KR0180468B1 - Bactericide and algicide of phytic acid - Google Patents

Bactericide and algicide of phytic acid Download PDF

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KR0180468B1
KR0180468B1 KR1019960032377A KR19960032377A KR0180468B1 KR 0180468 B1 KR0180468 B1 KR 0180468B1 KR 1019960032377 A KR1019960032377 A KR 1019960032377A KR 19960032377 A KR19960032377 A KR 19960032377A KR 0180468 B1 KR0180468 B1 KR 0180468B1
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acid
algae
phytic acid
seaweed
phytic
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KR19980013754A (en
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이기선
박인
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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
    • A01N57/00Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/12Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing acyclic or cycloaliphatic radicals
    • 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
    • A01N25/02Biocides, 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 liquids as carriers, diluents or solvents
    • 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
    • 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
    • A01N37/06Unsaturated 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
    • 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
    • A01N37/36Biocides, 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 at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • 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
    • A01N2300/00Combinations or mixtures of active ingredients covered by classes A01N27/00 - A01N65/48 with other active or formulation relevant ingredients, e.g. specific carrier materials or surfactants, covered by classes A01N25/00 - A01N65/48

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  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
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Abstract

본 발명은 곡물에서 추출한 피틴산을 이용하여 해수에 발생하는 파래, 먹태 및 담수에 발생하는 이끼, 가래, 규조류, 녹조류, 김양식시 부생하는 병균 등을 독성없이 방제할 수 있는 살조제에 관한 것으로서, 피틴산을 함유하는 것을 특징으로 하며, 이러한 피틴산에 포화지방족 모노카본산 및 포화 또는 불포화 디카본산, 주석산(tartaric acid), 사과산(malic acid), 호박산(succinic acid), 구연산(citric acid)등으로 이루어지는 군에서 선택된 1종 이상의 유기산을 더 첨가하여 사용할 수 있고, 이러한 본 발명의 살균살조제로 인하여 우리나라의 농수산업 분야에서는 높은 생산성과 생산작업상의 높은 안정성을 보장받을 수 있으며, 해양 환경의 오염방지에도 크게 기여할 수 있게 된다.The present invention relates to an algae that can control the seaweed, phlegm, diatoms, green algae, seaweeds, and other by-products of seaweed production in seawater using phytic acid extracted from grains without toxic. Characterized in that it contains a group of saturated aliphatic monocarboxylic acid and saturated or unsaturated dicarboxylic acid, tartaric acid, malic acid, succinic acid, citric acid and the like in the phytic acid It can be used by adding more than one organic acid selected from the, and because of the sterilizing algae of the present invention can be ensured high productivity and high stability in the production industry in the agricultural and agricultural industry of our country, greatly contribute to the prevention of pollution of the marine environment It becomes possible.

Description

피틴산으로 된 살균살조제Bactericidal Aids with Phytic Acid

본 발명은 해수와 담수에 서식하는 조류 및 김양식 저해세균을 살조(殺藻)및 살균하는 조성물에 관한 것으로서, 좀 더 구체적으로는 곡물에서 추출한 피틴산을 이용하여 해수에 발생하는 파래, 먹태 및 담수에 발생하는 이끼, 가래, 규조류, 녹조류 및 오염된 바닷물이나 김양식시 김망에 부착하는 세균 등을 독성없이 방제할 수 있는 살균살조제에 관한 것이다.The present invention relates to a composition for killing and sterilizing algae and seaweed inhibiting bacteria inhabiting seawater and freshwater, and more specifically, to the green, salted and fresh water generated in seawater using phytic acid extracted from grains. The present invention relates to a bactericidal algae that can control moss, phlegm, diatoms, green algae, and contaminated seawater or bacteria attached to seaweeds during seaweed farming without toxicity.

종래 인공적으로 김을 기르고 번식시키는 김양식에 있어서, 대나무쪽을 엮은 대발이나 합성섬유 그물로 된 그물발을 이용하여 김을 인공적으로 양식하는 과정에서 김엽체에 파래나 녹조류, 규조류 등이 번식하여 김의 생육이 나빠지거나, 또는 붉은 갯병균이나 호상균이 번식하여 생산되는 김의 품질을 저하시키고 그 수율을 떨어뜨리는 원인이 되었는데, 김에 아무런 독성을 주지 않으면서 이러한 붉은 갯병균이나 호상균을 손쉽고 완전하게 살균하고 파래등의 조류를 살조하는 방법은 개발된 바 없었다.In the conventional seaweed farming, which artificially grows and breeds seaweed, laver, green algae, diatoms, etc. grow on the laver in the process of artificially farming seaweed by using bamboo bales or nets made of synthetic fiber. Poor growth, or red spores or staphylococcus bacteria, caused the deterioration of the quality of the seaweed produced and the yield of the seaweed, which reduced the yield. Methods of sterilizing and killing algae, such as blue, have not been developed.

또한 어류양식에서 파래나 녹조류 등이 부착번식할 경우 해수의 흐름을 방해하여 고기가 질식사한다거나, 공업용 냉각수의 순환계 풀장의 물에 이끼나 조류가 번식할 경우 냉각효율을 저하시키거나 오염을 발생하는 문제점이 있었으며, 농업분야에서는 논에 이끼나 가래가 번성하여 비료의 효과를 저해하는 등, 파래나 가래, 녹조류나 규조류 등의 번식으로 인하여 농,어업분야에서 많은 문제점을 야기하였다.In addition, when the breeding of green or green algae in the fish farming, the meat is choked due to obstruction of seawater flow, or if moss or algae breeds in the circulation pool of industrial cooling water, the cooling efficiency is deteriorated or pollution occurs. In agriculture, moss and sputum thrive in paddy fields, which hinders the effects of fertilizers, and caused many problems in the agriculture and fishery fields due to the breeding of green grass, sputum, green algae and diatoms.

종래 이러한 조류를 처리하기 위하여 차아염소산소다 또는 펜타클로로페놀(pentachlorophenol), 묽은 염산 등이 사용되기는 하였으나, 차아염소산소다는 식용이 아니어서 사용후 분해되지 않을 경우 인체에 악영향을 줄 수 있었으며, 나머지 처리액들도 살균력은 뛰어나지만 잔류시간이 매우 길어서 쉽게 분해되지 않음으로 인하여 어패류등에 2차독성을 미치는 등 악영향을 미칠 우려가 있었고, 해수환경을 오염시키는 등의 문제를 야기하였다.Conventionally, sodium hypochlorite, pentachlorophenol, and dilute hydrochloric acid have been used to treat such algae, but sodium hypochlorite was not edible and could adversely affect the human body if it was not decomposed after use. The liquids also have excellent sterilizing power, but because the residence time is very long, they are not easily decomposed, which may adversely affect secondary fish and shellfish, and cause problems such as polluting the seawater environment.

한편 일반적으로 유해세균 및 조류와 미생물은 상기의 염소를 함유하는 산 이나 각종 유기산에 의해 pH가 2-3의 범위로 조정됨으로써 그 발육이 억제되어 활동이 정지되지만, 세균이나 조류 자체가 사멸되는 것은 아니어서 적당한 온도와 배지조건을 맞추어주면 재활성화되었다.On the other hand, in general, harmful bacteria, algae and microorganisms are controlled by the acid containing chlorine or various organic acids to adjust their pH to a range of 2-3 so that their growth is inhibited and their activities are stopped. No, it was reactivated if the proper temperature and medium conditions were met.

이에 본 발명자는 어패류나 양식용 김에 전혀 독성을 미치지 않으면서, 이들에게 해를 주는 녹조류나 규조류, 파래, 가래 및 먹태등의 살조력이 뛰어나며, 환경오염을 전혀 일으키지 않는 살균살조제를 연구, 개발하던 중 곡물에서 추출한 피틴산(phytic acid)이 이러한 용도에 매우 우수한 효과를 나타내면서도 조류가 재번식할 우려가 전혀 없고 인체나 해생생물에 전혀 무해함을 발견하여, 본 발명을 완성하게 되었다.Accordingly, the present inventors research and develop sterilizing algae that have no toxic effects on fish and shellfish or aquaculture laver, and have excellent killing powers such as green algae, diatoms, seaweed, sputum, and larvae, and do not cause any environmental pollution. While the phytic acid extracted from the grain shows a very good effect for this use, there is no fear of algae to re-produce, and it is harmless to humans or marine organisms, thereby completing the present invention.

피틴산은 식물체 중에 함유되어 있으며, 특히 씨앗이나 곡물의 외피 및 씨눈에 함유되어 있는 천연물질로서 식(1)과 같은 구조를 갖는다.Phytic acid is contained in the plant, and is a natural substance contained in the shell and seeds of seeds or grains.

이러한 피틴산은 1996년 국내 식품첨가물 공정서에 천연식품 첨가물 제91호로 지정되었으며, 인간이 유사이래 매일매일의 식생활에서 섭취하는 곡물에 많이 함유되어 있어서, 그것의 무독성에 대하여는 다언을 요하지 아니할 정도라 명백하다 할 것이다.This phytic acid was designated as a natural food additive No. 91 in the 1996 Korean Food Additives Process, and since it is similar, it is contained in a large amount of grains in humans' daily diet since it is similar. Will do.

피틴산은 종래 금속이론에 대하여 킬레이트제로 작용하여, 항산화제로 이용되거나 철, 주석, 알루미늄 합금, 납등의 금속표면에 불용성의 조밀한 킬레이트 막을 형성하여 강력한 항부식제로서 유용하게 이용되었으며, pH 4-9의 범위에서 강력한 완충작용을 나타내고, 또한 pH 6-8의 범위내에서 강력한 발효촉진제로서 이용되는 등 다양한 용도로 이용되어 왔다.Phytic acid acts as a chelating agent against conventional metal theory, and is used as an antioxidant or as a powerful anticorrosive agent by forming insoluble dense chelating membranes on metal surfaces such as iron, tin, aluminum alloys, and lead. It has a strong buffering effect in the range, and has been used for various purposes such as being used as a strong fermentation promoter within the range of pH 6-8.

이러한 피틴산의 특성을 이용한 특허출원으로서 국내에 공지된 예를 들면, 1991. 5. 27자 출원되고 1993. 9. 15자 공고된 특허공고 제 93-8763호의 화장료 조성물에서는 쑥추출물, 지용성 플라보노이드, 수용성 플라보노이드 및 피틴산을 포함하는 것을 특징으로 하는 화장료 조성물을 개시하면서, 철이온을 효과적으로 킬레이트화하여 철이 산화하는 것을 막기 위한 항산화작용제로서 피틴산을 이용하였으며, 1986. 9. 5자 출원하여 1994. 1. 26자 공고된 특허공보 제 94-615 호 저 피틴산 콩단백질 단리체를 제조하는 방법에서는 피틴산 복합체가 포유동물의 광물질 흡수를 방해하는 것을 저지하기 위한 방법으로서, 콩단백질을 가용화시키면서 피틴산염의 추출을 감소시키기에 충분한 시간동안 pH 8-10 범위내 및 65℃ 이상의 온도의 수성매질을 사용하여 슬러리를 형성시켜 콩단백질을 함유하는 탈지 콩원료를 처리하고, 상기 슬러리를 다당류 및 불용성 피틴산염의 상당한 부분을 함유하는 불용성 유분과 가용화된 콩단백질을 함유하는 가용성 유분으로 분리시키고, 상기 가용성 유분의 pH를 약 5.0-5.5로 조절하여 콩단백질을 침전시킴으로써 가용성 피틴산염을 함유하는 유장유분과 피틴산염 농도가 0.3%이하이고 수성매질로 세척할 수 있는 콩단백질 고체유분을 생성시키며, 상기 현탁된 콩단백질 고체유분을 상기 세척매질로부터 분리시킴을 특징으로 하여, 현저하게 알루미늄 함량이 감소되고 피틴산염이 거의 함유되지 않은 콩단백질 단리체를 제조하는 방법을 개시한 것을 예로 들 수 있다.For example, in the cosmetic composition of Korean Patent Application No. 93-8763, filed on May 27, 1991 and published on September 15, 1993, the patent application using the properties of phytic acid is known as mugwort extract, fat-soluble flavonoid, water-soluble. While starting a cosmetic composition comprising flavonoids and phytic acid, phytic acid was used as an antioxidant for effectively chelation of iron ions to prevent iron from oxidizing, and filed on Sep. 5, 1986. In the method for preparing the low phytic acid soy protein isolate, a method for preventing the phytic acid complex from interfering with the absorption of minerals from mammals, the solubilizing soy protein while reducing the extraction of phytic acid salt To form a slurry using an aqueous medium at a temperature in the range of pH 8-10 and at To treat skimmed soybean meal containing soy protein, separating the slurry into insoluble oil containing a significant portion of polysaccharides and insoluble phytic acid salts and soluble oil containing solubilized soy protein, and adjusting the pH of the soluble oil to about 5.0. The soy protein is adjusted to -5.5 to produce whey fraction containing soluble phytate and soy protein solid fraction of 0.3% or less and washable with aqueous medium, and the suspended soy protein solid fraction Characterizing the separation from the washing medium, for example, a method for producing a soy protein isolate that is significantly reduced in aluminum content and contains little phytic acid salt.

즉, 종래 피틴산의 제특성은 상기한 바와 같이 여러가지 응용예를 통하여 공지되어 왔으며 이러한 피틴산의 특성을 이용한 특허출원 또한 다양하게 공지되어 왔으나, 녹조류 또는 규조류등의 조류 및 병균에 대하여 강력하고 근본적인 살균살조기능을 가져서 농,수산업 분야에서 생산품의 품질을 현저히 개선하기 위한 살균살조제로서는 개발된 예가 없었다.That is, the conventional properties of phytic acid have been known through various applications as described above, and patent applications using the properties of phytic acid have also been known in various ways, but it is a powerful and fundamental sterilizing algae against algae and germs such as green algae or diatoms. As a sterilizing algae for improving the quality of products in the agricultural and fisheries fields with no function, no examples have been developed.

이에 본 발명자들은 해마다 심각한 환경문제 및 보건문제를 일으키는 조류를 재발없이 완전히 사멸시키고 김양식시 착생하는 붉은갯병균이나 호상균을 근본적으로 치유하며 인체나 동, 식물에 잔류하지 않는 등 독성이 없고 분해능력이 우수한 살균살조제에 대한 연구를 거듭한 결과, 쌀겨 등의 곡물이나 종자에서 추출되는 피틴산이 상기의 목적에 부합하며, 병균이나 조류의 세포막에 작용하여 우수한 살균 및 살조작용을 나타냄을 이용하여 본 발명을 완성하게 되었다.Therefore, the present inventors completely kill the algae causing serious environmental and health problems every year without recurrence, and fundamentally heal red fungus or staphylococci that grow in seaweed farming and do not remain in the human body, animals or plants. As a result of repeated studies on this excellent disinfectant disinfectant, phytic acid extracted from grains and seeds such as rice bran meets the above purpose, and shows excellent sterilization and killing action by acting on cell membranes of germs and algae. The invention was completed.

즉, 본 발명의 목적은 천연의 피틴산을 이용하여, 농,수산물의 품질을 떨어뜨리며 환경문제를 일으키는 조류를 근본적으로 손쉽고 안전하게 사멸시키면서 독성이 전혀 없는 피틴산으로 된 살균살조제를 제공하는 것이다.That is, an object of the present invention is to provide a bactericidal killing agent made of phytic acid, which is completely non-toxic, while easily and safely killing algae that degrades agricultural and marine products and causes environmental problems by using natural phytic acid.

본 발명의 또 다른 목적은 피틴산을 주성분으로 하고, 포화지방족 모노카본산과 포화 또는 불포화 디카본산, 주석산, 사과산, 호박산, 구연산 등의 천연유기산 중 1종 이상을 함유하는 살균살조제를 제공하는 것이다.Still another object of the present invention is to provide a bactericidal algae containing phytic acid as a main component and containing at least one of saturated aliphatic monocarboxylic acid and natural organic acids such as saturated or unsaturated dicarboxylic acid, tartaric acid, malic acid, succinic acid and citric acid.

본 발명은 조류나 병균의 세포막의 구성요소인 인지질이 해수중에서 마그슘이온(Mg2+)과 결합하거나 또는 육상에서 칼슘이온(Ca2+)과 결합하여 안정한 상태를 이루고 있는 것에 대하여, 피틴산을 첨가함으로써 상기 금속이온을 킬레이트화하여 세포막의 기능조절이 파괴되어 생장억제 및 사멸되도록 하는 것이다.The present invention relates to phytic phospholipid, which is a component of the cell membrane of algae or germs, in which phytic acid is stabilized by binding to magnesium ions (Mg 2+ ) in seawater or calcium ions (Ca 2+ ) in land. By chelating the metal ions by addition, functional regulation of the cell membrane is disrupted to inhibit growth and kill.

즉, 생물체의 세포막은 인지질과 단백질로 이루어지며, 이러한 세포막을 통해 생물체는 신진대사 및 생장을 위하여 영양분을 섭취하고 반대로 노폐물은 세포막을 통하여 세포 밖으로 배출하는데, 이러한 막구조가 피틴산의 첨가로 인하여 파괴되어 세포막의 투과작용이 조절되지 못함으로써 세균이나 조류가 사멸하는 점을 이용하는 것이다.That is, the cell membrane of the organism is composed of phospholipids and proteins, through which the organism receives nutrients for metabolism and growth, and waste products are discharged out of the cell through the cell membrane, and this membrane structure is destroyed by the addition of phytic acid. As a result, the permeation of the cell membrane is not controlled, and the germ or algae are killed.

좀 더 구체적으로 세포막의 구성성분인 인지질은 지방산과 글리세롤 및 콜린의 결합체이며, 이러한 인지질은 자체구조 내에 -이온과 +이온을 가져서 불안한 상태에 있다가 해수중의 마그네슘 이온과 결합하여 안정한 상태를 유지하게 되는데, 여기에 킬레이트제인 피틴산을 첨가하여 마그네슘 이온을 불활성화시키면 인지질이 다시 불안정한 상태로 되어 세포막의 투과기능의 균형이 유지되지 못하여 세포막 구조의 안정성이 파괴됨과 동시에 세포막의 단백질이 응고되어 세포가 사멸하는 것이다.More specifically, phospholipids, which are components of cell membranes, are a combination of fatty acids, glycerol and choline, and these phospholipids are in an unstable state with-and + ions in their own structure, and remain stable by binding to magnesium ions in seawater. When the chelating agent, phytic acid, is added to inactivate magnesium ions, phospholipids become unstable again, and the permeability of the cell membranes cannot be balanced, and the stability of the cell membrane structure is destroyed. To die.

김양식 과정에서 김을 피틴산에 침지시키면 김은 산성조건에 대한 내성을 가지므로 아무런 영향을 받지 않지만 김망에 부생하는 파래, 먹태 등의 녹조류와 규조류는 산성조건에서 활성이 둔화됨과 함께 세포막이 파괴되는 것이며, 김망에 부착되어 기생하는 붉은갯병이나 호상균등도 피틴산용액에 김망을 짧은 시간동안 침지시킴으로써 그 세포막 구조가 불안정해져서 근본적으로 사멸되는 것이다.When seaweed is immersed in phytic acid during seaweed farming, seaweed is not affected because seaweed has resistance to acidic condition, but green algae and diatoms such as green seaweed and muktae, which are by-products of seaweed, are degraded under acidic conditions and cell membranes are destroyed. In addition, parasitic red glands or staphylococci, attached to the laver, can be destabilized and radically killed by immersing the laver in phytic acid solution for a short time.

이 과정을 식으로 나타내면 다음과 같다.This process is expressed as follows.

본 발명에서 사용되는 피틴산은 곡물, 특히 쌀겨로부터 일반적인 추출방법에 의해 얻어지는 것이다.The phytic acid used in the present invention is obtained by a general extraction method from grains, especially rice bran.

본 발명에 의하면 상기의 피틴산을 주성분으로 하고 이에 포화지방족 모노카본산 및 포화 또는 불포화 디카본산, 주석산(tartaric acid), 사관산(malic acid), 호박산(succinic acid), 구연산(citric acid)등으로 이루어지는 군에서 선택된 1종 이상의 유기산을 함유한 살균살조제 또한 제공된다.According to the present invention, the phytic acid is the main ingredient, and thus, saturated aliphatic monocarboxylic acid and saturated or unsaturated dicarboxylic acid, tartaric acid, malic acid, succinic acid, citric acid, etc. Also provided are bactericides containing at least one organic acid selected from the group consisting of:

피틴산 외에 첨가되는 이상의 유기산들은 종래 단독 또는 결합된 형태로 사용되던 것으로서, 본 발명에서는 피틴산과 결합하려 각각 쓰이는 경우보다 상승효과를 나타내고 pH 변화에 대한 완충작용도 하게 된다.The organic acids added in addition to the phytic acid are conventionally used alone or in a combined form. In the present invention, the synergistic effect and buffering effect against the pH change are also exhibited in the present invention.

보통 피틴산과 상기 유기산의 함유비율은 1:2가 바람직하고 이러한 비율이 경제적이나, 이는 상기 피틴산과 유기산의 혼합물이 적용되는 해수조건 및 적용 여건의 변화에 따라 얼마든지 조절될 수 있다.Usually, the content ratio of phytic acid and the organic acid is preferably 1: 2, and such a ratio is economical, but it can be adjusted as much as the seawater conditions and application conditions to which the mixture of phytic acid and organic acid are applied.

본 발명의 살균살조용 조성물의 사용농도는 적용대상 및 적용환경의 요인에 따라 다르다. 예를 들어 김양식시 김망에 부착되는 파래나 먹태, 규조류 및 붉은갯병균, 호상균 등 기타 병균을 방제하기 위해서는 0.4∼10.0%로 희석한 피틴산용액에 5내지 10분간 침지시키기만 하면 상기 병균들이 완전사멸되어 우수한 품질의 김이 얻어질 수 있으며, 논에 끼는 이끼나 가래의 번식을 막기 위해서는 20ppm-100ppm으로 희석한 피틴산용액을 논에 산포하면 완전히 방제 가능하다. 상기 김양식시 피틴산 용액의 pH는 약 2-3범위의 산성조건인 것이 바람직하다. 적례균이나 붉은갯병균, 규조류를 비롯한 법정 전염성 세균인 콜레라와 장티프스균의 발육가능 pH 및 최적 pH는 아래의 그래프와 같은데, 이들을 방제하기 위하여 종래 사용되던 피틴산이 아닌 살균살조제들은 대부분 하기의 발육가능한 pH범위를 벗어난 강산성의 조건을 조성하여 주는 것이었으며, 이 경우 적당한 농도와 배지조건하에서 하기 병균 및 조류는 다시 활성화되었던 것인 바, 본 발명의 살균살조제는 이와는 달리, 피틴산이 pH 1 내지 12까지에 걸쳐 광범위한 금속이온 킬레이트 작용을 가지고 산성조건에서 세포자체를 파괴하므로, 그 적용범위 및 효능이 더 강력하다 할 것이며, 이러한 면에서도 본 발명은 상기 병균 및 조류의 살균, 살조작용이 매우 우수한 것임을 알 수 있다.The concentration of use of the composition for bactericidal killing of the present invention depends on the application target and the environment of the application. For example, in order to control other pathogens such as seaweed, macromolecular, diatoms and red cod fungus, staphylococcus aureus, which are attached to seaweed during seaweed farming, they are immersed in phytic acid solution diluted to 0.4 to 10.0% for 5 to 10 minutes. It can be killed to obtain a good quality laver. To prevent the growth of moss and phlegm in the paddy field, it is possible to completely control the phytic acid solution diluted to 20ppm-100ppm in the paddy field. The pH of the seaweed phytic acid solution is preferably in an acidic condition of about 2-3 ranges. The possible pH and optimum pH of the legal infectious bacteria cholera and typhoid bacteria, including fungi, red fungus and diatoms, are as shown in the graph below.The most common non-phytic acid fungicides used to control them are the following It was intended to create a strong acid conditions out of the possible pH range, in which case the following germs and algae were reactivated under the appropriate concentration and medium conditions, the fungicide of the present invention, unlike phytic acid pH 1 to 1 Since it has a wide range of metal ion chelate action over 12 and destroys the cell itself in acidic conditions, its scope and efficacy will be more powerful. In this respect, the present invention is excellent in sterilizing and killing the germs and algae. It can be seen that.

이하 본 발명의 바람직한 실시예를 기재하도록 하겠으며, 하기의 실시예는 본 발명의 권리범위를 한정하는 것은 아니다.Hereinafter, preferred embodiments of the present invention will be described, and the following examples do not limit the scope of the present invention.

[실시예 1]Example 1

4.8%의 피틴산수용액과 10.7%의 구연산수용액을 원액으로 하고 이를 해수에 혼합하여 0.67%의 농도가 되게 한 다음(pH는 약 2.5) 500m1의 비이커에 넣은 후 김망사 5cm를 통기배양하면서 3개월간 실내에서 19회 침지시험하여 붉은갯병 및 쪼그랑병, 구멍갯병등의 발생률을 관찰한 결과 그 발생률이 1.0% 미만임을 알 수 있었으며, 이를 다시 중성의 해수조건으로 옮겨서 배양한 결과 상기 병균의 발생을 전혀 관찰한 수 없었던 바, 이들이 재발가능성 없이 거의 완전 사멸되었음을 알 수 있었다.4.8% aqueous phytic acid solution and 10.7% citric acid solution is used as a stock solution, mixed with seawater to a concentration of 0.67% (pH is about 2.5), and placed in a 500m1 beaker, followed by incubation of 5cm of Kimmansa for 3 months. In the 19 immersion tests at, the incidence rate of red cane, squat, and canine was observed. The incidence rate was less than 1.0%, and it was transferred to neutral seawater conditions and cultured. It could not be seen that they were almost completely killed without the possibility of recurrence.

[실시예 2]Example 2

실시예 1과 같은 방법으로 피틴산과 구연산의 혼합원액을 조제한 후 이를 해수에 혼합하여 2.0%의 농도가 되게 한 다음(pH는 2.16) 김망사를 배양하면서 파래, 먹태, 녹조류, 규조류 등의 발생률을 관찰한 결과 거의 0%에 가까울 정도로 상기 조류의 생성이 관찰되지 않았으며, 다시 보통의 해수조건으로 복귀시켜도 상기 조류가 전혀 착생되지 않았고, 이에 반하여 피틴산 및 구연산으로 처리하지 않은 대조군에서의 상기 조류의 착생률은 4.9-14.0%였다.Prepare a mixture of phytic acid and citric acid in the same manner as in Example 1, and then mix it with seawater to have a concentration of 2.0% (pH is 2.16), while incubating gimmansa, the incidence rate of green, black, green algae, and diatoms As a result, the production of the algae was not observed to almost 0%, and the algae did not engraft at all even when returned to normal seawater conditions, whereas the algae of the algae in the control group not treated with phytic acid and citric acid were observed. The germination rate was 4.9-14.0%.

또한, 본 실시예의 살균살조제를 처리한 후의 김을 색택, 향미, 품질의 면에서 대조군의 것과 비교한 결과 그 색택이나 향미, 품질이 훨씬 더 우수함을 알 수 있었다.In addition, as a result of comparing the seaweed after the treatment of the bactericidal killing agent of this embodiment with that of the control group in terms of color tack, flavor and quality, it was found that the color tack, flavor and quality were much better.

[실시예 3]Example 3

실시예 1에서 얻어진 혼합용액을 80ppm으로 농도조절하여 논에 산포하여 일주일 후 관찰한 결과 이끼나 가래 등 농작물에 피해를 주던 조류가 전혀 번식하지 아니함을 알 수 있다.The concentration of the mixed solution obtained in Example 1 to 80ppm was distributed in rice fields and observed after a week, it can be seen that the algae that damage the crops such as moss and phlegm do not breed at all.

[실시예 4]Example 4

피틴산 수용액과 구연산수용액을 1:2의 비율로 혼합한 것을 김양식장 및 그로부터 50m 떨어진 해수에 산포하여 3개월간 월 1회씩, 3차에 걸쳐 각 지점의 표층 및 저층해수를 채수하여 식물성, 동물성 부유생물을 채집하여 어장환경을 비교하였다.A mixture of phytic acid aqueous solution and citric acid solution in a ratio of 1: 2 is dispersed in a seaweed farm and 50 meters of seawater, and once a month for three months, the surface and bottom seawater of each branch is collected three times, and vegetable and animal floating organisms are collected. Were collected and the fishing environment was compared.

보통 유기산 시험약제의 사용시 민감하게 변할 수 있는 수질성분은 수소이온농도와 영양염이라 할 수 있는데, 조사해역의 수소이온농도(pH)는 본 실시예의 산성혼합용액을 처리하기 전에 7.89-8.08, 처리한 후에 7.90-8.09, 50m 떨어진 외양은 7.91-8.08의 범위로서 별다른 차이를 나타내지 않았고 유기산 산포 후 금방 정상해수로 회복됨을 알 수 있었으며, 인산염의 양은 본 실시예의 혼합용액을 처리하기 전에 0,14-0.44㎍-at/l, 처리후에 0.13-0.88㎍-at/l, 외양이 0.14-0.92㎍-at/1의 범위임을 알 수 있었다.In general, the water components that can be sensitively changed when using the organic acid test drug are hydrogen ion concentration and nutrient salt. The hydrogen ion concentration (pH) in the irradiated sea area is treated with 7.89-8.08, before treating the acid mixture solution of this example. Afterwards, the appearance of 7.90-8.09 and 50m away was 7.91-8.08, which did not show any difference, and it was found that the organic acid was recovered to normal seawater soon after the dispersion of organic acid, and the amount of phosphate was 0,14-0.44 before treatment of the mixed solution of this example. After the treatment, it was found that after treatment, 0.13-0.88 µg-at / l and the appearance were in the range of 0.14-0.92 µg-at / 1.

또한 용존무기질소(DIN)의 양도 본 실시예의 용액처리전에는 2.80-9.44㎍-at/l, 처리후에 3.81-8.02㎍-at/l, 외양이 4.38-8.96㎍-at/l 임을 알 수 있었던 바, 본 발명의 살균살조제를 처리하더라도 해수의 희석, 혼합, 확산작용 및 완충 작용으로 인하여 수질환경에는 거의 영향을 미치지 않음을 알 수 있었다.Also, the amount of dissolved inorganic nitrogen (DIN) was 2.80-9.44 μg-at / l, 3.81-8.02 μg-at / l after treatment, and 4.38-8.96 μg-at / l before the solution treatment of this example. , The treatment of the bactericide of the present invention was found to have little effect on the water environment due to dilution, mixing, diffusion and buffering of seawater.

이상과 같이 본 발명의 살조제는 생물체의 세포막을 이루는 인지질을 불활성화시켜 세포막의 구조를 파괴함으로써 각종 김생장 저해균 및 조류 등을 아무런 독성없이 사멸시키고, 그러한 살균 및 살조작용으로 인하여 해양환경에는 어떠한 악영향도 미치지 않을 뿐 아니라 간편하고 완전하게 살균 및 살조작용을 할 수 있는 매우 유용한 발명인 것이다.As described above, the algae of the present invention inactivates the phospholipids forming the cell membranes of organisms and destroys the structure of the cell membranes, thereby killing various ginseng inhibiting bacteria and algae without any toxicity. Not only does it have any adverse effects, it is a very useful invention that can be easily and completely sterilized and killed.

본 발명의 살균살조제는 콜레라나 장티프스균과 같은 전염성 세균에 대하여도 세균 자체를 파괴함으로써 살균제로서 유용하게 이용될 수 있을 것으로 판단된다.The fungicides of the present invention are considered to be useful as fungicides by destroying the bacteria themselves against infectious bacteria such as cholera and typhoid bacteria.

본 발명의 살균살조제로 인하여 우리나라의 농수산업 분야에서는 높은 생산성과 생산작업상의 높은 안정성을 보장받을 수 있으며, 해양환경의 오염방지에도 크게 기여할 수 있게 된다.Due to the bactericidal disinfectant of the present invention, it is possible to ensure high productivity and high stability in the production industry in the agricultural and fishery industry of Korea, and greatly contribute to prevention of pollution of the marine environment.

Claims (3)

피틴산을 함유하는 것을 특징으로 하는 살균살조제.A bactericide that contains phytic acid. 제1항에 있어서, 상기 피틴산에 포화지방족 모노카본산 및 포화 또는 불포화 디카본산, 주석산(tartaric acid), 사과산(malic acid), 호박산(succinic acid), 구연산(citric acid)등으로 이루어지는 군에서 선택된 1종 이상의 유기산을 더 포함하는 살균살조제.According to claim 1, wherein the phytic acid is selected from the group consisting of saturated aliphatic monocarboxylic acid and saturated or unsaturated dicarboxylic acid, tartaric acid, malic acid, succinic acid, citric acid and the like. A sterilizing algae further comprising at least one organic acid. 제1항에 있어서, 상기 유기산과 상기 피틴산은 중량비로 약 1:2로 혼합되어 사용되는 것을 특징으로 하는 살균살조제.The bactericide according to claim 1, wherein the organic acid and the phytic acid are mixed in a weight ratio of about 1: 2.
KR1019960032377A 1996-08-02 1996-08-02 Bactericide and algicide of phytic acid KR0180468B1 (en)

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KR20040049152A (en) * 2002-12-05 2004-06-11 이기선 Acidic agent for use in a laver farm
KR101804634B1 (en) 2015-07-01 2018-01-10 고려대학교 산학협력단 Antimicrobial composition comprising phytic acid and electrolytes

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