CN105121416B - The crystalline polymorphic form and its manufacturing method of isoxazoline substituted benzamide compound - Google Patents

Abstract

The object of the present invention is to provide (Z) -, [5- (3,5- dichlorophenyl) -5- trifluoromethyl -4,5- dihydro is differentAzoles -3- base]-N- (methoxyimino methyl) -2- methyl benzamide crystalline form, its manufacturing method and the suspension composition containing it.It is that (Z)-[5- (3,5- dichlorophenyl) -5- trifluoromethyl -4,5- dihydro is different as the method for solving project of the present inventionAzoles -3- base]-N- (methoxyimino methyl) -2- methyl benzamide I type crystallization or II type crystallization.The good suspension composition of storage stability containing I type crystallization and decentralized medium.The good suspension composition of storage stability containing I type crystallization and decentralized medium.

Description

The crystalline polymorphic form of isoxazoline substituted benzamide compound and its manufacture Method

Technical field

The present invention relates to (Z) -4-, [5- (3,5- dichlorophenyl) -5- trifluoromethyl -4,5- dihydro is differentAzoles -3- base]-N- (methoxyimino methyl) -2- methyl benzamide (hereinafter referred to as compound A.) crystalline polymorphic form, its manufacturer The suspension composition of method and the crystalline polymorphic form containing compound A.

Background technique

The solid state of chemical compound can be amorphism (that is, the position of atom does not have order over long distances) or crystallinity (that is, atom is arranged with Methodistic pattern repeatedly).Solid state about most compounds, it is known that be only single crystalline substance Shape, but for some compounds, it was found that polymorph.Term as " polymorph " refers to solid state and can be with two Kind or more chemical compound existing for crystalline form specific crystalline form (that is, structure of lattice).

On the other hand, it is known that the compound A that the present invention is included is useful (for example, ginseng as noxious organism control agent According to patent document 1.).So-called noxious organism control agent in the present invention refers to agriculture and garden field or livestock products, health neck Domain (the internal or external parasite agent, home-use and work as domestic animal, the mammal of pet animal or birds Sanitary insect pest, offensive insect pest control agent) etc. in insect pest control agent of the harmful arthropod as object.

Existing technical literature

Patent document

Patent document 1: International Publication No. 2007/026965

Summary of the invention

Problems to be solved by the invention

Predict that the physical characteristics such as fusing point, the water solubility of crystallization of chemical compound are still impossible.Further, in advance Survey compound solid state whether be two or more crystalline forms, i.e., whether can with crystalline polymorphic form exist be also can not Can.

The object of the present invention is to provide the new crystalline polymorphic forms and its manufacturing method of compound A.Of the invention is another One purpose is to provide the suspension composition that the storage stability containing compound A improves.

The method used for solving the problem

The inventors of the present invention have made intensive studies, as a result, it has been found that the new crystalline polymorphic form of compound A.This outgoing It is existing, suspension composition is being modulated using the compound A for containing these crystalline polymorphic forms with specific weight rate In the case of, the storage stability of the suspension composition improves significantly.

That is, the present invention relates to following (1)~(17).

〔1〕

(Z) [5- (3,5- dichlorophenyl) -5- trifluoromethyl -4,5- dihydro is different by -4-Azoles -3- base] (methoxyl group is sub- by-N- Amino methyl) -2- methyl benzamide be named as I type crystallization crystalline polymorphic form, utilize the Alpha-ray powder of Cu-K In last X-ray diffraction, 2 θ of the angle of diffraction=(7.45 ± 0.2,11.05 ± 0.2,12.79 ± 0.2,15.30 ± 0.2,20.90 ± 0.2,21.89 ± 0.2 and 24.32 ± 0.2) there is peak.

〔2〕

It is named as the crystalline polymorphic form of I type crystallization according to (1), is penetrated using the Alpha-ray powder X-ray of Cu-K In line diffraction, the display diffraction curve substantially the same with Fig. 1 of present specification attached drawing.

〔3〕

(Z) [5- (3,5- dichlorophenyl) -5- trifluoromethyl -4,5- dihydro is different by -4-Azoles -3- base] (methoxyl group is sub- by-N- Amino methyl) -2- methyl benzamide be named as II type crystallization crystalline polymorphic form, using Cu-K it is Alpha-ray In powder x-ray diffraction, in 2 θ of the angle of diffraction=(5.00 ± 0.2,9.24 ± 0.2,13.39 ± 0.2,16.45 ± 0.2,19.35 ± 0.2,23.17 ± 0.2 and 26.21 ± 0.2) there is peak.

〔4〕

It is named as the crystalline polymorphic form of II type crystallization according to (3), is utilizing the Alpha-ray powder X-ray of Cu-K In x ray diffraction, the display diffraction curve substantially the same with Fig. 2 of present specification attached drawing.

〔5〕

(Z) [5- (3,5- dichlorophenyl) -5- trifluoromethyl -4,5- dihydro is different by -4-Azoles -3- base] (methoxyl group is sub- by-N- Amino methyl) -2- methyl benzamide crystalline polymorphic form, wherein I type described in above-mentioned (1) crystallization containing ratio be 50~100 weight %.

〔6〕

(Z) [5- (3,5- dichlorophenyl) -5- trifluoromethyl -4,5- dihydro is different by -4-Azoles -3- base] (methoxyl group is sub- by-N- Amino methyl) -2- methyl benzamide crystalline polymorphic form, wherein II type described in above-mentioned (3) crystallization containing ratio be 99.5~100 weight %.

〔7〕

It is named as the manufacturing method of the crystalline polymorphic form of I type crystallization described in above-mentioned (1), wherein

(a) modulation makes (Z) -4- [5- (3,5- dichlorophenyl) -5- trifluoromethyl -4,5- dihydro is differentAzoles -3- base]-N- (methoxyimino methyl) -2- methyl benzamide is dissolved in solution obtained by solvent,

(b) cooling of above-mentioned solution is made into its partial crystallization.

〔8〕

It is named as the manufacturing method of the crystalline polymorphic form of II type crystallization described in above-mentioned (3), wherein

(a) modulation makes (Z) -4- [5- (3,5- dichlorophenyl) -5- trifluoromethyl -4,5- dihydro is differentAzoles -3- base]-N- (methoxyimino methyl) -2- methyl benzamide is dissolved in solution obtained by solvent,

(b) make its partial crystallization by the way that above-mentioned solution to be added dropwise in the solvent cooled.

〔9〕

It is named as the manufacturing method of the crystalline polymorphic form of I type crystallization described in above-mentioned (1), which is characterized in that make The crystallization of II type described in above-mentioned (3) is suspended in decentralized medium, and resulting aaerosol solution is stood or stirred.

〔10〕

A kind of suspension composition contains the crystallization of I type described in above-mentioned (1) and decentralized medium.

〔11〕

A kind of aqueous suspension shape composition, containing the crystallization of I type described in above-mentioned (1), surfactant and as dispersion The water of medium.

〔12〕

A kind of suspension composition contains the crystallization of II type described in above-mentioned (3) and decentralized medium.

〔13〕

A kind of aqueous suspension shape composition, containing the crystallization of II type described in above-mentioned (3), surfactant and as dispersion The water of medium.

〔14〕

A kind of suspension composition, the containing ratio containing the crystallization of I type described in above-mentioned (1) are 50~100 weight %'s (Z) [5- (3,5- dichlorophenyl) -5- trifluoromethyl -4,5- dihydro is different by -4-Azoles -3- base]-N- (methoxyimino first Base) -2- methyl benzamide and decentralized medium.

〔15〕

According to suspension composition described in above-mentioned (14), further contain surfactant, decentralized medium is water.

〔16〕

A kind of suspension composition, the containing ratio containing the crystallization of II type described in above-mentioned (3) are 99.5~100 weight % (Z) -4- [5- (3,5- dichlorophenyl) -5- trifluoromethyl -4,5- dihydro is differentAzoles -3- base]-N- (methoxyimino first Base) -2- methyl benzamide and decentralized medium.

〔17〕

According to suspension composition described in above-mentioned (16), further contain surfactant, decentralized medium is water.

The effect of invention

In accordance with the invention it is possible to control the crystalline polymorphic form of compound A.In addition, containing the compound of the present invention A's The storage stability of suspension composition is good, timely the suspended particles growth of inhibiting compound A, as a result, also not sending out The problem of raw Pesticidal activity as caused by the growth of the suspended particles of compound A reduces.

Detailed description of the invention

Fig. 1 shows the x-ray diffractogram of powder of I type crystallization.

Fig. 2 indicates the x-ray diffractogram of powder of II type crystallization.

Fig. 3 is indicated in example 4, from the dried object of the compound A of the aqueous suspension shape composition pesticide taking-up after rigid manufacture X-ray diffractogram of powder.

Fig. 4 is indicated in example 17, from the dried object of the compound A of the aqueous suspension shape composition pesticide taking-up after rigid manufacture X-ray diffractogram of powder.

Specific embodiment

Compound A is that [5- (3,5- dichlorophenyl) -5- trifluoromethyl -4,5- dihydro is different by (Z) -4-Azoles -3- base]-N- (methoxyimino methyl) -2- methyl benzamide.

The molecular structure of compound A can exist in a manner of two different stereoisomers (that is, enantiomer).So And the present invention relates to the racemic mixtures for the compound A for equal amount including both possible enantiomers.

In addition, the geometric isomer sometimes comprising the E body from iminomethyl structure is as impurity in compound A. As the ratio of geometric isomer, (Z body: E body)=80:20~100:0 can be enumerated, preferably (Z body: E body)=90:10~ 100:0, further preferably (Z body: E body)=95:5~99.5:0.5, more preferably (Z body: E body)=96:4~99.5: 0.5, most preferably (Z body: E body)=97:3~99.5:0.5.

The feature of the crystallization of I type and the crystallization of II type as compound A, powder x-ray diffraction peak is shown in the 1st table.

[table 1]

1st table

In addition, the peak value of the crystallization of I type documented by the 1st table is 7 obtained according to method documented by embodiment below The average value of the peak value of the I type crystallization of a batch.

In addition, the peak value of the crystallization of II type documented by the 1st table is the II type crystallization of 6 batches in the same manner as the crystallization of I type The average value of peak value.

In addition, the error as powder x-ray diffraction peak, usually ± 0.2, it according to circumstances can use ± 0.1, therefore consider The peak value of the I type crystallization of error be usually 2 θ=7.45 ± 0.2,11.05 ± 0.2,12.79 ± 0.2,15.30 ± 0.2, 20.90 ± 0.2,21.89 ± 0.2,24.32 ± 0.2, be according to circumstances 2 θ=7.45 ± 0.1,11.05 ± 0.1,12.79 ± 0.1、15.30±0.1、20.90±0.1、21.89±0.1、24.32±0.1。

Furthermore consider error II type crystallization peak value be usually 2 θ=5.00 ± 0.2,9.24 ± 0.2,13.39 ± 0.2,16.45 ± 0.2,19.35 ± 0.2,23.17 ± 0.2,26.21 ± 0.2, it is according to circumstances 2 θ=5.00 ± 0.1,9.24 ±0.1、13.39±0.1、16.45±0.1、19.35±0.1、23.17±0.1、26.21±0.1。

(powder x-ray diffraction)

Kinds of machine title: X ' PERT-PRO MPD (ス ペ Network ト リ ス Co., Ltd.)

Measuring method: transmission beam method

X-ray: Cu-K α

Voltage: 45kV

Electric current: 40mA

Sampling interval: 0.026deg

Data area: 2 θ=2~40deg

The I type crystallization of compound A can be manufactured using following methods.By compound A being heated in a solvent and molten Resulting solution is slowly cooled down the method crystallize it by solution；Or solvent is distilled off from resulting solution The method for crystallizing it, to obtain the I type crystallization of compound A.As used solvent, as long as being to compound A Inactive solvent can be used for example, Anaesthetie Ether, methyl t-butyl ether, tetrahydrofuran, dimethoxymethane, two Ethoxy methane, ethylene glycol dimethyl ether, ethylene glycol Anaesthetie Ether, ethylene glycol dibutyl ethers, diethylene glycol dimethyl ether, diethyl Glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, 1,4- bis-The ether series solvents such as alkane, methanol, second It is alcohol, 1- propyl alcohol, 2- propyl alcohol, n-butyl alcohol, 2- butanol, isobutanol, 2- methyl-2-propanol, methyl cellosolve, ethyl cellosolve, different Propyl cellosolve, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, cyclohexanol, benzyl alcohol etc. The aliphatic hydrocarbons such as alcohol series solvent, pentane, hexane, hexamethylene, hexahydrotoluene, heptane, octane, decane series solvent, benzene, toluene, The aromatic hydrocarbon series solvents such as dimethylbenzene, chlorobenzene, o-dichlorohenzene, m-dichlorobenzene, paracide, nitrobenzene, naphthane, acetonitrile, third The ester series solvents such as the nitrile series solvents such as nitrile, methyl acetate, ethyl acetate, butyl acetate, ethyl propionate, methylene chloride, chloroform, tetrachloro Change halogenated hydrocarbon system solvent, N,N-dimethylformamide, the N such as carbon, 1,2- dichloroethanes, 1,1,2- trichloroethanes, N- dimethyl second The acid amides series solvents such as amide, N-Methyl pyrrolidone, 1,3- dimethyl-imidazolinone, N, N, N ', the ureas such as N '-tetramethylurea system is molten The sulfur-bearings such as agent, dimethyl sulfoxide, sulfolane system polar solvent, pyridine, 2- picoline, 3- picoline, 4- picoline, 5- ethyl -2- Pyridines series solvent such as picoline etc., these solvents can be used alone or be use mixing two or more.In these solvents, excellent Be selected as aliphatic hydrocarbon series solvent, aromatic hydrocarbon series solvent or nitrile series solvent, be even more preferably heptane, dimethylbenzene, toluene or Acetonitrile.

1 parts by weight of the usage amount of used solvent relative to compound A, usually 0.5~50 parts by weight, preferably 1~30 parts by weight.

So that compound A is dissolved in the temperature of solvent is usually 30~150 DEG C, and preferably 30~100 DEG C.

Cooling speed is usually 0.1~40 DEG C/h, preferably 1~30 DEG C/h, can be at any time in above range Inside it is changed to arbitrary cooling velocity.

The temperature for taking out solution when crystallization be precipitated is usually -30~50 DEG C, preferably -20~30 DEG C.

Time required for partial crystallization is usually 0.1~100 hour, and preferably 1~50 hour.

It, can be under atmospheric pressure by being heated to the boiling point of solvent in addition, in the case where solvent to be distilled off It is distilled off above.Furthermore by adjusting the degree of decompression in container, so as to up to the solvent boiling point under decompression Until arbitrary temp solvent is distilled off.

The II type crystallization of compound A can be manufactured using following methods.By compound A being heated in a solvent and molten Resulting solution is promptly cooled down the method crystallize it by solution；Compound A is heated and dissolved in a solvent, by institute The solution of the compound A obtained is added dropwise in the solvent of low temperature the method for crystallizing it；Or compound A is added in a solvent Temperature simultaneously dissolves, in the method for the solvent that low temperature is wherein added dropwise, to can get the II type crystallization of compound A.As can adjust The solvent used when the solution of produced compounds A can be used as long as being inactive solvent to compound A for example, two Ethylether, methyl t-butyl ether, tetrahydrofuran, dimethoxymethane, diethoxymethane, ethylene glycol dimethyl ether, ethylene glycol Anaesthetie Ether, ethylene glycol dibutyl ethers, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, three Ethylene glycol dimethyl ether, 1,4- bis-It is the ether series solvents such as alkane, methanol, ethyl alcohol, 1- propyl alcohol, 2- propyl alcohol, n-butyl alcohol, 2- butanol, different Butanol, 2- methyl-2-propanol, methyl cellosolve, ethyl cellosolve, ispropyl cellosolve, diethylene glycol monomethyl ether, diethyl two Alcohol series solvents, pentane, hexane, hexamethylene, the methyl cyclohexanes such as alcohol list ethylether, diethylene glycol monobutyl ether, cyclohexanol, benzyl alcohol The aliphatic hydrocarbons such as alkane, heptane, octane, decane series solvent, benzene,toluene,xylene, chlorobenzene, o-dichlorohenzene, m-dichlorobenzene, to two The nitrile series solvents such as the aromatic hydrocarbon series solvents such as chlorobenzene, nitrobenzene, naphthane, acetonitrile, propionitrile, methyl acetate, ethyl acetate, acetic acid The ester series solvents such as butyl ester, ethyl propionate, methylene chloride, chloroform, carbon tetrachloride, 1,2- dichloroethanes, 1,1,2- trichloroethanes etc. The acid amides series solvents such as halogenated hydrocarbon system solvent, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, 1, 3- dimethyl-imidazolinone, N, N, N ', the sulfur-bearings system such as the ureas such as N '-tetramethylurea series solvent, dimethyl sulfoxide, sulfolane polarity is molten Pyridines series solvents such as agent, pyridine, 2- picoline, 3- picoline, 4- picoline, 5- ethyl -2- picoline etc., these solvents can be with It is used alone or is use mixing two or more.In these solvents, preferably aromatic hydrocarbon series solvent, nitrile series solvent or ester system Solvent is even more preferably dimethylbenzene, toluene, acetonitrile, ethyl acetate or butyl acetate.

Make 1 parts by weight of the usage amount of the solvent of compound A dissolution relative to compound A, usually 0.5~50 weight Part, preferably 1~30 parts by weight.

In addition, the solvent as low temperature, as long as can be used to be inactive solvent to compound A for example, two Ethylether, methyl t-butyl ether, tetrahydrofuran, dimethoxymethane, diethoxymethane, ethylene glycol dimethyl ether, ethylene glycol Anaesthetie Ether, ethylene glycol dibutyl ethers, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, three Ethylene glycol dimethyl ether, 1,4- bis-It is the ether series solvents such as alkane, methanol, ethyl alcohol, 1- propyl alcohol, 2- propyl alcohol, n-butyl alcohol, 2- butanol, different Butanol, 2- methyl-2-propanol, methyl cellosolve, ethyl cellosolve, ispropyl cellosolve, diethylene glycol monomethyl ether, diethyl two Alcohol series solvents, pentane, hexane, hexamethylene, the methyl cyclohexanes such as alcohol list ethylether, diethylene glycol monobutyl ether, cyclohexanol, benzyl alcohol The aliphatic hydrocarbons such as alkane, heptane, octane, decane series solvent, benzene,toluene,xylene, chlorobenzene, o-dichlorohenzene, m-dichlorobenzene, to two The nitrile series solvents such as the aromatic hydrocarbon series solvents such as chlorobenzene, nitrobenzene, naphthane, acetonitrile, propionitrile, methyl acetate, ethyl acetate, acetic acid The ester series solvents such as butyl ester, ethyl propionate, methylene chloride, chloroform, carbon tetrachloride, 1,2- dichloroethanes, 1,1,2- trichloroethanes etc. The acid amides series solvents such as halogenated hydrocarbon system solvent, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone, 1, 3- dimethyl-imidazolinone, N, N, N ', the sulfur-bearings system such as the ureas such as N '-tetramethylurea series solvent, dimethyl sulfoxide, sulfolane polarity is molten Pyridines series solvents such as agent, pyridine, 2- picoline, 3- picoline, 4- picoline, 5- ethyl -2- picoline etc., these solvents can be with It is used alone or is use mixing two or more.In these solvents, preferably aliphatic hydrocarbon series solvent, aromatic hydrocarbon series solvent Or nitrile series solvent, it is even more preferably heptane, dimethylbenzene, toluene or acetonitrile.Furthermore the solvent of the low temperature can be with dissolutionization The solvent for closing object is identical, can also be different.

Using low temperature solvent in the case where 1 parts by weight of the usage amount relative to compound A, usually 1~100 weight Part, preferably 5~50 parts by weight.

Speed when solution containing compound A is promptly cooled down is usually 40 DEG C/h or more.

The temperature of the solvent of low temperature is usually -30~50 DEG C, preferably -20~30 DEG C.

The temperature for taking out the solution when crystallization being precipitated is usually -30~50 DEG C, preferably -20~30 DEG C.

In addition, the I type crystallization of compound A can be according to following documented method, by crystallizing the II type of compound A Be converted acquisition.

(1) suspension method:

The compound A of the solid state crystallized containing II type is added into decentralized medium, by by resulting suspension It stands or stirs certain time, to can get the I type crystallization of compound A.As decentralized medium, above-mentioned I type knot can be used Used solvent when the manufacture of crystalline substance.In these decentralized media, preferably aromatic hydrocarbon or nitrile, particularly preferably diformazan Benzene, toluene or acetonitrile.The temperature of suspension when standing or stirring is usually -20~100 DEG C.In order to obtain the I type of purity is high Crystallization, the longer the better for standing or mixing time, usually stand or stir 1 hour or more.

(2) crystallization+suspension method:

In the case where the mixture of the crystallization of I type and the crystallization of II type for obtaining compound A in above-mentioned crystallization, pass through Resulting suspension is stood or stirred certain time, so as to be converted into the crystallization of I type.

(3) heating:

By heating the compound A of the solid state crystallized containing II type, so as to be converted into the crystallization of I type. As heating method, it can enumerate and utilize the method contacted with high temperature non-active gas；With the mixing for being equipped with heating device The method that machine is mixed.In addition, by the suspension of the II type crystallization of compound A or the crystallization of II type and the mixture of I type crystallization It is heated, the crystallization of I type can also be converted into.

(4) case of wet attrition method:

Case of wet attrition is carried out by the suspension for the solid for crystallizing the II type containing compound A, so as to be converted into I Type crystallization.As wet crushing mill, online grinding machine or ball mill etc. can be used.

(5) dry grinding method:

Dry grinding is carried out by the solid for crystallizing the II type containing compound A, so as to be converted into the crystallization of I type. As Dry-crusher, hammer-mill, pin rod mill, jet mill, ball mill or roller mill etc. can be used.

The I type of compound A crystallizes or the crystallization of II type respectively not only has raising preparation stability, but also has to improve and live Property, improve the technical characteristics such as handling easiness.

Next, for containing the compound of the present invention A I type crystallization or II type crystallization suspension composition (hereinafter, The referred to as present composition.), it is described in detail.

The present composition can be used water or compound A be difficult to the organic liquid dissolved as its decentralized medium.Make For the organic liquid, the alcohols such as ethylene glycol, diethylene glycol (DEG), propylene glycol, dipropylene glycol and isopropanol, butyl cellosolve can be enumerated The sour amide such as esters, N-Methyl pyrrolidone and the n-octylpyrrolidone such as ketone, the gamma-butyrolactons such as equal ethers, cyclohexanone, dimethylbenzene, Aromatic hydrocarbons, machinery oil, normal paraffin hydrocarbons, isoparaffin and the cycloalkane such as alkylbenzene, phenyl xylyl ethane and alkylnaphthalene etc. The mixture of the aromatic hydrocarbons such as aliphatic hydrocarbon, kerosene and aliphatic hydrocarbon, soya-bean oil, Linseed oil, rapeseed oil, coconut oil, cottonseed oil With the greases such as castor oil.

The I type of compound A crystallizes and/or the content of II type crystallization is relative to 100 parts by weight of the present composition, usually 0.1~50 parts by weight, more preferably 1~30 parts by weight.

Containing compound A I type crystallization suspension composition can inhibit compound A suspended particles through when growth. In addition, the suspension composition for the compound A that the containing ratio containing the crystallization of I type is 50~100 weight % also can inhibit compound A Suspended particles through when grow.

Containing compound A II type crystallization suspension composition can inhibit compound A suspended particles through when growth. In addition, the suspension composition for the compound A that the containing ratio containing the crystallization of II type is 99.9~100 weight % also can inhibit chemical combination The suspended particles of object A through when grow.

In the present composition other than compound A, it can also further contain a kind of pesticide above known, example again Such as herbicide, insecticide, acaricide, nematicide, antivirotic, plant growth regulator, fungicide, synergist, attractant With repellant etc., in this case, the further excellent preventive effect of display sometimes.It is particularly preferred as well known pesticide Pesticide is fungicide, bactericide, nematicide, acaricide and insecticide.Specifically, if illustrating its adopted name, It is as follows, but not necessarily only it is defined in these.

Fungicide: Acibenzolar (acibenzolar-S-methyl), acyl amino benzamide (acylaminobenzamide), eight or nine ten nitration mixture (acypetacs), aldimorph, azoles mepanipyrim (ametoctradin), Amisulbrom (amisulbrom), ambam (amobam), ammonia propyl-phosphine sour (ampropyfos), anilazine (anilazine), Oxygen ring azoles (azaconazole), azithiram (azithiram), Fluoxastrobin (azoxystrobin), solbar (bariumpolysulfide), M 9834 (benalaxyl), benalaxyl-M (benalaxyl-M), benodanil (benodanil), benomyl (benomyl), benquinox (benquinox), the third azoles grass grand (bentaluron), Benthiavalicarb, benthiozole (benthiazole), section olefin(e) acid (benzamacril), Benzene (benzamorf), Bethoxazine, binapacryl (binapacryl), biphenyl (biphenyl), bitertanol (bitertanol), blasticidin S (blasticidin-S), biphenyl pyrrole bacterium amine (bixafen), Bordeaux mixture (bordeaux mixture), niacinamide (boscalid), bromuconazole (bromoconazole), bupirimate (bupirimate), buthiobate (buthiobate), Lime sulfur (calcium polysulfide), lime sulfur (calcium polysulfide), difoltan (captafol), Captan (captan), ring propionyl bacterium amine (carpropamid), carbamorph (carbamorph), carbendazim (carbendazim), carboxin (carboxin), carvol (carvone), cheshunt mixture (cheshunt Mixture), chinomethionat (chinomethionat), pest of going out azoles (chlobenthiazone), Imugan (chloraniformethane), tetrachloroquinone (chloranil), benzene imidazoles bacterium (chlorfenazol), chloroanisole (chloroneb), chloropicrin (chloropicrin), Bravo (chlorothalonil), four chloroquinesQuinoline (chlorquinox), chlozolinate (chlozolinate), Climbazole (climbazole), clotrimazole (clotrimazole), second Sour copper (copper acetate), basic copper carbonate (copper carbonate, basic), Kocide SD (copper Hydroxide), copper naphthenate (copper naphthenate), copper oleate (copper oleate), copper oxychloride (copper Oxychloride), copper sulphate (copper sulfate), basic copper sulfate (copper sulfate, basic), copper chromate zinc (copper zincchromate), cufraneb (cufraneb), cuprobam (cuprobam), cyazofamid (cyazofamid), Ring bacterium amine (cyclafuramid), cycloheximide (cycloheximide), ring fluorine benzyl amide (cyflufenamid), cymoxanil (cymoxanil), cypendazole (cypendazole), Cyproconazole (cyproconazol), cyprodinil (cyprodinil), Cyprofuram (cyprofuram), dazomet (dazomet), debacarb (debacarb), decafentin (decafentin), dehydroactic acid (dehydroacetic acid), dichlofluanid (dichlofluanid), dichlone (dichlone), antiphen (dichlorophen), sclex (dichlozoline), diclobutrazol (diclobutrazol), double chlorine zarilamid (diclocymet), diclomezin (diclomedine), botran (dicloran) etc..

Fungicide (continuation): diethofencarb (diethofencarb), difenoconazole (difenoconazole), the phonetic bacterium of fluorine Amine (diflumetorim), dimethirimol (dimethirimol), dimethomorph (dimethomorph), dimoxystrobin (dimoxystrobin), olefin conversion (diniconazole), efficient olefin conversion (diniconazole-M), dinobuton (dinobuton), dinitro crotons phenolic ester (dinocap), dinitro crotons phenolic ester -4 (dinocap-4), dinitro crotons phenolic ester -6 (dinocap-6), dinitro ester (dinocton), nitre monooctyl ester (dinosulfon), dinoterbon (dinoterbon), diphenylamines (diphenylamine), pyrrole bacterium sulphur (dipyrithione), Plondrel (ditalimfos), dithianon (dithianon), Dodemorph (dodemorph), dodine (dodine), drazoxolon (drazoxolon), edifenphos (edifenphos), fluorine Ring azoles (epoxiconazole), etaconazole (etaconazole), Guardian (ethaboxam), Ethisul (etem), second are phonetic Phenol (ethirimol), ethoxyquin (ethoxyquin), Grandox fumigant (etridiazole),Cycloheximide triazole (famoxadone), Fenarimol (fenarimol), febuconazole, Fenamidone (fenamidone), fenaminosulf (fenaminosulf), Fenapanil (fenapanil), fendazosulam, fenfuram (fenfuram), fenhexamid (fenhexamid), kind clothing ester (fenitropan), fenoxanil (fenoxanil), fenpiclonil (fenpiclonil), fenpropidin (fenpropidin), amine benzene Pyrrole bacterium ketone (fenpyrazamine), butadiene morpholine (fenpropimorph), fentin (fentin), fervam (ferbam), Ferimzone (ferimzone), fluazinam (fluazinam), fludioxonil (fludioxonil), fluorine acyl bacterium amine (flumetover), Flumorph (flumorph), fluopicolide (fluopicolide), fluopyram (fluopyram), fluoromide (fluoroimide), fluotrimazole (fluotrimazole), fluoxastrobin (fluoxastrobin), Fluquinconazole (fluquinconazole), Flusilazole (flusilazole), flusulfamide (flusulfamide), fluorine thiophene bacterium are net (flutianil), flutolanil (flutolanil), Flutriafol (flutriafol), fluxapyroxad (fluxapyroxad), go out Bacterium pellet (folpet), phosethyl-Al (fosetyl-aluminium), furidazol (fuberidazole), furalaxyl (furalaxyl), furametpyr (furametpyr), furcarbanil (furcarbanil), furconazole (furconazole), Furconazole_cis (furconazole-cis), seed dressing amine (furmecyclox), furphanate, glyodin (glyodin), ash sprout are mould Element (griseofulvin), the pungent salt of biguanides (guazatine), halacrinate (halacrinate), hexachloro-benzene (hexachlorobenzene), hexaconazole (hexaconazole), hexamethylene sulphur phosphorus (hexylthiofos), 8-hydroxyquinoline sulphur Hydrochlorate (8-hydroxyquinoline sulfate),Mould spirit (hymexazol), imazalil (imazalil), glyoxalin (imibenconazole), iminoctadine (iminoctadine), kind bacterium azoles (ipconazole), different rice blast net (iprobenfos), iprodione (iprodione), iprovalicarb (iprovalicarb), Isoprothiolane (isoprothiolane), chlorine Benzene Climbazole (isovaledione) etc..

Fungicide (continuation): kasugarnycin (kasugamycin), kresoxim-methyl (kresoxim-methyl), mancopper (mancopper), Mancozeb (mancozeb), mandipropamid (mandipropamid), maneb (maneb), mebenil (mebenil), mecarbinzid, mepanipyrim (mepanipyrim), mebenil (mepronil), metalaxyl (metalaxyl), Mefenoxam (metalaxyl-M), metham-sodium (metam), metazoxolon, metconazole (metconazole), methasulfocarb (methasulfocarb), methuroxam (methfuroxam), enemy line ester (methyl isothiocyanate), Carbatene (metiram), SSF 126 (metominostrobin), metrafenone (metrafenone), metsulfovax (metsulfovax), Milneb (milneb), nitrile bacterium azoles (myclobutanil), myclozolin (myclozolin), Dithane A40 (nabam), Natamycin (natamycin), dimethylamino dithiocarbonic acid nickel (nickel bis (dimethyldithiocarbamate)), nitrobenzene Ethylene (nitrostyrene), nitrothalisopropyl (nitrothal-isopropyl), nuarimol (nuarimol), OCH, pungent thiophene Ketone (octhilinone), ofurace (ofurace), orysastrobin (orysastrobin),It is white clever (oxadixyl), organic Copper (oxine copper), oxycarboxin (oxycarboxin),Oxpoconazole fumarate (oxpoconazole Fumarate), pefurzoate, penconazole (penconazole), fluorine azoles bacterium aniline (penflufen), Pencycuron (pencycuron), pyrrole metsulfovax (penthiopyrad), o-phenyl phenol (o-phenylphenol), phosdiphen (phosdiphen), Rabcide (phthalide), ZEN 90160 (picoxystrobin), disease spend spirit (piperalin), generation Gloomy ziram (polycarbamate), polyoxin (polyoxins), Polyoxin (polyoxorim), potassium azide (potassium azide), saleratus (potassiumhydrogencarbonate), the third oxygen quinoline (proquinazid), Probenazole (probenazole), Prochloraz (prochloraz), procymidone (procymidone), propamocarb (propamocarb hydrochloride), propiconazole (propiconazole), Propineb (propineb), prothiocarb (prothiocarb), prothioconazoles (prothioconazole), pyracarbolin (pyracarbolid), pyraclostrobin (pyraclostrobin), pyrazophos (pyrazophos), pyridinitril (pyridinitril), pyrifenox (pyrifenox), phonetic Mould amine (pyrimethanil), pyriofenone, pyroquilon (pyroquilon), chloromethane oxy picolinate (pyroxychlor), Pyroxyfur, chinomethionat (quinomethionate), quinoxyfen (quinoxyfen), pentachloronitrobenzene (quintozene), quinacetal-sulphate (quinacetol-sulfate), ester bacterium hydrazone (quinazamid), Fluquinconazole (quinconazole), pyrrole imidazoles (rabenzazole) etc..

Fungicide (continuation): sodium azide (sodium azide), sodium bicarbonate (sodium hydrogen Carbonate), sodium hypochlorite (sodium hypochlorite), Sulfur (sulfur), volution bacterium amine (spiroxamine), Salicylanilide (salycylanilide), Silthiopham (silthiofam), simeconazoles (simeconazole), Tebuconazole (tebuconazole), tecnazene (tecnazene), Aateck (tecoram), tetraconazole (tetraconazole), Probenazole (thiabendazole), thiadifluor, thicyofen (thicyofen), thifluzamide (thifluzamide), benzene Bacterium amine (thiochlorfenphim), thiophanate (thiophanate), thiophanate-methyl (thiophanate-methyl), gram Mite killing (thioquinox), thiram (thiram), tiadinil (tiadinil), sulphur benzonitrile formamide (tioxymid), first Base stand withered phosphorus (tolclofos-methyl), toluene flusulfamide (tolylfluanid), triazolone (triadimefon), Toriadimenol, triamiphos (triamiphos), triarimol (triarimol), triazoxide (triazoxide), butrizol (triazbutil), tributyltin oxide (tributyltin oxide), trichlamide (trichlamide), tricyclazole (tricyclazole), tridemorph (tridemorph), trifloxystrobin (trifloxystrobin), fluorine bacterium azoles (triflumizole), triforine (triforine), triticonazole (triticonazole), valida (validamycin), Valifenalate, vinclozolin (vinclozolin), zarilamid (zarilamide), zinc sulfate (zinc sulfate), Zineb (zineb), ziram (ziram), zoxamide (zoxamide) and shiitake mushroom hypha extract etc..

Bactericide: benzalkonium chloride (benzalkonium chloride), chlorine match more (bithionol), bronopol (bronopol), cresols (cresol), formaldehyde (formaldehyde), trichloromethyl pyridine (nitrapyrin), oxolinic acide (oxolinic acid), terramycin (oxyterracycline), streptomysin (streptomycin) and tecloftalam (tecloftalam) etc..

Nematicide: aldoxycarb (aldoxycarb), cadusafos (cadusafos), DBCP, dichlofenthion (dichlofenthion), DSP, phonamiphos (ethoprophos), fenamiphos (fenamiphos), fensulfothion (fensulfothion), fluensulfone, fosthiazate (fosthiazate), fosthietan (fosthietan), new cigarette phosphorus (imicyafos), isamidofos, isazofos (isazofos), oxamyl (oxamyl) and thionazin (thionazin) etc..

Acaricide: acequinocyl (acequinocyl), acrinathrin (acrinathrin), Amitraz (amitraz), BCI- 033 (test name), Bifenazate (bifenazate), fenisobromolate (bromopropylate), chinomethionat (chinomethionat), chlorobenzilate (chlorobezilate), clofentezine (clofentezine), nitrile pyrrole mite ester (cyenopyrafen), cyflumetofen (cyflumetofen), plictran (cyhexatine), dicofol (dicofol), Gram (dienochlor), DNOC, etoxazole (etoxazole), fenazaquin (fenazaquin), fenbutatin oxide everywhere (fenbutatin oxide), fenothiocarb (fenothiocarb), Fenpropathrin (fenpropathrin), fenpyroximate (fenpyroximate), fluacrypyrim (fluacrypyrim), halfenprox (halfenprox), Hexythiazox (hexythiazox), Milbemectin (milbemectin), propargite (propargite), pyridaben (pyridaben), pyrimidifen (pyrimidifen), S-1870 (test name), Envidor (spirodiclofen), spyromesifen, NNI-0711 (test Name), CL900167 (test name) and tebufenpyrad (tebufenpyrad) etc..

Insecticide: avermectin (abamectin), orthene (acephate), Acetamiprid (acetamipirid), Alanycarb (alanycarb), Aldicarb (aldicarb), allethrin (allethrin), methyl pyrrolePhosphorus (azamethiphos), azinphos-methyl (azinphos-methyl), Dipel (bacillus thuringiensis), Worm prestige (bendiocarb), transfluthrin (benfluthrin), rosickyite gram hundred salty (benfuracarb), bensultap (bensultap), Biphenthrin (bifenthrin), bioallethrin (bioallethrin), bioresmethrin (bioresmethrin), bistrifluron (bistrifluron), Buprofezin (buprofezin), butocarboxim (butocarboxim), carbaryl (carbaryl), carbofuran (carbofuran), carbosulfan (carbosulfan), kill Snout moth's larva pellet (cartap), chlorantraniliprole (chlorantraniliprole), chlorethxyfos, capillary (chlorfenapyr), chlorfenviphos (chlorfenvinphos), chlorfluazuron (chlorfluazuron), chlormephos (chlormephos), chlopyrifos (chlorpyrifos), chlorpyrifos-methyl (chlorpyrifos-methyl), ring tebufenozide (chromafenozide), clothianidin (clothianidin), cyanogen insect amide (cyantraniliprole), cycloprothrin (cycloprothrin), cyflumetofen (cyflumetofen), cyfloxylate (cyfluthrin), betacyfluthrin (beta-cyfluthrin), lambda-cyhalothrin (cyhalothrin), gamma cyhalothrin (lambda-cyhalothrin), Cypermethrin (cypermethrin), alphamethrin (alpha-cypermethrin), effective cypermethrin (beta- Cypermethrin), zeta- cypermethrin (zeta-cypermethrin), cyromazine (cyromazine), decis (deltamethrin), diacloden, diafenthiuron (diafenthiuron), diazinon (diazinon), DDVP (dichlorvos), diflubenzuron (diflubenzuron), dimethylvinphos (dimethylvinphos), dinotefuran (dinotefuran), difenolan (diofenolan), disulfoton (disulfoton), Rogor (dimethoate), methylamino Ah Tie up rhzomorph benzoate (emamectin-benzoate), empenthrin (empenthrin), 5a,6,9,9a-hexahydro-6,9-methano-2,4 (endosulfan), α -5a,6,9,9a-hexahydro-6,9-methano-2,4 (alpha-endosulfan), EPN, S- fenvalerate (esfenvalerate), ethiofencarb (ethiofencarb), ethiprole (ethiprole), ethofenprox (etofenprox), etrimfos (etrimfos), kill snout moth's larva sulphur Phosphorus (fenitrothion), Bassa (fenobucarb), fenoxycarb (fenoxycarb), Fenpropathrin (fenpropathrin), Entex (fenthion), fenvalerate (fenvalerate), Fipronil (fipronil), fluorine pyridine Insect amide (flonicamid), Flubendiamide (flubendiamide), flucythrinate (flucythrinate), phonetic worm amine (flufenerim), flufenoxuron (flufenoxuron), trifluoro ethofenprox (flufenprox), flumethrin (flumethrin), taufluvalinate (fluvalinate), taufluvalinate (tau-fluvalinate), Fonofos (fonophos), Carzol (formetanate), formothion (formothion), furathiocarb (furathiocarb), butylene fluorine Worm nitrile (flufiprole), flupyradifurone, flometoquin etc..

Insecticide (continuation): chlorine tebufenozide (halofenozide), flubenzuron (hexaflumuron), hydramethylnon (hydramethylnon), imidacloprid (imidacloprid), isofenphos (isofenphos), indoxacarb (indoxacarb), Mobucin (isoprocarb),Azoles phosphorus (isoxathion), rayperidin (lepimectin), lufenuron (lufenuron), malathion (malathion), fluorine chlorine ether pyrethroids (meperfluthrin), metaflumizone (metaflumizone), the methaldehyde (metaldehyde), acephatemet (methamidophos), methidathion (methidathion), methacrifos (methacrifos), metaflumizone (metaflumizone), MTMC (metalcarb), Methomyl (methomyl), methoprene (methoprene), methoxychlor (methoxychlor), methoxyfenozide (methoxyfenozide), bromomethane (methyl bromide), Azodrin (monocrotophos), muscalure (muscalure), Nitenpyram (nitenpyram), novaluron (novaluron), noviflumuron (noviflumuron), oxygen are happy Fruit (omethoate), oxamyl (oxamyl), oxydemeton_methyl (oxydemeton-methyl), oxydeprofos (oxydeprofos), Parathion (parathion), parathion-methyl (parathion-methyl), pentachlorophenol (pentachlorophenol (PCP)), Permethrin (permethrin), phenothrin (phenothrin), phenthoate dimephenthoate cidial (phenthoate), phoxim (phoxim), thimet (phorate), Phosalone (phosalone), phosmet (phosmet), phosphamidon (phosphamidon), Aphox (pirimicarb), pirimiphos-methyl (pirimiphos-methyl), Profenofos (profenofos), Toyodan (prothiofos), Kayaphos (propaphos), protrifenbute, pymetrozine (pymetrozine), pyraclofos (pyraclofos), pyrethrin (pyrethrins), pyridine worm ether (pyridalyl), Pyrifluquinazon, pyriprole, pyrafluprole, Nylar (pyriproxyfen), resmethrin (resmethrin), rotenone (rotenone), SI-0405 (test name), sulprofos (sulprofos), silafluofene (silafluofen), ethyl pleocidin (spinetoram), multiple killing teichomycin (spinosad), spiral shell worm ethyl ester (spirotetramat), sulfone worm pyridine (sulfoxaflor), sulfotep (sulfotep), SYJ-159 (test name), Tebfenozide, it fluorobenzene urea (teflubenzuron), Tefluthrin (tefluthorin), terbufos (terbufos), kills Worm fears (tetrachlorvinphos), tetramethrin (tetramethrin), dtetramethrin (d-tetramethrin), tetrafluoro Ethofenprox (tetramethylfluthrin), thiacloprid (thiacloprid), thiocyclam (thiocyclam), thiodicarb (thiodicarb), Diacloden (thiamethoxam), thiofanox (thiofanox), thiometon (thiometon), azoles Insect amide (tolfenpyrad), metrifonate (trichlorfon), triazuron, kills bell at tralomethrin (tralomethrin) Urea (triflumuron), vamidothion (vamidothion) and ME-5343 (test name) etc..

In the present composition, surfactant can also be added as needed.As these surfactants, can enumerate (A) below, (B), (C), (D) and (E).

(A) nonionic surfactant:

(A-1) polyethylene glycol type surfactant: for example, polyxyethylated (such as C_8~18) ether, alkyl naphthol oxygen Change Addition on ethylene object, polyoxyethylene (single or two) alkyl (such as C_8~12) phenyl ether, polyoxyethylene (single or two) alkyl (such as C_8~12) phenyl ether formaldehyde condensation products, polyoxyethylene (mono-, di- or three) phenyl ether, polyoxyethylene (mono-, di- or three) benzyl Phenyl ether, polyoxypropylene (mono-, di- or three) benzyl phenyl ether, polyoxyethylene (mono-, di- or three) styrylphenyl ether, polyoxy third Alkene (mono-, di- or three) styrylphenyl ether, the polymer of polyoxyethylene (mono-, di- or three) styrylphenyl ether, polyoxy second Alkene polyoxypropylene (mono-, di- or three) styrylphenyl ether, polyoxyethylene polyoxypropylene block polymer, alkyl (such as C_8~18) Polyoxyethylene polyoxypropylene block polymer ether, alkyl (such as C_8~12) phenyl polyoxyethylene polyoxypropylene block polymer ether, The double phenyl ether of polyoxyethylene, polyoxyethylene resin acid ester, polyoxyethylene fatty acid (such as C_8~18) monoesters, polyoxyethylene fatty acid (such as C_8~18) diester, polyoxyethylene sorbitan (mono-, di- or three) fatty acid (such as C_8~18) ester, fatty acid glyceride Ethylene oxide adduct, castor oil ethylene oxide adduct, hardened castor oil ethylene oxide adduct, alkyl (such as C_8~18) amine Ethylene oxide adduct and fatty acid (such as C_8~18) amide ethylene oxide adduct etc..

(A-2) EPE polyol EPE: for example, fatty acid glyceride, polyglyceryl fatty acid ester, pentaerythrite are fatty Acid esters, polyoxyethylensorbitan fatty acid (such as C_8~18) ester, anhydrosorbitol (mono-, di- or three) fatty acid (such as C_8~18) ester, sugarcane Sugar fatty acid ester, polyol alkyl ether, alkyl glycosides, alkyl poly glucoside and Marlamid etc..

(A-3) alkyne series surfactant: for example, the ethylene oxide adduct and alkynes of acetylenediol, acetylene alcohol, acetylenediol Belong to the ethylene oxide adduct etc. of alcohol.

(B) anionic surfactant:

(B-1) carboxylic acid type surfactant: for example, polyacrylic acid, polymethylacrylic acid, poly, polymaleic anhydride, The copolymerization of the copolymer, acrylic acid and itaconic acid of maleic acid or maleic anhydride and alkene (such as isobutene and diisobutylene etc.) Copolymer, acrylic acid and the methyl-prop of object, the copolymer of methacrylic acid and itaconic acid, maleic acid or maleic anhydride and styrene Copolymer, acrylic acid and the horse of the copolymer of olefin(e) acid, the copolymer of acrylic acid and methyl acrylate, acrylic acid and vinyl acetate Come sour or maleic anhydride copolymer, polyxyethylated (such as C_8~18) ether acetic acid, N- methyl-fatty acid (such as C_8~18) flesh Propylhomoserin salt, resin acid and fatty acid (such as C_8~18) etc. carboxylic acids and these carboxylic acids salt.

(B-2) sulfuric acid ester type surfactant: for example, alkyl (such as C_8~18) sulfuric ester, it is polyxyethylated (such as C_8~18) ether sulfuric ester, polyoxyethylene (single or two) alkyl (such as C_8~12) phenyl ether sulfuric ester, polyoxyethylene (list or two) alkyl (such as C_8~12) sulfuric ester of polymer of phenyl ether, polyoxyethylene (mono-, di- or three) phenyl ether sulfuric ester, polyoxyethylene (mono-, di- or three) benzyl phenyl ether sulfuric ester, polyoxyethylene (mono-, di- or three) styrylphenyl ether sulfuric ester, polyoxyethylene The sulfuric ester of the polymer of (mono-, di- or three) styrylphenyl ether, polyoxyethylene polyoxypropylene block polymer sulfuric ester, The sulfuric ester of sulfonated oil, sulfated fatty acid ester, sulfated fatty acid and sulphation alkene etc. and the salt of these sulfuric esters.

(B-3) sulfonic acid type surfactant: for example, paraffin (such as C_8~22) sulfonic acid, alkyl (such as C_8~12) benzene sulfonic acid, alkane Base (such as C_8~12) formaldehyde condensation products of benzene sulfonic acid, the formaldehyde condensation products of cresol sulfonic acid, alpha-olefin (such as C_8~16) sulfonic acid, dioxane Base (such as C_8~12) sulfosuccinic acid, lignin sulfonic acid, polyoxyethylene (single or two) alkyl (such as C_8~12) phenyl ether sulfonic acid, poly- Ethylene oxide alkyl (such as C_8~18) ether sulfosuccinic acid half ester, naphthalene sulfonic acids, (single or two) alkyl (such as C_1~6) naphthalene sulfonic acids, naphthalene sulphur The formaldehyde condensation products of acid, (single or two) alkyl (such as C_1~6) formaldehyde condensation products of naphthalene sulfonic acids, creasote sulfonic acid formaldehyde condensation Object, alkyl (such as C_8~12) diphenyl ether disulfonic acid, イ ゲ Port Application T (trade name), polystyrolsulfon acid and styrene sulfonic acid with The salt of the sulfonic acid such as the copolymer of methacrylic acid and these sulfonic acid.

(B-4) phosphate-type surfactant: for example, alkyl (such as C_8~12) phosphate, it is polyxyethylated (such as C_8~18) ether phosphate, polyoxyethylene (single or two) alkyl (such as C_8~12) phenyl ether phosphate, polyoxyethylene (mono-, di- or three) Alkyl (such as C_8~12) phenyl ether polymer phosphate, polyoxyethylene (mono-, di- or three) phenyl ether phosphate, polyoxy Ethylene (mono-, di- or three) benzyl phenyl ether phosphate, polyoxyethylene (mono-, di- or three) styrylphenyl ether phosphate, polyoxy The phosphorus of the phosphate of the polymer of ethylene (mono-, di- or three) styrylphenyl ether, polyoxyethylene polyoxypropylene block polymer The phosphate and these phosphorus of acid esters, phosphatidyl choline, phosphatidyl ethanol imines and condensed phosphoric acid (such as three polyphosphoric acid etc.) etc. The salt of acid esters.

As the counter ion counterionsl gegenions of the salt in above-mentioned (B-1)~(B-4), alkali metal (lithium, sodium and potassium etc.), alkaline earth gold can be enumerated Category (calcium and magnesium etc.), ammonium and various amine (such as alkylamine, Cycloalkyl amine and alkanolamine etc.) etc..

(C) cationic surfactant:

For example, the ethylene oxide adduct of alkylamine, alkyl quaternary ammonium salts, alkylamine and the ethylene oxide of alkyl quaternary ammonium salts add At object etc..

(D) amphoteric surfactant:

(D-1) betaine type amphoteric surfactant: can enumerate for example, alkyl (such as C_8~18) the sour-sweet dish of dimethylaminoethyl Alkali, acyl group (such as C_8~18) dimethyl oxyneurine, alkyl (such as C_8~18) hydroxyl sulfo betaine and 2- alkyl (such as C_8~18)-N- carboxymethyl group-N- hydroxyethyl imidazolinesGlycine betaine.

(D-2) amino acid type surfactant: can enumerate for example, alkyl (such as C_8~18) alanine, alkyl (such as C_8~18) amino dipropionic acid and N- acyl group (such as C_8~18)-N '-carboxy ethyl-N '-hydroxyethyl ethylene diamine.

(D-3) amine oxide type surfactant: can enumerate for example, alkyl (such as C_8~18) dimethyl amine and acyl group (such as C_8~18) dimethyl amine oxide etc..

(E) other surfactants:

(E-1) silicon-based surfactant: can enumerate for example, polyoxyethylene-methyl polysiloxane copolymer, polyoxypropylene- Methyl polysiloxane copolymer and poly- (oxyethylene-oxypropylene)-methyl polysiloxane copolymer etc..

(E-2) fluorine system surfactant: can enumerate for example, perfluor benzene sulfonate, fluorinated alkyl sulfonate, perfluor alkane Yl carboxylic acid salt, perfluor polyoxyethylene ether, perfluoroalkyl polyoxyethylene ether and perfluoroalkyl leptodactyline etc..

These surfactants can be used alone or it is two or more be used in mixed way, the ratio in the case where mixing can also from It is selected by ground.The content of the surfactant in the present composition can be selected suitably, but relative to the present composition 100 parts by weight, the preferably range of 0.1~20 parts by weight.

In the present composition, it can further contain various adjuvants.As the adjuvant that can be used, there is thickening Agent, organic solvent, antifreezing agent, defoaming agent, fungi-proofing mould inhibitor and colorant etc., can enumerate following adjuvants.

It as thickener, is not particularly limited, organic and inorganic natural goods, composite and semi-synthetic can be used, it can To illustrate for example, heteropolysaccharides, polyvinyl alcohol, the polyethylene pyrrole such as xanthan gum (xanthan gum), Weilan gum and sandlwood carbohydrate gum The water-soluble high-molecular compounds such as pyrrolidone, polyacrylic acid, Sodium Polyacrylate and polyacrylamide, methylcellulose, carboxyl first The cellulose derivatives such as base cellulose, carboxy ethyl cellulose, hydroxy ethyl cellulose and hydroxy propyl cellulose, montmorillonite, Smectites system clay minerals such as saponite, hectorite, bentonite, synthetic soapstone and synthesis smectite etc..These thickeners can Think one or two or more kinds of mixing, the ratio in the case where mixing can also freely select.These thickeners can directly add Add, furthermore can add the thickener for being scattered in water in advance.In addition, the content in the present composition can also be selected freely It selects.

As organic solvent, the alcohols such as ethylene glycol, diethylene glycol (DEG), propylene glycol, dipropylene glycol and isopropanol, fourth can be enumerated The acid such as the esters such as the ketone such as the ethers such as base cellosolve, cyclohexanone, gamma-butyrolacton, N-Methyl pyrrolidone and n-octylpyrrolidone amide, Aromatic hydrocarbons, machinery oil, normal paraffin hydrocarbons, isoparaffin and the rings such as dimethylbenzene, alkylbenzene, phenyl xylyl ethane and alkylnaphthalene The mixture of the aromatic hydrocarbons such as the aliphatic hydrocarbons such as alkane, kerosene and aliphatic hydrocarbon, soya-bean oil, Linseed oil, rapeseed oil, coconut oil, The greases such as cottonseed oil and castor oil.

As antifreezing agent, can be used such as ethylene glycol, diethylene glycol (DEG) and propylene glycol, glycerol.Preferably propylene glycol, sweet Oil.In addition, the content in the present composition can also freely select.

The defoaming agents such as organic silicon-type lotion, fungi-proofing mould inhibitor and colorant etc. can further be cooperated.

The manufacturing method of the present composition is not particularly limited, and adds above-mentioned each ingredient in a dispersion medium, using stirring The machine of mixing is mixed to obtain.In addition, pesticide activity component, surfactant and other adjuvants can according to need list respectively Solely or mixing to carry out Crushing of Ultrafine by dry type and wet crushing mill.

Dry grinding can use hammer-mill, pin rod mill, jet mill, ball mill or roller mill etc. and carry out.Using wet Formula crushes the Crushing of Ultrafine carried out and can be carried out by wet crushing mills such as online grinding machine or ball mills.

The present composition can be applied using following methods: for example by stoste or be diluted with water to 50~5000 times of left sides The right side is disseminated to the method for the soil of crop, trees or their growths using spraying machine etc.；Helicopter etc. is used from aerial, By stoste or it is diluted with water to 2~100 times or so the methods spread.

Embodiment

Next, enumerate embodiment illustrates the present invention in further detail, but the present invention is not limited thereto.In embodiment High performance liquid chromatography (HPLC), powder x-ray diffraction and DSC measurement (differential scanning calorimetry measurement) are in measurement strip as shown below It is carried out under part.

〔HPLC〕

Column: Inertsil ODS-SP, φ 4.6mm, length 150mm,

3 μm of (ジ ー エ Le サ イ エ Application ス society systems of partial size)

Flow velocity: 1.0ml/min

Eluent: acetonitrile/water/acetic acid=600/400/1 (volume ratio)

Detection: UV254nm

(powder x-ray diffraction)

Kinds of machine title: X ' PERT-PRO MPD (ス ペ Network ト リ ス Co., Ltd.)

Measuring method: transmission beam method

X-ray: Cu-K α

Voltage: 45kV

Electric current: 40mA

Sampling interval: 0.026deg

Data area: 2 θ=2~40deg

(DSC measurement) (aerial measurement)

Kinds of machine title: Shimadzu Seisakusho Ltd. differential scanning calorimetry (DSC) DSC-60

Compare substance: aluminium oxide

Planchet: aluminium

Sample rate: 1 second

Heating rate: 5 DEG C/min

(embodiment 1) is named as the manufacture of the crystalline polymorphic form of the compound A of I type crystallization

By 4-, [5- (3,5- dichlorophenyl) -5- trifluoromethyl -4,5- dihydro is differentAzoles -3- base] -2- methyl benzamide The toluene 10ml solution of 2.00g, triethyl orthoformate 4.26g and methoxy amine hydrochlorate 0.60g stir 24 hours at 35 DEG C.It stirs After mixing, toluene 10ml is added in the reaction solution.After addition, which is heated to 60~65 DEG C, into Row washing (4ml × 3 time).By the toluene solution resulting after washing by HPLC analyze as a result, eliminate quite The relative area percentage at peak after the area of toluene, from main product is 90.4%, from secondary product Peak relative area percentage be 3.4%.

From the toluene solution, toluene 10ml is distilled off under reduced pressure.After being distilled off, by the toluene solution with About 20 DEG C/h of speed is from about 70 DEG C of coolings, after generating crystallization in the toluene solution, stirs 3 hours at 0~5 DEG C.It stirs After mixing, the crystallization of precipitation is taken out using being filtered under diminished pressure, resulting crystallization is dried under reduced pressure, to obtain The white crystals of 1.92g.

By resulting white crystals by HPLC analyzed as a result, from main product peak it is opposite Area percentage is 93.0%, and the relative area percentage from the peak of secondary product is 3.3%.

In addition, by it is resulting crystallization by LC Mass (LC-MS) analysis obtain as a result, main product It is all [M with pair biology⁺+ H]=473.9 identical value.In addition, having carried out LC-MS analysis using following documented condition.

LC-MS device: Waters Alliance HPLC system

2695 separation modules

2998 photodiode array detectors

Analysis condition

Column: SunFire C18,2.5 μm, 2.1 × 50mm (Waters)

Column temperature: 40 DEG C

Detection: UV254nm

Eluent: A=acetonitrile, B=0.1 volume % aqueous formic acid

0~5 minute；A:B=50:50 → 95:5 (volume ratio)

5~8 minutes；A:B=95:5 (volume ratio)

Flow velocity: 0.3ml/min

Mass spectral analysis meter: 3100 mass detectors

Ionization method: electron spray (just)

Further, for resulting crystallization, nuclear magnetic resonance (NMR) is carried out using following documented condition and is measured.

Device: AVANCE III 600 (Block ル カ ー バ イ オ ス ピ Application Co., Ltd.)

Resonant frequency: 600MHz

Measure solvent: deuterated chloroform (CDCl₃)

Primary standard substance: tetramethylsilane [S_i(CH₃)₄]

Proton magnetic resonance (PMR) (¹H-NMR) measurement as a result, obtain it is following documented by chemical displacement value.

¹H-NMR δ (ppm) 8.49 (d, J=9.6Hz, 1H), 7.77 (d, J=9.6Hz, 1H), 7.58 (d, J=8.6Hz, 1H), 7.57 (s, 1H), 7.54 (d, J=8.6Hz, 1H), 7.51 (d, J=1.9Hz, 2H), 7.44 (dd, J=1.9Hz, 1H), 4.09 (d, J=17.2Hz, 1H), 3.90 (s, 3H), 3.71 (d, J=17.2Hz, 1H), 2.53 (s, 3H).

In addition,¹Symbol in H-NMR chemical displacement value indicates following meanings.

S: unimodal, d: bimodal, J: coupling constant, aH: a hydrogen atom calculated by integrated value.

Further, it uses¹H-NMR measures used sample, has carried out HSQC (the heteronuclear list as a kind of two-dimentional NMR Quantum coherent, Hetero-nuclearSingleQuantumCoherence) measurement as a result, observe 7.77ppm come Peak derived from hydrogen atom is related to from the peak of carbon atom, but be not observed 8.49ppm peak from hydrogen atom and It is related from the peak of carbon atom.By as a result, the peak from hydrogen atom of 8.49ppm belongs to the nitrogen-atoms of amide structure On hydrogen atom.At Organic Letters 2011, volume 13, in page 5160 and SupportingInfomation, to The chemical displacement value at the peak of the hydrogen atom on the nitrogen-atoms of amide structure in the similar compound of the structure of compound A The chemistry at the peak of (the hereinafter referred to as chemical displacement value of amide) and the hydrogen atom on the carbon atom of iminomethyl structure The comparison of shift value (the hereinafter referred to as chemical displacement value of iminomethyl) is recorded.According to the record, in geometrical isomerism In the case where compound for Z, the chemical displacement value of amide is compared with the chemical displacement value of iminomethyl, to downfield sidesway It is dynamic.On the other hand, in the case where geometrical isomerism is the compound of E, the chemical displacement value of amide and the chemistry of iminomethyl Shift value is compared, mobile to highfield side.

In the case where the compound A obtained by the present embodiment, the chemical displacement value of amide is 8.49ppm, imino group first The chemical displacement value of base is 7.77ppm.

Therefore, identifying main product is compound A (geometrical isomerism Z), and secondary product is the geometrical isomerism of compound A For E (the hereinafter referred to as E body of compound A.).

Measure it is that the powder x-ray diffractions of resulting white crystals obtains as a result, display Fig. 1 diffraction pattern, name For the crystallization of I type.

In addition, it is that the DSC for implementing resulting crystallization is measured as a result, show that summit is 171.2 DEG C of endothermic peak, In temperature in addition to this, endothermic peak is not shown.

(embodiment 2) is named as the manufacture of the crystalline polymorphic form of II type crystallization

0.5g (HPLC relative area percentage chemical combination is crystallized in the I type of the compound A obtained according to the method for embodiment 1 Object A: compound A E body=97.0:2.6) in add toluene 15ml, modulate the toluene suspension of compound A.By should Aaerosol solution is in 85 DEG C of progress heating stirrings, so that the crystallization of compound A be made to be completely dissolved, the toluene for modulating compound A is molten Liquid.

In the n-hexane 15ml being cooled with ice, through 10 minutes be added dropwise above compound A toluene solution so that just oneself The temperature of alkane is no more than 5 DEG C.After completion of dropwise addition, by the solution in the lower stirring 5 minutes that is cooled with ice.It is after stirring, this is molten The crystallization being precipitated in liquid resulting crystallization is dried under reduced pressure, using taking-up is filtered under diminished pressure to obtain 0.45g's White crystals.

By it is resulting crystallization by HPLC analyze as a result, the relative area percentage of compound A be 97.3%, The relative area percentage of the E body of compound A is 2.4%.

In addition, it is that the powder x-ray diffraction for measuring resulting crystallization obtains as a result, display Fig. 2 diffraction pattern, show It obtains and crystallizes entirely different crystallization with what is obtained by above-described embodiment 1, be named as the crystallization of II type.

In addition, implementing the DSC measurement of resulting crystallization, summit is 164.3 DEG C of endothermic peak out as the result is shown, except this with Outer temperature, does not show endothermic peak.

The manufacture for the I type crystallization that the suspension that II type crystallizes is stirred by (embodiment 3)

The II type of the compound A obtained according to the method for embodiment 2 is crystallized into 0.19g (HPLC relative area percentage Close object A: compound A E body=96.8:2.8) and toluene 0.77g suspension 60 DEG C stirring 4 hours.It, will after stirring The suspension is filtered under diminished pressure, and resulting crystallization is dried under reduced pressure, to obtain white crystals 0.12g.

Resulting crystallization is subjected to HPLC analysis, the result is that the relative area percentage of compound A is 97.3%, compound The relative area percentage of the E body of A is 2.5%.

In addition, that the powder x-ray diffraction for measuring resulting crystallization obtains as a result, being shown to be display and the substantial phase of Fig. 1 The I type crystallization of same pattern.

(example 4~17)

Hereinafter, " part " is all referring to parts by weight.

1. crushing the modulation of slurry

In 56.86 parts of water, make the mixture (commodity of polyoxyethylene styrylphenyl ether and polyether polyols Name: ソ ル ポ ー Le 3353, eastern nation's chemical industry (strain) system) 3 parts, organic silicon-type defoaming agent (trade name: KM-73, SHIN-ETSU HANTOTAI's chemistry Industrial (strain) system) 0.1 part, the I type crystallization of 10 parts of propylene glycol and compound A add up to 10.04 parts with the crystallization of II type and dispersed, Using 0.8-1.2mm φ bead 200g, case of wet attrition is carried out with sand mill (ア イ メ ッ Network ス (strain) system), is crushed 80 parts of slurry.

As shown in the 2nd table, so that the I type contained by compound A is crystallized the weight rate crystallized with II type and arbitrarily change.

2. the modulation of decentralized medium

In 19.55 parts of water, make 1,2-benzisothiazolin-3-one (trade name: PROXEL GXL, ア ビ シ ア (strain) System) 0.05 part, 0.1 part of xanthan gum (trade name: KELZAN ASX, CP Kelco society system), smectite clay (trade name: VEEGUM R, R.T.Vanderbilt society system) 0.3 part successively dispersed, obtain 20 parts of decentralized medium.

3. the modulation of aqueous suspension composition pesticide

80 parts of above-mentioned crushing slurry are mixed with 20 parts of decentralized medium, obtains uniform aqueous suspension shape pesticide group Close 100 parts of object.

Take aqueous suspension shape agriculture obtained by example 4 (containing ratio I type crystallization: II type crystallization=100:0), after just manufacture Drug composition about 5g is placed in whizzer to remove supernatant.Resulting sediment is spread out on filter paper, in drier It makes it dry.Measure it is that the powder x-ray diffraction of resulting dried object obtains as a result, display Fig. 3 diffraction pattern, show The substantially identical diffraction pattern with Fig. 1.That is, in the stage of the modulation in aqueous suspension composition pesticide, do not observe the crystallization of I type Transformation.

In addition, taking being obtained by example 17 (containing ratio I type crystallization: II type crystallization=0:100), aqueous outstanding after just manufacture Floating shape composition pesticide about 5g, is placed in whizzer to remove supernatant.Resulting sediment is spread out on filter paper, dry It is made it dry in dry device.Measure it is that the powder x-ray diffraction of resulting dried object obtains as a result, display Fig. 4 diffraction pattern, Show the diffraction pattern substantially identical with Fig. 2.That is, in the stage of the modulation in aqueous suspension composition pesticide, do not observe II The transformation of type crystallization.

It determines after the rigid manufacture of resulting aqueous suspension shape composition pesticide and further places them into 8ml capacity Bottle in and 54 DEG C of thermostat save 14 days after partial size.In addition, average grain diameter measurement is in measurement strip as shown below It is carried out under part.

(average grain diameter measurement)

Kinds of machine title: ベ ッ Network マ ン コ ー ル タ ー society granulation degree measure of spread machine LS-13320

Measuring method: laser diffraction scattering method

It shows the result in the 2nd table.Wherein, " % " refers to weight %.

[table 2]

2nd table

Industry utilizability

In accordance with the invention it is possible to manufacture two kinds of crystalline forms of compound A.In addition, the suspension composition containing the crystalline form Storage stability is good, is useful as noxious organism control agent.

Claims (6)

1. [5- (3,5- dichlorophenyl) -5- trifluoromethyl -4,5- dihydro is different by (Z) -4-Azoles -3- base]-N- (methoxyl group imido Ylmethyl) -2- methyl benzamide crystalline polymorphic form, wherein I type crystallization crystallization containing ratio be 50~100 weights % is measured, the I type crystallization is in utilizing the Alpha-ray powder x-ray diffraction of Cu-K, in 2 θ of the angle of diffraction=(7.45 ± 0.2,11.05 ± 0.2,12.79 ± 0.2,15.30 ± 0.2,20.90 ± 0.2,21.89 ± 0.2 and 24.32 ± 0.2) there is peak.

2. crystalline polymorphic form according to claim 1, the I type crystallization is utilizing the Alpha-ray X-ray powder of Cu-K In diffraction, the display diffraction curve substantially the same with Fig. 1 of present specification attached drawing.

3. being named as (Z) -4- that I type crystallizes, [5- (3,5- dichlorophenyl) -5- trifluoromethyl -4,5- dihydro is differentAzoles -3- Base]-N- (methoxyimino methyl) -2- methyl benzamide crystalline polymorphic form manufacturing method, wherein

(a) modulation makes (Z) -4- [5- (3,5- dichlorophenyl) -5- trifluoromethyl -4,5- dihydro is differentAzoles -3- base]-N- (methoxy Base iminomethyl) -2- methyl benzamide is dissolved in solution obtained by solvent, and the solvent is molten selected from aliphatic hydrocarbon system It is at least one kind of in agent, aromatic hydrocarbon series solvent and nitrile series solvent, relative to (Z) -4- [5- (3,5- dichlorophenyl) -5- fluoroform Base -4,5- dihydro is differentAzoles -3- base] 1 mass parts of-N- (methoxyimino methyl) -2- methyl benzamide, the solvent Amount be 0.5~50 mass parts, temperature when dissolution is 30~150 DEG C,

(b) make its partial crystallization for the solution is cooling, cooling velocity is 0.1~40 DEG C/h, molten when taking out crystallization be precipitated Liquid temperature is -30~50 DEG C, and the time required for partial crystallization is 0.1~100 hour,

The I type crystallization is in utilizing the Alpha-ray powder x-ray diffraction of Cu-K, in 2 θ of the angle of diffraction=(7.45 ± 0.2,11.05 ± 0.2,12.79 ± 0.2,15.30 ± 0.2,20.90 ± 0.2,21.89 ± 0.2 and 24.32 ± 0.2) there is peak.

4. being named as (Z) -4- that I type crystallizes, [5- (3,5- dichlorophenyl) -5- trifluoromethyl -4,5- dihydro is differentAzoles -3- Base]-N- (methoxyimino methyl) -2- methyl benzamide crystalline polymorphic form manufacturing method, which is characterized in that So that the crystallization of II type is suspended in decentralized medium, resulting aaerosol solution is stood or stirred, the II type crystallization is penetrated using Cu-K α In the powder x-ray diffraction of line, 2 θ of the angle of diffraction=(5.00 ± 0.2,9.24 ± 0.2,13.39 ± 0.2,16.45 ± 0.2, 19.35 ± 0.2,23.17 ± 0.2 and 26.21 ± 0.2) there is peak, the decentralized medium is that aromatic hydrocarbon series solvent or nitrile system are molten Agent, suspension temperature when standing or stirring are -20~100 DEG C, stand or mixing time is 1 hour or more,

The I type crystallization is in utilizing the Alpha-ray powder x-ray diffraction of Cu-K, in 2 θ of the angle of diffraction=(7.45 ± 0.2,11.05 ± 0.2,12.79 ± 0.2,15.30 ± 0.2,20.90 ± 0.2,21.89 ± 0.2 and 24.32 ± 0.2) there is peak.

5. a kind of suspension composition contains (Z) -4- described in claim 1 [5- (3,5- dichlorophenyl) -5- fluoroform Base -4,5- dihydro is differentAzoles -3- base]-N- (methoxyimino methyl) -2- methyl benzamide crystalline polymorphic form And decentralized medium.

6. suspension composition according to claim 5, further contains surfactant, decentralized medium is water.