KR100420758B1 - Photostabilized Fungicide That Contains Ethaboxam and its Photostabilizer, Method for Fungicidal Use and Method for Increasing Photostability of Ethaboxam - Google Patents
Photostabilized Fungicide That Contains Ethaboxam and its Photostabilizer, Method for Fungicidal Use and Method for Increasing Photostability of Ethaboxam Download PDFInfo
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION 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
- A01N25/00—Biocides, 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
- A01N25/22—Biocides, 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
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Abstract
본 발명은 에타복삼(N-(α-시아노-2-테닐)-4-에틸-2-에틸아미노-5-티아졸카르복사미드) 및 그의 광안정화제를 함유하는 광안정화 살균제 조성물, 이를 이용한 살균방법 및 에타복삼의 광안정성 개선방법에 관한 것으로서, 에타복삼 및 그의 광안정화제인 3, 5-디-터서리-부틸-4-하이드록시벤질 포스포닉 디에틸 에스테르, 2,2′-치오디에틸-비스[3-(3, 5-디-터서리-부틸-4-하이트록시페닐)-프로피오네이트, 2,6-디-터서리-부틸-4-메틸페놀, 2-하이드록시-4-메톡시벤조페논, 옥틸 메톡시 시나메이트, 2,4,6-트리아닐리노-파라-(카르보-2'-에틸헥실-1'-옥시)-1,3,5-트리아진을 함유하는 광안정성 및 악효 지속 기간이 증진된 광안정화 살균제 조성물, 이를 이용한 식물 병원균의 살균방법 및 상기 광안정화제에 의한 에타복삼의 광안정성 개선방법을 제공한다.The present invention relates to a photostabilizing bactericide composition containing etaboksam ( N- (α-cyano-2-tenyl) -4-ethyl-2-ethylamino-5-thiazolecarboxamide) and a light stabilizer thereof, The present invention relates to a sterilization method and a method for improving the light stability of etaboksam, wherein etaboksam and its photostabilizer are 3,5-di-tert-butyl-4-hydroxybenzyl phosphonic diethyl ester, 2,2'-chiodi Ethyl-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate, 2,6-di-tert-butyl-4-methylphenol, 2-hydroxy- 4-methoxybenzophenone, octyl methoxy cinnamate, 2,4,6-trianilino-para- (carbo-2'-ethylhexyl-1'-oxy) -1,3,5-triazine Provided is a light stabilized fungicide composition containing enhanced photo stability and duration of adverse effects, a method for sterilizing plant pathogens using the same, and a method for improving light stability of etaboksam by the light stabilizer.
Description
본 발명은N-(α-시아노-2-테닐)-4-에틸-2-에틸아미노-5-티아졸카르복사미드(ISO 제안명: ethaboxam, 에타복삼, 이하 "에타복삼"이라 한다) 및 그의 광안정화제를 함유하는 광안정화 살균제 조성물, 이를 이용한 살균방법 및 에타복삼의 광안정성 개선방법에 관한 것으로서, 보다 상세하게는 에타복삼의 광안정화제인 3,5-디-터서리-부틸-4-하이드록시벤질 포스포닉 디에틸 에스테르, 2,2′-치오디에틸-비스[3-(3, 5-디-터서리-부틸-4-하이트록시페닐)-프로피오네이트, 2,6-디-터서리-부틸-4-메틸페놀, 2-하이드록시-4-메톡시벤조페논, 옥틸 메톡시 시나메이트, 2,4,6-트리아닐리노-파라-(카르보-2'-에틸헥실-1'-옥시)-1,3,5-트리아진을 이용하여,N-(α-시아노-2-테닐)-4-에틸-2-에틸아미노-5-티아졸카르복사미드의 광안정성 및 약효지속기간이 증진된 광안정화 살균제 조성물, 이를 이용한 살균방법 및 상기 광안정화제에 의한 에타복삼의 광안정성 개선방법에 관한 것이다.The present invention relates to N- (α-cyano-2-tenyl) -4-ethyl-2-ethylamino-5-thiazolecarboxamide (ISO proposal name: ethaboxam, etaboksam, hereinafter referred to as "etaboksam") And a light stabilizing fungicide composition containing the light stabilizer, a sterilization method using the same, and a method of improving the light stability of etaboksam, and more particularly, 3,5-di-tertries-butyl-4, which is a light stabilizer of etaboksam. -Hydroxybenzyl phosphonic diethyl ester, 2,2'-thiodiethyl-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionate, 2,6- Di-tert-butyl-4-methylphenol, 2-hydroxy-4-methoxybenzophenone, octyl methoxy cinnamate, 2,4,6-trianilino-para- (carbo-2'-ethyl Of N- (α-cyano-2-tenyl) -4-ethyl-2-ethylamino-5-thiazolecarboxamide using hexyl-1′-oxy) -1,3,5-triazine Photo-stabilizing disinfectant composition with enhanced photo-stability and drug duration, It relates to a sterilization method using the same and a method for improving the light stability of etaboksam by the light stabilizer.
최근 들어, 농약에 의한 환경오염 문제가 크게 대두되면서 농약의 개발 및 사용은 인간과 환경에 대한 안전성 확보가 전제되어야 하는 실정이다. 따라서, 최근에 개발되고 있는 농약 원제는 일반적으로 저약량으로 사용하여도 약효는 우수하고, 환경 및 인축에 대한 안전성은 기존 농약 원제에 비해 높은 것을 특징으로 하고 있다.In recent years, as the environmental pollution problem caused by pesticides has emerged significantly, the development and use of pesticides should be premised on securing safety for humans and the environment. Therefore, recently developed pesticide raw materials are generally excellent in drug efficacy even when used in low doses, and is characterized by high environmental and human safety compared to conventional pesticide raw materials.
그로 인하여, 최근에 개발되고 있는 농약 원제의 상당수는 화학구조가 특수하거나 복잡하며, 분자내에 특수한 치환기 도입, 이중 결합 및 삼중결합의 도입, 자외선 흡수부의 존재 등으로 인해 광에 대해 불안정한 요인이 존재하게 된다. 또한, 농약 원제의 생물학적 활성의 최적화는 광분해성 등의 화학적 불안정화를 수반하기도 한다. 이러한 화합물들은 저독성 및 고활성의 장점에도 불구하고 포장 조건하에서 자외선 등에 의한 광화학적 반응에 의해 분해되어 활성을 상실하게 된다. 이 경우, 적절한 약효를 발현시키기 위한 농약의 사용회수가 증가하여 환경중에 투여되는 농약 원제의 총량은 증가하게 되고, 과도하게 사용된 농약 원제 및 그 분해산물들은 토양 및 수계에 잔류하거나 유입되어 환경 문제를 야기시킨다. 따라서, 광 조건에 민감한 농약 원제의 광안정성 증진은 농약 원제의 상품화뿐만아니라 환경 문제와 관련하여 필수적으로 고려되어야 할 사항이다.Therefore, many of the recently developed pesticide raw materials have a special or complex chemical structure, and there are factors that are unstable to light due to the introduction of special substituents in the molecule, the introduction of double bonds and triple bonds, and the presence of ultraviolet absorbers. do. In addition, optimization of biological activity of pesticide raw materials may involve chemical destabilization such as photodegradability. Despite the advantages of low toxicity and high activity, these compounds are decomposed by photochemical reactions such as ultraviolet rays and lose their activity under packaging conditions. In this case, the number of times of use of pesticides to express the appropriate medicinal effect is increased, the total amount of pesticides administered in the environment is increased, and the excessively used pesticides and their degradation products remain or enter the soil and water system, causing environmental problems. Cause. Therefore, enhancement of photostability of pesticide raw materials sensitive to light conditions is an essential consideration in relation to environmental issues as well as commercialization of pesticide raw materials.
광에 민감한 농약 원제의 광안정성을 부여하는 방법은 농약 원제의 종류와 광안정제의 종류 및 사용량에 따라 차이를 보인다. 일반적으로 농약 원제의 광안정성을 증진시킬 수 있는 광안정제의 종류는 크게 유기 화합물인 자외선 흡수제(미합중국 특허 5597574)와 금속염 등과 같은 무기물질에 의한 자외선 차폐제 (일본국특개평 11-292707)로 대별된다.The method of imparting photostability of pesticides that are sensitive to light differs depending on the types of pesticides and the types and amounts of photostabilizers used. In general, the type of light stabilizer that can improve the light stability of the pesticide raw material is roughly divided into ultraviolet light shielding agent (Japanese Patent Laid-Open No. 11-292707) by inorganic substances such as ultraviolet absorbers (US Pat. No. 5597574), which are organic compounds, and metal salts.
광안정제의 사용에 의해 농약 원제의 광분해 방지 효과를 증진시키기 위해서는 제형을 캡슐화하거나, 농약이 살포된 작물의 표면에 비수용성 필름을 형성시키는 방법 등이 이용되고 있다(미합중국 특허 5597574, 일본국 특개소 51-133419).In order to enhance the photodegradation effect of the pesticide raw material by the use of a light stabilizer, a method of encapsulating the formulation or forming a water-insoluble film on the surface of the crop sprayed with pesticides is used (US Patent 5597574, Japanese Patent Laid-Open). 51-133419).
광안정제 사용에 의한 농약의 약효 증진은 곤충 호르몬 및 곤충에서 유래된 농약 활성물질 등과 같이 광에 불안정한 화합물의 경우에 뚜렷이 관찰되며, 이러한 농약 활성 화합물의 광분해성을 개선하여 상품성을 높이기 위한 노력이 끊임없이 행하여지고 있다(미합중국 특허 4045555, 5994266).The enhancement of pesticides by the use of light stabilizers is clearly observed in the case of light unstable compounds such as insect hormones and pesticide active substances derived from insects, and efforts to improve the commercialization by improving the photodegradability of these pesticide active compounds are constantly made. (US Pat. Nos. 4045555, 5994266).
한편 2-아미노티아졸카르복사미드 유도체의 일종인 화학식(1)의 에타복삼은 대한민국 특허 제124552호(출원번호: 94-19960, 이는 본원에서 참고로서 특별히 인용된다)에 작물 보호용 살균 활성 물질로 이미 기술되어 있으며, 에타복삼을 함유하는 제제((주)미성에 의해 상품화 - 상표명: 가디안(수화제)) 또한 공지되어 있다;Meanwhile, etaboxam of formula (1), which is a kind of 2-aminothiazolecarboxamide derivative, is a bactericidal active substance for crop protection in Korean Patent No. 124552 (Application No. 94-19960, which is specifically cited herein). Already described, preparations containing etaboxam (commercialized by Ami Co., Ltd.—trade name: Guardian (hydrate)) are also known;
본 발명자 등은 상기 에타복삼의 광안정성 증진에 의한 약효 지속기간을 증진시키기 위해 타 산업 분야에서 널리 사용되고 있는 다양한 종류의 광안정성 증진 효과를 보이는 물질군을 구조적인 특징에 근거하여 선발하여 에타복삼의 광안정성 증진 시험을 수행하던 중에, 일부 물질군에서 에타복삼의 광안정성 증진 효과가 있음을 기기 분석적인 방법에 의해 확인하였고, 이들을 첨가한 단일 포장된 살균제를 제조하여 약효의 지속기간 증진 시험을 수행하게 되었다. 그 결과, 동일한 에타복삼의 농도에서 일부의 에타복삼용 광안정화제 후보물질 첨가에 의해 약효 지속기간이 뚜렷이 증진됨을 밝혀내고 본 발명을 완성하게 되었다.The present inventors have selected a group of substances exhibiting various types of photostability enhancing effects widely used in other industries in order to enhance the duration of medicinal effects by enhancing the photostability of etaboksam based on their structural characteristics. During the photostability enhancement test, it was confirmed by instrumental analytical method that some of the substance groups had the photostability enhancement effect of etaboksam, and a single packaged bactericide containing them was prepared to conduct the duration improvement test of the drug efficacy. Was done. As a result, it was found that the duration of the medicament was markedly enhanced by the addition of some candidates for the light stabilizer for etaboksam at the same concentration of etaboksam, thereby completing the present invention.
따라서 본 발명은, 환경중에서 에타복삼의 광에 의한 분해속도를 감소시킴으로써, 기존 에타복삼 함유 제제에 비해 식물 병에 대한 약효의 지속기간이 증진되고 환경적으로도 유리한 살균제 조성물, 이를 이용한 살균방법 및 에타복삼의 광안정성 개선방법을 제공함을 목적으로 한다.Therefore, the present invention, by reducing the degradation rate of the etaboksam by light in the environment, the duration of the medicinal effect against the plant disease compared to the existing etaboksam containing formulations and environmentally beneficial fungicide composition, sterilization method using the same and The purpose of the present invention is to provide a method for improving the light stability of etaboksam.
상기와 같은 목적을 달성하기 위하여 본 발명은, 에타복삼 및 에타복삼의 광안정화제인 3, 5-디-터서리-부틸-4-하이드록시벤질 포스포닉 디에틸 에스테르 (화학식 2), 2, 2′-치오디에틸-비스[3-(3, 5-디-터서리-부틸-4-하이트록시페닐)-프로피오네이트 (화학식 3), 2, 6-디-터서리-부틸-4-메틸페놀 (화학식 4), 2-하이드록시-4-메톡시벤조페논 (화학식 5), 옥틸 메톡시 시나메이트 (화학식 6), 2, 4, 6-트리아닐리노-파라-(카르보-2'-에틸헥실-1'-옥시)-1, 3, 5-트리아진 (화학식 7)을 하나이상 함유하는 살균제 조성물, 이를 이용한 식물병원균의 살균방법 및 상기 광안정화제에 의한 에타복삼의 광안정성 개선방법을 제공한다.In order to achieve the above object, the present invention, etaboksam and 3,5-di-tert-butyl-4-hydroxybenzyl phosphonic diethyl ester as a light stabilizer of etaboksam (Formula 2), 2, 2 ′ -Thiodiethyl-bis [3- (3, 5-di-tersus-butyl-4-hydroxyphenyl) -propionate (Formula 3), 2, 6-di-tersus-butyl-4- Methylphenol (Formula 4), 2-hydroxy-4-methoxybenzophenone (Formula 5), octyl methoxy cinnamate (Formula 6), 2, 4, 6-trianilino-para- (carbo-2 Fungicide composition containing one or more '-ethylhexyl-1'-oxy) -1, 3, 5-triazine (Formula 7), sterilization method of phytopathogens using the same and improving the light stability of etaboksam by the light stabilizer Provide a method.
이하 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명에서 에타복삼에 대해 광분해 억제 작용을 보이는 물질은 비농약성분인 3, 5-디-터서리-부틸-4-하이드록시벤질 포스포닉 디에틸 에스테르 (화학식 2), 2, 2′-치오디에틸-비스[3-(3, 5-디-터서리-부틸-4-하이트록시페닐)-프로피오네이트 (화학식 3), 2, 6-디-터서리-부틸-4-메틸페놀 (화학식 4), 2-하이드록시-4-메톡시벤조페논 (화학식 5), 옥틸 메톡시 시나메이트 (화학식 6), 2, 4, 6-트리아닐리노-파라-(카르보-2'-에틸헥실-1'-옥시)-1, 3, 5-트리아진 (화학식 7) 등이다.In the present invention, the material showing photodegradation inhibitory effect on etaboksam is a non-pesticide component, 3,5-di-tert-butyl-4-hydroxybenzyl phosphonic diethyl ester (Formula 2), 2, 2'-value Odiethyl-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionate (Formula 3), 2, 6-di-tert-butyl-4-methylphenol ( 2-hydroxy-4-methoxybenzophenone (Formula 5), octyl methoxy cinnamate (Formula 6), 2, 4, 6-trianilino-para- (carbo-2'-ethyl Hexyl-1'-oxy) -1, 3, 5-triazine (Formula 7) and the like.
특히, 2-하이드록시-4-메톡시 벤조페논이 에타복삼의 광분해 억제에 가장 우수한 효과를 보였다.In particular, 2-hydroxy-4-methoxy benzophenone showed the best effect on the inhibition of photolysis of etaboksam.
본 발명의 광안정성이 증진된 에타복삼 살균제 조성물은 에타복삼 1 내지 70 중량%, 바람직하게는 5 내지 50 중량%, 광분해 억제제 1 내지 70 중량%, 바람직하게는 2.5 내지 20 중량%, 고체 또는 액체 담체 또는 첨가제 29 내지 98 중량% 및 계면활성제 0 내지 69 중량%, 바람직하게는 0.1 내지 10 중량%를 함유한다. 에타복삼의 사용량이 1 중량% 미만인 경우에는 희석배수를 맞추기가 곤란하며, 70 중량%를 초과하는 경우는 광분해 억제제를 첨가하여 제제의 물성을 유지하기가 곤란하다.Etaboxam fungicide composition of the present invention with enhanced stability is 1 to 70% by weight, preferably 5 to 50% by weight, 1 to 70% by weight, preferably 2.5 to 20% by weight, photolysis inhibitor, solid or liquid 29 to 98% by weight of carrier or additive and 0 to 69% by weight of surfactant, preferably 0.1 to 10% by weight. When the amount of etaboksam is less than 1% by weight, it is difficult to match the dilution factor, and when it exceeds 70% by weight, it is difficult to maintain the physical properties of the formulation by adding a photolysis inhibitor.
본 발명에 따른 조성물에서 3, 5-디-터서리-부틸-4-하이드록시벤질 포스포닉 디에틸 에스테르, 2, 2′-치오디에틸-비스[3-(3, 5-디-터서리-부틸-4-하이트록시페닐)-프로피오네이트, 2, 6-디-터서리-부틸-4-메틸페놀, 2-하이드록시-4-메톡시벤조페논, 옥틸 메톡시 시나메이트, 2, 4, 6-트리아닐리노-파라-(카르보-2'-에틸헥실-1'-옥시)-1, 3, 5-트리아진은 인공광 및 자연광 조건에서 에타복삼의 광안정성을 증진시켰다. 따라서, 상기 광안정제의 사용에 의해 에타복삼의 광분해 속도가 감소되어 살균제 조성물의 약효는 안정적으로 발현될 수 있다.3, 5-di-tersus-butyl-4-hydroxybenzyl phosphonic diethyl ester, 2, 2′-thiodiethyl-bis [3- (3, 5-di-tersery in the composition according to the invention -Butyl-4-hydroxyphenyl) -propionate, 2, 6-di-terresy-butyl-4-methylphenol, 2-hydroxy-4-methoxybenzophenone, octyl methoxy cinnamate, 2, 4, 6-trianilino-para- (carbo-2'-ethylhexyl-1'-oxy) -1, 3, 5-triazine enhanced the photostability of etaboxam under artificial and natural light conditions. Therefore, the photolysis rate of etaboksam is reduced by the use of the light stabilizer, so that the efficacy of the fungicide composition may be stably expressed.
광분해 억제 물질이 식물병에 대한 에타복삼의 약효를 증진시키는 이유는 살포된 에타복삼의 광안정성을 향상시켜 약효의 지속 기간을 증진시키기 때문인 것으로 판단되며, 이는 광분해 방지물질의 유무에 따른 광분해 정도의 차이에서 유추 가능하다.The reason why the photodegradation substance enhances the efficacy of etaboksam against plant diseases is believed to be due to improving the photostability of the sprayed etaboksam to enhance the duration of the medicinal effect. Can be deduced from the difference.
본 발명에서 에타복삼 대 광분해 억제제는 약 1 : 0.1 내지 1 : 1, 바람직하게는 약 1 : 0.2 내지 1 : 0.5의 중량비로 사용된다.In the present invention, etaboxam to photolysis inhibitor is used in a weight ratio of about 1: 0.1 to 1: 1, preferably about 1: 0.2 to 1: 0.5.
본 발명에 따른 살균제 조성물은 하기 작물의 병원균이 일으키는 병의 예방 및 치료에 효과적이다: 거베라 역병[병원균: 파이토프토라 크립토지아 (Phytophthora cryptogea)], 감자 역병[병원균: 파이토프토라 인페스탄스 (Phytophthora infestans)], 고추 역병[병원균: 파이토프토라 캡시시(Phytophthora capsici), 토마토 역병[병원균: 파이토프토라 인페스탄스(Phytophthora infestans)], 담배 역병[병원균: 파이토프토라 니코티아네(Phytophthora nicotianaevar.nicotianae)], 참깨 역병[병원균: 파이토프토라 니코티아네 (Phytophthora nicotianaevar.parasitica)], 사과 역병[병원균: 파이토프토라 칵토럼(Phytophthora cactorum)], 참외 노균병[병원균: 슈도페로노스포라 큐벤시스 (Pseudoperonospora cubensis)], 멜론 노균병[병원균: 슈도페로노스포라 큐벤시스 (Pseudoperonospora cubensis)], 오이 노균병[병원균: 슈도페로노스포라 큐벤시스 (Pseudoperonospora cubensis)], 배추 노균병[병원균: 페로노스포라 파라지티카 (Peronospora parasitica)], 상추 노균병[병원균: 브레미아 락투캐(Bremia lactucae)], 장미 노균병[병원균: 페로노스포라 스파르사(Peronospora sparsa)], 포도 노균병[병원균: 플라스모파라 비티콜라(Plasmopara viticola)], 호프 노균병[병원균: 슈도페로노스포라 휴물리(Pseudoperonospora humuli)], 잔디 피시움블라이트병[병원균: 피시움 속(Phythiumspp.)]The fungicide composition according to the present invention is effective for the prevention and treatment of diseases caused by pathogens of the following crops: gerbera late blight [pathogen: Phytophthora cryptogea ], potato late blight [pathogen: phytophthora infestans ( Phytophthora infestans)], pepper blight [pathogens: Pastry Saratov Torah kaepsi City (Phytophthora capsici), tomato late blight [pathogens: Pastry Saratov Torah inpe Afghanistan's (Phytophthora infestans)], tobacco epidemic [pathogens: Pastry Saratov Torah Nico Tia four (Phytophthora nicotianae var.nicotianae )], sesame late blight [pathogen: Phytophthora nicotianae var. parasitica ], apple late blight [pathogen: Phytophthora cactorum ], melon mycobacterium [pathogen: Pseudofero Pseudoperonospora cubensis ], melon mycobacterium [pathogen: Pseudoperonospora cubensis ], cucumber mycobacteria [pathogen: Pseudoperonospora cubensis ], Chinese cabbage fungus [pathogen: Peronospora parasitica ], lettuce fungi [pathogen: Bremia lactucae ], rose fungus [pathogen: Ferro Peronospora sparsa ], Staphylococcus aureus [pathogen: Plasmopara viticola ], Hoff aureus [pathogen: Pseudoperonospora humuli ], grass pisium blight disease [pathogen] : Phythium spp.]
본 발명에 의한 광분해 억제제를 함유하는 살균제 조성물은 필요한 경우, 담체, 계면활성제 또는 제형 기술분야에서 일반적으로 사용되는 보조제와 함께 사용된다. 예를 들어, 이들은 공지 방식에 따라 비개질 형태로 가공되어, 예를 들어 활성성분을 증량제[예: 용매, 고체 담체 및 적절한 경우 계면활성제]와 균일하게 혼합 및/또는 분쇄한 수화제, 분산성 액제, 유제, 입상수화제, 액상수화제, 오일상 현탁제 등의 제형으로 가공되어 식물체의 엽면 및 줄기에 살포함으로써 사용된다. 투여 회수 및 투여율은 병원균의 생물학적 특성 및 기후 환경에 따라 달라진다.Fungicide compositions containing photodegradation inhibitors according to the present invention, where necessary, are used in combination with carriers, surfactants or auxiliaries commonly used in the formulation art. For example, they are processed in unmodified form according to known methods, for example, wetting agents, dispersible liquids, in which the active ingredient is uniformly mixed and / or ground with an extender [e.g., a solvent, a solid carrier and, if appropriate, a surfactant]. It is processed into formulations such as emulsions, granulating water hydrants, liquid hydrating agents and oily suspensions, and used by spraying on foliar and stem of plants. Dosage frequency and dosing rate depend on the biological characteristics of the pathogen and the climatic environment.
적합한 담체 및 첨가제는 고체 또는 액체일 수 있으며, 제형 기술분야에서 유용한 성분, 예를 들어 천연 또는 합성 무기물질, 용매, 분산제, 습윤제, 희석제 등이 이용된다.Suitable carriers and additives may be solid or liquid and ingredients useful in the formulation art are used, for example natural or synthetic inorganics, solvents, dispersants, wetting agents, diluents and the like.
용매로서 가능한 것은N-메틸-2-피롤리돈, 디메틸 술폭사이드 또는 디메틸 포름아미드와 같은 극성용매이다. 또한, 보조용매로는N-옥틸-2-피롤리돈, 치환된 나프탈렌, 크실렌 혼합물, 치환된 벤젠, 데실 알코올, 도데실 알코올 등의 장쇄 알코올 및 장쇄 에스테르 화합물과 같은 것이 있다.Possible solvents are polar solvents such as N -methyl-2-pyrrolidone, dimethyl sulfoxide or dimethyl formamide. Cosolvents also include long chain alcohols such as N -octyl-2-pyrrolidone, substituted naphthalenes, xylene mixtures, substituted benzenes, decyl alcohols, dodecyl alcohols and long chain ester compounds.
고체 담체로서 가능한 것은 활석, 카올린, 탄산칼슘, 규조토, 납석과 같은 미세하게 분쇄된 천연광물이다. 또한, 제제의 물리적 특성, 특히 수화성을 개선하기 위해 무수 황산나트륨 등의 수용성 이온 화합물 또는 친수성의 다공성 합성 화합물을 사용할 수 있다.Possible as solid carriers are finely ground natural minerals such as talc, kaolin, calcium carbonate, diatomaceous earth, leadstone. In addition, water-soluble ionic compounds such as anhydrous sodium sulfate or hydrophilic porous synthetic compounds can be used to improve the physical properties of the formulation, in particular the hydration properties.
적절한 계면활성제는 에타복삼의 성질 및 제형에 따라 다양한 특성을 가지는 것이 사용되나, 주로 양호한 습윤, 분산력을 가지는 비이온 및/또는 음이온 계면활성제를 예로 들 수 있다. 본원에서 계면활성제는 계면활성제 혼합물도 의미한다.Suitable surfactants are used having a variety of properties depending on the nature and formulation of etaboxam, but mainly nonionic and / or anionic surfactants having good wetting and dispersing power. Surfactant herein also means a surfactant mixture.
습윤제로서는 라우릴 황산나트륨, 폴리옥시알킬렌 알킬 페닐 에테르 술폰산의 염, 디알킬 설포숙시네이트의 염, 디알킬 나프탈렌 술폰산의 염, 폴리옥시알킬렌 알킬 에테르 설페이트의 염 등의 음이온성 습윤제 및 아세틸렌 계열의 비이온성 계면활성제, 비이온성 계면활성제의 요소복합체 등이 사용가능하나, 보다 적절한 것은 라우릴 황산나트륨, 폴리옥시알킬렌 알킬 아릴 에테르 술폰산의 염, 폴리옥시알킬렌 알킬 에테르 설페이트의 염, 비이온성 계면활성제의 요소 복합체 등이다.As the wetting agent, anionic wetting agents such as sodium lauryl sulfate, salts of polyoxyalkylene alkyl phenyl ether sulfonic acid, salts of dialkyl sulfosuccinate, salts of dialkyl naphthalene sulfonic acid, salts of polyoxyalkylene alkyl ether sulfate and acetylene series Nonionic surfactants, urea complexes of nonionic surfactants, etc. may be used, but more suitable are sodium lauryl sulfate, salts of polyoxyalkylene alkyl aryl ether sulfonic acid, salts of polyoxyalkylene alkyl ether sulfate, nonionic interface Urea complexes of the active agent.
분산제로서는 분말 제제인 경우 리그닌 술폰산의 염, 나프탈렌 술폰산의 염, 라우릴 황산의 염, 라우릴 술폰산의 염, 폴리옥시알킬렌 알킬 아릴 에테르 설페이트의 염, 폴리옥시알킬렌 알킬 에테르 설페이트의 염과 같은 음이온성 분산제 및 폴리옥시알킬렌 알킬 아릴 에테르, 폴리옥시알킬렌 알킬 에테르, 아크릴 그래프트 중합체(acrylic graft copolymer)와 같은 비이온성 분산제 등을 예로 들 수 있다.As a dispersant, in the case of powder formulations, such as salts of lignin sulfonic acid, salts of naphthalene sulfonic acid, salts of lauryl sulfate, salts of lauryl sulfonic acid, salts of polyoxyalkylene alkyl aryl ether sulfate, salts of polyoxyalkylene alkyl ether sulfate And anionic dispersants and nonionic dispersants such as polyoxyalkylene alkyl aryl ethers, polyoxyalkylene alkyl ethers, acrylic graft copolymers, and the like.
액상 제제인 경우 분산제는 폴리옥시알킬렌 알킬 아릴 에테르, 바람직하게는 폴리옥시알킬렌 트리스티릴 페놀 에테르 및 폴리옥시알킬렌 알킬 에테르 등과 같은 분산력이 우수한 비이온성 계면활성제를 사용할 수 있다. 이들 분산제는 습윤제로서도 유용한 경우가 많다.In the case of liquid formulations, dispersants may use nonionic surfactants having good dispersibility, such as polyoxyalkylene alkyl aryl ethers, preferably polyoxyalkylene tristyryl phenol ethers and polyoxyalkylene alkyl ethers. These dispersants are often useful as wetting agents.
습윤제 및 분산제는 상술된 것에 한정되지 않으며 비이온성, 음이온성 계면활성제 중에서 적당한 것을 사용할 수 있다.Wetting agents and dispersants are not limited to those described above, and any suitable nonionic, anionic surfactant may be used.
이하, 실시예, 비교예 및 시험예를 들어 본 발명을 구체적으로 설명하나, 이들은 본 발명의 일부일 뿐이지 본 발명을 한정하지는 않는다.Hereinafter, although an Example, a comparative example, and a test example are given and this invention is demonstrated concretely, these are only a part of this invention and do not limit this invention.
실시예 1. 본 발명의 살균제 조성물 및 비교예의 살균제 조성물의 제조Example 1 Preparation of Fungicide Compositions of the Present Invention and Fungicide Compositions of Comparative Examples
하기 제제예의 성분을 함유하는 살균제 조성물을 제조하였다.A fungicide composition containing the component of the following formulation example was prepared.
실시예에서 별도의 언급이 없으면 %는 중량%를 의미한다. 표에서 Escalol은 International Specialty Products(미국) 제품을, Irganox는 Ciba Specialty Products(스위스) 제품을, Uvinol은 BASF(독일) 제품을 각각 나타낸다.In the Examples, unless otherwise stated,% means% by weight. In the table, Escalol represents International Specialty Products (US), Irganox represents Ciba Specialty Products (Switzerland), and Uvinol represents BASF (Germany).
제제예 1∼6 (수화제)Formulation Examples 1-6 (Hydrating Agent)
유효성분인 에타복삼과 각각의 에타복삼용 광분해 억제 물질, 계면활성제, 증량제를 비닐백을 이용하여 균일하게 혼합한 후 적합한 밀에서 분쇄시켜 목적하는 수화제를 제조하였다(표 1).The active ingredient etaboksam and each of the etaboksam photolysis inhibitors, surfactants, and extenders were uniformly mixed using a plastic bag and then pulverized in a suitable mill to prepare a desired hydrating agent (Table 1).
주1) : 리그닌 술폰산 칼슘염Note 1): Lignin sulfonic acid calcium salt
주2) : 라우릴 황산 나트륨염Note 2): Sodium Lauryl Sulfate
주3) : 3, 5-디-터서리-부틸-4-하이드록시벤질 포스포닉 디에틸 에스테르Note 3: 3, 5-di-terther-butyl-4-hydroxybenzyl phosphonic diethyl ester
주4) : 2, 2′-치오디에틸-비스[3-(3, 5-디-터서리-부틸-4-하이트록시페닐)-프로피오네이트Note 4): 2, 2'-thiodiethyl-bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionate
주5) : 2, 6-디-터서리-부틸-4-메틸페놀Note 5): 2, 6-di-tert-butyl-4-methylphenol
주6) : 2-하이드록시-4-메톡시 벤조페논Note 6) 2-hydroxy-4-methoxy benzophenone
주7) : 옥틸 메톡시 시나메이트Note 7: Octyl methoxy cinnamate
주8) : 2, 4, 6-트리아닐리노-파라-(카르보-2'-에틸헥실-1'-옥시)-1, 3, 5-트리아진Note 8): 2, 4, 6-trianilino-para- (carbo-2'-ethylhexyl-1'-oxy) -1, 3, 5-triazine
제제예 7∼12 (분산성액제)Formulation Examples 7-12 (Dispersable Liquid)
원제인 에타복삼을 용매인N-메틸-2-피롤리돈에 녹인후 에타복삼용 광분해 억제 물질 및 기타 보조제를 첨가하여 녹여 분산성 액제를 제조하였다(표 2)Dissolved Etaboxam was dissolved in N -methyl-2-pyrrolidone as a solvent, and then dissolved by adding a photolysis inhibitor and other auxiliary agent for Etaboxam (Table 2).
주1) : 폴리옥시에틸렌 트리스티릴 페닐 에테르(코씰 제품)Note 1): Polyoxyethylene Tristyryl Phenyl Ether (Coseal Products)
주2) :N-메틸-2-피롤리돈Note 2) N -methyl-2-pyrrolidone
제제예 13∼15 (수화제)Formulation Examples 13-15 (Hydrating Agent)
제제예 1∼6에서와 같은 방법에 의해 수화제를 제조하였다(표 3)Wetting agents were prepared by the same method as in Preparation Examples 1 to 6 (Table 3).
비교제제예Comparative Example
비교제제예 1 (수화제)Comparative Example 1 (Hydrating)
에타복삼, 보조제 및 증량제를 모두 비닐백에 넣고 균일하게 혼합한 후 적합한 밀에서 분쇄시켜 수화제를 제조하였다(표 4).Ethaboxam, auxiliaries and extenders were all put in a plastic bag, mixed uniformly and ground in a suitable mill to prepare a hydrating agent (Table 4).
비교제제예 2 (분산성 액제)Comparative Preparation Example 2 (Dispersable Liquid)
에타복삼을 용매인N-메틸-2-피롤리돈에 녹인 후 나머지 보조제를 첨가하여 녹여 분산성 액제를 제조하였다(표 5).Etaboxam was dissolved in N -methyl-2-pyrrolidone as a solvent and then dissolved by adding the remaining auxiliary agent to prepare a dispersible liquid (Table 5).
실시예 2. 광안정성 평가Example 2 Light Stability Evaluation
광분해 억제 물질이 첨가된 에타복삼 살균제 조성물에서의 에타복삼의 광안정성이 광분해 억제 물질이 첨가되지 않은 조성물에서보다 높은 경우 광분해 억제제 첨가에 의한 에타복삼의 광분해 억제 효과가 존재함을 의미한다.If the photostability of etaboxam in the etaboxam fungicide composition to which the photolysis inhibitor is added is higher than that in the composition to which the photolysis inhibitor is not added, it means that there is a photolysis inhibitory effect of etaboksam by the addition of the photolysis inhibitor.
시험예 1 : 인조광에서의 광안정성 평가Test Example 1: Evaluation of light stability in artificial light
시험제제를 원제 기준으로 160mg/L가 되도록 물에 희석하여 조제하고 직경87mm의 페트리디쉬에 1ml씩 분주하여 원제 기준으로 160㎍이 페트리디쉬에 담기도록 하였다. 물을 4ml씩 가하고 흔들어 주어 조제액이 페트리디쉬에 고루 퍼지도록 한 후 50℃로 조절된 오븐에서 물이 모두 증발하도록 방치하였다. 약제가 들어 있는 페트리디쉬를 인조광(울트라바이탈룩스 램프, 오스람 제품) 아래에서 1 내지 4시간 동안 광을 조사하였다. 처리가 끝난 페트리디쉬는 아세토니트릴 5ml씩 가하여 녹여낸 후, HPLC를 이용하여 분해되지 않은 에타복삼을 정량 분석하였다.The test preparation was prepared by diluting the test preparation with water to 160 mg / L based on the raw material, and dispensing 1 ml of the petri dishes with a diameter of 87 mm to put 160 µg into the petri dishes. 4 ml of water was added and shaken to allow the preparation to spread evenly in Petri dishes, and then allowed to evaporate in an oven controlled at 50 ° C. Petri dishes containing drugs were irradiated with light for 1 to 4 hours under artificial light (ultravitalux lamps, OSRAM). The treated petri dish was dissolved by adding 5 ml of acetonitrile, and quantitatively analyzed undecomposed etaboksam using HPLC.
결과를 하기 표 6, 표 7에 나타내었다. 전반적으로, 수화제 처리구가 분산성 액제 처리구보다 에타복삼의 광안정성이 우수하였으며, 광안정제 후보물질이 첨가된 처리구에서는 첨가되지 않은 처리구에 비해 에타복삼의 광분해가 억제되었다. 특히, 2-하이드록시-4-메톡시 벤조페논이 첨가된 제제예 4의 수화제를 처리한 시험구에서 가장 우수한 결과가 관찰되었다.The results are shown in Table 6 and Table 7 below. In general, the hydrated treatment was better in light stability of etaboksam than the dispersible liquid treatment, and the photodegradation of etaboksam was suppressed in the treatment added with the light stabilizer candidate compared to the treatment without addition. In particular, the best results were observed in the test zone treated with the hydrating agent of Formulation Example 4 to which 2-hydroxy-4-methoxy benzophenone was added.
시험예 2 : 자연광에서의 광안정성 평가Test Example 2 Evaluation of Light Stability in Natural Light
시험제제를 원제 기준으로 160mg/L가 되도록 물에 희석하여 조제하고 직경 87mm의 페트리디쉬에 1ml씩 분주하여 원제 기준으로 160㎍이 페트리디쉬에 담기도록 하였다. 물을 4ml씩 가하고 흔들어 주어 조제액이 페크리디쉬에 고루 퍼지도록 한 후 50℃로 조절된 오븐에서 물이 모두 증발하도록 방치하였다. 약제가 들어 있는 페트리디쉬를 자연광 아래에서 1 내지 7일 동안 광을 조사하였다. 처리가 끝난 페트리디쉬는 아세토니트릴 5ml씩 가하여 녹여낸 후, HPLC를 이용하여 분해되지 않은 에타복삼을 정량 분석하였다.The test preparation was prepared by diluting the test preparation with water to 160 mg / L based on the raw material, and dispensing 1 ml of the petri dishes with a diameter of 87 mm to put 160 µg into the petri dishes. 4 ml of water was added and shaken to allow the preparation to spread evenly on the Pecrichish, and then allowed to evaporate in an oven controlled at 50 ° C. Petri dishes containing the drug were irradiated with light for 1 to 7 days under natural light. The treated petri dish was dissolved by adding 5 ml of acetonitrile, and quantitatively analyzed undecomposed etaboksam using HPLC.
결과를 하기 표 8, 표 9에 나타내었다. 전반적으로, 자연광을 처리한 경우는 인공광 처리구에 비해 에타복삼의 광안정성이 높았으며, 인공광을 처리한 경우와 마찬가지로 광분해 억제 물질이 첨가된 처리구에서는 에타복삼의 분해가 억제되었다. 특히, 2-하이드록시-4-메톡시 벤조페논이 첨가된 제제예 4의 수화제를 처리한 시험구에서 가장 우수한 결과가 관찰되었다.The results are shown in Table 8 and Table 9 below. Overall, the light stability of etaboksam was higher in the natural light treatment than in the artificial light treatment, and the decomposition of etaboksam was suppressed in the treatment treatment to which the photodegradation inhibitor was added as in the artificial light treatment. In particular, the best results were observed in the test zone treated with the hydrating agent of Formulation Example 4 to which 2-hydroxy-4-methoxy benzophenone was added.
실시예 3. 생물학적 활성 평가Example 3. Biological Activity Assessment
생물학적 활성 평가는 상기 시험예 1, 2에 의해 에타복삼의 광분해 억제효과가 가장 우수한 것으로 관찰된 2-하이드록시-4-메톡시 벤조페논이 함유된 에타복삼의 수화제를 사용하여 토마토 역병에 대한 약효의 지속 기간 증진 효과 시험을 통하여 행하였다.The biological activity was evaluated using the hydration agent of etaboxam containing 2-hydroxy-4-methoxy benzophenone, which was observed to have the highest photodegradation inhibitory effect of etaboksam according to Test Examples 1 and 2, and the medicinal effect against tomato late blight. Was conducted through a duration improvement effect test of.
토마토 종자를 직경 6cm 포트의 원예용 상토에 파종하고 4주간 온실에서 재배하였다. 제제예 4, 제제예 13∼15 및 비교제제예에 의해 제조된 제제와 가디안 수화제를 원제기준으로 1, 5, 10, 50, 100㎎/L의 농도로 살포액을 조제하고 오토마이저를 이용하여 포트당 살포액 5㎖를 토마토 잎 및 줄기에 살포하고 야외에서 1, 5, 10일간 방치하여 광을 충분히 받도록 하였다. 약제 살포 1, 5, 10일 후 5×104유주자/㎖의 농도로 준비한 토마토 역병 균주인 파이토프토라 인페스탄스를 오토마이저를 이용하여 식물체에 접종하였다. 접종한 토마토는 20℃, 100%의 상대습도 조건에서 3 내지 4일간 발병시킨 후, 무처리구의 발병율이 80% 정도 되었을 때 꺼내어 발병도를 조사하였다.Tomato seeds were sown in horticultural tops of 6 cm diameter pots and grown in greenhouses for 4 weeks. Using the preparation prepared in Formulation 4, Formulations 13-15 and Comparative Example, and a guardian hydrating agent at a concentration of 1, 5, 10, 50, 100 mg / L, based on the original formulation, 5 ml of spray solution per pot was sprayed onto tomato leaves and stems, and left for 1, 5, and 10 days in the open air to receive sufficient light. Phytophthora infestans, a tomato late blight strain prepared at a concentration of 5 × 10 4 strainers / ml after 1, 5 and 10 days of drug spraying, was inoculated into plants using an automator. Inoculated tomatoes were developed at 20 ° C. and 100% relative humidity conditions for 3 to 4 days, and then removed when the incidence of the untreated plots was about 80%, and the incidence was examined.
결과는 자연광 1일 처리후의 방제가(표 10), 자연광 5일 처리후의 방제가(표 11), 자연광 10일 처리후의 방제가(표 12)로 구분하여 나타내었다. 자연광 1일 처리구의 방제가는 모든 처리구에서 비슷한 결과를 보였으나, 자연광 10일 처리구의 방제가는 2-하이드록시-4-메톡시 벤조페논이 첨가된 처리구에서 첨가되지 않은 처리구에 비해 약효가 증진되었음을 관찰할 수 있었다(표 12).The results were shown by dividing the control value after natural day treatment (Table 10), the control value after natural day 5 treatment (Table 11), and the control value after natural day 10 treatment (Table 12). The control value of the natural light treatment group showed similar results in all treatments, but the control value of the natural light treatment group showed enhanced efficacy compared to the treatment group without the addition of 2-hydroxy-4-methoxy benzophenone. It was possible (Table 12).
따라서, 2-하이드록시-4-메톡시 벤조페논 첨가에 의한 약효의 지속기간의 증진 현상은 뚜렷하며, 이는 에타복삼의 광분해가 억제되었기 때문인 것으로 판단되어 진다.Therefore, the phenomenon of enhancement of the duration of the medicinal effect by the addition of 2-hydroxy-4-methoxy benzophenone is apparent, which is considered to be due to the suppressed photolysis of etaboksam.
상기한 바와 같이, 본 발명에 따르면, 에타복삼의 광안정화제가 에타복삼의 광안정성을 증진시킴으로써, 환경중에서 에타복삼의 광에 의한 분해속도를 감소시켜 기존 에타복삼 함유 제제에 비해 식물 병에 대한 약효의 지속기간을 증진시킬 수 있고, 환경적인 관점에서도 농약의 살포회수 및 살포량을 최소화함으로써 토양 및 수질 환경의 보존이라는 바람직한 효과가 있다.As described above, according to the present invention, the light stabilizer of etaboksam enhances the light stability of etaboksam, thereby reducing the degradation rate of the light by etaboksam in the environment, and compared to the conventional etaboksam-containing formulation, In addition, it is possible to improve the duration of the pesticides, and from the environmental point of view, there is a desirable effect of preserving the soil and water environment by minimizing the number of spraying and spreading of pesticides.
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JPS61148106A (en) * | 1984-12-22 | 1986-07-05 | Nissan Chem Ind Ltd | Light stabilized insecticidal and acaricidal composition |
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KR960022514A (en) * | 1994-12-30 | 1996-07-18 | 성재갑 | Method for preparing 2-aminothiazole carboxamide derivative |
KR19990000959A (en) * | 1997-06-11 | 1999-01-15 | 성재갑 | Method for preparing 2-aminothiazolecarboxamide derivative |
US5938825A (en) * | 1998-05-21 | 1999-08-17 | Troy Technology Corporation Inc. | Stabilized antimicrobial compositions containing halopropynyl compounds |
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JPS61148106A (en) * | 1984-12-22 | 1986-07-05 | Nissan Chem Ind Ltd | Light stabilized insecticidal and acaricidal composition |
EP0434620A2 (en) * | 1989-12-21 | 1991-06-26 | Ciba-Geigy Ag | Pesticides |
US5514643A (en) * | 1993-08-16 | 1996-05-07 | Lucky Ltd. | 2-aminothiazolecarboxamide derivatives, processes for preparing the same and use thereof for controlling phytopathogenic organisms |
KR960022514A (en) * | 1994-12-30 | 1996-07-18 | 성재갑 | Method for preparing 2-aminothiazole carboxamide derivative |
KR19990000959A (en) * | 1997-06-11 | 1999-01-15 | 성재갑 | Method for preparing 2-aminothiazolecarboxamide derivative |
US5938825A (en) * | 1998-05-21 | 1999-08-17 | Troy Technology Corporation Inc. | Stabilized antimicrobial compositions containing halopropynyl compounds |
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