KR100429139B1 - Synergistic herbicidal composition containing cyhalofop-butyl and metamifop as an effective ingredient and method of controling grass weeds - Google Patents

Synergistic herbicidal composition containing cyhalofop-butyl and metamifop as an effective ingredient and method of controling grass weeds Download PDF

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KR100429139B1
KR100429139B1 KR10-2002-0010810A KR20020010810A KR100429139B1 KR 100429139 B1 KR100429139 B1 KR 100429139B1 KR 20020010810 A KR20020010810 A KR 20020010810A KR 100429139 B1 KR100429139 B1 KR 100429139B1
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metamihof
herbicide
cyhalhof
treatment
control
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KR20030071215A (en
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조광연
김진석
김태준
장해성
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한국화학연구원
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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
    • A01N37/00—Biocides, 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
    • A01N37/36—Biocides, 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
    • A01N37/38—Biocides, 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 having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A01N37/40—Biocides, 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 having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
    • 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
    • A01N25/02—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 liquids as carriers, diluents or solvents
    • 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
    • A01N25/30—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 characterised by the surfactants
    • 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
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles

Abstract

본 발명은 싸이할로호프 (cyhalofop-butyl)와 메타미호프(metamifop)를 유효성분으로 하는 제초제 조성물에 관한 것으로, 구체적으로 제초제 성분 총량을 기준으로 하기화학식 1로 표시되는 싸이할로호프 5 내지 85 중량%와 하기화학식 2로 표시되는 메타미호프 15 내지 95 중량%가 혼합된 제초화합물을 포함하는 제초제 조성물 및 이를 이용하여 화본과 잡초를 방제하는 방법에 관한 것이다. 본 발명의 제초제 조성물은 싸이할로호프와 메타미호프의 조합을 통해 방제활성 발현속도와 효과를 증진시켜 화본과 잡초의 방제에 유용하게 사용될 수 있다.The present invention relates to a herbicide composition comprising cyhalofop-butyl and metamifop as an active ingredient, specifically, to the hahalhof 5 represented by the following formula (1) based on the total amount of herbicide components: The present invention relates to a herbicide composition comprising a herbicide compound in which 85% by weight and 15 to 95% by weight of metamihof represented by the following Chemical Formula 2 are mixed, and a method for controlling flowers and weeds using the same. The herbicide composition of the present invention can be usefully used for the control of flowers and weeds by increasing the speed and effect of controlling activity through the combination of sihalhof and metamihof.

Description

싸이할로호프와 메타미호프를 유효성분으로 하는 제초제 조성물 및 이를 이용하여 화본과 잡초를 방제하는 방법{SYNERGISTIC HERBICIDAL COMPOSITION CONTAINING CYHALOFOP-BUTYL AND METAMIFOP AS AN EFFECTIVE INGREDIENT AND METHOD OF CONTROLING GRASS WEEDS}SYHERGISTIC HERBICIDAL COMPOSITION CONTAINING CYHALOFOP-BUTYL AND METAMIFOP AS AN EFFECTIVE INGREDIENT AND METHOD OF CONTROLING GRASS WEEDS}

본 발명은 싸이할로호프 (cyhalofop-butyl)와 메타미호프 (metamifop)를 유효성분으로 하는 제초제 조성물 및 이를 이용하여 화본과 잡초를 방제하는 방법에 관한 것이다.The present invention relates to a herbicide composition comprising cyhalofop-butyl and metamifop as an active ingredient, and a method for controlling flowers and weeds using the same.

작물과 잡초가 다양한 만큼 이들의 생육을 조절하기 위하여 여러 가지 제초제가 개발되었는데, 이들의 제초특성은 대상 작물, 잡초 종류, 화합물의 화학적 성질, 작용점, 사용방법 등에 따라 다양하게 나타난다.Various herbicides have been developed to control their growth as crops and weeds vary, and their herbicidal properties vary depending on the target crop, weed type, chemical properties of the compound, point of use, and method of use.

제초제들 중에는 지방산 생합성 과정에서 아세틸-CoA-카르복실라아제 (acetyl-CoA-carboxylase)를 저해하여 화본과 잡초만을 선택적으로 죽이고 광엽작물에 대해서는 매우 안전한 화합물 계열이 있는데, 아릴옥시페녹시프로피오네이트 (aryloxyphenoxypropionate) 계열과 싸이클로헥산다이온 (cyclohexandion) 계열이 이에 속한다 (김 등, 한잡초지 21(2):122-145, 2001). 이들은 2000년도 현재 992백만 불의 세계 시장을 갖고 있으며 이는 전체 제초제 세계시장 (13,794백만 불)의 7.2%를 차지하는 것이다 (Wood Mackenzie, Agrochemical service. Update of the products section, p44-48, 2001). 우리나라의 경우도 단일제형과 혼합제형 처리를 포함하여 이 계통에 속하는 제초제 시장은 2000년도의 경우 약 100억 원에 육박하였다 (농약공업협회, 농약년보, p138-181, 2001).Among herbicides, there is a class of compounds that inhibit acetyl-CoA-carboxylase in the fatty acid biosynthesis process, selectively kill only flowers and weeds, and are very safe for broadleaf crops, such as aryloxyphenoxypropionate ( The aryloxyphenoxypropionate family and the cyclohexandion family belong to this group (Kim et al., Hanja Grassland 21 (2): 122-145, 2001). They have a global market of $ 992 million as of 2000, accounting for 7.2% of the total herbicide global market ($ 13,794 million) (Wood Mackenzie, Agrochemical service.Update of the products section, p44-48, 2001). In Korea, the herbicide market belonging to this system, including single and mixed formulations, reached nearly 10 billion won in 2000 (Pesticide Industry Association, Pesticide Report, p138-181, 2001).

현재 두 계통 중에서 아릴옥시페녹시프로피오네이트 계열에 속하는 제초제가 싸이클로헥산다이온 계열에 속하는 제초제보다 폭넓게 사용되고 있는데, 그 이유는 방제활성이 보다 강하며, 아릴옥시페녹시프로피오네이트 계열의 제초제 중에는 광엽작물 뿐만 아니라 화본과 작물에 대해서도 선택성 방제효과를 가지는 화합물이몇 가지 개발되어 사용되고 있기 때문이다. 즉, 아릴옥시페녹시프로피오네이트 계열에 속하는 화합물은 광엽작물에 모두 사용 가능한데, 그 중에서 페녹사프로프에틸 (fenoxaprop-ethyl)은 밀에, 싸이할로호프부틸 (cyhalofop-butyl)은 벼에도 사용 가능하다. 최근에 한국에서 개발된 메타미호프 (metamifop, 디비에취129)도 벼에 안전하게 사용될 수 있는 화합물로 알려져 있다 (한국 물질특허 출원번호 제 1999-30067 호; 김 등, 한국농약과학회 춘계학술발표회 발표요지, p45, 2001). 이들 아릴옥시페녹시프로피오네이트 계열에 속하는 화합물은 주로 경엽처리 효과가 강하며, 환경조건 또는 화합물 종류에 따라 차이가 있지만 대략 약제 처리 후 5 내지 6일이 지나면 제초효과가 나타나기 시작하고 10일 정도 이후가 되면 잡초가 죽게되는 지효성 방제효과를 가진다 (김 등, 한잡초지 19(4):261-287; Anderson W. P., Weed Science principles and applications (3rd ed.), 171-174, 1996).Currently, the herbicides belonging to the aryloxyphenoxypropionate series are used more widely than the herbicides belonging to the cyclohexanedione series. The reason for this is that the control activity is stronger, and among the aryloxyphenoxypropionate herbicides, This is because several compounds having selective control effects have been developed and used not only for broadleaf crops but also for plants and crops. That is, the aryloxyphenoxypropionate-based compounds can be used for all broad-leaf crops, among which phenoxaprop-ethyl is used in wheat and cyhalofop-butyl is used in rice. Can be used Recently, metamifop (Divièch 129), which was developed in Korea, is also known as a compound that can be safely used in rice (Korean Patent Application No. 1999-30067; Kim et al. , p45, 2001). Compounds belonging to these aryloxyphenoxypropionate series have a strong foliage treatment effect, and vary depending on environmental conditions or compound types, but approximately 5 to 6 days after drug treatment, herbicidal effect starts to appear. Later, weeds have a slow-release control effect that causes the weeds to die (Kim et al., Han Weed, 19 (4): 261-287; Anderson WP, Weed Science principles and applications (3rd ed.), 171-174, 1996).

한편, 이들 약제는 처리조건 또는 환경조건에 따라 제초효과, 방제작용 발현속도, 잡초의 재생 등에 있어서 문제가 있는 것으로 알려져 있다 (김 등, 한잡초지 19(4):261-287; Davis and Caseley, BCPC conference proceedings, 519-524, 2001; Anderson W. P., Weed Science principles and applications (3rd ed.), 171-174, 1996). 그리고, 대부분의 화합물은 단일제형으로 사용할 경우 어독성 Ⅱ 급류에 속하기 때문에 (농약사용지침서, p600, 2000; Tomlin C. D. S., The pesticide manual, 12th ed., 2000) 일반적으로 보다 낮은 처리량이 요구된다.On the other hand, these drugs are known to have problems in herbicidal effect, control expression rate, weed regeneration, etc., depending on treatment conditions or environmental conditions (Kim et al., Hanja Grassland 19 (4): 261-287; Davis and Caseley) , BCPC conference proceedings, 519-524, 2001; Anderson WP, Weed Science principles and applications (3rd ed.), 171-174, 1996). And, because most of the compounds are of fish toxicity II rapids when used in a single formulation (Pesticide Instructions, p600, 2000; Tomlin C. D. S., The pesticide manual, 12th ed., 2000), generally lower throughput is required.

이러한 문제점들을 해결하고 아릴옥시페녹시프로피오네이트 계열 화합물의 사용 증진을 위해서는 1) 화합물의 저농도 처리가 가능하도록 상승효과를 가지는혼합제형 조합의 탐색, 2) 제초효과를 보다 빨리 발현시키는 방법, 3) 후기처리에서도 제초효과를 유지시킬 수 있는 방법, 4) 화합물의 합성 단가를 낮추는 공정 개발 등이 기술적으로 극복되어야 한다. 따라서, 이 분야에 대해 종래의 화합물이나 처리 기술보다 우수한 것이 개발되면 그 경제적 가치는 매우 높다 하겠다.In order to solve these problems and improve the use of aryloxyphenoxypropionate-based compounds, 1) searching for a combination formulation having a synergistic effect to allow low concentration treatment of the compound, 2) expressing herbicidal effect more quickly, 3 4) The method of maintaining herbicidal effect in the post-treatment, and 4) the development of a process to lower the cost of synthesis of the compound should be overcome technically. Therefore, the economic value is very high if the development of superior to the conventional compounds and processing technology in this field.

현재 여러 가지 벼용 제초제들이 개발되어 사용되고 있지만 아직도 논농사에 있어서 가장 문제가 되고 있는 잡초는 피이다. 예컨대, 1 ㎡당 피 10주가 발생하는 경우 쌀 수확량은 30% 정도 감소하고 (Ntanos 등,Agric. Med. 122:54-58, 1992), 50주가 발생하는 경우 "레몬"이라는 벼 품종의 수확량은 65%까지 감소된다고 보고된 바 있다 (Smith R. J. Jr.,Weed Technol. 2:232-241, 1988). 따라서, 농업 경제적 측면이나 농약 산업적으로도 피 방제 제초제에 대한 필요성이 매우 크며 더욱이 피에 대해 탁월한 방제효과가 있는 것으로 알려졌던 후기 경엽 처리제 퀸클로락 (quinclorac, BASF사)이 후작물 영향 때문에 사용이 불가능해진 이후로는 그 요구가 더욱 절실한 실정이다.Currently, various herbicides for rice have been developed and used, but weed, which is still the most problematic problem in paddy farming, is blood. For example, rice yields are reduced by 30% for every 10 weeks of blood per m2 (Ntanos et al., Agric. Med . 122: 54-58, 1992), and for 50 weeks, the yield of rice varieties called "lemons" It has been reported to be reduced by 65% (Smith RJ Jr., Weed Technol . 2: 232-241, 1988). Therefore, the need for pesticide herbicides is also very important in terms of agronomy and pesticide industry, and the late foliage treatment quinclorac (BASF), which has been known to have an excellent control effect on blood, is not available due to the effects of crops. Since it is impossible, the demand is more urgent.

한편, 싸이할로호프는 벼 재배시에 화본과 잡초, 특히 피를 효과적으로 방제할 수 있는 화합물들로서 화학명이 (R)-부틸 2-(4-(4-시아노-2-플루오로페녹시)페녹시)-프로피오네이트 ([R]-butyl 2-[4-(4-cyano-2-fluorophenoxy) phenoxy]-propionate)이다 (Ray 등, Proceeding of 14th Asian Pacific Weed Science Society Conference: 41-45, 1993).Cyhalohof, on the other hand, has a chemical name (R) -Butyl 2- (4- (4-cyano-2-fluorophenoxy) phenoxy, which is a compound capable of effectively controlling flowers and weeds, particularly blood, during cultivation of rice. ) -Propionate ([R] -butyl 2- [4- (4-cyano-2-fluorophenoxy) phenoxy] -propionate) (Ray et al., Proceeding of 14th Asian Pacific Weed Science Society Conference: 41-45, 1993).

싸이할로호프는 식물체내 이행성이 매우 높아 초기의 피 생장을 강하게 억제하지만 화합물의 대사가 신속히 진행됨으로 인해 특히 저농도 처리에서 피가 후기에 재생하고 (오 등, 한국잡초학회 발표요지 21(2):91-95; Ito 등,J. Weed Sci. Tech. 43(2):122-128, 1998), 약제 처리된 경엽에서의 황화 및 괴사가 동일 계열의 다른 화합물에 비해 상대적으로 늦게 나타남에 따라 본래 가지고 있는 작용점 저해능력을 충분히 발휘하지 못하는 단점을 가지고 있다. 그리고, 피 생장의 초기에 처리하면 제초효과가 효과적으로 나타나지만 5 내지 6엽기의 늦은 엽기처리에서는 방제력이 현저히 떨어지는 경향이 있다.Cyhalofov is highly transferable in plants and strongly inhibits early growth, but due to the rapid progress of metabolism of the compounds, blood regenerates later, especially at low concentrations (Oh et al. (91) -91; Ito et al., J. Weed Sci. Tech . 43 (2): 122-128, 1998), which showed that yellowing and necrosis in the medicinal treated foliage appeared relatively later than other compounds of the same family. Therefore, it has a disadvantage that does not fully exhibit its own function of inhibiting the functioning point. In the early stages of growth, herbicidal effect appears effectively, but in the late foliar treatment of 5 to 6 leaf phases, the control ability tends to be significantly lowered.

메타미호프는 화학명이 (R)-2-(4-(6-클로로-2-벤조옥사졸일옥시)-페녹시)-프로피온산-N-(2-플루오로페닐)-N-메틸 아미드 ([R]-2-[4-(6-chloro-2-benzoxazolyl-Metamihof has the chemical name (R) -2- (4- (6-chloro-2-benzooxazolyloxy) -phenoxy) -propionic acid-N- (2-fluorophenyl) -N-methyl amide ( [R] -2- [4- (6-chloro-2-benzoxazolyl-

oxy) phenoxy]-propionic acid-N-(2-fluorophenyl)-N-methyl amide)인 화합물로서 (김 등, 한국농약과학회 춘계학술발표요지 p45, 2001), 체내 흡수 및 이행성이 싸이할로호프 보다 상대적으로 늦어 초기의 피 생장을 강하게 억제하지는 못한다. 또한, 약제 처리된 경엽에서의 황화 및 괴사가 싸이할로호프 보다는 빠르지만, 약제 처리 반응이 비교적 빠른 편에 속하는 페녹사프로프에틸 보다는 상대적으로 늦다. 더욱이, 메타미호프의 합성 과정은 싸이할로호프에 비해 약간 복잡하기 때문에 화합물 생산단가가 싸이할로호프 보다 상대적으로 높다. 그러나, 일단 흡수된 화합물은 대사가 비교적 완만하게 진행되며 이행이 서서히 일어나기 때문에 피의 재생정도도 낮고, 5 내지 6엽의 늦은 엽기 처리에서도 방제력을 유지하는 특성을 갖는다 (김 등, 한국농약과학회 춘계학술발표, p45, 2001).oxy) phenoxy] -propionic acid-N- (2-fluorophenyl) -N-methyl amide) (Kim et al., Korean Society of Pesticide Science, p45, 2001). It is relatively late and does not strongly inhibit early growth. In addition, although sulfidation and necrosis in the drug-treated foliage is faster than Cyhalhof, the drug treatment reaction is relatively slower than phenoxapropethyl, which is relatively fast. Moreover, the synthesis process of metamihof is slightly more complicated than that of cyhalhof, so that the cost of producing the compound is relatively higher than that of cyhalhof. However, once absorbed, the metabolism proceeds relatively slowly and the transition occurs slowly, so the regeneration of blood is low and the control ability is maintained even in the late foliar treatment of 5 to 6 leaves (Kim et al. (P45, 2001).

이와 같이 싸이할로호프와 메타미호프는 각기 나름대로 제초 특성상 몇 가지서로 상반되는 특성을 보이기 때문에 보다 효율적인 사용을 위해서는 각각을 보완해 줄 수 있는 조합의 탐색이 필요하다.Thus, because Cyhalhof and Metamihof each have some characteristics of herbicidal characteristics that are opposite to each other, it is necessary to search for combinations that can complement each other for more efficient use.

이에 본 발명자들은 싸이할로호프와 메타미호프를 대상으로 두 가지 성분을 혼합 처리하여 각각의 단독 처리시 관찰되는 제초 특성의 단점을 보완하고 방제활성 발현속도와 효과를 증진시킨 제초제 조성물을 개발함으로써 본 발명을 완성하였다.Accordingly, the present inventors have developed a herbicide composition that supplements the disadvantages of the herbicidal properties observed in each treatment by mixing the two components of the sihalhof and metamihof and enhances the expression and effect of the control activity. The present invention has been completed.

본 발명의 목적은 싸이할로호프와 메타미호프의 조합을 통해 방제활성 발현 속도와 효과를 증진시켜 광범위한 제초 스펙트럼을 나타냄으로써 화본과 잡초의 방제에 유용하게 사용될 수 있는 제초제 조성물을 제공하는 것이다.It is an object of the present invention to provide a herbicide composition that can be useful for controlling plants and weeds by exhibiting a wide range of herbicidal spectrum by enhancing the rate and effect of control activity through the combination of sihalhof and metamihof.

도 1은 본 발명에 따른 싸이할로호프와 메타미호프 혼합제형의 피에 대한 방제효과 (경엽의 황화고사)를 처리 후 시간 경과별로 나타낸 것이고, Figure 1 shows the control effect (blood filament sulphide) for the blood of the sihalhof and metamihof mixture formulation according to the present invention over time after treatment,

도 2는 본 발명에 따른 싸이할로호프와 메타미호프 혼합제형의 처리량을 30 g/ha로 하였을 때, 두 화합물의 혼합처리 비율에 따른 피에 대한 방제효과를 비교한 것이고, Figure 2 is a comparison of the control effect on the blood according to the mixing treatment ratio of the two compounds when the throughput of the mixture of sihalhof and metamihof according to the present invention is 30 g / ha,

DAT: 약제 처리 후 일수,DAT: days after drug treatment,

C30+K0: 싸이할로호프 30 g,C30 + K0: 30 g of Cyhalhof,

C0+K30: 메타미호프 30 g,C0 + K30: metamihof 30 g,

C5+K25: 싸이할로호프 5 g + 메타미호프 25 g,C5 + K25: Cyhalhof 5 g + Metamihof 25 g,

C10+K20: 싸이할로호프 10 g + 메타미호프 20 g,C10 + K20: Cyhalhof 10 g + Metamihof 20 g,

C15+K15: 싸이할로호프 15 g + 메타미호프 15gC15 + K15: Cyhalhof 15 g + Metamihof 15 g

도 3은 본 발명에 따른 싸이할로호프와 메타미호프 혼합제형의 처리량을 40g/ha로 하였을 때, 두 화합물의 혼합처리 비율에 따른 피에 대한 방제효과를 비교한 것이고, Figure 3 is a comparison of the control effect on the blood according to the mixing treatment ratio of the two compounds when the throughput of the mixture of sihalhof and metamihof formulation according to the present invention is 40g / ha,

DAT: 약제 처리 후 일수,DAT: days after drug treatment,

C40+K0: 싸이할로호프 40 g,C40 + K0: 40 g of Cyhalhof,

C0+K40: 메타미호프 40 g,C0 + K40: metamihof 40 g,

C20+K20: 싸이할로호프 20 g + 메타미호프 20 g,C20 + K20: 20 g of Cyhalhof + 20 g of metamihof,

C30+K10: 싸이할로호프 30 g + 메타미호프 10gC30 + K10: Cyhalhof 30 g + Metamihof 10 g

도 4는 본 발명에 따른 싸이할로호프와 메타미호프 혼합제형의 처리량을 35 g/ha와 40 g/ha로 하였을 때, 두 화합물의 혼합처리 비율에 따른 피에 대한 방제효과를 비교한 것이다. Figure 4 compares the control effect on blood according to the mixing treatment ratio of the two compounds when the throughput of the sihalhof and metamihof formulation according to the present invention is 35 g / ha and 40 g / ha .

DAT: 약제 처리 후 일수,DAT: days after drug treatment,

C15+K20: 싸이할로호프 15 g + 메타미호프 20 g,C15 + K20: Cyhalhof 15 g + Metamihof 20 g,

C20+K15: 싸이할로호프 20 g + 메타미호프 15 g,C20 + K15: 20 g of Cyhalhof + 15 g of metamihof,

C20+K20: 싸이할로호프 20 g + 메타미호프 20 g,C20 + K20: 20 g of Cyhalhof + 20 g of metamihof,

C30+K10: 싸이할로호프 30 g + 메타미호프 10gC30 + K10: Cyhalhof 30 g + Metamihof 10 g

상기 목적을 달성하기 위하여, 본 발명은 싸이할로호프와 메타미호프를 유효성분으로 하고 여기에 적당한 부형제로 담체 및 계면활성제를 혼합하여 제조된 제초제 조성물을 제공한다.In order to achieve the above object, the present invention provides a herbicide composition prepared by mixing the sihalhof and metamihof as an active ingredient and the carrier and the surfactant as a suitable excipient.

또한, 본 발명은 상기 제초제 조성물을 이용하여 화본과 잡초를 방제하는 방법을 제공한다.In addition, the present invention provides a method for controlling the flower and weeds using the herbicide composition.

이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.

본 발명은 하기화학식 1의 싸이할로호프와화학식 2의 메타미호프를 유효성분으로 하는 제초제 조성물을 제공한다.The present invention provides a herbicide composition comprising sihalofhof of formula 1 and metamihof of formula 2 as an active ingredient.

<화학식 1><Formula 1>

<화학식 2><Formula 2>

싸이할로호프와 메타미호프의 혼합조제시, 두 제초성분 총량을 기준으로 싸이할로호프의 함량은 5 내지 85 중량%가 바람직하고, 더욱 바람직하게는 15 내지 75 중량%이며, 메타미호프의 함량은 15 내지 95 중량%가 바람직하고, 더욱 바람직하게는 25 내지 85 중량%이다.When preparing a mixture of sihalhof and metamihof, the content of the cyhalhof is preferably 5 to 85% by weight, more preferably 15 to 75% by weight, based on the total amount of the two herbicidal components, metamihof The content of is preferably from 15 to 95% by weight, more preferably from 25 to 85% by weight.

본 발명의 제초제 조성물은 제제화를 돕기 위해 농약 분야에서 통상적으로 사용되는 담체를 추가로 포함할 수 있으며, 이 경우 전체 제초제 조성물 중 제초화합물의 함량은 2 내지 50 중량%, 바람직하게는 5 내지 20 중량%일 수 있다.The herbicide composition of the present invention may further include a carrier commonly used in the pesticide field to aid formulation, in which case the content of the herbicide compound in the total herbicide composition is 2 to 50% by weight, preferably 5 to 20% by weight. May be%.

본 발명에 따른 조성물 중의 담체는 목적하는 부위에 활성성분이 적용되는 것을 용이하게 하거나, 또는 저장을 간편하게, 또는 운반 또는 조작을 용이하게 조성시킬 수 있는 것이면 어떤 물질이든 무방하다. 담체는 보통은 기체이나, 액체를 형성하도록 압축된 물질을 포함하여, 액체 또는 고체일 수 있으며, 제초제 조성물을 형성하는데 일반적으로 사용되는 모든 담체를 사용할 수 있다.The carrier in the composition according to the present invention may be any material as long as it facilitates application of the active ingredient to the desired site, or facilitates storage, or facilitates transport or manipulation. The carrier is usually a gas, but may be liquid or solid, including materials compressed to form a liquid, and any carrier commonly used to form herbicide compositions can be used.

적절한 고체 담체로는 규조토 등의 천연 실리카와 같은 천연 및 합성 점토와 실리케이트류; 탈크와 같은 마그네슘 실리케이트류; 에터펄자이트 및 버미큘라이트와 같은 마그네슘 알루미늄 실리케이트류; 카올리나이트, 몬토모릴로나이트 및 운모와 같은 알루미늄 실리케이트류; 칼슘 카보네이트; 칼슘 설페이트; 암모늄 설페이트; 합성 수화 실리콘 옥사이드류 및 합성 칼슘 또는 알루미늄 실리케이트류; 탄소 및 황과 같은 원소; 쿠마론 수지, 폴리비닐 클로라이드 및 스티렌 폴리머류 및 코폴리머류와 같은 천연 및 합성수지; 고체 폴리클로로페놀류; 역청; 왁스류; 및 수퍼포스페이트류와 같은 고체 농약 등을 들 수 있다.Suitable solid carriers include natural and synthetic clays and silicates such as natural silica such as diatomaceous earth; Magnesium silicates such as talc; Magnesium aluminum silicates such as etherpulzite and vermiculite; Aluminum silicates such as kaolinite, montmorillonite and mica; Calcium carbonate; Calcium sulfate; Ammonium sulfate; Synthetic hydrated silicon oxides and synthetic calcium or aluminum silicates; Elements such as carbon and sulfur; Natural and synthetic resins such as coumarone resins, polyvinyl chloride and styrene polymers and copolymers; Solid polychlorophenols; bitumen; Waxes; And solid pesticides such as superphosphates.

적절한 액체 담체에는 물; 이소프로판올 및 글리콜류과 같은 알코올; 아세톤, 메틸 에틸 케톤, 메틸 이소부틸 케톤 및 시클로헥사논과 같은 케톤류; 에테르류; 벤젠, 톨루엔 및 크실렌과 같은 방향족 또는 아르지방족 탄화수소류; 케로신 및 경질 미네랄유와 같은 퍼트롤륨 분획; 사염화탄소, 퍼클로로에틸렌 및 트리클로로에탄과 같은 염소화 탄화수소류 등을 들 수 있다.Suitable liquid carriers include water; Alcohols such as isopropanol and glycols; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; Ethers; Aromatic or araliphatic hydrocarbons such as benzene, toluene and xylene; Pertrolium fractions such as kerosine and light mineral oils; Chlorinated hydrocarbons such as carbon tetrachloride, perchloroethylene and trichloroethane; and the like.

본 발명의 제초제 조성물은 종종 농축된 형태로 조성 및 유통되어 사용 전에 사용자에 의해 희석될 수 있다. 계면활성제인 담체가 소량 존재하면 이 희석 과정을 용이하게 해준다. 그러므로, 본 발명에 따른 조성물에 사용되는 담체들 중 적어도 한 가지는 계면활성제인 것이 바람직하다. 예컨대, 조성물은 적어도 두 가지의 담체를 함유할 수 있으며, 그 중 적어도 한 가지는 계면활성제인 것이 좋다.Herbicide compositions of the present invention are often formulated and distributed in concentrated form and can be diluted by the user prior to use. The presence of a small amount of carrier, a surfactant, facilitates this dilution process. Therefore, at least one of the carriers used in the composition according to the invention is preferably a surfactant. For example, the composition may contain at least two carriers, at least one of which is a surfactant.

계면활성제는 유화제, 분산제 또는 보습제일 수 있으며 이 계면활성제는 이온성 또는 비이온성일 수 있다. 적절한 계면활성제의 예로는 폴리아크릴산의 나트륨 또는 칼슘염류 및 리그닌 설폰산; 분자 중 탄소원자를 적어도 12개 함유하는 지방산 또는 지방족 아민 또는 아미드류와 에틸렌옥사이드 및/또는 프로필렌 옥사이드와의 축합생성물; 글리세롤의 지방산 에스테르, 소르비탄, 수크로스 또는 펜타에리쓰리톨; 에틸렌 옥사이드 및/또는 프로필렌 옥사이드와 이들과의 축합물; p-옥틸페놀 또는 p-옥틸크레졸과 에틸렌옥사이드 및/또는 프로필렌 옥사이드와의 축합생성물과 같은 지방알코올 또는 알킬 페놀류; 이들 축합 생성물의 설페이트류 또는 설포네이트류; 분자 내에 탄소원자를 적어도 10개 함유하는 황산 또는 설폰산 에스테르의 알칼리 또는 알칼리토 금속염, 바람직하게는 나트륨 염, 예컨대 라우릴황산나트륨, 2차 알킬 황산나트륨, 설폰화 카스터유의 나트륨염, 및 도데실벤젠 설포네이트와 같은 알킬아릴설폰산 나트륨; 및 에틸렌옥사이드의 폴리머류 및 에틸렌옥사이드와 프로필렌 옥사이드와의 코폴리머류를 들 수 있다.The surfactant may be an emulsifier, dispersant or moisturizer and the surfactant may be ionic or nonionic. Examples of suitable surfactants include sodium or calcium salts of polyacrylic acid and lignin sulfonic acid; Condensation products of fatty acids or aliphatic amines or amides containing at least 12 carbon atoms in a molecule with ethylene oxide and / or propylene oxide; Fatty acid esters of glycerol, sorbitan, sucrose or pentaerythritol; Ethylene oxide and / or propylene oxide and their condensates; fatty alcohols or alkyl phenols such as condensation products of p-octylphenol or p-octylcresol with ethylene oxide and / or propylene oxide; Sulfates or sulfonates of these condensation products; Alkali or alkaline earth metal salts of sulfuric acid or sulfonic acid esters containing at least 10 carbon atoms in the molecule, preferably sodium salts such as sodium lauryl sulfate, secondary alkyl sodium sulfate, sodium salts of sulfonated castor oil, and dodecylbenzene sulfo Sodium alkylarylsulfonates such as nates; And polymers of ethylene oxide and copolymers of ethylene oxide and propylene oxide.

본 발명의 조성물은 제초효과를 극대화시키고 처리를 간편하게 하기 위하여 다른 보조 화합물을 추가로 혼합할 수 있을 뿐만 아니라 유제, 수화제, 수용제, 입제, 방출조절제, 점보제 등 여러 가지의 제제화가 가능하다. 이들 제제들은 직접 사용될 수 있고 적절한 매체에 희석하여 처리할 수 있다.The composition of the present invention can be mixed with other auxiliary compounds to maximize the herbicidal effect and simplify the treatment, as well as various formulations such as emulsions, wetting agents, water solubles, granules, release control agents, jumbo agents. These formulations can be used directly and can be processed by dilution in appropriate media.

본 발명의 제초제 조성물은 싸이할로호프와 메타미호프를 유효성분으로 함유하여 화본과 잡초의 방제에 효과적인 향상된 방제활성을 갖는다.The herbicide composition of the present invention contains cyhalofhof and metamihof as active ingredients, and has an improved control activity effective for controlling plants and weeds.

본 발명의 제초제 조성물의 방제활성을 조사한 결과, 싸이할로호프와 메타미호프를 여러 가지 농도별로 혼합하여 화본과 잡초에 경엽처리하면 방제활성 발현속도가 빨라지고 방제효과도 뚜렷한 상승작용을 나타내면서 높아진다. 또한, 본 발명의 조성물은 담수조건에서 자라고 있는 피에 대해서도 동일한 방제효과를 나타낸다. 싸이할로호프와 메타미호프의 혼합제형을 처리하는 경우 각각의 단일제형을 처리하는 경우에 비하여 방제활성 발현속도가 2배정도 빨라지는 경향을 나타내며, 특히 메타미호프의 단일제형 보다는 탁월한 방제효과를 나타낸다. 따라서, 본 발명의 싸이할로호프와 메타미호프 혼합 제초제 조성물은 벼 재배시 화본과 잡초를 방제하는데 특히 유용하며 포장에서 발생량이 많은 피를 효과적으로 방제하는데 보다 탁월한 효과를 거둘 수 있어 벼 재배시의 노동력을 적게 투입하면서 수확량 증진을 꾀할 수 있다.As a result of investigating the control activity of the herbicide composition of the present invention, when the hahalhof and metamihof are mixed at various concentrations and treated with foliage on the flower beds and weeds, the expression rate of the control activity is increased and the control effect is also markedly increased. In addition, the composition of the present invention shows the same control effect on the blood growing in fresh water conditions. When the mixed formulation of sihalhof and metamihof is treated, the expression rate of the control activity is about 2 times faster than that of each single formulation, and in particular, the control effect is superior to that of metamihof. Indicates. Thus, the sihalhof and metamihof mixed herbicide compositions of the present invention are particularly useful for controlling plants and weeds during rice cultivation, and have an excellent effect in effectively controlling the blood generated in the package effectively. Increasing yields can be achieved with fewer feeds.

또한, 본 발명은 상기 제초제 조성물을 이용하여 화본 및 잡초를 효과적으로 방제하는 방법을 제공한다.In addition, the present invention provides a method for effectively controlling flowers and weeds using the herbicide composition.

본 발명의 싸이할로호프와 메타미호프 혼합제형의 제초제 조성물은 피 (Barnyardgrass), 존슨그래스 (Johnsongrass), 수수 (Shattercane), 개기장 (Fall panicum), 드렁새 (Chinese sprangletop), 우산잔듸 (Burmudagrass), 바랭이 (Large crabgrass), 강아지풀 (Green foxtail), 금강아지풀 (Yellow foxtail), 조개풀 (Jointhead arthraxon), 메귀리 (Wild oat), 야생옥수수 (Corn), 왕바랭이 (Goosegrass), 그령 (Eragrostis), 둑새풀 (Water foxtail), 오리새 (Orchardgrass), 카나리새풀 (Canarygrass), 쥐꼬리둑새풀 (Blackgrass), 물참새피 (Jointgrass), 새포아풀 (Annual bluegrass), 참새귀리 (Japanese brome), 개밀 (Quackgrass) 또는 기타 화본과 잡초를 방제하는데 유용하게 사용될 수 있다.The herbicide composition of the Sihalofhof and Metamihof formulations of the present invention may be used as Barnyardgrass, Johnsongrass, Shattercane, Fall panicum, Chinese sprangletop, Umbrella grass ( Burmudagrass, Large crabgrass, Green foxtail, Yellow foxtail, Seashell (Jointhead arthraxon), Wild oat, Corn, Corn, Goosegrass, Erragrostis ), Water foxtail, Orchardgrass, Canarygrass, Canarygrass, Blackgrass, Jointgrass, Annual bluegrass, Japanese brome, Wheatgrass Or it can be usefully used to control other flowers and weeds.

본 발명의 제초제 조성물은 벼를 비롯한 작물의 지상부에 분무 또는 살포하여 경엽처리하거나 담수조건에서 수면 처리하여 화본과 식물이나 잡초를 방제할 수 있다. 이때, 살포되는 제초제 조성물의 유효량은 잡초의 종류, 생육단계, 처리조건 (담수조건, 건답조건), 환경조건, 보조제 사용 여부에 따라 달라질 수 있으며, 내성잡초, 생육 후기단계, 담수조건, 보조제 무사용시에는 상대적으로 높은 처리량이 필요하다. 예를 들어, 온실조건에서 경엽처리에 의한 피 방제의 경우 본 발명의 제초제 조성물을 물 14 ㎖에 혼합하여 350 ㎠ 넓이의 면적에 골고루 분무하고, 담수조건에서 수면처리에 의한 피 방제의 경우 본 발명의 제초제 조성물을 물 4 ㎖에 혼합하여 140 ㎠ 넓이의 면적에 골고루 분무하여 싸이할로호프와 메타미호프의 최종 살포농도 (유효성분)가 7.5 내지 300 g ai/ha가 되도록 하는 것이 바람직하다. 본 발명의 제초제 조성물의 화본과 잡초 방제를 위한 처리 적기는 2 내지 6엽기 범위로 광범위한 제초 처리시기 스펙트럼을 나타낸다.The herbicide composition of the present invention can be sprayed or sprayed on the ground of crops, including rice, by the foliage treatment or by surface treatment in fresh water conditions to control the flowers and plants or weeds. At this time, the effective amount of the herbicide composition to be sprayed may vary depending on the type of weeds, growth stages, treatment conditions (freshwater conditions, dry conditions), environmental conditions, and the use of supplements, resistant weeds, late stages of growth, freshwater conditions, no additives In use, relatively high throughput is required. For example, the herbicide composition of the present invention is mixed with 14 ml of water and sprayed evenly over an area of 350 cm 2 area in the case of greenhouse control in the greenhouse conditions, the present invention in the case of the control by sleep treatment in fresh water conditions It is preferable to mix the herbicide composition of to 4 ml of water and spray evenly over an area of 140 cm 2 area so that the final spraying concentration (active ingredient) of the Cyhalhof and Metamihof is 7.5 to 300 g ai / ha. Treatment timelines for the weed control and weed control of the herbicidal compositions of the present invention exhibit a broad spectrum of herbicide treatment timing in the 2-6 leaf phase.

본 발명의 싸이할로호프와 메타미호프를 유효성분으로 하는 제초제 조성물은 하기와 같은 직·간접적인 효과로 인해 특히 벼 재배시의 경제적 파급효과는 매우 클 것으로 판단된다.The herbicide composition comprising the sihalhof and metamihof of the present invention as an active ingredient is considered to have a very large economic ripple effect, particularly in rice cultivation, due to the following direct and indirect effects.

첫째, 벼 재배시 지속적으로 다량 발생하는 피는 효과적인 방제가 어려운 초종으로 알려져 있는데, 과거에는 퀸클로락을 피 방제 전문용으로 후기 처리시 사용했지만 이는 후작물에 대한 부작용으로 인해 그 사용이 금지되어 현재는 후기 처리용 피 방제제가 없는 상태이다. 따라서, 본 발명의 제초제 조성물은 어린 시기부터 늦은 엽기의 피를 효과적으로 방제하여 광범위한 제초 처리시기 스펙트럼을 나타내기 때문에 피 방제 후기 처리용으로도 유용하게 사용할 수 있으며, 싸이할로호프의 단독 처리시에 염려되는 후기 재생도 적어 방제효과가 높다.First, it is known that it is difficult to effectively control the blood which is continuously generated during rice cultivation. In the past, quinclorac was used for the later treatment as a blood control specialist, but it is banned because of its side effect on crops. Is the absence of a control agent for later treatment. Therefore, the herbicide composition of the present invention can be effectively used for the late treatment of blood control because it effectively controls the blood of the late leafy stage and exhibits a broad spectrum of herbicide treatment time. There is also little worry about late regeneration, which is highly effective.

둘째, 본 발명의 제초제 조성물은 싸이할로호프와 메타미호프의 혼합 비율이 대략 3:1 내지 1:5 범위인 경우 혼합제형과 단일제형간의 동량 처리에서도 혼합제형 처리에서 더 높은 제초효과를 나타낸다. 따라서, 생산단가가 상대적으로 높은 메타미호프 대신 보다 가격이 저렴한 싸이할로호프로 일부를 대체하여 동일한 제초효과를 거둘 수 있기 때문에 원제 비용이 절감되어 생산 단가가 저렴해진다.Second, the herbicide composition of the present invention exhibits a higher herbicidal effect in the mixed formulation treatment even when the mixing ratio of the sihalhof and metamihof is in the range of about 3: 1 to 1: 5 even in the same amount treatment between the mixed formulation and the single formulation. . Therefore, the cost of the raw material is reduced and the production cost is lowered because the same herbicidal effect can be obtained by substituting a part of the cheaper Cyhalhof instead of the relatively high metamihof.

셋째, 본 발명에서와 같은 싸이할로호프와 메타미호프의 조합은 상승적인 제초작용을 나타내기 때문에 결국 환경에로의 제초제 투입량을 감소시킬 수 있어 인축독성, 어독성, 환경독성 측면에서 유리한 특성을 갖는다.Third, since the combination of sihalhof and metamihof as shown in the present invention shows synergistic herbicidal action, it is possible to reduce herbicide input into the environment, which is advantageous in terms of phosphorus toxicity, fish toxicity, and environmental toxicity. Has

이하, 본 발명을 실시예에 의해 상세히 설명한다.Hereinafter, the present invention will be described in detail by way of examples.

단, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기 실시예에 한정되는 것은 아니다.However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited to the following examples.

<실시예 1> 싸이할로호프와 메타미호프 혼합제형의 밭조건 경엽처리Example 1 Field Condition Foliage Treatment of Cyhalhof and Metamihof Mixture

벼를 비롯한 작물 재배시에 문제가 된다고 알려진 대표적인 몇 가지 화본과 잡초를 밭조건에서 키운 후, 싸이할로호프와 메타미호프를 여러 가지 농도별로 혼합하여 제조한 혼합제형을 경엽 처리하였을 때 제초효과에 대한 이들의 상호작용이 어떻게 나타나는지를 조사하였다.Several plants and weeds that are known to be a problem when growing crops including rice are grown in field conditions, and then mixed formulations prepared by mixing Cyhalhof and Metamihof at various concentrations are applied to the herbicidal effect. We investigated how their interaction with each other appeared.

구체적으로, 피, 조개풀, 왕바랭이, 메귀리, 바랭이, 강아지풀, 미국개기장, 새포아풀의 잡초종자를 (표 1) 350 ㎠ 사각 폿트에 파종한 후 온실조건 (주간 온도 25 내지 35℃/ 야간온도 20 내지 25℃)에 두어 생육시켰다. 파종 후 2주쯤 경과되어 피가 3엽 말기 내지 4엽 초기에 이르렀을 때 싸이할로호프 (미국특허등록 제 4894085 호에 기재된 바에 따라 합성) 및 메타미호프 (한국특허출원 제 1999-30067 호에 기재된 바에 따라 합성) 단일제형과 이들의 혼합제형 각각을 살포기를 이용하여 14 ㎖/350 ㎠ 폿트 수준으로 처리하였다. 상기 제형들은 각각의 유효성분을 칭량하여 아세톤에 용해시킨 후 이를 계면활성제로 트윈-20을 함유하는 증류수에 희석하여 해당 농도가 되도록 혼합하여 만들었다. 용액내의 아세톤 및 트윈-20의 최종농도는 각각 50% 및 0.1%였으며 이 수준에서 약해는 관찰되지 않았다. 기타 실험방법은 한국화학연구원에서 시행하고 있는 제초제 온실 스크리닝의 표준시험법에 따라 수행하였다 (농약스크리닝 Ⅲ, 특정연구개발사업보고서 (한국화학연구소), 1995). 단일제형 및 혼합제형을 잡초에 처리한 후 온실조건에 9일간 두면서 시간 경과별로 제초효과를 달관조사하여 퍼센트 단위로 나타내었다 (0%: 약효가 전혀 없음, 100%: 완전 방제). 그 후 화합물의 상호작용을 콜비 방법 (Colby S. R.,Weeds15:20-22, 1967)으로 하기 수학식 1에 따라 평가하였고, 그 결과를 하기표 2에 나타내었다.Specifically, weed seeds of blood, clam grass, king leek, buckwheat, leek, pup grass, american dog breed, and sapphire grass (Table 1) Seeded in 350 cm 2 square pot and grown under greenhouse conditions (weekly temperature 25-35 ° C./night temperature 20-25 ° C.). 2 weeks after sowing, when the blood reaches the end of the 3rd to the 4th leaf, the Cyhalhof (synthesized as described in US Patent No. 4894085) and Metamihof (Korean Patent Application No. 1999-30067) Synthesized as described) Each of the single and mixed formulations were dispensed using a spreader to 14 ml / 350 cm 2. Treated to the pot level. The formulations were prepared by weighing and dissolving each active ingredient in acetone, then diluting it in distilled water containing Tween-20 as a surfactant and mixing it to the corresponding concentration. Final concentrations of acetone and tween-20 in the solution were 50% and 0.1%, respectively, and no harm was observed at this level. Other experiments were carried out in accordance with the standard test method of herbicide greenhouse screening conducted by the Korea Research Institute of Chemical Technology (Pesticide Screening III, Report of Specific Research and Development Project (Korea Research Institute of Chemical Technology), 1995). Single and mixed formulations were treated in weeds and placed in greenhouse conditions for nine days, and the herbicidal effects were observed over time, expressed in percent (0%: no efficacy, 100%: complete control). Subsequent interactions of the compounds were carried out by the Colby method (Colby S. R.,Weeds15: 20-22, 1967) and evaluated according to Equation 1 below.TABLE 2Shown in

E (기대값) = X + Y - XY/100E (expected value) = X + Y-XY / 100

X = 싸이할로호프의 A 농도에서의 방제가 (%)X = control at Cy concentration in A concentration (%)

Y = 메타미호프의 B 농도에서의 방제가 (%)Y = control at B concentration of metamihof (%)

만일 혼합제형의 처리에 의해 나타난 실제의 방제가 (실측값, observed value)가 기대값 (E값) 보다 클 경우는 상승작용, 같을 경우는 상가작용, 작을 경우는 길항작용을 나타내는 것이다.If the actual control indicated by the treatment of the mixed formulation is greater than the expected value (E value), then synergism, equivalent addition, and antagonism if smaller.

학명Scientific name 일반명 (영명)Common name (English name) Echinochloa crus-galliP. BeauvArthraxon hispidusMakinoEleusine indica(L.) GaertnAvena fatuaL.Digitaria sanguinalis(L.) Scop.Setaria viridisP. BeauvPanicum dichotomiflorumMichx.Poa annuaL. Echinochloa crus-galli P. Beauv Arthraxon hispidus Makino Eleusine indica (L.) Gaertn Avena fatua L. Digitaria sanguinalis (L.) Scop. Setaria viridis P. Beauv Panicum dichotomiflorum Michx. Poa annua L. 피 (Barnyardgrass)조개풀 (Jointhead arthraxon)왕바랭이 (Goosegrass)메귀리 (Wild oat)바랭이 (Large crabgrass)강아지풀 (Green foxtail)미국개기장 (Fall panicum)새포아풀 (Annual bluegrass)BarnyardgrassJointhead arthraxonGoosegrassWild oatLarge crabgrassLarge foxtailFall panicumAnnual bluegrass

C + K1)(g ai/ha)C + K 1) (g ai / ha) 화본과 잡초의 종류2) Types of flowers and weeds 2) 평균방제가(%)3) Average Controlled Price (%) 3) 기대값4)(E)Expected value 4) (E) 피blood 조개풀Shellfish 왕바랭이King 메귀리Mekong 바랭이wire grass 강아지풀Foxtail 미국개기장United States 새포아풀Sappoul 0+00+3.80+7.50+150+300 + 00 + 3.80 + 7.50 + 150 + 30 00023550002355 00010250001025 00815180081518 0000000000 00513400051340 000015000015 0005800058 0000000000 001.68.320.1001.68.320.1 001.68.320.1001.68.320.1 7.5+07.5+3.87.5+7.57.5+157.5+307.5 + 07.5 + 3.87.5 + 7.57.5 + 157.5 + 30 20253570952025357095 0020506500205065 20233060752023306075 000020000020 1515358010015153580100 00015550001555 10151550831015155083 0000000000 8.19.816.940.661.68.19.816.940.661.6 8.18.19.615.726.68.18.19.615.726.6 0+015+3.815+7.515+1515+300 + 015 + 3.815 + 7.515 + 1515 + 30 3535608010035356080100 18202028681820202868 30304568753030456875 108253550108253550 3548639010035486390100 30404545703040454570 50506085905050608590 00013230001323 2628.939.855.572.02628.939.855.572.0 26.026.027.232.140.926.026.027.232.140.9 30+030+3.830+7.530+1530+3030 + 030 + 3.830 + 7.530 + 1530 + 30 4040609310040406093100 18151830401815183040 40607070754060707075 20506060602050606060 556575100100556575100100 60606580936060658093 6570708510065707085100 0010203000102030 37.345.053.567.374.837.345.053.567.374.8 37.337.338.342.449.937.337.338.342.449.9 60+060+3.860+7.560+1560+3060 + 060 + 3.860 + 7.560 + 1560 + 30 6075809010060758090100 20233540702023354070 60758070856075807085 60606065706060606570 6075809010060758090100 65707380906570738090 6570808010065708080100 0010203000102030 48.856.062.366.980.648.856.062.366.980.6 48.848.849.653.059.148.848.849.653.059.1 1) C+K: 싸이할로호프 + 메타미호프;ai: 제초 활성성분 (active ingredient)2) 화본과 잡초종의 약어에 대한 해설은표 1에 나타나 있음.3) 제초제 처리 후 9일째의 화본과 잡초 전체에 대한 방제가의 평균4) 각 처리농도 조합에서의 콜비 방법에 의해 계산된 기대값1) C + K: cyhalohof + metamihof; ai: active ingredient herbicides 2) Explanations of the abbreviations of the flower and weed species are shown in Table 1. 3) 4) Expected value calculated by Colby method at each treatment concentration combination

그 결과,표 2에서 보는 바와 같이, 단일제형의 처리보다는 혼합제형의 처리에서 보다 빠른 제초활성을 보였고 농도조합에 따라 정도 차이가 있지만 분명한 상승작용이 관찰되었다. 예를 들면, 처리 후 9일째 검정의 경우 메타미호프 30 g 단독 처리에서는 20.1%의 방제가를, 싸이할로호프 15 g 단독 처리에서는 26%의 방제가를 나타낸 반면, 메타미호프 30 g과 싸이할로호프 15 g를 혼합 처리한 경우에는 72%의 높은 방제가를 나타내었다.As a result, as shown in Table 2 , it showed faster herbicidal activity in the treatment of the mixed formulation than in the treatment of a single formulation, and apparent synergism was observed although there was a degree of difference depending on the concentration combination. For example, on day 9 post-treatment assays, 20.1% control value was shown for metamihof 30 g alone and 26% control value for 15 g single treatment with Cyhalhof, whereas When 15 g of Sihalhof was mixed, a high control value of 72% was obtained.

<실시예 2> 싸이할로호프와 메타미호프 혼합제형의 담수조건 수면처리Example 2 Freshwater Condition Sleep Treatment of Cyhalhof and Metamihof Mixtures

논 토양에 적당량의 비료를 혼합하고 물을 부어 곤죽을 만든 후 시험용 폿트 (140 ㎠)에 일정량의 곤죽을 담았다. 벼와 피 종자를 파종하고 잘 다져서 종자가 토양 내에 혼입되도록 한 후 3 ㎝ 깊이로 담수하였다. 이를 온실조건에 두어 10일 동안 키워 피가 2엽기가 되었을 때 상기 실시예 1과 같이 제조된 단일제형 및 혼합제형을 수면에 점적처리하였다. 처리 후 2주간 키우면서 시간 경과별로 제초효과를 달관조사하여 퍼센트 단위로 나타내었다 (0%: 약효가 전혀 없음, 100%: 완전 방제). 그 후 화합물의 상호작용을 상기 실시예 1과 동일한 방법으로 평가하였고, 그 결과를 하기표 3에 나타내었다.An appropriate amount of fertilizer was mixed in the paddy soil, water was poured into the rice cake, and a pot of rice was put in a pot for testing (140 cm 2). Rice and seed were sown and compacted to allow seed to be incorporated into the soil, and then freshwater to a depth of 3 cm. It was placed in a greenhouse condition and grown for 10 days, when the blood became a two-leaf phase. The single and mixed formulations prepared as in Example 1 were dipped into the water. After two weeks of treatment, the herbicidal effect was examined over time as a percentage (0%: no effect, 100%: complete control). Thereafter, the interaction of the compound was evaluated in the same manner as in Example 1, and the results are shown in Table 3 below.

싸이할로호프처리량(g ai/ha)Cyhalhof throughput (g ai / ha) 메타미호프 처리량 (g ai/ha)Metamihof throughput (g ai / ha) 00 1515 3030 6060 120120 처리 후 8일째 검정Assay 8 days after treatment 0306012024003060120240 0.015.036.761.765.00.015.036.761.765.0 10.023.3 (23.5)68.3 (43.0)80.0 (65.5)71.7 (68.5)10.023.3 (23.5) 68.3 (43.0) 80.0 (65.5) 71.7 (68.5) 15.036.7 (27.8)68.3 (46.2)83.3 (67.4)88.3 (70.3)15.036.7 (27.8) 68.3 (46.2) 83.3 (67.4) 88.3 (70.3) 16.748.3 (29.2)76.7 (47.2)85.0 (68.1)88.3 (70.8)16.748.3 (29.2) 76.7 (47.2) 85.0 (68.1) 88.3 (70.8) 15.046.7 (27.8)88.3 (46.2)88.3 (79.6)93.3 (70.3)15.046.7 (27.8) 88.3 (46.2) 88.3 (79.6) 93.3 (70.3) 처리 후 14일째 검정14 days post-treatment 0306012024003060120240 0.08.311.740.050.00.08.311.740.050.0 0.08.3 (8.3)28.3 (11.7)75.0 (40.0)56.7 (50.0)0.08.3 (8.3) 28.3 (11.7) 75.0 (40.0) 56.7 (50.0) 6.716.7 (14.4)41.7 (17.6)76.7 (44.0)85.0 (53.3)6.716.7 (14.4) 41.7 (17.6) 76.7 (44.0) 85.0 (53.3) 6.733.3 (14.4)63.3 (17.6)80.0 (44.0)93.3 (53.3)6.733.3 (14.4) 63.3 (17.6) 80.0 (44.0) 93.3 (53.3) 10.043.3 (17.5)81.7 (20.5)83.3 (66.0)100 (55.0)10.043.3 (17.5) 81.7 (20.5) 83.3 (66.0) 100 (55.0) * 괄호 안의 숫자는 콜비 방법에 의해 계산된 기대값을 나타낸 것으로, 관측값 (방제가)이 기대값 보다 클 경우 상승적 효과가 있음.* The numbers in parentheses represent the expected values calculated by the Colby method, which has a synergistic effect if the observed value is greater than the expected value.

그 결과,표 3에서 보는 바와 같이, 단독제형과 혼합제형 모두에서 벼에 대한 약해는 전혀 나타나지 않았으며, 피에 대한 방제가의 경우 단독제형의 처리보다는 혼합제형의 처리에서 보다 빠른 방제활성을 보였고 농도조합에 따라 정도 차이가 있지만 분명한 상승작용이 관찰되었다. 예를 들면, 처리 후 8일째 검정의 경우 메타미호프 120 g의 단독 처리에서는 15%의 방제가를, 싸이할로호프 60 g의 단독처리에서는 36.7%의 방제가를 나타낸 반면, 메타미호프 120 g과 싸이할로호프 60 g을 혼합하여 처리한 경우에는 88.3%의 방제가를 나타내었다. 처리 후 14일째 검정의 경우 메타미호프 60 g의 단독 처리에서는 6.7%의 방제가를, 싸이할로호프 240 g의 단독 처리에서는 50%의 방제가를 나타낸 반면, 메타미호프 60 g과 싸이할로호프 240 g를 혼합하여 처리한 경우에는 93.3%의 방제가를 나타내었다.As a result, as shown in Table 3 , there was no weakness against rice in both the single formulation and the mixed formulation, and the control against blood showed faster control activity in the mixed formulation than in the single formulation. Although there was a degree of difference in the concentration combinations, a clear synergy was observed. For example, on day 8 post-treatment assays, 15% control value was shown for metamihof 120 g alone and 36.7% control value for 60 g of Cyhalhof, whereas metamihof 120 When g and 60 g of hahalhof were mixed and treated, 88.3% of control value was obtained. On day 14 post-treatment assay, 6.7% control value was obtained for 60 g of metamihof alone, and 50% control value for only 240 g of cyhalhof was compared with 60 g of metamihof. When treated with a mixture of 240 g of Rohof, the control value was 93.3%.

한편, 실시예 1의 경엽처리 결과와 비교할 때, 본 발명의 혼합제형을 담수조건에 처리할 때는 제초효과 발현이 늦고 동일한 제초효과를 유지하는데 더욱 많은 처리량이 요구되었다.On the other hand, compared with the results of the foliage treatment of Example 1, when treating the mixed formulation of the present invention in fresh water conditions, the herbicidal effect was slow to develop and more throughput was required to maintain the same herbicidal effect.

<실시예 3> 싸이할로호프와 메타미호프 혼합제형의 농도별 방제효과<Example 3> Control effect of each concentration of the Cyhalohof and Metamihof formulation

싸이할로호프와 메타미호프를 여러 가지 농도별로 혼합하여 피의 경엽부에 처리하였을 때 제초효과에 대한 이들의 상호작용을 조사하기 위하여 하기와 같은 실험을 수행하였다.The following experiments were carried out to investigate their interactions with herbicidal effects when cyhalhof and metamihof were mixed at various concentrations and treated in the foliage of blood.

구체적으로, 피 종자를 350 ㎠ 사각 폿트에 파종한 후 온실조건 (주간 온도 25-35℃/ 야간온도 20-25℃)에 두어 생육시켰다. 파종 후 2주쯤 경과되어 피가 3엽 말기 내지 4엽 초기에 이르렀을 때 제초제 혼합제형을 살포기를 이용하여 14 ㎖/350 ㎠ 폿트 수준으로 처리하였다. 상기 혼합제형은 각각의 유효성분을 칭량하여 아세톤에 용해시킨 후 트윈-20이 포함된 증류수에 희석하여 해당 농도가 되도록 혼합하였다. 용액내의 아세톤 및 트윈-20의 최종농도는 각각 50% 및 0.1%였으며 이 수준에서 약해는 관찰되지 않았다. 기타 실험방법은 한국화학연구원에서 시행하고 있는 제초제 온실 스크리닝의 표준시험법에 따라 수행하였다 (농약스크리닝 Ⅲ, 특정연구개발사업보고서 (한국화학연구소), 1995). 상기 혼합제형을 잡초에 처리한 후 온실조건에 2주간 두면서 시간 경과별로 경엽의 황화고사 정도를 달관조사하여 퍼센트 단위로 나타내었다 (0%: 약효가 전혀 없음, 100%: 완전 방제). 그 후 화합물의 상호작용을 상기 실시예 1과 동일한 방법으로 평가하였고 이를도 1에 나타내었다. 여기서, 실선 상단에 있는 점들은 상승작용을, 실선 하단에 있는 점들은 길항작용을, 실선 선상에 있는 점들은 상가작용을 나타낸다.Specifically, seeds were sown in 350 cm 2 square pots and grown under greenhouse conditions (weekly temperature 25-35 ° C./night temperature 20-25 ° C.). 2 weeks after sowing, when the blood reaches the end of the 3rd to the 4th leaf, the mixture of herbicide is 14 ml / 350 cm2 using a sprayer. Treated to the pot level. In the mixed formulation, each of the active ingredients was weighed and dissolved in acetone, and then diluted in distilled water containing Tween-20 and mixed to a corresponding concentration. Final concentrations of acetone and tween-20 in the solution were 50% and 0.1%, respectively, and no harm was observed at this level. Other experiments were carried out in accordance with the standard test method of herbicide greenhouse screening conducted by the Korea Research Institute of Chemical Technology (Pesticide Screening III, Report of Specific Research and Development Project (Korea Research Institute of Chemical Technology), 1995). The mixed formulation was treated in weeds and placed in greenhouse conditions for two weeks, and the degree of sulphide death of the foliage was examined over a period of time. Then the interaction of the compound was evaluated in the same manner as in Example 1 and this1Shown in Here, the points at the top of the solid line represent synergy, the points at the bottom of the solid line represent antagonism, and the points on the solid line represent additive action.

도 1에서 보는 바와 같이, 싸이할로호프와 메타미호프의 혼합 처리에 의해 높은 상승작용이 관찰되었으며, 이러한 상승작용은 처리 후 4 내지 6일째에 강하게 나타났다.As shown in Fig. 1 , a high synergy was observed by the mixing treatment of the Cyhalhof and Metamihof, and this synergy was strong 4 to 6 days after the treatment.

<실시예 4> 싸이할로호프와 메타미호프 혼합제형의 방제활성 발현속도Example 4 Expression of Control Activity of Cyhalohof and Metamihof Formulations

싸이할로호프와 메타미호프를 여러 가지 농도별로 혼합하여 피의 경엽부에 처리하였을 때 방제활성 발현속도에 대한 이들의 상호작용을 조사하기 위하여 하기와 같은 실험을 수행하였다.The following experiments were performed to investigate their interactions with the control activity expression rate when Cyhalhof and Metamihof were mixed at various concentrations and treated in the foliage of blood.

구체적으로, 피 종자를 350 ㎠ 사각 폿트에 파종한 후 온실조건 (주간 온도 25-35℃/ 야간온도 20-25℃)에 두어 생육시켰다. 파종 후 2주쯤 경과되어 피가 3엽 말기 내지 4엽 초기에 이르렀을 때 싸이할로호프 10 g + 메타미호프 20 g, 싸이할로호프 20 g + 메타미호프 20 g의 혼합제형과 싸이할로호프 10 g, 싸이할로호프 20 g, 메타미호프 20 g의 단독제형 각각을 살포기를 이용하여 폿트당 14 ㎖ 수준으로 처리하였다. 기타 방법은 실시예 3과 동일한 방법으로 수행하였다. 상기 제형들을 피에 처리한 후 온실조건에 2주간 두면서 시간 경과별로 경엽의 황화고사 정도를 달관조사하였고 이를 퍼센트 단위로 나타내었다 (0%: 약효가 전혀 없음, 100%: 완전 방제).Specifically, seeds were sown in 350 cm 2 square pots and grown under greenhouse conditions (weekly temperature 25-35 ° C./night temperature 20-25 ° C.). Two weeks after sowing, when the blood reaches the end of the 3rd to the 4th leaf, Sihalhof 10 g + Metamihof 20 g, Cyhalhof 20 g + Metamihof 20 g Each of the single formulations of Rohof, 20 g of Cyhalhof, and 20 g of Metamihof were treated to a level of 14 ml per pot using a sparger. Other methods were carried out in the same manner as in Example 3. The formulations were treated with blood and placed in greenhouse conditions for two weeks, and the degree of sulphide death of the foliage was examined over time and expressed in percent (0%: no effect, 100%: complete control).

제초제 유효성분량C+K1)(g ai/ha)Herbicide active ingredient C + K 1) (g ai / ha) 처리 후 일수Days after processing 44 55 66 77 99 1414 C0 + K20C10 + K20C20 + K20C10 + K0C20 + K0C0 + K20C10 + K20C20 + K20C10 + K0C20 + K0 0.0±0.0*37.5±2.535.0±2.93.8±2.45.0±2.00.0 ± 0.0 * 37.5 ± 2.535.0 ± 2.93.8 ± 2.45.0 ± 2.0 6.3±1.355.0±2.953.0±0.03.8±2.43.8±1.36.3 ± 1.355.0 ± 2.953.0 ± 0.03.8 ± 2.43.8 ± 1.3 10.0±0.062.5±2.567.5±3.25.0±2.95.0±2.010.0 ± 0.062.5 ± 2.567.5 ± 3.25.0 ± 2.95.0 ± 2.0 22.5±6.375.0±2.986.3±3.85.0±2.96.3±2.422.5 ± 6.375.0 ± 2.986.3 ± 3.85.0 ± 2.96.3 ± 2.4 32.5±4.387.5±2.592.5±3.210.0±0.018.8±1.332.5 ± 4.387.5 ± 2.592.5 ± 3.210.0 ± 0.018.8 ± 1.3 65.0±6.596.3±2.495.0±2.022.5±2.542.5±7.565.0 ± 6.596.3 ± 2.495.0 ± 2.022.5 ± 2.542.5 ± 7.5 * 데이터는 3반복의 방제활성 평균치 ±표준편차로 나타냄.1) C+K: 싸이할로호프 + 메타미호프* Data is expressed as mean of average of three repetitive control activities ± standard deviation. 1) C + K: Cyhalofov + Metamihof

상기표 4에 나타난 바와 같이, 경엽의 황화고사 정도를 보면 싸이할로호프 10 g, 싸이할로호프 20 g 및 메타미호프 20 g이 각각 단독으로 처리된 경우 방제활성이 매우 늦게 나타나 처리 후 9일째에 각각 8%, 20% 및 38%를 나타낸 반면, 싸이할로호프 10 g + 메타미호프 20 g 및 싸이할로호프 20 g + 메타미호프 20 g의 혼합제형 처리에서는 각각 88% 및 95%의 방제활성을 보여 발현 속도가 매우 빨랐다. 즉, 약제 처리 후 경엽의 황화고사가 40% 정도 나타나는 기간을 비교할 때, 싸이할로호프나 메타미호프를 단독으로 처리하는 경우에는 각각 13.5일 또는 10일이 소요되지만 싸이할로호프와 메타미호프를 혼합하여 처리하는 경우에는 4일이면 충분하였다.As shown in Table 4 , the degree of sulfidation of the leaves showed that the control activity was very late when 10 g of Cyhalhof, 20 g of Cyhalhof and 20 g of Metamihof were treated alone, respectively. 8%, 20%, and 38%, respectively, on day 1, whereas 88% and 95, respectively, in the mixed formulation treatment of 10 g of Cyhalhof + 20 g of Metamihof and 20 g of Cyhalhof + 20 g of Metamihof, respectively. The rate of expression was very fast with% control activity. In other words, when comparing the period when the yellowing of the leaves showed about 40% of sulphide, the treatment with Cyhalhof or Metamihof alone takes 13.5 days or 10 days, respectively. 4 days was sufficient when the hops were mixed and treated.

<실시예 5> 싸이할로호프와 메타미호프의 혼합처리 비율에 따른 경엽처리에서의 방제활성Example 5 Control Activity in Foliar Treatment According to the Mixing Ratio of Cyhalhof and Metamihof

일반적으로 혼합제형이 실용화되기 위해서는 상승적인 방제작용이 나타난다 할지라도 혼합제형에 함유되는 유효성분의 함량이 단독제형의 경우보다 더 낮은 것이 바람직하다. 이를 확인하기 위하여, 최종적인 제초제 유효성분의 함량을 고정시키고 두 제초제 성분의 혼합비율을 달리하여 방제효과를 비교하였다.In general, in order for the mixed formulation to be commercialized, even if synergistic control action appears, the content of the active ingredient contained in the mixed formulation is preferably lower than that of the single formulation. To confirm this, the final herbicide content of the active ingredient was fixed, and the control effect was compared by varying the mixing ratio of the two herbicide components.

구체적으로, 피 종자를 350 ㎠ 사각 폿트에 파종한 후 온실조건 (주간 온도 25-35℃/ 야간온도 20-25℃)에 두어 생육시켰다. 싸이할로호프와 메타미호프를 각각 1:5, 2:3, 1:2, 1:1, 3:4, 4:3, 3:1, 2:1 및 3:2의 중량비로 혼합하되 제초제 유효성분의 총 함량이 50 g 이하가 되도록 제조하였다. 아울러, 혼합제형의 처리량에 해당되는 각각의 단일제형을 대조구로 하여 이들 제초제 용액을 3엽 말기 내지 4엽 초기까지 생육된 피 지상부에 살포기를 이용하여 폿트당 14 ㎖ 수준으로 처리하였다. 상기 제형들은 실시예 3과 동일한 방법으로 제조되었다. 각각의 제형을 피 지상부에 처리한 후 온실조건에 2주간 두면서 시간 경과별로 경엽의 황화고사 정도를 달관조사하여 퍼센트 단위로 나타내었다 (0%: 약효가 전혀 없음, 100%: 완전 방제).Specifically, seeds were sown in 350 cm 2 square pots and grown under greenhouse conditions (weekly temperature 25-35 ° C./night temperature 20-25 ° C.). Mix Cyhalhof and Metamihof in a weight ratio of 1: 5, 2: 3, 1: 2, 1: 1, 3: 4, 4: 3, 3: 1, 2: 1 and 3: 2, respectively. The total content of herbicide active ingredient was prepared to be 50 g or less. In addition, each herbicide solution corresponding to the throughput of the mixed formulation was used as a control, and these herbicide solutions were treated at the level of 14 ml per pot using a sprayer on the grown ground from the end of the third to the fourth leaf. The formulations were prepared in the same manner as in Example 3. Each formulation was treated in the ground and placed in greenhouse conditions for two weeks, and the degree of sulphide death of the leaves was measured in percent (0%: no effect, 100%: complete control).

유효성분의 총 함량이 30 g이 되도록 여러 중량비로 제조된 제형을 피에 경엽 처리한 후 9일째의 황화고사 정도를 조사한 결과,도 2에 나타난 바와 같이, 싸이할로호프 30 g 단독 처리에서는 25%, 메타미호프 30 g 단독 처리에서는 55%의 방제활성을 나타낸 반면, 1:5 혼합제형 (싸이할로호프 5 g + 메타미호프 25 g), 1:2 혼합제형 (싸이할로호프 10 g + 메타미호프 20 g) 및 1:1 혼합제형 (싸이할로호프 15 g + 메타미호프 15 g) 처리에서는 각각 85%, 90% 및 85%로서 상대적으로 높은 방제활성을 보였다. 싸이할로호프와 메타미호프의 처리비율에 따른 방제활성의 차이를 살펴보면, 1:2 혼합비율에서 보다 빠른 방제활성을 나타내었으나 처리 7일 이후에서는 상기 세 조합간의 차이가 거의 없었다.As a result of investigating the degree of sulfidation on the 9th day after the foliage treatment of the formulation prepared in various weight ratios so that the total content of the active ingredient was 30 g, as shown in FIG . %, Metamihof 30 g alone treatment showed 55% control activity, whereas 1: 5 mixed formulation (5 haloHypsy + 25 g metamihof), 1: 2 mixed form (cyhalohof 10 g + metamihof 20 g) and 1: 1 mixed formulations (Sihalofov 15 g + metamihof 15 g) showed relatively high control activity, respectively 85%, 90% and 85%. Looking at the difference in the control activity according to the treatment ratio of the Cyhalhof and Metamihof, showed a faster control activity in the 1: 2 mixing ratio, but after 7 days of treatment there was almost no difference between the three combinations.

유효성분의 총 함량이 40 g이 되도록 제조된 제형을 피에 경엽 처리한 후 9일째의 황화고사 정도를 조사한 결과,도 3에 나타난 바와 같이, 싸이할로호프 40 g 단독 처리에서는 38%, 메타미호프 40 g 단독 처리에서는 75%의 방제활성을 나타낸 반면, 1:1 혼합제형 (싸이할로호프 20 g + 메타미호프 20 g) 및 3:1 혼합제형 (싸이할로호프 30 g + 메타미호프 10 g)의 처리에서는 각각 93% 및 90%로 상대적으로 높은 방제활성을 보였다. 싸이할로호프와 메타미호프의 처리비율에 따른 방제활성의 차이를 살펴보면, 1:1 혼합제형이 3:1 혼합제형보다 빠른 방제활성을 나타내었다. 유효성분의 총 함량이 35 g이 되도록 제조된 제형을 처리한 경우에도도4에서와 같이 혼합제형이 단일제형보다 높은 방제활성을 보였으며, 싸이할로호프와 메타미호프의 처리비율에 따른 활성차이의 경우를 보면 3:4 혼합제형 (싸이할로호프 15 g + 메타미호프 20 g)이 4:3 혼합제형 (싸이할로호프 20 g + 메타미호프 15 g) 보다 방제활성 발현이 빠르고 효과도 우수하였다. 또한, 메타미호프의 처리량을 고정시키고 싸이할로호프 처리량을 변화시킬 경우에는 방제활성의 변화폭이 낮지만 싸이할로호프의 처리량을 고정시키고 메타미호프의 처리량을 변화시킬 경우에는 방제활성 변화폭이 보다 크게 나타났다.As a result of investigating the degree of sulfidation on the ninth day after the foliage treatment of the formulation prepared so that the total content of the active ingredient was 40 g, as shown in FIG . Mihof 40 g alone showed 75% control activity, whereas 1: 1 mixed formulation (20 g of Cyhalhof + 20 g Metamihof) and 3: 1 mixed formulation (30 g + Metahalhof) Mihof 10 g) showed relatively high control activity of 93% and 90%, respectively. Looking at the difference in the control activity according to the treatment ratio of Sihalhof and Metamihof, the 1: 1 mixed formulation showed faster control activity than the 3: 1 mixed formulation. Even in the case of treating the formulation prepared so that the total content of the active ingredient was 35 g, the mixed formulation showed higher control activity than the single formulation, as shown in FIG. 4 , and the activity according to the treatment ratio of Cyhalhof and Metamihof In the case of differences, the 3: 4 blend formulation (15 g of Cyhalhof + 20 g) is faster than the 4: 3 blend formulation (20 g of Cyhalhof + 15 g Metamihof). The effect was also excellent. In addition, when the metamihof throughput is fixed and the Cyhalhof throughput is changed, the change of the control activity is low. However, when the throughput of the Cyhalhof is fixed and the throughput of the Metamihof is changed, Greater than

<실시예 6> 싸이할로호프와 메타미호프 혼합제형의 경엽처리에 따른 피 생육단계별 제초효과<Example 6> Herbicidal effect of each stage of growth according to the foliage treatment of Cyhalhof and Metamihof formulations

싸이할로호프와 메타미호프를 혼합하여 경엽 처리하는 경우, 피의 어느 생육단계까지 방제할 수 있으며 어느 정도의 처리 적정량이 필요한지를 알아보기 위하여 하기 실험을 수행하였다.In the case of the foliage treatment by mixing the sihalhof and metamihof, the following experiment was performed to find out which growth stage of the blood can be controlled and how much treatment is required.

구체적으로, 시험 대상잡초는 2엽기에서 6엽기까지 생육된 피를 사용하였다. 싸이할로호프와 메타미호프를 실시예 5에서와 같은 방법으로 각각 1:1 및 1:2 중량비로 혼합하여 최종 처리량이 3.75 g/ha 내지 250 g/ha이 되도록 제조한 후 이를 피 엽기별 (생육 단계별)로 처리하였다. 그 후 온실조건에 2주간 두면서 시간 경과별로 제초활성 정도를 달관조사하여 이를 퍼센트 단위로 나타내었다 (0%: 약효가 전혀 없음, 100%: 완전 방제).Specifically, the test weeds used blood grown from the second to sixth stage. Sihalofhof and Metamihof were mixed in the same manner as in Example 5 in a 1: 1 and 1: 2 weight ratio, respectively, to prepare a final throughput of 3.75 g / ha to 250 g / ha, and then by (Growth step). After two weeks in greenhouse conditions, the degree of herbicidal activity was examined over time and expressed as a percentage (0%: no effect, 100%: complete control).

처리화합물1) Treated Compound 1) 유효성분량(g/ha)Effective amount (g / ha) 2 엽기2 bizarre 3 엽기3 bizarre 4 엽기4 bizarre 5 엽기5 bizarre 6 엽기6 bizarre 66 14DAT2) 14DAT 2) 66 14DAT14DAT 66 14DAT14DAT 66 14DAT14DAT 66 14DAT14DAT ABCABC 3.757.51530601252503.757.51530601252503.757.51530601252503.757.51530601252503.757.51530601252503.757.5153060125250 60.0±8.23)63.3±5.285.0±8.4100±0.0---95.0±5.597.5±4.2100±0.0100±0.0---100±0.0100±0.0100±0.0100±0.0---60.0 ± 8.2 3) 63.3 ± 5.285.0 ± 8.4100 ± 0.0 --- 95.0 ± 5.597.5 ± 4.2100 ± 0.0100 ± 0.0 --- 100 ± 0.0100 ± 0.0100 ± 0.0100 ± 0.0 --- 85.0±5.5100±0.0100±0.0100±0.0---100±0.0100±0.0100±0.0100±0.0---100±0.0100±0.0100±0.0100±0.0---85.0 ± 5.5100 ± 0.0100 ± 0.0100 ± 0.0 --- 100 ± 0.0100 ± 0.0100 ± 0.0100 ± 0.0 --- 100 ± 0.0100 ± 0.0100 ± 0.0100 ± 0.0 --- 13.3±2.139.0±4.458.3±1.774.2±2.7---41.7±4.060.0±2.681.7±3.195.0±2.2---36.7±2.163.3±3.381.7±3.193.3±2.1---13.3 ± 2.139.0 ± 4.458.3 ± 1.774.2 ± 2.7 --- 41.7 ± 4.060.0 ± 2.681.7 ± 3.195.0 ± 2.2 --- 36.7 ± 2.163.3 ± 3.381.7 ± 3.193.3 ± 2.1 --- 75.0±2.3100±0.0100±0.0100±0.0---68.3±3.198.3±0.1100±0.0100±0.0---91.7±2.8100±0.0100±0.0100±0.0---75.0 ± 2.3100 ± 0.0100 ± 0.0100 ± 0.0 --- 68.3 ± 3.198.3 ± 0.1100 ± 0.0100 ± 0.0 --- 91.7 ± 2.8100 ± 0.0100 ± 0.0100 ± 0.0 --- -4)2.5±1.111.7±0.719.2±2.725.8±2.7---18.3±1.732.5±2.163.3±2.173.3±6.1---25.8±3.339.2±3.556.7±2.175.0±2.2-- 4) 2.5 ± 1.111.7 ± 0.719.2 ± 2.725.8 ± 2.7 --- 18.3 ± 1.732.5 ± 2.163.3 ± 2.173.3 ± 6.1 --- 25.8 ± 3.339.2 ± 3.556.7 ± 2.175 .0 ± 2.2-- -66.7±3.389.2±4.9100±0.0100±0.0---61.2±4.085.0±2.2100±0.0100±0.0---80.0±5.2100±0.0100±0.0100±0.0---66.7 ± 3.389.2 ± 4.9100 ± 0.0100 ± 0.0 --- 61.2 ± 4.085.0 ± 2.2100 ± 0.0100 ± 0.0 --- 80.0 ± 5.2100 ± 0.0100 ± 0.0100 ± 0.0-- --0.0±0.025.0±2.231.7±1.731.7±1.7---15.0±2.233.3±3.345.0±2.256.7±3.1---16.7±3.333.3±3.350.0±0.053.3±2.5---0.0 ± 0.025.0 ± 2.231.7 ± 1.731.7 ± 1.7 --- 15.0 ± 2.233.3 ± 3.345.0 ± 2.256.7 ± 3.1 --- 16.7 ± 3.333.3 ± 3.350.0 ± 0.053. 3 ± 2.5- --63.3±3.399.0±0.8100±0.0100±0.0---61.7±3.187.5±6.1100±0.0100±0.0---76.7±6.198.3±1.7100±0.0100±0.0--63.3 ± 3.399.0 ± 0.8100 ± 0.0100 ± 0.0 --- 61.7 ± 3.187.5 ± 6.1100 ± 0.0100 ± 0.0 --- 76.7 ± 6.198.3 ± 1.7100 ± 0.0100 ± 0.0 ---0.0±0.00.0±0.010.0±0.014.0±1.5---0.0±0.06.7±2.115.0±2.218.3±2.8---7.5±1.76.7±2.118.3±4.018.3±1.7--- 0.0 ± 0.00.0 ± 0.010.0 ± 0.014.0 ± 1.5 --- 0.0 ± 0.06.7 ± 2.115.0 ± 2.218.3 ± 2.8 --- 7.5 ± 1.76.7 ± 2.118.3 ± 4.018 .3 ± 1.7 ---68.3±6.085.8±8.2100±0.0100±0.0---61.7±1.7100±0.0100±0.0100±0.0---98.3±1.793.3±6.7100±0.0100±0.0--- 68.3 ± 6.085.8 ± 8.2100 ± 0.0100 ± 0.0 --- 61.7 ± 1.7100 ± 0.0100 ± 0.0100 ± 0.0 --- 98.3 ± 1.793.3 ± 6.7100 ± 0.0100 ± 0.0 1) A: 메타미호프 단독처리; B: 싸이할로호프와 메타미호프 1:1 혼합;C: 싸이할로호프와 메타미호프 1:2 혼합.2) DAT: 약제처리 후 일수 (Days after treatment).3) 모든 데이터는 6반복의 평균±표준오차로 나타냄.4) 해당농도를 처리하지 않음.1) A: metamihof alone treatment; B: Cyhalhof and Metamihof 1: 1 mix; C: Cyhalhof and Metamihof 1: 2 mix. 2) DAT: Days after treatment. 3) All data is 6 Expressed as the mean ± standard error of the repetition. 4) The concentration is not treated.

상기표 5에 나타난 바와 같이, 메타미호프 단독처리의 경우에는 처리 당시 2, 3, 4, 5 및 6엽기의 피를 거의 완전히 방제하기 위해 소요되는 처리량은 각각 7.5 g, 15 g, 30 g, 60 g 및 125 g 정도였다. 그러나, 싸이할로호프와 메타미호프 성분량을 1:1 중량비로 혼합한 경우에는 처리 당시 2, 3, 4, 5 및 6엽기의 피를 완전히 방제하기 위해 소요되는 처리량은 각각 3.75 g 이하, 7.5 g, 30 g, 60 g 및 60 g 정도였으며, 1:2 중량비로 혼합한 경우에는 처리 당시 2, 3, 4, 5, 6엽기의 피를 완전히 방제하기 위해 소요되는 처리량은 각각 3.75 g 이하, 7.5 g, 15 g, 30 g, 60 g 정도로서, 1:1 혼합제형보다 약간 강한 방제효과를 보였고 메타미호프 단독제형의 처리와 비교하여 절반정도의 약량으로도 동일한 방제효과를 나타내었다. 또한, 실시예 4의 결과와 마찬가지로 혼합제형이 메타미호프를 단독으로 처리한 것보다 방제활성이 빠르게 나타났다.As shown in Table 5, in the case of metamihof alone treatment, the throughput required for almost completely controlling the blood of 2, 3, 4, 5 and 6 leaf stages at the time of treatment was 7.5 g, 15 g, 30 g, respectively. About 60 g and 125 g. However, when the amount of the Cyhalhof and Metamihof components are mixed in a 1: 1 weight ratio, the throughput required to completely control the blood of 2, 3, 4, 5 and 6 leaf stages at the time of treatment is 3.75 g or less and 7.5, respectively. g, 30 g, 60 g and 60 g, and when mixed in a 1: 2 weight ratio, the throughput required to completely control the blood of the 2nd, 3rd, 4th, 5th and 6th leaves at the time of treatment was 3.75 g or less, respectively. 7.5 g, 15 g, 30 g, and 60 g, which showed a slightly stronger control effect than the 1: 1 mixed formulation, and showed the same control effect at about half the dose compared to the treatment of the metamihof alone formulation. In addition, as in the result of Example 4, the mixed formulation showed a faster control activity than the metamihof treatment alone.

상기에서 살펴본 바와 같이, 본 발명의 조성물은 싸이할로호프와 메타미호프의 조합을 통해 방제활성 발현 속도와 효과를 증진시켜 어린 시기부터 늦은 엽기까지의 피를 효과적으로 방제함으로써 화본과 잡초의 방제에 유용하게 사용될 수 있다.As described above, the composition of the present invention is useful for the control of flowering plants and weeds by effectively controlling the blood from early childhood to late leafy season by enhancing the speed and effect of controlling activity through the combination of sihalofhof and metamihof. Can be used.

Claims (6)

유효성분으로 싸이할로호프 (cyhalofop-butyl)와 메타미호프 (metamifop)를 함께 함유하는 제초제 조성물.A herbicide composition containing cyhalofop-butyl and metamifop as an active ingredient. 제 1항에 있어서,The method of claim 1, 제초제 유효성분 총량을 기준으로 싸이할로호프의 함량이 5 내지 85 중량%이고, 메타미호프의 함량이 15 내지 95 중량%인 것을 특징으로 하는 제초제 조성물.A herbicide composition, characterized in that the content of cyhalhof is 5 to 85% by weight, and the content of metamihof is 15 to 95% by weight based on the total amount of the herbicide active ingredient. 제 2항에 있어서,The method of claim 2, 제초제 유효성분 총량을 기준으로 싸이할로호프의 함량이 15 내지 75 중량%이고, 메타미호프의 함량이 25 내지 85 중량%인 것을 특징으로 하는 제초제 조성물.A herbicide composition, characterized in that the content of cyhalhof is 15 to 75% by weight, and the content of metamihof is 25 to 85% by weight based on the total amount of the herbicide active ingredient. 제 1항의 제초제 조성물을 재배지에 지상부 경엽처리하거나 담수조건에서 수면처리하여 화본과 잡초를 방제하는 방법.A method of controlling flower beds and weeds by treating the herbicide composition of claim 1 on the cultivated land with surface foliage or sleeping under fresh water conditions. 제 4항에 있어서,The method of claim 4, wherein 화본과 잡초가 피 (Barnyardgrass), 존슨그래스 (Johnsongrass), 수수 (Shattercane), 개기장 (Fall panicum), 드렁새 (Chinese sprangletop), 우산잔듸 (Burmudagrass), 바랭이 (Large crabgrass), 강아지풀 (Green foxtail), 금강아지풀 (Yellow foxtail), 조개풀 (Jointhead arthraxon), 메귀리 (Wild oat), 야생옥수수 (Corn), 왕바랭이 (Goosegrass), 그령 (Eragrostis), 둑새풀 (Water foxtail), 오리새 (Orchardgrass), 카나리새풀 (Canarygrass), 쥐꼬리둑새풀 (Blackgrass), 물참새피 (Jointgrass), 새포아풀 (Annual bluegrass), 참새귀리 (Japanese brome) 및 개밀 (Quackgrass)로 구성된 군으로부터 선택되는 것을 특징으로 하는 방법.Flower and weed grass (Barnyardgrass), Johnsongrass, Shattercane, Fall panicum, Chinese sprangletop, Burmudagrass, Large crabgrass, Green foxtail Yellow foxtail, Seashell (Jointhead arthraxon), Wild oat, Corn, Goosegrass, Erragtis, Water foxtail, Duck grass, Canary Method selected from the group consisting of Canarygrass, Blackgrass, Jointgrass, Annual bluegrass, Japanese brome and Wheatgrass. 제 4항에 있어서,The method of claim 4, wherein 제초제 조성물 내 제초제 유효성분의 최종 살포농도가 7.5 내지 300 g ai/ha인 것을 특징으로 하는 방법.Final spray concentration of the herbicide active ingredient in the herbicide composition is characterized in that the 7.5 to 300 g ai / ha.
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