WO2006065094A1

WO2006065094A1 - Synergistic herbicidal compositions

Info

Publication number: WO2006065094A1
Application number: PCT/KR2005/004337
Authority: WO
Inventors: Do Soon Kim; Jong Nam Lee; Ki Hwan Hwang; Suk Jin Koo
Original assignee: Lg Life Sciences Ltd.
Priority date: 2004-12-17
Filing date: 2005-12-16
Publication date: 2006-06-22
Also published as: CN101675739B; CN104522018A; CN109077059A; CN101102671B; CN103081936A; CN101102671A; CN106689174B; CN101675739A; KR20060069304A; JP4625089B2; KR101280059B1; BRPI0519121A2; JP2008524206A; BRPI0519121B1; CN106689174A

Abstract

The present invention relates to a synergistic herbicidal composition comprising N- [ [(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl] -2- [2-fluoro- 1 -(methoxymethylcarbony loxy)propyl] -3 -pyridine sulfonamide or N-[[(4,6-dimethoxy-2-pyrimidinyl)amino] carbonyl]-2-[2-fluoro-l-(hydroxy)propyl]-3-pyridine sulfonamide and other herbicidal active materials as active ingredient. The herbicidal composition of the present invention can increase the herbicidal efficacy against major weeds, and can reduce the use amount of active ingredients per unit area, due to the synergistic effect by mixing two herbicidal active ingredient having different physiological functions or different herbicidal activities.

Description

SYNERGISTIC HERBICID AL COMPOSITIONS

TECHNICAL FIELD

The present invention relates to a synergistic herbicidal composition comprising a

compound of the following formula (1) (N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]

carbonyl]-2-[2-fluoro-l-(methoxymethylcarbonyloxy)propyl]-3-pyridine sulfonamide) or a

compound of the following formula (2) (N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]

carbonyl]-2-[2-fluoro-l-(hydroxy)propyl]-3-pyridine sulfonamide), and other herbicidal

active materials having different physiological functions or different herbicidal activities

from the compound of the formula (1) or (2), characterized in that herbicidal activity is

increased, herbicidal spectrum is wide and the amount of active ingredients used can be

saved, compared with a single agent. In particular, the present invention relates to a

herbicidal composition comprising the compound of the formula (1) or (2), and one or more

other active ingredients selected from the group consisting of photosynthesis inhibitor

bentazone, protoporphyrinogen IX oxidase inhibitor carfentrazone-ethyl and auxin-type

herbicides, characterized in that herbicidal activity against perennial weeds and sulfonylurea

herbicide-resistant weeds is synergistically increased, antagonism for the control of grass

weeds, particularly Echinochloa species, is avoided or minimized, and safety to rice for

foliar application is improved.

BACKGROUND ART

The present invention relates to a synergistic herbicidal composition comprising

N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-2-[2-fluoro-l-(methoxymethylcarbony

loxy)propyl] -3 -pyridine sulfonamide or N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]

carbonyl]-2-[2-fluoro-l-(hydroxy)propyl]-3-pyridine sulfonamide and other herbicidal

active materials as active ingredient.

In crop cultivation, it is important to control weeds that inhibit growth of crops and

cause yield reduction and to protect crops. In order to reduce damages such as poor

growth or yield reduction of crops due to weeds in crop cultivation, some herbicidal active

ingredients which can effectively control such weeds and are safe for crops have been

developed. A large number of herbicides developed up to now have been registered and

used for controlling weeds for certain crops. Herbicides used for controlling weeds in a

specific crop cultivation should have a sufficiently high herbicidal activity and a wide herbicidal spectrum, and should be safe enough for environment and crops. However, not

all herbicides perfectly satisfy such requirements.

The most frequently used method for increasing herbicidal activity and extending

herbicidal spectrum of existing herbicides is to mix two or more herbicidal active materials

having different herbicidal activities from each other. In case of mixing two or more

herbicidal active materials, more excellent herbicidal efficacy may be exhibited than

individual herbicide application (solo application). Like this, when the efficacy of

mixture of two of more components is greater than a level expected from those of

individual components, we call this "Synergism (synergistic action)". However, such

synergistic action in herbicide mixture of two or more herbicidal active materials can be

seen only in some cases, hi most cases of mixture, the herbicidal activity is lower than

solo application of individual components due to differences of herbicidal properties,

absorption rates, translocation, metabolism, etc. "Antagonism (antagonistic effect)"

indicates such a case that the herbicidal efficacy of a mixture of two or more herbicidal

active materials is lower than solo application of individual components. And, "additive

action" indicates a case that the herbicidal efficacy of a mixture of two or more herbicidal

active materials is the same as solo application of individual components.

Meanwhile, KR Patent No. 10-0399366 (Application No. 10-2000-0059990)

disclosed a herbicidal active material of sulfonylurea herbicide, the compound of the

following formula (1) [ISO proposed name: flucetosulfuron].

Said flucetosulfuron is known to be safe for rice plant, wheat, barley (optimum

amount of use: 10~40g a.i./ha) and grass (optimum amount of use: 50~200g a.i./ha), in soil

or foliar application, and to have excellent weed control effects for a wide range of weed

species such as broad-leaved weeds, grass weeds (Gramineae), sedge weeds

(Cyperaceae), annual and perennial weeds, etc.

KR Patent No. 10-0107924 (Application No. 10-1993-0006915) disclosed another

herbicidal active material of sulfonylurea herbicide,

N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-2-[2-fluoro-l-(hydroxy)propyl]-3-pyri

dine sulfonamide, the compound of the following formula (2):

The above compound is known to be effective for preventing monocotyledon or

dicotyledon weeds, such as barnyardgrass {Echinochloa crus-galli), Monochoria vaginalis,

or Sagittaria pygmaea, and safe for rice plant.

However, it is also reported that when the flucetosulfuron of the formula (1) and

dine sulfonamide of the formula (2) are applied to rice field by foliar and soil application, they show low herbicidal efficacy to some grass weeds; sulfonylurea herbicide-resistant

ecotypes among Monochoria vaginalis, Scirpus juncoides, Lindernia species, and Cyperus

difformis evolved due to continuous use of sulfonylurea herbicide for a long-period of

time; and some perennial weeds such as Eleocharis kuroguwai, Cyperus serotinus,

Sagittaria trifolia, etc. Also, when used in wheat or barley fields by foliar application,

they showed low herbicidal efficacy to some grass weeds such as Alopecurs myosuroides,

Poa spp., etc. and broad-leaved weeds such as Veronica persica and Viola arvensis.

Furthermore, in weed control in turf field, they showed low herbicidal efficacy against

Veronica persica and Poa annua.

Photosynthesis inhibitor is a herbicide showing its herbicidal activity by inhibiting

photosynthesis through disturbing or blocking electron transfer in photosynthesis of plant,

and is mainly absorbed through treated leaves. This herbicide exhibits immediate effect

in treated region, and is frequently used for rice, wheat, and barley since it is relatively safe

for grass crops. Bentazone, a representative herbicide of photosynthesis inhibitor, is

widely used for wheat, barley, and rice mainly by foliar application, and by soil application

only for rice. Bentazone cannot control grass weeds in solo application, and so has been

used for the purpose of controlling only broad-leaved weeds. However, in order to

control grass weeds, particularly barnyardgrass, bentazone is often used as mixture with

graminicide that is a herbicide particularly effective for controlling grass weeds such as

Acetyl-CoA carboxylase inhibitor (herbicide inhibiting Acetyl-CoA carboxylase that is an

important enzyme in fatty acid biosynthesis, also called as ACCase inhibitor, and

chemically divided into aryloxyphenoxy propionic acid and cyclohexanedion, wherein cyhalofop-butyl, etc. belong to the former, and tralcoxydim, etc. to the latter). Its

representative example is the mixture of bentazone and cyhalofopbutyl. When

graminicide such as cyhalofop-butyl is used in solo application, it has a good preventive

effect on grass weeds. However, graminicides such as cyhalofop-butyl is used in a

mixture with bentazone, the herbicidal efficacy is often significantly decreased due to

antagonism, compared with solo application (Weed Technol. 9, 741 (1995). Thus,

development as such mixture has been frequently limited, or efficacy expected from such

mixture cannot be sufficiently obtained.

Another example of mixture showing antagonism is reported when propanil of

photosynthesis inhibitor is used with pyribenzoxim of acetolactate synthase inhibitor

[Pesticide Biochemistry and Physiology, Volume 67, Number 1, May 2000, pp. 46-53(8)].

Generally, a representative example of such antagonistic effect is often reported when a

contact-type herbicide, such as photosynthesis inhibitor including bentazone or propanil, or

protoporphyrinogen IX oxidase inhibitor including carfentrazone-ethyl, is used as a

mixture with a systemic herbicide such as acetyl-CoA carboxylase inhibitor including

cyhalofop-butyl, or acetolactate synthase inhibitor [herbicide inhibiting Acetolactate

synthase (ALS) that is an important enzyme in biosynthesis of branched-chain amino acid,

and chemically divided into sulfonylurea, imidazolinone, triazolopyrimidine, and

pyrimidinyl(thio)benzoate, wherein flucetosulfuron belongs to sulfonylurea] including

flucetosulfuron (Weed Science, 1989, Vol. 37, No. 3, pp. 400-404), which is a major

restriction to the development as mixture.

Herbicide belonging to protoporphyrinogen IX oxidase inhibitor shows its herbicidal activity by inhibiting protoporphyrinogen IX oxidase related to chloroplast

biosynthesis, and is mainly absorbed in the treated leaves for its herbicidal action. This

herbicide shows immediate effect, but may give damage (phytotoxicity) to crops when

sprayed by foliar application, and so its development as foliar applicable herbicide is

limited, hi particular, carfentrazone-ethyl has been difficult to develop as foliar

applicable herbicide for rice due to such damage. In addition, carfentrazone-ethyl has

extremely low efficacy to grass weeds, particularly barnyardgrass, and so needs to be used

as mixture with other herbicides. However, when used as mixture with other herbicide,

the herbicidal efficacy of carfentrazone-ethyl has been often decreased, compared to its

solo application due to its antagonistic action (Arkansas Agricultural Experiment Station,

B.R. Wells Rice Research Studies 2001, pp. 65-69), and so its development as mixture has

been limited.

An auxin herbicide has a similar physiological function to plant hormone auxin,

but may disturb the physiological function of plant over certain concentration to show its

herbicidal activity. Auxin herbicide has been widely used to control weeds, particularly

broad-leaved weeds. However, when this auxin herbicide, particularly 2,4-D, MCPA,

MCPB, etc., is used for rice plant by foliar or soil application, if the application timing is

not correct or the amount of use is over optimum use rate, it is generally known to cause a

severe damage to rice enough to lead yield reduction. For example, in case of 2,4-D, it is

recommended to use at the optimum application rate of 280 g a.i./ha during the period

between effective tillering stage and panicle initiation (Korean Crop Protection

Association, 2004, Pesticide Use Manual, 74Ip). Due to such rice damage, although the auxin herbicide has been used for a long time, but its development and usage as herbicide

for rice has been limited. Furthermore, when this herbicide is used as mixture with other

herbicides, its herbicidal efficacy is decreased because of antagonism, and so its

development as mixture has also been limited.

SUMMARY OF THE INVENTION

To increase the herbicidal activity and extend the herbicidal spectrum of

flucetosulfuron of the formula (1) and

dine sulfonamide of the formula (2), the present inventors selected herbicidal active

ingredients having complementary properties, based on individual herbicidal activity, and

confirmed them by biological examination. Selection of the herbicidal active ingredients

having complementary properties was made by dividing them into ones having different

biochemical functions and ones having different herbicidal spectrums from flucetosulfuron

or the compound of the formula (2), and further dividing them into ones having special

effects on grass weeds, broad-leaved weeds or sulfonylurea- resistant weeds, and perennial

weeds. As a result, surprisingly, it is discovered that when a composition comprising such

herbicidal active ingredients having complementary properties is mixed with

flucetosulfuron or the compound of the formula (2), the composition exhibits synergistic

action enough to clearly show increased herbicidal activity and extended herbicidal

spectrum, and some mixtures exhibit less damage as well as such synergistic action on grass weeds, to complete the present invention.

Therefore, it is an object of the present invention to provide a herbicidal

composition, characterized in that less amounts of herbicidal ingredients can be used due to

their increased herbicidal activity and extended herbicidal spectrum, compared to sole

application of flucetosulfuron of the formula (1) or

dine sulfonamide of the formula (2), or herbicidal active materials selected as a partner for

mixture, and the cost for weed control can be saved by reducing labor for herbicide

application by co-application of flucetosulfuron of the formula (1) or the compound of the

formula (2) with other herbicidal active materials contained in the herbicidal composition.

Another object of the present invention is to provide a herbicidal composition,

characterized in that by co-application of flucetosulfuron of the formula (1) or the

compound of the formula (2) with some herbicidal active materials which particularly have

significantly decreased effects on specific weeds due to antagonism when used as mixture

with other herbicides, or limited use due to crop damage when used as solo application,

among existing herbicides, reduced herbicidal activity to the specific weed can be solved,

the herbicidal activity on Eleocharis kuroguwai or resistant weed which is difficult to

control can be increased, and the crop safety can be increased by application as mixture

rather than individual solo application.

DISCLOSURE OF THE INVENTION To achieve the above objects, the present invention provides a herbicidal

composition comprising N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-2-[2-fluoro-

l-(methoxymethylcarbonyloxy)propyl]-3-pyridine sulfonamide of the above formula (1),

i.e., flucetosulfuron [herbicidal active ingredient (Al), below] or the compound of the above

formula (2), N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-2-[2-fluoro-l-

(hydroxy)propyl]-3-pyridine sulfonamide [herbicidal active ingredient (A2), below], and

other herbicidal active ingredient [herbicidal active ingredient (B), below].

Therefore, the present invention relates to a herbicidal composition, comprising

herbicidal active ingredient (Al) or (A2) basically, and herbicidal active ingredient (B),

wherein (Al) is flucetosulfuron (N-[[(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl]-2-

[2-fluoro-l-(methoxymethylcarbonyloxy)propyl]-3-pyridine sulfonamide); (A2) is

N- [ [(4,6-dimethoxy-2-pyrimidinyl)amino]carbonyl] -2-[2-fluoro- 1 -(hydroxy)propyl] -3 -pyri

dine sulfonamide; and (B) is one or more herbicides selected from the compound group (Bl

to B9) consisting of the following herbicides, having different chemical structure or

biological herbicidal activity from herbicide (Al) or (A2) contained in each case.

Suitable partners (B) for mixture may be any compounds which belong to the

following sub-groups (Bl) to (B9). The names of most herbicides are from their general

names for active compounds according to "The Pesticide Manual," 12¹ edition, 2000,

British Crop Protection Council (PM, below), and separate references are shown for some

herbicides.

(Bl) Acetyl-CoA carboxylase inhibitor (Bl.1) Diclofop and ester thereof, in particular, methyl ester (PM, pp. 279-280)

(B 1.2) Metamifop (Proceedings of the BCPC International Congress-Crop Science

& Technology 2003, pp. 85-92)

(B 1.3) Cyhalofop-butyl (PM, pp. 223-224)

(B1.4) Clodinafop-propargyl (PM, pp. 186-187)

(B 1.5) Fenoxaprop-P and ester thereof, in particular, ethyl ester (PM, pp. 393-394)

(B1.6) Flamprop-M and ester thereof (PM, pp. 415-416)

(B1.7) Tralcoxydim (PM, pp. 914-915)

(B1.8) Profoxydim(PM, pp. 61-62)

(B2) Acetolactate synthase inhibitor

(B2.1) Thifensulfuron-methyl (PM, pp. 899-900)

(B2.2) Metsulfuron-methyl (PM, pp. 644-645)

(B2.3) Prosulfuron (PM, pp. 787-788)

(B2.4) Tribenuron-methyl (PM, pp. 928-929)

(B2.5) Mesosulfuron-methyl (Proceedings of the BCPC Conference - Weeds 2001,

pp. 43-48)

(B2.6) Flazasulfuron (PM, pp. 417-418)

(B2.7) Sulfosulfuron (PM, pp. 853-854)

(B2.8) Iodosulfuron and ester thereof, in particular, methyl ester (PM, pp.

547-548)

(B2.9) Flupyrsulfuron and ester thereof, in particular, methyl ester (PM, pp. 447-448)

(B2.10) Bensulfuron and ester thereof, in particular, methyl ester (PM, pp. 76-77)

(B2.11) Cyclosulfamuron (PM, pp. 217-218)

(B2.12) Cinosulfuron (PM, pp. 183-184)

(B2.13) Azimsulfuron (PM, pp. 48-49)

(B2.14) rmazosulfuron (PM, pp. 534-544)

(B2.15) Pyrazosulfuron-ethyl (PM, pp. 795-797)

(B2.16) Penoxulam (Proceedings of the BCPC International Congress-Crop

Science & Technology 2003, pp. 85-92)

(B2.17) Florasulam (PM, pp. 420-421)

(B2.18) Bispyribac-sodium (PM, pp. 97-98)

(B2.19) Pyribenzoxim (PM, pp. 801)

(B3) Photosynthesis inhibitor

(B3.1) Bentazone (PM, pp. 80-81)

(B3.2) Bromoxynil or bromoxynil-octanoate (PM, pp. 110-112)

(B3.3) Ioxynil, and ester and salt thereof (PM, pp. 548-550)

(B3.4) Terbutryn (PM, pp. 883-884)

(B3.5) Simetryn (PM, pp. 837-834)

(B3.6) Chlorotoluron (PM, pp. 169-170)

(B3.7) Isoproturon (PM, pp. 559-560) (B4) Protoporphyrinogen IX oxidase inhibitor

(B4.1) Oxyfluorfen (PM, pp. 702-703)

(B4.2) Pyraflufen-ethyl (PM, pp. 792-793)

(B4.3) Carfentrazone-ethyl (PM, pp. 141-142)

(B4.4) Cinidon-ethyl (PM, pp. 181-182)

(B4.5) Oxadiargyl (PM, pp. 690-691)

(B4.6) Pentoxazone (PM, pp. 718-719)

(B5) Carotenoid biosynthesis inhibitor

(B5.1) Diflufenican (PM, pp. 296-297)

(B5.2) Picolinafen (PM, pp. 742-743)

(B5.3) Mesotrione (PM, pp. 602)

(B5.4) Pyrazoxyfen (PM, pp. 797-798)

(B5.5) Pyrazolate (PM, pp. 793-794)

(B5.6) Benzobicyclon (PM, pp. 82)

(B5.7) Clomazone (PM, pp. 190-191)

(B6) Cell wall synthesis inhibitor

(B6.1) Butachlor (PM, pp. 117-118)

(B6.2) Flufenacet (PM, pp. 434-435)

(B6.3) Mefenacet (PM, pp. 593-594)

(B6.4) Fentrazamide (PM, pp. 406-407) (B6.5) Pretilachlor (PM, pp. 755-756)

(B6.6) Carfenstrole (cafenstrole, PM, pp. 128-129)

(B6.7) Isoxaben (PM, pp. 561-562)

(B7) Lipid biosynthesis inhibitor

(B7.1) Benfuresate (PM, pp. 71-72)

(B7.2) Ethofumesate (PM, pp. 364-365)

(B7.3) Prosulfocarb (PM, pp. 786-787)

(B7.4) Triallate (PM, pp. 921-922)

(B7.5) Thiobencarb (PM, pp. 901-902)

(B 8) Auxin herbicide

(B8.1) Triclopyr (PM, 933-934)

(B8.2) Fluroxypyr and ester thereof (PM, pp. 455-457)

(B8.3) 2,4-D and ester thereof (PM, pp. 243-246)

(B8.4) MCPA and ester thereof, in particular, thioethyl (PM, pp. 583-586)

(B8.5) MCPB and ester thereof, in particular, ethyl ester (PM, pp. 586-588)

(B8.6) Mecoprop and its pure R-isomer, mecoprop-P (PM, pp. 489-592)

(B8.7) Clomeprop (PM, pp. 191-192)

(B8.8) Dicamba (PM, pp. 265-267)

(B9) others (B9.1) Pendimethalin (PM, pp. 714-715)

(B9.2) Dithiopyr (PM, pp. 330)

(B9.3) Difenzoquat-methyl sulfate (PM, pp. 291-292)

(B9.4) Bromobutide (PM, pp. 108)

(B9.5) Indanofan (PM, pp. 543-544)

(B9.6) Pyributicarb (PM, pp. 802)

Synergistic action obtained by mixing and using herbicidal active ingredients (Al)

or (A2) and (B) in one composition according to the present invention can be often

observed when these active ingredients are sprayed at different times.

The treatment amounts of herbicidal active ingredients (Al) and (A2) which are

commonly contained in the herbicidal composition of the present invention may vary

depending on subject crops, but the amount of active ingredient per hectare (ha) is from

2Og to 30Og. The composition of the present invention needs to have a lower treatment

amount for certain active ingredient than individual application case.

Therefore, in the composition of the present invention, the treatment amount of

herbicidal active ingredient per hectare generally should be 1 to 300g, preferably 10 to

20Og, for active ingredient (A), and 1 to 400Og, preferably 2 to 200Og, for active ingredient

B. The weight ratio of A:B used in the composition may vary in a wide range, preferably

in the range of 1:200 to 200:1, more preferably in the range of 1 :100 to 20:1, but not

limited thereto. The final weight ratio may vary depending on specific application field,

weed spectrum, and combination of active compounds to be used, and may be determined in pre-test.

The composition of the present invention can be used in crop fields to selectively

control annul and perennial grass weeds, sedge weeds, and broad-leaved weeds. The

above crop fields include rice cultivations, cereals (wheat, barley, oats, rye, etc.)

cultivations, and grass or pasture. Furthermore, the composition also can be used to

control unwanted weeds in non-cropping area, in particular, railroad tracks or banks around

rice fields.

The composition of the present invention can be used in crop fields and

non-cropping area without limit by any conventional application methods such as soil

application, water surface application, foliar application, etc., and preferably by foliar

application.

Among the compositions according to the present invention, compared with the

application of a composition comprising only active ingredient (Al) or (A2) as herbicidal

active compound, the following compounds are selected from active ingredient (B) as

ingredients having higher activity on broad-leaves weeds to complement herbicidal activity

on some major broad-leaves weeds, for example, Veronica persica, Viola arvensis, Galium

aparine, Papaver rhoeas, etc.:

(B2.1) thifensulfuron-methyl, (B2.2) metsulfuron-methyl, (B2.3) prosulfuron,

(B2.4) tribenuron-methyl, (B2.16) penoxulam, (B2.17) fiorasulam, (B3.1) bentazone,

(B3.2) bromoxynil, (B3.3) ioxynil, (B3.5) simetryne, (B4.1) oxifluorfen, (B4.2)

pyraflufen-ethyl, (B4.3) carfentrazone-ethyl, (B4.4) cinidon-ethyl, (B4.5) oxadiargyl, (B4.6) pentoxazone, (B5.1) diflufenican, (B5.2) picolinafen, (B5.3) mesotrione, (B5.5)

pyrazolate, (B5.6) benzobicyclon, (B5.7) clomazone, (B6.1) butachlor, (B6.3) mefenacet,

(B6.4) fentrazamide, (B6.5) pretilachlor, (B6.6) carfenstrole, (B6.7) isoxaben, (B7.5)

thiobencarb, (B8.1) triclopyr, (B8.2) fluroxypyr, (B8.3) 2,4-D, (B8.4) MCPA, (B8.5)

MCPB, (B8.6) mecoprop or mecoprop-P, (B8.7) clomeprop, (B8.8) dicamba, (B9.2)

dithiopyr, (B9.4) bromobutide, (B9.5) indanofan, (B9.6) pyributicarb.

Among the compositions according to the present invention, compared with the

ingredients having higher activity on perennial weeds to complement herbicidal activity on

some perennial weeds, in particular, Eleocharis kuroguwai, Scirpus planiculmis, Cyperus

serotinus and Sagittaria trifolia:

(B2.10) bensulfuron-methyl, (B2.l l) cyclosulfamuron, (B2.12) cinosulfuron,

(B2.13) azimsulfuron, (B2.14) imazosulfuron, (B2.15) pyrazosulfuron-ethyl, (B3.1)

bentazone, (B4.3) carfentrazole-ethyl, (B5.4) pyrazoxyfen, (B5.5) pyrazolate, (B7.1)

benfuresate, (B8.3) 2,4-D or ester, (B8.4) MCPA or ester, thioethyl, (B8.5) MCPB or ester,

ethylester.

Also, among the compositions according to the present invention, compared with

the application of a composition comprising only active ingredient (Al) or (A2) as

herbicidal active compound, the following compounds are selected from active ingredient (B) as ingredients having higher activity on grass weeds to complement herbicidal activity

on some grass weeds:

(BLl) diclofop-methyl, (B 1.2) metamifop, (B 1.3) cyhalofop-butyl, (B 1.4)

clodinafop-propargyl, (B 1.5) fenoxaprop-P-ethyl, (B 1.6) flamprop-M, (B 1.7) tralcoxydim,

(B 1.8) profoxydim, (B2.5) mesosulfuron-methyl, (B2.6) flazasulfuron, (B2.7)

sulfosulfuron, (B2.8) iodosulfuron-methyl, (B2.9) flupyrsulfuron-methyl, (B2.18)

bispyribac-sodium, (B2.19) pyribenzoxim, (B3.4) terbutryn, (B3.6) chlorotoluron, (B3.7)

isoproturon, (B6.2) flufenacet, (B7.2) ethofumesate, (B7.3) prosulfocarb, (B7.4) triallate,

(B9.1) pendimethalin, (B9.3) difenzoquat methylsulfate.

Also, among the compositions according to the present invention, compared with

herbicidal active compound, the following compounds are selected from active ingredient

(B) as ingredients having higher herbicidal activity on resistant weeds to complement

herbicidal activity on some sulfonylurea herbicide-resistant weeds, for example, resistant

Monochoria vaginalis, Lindernia species, Scirpus juncoides and Cyperus difformis:

(B3.1) bentazone, (B3.2) bromoxynil, (B3.5) simetryne, (B4.1) oxyfluorfen,

(B4.2) pyraflufen-ethyl, (B4.3) carfentrazone-ethyl, (B4.4) cinidon-ethyl, (B4.5)

oxadiargyl, (B4.6) pentoxazone, (B5.1) diflufenican, (B5.2) picolinafen, (B5.3) mosotrione,

(B5.5) pyrazolate, (B5.6) benzobicyclon, (B5.7) clomazone, (B6.1) butachlor, (B6.3)

mefenacet, (B6.4) fentrazamide, (B6.5) pretilachlor, (B6.6) carfenstrole, (B6.7) isoxaben,

(B7.5) thiobencarb, (B8.1) triclopyr, (B8.2) fluroxypyr, (B8.3) 2,4-D, (B8.4) MCPA, (B8.5) MCPB, (B8.6) mecoprop or mecoprop-P, (B8.7) clomeprop, (B8.8) dicamba, (B9.2)

dithiopyr, (B9.4) bromobutide, (B9.5) indanofan, (B9.6) pyributicarb.

Also, among the compositions according to the present invention, the following

compounds are selected from active ingredient (B) to be used as mixture with a composition

comprising only active ingredient (Al) or (A2) as herbicidal active compound to solve

antagonistic action on certain weeds, in particular, barnyardgrass (Echinochloa crus-galli),

which was often observed in other mixtures, to increase herbicidal activity on resistant

weeds as well as perennial Eleocharis kuroguwai, and to increase safety to rice for foliar

application:

(B3.1) bentazone, (B4.3) carfentrazone-ethyl, (B8.2) fluroxypyr, (B8.3) 2,4-D,

(B8.4) MCPA, (B8.5) MCPB, (B8.6) mecoprop or mecoprop-P, (B8.7) clomeprop, (B8.8)

dicamba.

Furthermore, the herbicidal composition of the present invention may comprise

other components, if necessary, for example, one or more selected from the group

consisting of other herbicides, insecticides, fungicides, safener (compound used to reduce

crop damage by herbicide), and plant growth regulator. These other components may be

used as one formulation by co-formulating, mixed and used in a spray tank by separate

formulating, or used sequentially.

Furthermore, the herbicidal composition of the present invention maybe formulated with carriers, surfactants or additives which are conveniently used in the art of formulation.

For example, they may be processed into non-reforming form according to conventional

methods, and active ingredients are uniformly mixed with extenders (e.g.: solvents, solid

carriers and surfactants, if necessary), processed into wettable powder, suspension

concentrate, water dispersible granule, granule, flowable, tablet, jumbo formulations, etc, by

such processes as grinding, granulating, tabletting, etc., and then applied to soil and water

surface, or foliage of plant.

Suitable carriers and additives may be solid or liquid, including components useful

in the art of formulation, for example, natural or synthetic inorganic materials, solvents,

dispersing agent, wetting agent, rheology modifier, binders, adjuvant, etc.

Solvents may include aromatic carbohydrate, for example, xylene mixture, or

alcohol and glycol, and ether and ester thereof, such as substituted naphthalene ethanol,

ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether;

ketone such as cyclo hexanon; strong polar solvents such as iV-methyl-2-pyrrolidone,

dimethylsulfoxide or dimethylformamide; epoxidated or non-epoxidated vegetable oil such

as epoxidated coconut oil or soybean oil; water, etc. These solvents may be used as

solvents for liquid-type formulation or supplementary solvents for granule-type formulation.

Solid carriers may include minutely grinded natural or synthetic inorganic mineral

such as talc, kaolin, bentonite, calcium carbonate, diatomite, or agalmatolite.

Dispersing agents may include anionic dispersing agent such as salts of lignin

sulfonic acid, salts of naphthalene sulfonic acid, salts of lauryl sulphuric acid, salts of

lauryl sulfonic acid, and salts of polyoxyalkylene alkyl ether sulfate; polyoxyalkylene alkyl aryl ether; polyoxyalkylene alkyl ether; etc. Dispersing agents are not limited to those

described above, and may be selected from non-ionic surfactants and anionic surfactants,

or cationic surfactants, if necessary.

Wetting agents may include anionic wetting agent such as sodium lauryl surfate,

salts of polyoxyalkylene alkylphenyl ether sulfonic acid, salts of dialkyl sulfosuccinate,

salts of dialkyl naphthalene sulfonic acid, salts of polyoxyalkylene alkyl ether sulfate;

acetylene family non-ionic surfactants; urea complex of non-ionic surfactants, etc.

Suitable rheology modifier may be divided into polysaccharide such as homo-type

saccharide and hetero-type saccharide, and inorganic materials such as montmorillorite,

smectite, sepiolite, hectoliter, and hydrophilic/hydrophobic silica. The homo-type

saccharide may be furan gum, and the hetero-type saccharide may be guar gum, xanthan

gum, wellan gum, etc.

Suitable binders may include starch, dextrin, alpha starch, sodium alginate, Arabia

gum, gelatin, lignin sulfonate, glucose, sorbitol, polyethylene glycol, hydroxypropyl

cellulose (HPC), hydroxypropyl methyl cellulose, polyvinyl pyrrolidone, etc.

Adjuvant refers to materials added in the formulation process to increase chemical

effects, or diluted in the preparation process of spray solution. Anionic surfactants,

cationic surfactants, non-ionic surfactants, etc., are commonly used as adjuvant. Suitable

adjuvant may include salts of dialkyl sulfosuccinate, acetylene family non-ionic surfactants,

polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenol ether, polyoxyethylene

alkylamine, ethoxylated sorbitan ester, polyoxyethylene fatty acid ester,

polyoxyethylene-polyoxypropylene-polyoxyethylene triblock copolymer, alkoxylated trisiloxane, etc.

The following examples are to exemplify the effects of the compositions of the

present invention, but the scope of the present invention should not be construed to be

limited thereby in any manner.

Example

One example of the formulation according to the invention is as follows.

10 parts (10% w/w) of a mixture of herbicidal active ingredient (Al or

A2)/herbicidal active ingredient (B), 2 parts (2% w/w) of sodium dodecyl sulfate

(commercial name: NK-SDS, Coseal), 8 parts (8% w/w) of sodium lignin sulfonate

(commercial name: NK-SLS, Coseal), and 80 parts (80% w/w) of kaolin were mixed, and

then grinded by using a hammer mill (model name: KDW-I, PAUD AL) to have an

average particle size of 5~10μ, to give a wettable powder.

10 parts (10% w/w) of a mixture of herbicidal active ingredient (Al or

A2)/herbicidal active ingredient (B), 1 part of sodium dodecyl sulfate (commercial name:

NK-SDS, Coseal), 3 parts (3% w/w) of sodium naphthalene-formaldehyde condensate

(commercial name: Morwet-D425, Whittko), 5 parts (5% w/w) of propylene glycol, 0.5

part (0.5% w/w) of bentonite of gel-grade (commercial name: NK-KNP, Coseal), and 80.5

parts (80.5% w/w) of purified water were mixed, and then grinded by using DYNO mill

(model name: Typ KDL A) to have an average particle size of 2-3 μ, to give a suspension

concentrate. 10 parts (10% w/w) of a mixture of herbicidal active ingredient (Al or

A2)/herbicidal active ingredient (B), 5 parts (5% w/w) of calcium dodecyl benzene

sulfonate (commercial name: CR-DBC64, Yusungwhayeontech), 2.5 parts (2.5% w/w) of

ethoxylated (average EO addition mole number: 10) oleyl alcohol (commercial name:

Koremul OElO, Hannongwhasung), 2.5 parts (2.5% w/w) of ethoxylated (average EO

addition mole number: 40) castor oil (commercial name: Koremul CO40,

Hannongwhasung), and alkyl benzene family naphtha solvent (commercial name: Kocosol

150, SK Corp.) were uniformly mixed by using an appropriate mixer, to give an

emulsifϊable concentrate.

Biological Example

The method for evaluating synergistic herbicidal activity and safety on crops by

mixed treatment of active ingredient (Al) or (A2) and one or more active ingredients (B)

selected from the group consisting of active ingredients (Bl) to (B9), and results thereof

are as follows.

1. Greenhouse pot test

Seeds or parts of reserve organ (propagule; tuber, stem, etc) of monocotyledon

weeds (Gramineae and Cyperaceae) and dicotyledon weeds (broad-leaved weed) were

seeded or transplanted into sandy loam soil in pot, and then grown under proper

greenhouse growth conditions (temperature, atmosphere humidity, and irrigation). For

the test under the conditions of paddy rice cultivation, the water was maintained at 3cm. After a certain period of time from seeding or transplantation, when the growth of the test

plants reached a certain stage, the composition of this invention was treated thereto. In

the case of soil application, the composition in fixed amount was directly applied to

flooded soil. In the case of foliar application, irrigated water was drained therefrom, and

then the composition in fixed amount was diluted with water and sprayed to the test plants

by using CO₂ pressurized belt-driven sprayer (R&D spray, USA) to deliver the spray

solution of 200 to 1000L/ha. Then, the treated plants were maintained in greenhouse

under the standard greenhouse growth conditions for about 3 to 4 weeks. Visual

assessment was then made to evaluate the herbicidal efficacy of the composition on the

treated plants in comparison with untreated control. The herbicidal efficacy of the

composition was recorded by % weed control, and was rated by 0% to 100% in

comparison with untreated control. 0% means no effect on weeds, and 100% means

complete death of weeds. Each treatment consisted of three or four replicates.

2. Field test

Crops were seeded or transplanted under field conditions where they can normally

grow, and at the same time, seeds or propagules (tuber, stem, etc) of monocotyledon and

dicotyledon were seeded or transplanted into plots placed in the field to grow them, or

uniformly and naturally established weeds were grown to a certain growth stage in the field.

When the growth of these weeds reached a certain stage, the composition of this invention

was treated. In the case of soil application, the composition in fixed amount was directly

applied to flooded soil. In the case of foliar application, the composition in fixed amount was immediately diluted with water, and sprayed to the test plants by using a CO₂

pressurized knapsack sprayer to deliver 200 to IOOOL ha^"1 of diluted solution. Prior to

foliar application, irrigated water was drained in the paddy condition. After about 5 to 7

weeks from the application of the composition, the herbicidal efficacy and phytotoxicity

were measured by the visual evaluation in comparison with untreated control by the same

scale as used in the above greenhouse pot test. Each treatment consisted of three or four

replicates.

3. Evaluation of synergistic effects

In cased of using the herbicidal composition of the invention, its herbicidal

efficacy against weeds exceeds the sum of individual herbicidal efficacies when each

herbicidal compound contained in the present composition is independently sprayed.

Therefore, it was observed that the composition of this invention provided the same

herbicidal efficacy against weeds with a lower rate of herbicidal compound, compared to

individual application of each herbicidal compound. Such increase in herbicidal activity

and efficacy or decrease in the treatment rate of active ingredient can be the strong

evidence to show synergistic effects of this invention. The evaluation of synergistic

effects shown in mixed application of two or more herbicidal active ingredients was

determined based on Colby's method described in "Calculation Synergistic and

Antagonistic Response of Herbicide Combinations" (Weeds 15/1 (1967) by S.R. Colby).

Therefore, the following formula was used for this purpose: E = X ₊ Y- ™) { 100 J

wherein X indicates weed control (%) by the herbicide A at a dose of X g a.i. ha^"1,

Y indicates weed control (%) by the herbicide B at a dose of Y g a.i. ha^"1, and

E indicates expected value in weed control (%) at a dose of X+Y g a.i. ha^"1.

If the actual weed control value observed in the biological test exceeds the

expected value (E) calculated by using the Colby's method, it means that the efficacy of

the herbicidal composition is greater than the sum of efficacies of individual components,

which means that the composition has synergistic effect.

4. Evaluation of increased crop safety

The crop safety is described by the term of "crop phytotoxicity," which means

damage on crop, and so a lower degree of phytotoxicity to crop means higher safety on

crop. The Crop phytotoxicity of the herbicidal composition of the present invention is

lower than the sum of crop phytotoxicities of individual herbicidal compounds contained in

the composition when independently sprayed. Therefore, the composition of the

invention has higher safety on crops, compared with compositions comprising individual

herbicidal active ingredients, and so the crop phytotoxicity occurred in a single component

application is significantly decreased enough to use for subject crops. Such increase in

safety can be calculated by the above Colby's method. If actual crop phytotoxicty (%)

observed in the mixture is lower than expected value (E) calculated by the Colby method, it means that the mixture has lower phytotoxicity than the sum of individual components, i.e.

the composition has synergistic safety effect.

The results of the above tests are shown in the following Tables 1 to 26.

Table 1

Herbicidal performance of compound (Al) and diclofop (Bl.1) against grass weed, Poa

annua in the field (by foliar application)

Table 2

Herbicidal performance of compound (Al) and metamifop (B 1.2) against grass weeds in

the field (by foliar application)

Table 3 Herbicidal performance of compound (Al) and clodinafop (Bl.4) against grass weed, Poa

annua in the field (by foliar application)

Table 4

Herbicidal performance of compound (Al) and thifensulfuron (B2.1) against broad-leaved

weeds in the field (by foliar application)

Table 5

Herbicidal performance of compound (Al) and flupyrsulfuron (B2.9) against grass weed,

Alopecurs myosuroides in the field (by foliar application)

Compound / Dose (g a.i. ha^" ) % weed control

Table 6

Herbicidal performance of compound (Al) and bensulfuron-methyl (B2.10) against

perennial weed, Eleocharis kuroguwai in the greenhouse (by soil application)

Table 7

Herbicidal performance of compound (Al) and cyclosulfamuron (B2.l l) against perennial

weeds in the greenhouse (by soil application)

Table 8

Herbicidal performance of compound (Al) and cinosulfuron (B2.12) against perennial

weed, Eleocharis kuroguwai in the greenhouse (by soil application)

Table 9

Herbicidal performance of compound (Al) and azimsulfuron (B2.13) against perennial

weeds in the greenhouse (by soil application)

Table 10

Herbicidal performance of compound (Al) and pyrazosulfuron-ethyl (B2.15) against

perennial weed, Cyperus serotinus in the greenhouse (by soil application)

Table 11

Herbicidal performance of compound (Al) and bentazone (B3.1) against Eleocharis

kuroguwai, barnyardgrass (Echinochloa crus-galli), and rice in the field (by foliar

application)

Table 12

Herbicidal performance of compound (Al) and simetryn (B3.5) against sulfonylurea

herbicide-resistant weeds in the greenhouse (by soil application)

Table 13

Herbicidal performance of compound (Al) and carfentrazone- ethyl (B4.3) against major

rice weeds, and rice in the field (by foliar application)

Table 14

Herbicidal performance of compound (Al) and carfentrazone-ethyl (B4.3) against

broad-leaved weed, Monochoria vaginalis in the greenhouse (by foliar application)

Table 15

Herbicidal performance of compound (Al) and carfentrazone-ethyl (B4.3) against major

weed, clover (Tήfolium repens) in a turf field (by foliar application)

*DAA: days after application

Table 16

Herbicidal performance of compound (Al) and carfentrazone-ethyl (B4.3) against

broad-leaved weeds in the field (by foliar application)

Table 17

Herbicidal performance of compound (Al) and pentoxazone (B4.6) against sulfonylurea

herbicide-resistant weeds in the greenhouse (by soil application)

Table 18

Herbicidal performance of compound (Al) and diflufenican (B5.1) against broad-leaved

weeds in the field (by foliar application)

Table 19

Herbicidal performance of compound (Al) and pyrazolate (B5.5) against sulfonylurea

herbicide-resistant weeds in the greenhouse (by soil application)

Table 20

Herbicidal performance of compound (Al) and butachlor (B6.1) against sulfonylurea

herbicide-resistant weeds in the greenhouse (by soil application)

Table 21

Herbicidal performance of compound (Al) and benfuresate (B7.1) against perennial weed,

Eleocharis kuroguwai in the greenhouse (by soil application)

Table 22 Herbicidal performance of compound (Al) and thiobencarb (B7.5) against sulfonylurea

herbicide-resistant weeds in the greenhouse (by soil application)

Table 23

Herbicidal performance of compound (Al) and 2,4-D (B8.3) against broad-leaved weeds

in the field (by foliar application)

Table 24

Herbicidal performance of compound (Al) and clomeprop (B8.7) against sulfonylurea

herbicide-resistant weeds in the greenhouse (by soil application)

Table 25

Herbicidal performance of compound (Al) and dithiopyr (B9.2) against sulfonylurea

herbicide-resistant Monochoria vaginalis in the greenhouse (by soil application)

Table 26

INDUSTRIAL APPLICABILITY

The herbicidal composition of the present invention has increased herbicidal

efficacy and extended weed spectrum, and so the amount of used herbicidal ingredients can

be reduced due to synergistic effect by mixing two herbicidal compounds having different

functions or different herbicidal efficacies, compared to individual application of each

herbicidal compound, and so the cost for weed control can be reduced by saving labor

through co-application of flucetosulfuron and other herbicidal compounds contained in the

herbicidal composition. Furthermore, the herbicidal composition comprising the

compound of the formula (1) or (2) and one or more other herbicidal compounds selected

from the group consisting of photosynthesis inhibitor bentazone, protopropyrinogen IX oxidase inhibitor carfentrazone-ethyl, and auxin-type herbicides, has synergistic effect to

increase herbicidal activity for perennial weeds and sulfonylurea resistant weeds, and can

resolve antagonism for grass weeds, particularly barnyardgrass, and can increase the safety

on rice for foliar application.

Claims

WHAT IS CLAIMED IS

1. A herbicidal composition comprising a compound of the following formula (1)

(herbicidal active ingredient (Al));

and one or more other active ingredients selected from the group (B) consisting of (B 1.1)

diclofop and ester thereof, (B 1.2) metamifop, (B 1.3) cyhalo fop-butyl, (B 1.4)

clodinafop-propargyl (Bl.5) fenoxaprop-P and ester thereof, (Bl.6) flamprop-M and ester

thereof, (Bl.7) tralcoxydim, (B1.8) profoxydim, (B2.1) thifensulfuron-methyl, (B2.2)

metsulfuron-methyl, (B2.3) prosulfuron, (B2.4) tribenuron-methyl, (B2.5)

mesosulfuron-methyl, (B2.6) flazasulfuron, (B2.7) sulfosulfuron, (B2.8) iodosulfuron and

ester thereof, (B2.9) flupyrsulfuron and ester thereof, (B2.10) bensulfuron and ester thereof,

(B2.l l) cyclosulfamuron, (B2.12) cinosulfuron, (B2.13) azimsulfuron, (B2.14)

imazosulfuron, (B2.15) pyrazosulfuron-ethyl, (B2.16) penoxulam, (B2.17) florasulam,

(B2.18) bispyribac-sodium, (B2.19) pyribenzoxim, (B3.1) bentazone, (B3.2) bromoxynil

and bromoxynil-octanoate, (B3.3) ioxynil, and ester and salt thereof, (B3.4) terbutryn,

(B3.5) simetryn, (B3.6) chlorotoluron (B3.7) isoproturon, (B4.1) oxyfluorfen, (B4.2)

pyraflufen-ethyl, (B4.3) carfentrazone-ethyl, (B4.4) cinidon-ethyl, (B4.5) oxadiargyl,

(B4.6) pentoxazone, (B5.1) diflurfenican, (B5.2) picolinafen, (B5.3) mesotrione, (B5.4) pyrazoxyfen, (B5.5) pyrazolate, (B5.6) benzobicyclon, (B5.7) clomazone, (B6.1) butachlor,

(B6.2) flufenacet, (B6.3) mefenacet, (B6.4) fentrazamide, (B6.5) pretilachlor, (B6.6)

cafenstrole, (B6.7) isoxaben, (B7.1) benfuresate, (B7.2) ethofumesate, (B7.3) prosulfocarb,

(B7.4) triallate, (B7.5) thiobencarb, (B8.1) triclopyr, (B8.2) fluroxypyr and ester thereof,

(B8.3) 2,4-D and ester thereof, (B8.4) MCPA and ester thereof, (B8.5) MCPB and ester

thereof, (B8.6) mecoprop and mecoprop-P, (B8.7) clomeprop, (B8.8) dicamba, (B9.1)

pendimethalin, (B9.2) dithiopyr, (B9.3) difenzoquat-methyl sulfate, (B9.4) bromobutide,

(B9.5) indanofan, and (B9.6) pyributicarb.

2. A herbicidal composition comprising a compound of the following formula (2)

(herbicidal active ingredient (A2));

and one or more other active ingredients selected from the group (B) as defined in claim 1.

3. The herbicidal composition of claim 1 or 2, wherein the weight ratio of the active

ingredient Al or A2 and the active ingredient B is 1:200 to 200:1.

4. The herbicidal composition of claim 3, wherein the weight ratio of the active

ingredient Al or A2 and the active ingredient B is 1:100 to 20:1.

5. The herbicidal composition of claim 1 or 2, further comprising one or more

selected from the group consisting of insecticide, fungicide, safener and plant growth

regulator.

6. The herbicidal composition of claim 1 or 2, further comprising one or more

selected from the group consisting of carriers, surfactants and additives.

7. A method for controlling weed, comprising applying the herbicidal composition of

claim 1 or 2 to crop fields or non-cropping area.

8. A method for controlling weed, comprising applying the herbicidal composition of

claim 1 or 2 to rice cultivation.

9. A method for controlling weed, comprising applying the herbicidal composition of

claim 1 or 2 to cereals cultivation.

10. A method for controlling weed, comprising applying the herbicidal composition of

claim 1 or 2 to grass or pasture.

11. The method of claim 7, wherein the herbicidal composition is treated by foliar

application.

12. The method of claim 11, wherein the active ingredient B is one or more selected

from the group consisting of (B3.1) bentazone, (B4.3) carfentrazone-ethyl, (B8.2)

fluroxypyr and ester thereof, (B8.3) 2,4-D and ester thereof, (B8.4) MCPA and ester

thereof, (B8.5) MCPB and ester thereof, (B8.6) mecoprop and mecoprop-P, (B8.7)

clomeprop and (B8.8) dicamba.