of organic matter.

그러나, 과초산계 소독제는 과초산 농도가 반으로 줄어드는 반감기가 제품 종류에 따라 상온에서 2 내지 3일 또는 길어야 10일 정도로 짧은 문제가 있다. 기존의 연구 결과들에 따르면 과초산의 분해속도는 사용된 노출 온도, 희석수의 종류, 과초산 농도, 과산화수소 및 아세트산의 농도, 황산 촉매의 유무 등에 의존한다. 이중에서 아세트산의 농도 증가 및 황산의 존재는 소독제의 pH를 낮춰 금속의 부식성을 높이는 문제가 추가로 발생한다. However, the peracetic acid-based disinfectant has a problem that the half-life in which the peracetic acid concentration is reduced by half is as short as 2 to 3 days or at most 10 days at room temperature depending on the type of product. According to the results of previous studies, the decomposition rate of peracetic acid depends on the exposure temperature used, the type of dilution water, the peracetic acid concentration, the concentrations of hydrogen peroxide and acetic acid, and the presence or absence of a sulfuric acid catalyst. Among them, an increase in the concentration of acetic acid and the presence of sulfuric acid lower the pH of the disinfectant to further increase the corrosiveness of the metal.

과산화수소 함량이 높을수록 과초산 분해가 억제되고 오히려 생성될 수 있는데 과산화수소 농도는 규제 대상으로 허용치 이상으로 첨가할 수는 없다. 보관 온도는 가급적 낮을수록 과초산 분해가 억제되며 어는점이 각 성분의 함량에 따라 다르지만 얼릴 경우에는 거의 분해가 일어나지 않는다. 희석수로는 이온교환수(3차 증류수), 역삼투압수(2차 증류수), 1차 증류수, 수돗물, 지하수 순으로 초순수에 가까울수록 과초산 분해가 적다. The higher the hydrogen peroxide content, the more inhibited the decomposition of peracetic acid, and the more it can be generated. As the storage temperature is as low as possible, decomposition of peracetic acid is suppressed, and although the freezing point varies depending on the content of each component, almost no decomposition occurs when frozen. As dilution water, ion-exchange water (tertiary distilled water), reverse osmosis water (second distilled water), primary distilled water, tap water, and groundwater in the order of ultrapure water, the closer to ultrapure water, the less peracetic acid decomposition.

한편, 기존에 적용된 과초산 안정제는 금속 양이온을 캡쳐하는 킬레이터(chelator)로 과산화수소 안정제로 사용된 1-Hydroxyethylidene-1,1-diphosphonic acid(HEDP 혹은 editronic acid), cyclohexane-1,2-diamino tetra(methylene phosphonic acid)(CDTMP) 등이 사용된다. Meanwhile, the conventionally applied peracetic acid stabilizer is a chelator that captures metal cations, and 1-Hydroxyethylidene-1,1-diphosphonic acid (HEDP or editronic acid), cyclohexane-1,2-diamino tetra, used as a hydrogen peroxide stabilizer. (methylene phosphonic acid) (CDTMP) and the like are used.

여기서 HEDP(Monsanto사의 Dequest 2010)는 제지 표백에 사용되는 알칼리 조건의 과산화수소를 안정화시키기 위해 또는 부식방지제 등으로 적용된 것으로 산성 조건인 과초산 소독제에서도 과초산 안정화 효과가 있어 현재 국내에서 많이 사용되고 있다. HEDP의 경우 국내에서 30ppm 이하로 사용량이 제한되어 있고 이 농도에서 과초산 안정화 효과는 비교적 작은 편이다. 물론, 저농도 과초산계 소독제에서 안정화제 농도에 비례하여 반드시 과초산의 안정성이 증가하는 것은 아니다. 이온 킬레이팅 약품들은 경수(또는 지하수) 사용 시 전이금속에 의한 과산화수소 또는 과초산의 분해가 촉진되는 것을 막기 위한 것으로 이온교환수나 역삼투압수를 사용하는 경우에는 그 효과가 크지 않을 수 있다.Here, HEDP (Monsanto's Dequest 2010) is applied to stabilize hydrogen peroxide in alkaline conditions used for paper bleaching or as a corrosion inhibitor. In the case of HEDP, the amount of use is limited to less than 30 ppm in Korea, and the effect of stabilizing peracetic acid at this concentration is relatively small. Of course, in the low-concentration peracetic acid-based disinfectant, the stability of peracetic acid does not necessarily increase in proportion to the stabilizer concentration. Ion chelating agents are to prevent the accelerated decomposition of hydrogen peroxide or peracetic acid by transition metals when hard water (or groundwater) is used.

특허문헌 0001에는 퍼옥시컴파운드에 대한 안정화제로 피로인산(pyrophosphorus acid) 또는 염, 과붕산 나트륨(sodium perborate), 포타슘 퍼옥시모노설페이트(potassium monopersulfate), 아세토포스폰산 나트륨(sodium acetophospnonate)등이 사용되고 요소 화합물, 과붕산 화합물, 과황산 화합물 및 과산류(peracids) 등과 이들의 나트륨염, 칼륨염 또는 에탄올아민과 같은 유기아민의 염이 사용된다. 그러나, pH가 10 이상인 알칼리 조건에서 고농도의 과산화수소에 대한 안정화제로 사용되는 것으로 아세토포스폰산 나트륨(sodium acetophospnonate)과 1-Hydroxyethylidene-1,1-diphosphonic acid(HEDP 혹은 editronic acid)가 가장 우수한 과산화수소 안정화 효과를 보였다.In Patent Document 0001, pyrophosphorus acid or salt, sodium perborate, potassium peroxymonosulfate, sodium acetophosphonate, etc. are used as a stabilizer for peroxy compound, and urea Compounds, perboric acid compounds, persulfate compounds, peracids, and the like, and their sodium salts, potassium salts, or salts of organic amines such as ethanolamine are used. However, sodium acetophospnonate and 1-Hydroxyethylidene-1,1-diphosphonic acid (HEDP or editronic acid) are used as stabilizers for high concentrations of hydrogen peroxide in alkaline conditions with a pH of 10 or more. showed

특허문헌 0002에는 퍼옥시컴파운드에 대한 안정화제로 아크릴산계 고분자를 증점제(thickenig agent)로 0.05 내지 10% 첨가하는 방법과 특허문헌 0003에는 중성세제인 지방족 알콜 에톡실레이트(EO 부가수 >4)를 0.1 내지 5중량%를 첨가하는 방법이 개시되어 있다. 아크릴산 고분자나 지방족 알콜 에톡실레이트의 경우에도 낮은 함량에서 저농도 과초산계 소독제에서 과초산에 대한 안정화 효과가 있으나 그리 크지 않거나 고함량에서는 오히려 아무것도 첨가하지 않은 경우보다 나쁠 수 있다. In Patent Document 0002, a method of adding 0.05 to 10% of an acrylic acid polymer as a thickener as a stabilizer for a peroxy compound, and in Patent Document 0003, an aliphatic alcohol ethoxylate (EO addition number >4) as a neutral detergent is 0.1 A method of adding to 5% by weight is disclosed. Even in the case of acrylic acid polymer or aliphatic alcohol ethoxylate, a low-concentration peracetic acid-based disinfectant at a low content has a stabilizing effect on peracetic acid, but at a low content or at a high content, it may be worse than when nothing is added.

특허문헌 0004에는 과산화수소 및 과초산 안정제로 탄소수가 2 내지 9인 저급 지방족 퍼애시드(C2∼C9 aliphatic peracid)를 기존 안정제에 추가하여 첨가하는 방법이 소개되어 있고 과초산 안정제로 dipicolinic acid(DPA)와 포스폰산(phosphonic acid) 또는 그 염화합물들(Monsanto사의 Dequest 제품들로 hydroxyethylenediphosphonate, diethylenetriaminepentamethylene phosphonate, ethylenediaminetetramethylene phosphonate 등)을 사용하였고, 부식방지제로 알칼리 금속의 인산염인 dipotassium hydrogen orthophosphate(K2HPO4)를 첨가하였다. 또한, 특허문헌 0005에는 합성촉매인 황산을 NaOH로 중화하고 Dequest 2010(HEDP) 200ppm과 DPA 50ppm을 사용하였다.Patent Document 0004 introduces a method of adding hydrogen peroxide and a lower aliphatic peracid having 2 to 9 carbon atoms (C 2 to C 9 aliphatic peracid) as a peracetic acid stabilizer to an existing stabilizer and adding dipicolinic acid (DPA) as a peracetic acid stabilizer. ) and phosphonic acid or its salt compounds (Monsanto's Dequest products, hydroxyethylenediphosphonate, diethylenetriaminepentamethylene phosphonate, ethylenediaminetetramethylene phosphonate, etc.) were used, and dipotassium hydrogen orthophosphate (K 2 HPO 4 ), an alkali metal phosphate, was used as a corrosion inhibitor. was added. In addition, in Patent Document 0005, sulfuric acid, which is a synthesis catalyst, was neutralized with NaOH, and 200 ppm of Dequest 2010 (HEDP) and 50 ppm of DPA were used.

특허문헌 0006에는 과초산, 초산, 인산, 1,1-디포스폰산 및 역삼투압수를 혼합하여 사용하는 방법이 개시되어 있고, 특허문헌 0007에는 과초산 1 내지 25중량%, 초산 0.5 내지 15중량%, 과산화수소 1 내지 25중량%, 유기산 1 내지 15중량%, 킬레이트제 1 내지 5중량%와 나머지는 물인 과초산 수용액을 개시하고 있다. 여기서 유기산은 평형반응(과산화수소+초산->과초산+물)을 촉진시키는 역할을 수행하는 산 촉매로 시트릭산, 말릭산, 글리콜릭산, 옥살산, 숙신산, 포름산이며 상기 킬레이트제는 HEDP, [(카르복시메틸)이미노]비스(에틸렌니트릴로)테트라아세트산, EDTA 소듐염 및 이들의 혼합물로 이루어진 군으로부터 선택될 수 있다. Patent Document 0006 discloses a method of using a mixture of peracetic acid, acetic acid, phosphoric acid, 1,1-diphosphonic acid and reverse osmosis water, and Patent Document 0007 discloses 1 to 25% by weight of peracetic acid, 0.5 to 15% by weight of acetic acid %, 1 to 25% by weight of hydrogen peroxide, 1 to 15% by weight of an organic acid, 1 to 5% by weight of a chelating agent and the remainder is water. Here, the organic acid is an acid catalyst that promotes the equilibrium reaction (hydrogen peroxide + acetic acid -> peracetic acid + water). Citric acid, malic acid, glycolic acid, oxalic acid, succinic acid, and formic acid. The chelating agent is HEDP, [(carboxy methyl)imino]bis(ethylenenitrilo)tetraacetic acid, EDTA sodium salt, and mixtures thereof.

특허문헌 0008에는 과산화초산(0.1 내지 10중량%), 과산화수소(1 내지 30중량%) 및 살리실계 화합물(0.01 내지 2 중량%)을 포함하는 살균 소독조성물로서 상기 살리실계 화합물은 N,N'-디살리실리덴-에틸렌디아민, N,N'-디살리실리덴-1,2-프로필렌디아민, N,N'-디살리실리덴-N-메틸-디프로필렌트리아민 중에서 선택되는 하나 또는 둘 이상의 혼합물이 소개되어 있다. 과산화초산 6.5중량%와 과산화수소 29중량%로 된 수용액에서 N,N'-디살리실리덴-1,2-프로필렌디아민 0.2g을 첨가하여 24℃에서 360일 보관 시 단지 과산화초산 농도가 2.3%의 농도변화를 보여 ±5% 이내의 기준치를 만족하였다. 다만 상기 살리실계 화합물들은 주로 연료첨가제로 사용되는 것으로 인체에 해롭고 환경에 문제를 일으킬 수 있다.Patent Document 0008 discloses a sterilization and disinfection composition comprising peracetic acid (0.1 to 10% by weight), hydrogen peroxide (1 to 30% by weight) and a salicylic compound (0.01 to 2% by weight), wherein the salicylic compound is N,N'- One or two or more selected from disalicylidene-ethylenediamine, N,N'-disalicylidene-1,2-propylenediamine, and N,N'-disalicylidene-N-methyl-dipropylenetriamine The mixture is introduced. In an aqueous solution of 6.5% by weight of peracetic acid and 29% by weight of hydrogen peroxide, 0.2 g of N,N'-disalicylidene-1,2-propylenediamine was added and stored at 24°C for 360 days. It showed a change in concentration and satisfied the standard value within ±5%. However, the salicyl-based compounds are mainly used as fuel additives and are harmful to the human body and may cause problems in the environment.

현재까지의 과초산 안정화 기술은 그 효과가 적거나 인체에 유해할 수 있는 물질들이 대부분이다. 따라서, 본 발명에서는 식품첨가물로 사용될 수 있는 물질 중에서 과초산을 안정화시킬 수 있는 것을 찾아 과초산을 최대로 안정화시키는 치적 함량 및 조합을 구하고자 하였다. Most of the peracetic acid stabilization technologies up to now have little effect or substances that can be harmful to the human body. Therefore, in the present invention, among the substances that can be used as a food additive, it was attempted to find a suitable content and combination for maximally stabilizing peracetic acid by finding one capable of stabilizing peracetic acid.

US3122417A (1964.02.25)US3122417A (1964.02.25) US5296239A (1994.03.22)US5296239A (1994.03.22) US5489706A (1996.02.06)US5489706A (1996.02.06) US5624634A (1997.04.29)US5624634A (1997.04.29) US6677477B2 (2004.01.13)US6677477B2 (2004.01.13) KR10-0363896B1 (2002.11.25)KR10-0363896B1 (2002.11.25) KR10-0597092B1 (2006.06.28)KR10-0597092B1 (2006.06.28) KR10-2034095B1 (2019.10.14)KR10-2034095B1 (2019.10.14)

이와 같은 종래의 문제점을 해결하기 위한 본 발명은 여름철이나 고온 환경에서 분해가 빨리 일어나는 과초산(peracetic acid)을 안정화시켜 살균력의 유효기간을 현저히 증가시킬 수 있는 안정성이 향상된 저농도 과초산계 소독제조성물을 제공함에 그 목적이 있다.The present invention for solving such conventional problems is a low-concentration peracetic acid-based disinfectant composition with improved stability that can significantly increase the effective period of sterilization by stabilizing peracetic acid, which decomposes quickly in summer or high-temperature environments. The purpose is to provide.

상기와 같은 목적을 달성하기 위한 본 발명은 과초산, 과산화수소, 초산 및 물을 포함하는 저농도 과초산조성물, 인산염 및 씀바귀 에탄올추출물을 포함하는 것을 특징으로 하는 안정성이 향상된 저농도 과초산계 소독제조성물을 제공한다.The present invention for achieving the above object provides a low-concentration peracetic acid-based disinfectant composition with improved stability, characterized in that it comprises a low-concentration peracetic acid composition comprising peracetic acid, hydrogen peroxide, acetic acid and water, phosphate, and an oleander extract do.

상기 인산염은 상기 저농도 과초산조성물에 25 내지 500ppm이 포함되는 것이 좋다. 그리고 상기 인산염은 트리폴리인산나트륨, 육메타인산나트륨 중 선택된 1종 이상으로 이루어질 수 있다.It is preferable that the phosphate is contained in an amount of 25 to 500 ppm in the low-concentration peracetic acid composition. And the phosphate may be made of at least one selected from sodium tripolyphosphate and sodium hexahexaphosphate.

그리고 상기 씀바귀 에탄올추출물은 상기 저농도 과초산조성물에 100 내지 1000ppm이 포함되는 것이 바람직하다. 상기 씀바귀 에탄올추출물은 꽃씀바귀, 불꽃씀바귀, 선씀바귀, 노랑선씀바귀, 좀씀바귀, 흰씀바귀, 벋음씀바귀, 벌씀바귀, 갯씀바귀, 냇씀바귀, 애기벋줄씀바귀 중 선택된 1종 또는 2종 이상을 에탄올추출하여 얻을 수 있다.And it is preferable that the ethanol extract of sagebrush contains 100 to 1000 ppm in the low-concentration peracetic acid composition. The above ethanol extract is ethanol extraction of one or two or more selected from among dandelion worms, ragweed wormwood, dandelion wormwood, yellow wormwood wormwood, white wormwood wormwood, dandelion wormwood, bee wormwood wormwood, ragweed wormwood, ragweed wormwood can be obtained by

특히, 상기 씀바귀 에탄올추출물은 벌씀바귀 잎, 뿌리 또는 전초를 건조한 것을 에탄올추출하여 얻은 것이 좋다.In particular, it is preferable that the ethanol extract of banyan tree is obtained by ethanol extraction of dried beetroot leaves, roots or outposts.

또한, 부식방지제, 완충제, 금속 봉쇄제, 재부착 방지제 및 계면활성제 중 선택된 1종 또는 2종 이상의 첨가제가 포함되는 것이 좋다. 이때 상기 첨가제는 상기 저농도 과초산조성물 100중량부에 대해 0.001 내지 0.5중량부가 포함되는 것이 바람직하다.In addition, it is preferable that one or two or more additives selected from a corrosion inhibitor, a buffer, a metal sequestrant, an anti-redeposition agent, and a surfactant are included. In this case, the additive is preferably included in an amount of 0.001 to 0.5 parts by weight based on 100 parts by weight of the low-concentration peracetic acid composition.

본 발명의 안정성이 향상된 저농도 과초산계조성물은 여름철이나 고온 환경에서 분해가 빨리 일어나는 과초산(peracetic acid)을 씀바귀 에탄올추출물 및 인산염에 의해 안정화시켜 살균력의 유효기간을 현저히 증가시킬 수 있고, 자연분해 시 물과 식초로 변하는 등 친환경적인 효과가 있다.The low-concentration peracetic acid-based composition with improved stability of the present invention can significantly increase the effective period of sterilizing power by stabilizing peracetic acid, which decomposes quickly in summer or high-temperature environments, by means of ethanol extract and phosphate salt, and naturally decomposes. It has an eco-friendly effect, such as turning into water and vinegar.

이하, 본 발명의 안정성이 향상된 저농도 과초산계조성물에 대하여 상세히 설명하면 다음과 같다.Hereinafter, the low-concentration peracetic acid-based composition with improved stability of the present invention will be described in detail as follows.

본 발명의 안정성이 향상된 저농도 과초산계조성물은 과초산, 과산화수소, 초산 및 물을 포함하는 저농도 과초산조성물, 인산염 및 씀바귀 에탄올추출물을 포함한다.The low-concentration peracetic acid-based composition with improved stability of the present invention includes a low-concentration peracetic acid composition containing peracetic acid, hydrogen peroxide, acetic acid and water, phosphate, and an ethanol extract of dandelion.

상기 저농도 과초산조성물은 과초산 원액을 저농도로 희석한 조성물로서, 과초산원액을 역삼투압수, 이온교환수, 1차 증류수, 수돗물, 지하수 등의 물을 이용하여 20 배 내지 1500배로 희석하여 사용할 수 있다.The low-concentration peracetic acid composition is a composition obtained by diluting the peracetic acid undiluted solution to a low concentration, and the peracetic acid undiluted solution is diluted 20 to 1500 times using reverse osmosis water, ion-exchanged water, primary distilled water, tap water, groundwater, etc. can

과초산 원액은 과초산 합성방법에 따라 조성이 달라지고, 황산 촉매를 미량 포함할 수 있다. 과초산 합성방법은 황산촉매로 합성하는 방법과, 무촉매로 합성하는 방법이 있다.The peracetic acid stock solution has a different composition depending on the peracetic acid synthesis method, and may contain a trace amount of a sulfuric acid catalyst. There are two methods for synthesizing peracetic acid: a method for synthesizing with a sulfuric acid catalyst and a method for synthesizing without a catalyst.

황산 촉매를 적용한 과초산 원액의 경우 반응물인 초산과 과산화수소의 몰비를 1:2 내지 1:15 사이로 사용가능하며 황산은 반응물의 중량 대비 1%를 첨가하여 50℃에서 4시간 반응시켜 제조할 수 있다. 황산 촉매를 사용하지 않은 과초산 원액의 경우에는 반응물의 몰비는 동일하나, 80℃에서 12시간 반응시켜 제조할 수 있다.In the case of the peracetic acid stock solution to which the sulfuric acid catalyst is applied, the molar ratio of the reactant, acetic acid and hydrogen peroxide, can be used in a range of 1:2 to 1:15, and sulfuric acid can be prepared by adding 1% of the weight of the reactant and reacting at 50°C for 4 hours. . In the case of a stock solution of peracetic acid without using a sulfuric acid catalyst, the molar ratio of the reactants is the same, but it can be prepared by reacting at 80° C. for 12 hours.

과초산과 과산화수소는 살균 성분으로 함량이 높을수록 살균효과는 크나 인체에 유해할 수 있으며, 과초산 함량이 0.008중량%이하의 경우 살균효과가 작아 접촉시간을 길게 유지하여 대장균 및/또는 식중독균을 죽일 수가 있고 과일 및 채소류의 세척 등에만 사용할 수 있다. Peracetic acid and hydrogen peroxide are sterilizing ingredients, and the higher the content, the greater the sterilization effect, but can be harmful to the human body. It can be used only for washing fruits and vegetables.

상기 인산염은 육메타인산나트륨(sodium hexametaphosphate, Na6[(PO4)6]) 또는 트리폴리인산나트륨(sodium tripolyphosphate, Na5P3O10)으로 단독 또는 병행하여 사용할 수 있으며, 둘 다 식품첨가제로 사용되는 것으로 섭취할 경우에도 인체에 무해한 수용성 무기화합물이다.The phosphate is sodium hexametaphosphate (sodium hexametaphosphate, Na 6 [(PO 4 ) 6 ]) or sodium tripolyphosphate (sodium tripolyphosphate, Na 5 P 3 O 10 ) It can be used alone or in combination, both as a food additive It is a water-soluble inorganic compound that is harmless to the human body even when ingested.

상기 인산염은 상기 저농도 과초산조성물에 25 내지 500ppm이 포함되는 것이 바람직하다. 상기 인산염을 25ppm 미만으로 사용할 경우 과초산을 안정화시키는 효과가 크게 감소한다.It is preferable that the phosphate is contained in an amount of 25 to 500 ppm in the low-concentration peracetic acid composition. When the phosphate is used in an amount of less than 25 ppm, the effect of stabilizing peracetic acid is greatly reduced.

그리고 상기 씀바귀 에탄올추출물은 과초산을 안정화시키고 살균 효과를 증진시키기 위한 것이다. And the ethanol extract of Swallowtail is for stabilizing peracetic acid and enhancing the bactericidal effect.

상기 씀바귀 에탄올추출물은 건조된 씀바귀 잎, 뿌리 또는 전초를 에탄올에 냉침하여 추출할 수 있고, 특히 더욱 과초산을 안정화시키기 위해서 씀바귀 잎만을 사용하여 에탄올 추출하는 것이 좋다.The ethanol extract can be extracted by refrigeration of dried sagebrush leaves, roots or outages in ethanol, and in particular, in order to further stabilize peracetic acid, it is preferable to ethanol extraction using only spruce leaves.

씀바귀(Ixreis dentata NAKAI)는 국화과에 속하는 식물로 국내에서 흔히 자라는 것으로 식용이 가능하며 해열, 건위, 폐렴, 간염, 종기의 치료제로 사용하고 있고, 이에 씀바귀 에탄올추출물은 인체에 유해하지 않은 천연 유래 물질이다.Asteraceae (Ixreis dentata NAKAI) is a plant belonging to the family Asteraceae and is commonly grown in Korea and is edible. It is used as a treatment for fever, dry stomach, pneumonia, hepatitis, and boils. to be.

상기 씀바귀는 그 종류에 크게 한정되는 것은 아니고, 꽃씀바귀, 불꽃씀바귀, 선씀바귀, 노랑선씀바귀, 좀씀바귀, 흰씀바귀, 벋음씀바귀, 벌씀바귀, 갯씀바귀, 냇씀바귀, 애기벋줄씀바귀 등을 사용할 수 있다.The above is not particularly limited to the type, and it is possible to use a flower squirrel, a fire ragweed, a dandelion locust, a yellow hornbill, a moth worm, a white wormwood, a lichen, a bee larva, a ragweed, a ragweed worm, and a ragweed ragweed. have.

현재 씀바귀 함유성분으로는 80여종 이상이 밝혀져 있고 풍미성분으로 헥세놀(hexenol), 플라본 중 하나인 시나로사이드(cynaroside)가 있고 지방산들(tridecanoic acid, hexadecanoic acid 등)과 그 에스터, 테르펜류로 알파- 및 베타-피넨(α- and β-pinene) 트리테르페노이드인 아미린(α- and β- amyrin), 올레아놀산(oleanoilc acid), 우르솔산(ursolic acid), 다당류로 이눌린(inulin), 이당류로 설탕(sucrose) 등이 있다. Currently, more than 80 kinds of ingredients containing sagebrush have been identified, and flavor ingredients include hexenol and cinaroside, one of the flavones, and fatty acids (tridecanoic acid, hexadecanoic acid, etc.), their esters, and terpenes. α- and β-pinene triterpenoids amyrin (α- and β-amyrin), oleanoilc acid, ursolic acid, polysaccharide inulin, Examples of disaccharides include sucrose.

상기 씀바귀 에탄올추출물은 건조된 씀바귀 잎, 뿌리 또는 전초를 에탄올에 냉침하여 추출할 수 있고, 특히 더욱 과초산을 안정화시키기 위해서 씀바귀 잎만을 사용하여 에탄올 추출하는 것이 좋다.The ethanol extract can be extracted by refrigeration of dried sagebrush leaves, roots or outages in ethanol, and in particular, in order to further stabilize peracetic acid, it is preferable to ethanol extraction using only spruce leaves.

상기 씀바귀 에탄올추출물은 상기 저농도 과초산조성물에 100 내지 1000ppm 사용하는 것이 좋다. 상기 씀바귀 에탄올 추출물이 100ppm 미만에서는 살균 및 안정화 효과가 작고, 1000ppm 초과에서는 살균 효과는 크나 안정화 효과가 좋지 못하다.It is preferable to use 100 to 1000 ppm of the banyan tree ethanol extract in the low-concentration peracetic acid composition. If the ethanol extract is less than 100ppm, the sterilization and stabilization effect is small, and if it exceeds 1000ppm, the sterilization effect is large but the stabilization effect is not good.

또한, 본 발명의 조성물은 부식방지제, 완충제, 금속 봉쇄제, 재부착 방지제 및 계면활성제 중에서 선택되는 단일 또는 두 가지 이상의 첨가제를 더 포함할 수 있다. 상기 첨가제는 그 함량이 0.001 내지 0.5 중량%로 포함될 수도 있다. In addition, the composition of the present invention may further include a single or two or more additives selected from a corrosion inhibitor, a buffer, a metal sequestering agent, an anti-redeposition agent, and a surfactant. The additive may be included in an amount of 0.001 to 0.5% by weight.

이하, 본 발명의 안정성이 향상된 저농도 과초산계 소독제조성물에 대하여 실시예를 들어 상세히 설명하면 다음과 같고, 본 발명의 권리범위는 하기의 실시예에 한정되는 것은 아니다.Hereinafter, the low-concentration peracetic acid-based disinfectant composition with improved stability of the present invention will be described in detail with reference to examples, and the scope of the present invention is not limited to the following examples.

[실시예 1 및 2][Examples 1 and 2]

초산 200g과 35% 과산화수소 800g 및 97% 황산(촉매) 10g을 반응기에 넣고 50℃에서 5시간 동안 300rpm으로 교반 가열하여 과초산 원액을 제조하였다. 제조된 과초산 원액은 과초산 7.3%, 과산화수소 21.3%, 초산 14.0%로 이루어지고 밀도는 1.1이다. 과초산 원액을 역삼투압수를 이용하여 36배 희석하여 1L의 저농도 과초산조성물을 얻었다.200 g of acetic acid, 800 g of 35% hydrogen peroxide, and 10 g of 97% sulfuric acid (catalyst) were put into a reactor, and stirred and heated at 300 rpm at 50° C. for 5 hours to prepare a stock solution of peracetic acid. The prepared undiluted peracetic acid solution consists of 7.3% peracetic acid, 21.3% hydrogen peroxide, and 14.0% acetic acid, and has a density of 1.1. The peracetic acid stock solution was diluted 36-fold using reverse osmosis water to obtain 1 L of a low-concentration peracetic acid composition.

저농도 과초산조성물 1L에 트리폴리인산나트륨(Sodium tripolyphosphate) 0.5g(500ppm) 및 벌씀바귀 잎 에탄올 추출물 0.5g(500ppm) 또는 1.0g(1000ppm)을 가하여 실시예 1 및 2의 저농도 과초산계 소독제조성물을 제조하였다.To 1 L of low-concentration peracetic acid composition, 0.5 g (500 ppm) of sodium tripolyphosphate and 0.5 g (500 ppm) or 1.0 g (1000 ppm) of beetle leaf ethanol extract were added to prepare the low-concentration peracetic acid-based disinfectant composition of Examples 1 and 2 prepared.

[비교예 1 내지 5][Comparative Examples 1 to 5]

실시예 1과 동일한 방법으로 제조한 저농도 과초산조성물에 표 1과 같이 안정제를 변화시켜 비교예 1 내지 5의 저농도 과초산계 소독제조성물을 제조하였다.The low-concentration peracetic acid-based disinfectant compositions of Comparative Examples 1 to 5 were prepared by changing the stabilizer as shown in Table 1 in the low-concentration peracetic acid composition prepared in the same manner as in Example 1.

[시간경과에 따른 과산화수소 및 과초산 농도의 측정][Measurement of hydrogen peroxide and peracetic acid concentration over time]

실시예 1 및 2, 비교예 1 내지 5의 저농도 과초산계 소독제조성물에 대하여 30℃ 또는 20℃오븐에 넣고 시간 경과에 따른 과산화수소 농도와 과초산 농도를 각각 아래에 주어진 적정법으로 측정하였고, 그 결과를 표 1로 나타냈다.The low-concentration peracetic acid-based disinfectant compositions of Examples 1 and 2 and Comparative Examples 1 to 5 were placed in an oven at 30° C. or 20° C., and the hydrogen peroxide concentration and the peracetic acid concentration over time were measured by the titration methods given below, respectively. is shown in Table 1.

과초산 및 과산화수소를 포함하는 수용액상의 각 조성물에서 10ml을 취하여 250ml 비이커에 담고 황산 10% 수용액 약 40ml을 가한 다음 0.05N 과망간산나트륨(KMnO4) 수용액으로 투명한 액이 핑크색으로 변하기 직전을 적정점으로 잡아 과산화수소 농도를 구하였고 바로 이어서 10% 아이오딘화칼륨(KI, potassium ioddide) 수용액 10ml을 가하여 적황색 용액으로 변한 것을 0.05N 싸이오황산나트륨(Na2S2O3, sodium thiosulfate) 적정액을 가하여 투명해지는 시점까지 적정하여 과초산 농도를 구하였다. 과산화수소 적정은 황산세륨(IV)(cerium sulfate)을 이용한 과산화수소 적정결과와 잘 일치하였고 과초산 농도는 과초산 측정지(Merck사) 결과와 거의 일치하였다.Take 10ml of each composition in aqueous solution containing peracetic acid and hydrogen peroxide, put it in a 250ml beaker, add about 40ml of 10% sulfuric acid aqueous solution, and then use 0.05N sodium permanganate (KMnO 4 ) aqueous solution to set the appropriate point just before the transparent solution turns pink The concentration of hydrogen peroxide was obtained, and then 10 ml of 10 % potassium iodide (KI, potassium ioddide ) aqueous solution was added to turn it into a red-yellow solution. The peracetic acid concentration was obtained by titration up to the time point. The hydrogen peroxide titration was in good agreement with the hydrogen peroxide titration using cerium sulfate (IV), and the peracetic acid concentration was almost consistent with the results of the peracetic acid measuring paper (Merck).

Figure pat00001
Figure pat00001

상기 표 1을 참조하면, 과초산 0.2 중량%(2000ppm)를 갖는 조성물에 안정제로 트리폴리인산나트륨(Sodium tripolyphosphate) 0.5g(500ppm) 및 벌씀바귀 잎 에탄올 추출물 0.5g(500ppm)을 가한 실시예 1과 트리폴리인산나트륨(Sodium tripolyphosphate) 0.5g(500ppm) 및 벌씀바귀 잎 에탄올 추출물 1.0g을 가한 실시예 2가 가장 안정성이 우수하였다. 30℃에서 실시예 1과 2는 반감기가 15일 정도이지만 아무것도 첨가하지 않은 비교예 1은 반감기가 10일로 5일이 증가한 것으로 나타났다. 20℃에서 실시예 1과 2는 반감기가 40일 이상으로 HEDP 30ppm과 카프릴산(octanoic acid) 100ppm을 첨가한 비교예 5의 반감기가 35일로 7일 이상이 증가한 것으로 나타났다.Referring to Table 1 above, Example 1 in which 0.5 g (500 ppm) of sodium tripolyphosphate and 0.5 g (500 ppm) of an ethanol extract of honeysuckle leaves were added to a composition having 0.2 wt % (2000 ppm) of peracetic acid as a stabilizer Example 2, in which 0.5 g (500 ppm) of sodium tripolyphosphate and 1.0 g of an ethanol extract from a honey bee leaf was added, had the best stability. At 30° C., the half-lives of Examples 1 and 2 were about 15 days, but Comparative Example 1 in which nothing was added had a half-life of 10 days, which was increased by 5 days. Examples 1 and 2 at 20 ° C. had a half-life of 40 days or more, and the half-life of Comparative Example 5 in which 30 ppm of HEDP and 100 ppm of caprylic acid were added was 35 days, which was increased by 7 days or more.

[실시예 3 및 4][Examples 3 and 4]

초산 200g과 35% 과산화수소 800g을 반응기에 넣고 80℃에서 12시간 동안 300rpm으로 교반 가열하여 과초산 원액을 제조하였다. 과초산 원액은 과초산 6.9%, 과산화수소 22.7%, 초산 14.6%로 이루어지고 밀도는 약 1.1이다.200 g of acetic acid and 800 g of 35% hydrogen peroxide were put into a reactor, and stirred and heated at 300 rpm at 80° C. for 12 hours to prepare a stock solution of peracetic acid. The undiluted peracetic acid solution consists of 6.9% peracetic acid, 22.7% hydrogen peroxide, and 14.6% acetic acid, and has a density of about 1.1.

과초산 원액을 역삼투압수를 이용하여 222배 희석하여 저농도 과초산조성물 1L 용액을 제조하였다.The stock solution of peracetic acid was diluted 222-fold using reverse osmosis water to prepare a 1L solution of a low-concentration peracetic acid composition.

저농도 과초산조성물 1L에 육메타인산나트륨(Sodium hexametaphosphate) 및 벌씀바귀 잎 에탄올 추출물을 가하여 저농도 과초산계 소독제조성물을 제조하였다. 이때, 육메타인산나트륨(Sodium hexametaphosphate) 0.5g(500ppm) 및 벌씀바귀 잎 에탄올 추출물 0.25g(250ppm)을 가하여 실시예 3의 저농도 과초산계 소독제조성물을 제조하였고, 육메타인산나트륨(Sodium hexametaphosphate) 0.25g(250ppm) 및 벌씀바귀 잎 에탄올 추출물 0.5g(500ppm)을 가하여 실시예 4의 저농도 과초산계 소독제조성물을 제조하였다.A low-concentration peracetic acid-based disinfectant composition was prepared by adding sodium hexametaphosphate and an ethanol extract of beetle leaf to 1L of the low-concentration peracetic acid composition. At this time, 0.5 g (500 ppm) of sodium hexametaphosphate and 0.25 g (250 ppm) of an ethanol extract of beetle leaf were added to prepare the low-concentration peracetic acid-based disinfectant composition of Example 3, and sodium hexametaphosphate (Sodium hexametaphosphate) 0.25 g (250 ppm) and 0.5 g (500 ppm) of an ethanol extract of beech leaves were added to prepare a low-concentration peracetic acid-based disinfectant composition of Example 4.

[비교예 6 내지 10][Comparative Examples 6 to 10]

실시예 3과 동일한 방법으로 제조한 저농도 과초산조성물에 표 2와 같이 안정제를 변화시켜 비교예 6 내지 10의 저농도 과초산계 소독제조성물을 제조하였다.The low-concentration peracetic acid-based disinfectant compositions of Comparative Examples 6 to 10 were prepared by changing the stabilizer as shown in Table 2 to the low-concentration peracetic acid composition prepared in the same manner as in Example 3.

[시간경과에 따른 과산화수소 및 과초산 농도의 측정][Measurement of hydrogen peroxide and peracetic acid concentration over time]

실시예 3 및 4, 비교예 6 내지 10의 저농도 과초산계 소독제조성물에 대하여 30℃ 또는 20℃ 오븐에 넣고 시간 경과에 따른 과산화수소 농도와 과초산 농도를 각각 아래에 주어진 적정법으로 측정하였고, 그 결과를 표 2로 나타냈다.The low-concentration peracetic acid-based disinfectant compositions of Examples 3 and 4 and Comparative Examples 6 to 10 were placed in an oven at 30° C. or 20° C., and the hydrogen peroxide concentration and the peracetic acid concentration over time were measured by the titration methods given below, respectively. is shown in Table 2.

과초산 및 과산화수소를 포함하는 수용액상의 각 조성물에서 10ml을 취하여 250ml 비이커에 담고 황산 10% 수용액 약 40ml을 가한 다음 0.01N 과망간산나트륨(KMnO4) 수용액으로 투명한 액이 핑크색으로 변하기 직전을 적정점으로 잡아 과산화수소 농도를 구하였고 바로 이어서 10% 아이오딘화칼륨(KI, potassium ioddide) 수용액 10ml을 가하여 적황색 용액으로 변한 것을 0.01N 싸이오황산나트륨(Na2S2O3, sodium thiosulfate) 적정액을 가하여 투명해지는 시점까지 적정하여 과초산 농도를 구하였다.Take 10 ml of each composition in an aqueous solution containing peracetic acid and hydrogen peroxide, put it in a 250 ml beaker, add about 40 ml of 10% sulfuric acid aqueous solution, and then use 0.01 N sodium permanganate (KMnO 4 ) aqueous solution to set the appropriate point just before the transparent solution turns pink. The concentration of hydrogen peroxide was obtained, and immediately thereafter, 10 ml of a 10 % potassium iodide (KI, potassium ioddide ) aqueous solution was added, which turned into a red - yellow solution. The peracetic acid concentration was obtained by titration up to the time point.

Figure pat00002
Figure pat00002

표 2에는 과초산 0.03 중량%(300ppm)을 갖는 조성물에 안정제로 육메타인산나트륨(Sodium hexametaphosphate) 0.5g(500ppm) 및 벌씀바귀 잎 에탄올 추출물 0.25g(250ppm)을 가한 실시예 3과 육메타인산나트륨(Sodium hexametaphosphate) 0.25g(250ppm) 및 벌씀바귀 잎 에탄올 추출물 0.5g(500ppm)을 가한 실시예 4가 가장 안정성이 우수하였다. 30℃에서 실시예 3과 4는 반감기가 각각 16일 및 18일 정도인데 HEDP 30ppm과 카프릴산(octanoic acid) 100ppm을 첨가한 비교예 10의 13일에 비해 3일 내지 5일이 증가한 것으로 나타났다. 20℃에서 실시예 3과 4는 반감기가 120일 이상으로 아무것도 첨가하지 않은 비교예 6의 반감기 62일 보다 대폭 증가한 것으로 나타났다. Table 2 shows Example 3 and hexametaphosphoric acid in which 0.5 g (500 ppm) of sodium hexametaphosphate and 0.25 g (250 ppm) of an ethanol extract of honeysuckle leaves were added to a composition having 0.03 wt % (300 ppm) of peracetic acid as a stabilizer Example 4, in which 0.25 g (250 ppm) of sodium hexametaphosphate and 0.5 g (500 ppm) of an ethanol extract from a beehive leaf was added, had the best stability. The half-lives of Examples 3 and 4 at 30° C. were about 16 and 18 days, respectively, and it was found that they increased by 3 to 5 days compared to 13 days of Comparative Example 10 in which 30 ppm of HEDP and 100 ppm of caprylic acid were added. . At 20°C, Examples 3 and 4 had a half-life of 120 days or more, which was significantly increased compared to the half-life of 62 days of Comparative Example 6 in which nothing was added.

[실시예 5 및 6][Examples 5 and 6]

초산 200g과 35% 과산화수소 800g을 반응기에 넣고 80℃에서 12시간 동안 300rpm으로 교반 가열하여 과초산 원액을 제조하였다. 과초산 원액은 과초산 6.9%, 과산화수소 22.7%, 초산 14.6%로 이루어지고, 밀도는 약 1.1이다. 과초산 원액을 역삼투압수를 이용하여 1333배 희석(원액 0.75ml+역삼투압수 999.25ml)하여 1L의 저농도 과초산 조성물을 제조하였다.200 g of acetic acid and 800 g of 35% hydrogen peroxide were put into a reactor, and stirred and heated at 300 rpm at 80° C. for 12 hours to prepare a stock solution of peracetic acid. The undiluted peracetic acid solution consists of 6.9% peracetic acid, 22.7% hydrogen peroxide, and 14.6% acetic acid, and has a density of about 1.1. The peracetic acid stock solution was diluted 1333 times using reverse osmosis water (0.75 ml of the stock solution + 999.25 ml of reverse osmosis water) to prepare 1 L of low-concentration peracetic acid composition.

저농도 과초산조성물 1L에 육메타인산나트륨(Sodium hexametaphosphate) 및 벌씀바귀 잎 에탄올 추출물을 가하여 저농도 과초산계 소독제조성물을 제조하였다. 이때, 육메타인산나트륨(Sodium hexametaphosphate) 0.05g(50ppm) 및 벌씀바귀 잎 에탄올 추출물 0.1g(100ppm)을 가하여 실시예 5의 저농도 과초산계 소독제조성물을 제조하였고, 육메타인산나트륨(Sodium hexametaphosphate) 0.025g(25ppm) 및 벌씀바귀 잎 에탄올 추출물 0.2g(200ppm)을 가하여 실시예 6의 저농도 과초산계 소독제조성물을 제조하였다.A low-concentration peracetic acid-based disinfectant composition was prepared by adding sodium hexametaphosphate and an ethanol extract of beetle leaf to 1L of the low-concentration peracetic acid composition. At this time, by adding 0.05 g (50 ppm) of sodium hexametaphosphate and 0.1 g (100 ppm) of an ethanol extract of beetle leaves to prepare the low-concentration peracetic acid-based disinfectant composition of Example 5, sodium hexametaphosphate (Sodium hexametaphosphate) 0.025 g (25 ppm) and 0.2 g (200 ppm) of an ethanol extract of bee larvae leaf were added to prepare a low-concentration peracetic acid-based disinfectant composition of Example 6.

[비교예 11 내지 15][Comparative Examples 11 to 15]

실시예 5와 동일한 방법으로 제조한 저농도 과초산조성물에 표 3과 같이 안정제를 변화시켜 비교예 11 내지 15의 저농도 과초산계 소독제조성물을 제조하였다.The low-concentration peracetic acid-based disinfectant compositions of Comparative Examples 11 to 15 were prepared by changing the stabilizer as shown in Table 3 to the low-concentration peracetic acid composition prepared in the same manner as in Example 5.

시간경과에 따른 과산화수소 및 과초산 농도의 측정은 실시예 3 등의 저농도 과초산계 소독제조성물의 측정방법과 동일한 방법으로 측정하였고, 그 결과를 표 3으로 나타냈다.The measurement of hydrogen peroxide and peracetic acid concentrations over time was measured in the same manner as in Example 3 and the same method for measuring low-concentration peracetic acid-based disinfectant compositions, and the results are shown in Table 3.

Figure pat00003
Figure pat00003

표 3에는 과초산 0.008 중량%(80ppm)을 갖는 조성물에 안정제로 육메타인산나트륨(Sodium hexametaphosphate) 0.05g(50ppm) 및 벌씀바귀 잎 에탄올 추출물 0.1g(100ppm)을 첨가한 실시예 5와 육메타인산나트륨(Sodium hexametaphosphate) 0.025g(25ppm) 및 벌씀바귀 잎 에탄올 추출물 0.2g(200ppm)을 가한 실시예 6이 가장 안정성이 우수하였다. 30℃에서의 과초산 농도의 반감기가 실시예 5는 35일, 실시예 6은 39일로 가장 길었으며 20℃에서도 둘 다 80일 이상으로 안정성이 가장 우수하였다.Table 3 shows that in Example 5 and yukmeta in which 0.05 g (50 ppm) of sodium hexametaphosphate and 0.1 g (100 ppm) of an ethanol extract of beech leaves were added as a stabilizer to a composition having 0.008 wt % (80 ppm) of peracetic acid Example 6, in which 0.025 g (25 ppm) of sodium hexametaphosphate and 0.2 g (200 ppm) of an ethanol extract from a honey bee leaf, was added, had the best stability. The half-life of the peracetic acid concentration at 30° C. was the longest at 35 days in Example 5 and 39 days in Example 6, and both had the best stability at 20° C., at 80 days or more.

우리나라에서 지역에 따라 약간의 차이는 있으나, 6월 및 9월의 평균기온이 20±2℃ 부근이며 5월과 10월은 15±3℃ 부근으로 본 발명의 20℃ 결과와 유사하고, 3월과 11월은 5±3℃, 1월, 2월 및 12월은 0℃ 부근(서울 경기 등 북쪽은 영하로 -2℃ 정도이며, 남해안 쪽은 1 내지 4℃)으로 겨울에는 과초산 농도의 경시변화가 크지 않아 과초산이 2000ppm의 높은 농도에서도 반감기가 120일 이상으로 예상되므로 안정제의 효능이 중요하지 않으나, 4월부터 10월까지는 본 발명의 안정화 기술이 매우 필요하다 할 수 있다. Although there are some differences depending on the region in Korea, the average temperature in June and September is around 20±2℃, and in May and October it is around 15±3℃, which is similar to the 20℃ result of the present invention, and in March In November and 5±3℃, in January, February and December, around 0℃ (in the north, including Seoul and Gyeonggi, it is about -2℃ below zero, and in the south coast, it is 1-4℃), and the concentration of peracetic acid in winter is The effect of the stabilizer is not important because the half-life of peracetic acid is expected to be more than 120 days even at a high concentration of 2000 ppm because there is no significant change over time, but it can be said that the stabilization technology of the present invention is very necessary from April to October.

pH의 경우 과초산 함량이 높을수록 낮게 나타났으나 과초산 함량이 2000ppm 부근인 실시예 1과 2도 인산염 첨가로 pH가 3.00 이상으로 증가되어 산성도가 다른 안정제를 첨가한 것에 비해 낮아 금속 부식성이 가장 낮을 것으로 사료된다. 과초산 함량이 가장 적은 실시예 5와 6은 pH가 4이상으로 나타났다.In the case of pH, the higher the peracetic acid content, the lower it was, but in Examples 1 and 2, where the peracetic acid content was around 2000 ppm, the pH was increased to 3.00 or higher with the addition of phosphate. is expected to be low. Examples 5 and 6 with the lowest peracetic acid content had a pH of 4 or higher.

Claims (8)

과초산, 과산화수소, 초산 및 물을 포함하는 저농도 과초산조성물, 인산염 및 씀바귀 에탄올추출물을 포함하는 것을 특징으로 하는 안정성이 향상된 저농도 과초산계 소독제조성물.
Peracetic acid, hydrogen peroxide, a low-concentration peracetic acid composition comprising acetic acid and water, a low-concentration peracetic acid-based disinfectant composition with improved stability, characterized in that it comprises an ethanol extract of phosphate and sagebrush.
제1항에 있어서,
상기 인산염은 상기 저농도 과초산조성물에 25 내지 500ppm이 포함되는 것을 특징으로 하는 안정성이 향상된 저농도 과초산계 소독제조성물.
The method of claim 1,
The phosphate is a low-concentration peracetic acid-based disinfectant composition with improved stability, characterized in that 25 to 500ppm is included in the low-concentration peracetic acid composition.
제1항에 있어서,
상기 인산염은 트리폴리인산나트륨, 육메타인산나트륨 중 선택된 1종 이상으로 이루어지는 것을 특징으로 하는 안정성이 향상된 저농도 과초산계 소독제조성물.
The method of claim 1,
The phosphate is a low-concentration peracetic acid-based disinfectant composition with improved stability, characterized in that it consists of at least one selected from sodium tripolyphosphate, sodium hexametaphosphate.
제1항에 있어서,
상기 씀바귀 에탄올추출물은 상기 저농도 과초산조성물에 100 내지 1000ppm이 포함되는 것을 특징으로 하는 안정성이 향상된 저농도 과초산계 소독제조성물.
The method of claim 1,
The low-concentration peracetic acid-based disinfectant composition with improved stability, characterized in that the ethanol extract of sagebrush contains 100 to 1000 ppm in the low-concentration peracetic acid composition.
제4항에 있어서,
상기 씀바귀 에탄올추출물은 꽃씀바귀, 불꽃씀바귀, 선씀바귀, 노랑선씀바귀, 좀씀바귀, 흰씀바귀, 벋음씀바귀, 벌씀바귀, 갯씀바귀, 냇씀바귀, 애기벋줄씀바귀 중 선택된 1종 또는 2종 이상을 에탄올추출하여 얻은 것을 특징으로 하는 안정성이 향상된 저농도 과초산계 소독제조성물.
5. The method of claim 4,
The above ethanol extract is ethanol extraction of one or two or more selected from among dandelion, ragweed, sagebrush, yellow sagebrush, moss worm, white wormwood, dandelion worm, bee worm, dandelion worm, brook wormwood, and baby wormwood. A low-concentration peracetic acid-based disinfectant composition with improved stability, characterized in that obtained by
제4항에 있어서,
상기 씀바귀 에탄올추출물은 벌씀바귀 잎, 뿌리 또는 전초를 건조한 것을 에탄올추출하여 얻은 것을 특징으로 하는 안정성이 향상된 저농도 과초산계 소독제조성물.
5. The method of claim 4,
The low-concentration peracetic acid-based disinfectant composition with improved stability, characterized in that the ethanol extract is obtained by ethanol extraction of dried beetroot leaves, roots or outposts.
제1항 내지 제6항 중 어느 한 항에 있어서,
부식방지제, 완충제, 금속 봉쇄제, 재부착 방지제 및 계면활성제 중 선택된 1종 또는 2종 이상의 첨가제가 포함되는 것을 특징으로 하는 안정성이 향상된 저농도 과초산계 소독제조성물.
7. The method according to any one of claims 1 to 6,
A low-concentration peracetic acid-based disinfectant composition with improved stability, characterized in that it contains one or two or more additives selected from a corrosion inhibitor, a buffer, a metal sequestering agent, a re-adhesion inhibitor, and a surfactant.
제7항에 있어서,
상기 첨가제는 상기 저농도 과초산조성물 100중량부에 대해 0.001 내지 0.5중량부가 포함되는 것을 특징으로 하는 안정성이 향상된 저농도 과초산계 소독제조성물.
8. The method of claim 7,
The additive is a low-concentration peracetic acid-based disinfecting composition with improved stability, characterized in that 0.001 to 0.5 parts by weight are included with respect to 100 parts by weight of the low-concentration peracetic acid composition.
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