JP2012153733A - Spreading agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a spreading agent composition which improves the spreading properties of a pesticide and also has excellent safety.SOLUTION: The spreading agent composition comprises a compound represented by general a formula (1) {for example, Pellicer(R)} (wherein: Rdenotes a 1 to 23C hydrocarbon group; Rdenotes hydrogen or a 1 to 3C hydrocarbon group which may have a carboxylic acid group or a sulfonic acid group; Y denotes a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group or their salts; Z denotes -NR'- (R' denotes hydrogen or a 1 to 10C hydrocarbon group), -O- or -S-; each of j and k denotes any of 0, 1 and 2 and also j and k are not simultaneously 0; n denotes an integer of 2 to 20; and X denotes a hydrocarbon chain with a molecular weight of ≤1,000,000 which may have a substituent).

Description

  The present invention relates to a spreading agent composition for agricultural chemicals containing a specific compound.

In general, pesticides are uniformly adhered to or absorbed by animals such as plants or pests by spraying, and thereby exert effects such as weeding, pest control and disease prevention. However, the surface of plants and pests generally tends to repel water, resulting in a problem that the expected effect of spraying agricultural chemicals cannot be obtained. Therefore, in order to make up for this drawback, spreading agents for agricultural chemicals are widely used in the agricultural field for the purpose of making the agricultural chemicals wet easily and spread.
Patent Document 1 describes that a specific alkylene oxide addition-type nonionic surfactant is used as a spreading agent for agricultural chemicals.

Patent No. 2959949

From the agrochemical spreader using the nonionic surfactant shown in Patent Document 1, a spreader for agrochemical that is further excellent in spreadability and safety has been demanded.
The object of the present invention is to provide a spreader composition that improves the spreadability of agricultural chemicals and is excellent in safety.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor has solved the above-mentioned problems by providing a specific compound, that is, a composition containing a specific compound having a plurality of hydrophobic groups and hydrophilic groups in the molecule. The inventors have found that the problem can be solved and have completed the present invention.

That is, the present invention is as follows.
[1] A spreading agent composition containing a compound represented by the following general formula (1).

(In the general formula (1), R ¹ represents a hydrocarbon group having 1 to 23 carbon atoms, and R ² has 1 to 3 carbon atoms which may have hydrogen, a carboxylic acid group or a sulfonic acid group. Y represents a carboxyl group, a sulfonic acid group, a sulfuric ester group, a phosphoric ester group, or a salt thereof. Z represents —NR ′ — (R ′ represents hydrogen or carbon number 1). -10 hydrocarbon group), -O-, or -S-, j and k are either 0, 1 or 2 and j and k are not 0 at the same time, and n is 2 to 20 X represents an optionally substituted hydrocarbon chain having a molecular weight of 1,000,000 or less.
[2] The spreading agent composition according to [1], wherein the carbon number of X in the general formula (1) is 1 to 40.
[3] The spreading agent composition according to [1] or [2], wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(In the above general formula (2), R ¹ represents a hydrocarbon group having 1 to 23 carbon atoms, and R ² is a carbon atom having 1 to 3 carbon atoms which may have hydrogen, a carboxylic acid group or a sulfonic acid group. Y represents a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, or a salt thereof, Z represents —NR ′ — (R ′ represents hydrogen or a carbon number of 1 to 10; X ′ represents a carboxyl group or a salt thereof, —NHR ′ group (R ′ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms), — A hydrocarbon chain having 1 to 20 carbon atoms and having at least one of an OH group and an —SH group, j and k are 0, 1 and 2, and j and k are simultaneously 0. is not.)
[4] The spreading agent composition according to any one of [1] to [3], including a solvent.
[5] An agrochemical composition comprising the spreading agent composition according to any one of [1] to [4].

  The composition of the present invention has the effect of improving the spreadability of agricultural chemicals and being excellent in safety.

Hereinafter, the present invention will be described in detail.
The composition of the present invention is a composition containing a compound represented by the specific general formula (1).
[Compound shown in general formula (1)]
The compound represented by the following general formula (1) will be described.

In the general formula (1), R ¹ is a hydrocarbon group, saturated or carbon atoms which may be substituted with a substituent unsaturated 1-23. Preferably, it is a hydrocarbon group having 7 to 17 carbon atoms. R ¹ may be any of a straight chain, a branched chain, or a cyclic chain (aromatic hydrocarbon chain).
In the general formula (1), R ² is hydrogen or a hydrocarbon group having 1 to 3 carbon atoms which may have a carboxylic acid group or a sulfonic acid group.

Specific examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxy (iso) propyl group, a dihydroxy (iso) propyl group, a carboxymethyl group, and a carboxyethyl group. , Carboxypropyl group, sulfoethyl group and the like.
R ² is preferably hydrogen.

In general formula (1), Y is a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, or a salt thereof. Preferably, it is a carboxyl group or a salt thereof.
Y can form salts with various basic substances. Specific examples of basic substances that can form salts are given below.

  Although it does not specifically limit as an alkali metal, Sodium, potassium, lithium, etc. are mentioned. Examples of the alkaline earth metal include calcium and magnesium. Examples of the metal other than the above include aluminum, zinc, iron, cobalt, titanium, zirconium, silver and the like.

The basic substance that can form other salts is not particularly limited, and examples thereof include organic amines, basic amino acids, ammonia, and polyvalent metals.
Examples of the organic amine include monoethanolamine, diethanolamine, triethanolamine, and triisopropanolamine.
Basic amino acids include arginine and lysine.
In addition, a polyvalent metal etc. are mentioned.
Moreover, in General formula (1), Y may contain the 2 or more types of salt formed from said basic substance.

In General formula (1), Z is -NR'- (R 'is hydrogen or a C1-C10 hydrocarbon group), -O-, or -S-.
In the general formula (1), j and k are either 0, 1 or 2, and j and k are not 0 at the same time, and n represents an integer of 2 to 20.

Next, X in the general formula (1) will be described.
X is a hydrocarbon chain having a molecular weight of 1 million or less which may have a substituent. X may be a straight chain, a branched chain, a cyclic chain, or an aromatic hydrocarbon chain. In addition, when X has a substituent, the substituent is preferably a carboxyl group. The number of carbon atoms in X is preferably 1 to 40, and the molecular weight is preferably 28 to 2000.

In addition, when X contains a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, or the like, salts may be formed with various basic substances. Examples of the metal capable of forming a salt and other basic substances include those described above. Moreover, there are n parts in parentheses in the general formula (1), which may be the same or different.
The compound represented by the general formula (1) is a compound having two or more hydrophilic groups Y and two or more hydrophobic groups R ¹ CO.

  The compound represented by the following general formula (2) is an example of a gemini surfactant in the case of n = 2 in the compound represented by the general formula (1). A composition using the compound is particularly preferred.

In the general formula (2), X ′ is a carboxyl group or a salt thereof, —NHR ′ group (R ′ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms), —OH group, or —SH group. The C1-C20 hydrocarbon chain which has any one is shown. R ¹ , R ² , Y, Z, j, and k are the same as those in the general formula (1).
For example, as such a compound, “Perisea (registered trademark) L-30” (manufactured by Asahi Kasei Chemicals Corporation) may be mentioned as a commercial product.

  When the composition of the present invention is used without containing water, the compound represented by the general formula (1) or (2) is such that Y is a carboxyl group, a sulfonic acid group, a sulfate ester group, or a phosphate ester. The group is preferable from the viewpoint of solubility. These compounds can be obtained, for example, without neutralization after the reaction in the production method described later.

[Production Method of Compound Shown by General Formula (1)]
As a method for producing the compound represented by the general formula (1), an N-acyl acidic amino acid anhydride represented by the following general formula (3) and m functional groups selected from a hydroxyl group, an amino group, and a thiol group are used. There is a method in which a compound represented by the general formula (1) is obtained by reacting a compound having a molecular weight of 1 million or less (hereinafter referred to as m-valent compound) having m (m is n or more).

In the general formula (3), R ¹ , R ² , j, and k are the same as those in the general formula (1).
The N-acyl acidic amino acid anhydride represented by the general formula (3) is an anhydride of an N-acylated acidic amino acid. The N-acyl acidic amino acid anhydride may be any of D-form, L-form, and racemate which are optical isomers.
In particular, an L-acidic amino acid which is an L-form is preferable because of its excellent biodegradability.

Acidic amino acids are those having more carboxyl groups than amino groups in the molecule. For example, monoaminodicarboxylic acid having 2 and 1 carboxyl groups and amino groups, respectively, can be mentioned.
The hydrogen of the amino group may be substituted with a hydrocarbon group having 1 to 3 carbon atoms.

Specific examples of the N-acylated acidic amino acid include N-acyl glutamic acid and N-acyl aspartic acid.
Specific examples of the general formula (3) include N-acyl glutamic acid and N-acyl aspartic anhydride.

  The m-valent compound is a compound having a molecular weight of 1,000,000 or less having m functional groups selected from a hydroxyl group, an amino group, and a thiol group (m ≧ n and an integer of 2 to 20). Here, the m-valent compound can form a bond derived from m functional groups. That is, a hydroxyl group can create an ester bond, an amino group can create an acid amide bond, and a thiol group can create a thioester bond. Moreover, this compound may have substituents other than said functional group.

  Specific examples of such m-valent compounds include the following. Specific examples of the compound having two or more hydroxyl groups in the molecule include the following.

  Examples of the divalent hydroxyl compound include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, pentanediol, , 6-hexanediol, cyclohexanediol, dimethylolcyclohexane, neopentyl glycol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, isoprene glycol, 3-methyl-1,5- Pentanediol, sorbite, catechol, resorcin, hydroquinone, bisphenol A, bisphenol F, hydrogenated bisphenol A, hydrogenated bisphenol F, dimer diol, dimethylolpropionic acid, dimethylolbutanoic acid, tartaric acid, dihydroxytartaric acid, mevalon , 3,4-dihydroxy cinnamic acid, 3,4-dihydroxy-hydro cinnamic acid, hydroxy benzoic acid, dihydroxy stearic acid, dihydroxyphenylalanine and the like.

  Examples of the trivalent hydroxyl compound include glycerin, trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1,2,3-propanetriol, and 2-methyl-2. , 3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexanetriol, 4-propyl-3,4,5-heptane Triol, 2,4-dimethyl-2,3,4-pentanetriol, 1,2,4-butanetriol, 1,2,4-pentanetriol, trimethylolethane, trimethylolpropane, diethanolamine, triethanolamine and triol Examples thereof include hydroxystearic acid.

  Examples of tetravalent hydroxyl compounds include pentaerythritol, erythritol, 1,2,3,4-pentanetetrol, 2,3,4,5-hexanetetrol, 1,2,4,5-pentanetetrol, , 3,4,5-hexanetetrol, diglycerin, sorbitan and the like.

  Examples of pentavalent hydroxyl compounds include adonitol, arabitol, xylitol, and triglycerin.

  Examples of the hexavalent hydroxyl compound include dipentaerythritol, sorbitol, mannitol, iditol, inositol, dulcitol, talose, and allose.

Or the dehydration condensate of said 2-6 valent hydroxyl compound, polyglycerol, etc. are mentioned.
Examples of the m-valent polyhydroxyl compound include saccharides. Specific examples are given below.

Examples of tetrose include erythrose, sreose and erythrulose.
Examples of pentose include ribose, arabinose, xylose, lyxose, xylulose and ribulose.

  Examples of monosaccharides include hexose such as allose, altrose, glucose, mannose, guylose, idose, galactose, talose, fructose, sorbose, psicose and tagatose.

  Examples of oligosaccharides include maltose, isomaltose, cellobiose, gentiobiose, melibiose, lactose, tulanose, trehalose, saccharose, mannitolose, cellotriose, gentianose, raffinose, meletitose, cellotetorose, and stachyose.

  Other sugars include residues such as heptose, deoxy sugar, amino sugar, thio sugar, seleno sugar, aldone sugar, uronic acid, sugar acid, ketoaldonic acid, anhydro sugar, unsaturated sugar, sugar ester, sugar ether and glycoside. Alternatively, polysaccharides such as starch, glycogen, cellulose, chitin and chitosan, or those obtained by hydrolyzing the above saccharides may be used.

  Specific examples of the compound having two or more amino groups in the molecule include the following.

  Aliphatic diamines include N, N′-dimethylhydrazine, ethylenediamine, N, N′-dimethylethylenediamine, diaminopropane, diaminobutane, diaminopentane, diaminohexane, diaminoheptane, diaminooctane, diaminononane, diaminodecane, diaminododecane , Diaminoadipic acid, diaminopropanoic acid, diaminobutanoic acid and the like.

  Aliphatic triamines include diethylenetriamine, triaminohexane, triaminododecane, 1,8-diamino-4-aminomethyl-octane, 2,6-diaminocapric acid-2-aminoethyl ester, 1,3,6- Examples include triaminohexane, 1,6,11-triaminoundecane, and di (aminoethyl) amine.

  Examples of the alicyclic polyamines include diaminocyclobutane, diaminocyclohexane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, and triaminocyclohexane.

  Examples of aromatic polyamines include diaminobenzene, diaminotoluene, diaminobenzoic acid, diaminoanthraquinone, diaminobenzenesulfonic acid, diaminobenzoic acid and the like.

  Examples of the araliphatic polyamines include diaminoxylene, di (aminomethyl) benzene, di (aminomethyl) pyridine, and di (aminomethyl) naphthalene. In addition, like diaminohydroxypropane, polyamines in which the above-described amine derivatives are substituted with hydroxyl groups can be used.

  Examples of amino acids include serine, threonine, cysteine, cystine, cystine disulfoxide, cystathionine, methionine, arginine, lysine, tyrosine, histidine, tryptophan, and oxyproline. These amino acids may be proteins, peptides, etc., or hydrolyzed ones thereof.

  Specific examples of the compound having two or more thiol groups in the molecule include dithiol compounds such as dithioethylene glycol, dithioerythritol and dithiothreitol. Here, the m-valent compound may have two or more functional groups selected from a hydroxyl group, an amino group, and a thiol group. Examples are given below.

  Examples of the compound having an amino group and a hydroxyl group in the molecule include aminoethanol, aminopropanol, aminobutanol, aminopentanol, aminohexanol, aminopropanediol, aminoethylethanolamine, aminoethylaminoethanol, aminocresol, aminonaphthol, Examples include aminonaphtholsulfonic acid, aminohydroxybenzoic acid, aminohydroxybutanoic acid, aminophenol, aminophenethyl alcohol, and glucosamine.

  Examples of the compound having a thiol group and a hydroxyl group in the molecule include mercaptoethanol, mercaptophenol, mercaptopropanediol, and glucothiose.

  Examples of the compound having a thiol group and an amino group in the molecule include aminothiophenol and aminotriazole thiol.

The m-valent compound may be any of the optical isomers D-form, L-form, and racemate, and may be each isomer.
Further, among m-valent compounds, those having 1 to 40 carbon atoms are preferable, and those having 1 to 20 carbon atoms are more preferable.
In addition, since naturally occurring compounds are more biodegradable, the m-valent compounds are preferably amino acids, peptides, saccharides and the like.

  When reacting the N-acyl acidic amino acid anhydride and the m-valent compound, a solvent may be used. Examples of the solvent used in the reaction include water, a mixed solvent of water and an organic solvent, or an inert solvent such as tetrahydrofuran, benzene, toluene, xylene, carbon tetrachloride, chloroform, and acetone. The reaction temperature is preferably −5 ° C. to 200 ° C. and mixed and reacted at a temperature equal to or higher than the melting point of the above compound.

  As another method for producing the compound represented by the general formula (1), not an N-acyl acidic amino acid anhydride but an N-acyl acidic amino acid mono-lower ester (for example, methyl ester, ethyl ester) and the above m-valent Examples thereof include a method of reacting a compound to obtain the compound represented by the general formula (1).

  For example, N-acyl acidic amino acid mono-lower ester and m-valent compound are dissolved in a suitable solvent such as dimethylformamide, a catalyst such as potassium carbonate is added, and the reaction is heated at -5 to 250 ° C. under reduced pressure. Then, the compound represented by the general formula (1) is obtained by removing the reaction solvent. The compound represented by the general formula (1) can also be obtained by heating and melting without solvent without using a solvent, adding a catalyst such as sodium hydroxide, and carrying out a transesterification reaction at room temperature to 250 ° C. .

[Spreading agent composition]
In the spreading agent composition of the present invention, the compound represented by the general formula (1) is preferably added in an amount of 0.0001% to 100% in the composition.
The method of using the spreader composition of the present invention includes a method of using various types of agrochemical compositions containing the spreader composition in advance, and a mixture of the spreader composition when diluting the pesticide. There is a method to use. In either method, the excellent spreading effect of the agrochemical targeted by the present invention can be obtained.

The spreading agent composition of the present invention may contain a solvent. Examples of the solvent include water and organic solvents, and water is preferred. The solvent may be a mixed solvent of a plurality of solvents.
A solvent may be used as a dispersion medium.

  Various materials can be added to the spreading agent composition of the present invention as necessary. For example, a fixing agent, a dispersant, an antifoaming agent, a preservative / bactericidal agent, a stabilizer, a surfactant, a polymer compound, and the like can be given.

  The fixing agent is not particularly limited, and examples thereof include carboxymethyl cellulose and casein.

  Although it does not specifically limit as a dispersing agent, For example, a naphthalenesulfonic acid formaldehyde condensate, a lignin sulfonate, etc. are mentioned.

  Although it does not specifically limit as an antifoamer, For example, a fatty acid, metal soap, alcohol and glycols insoluble in water, silicone, modified silicone, a silicone type antifoamer etc. are mentioned.

  Preservatives and bactericides are not particularly limited, but examples include sodium hypochlorite, sorbic acid, potassium sorbate, salicylic acid, sodium salicylate, benzoic acid, sodium benzoate, parabens, isothiazoline compounds, etc. Can be mentioned. The addition amount of the antifoaming agent is preferably 0.001 to 1.0 part by mass, and more preferably 0.005 to 0.8 part by mass with respect to 100 parts by mass of the spreading agent composition of the present invention.

  Although it does not specifically limit as a stabilizer, For example, polyvinyl alcohol, methylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, a sodium polyacrylate, a xanthan gum etc. are mentioned.

  Although it does not specifically limit as surfactant, For example, nonionic surface activity, such as polyoxyethylene alkyl (or aryl) ether, polyoxyethylene sorbitan ester, polyoxyethylene fatty acid ester, acetylene glycol type surfactant, etc. Agents, alkylbenzene sulfonates, dialkyl sulfosuccinates, alkyl sulfosuccinates, lignin sulfonates, polynaphthyl sulfonates, acylamino acids and their salts, anionic surfactants, alkylamine salts, quaternary ammonium Examples thereof include cationic surfactants such as salts, and silicone surfactants.

  Although it does not specifically limit as a high molecular compound, For example, a polyacrylate etc. are mentioned.

In the present invention, one or more additive components can be used in combination.
Moreover, the spreading agent composition of the present invention has no phytotoxicity to various crops and can be used safely.

[Agricultural chemical composition]
The agrochemical composition of the present invention contains the spreading agent composition of the present invention and a pesticide active ingredient. Here, the pesticide active ingredient is an active ingredient of the pesticide. The agrochemical composition of the present invention contains the spreading agent composition of the present invention and any pesticide base selected from fungicides, insecticides, acaricides, herbicides, and plant growth regulators. . The target of the agrochemical base is fungicides for fungi, pesticides for pests (insects), acaricides for mites, herbicides for weeds (plants that do not fall under crops), plant growth regulators for crops (for cultivation purposes) These may be a target object.

  The spreading agent composition of this invention is used for manufacture of the agrochemical composition of this invention. In this case, the spreading agent composition may be blended (internally added) in any of a series of steps for producing the agrochemical composition as one of the components constituting the agrochemical composition, or separately prepared agrochemicals. You may mix | blend (external addition) further to a composition. The addition amount of the spreading agent composition in the agrochemical composition is preferably 1 ppm to 50%, more preferably 10 ppm to 20%.

  Moreover, the formulation type of the agrochemical composition of the present invention is not particularly limited and may be any of emulsion, liquid, wettable powder, granule, powder, flowable formulation and the like. Therefore, an additive according to the formulation type, for example, an emulsifier, a solvent, a dispersant, a carrier and the like may be included. The agrochemical composition of the present invention is applied to a subject by a method according to the formulation type. For example, there is a method for applying an agrochemical composition in which the agrochemical composition is diluted with water and sprayed on plants.

  As an agrochemical raw material used for the agrochemical composition of this invention, the thing as described in the agrochemical handbook 2001 version (Japan Plant Protection Association) is mentioned, for example.

As a disinfectant, sulfur-based dineb (zinc ethylene bisdithiocarbamate), mannebu (manganese ethylene bisdithiocarbamate), as benzimidazole, benomyl (methyl-1- (butylcarbamoyl) -2-benzimidazole carbamate), di Carboximide-based vinclozolin (3- (3,5-dichlorophenyl) -5-methyl-5-vinyl-1,3-oxazolidine-2,4-dione),
Iprodione (3- (3,5-dichlorophenyl) -N-isopropyl-2,4-dioxoimidazolidine-1-carboxamide), procimidone (N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane- 1,2-dicarboximide), triazine (2,4-dichloro-6- (2-chloroanilino) -1,3,5-triazine), trifumizole ((E) -4-chloro-α, α, α-trifluoro-N- (1-imidazol-1-yl-2-propoxyethylidan) -o-toluidine),
Metalaxyl (methyl-N- (2-methoxyacetyl) -N- (2,6-xylyl) -D, L-alaninate), organic copper (Oxine-copper), cupric hydroxide (such as cocide Bordeaux), Antibacterial fungicides (streptomycin, tetracycline, polyoxy, blasticidin S, kasugamycin, validamycin) and the like are suitable, organic copper (Oxine-copper), cupric hydroxide, Trifumizole ((E) -4-chloro-α, α, α-trifluoro-N- (1-imidazol-1-yl-2-propoxyethylidan) -o-toluidine), iprodione (3- (3,5 -Dichlorophenyl) -N-isopropyl-2,4-dioxoimidazolidine-1-carboxamide).

In the case of insecticides, pyrethroid insecticides include permethrin ((3-phenoxybenzyl = (1RS, 3RS)-(1RS, 3RS) -3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropane). Carboxylate) and organophosphorus insecticides include CYAP (O, O-dimethyl-Op-cyanophenyl = thiophosphate), sumithion (MEP) (O, O-dimethyl-O- (3-methyl-4) -Nitrophenyl) thiophosphate), DDVP (dimethyl 2,2-dichlorovinyl phosphate),
Carbamate insecticides include bassa (O-sec-butylphenylmethylcarbamate), mesomil (S methyl-N [(methylcarbamoyl) oxy] thioacetimide), cartap (1,3-bis (carbamoylthio) -2- ( N, N-dimethylamino) propane hydrochloride) and the like are preferably permethrin, DDVP (dimethyl 2,2-dichlorovinyl phosphate), mesomil (S methyl-N [(methylcarbamoyl) oxy] thioacetimide). ).

  Examples of natural insecticides include pyrethrins derived from pesticide chrysanthemums, piperonyl butoxide agents, rotenone agents derived from leguminous shrub Deris, nicotine agents (3- (1-methyl-2-pyrrolidinyl) pyridine sulfate), and the like. Examples of the insect growth regulator (IGR agent) include diflubenzuron (1- (4 chlorophenyl) -3- (2,6-difluorobenzoyl) urea).

Examples of acaricides include CPCBS (parachlorophenyl parachlorobenzene sulfonate), phenisobromolate (isopropyl 4,4′-dibromobenzylate), hexothiazox (trans-5- (4-chlorophenyl) -N-cyclohexyl-4- Methyl-2-oxothiazolidine-3-carboxamide), tetradiphone (2,4,5,4′-tetrachlorodiphenylsulfone), phenothiocarb (S-4-phenoxybutyl = dimethylthiocarbamate), fenpyroximate (tert-butyl = ( E) -α- (1,3-dimethyl-5-phenoxypyrazol-4-ylmethyleneaminooxy) -p-toluate), amitraz (3-methyl-1,5-bis (2,4-xylyl) -1 , 3,5-triazapenta-1,4-die ) There is, etc.,
Preferred are phenisobromolate (isopropyl 4,4′-dibromobenzylate), hexothiazox (trans-5- (4-chlorophenyl) -N-cyclohexyl-4-methyl-2-oxothiazolidine-3- Carboxamide), amitraz (3-methyl-1,5-bis (2,4-xylyl) -1,3,5-triazapenta-1,4-diene), fenpyroximate (tert-butyl = (E) -α- ( 1,3-dimethyl-5-phenoxypyrazol-4-ylmethyleneaminooxy) -p-toluate).

  Examples of the herbicide include acid amide type herbicides such as stam (3,4-dichloropropionanilide, DCPA). Examples of urea herbicides include DCMU (3- (3,4-dichlorophenyl) -1,1-dimethylurea), linuron (3- (3,4-dichlorophenyl) -1-methoxy-1-methylurea), and the like. Can be mentioned. Examples of bipyridylium herbicides include paraquat (1,1′-dimethyl-4,4′-bipyridium dichloride) and diquat (6,7-dihydrodipyrido [1,2-a: 2 ′, 1′c] pyrazine. And dium dibromide). Examples of the diazine herbicide include bromacil (5-bromo-3-sec-butyl-6-methyluracil).

  Examples of S-triazine herbicides include simazine (2-chloro-4,6-bis (ethylamino) -1,3,5-triazine), simethrin (2,4-bis (ethylamino) -6-methylthio). -1,3,5-triazine) and the like. Examples of the nitrile herbicide include DBN (2,6-dichlorobenzonitrile). Examples of the dinitroaniline herbicide include trifluralin (α, α, α-trifluoro-2,6-dinitro-N, N-dipropyl-p-toluidine).

  Examples of carbamate type herbicides include benchiocarb (Saturn) (Sp-chlorobenzyl-N, N-diethylthiocarbamate), MCC (methyl-3,4-dichlorocarbanilate) and the like. Examples of the diphenyl ether herbicide include NIP (2,4-dichlorophenyl-p-nitrophenyl ether). Examples of the phenolic herbicide include PCP (sodium pentachlorophenoxide).

  Examples of the benzoic acid herbicide include MDBA (dimethylamine-3,6-dichloro-o-anisate). Examples of the phenoxy herbicide include 2,4-D sodium salt (sodium 2,4-dichlorophenoxyacetate), mapica ([(4-chloro-o-toluyl) oxy] aceto-o-chloroanilide), and the like. It is done. Examples of amino acid herbicides include glyphosate (N- (phosphonomethyl) glycine or a salt thereof), bialaphos (sodium salt of L-2-amino-4-[(hydroxy) (methyl) = phosphinoyl) butyryl-L-alanyl. -L-alanine), glyphosate (ammonium-DL-homoalanin-4-yl (methyl) phosphinate), and the like.

  Examples of the aliphatic herbicide include TCA sodium salt (sodium trichloroacetate), and preferable examples include DBN (2,6-dichlorobenzonitrile), DCMU (3- (3,4-dichlorophenyl) -1,1-dimethylurea), paraquat (1,1′-dimethyl-4,4′-bipyridium dichloride), diquat (6,7-dihydrodipyrido [1,2-a: 2 ′, 1′c] Pyrazinedium dibromide).

  Examples of plant growth regulators include indole butyric acid, ethiclozate (5-chloro-3 (1H) indazoline ethyl acetate), benzylaminopurine (6- (N-benzylamino) purine), forchlorphenuron (1- (2 -Chloro-4-pyridyl) -3-phenylurea), gibberellin, decyl alcohol, ethephone (2-chloroethylphosphonic acid) and the like.

Furthermore, the agrochemical composition of the present invention can be used by mixing one or more fertilizers, preservatives and the like other than those described above.
In addition, the agrochemical composition of the present invention may contain one or more of chelating agents, pH adjusting agents, inorganic salts, thickeners, and antifoaming agents as necessary.

  Although it does not specifically limit as a chelating agent, For example, aminopolycarboxylic acid type chelating agent, aromatic and aliphatic carboxylic acid type chelating agent, amino acid type chelating agent, ether polycarboxylic acid type chelating agent, phosphonic acid type Chelating agents (for example, iminodimethylphosphonic acid (IDP), alkyldiphosphonic acid (ADPA), etc.), dimethylglyoxime (DG), hydroxycarboxylic acid chelating agents, polymer electrolyte (including oligomers) chelating agents, etc. These may be in the form of an acid or a salt of sodium, potassium, ammonium or the like.

  Although it does not specifically limit as a pH adjuster, For example, they are a citric acid, phosphoric acid (pyrophosphate), gluconic acid etc., or these salts. The pH of the spreading agent composition of the present invention is not particularly limited, but is preferably 3-9, more preferably 4-8, from the viewpoint of improving the stability of the preparation.

  Examples of inorganic salts include, but are not particularly limited to, for example, inorganic mineral salts such as inorganic salt clay, talc, bentonite, zeolite, calcium carbonate, diatomaceous earth, white carbon, etc., and inorganic ammonium salts such as ammonium sulfate, Examples thereof include ammonium nitrate, ammonium phosphate, ammonium thiocyanate, ammonium chloride, and ammonium sulfamate.

  Although it does not specifically limit as a thickener, For example, a synthetic water-soluble thickener is mentioned. Specific examples include polyacrylate, polymaleate, polyvinyl pyrrolidone, pentaerythritol ethylene oxide adduct, and the like.

  Although it does not specifically limit as an antifoamer, For example, a fatty acid, metal soap, alcohol and glycols insoluble in water, silicone, modified silicone, a silicone type antifoamer etc. are mentioned.

  As a method for producing a crop using the spreading agent composition of the present invention, any one selected from the spreading agent composition of the present invention, a fungicide, an insecticide, an acaricide, a herbicide, and a plant growth regulator. A step of applying the agrochemical raw material to the object. Moreover, as a production method of the agricultural crop using the agrochemical composition of this invention, the process of applying the agrochemical composition of this invention to a target object is included.

  The method for applying the spreading agent composition, the pesticide active ingredient, or the pesticide composition to the object is not particularly limited. For example, the method of directly spraying the pesticide composition of the present invention on the leaves, stems, fruits, etc., water Examples thereof include a method of diluting and mixing with a hydroponic liquid or supply water that is in contact with the roots such as cultivation or rock wool, and supplying (coating) the root surface or the like. In order to effectively exert the effect of the spreading agent composition of the present invention, a method of spraying on the ground part of the object is preferable, and a method of spraying on the leaf surface is more preferable. Moreover, the spreading agent composition of this invention and an agrochemical raw material can also be separately provided to a target object with an above described method.

  The spreading agent composition of the present invention can enhance the efficacy of an agrochemical base by applying it to an object together with the agrochemical base selected from fungicides, insecticides, acaricides, herbicides, and plant growth regulators.

Hereinafter, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to only these examples.
The compound represented by the general formula (1) was produced by the method described below.

[Production Example 1]
9.1 g (0.05 mol) of L-lysine hydrochloride was mixed with 57 g of water. This liquid was stirred while adjusting the pH range to 10 to 11 with a 25% aqueous sodium hydroxide solution and maintaining the reaction temperature at 5 ° C. Under stirring, 31.1 g (0.1 mol) of N-lauroyl-L-glutamic anhydride was added over 2 hours to carry out the reaction. Thereafter, stirring was continued for another 30 minutes, and tertiary butanol was added to a concentration of 20% by mass in the liquid, 75% sulfuric acid was added dropwise to adjust the pH value of the liquid to 2, and the liquid temperature was adjusted to 65. Adjusted to ° C. After completion of the sulfuric acid addition, stirring was stopped, and the mixture was allowed to stand at 65 ° C. for 20 minutes to separate into an organic layer and an aqueous layer, and the organic layer was separated therefrom. Tertiary butanol and water were added to the separated organic layer, the temperature was raised to 65 ° C., and the mixture was stirred for 20 minutes. After the stirring was stopped, the mixture was allowed to stand to separate into an organic layer and an aqueous layer. After repeating the water washing operation for the obtained organic layer, the solvent was removed from the obtained organic layer, and the resulting solution was dissolved in an aqueous solution having a solid content of 30% by mass and pH 6.5 (25 ° C.) with sodium hydroxide. After preparing the sum, this was dried to obtain a compound represented by the following formula (4).

  In the reaction of N-lauroyl-L-glutamic anhydride and L-lysine hydrochloride, four types of compounds are produced as shown by the following formula (4) depending on the way of binding.

(In Formula 4, R is a hydrocarbon group having 11 carbon atoms, and M is each independently H or Na)

[Production Example 2]
The same procedure as in Production Example 1 was performed except that 0.1 mol of N-lauroyl-L-glutamic acid anhydride was changed to 0.1 mol of N-cocoyl-L-glutamic acid anhydride in Production Example 1.

[Production Example 3]
In Production Example 1, the neutralization treatment was carried out under the same conditions as in Production Example 1 except that the neutralization treatment was changed from sodium hydroxide to an aqueous ammonia solution.

[Production Example 4]
In the manufacture example 1, it implemented on the same conditions as the method of the manufacture example 1 except having changed and implemented the neutralization process from sodium hydroxide to triethanolamine.

[Examples 1 to 4, Comparative Example 1]
The compounds of Production Examples 1 to 4 and potassium laurate were mixed according to the formulation shown in Table 1. Table 1 shows the results of the human patch test and low temperature stability, and Table 2 shows the results of the surface tension. It can be seen that the compositions containing the compounds of Production Examples 1 to 4 have good spreadability and high safety.

[Evaluation test method]
(Human patch test)
0.1 g of the samples of Examples 1 to 4 and Comparative Example 1 were impregnated into 1 cm ² of filter paper, and this was occluded and pasted on the healthy skin of the forearms of 5 healthy male panelists for 24 hours. After 24 hours, the TEWL (moisture transpiration amount) of each panel was measured, and the human patch results were evaluated according to the following criteria. The measurement was performed using a CUTERTER MPA580 under the conditions of room temperature of 20 ° C. and humidity of 45%, and TEWAMETER TM300 was used as a probe. It is considered that the greater the TEWL increase rate, the greater the effect of destroying the skin barrier function and causing rough skin.
○: When the TEWL average increase rate is less than 10% △: When the TEWL average increase rate is 10% or more and less than 30% ×: When the TEWL average increase rate is 30% or more

(surface tension)
The surface tension (mN / m) at 25 ° C. was measured according to the Wilhelmy method using an aqueous solution (solid content 0.1%) obtained by diluting each composition shown in Table 1 1/25 times with water. The measurement was performed using fully automatic surface tension CBVP-Z. The case where it had a surface tension value of 39 (mN / m) or less, which is a standard for sufficiently wetting a plant that is difficult to wet, was marked with ◯, and the others were marked with x.
○: When the surface tension is less than 39 (mN / m) ×: When the surface tension is 39 (mN / m) or more

(Low temperature stability test)
Using the compositions of Examples 1 to 4 and Comparative Example 1, storage stability tests at low temperatures were performed according to the following criteria.
○: When stored at −5 ° C. and transparent for 3 days ×: When stored at −5 ° C. and becoming cloudy in 3 days

  A spreader composition having good spreadability and excellent safety can be provided.

Claims (5)

A spreading agent composition containing a compound represented by the following general formula (1).

(In the general formula (1), R ¹ represents a hydrocarbon group having 1 to 23 carbon atoms, and R ² has 1 to 3 carbon atoms which may have hydrogen, a carboxylic acid group or a sulfonic acid group. Y represents a carboxyl group, a sulfonic acid group, a sulfuric ester group, a phosphoric ester group, or a salt thereof. Z represents —NR ′ — (R ′ represents hydrogen or carbon number 1). -10 hydrocarbon group), -O-, or -S-, j and k are either 0, 1 or 2 and j and k are not 0 at the same time, and n is 2 to 20 X represents an optionally substituted hydrocarbon chain having a molecular weight of 1,000,000 or less.   The spreader composition according to claim 1, wherein the carbon number of X in the general formula (1) is 1 to 40. The spreading agent composition according to claim 1 or 2, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

(In the above general formula (2), R ¹ represents a hydrocarbon group having 1 to 23 carbon atoms, and R ² is a carbon atom having 1 to 3 carbon atoms which may have hydrogen, a carboxylic acid group or a sulfonic acid group. Y represents a carboxyl group, a sulfonic acid group, a sulfate ester group, a phosphate ester group, or a salt thereof, Z represents —NR ′ — (R ′ represents hydrogen or a carbon number of 1 to 10; X ′ represents a carboxyl group or a salt thereof, —NHR ′ group (R ′ is hydrogen or a hydrocarbon group having 1 to 10 carbon atoms), — A hydrocarbon chain having 1 to 20 carbon atoms and having at least one of an OH group and an —SH group, j and k are 0, 1 and 2, and j and k are simultaneously 0. is not.)   The spreader composition according to any one of claims 1 to 3, further comprising a solvent.   The agrochemical composition containing the spreading agent composition as described in any one of Claims 1-4.