JP2000095606A - Surfactant composition for agrochemical preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a surfactant composition quickly biodegradable after application without deteriorating the application performance by including a specific ester-type nonionic surfactant and two specific series of sulfosuccinates at specific ratios. SOLUTION: The objective composition contains (A) one or more kinds of ester-type nonionic surfactants selected from a polyoxyalkylenesorbitan fatty acid ester and a triglyceride derivative and (B) sulfosuccinic acid salts of formula I and formula II (R1 to R4 are each a 6-18C hydrocarbon group; A1 to A4 are each a (poly)oxyalkylene group composed of repeating 2-4C oxyalkylene units wherein the repetition number of the oxyalkylene unit is 1-10 and the content of the oxyethylene unit is >=50 mol%; (p), (q), (r) and (s) are each 0 or 1; M1 is an alkaline earth metal; M2 is an alkali metal or ammonium). The contents of the component A, the salt of formula I and the salt of formula II are 30-80 wt.%, 10-60 wt.% and 5-55 wt.%, respectively.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surfactant composition for agricultural chemicals used for preparing agricultural chemicals. Agrochemical preparations have various forms such as emulsions, emulsions, suspensions, wettable powders, granules, etc. In any of the forms, preparation of the same involves emulsification, dispersion, diffusion, etc. of the pesticidally active ingredient. Various surfactants are used for the purpose of improving the application performance. Conventionally, for pesticidally active ingredients in pesticide preparations,
Although those having a smaller effect on the environment have been studied, recently, the effects on the environment of surfactants used for preparing agricultural chemicals have been regarded as a problem. The present invention relates to a surfactant composition for agrochemical preparations that can undergo biodegradation promptly after application without significantly impairing the application performance of the pesticidally active ingredient, and can significantly reduce environmental problems due to residues.

[0002]

2. Description of the Related Art Conventionally, as surfactants for agricultural chemicals or compositions thereof, although there are some differences depending on the form of the formulation, various nonionic surfactants have been used in order to improve the application performance of pesticidally active ingredients. And anionic surfactants have been used alone or in combination. For example, an example using a nonionic surfactant and a hard type calcium alkylbenzene sulfonate or an alkaline earth metal salt of dialkyl sulfosuccinate (Japanese Patent Publication No. 38799/1983), polyalkoxyalkyl phenyl ether and alkoxypolyethoxyethyl phosphate Example using ester salt (JP-A-3-1
81329), an example using a nonionic surfactant having an HLB of 8 to 11 and an alkoxypolyalkoxyalkyl phosphate ester salt (JP-B-46-18514), a β-naphthalenesulfonic acid formalin condensate salt and a dioctyl sulfosuccinate sodium salt. Example (JP-A-58-124)
702), an example using an alkoxypolyalkoxyalkyl phosphate ester salt (JP-A-57-159703), an example using a dioctyl sulfosuccinate calcium salt, a polyoxyethylene polyoxypropylene block polymer and a polyoxyethylene tristyryl phenyl ether (JP-A-6-321713), an example using a dialkyl sulfosuccinate sodium salt (JP-B-63-37763),
Example using sulfosuccinic acid half ester (JP-B-56-17)
339), an example using a sulfate salt of a polyoxyethylene polyoxypropylene block polymer (Japanese Patent Publication No.
44802), an example using a polycarboxylic acid-based copolymer (JP-A-62-36302) and an example using a maleic acid-styrenesulfonic acid copolymer salt (JP-A-3-23630).
2) Examples of using a salt of formalin condensate of naphthalenesulfonic acid and an alkylnaphthalenesulfonic acid salt
264502), an example using lignin sulfonate and polyoxyethylene styryl phenyl ether sulfate (JP-A-5-43402), dialkyl sulfosuccinate, other sulfonic acid type surfactant and unsaturated carboxylate (JP-A-7-126106) and an example using a polyoxyalkylene alkyl sulfate salt and a sulfonate (JP-A-63-132804). However, even though these conventional surfactants and their compositions can improve the application performance of pesticidally active ingredients, they are less susceptible to biodegradation after application and have environmental problems due to residues.

[0003]

The problem to be solved by the present invention is that conventional surfactants for agrochemical preparations and compositions thereof can improve the application performance of pesticidally active ingredients to a corresponding degree,
It is less susceptible to biodegradation after application and has environmental problems due to residue.

[0004]

Means for Solving the Problems Thus, the present inventors have
As a result of research to solve the above problems, a surfactant composition for an agricultural chemical formulation comprising a specific ester-type nonionic surfactant and two specific sulfosuccinates and having them in a predetermined ratio is obtained. It was found that it was right and suitable as a product.

That is, the present invention comprises the following ester-type nonionic surfactant, a sulfosuccinate represented by the following formula 1, and a sulfosuccinate represented by the following formula 2,
30 to 80% by weight of the ester-type nonionic surfactant, 10 to 60% by weight of the sulfosuccinate represented by the formula 1, and 5 to 55% by weight of the sulfosuccinate of the formula 2
And a surfactant composition for agricultural chemicals.

[0006] Ester-type nonionic surfactant: one or more ester-type nonionic surfactants selected from the following polyoxyalkylene sorbitan fatty acid esters and the following triglyceride derivatives: polyoxyalkylene sorbitan fatty acid ester: carbon number A polyoxyalkylene sorbitan fatty acid ester obtained by reacting an alkylene oxide having 2 to 4 carbon atoms at a ratio of 5 to 40 mol with respect to 1 mol of an ester compound formed from a fatty acid of 12 to 22 and sorbitan, The ratio of ethylene oxide in the oxide is 5
0 mol% or more of polyoxyalkylene sorbitan fatty acid ester triglyceride derivative: 9 to 1 alkylene oxide having 2 to 4 carbon atoms per 1 mol of fat or oil mainly containing triglyceride having a fatty acid residue having 12 to 22 carbon atoms.
A triglyceride derivative reacted at a ratio of 20 mol, wherein the ratio of ethylene oxide in the alkylene oxide is 50 mol% or more.

[0007]

(Equation 1)

(Equation 2)

In the formulas 1 and 2, R ¹ , R ² , R ³ , R ⁴ : a hydrocarbon group having 6 to 18 carbon atoms A ¹ , A ² , A ³ , A ⁴ : an oxy group having 2 to ⁴ carbon atoms A (poly) oxyalkylene group composed of repeating alkylene units, wherein the number of repeating oxyalkylene units is from 1 to 10, and polyoxyalkylene having 50 mol% or more of oxyethylene units as the oxyalkylene units Group p, q, r, s: 0 or 1 M ¹ : alkaline earth metal M ² : alkali metal or ammonium

The ester type nonionic surfactant used in the present invention is one or more selected from polyoxyalkylene sorbitan fatty acid esters and triglyceride derivatives as described below.

The polyoxyalkylene sorbitan fatty acid ester is obtained by esterifying a fatty acid with sorbitan to form an ester compound, and then reacting the ester compound with an alkylene oxide. Ester compounds obtained by esterification of a fatty acid and sorbitan include sorbitan fatty acid monoesters, sorbitan fatty acid diesters, and sorbitan fatty acid triesters, depending on the reaction ratio of both.

The fatty acid to be subjected to the esterification reaction with sorbitan is a fatty acid having 12 to 22 carbon atoms. Examples of such fatty acids include 1) saturated fatty acids derived from natural fats and oils such as dodecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, icosanoic acid and docosanoic acid;
-Tetradecenoic acid, 9-hexadecenoic acid, 9-octadecenoic acid, 9,12-octadecadienoic acid, 9,12,1
5-octadecatrienoic acid, 6,9,12-octadecatrienoic acid, 9-icosenoic acid, 5,8,11,14-icosatetraenoic acid, 11-docosenoic acid, 13-docosenoic acid, 4,8,12, Unsaturated fatty acids derived from natural fats and oils, such as 15,19-docosapentaenoic acid, and 3) mixed fatty acids thereof. Among them, 9-octadecenoic acid and 9,12-octadecadienoic acid are 50% by weight in total. The mixed fatty acids contained above are preferred.

Examples of the alkylene oxide to be reacted with the ester compound include those having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, and 1,2-butylene oxide.
Alkylene oxide. These can be reacted alone or in a mixture, but in any case,
An alkylene oxide containing 50 mol% or more of ethylene oxide is reacted. The number of moles of the alkylene oxide to be reacted is 5 to 40 mol per 1 mol of the ester compound, and preferably 15 to 30 mol.

The polyoxyalkylene sorbitan fatty acid ester described above can be synthesized by a known method. For example, a sorbitan and a higher fatty acid are subjected to an esterification reaction in the presence of a base catalyst such as potassium hydroxide to obtain a sorbitan fatty acid ester, which is then reacted with an alkylene oxide such as ethylene oxide to form a polyoxyalkylene sorbitan fatty acid ester. obtain.

The above-mentioned triglyceride derivative is obtained by reacting an oil or fat mainly containing triglyceride having a fatty acid residue having 12 to 22 carbon atoms with an alkylene oxide. Examples of such fats and oils include 1) linseed oil, drill oil, kaya oil, walnut oil, soybean oil, poppy oil, sunflower oil,
Cottonseed oil, corn oil, sesame oil, rapeseed oil, rice bran oil,
Vegetable oils such as peanut oil, olive oil, camellia oil, castor oil, palm oil, palm kernel oil, coconut oil, cacao butter, and wax; 2) animal fats and oils such as tallow, lard and sheep tallow;
Each of these fats and oils contains 80% by weight or more of triglyceride having a fatty acid residue having 12 to 22 carbon atoms, and castor oil is particularly preferred.

As the alkylene oxide to be reacted with the fat or oil, ethylene oxide, propylene oxide,
Examples thereof include alkylene oxides having 2 to 4 carbon atoms such as 1,2-butylene oxide. These can be reacted alone or in a mixture. In any case, an alkylene oxide containing ethylene oxide in a proportion of 50 mol% or more is reacted. The number of moles of the alkylene oxide to be reacted is 9 to 120 moles per 1 mole of fat and oil, and preferably 15 to 80 moles.

The triglyceride derivatives described above are:
It can be synthesized by a known method. For example, a triglyceride derivative is obtained by reacting castor oil with an alkylene oxide such as ethylene oxide in the presence of a base catalyst such as potassium hydroxide.

The sulfosuccinate represented by the formula 1 used in the present invention includes: 1) a sulfosuccinate having two (poly) oxyalkylene groups in the molecule when p and q in the formula 1 are 1; Acid alkaline earth metal salts, 2) alkali sulfosuccinate having one (poly) oxyalkylene group in the molecule when one of p and q in the formula 1 is 1 and the other is 0 Earth metal salts; 3) alkaline earth metal sulfosuccinates having no (poly) oxyalkylene group in the molecule when p and q in Formula 1 are 0 are included.

In the formula (1), R ¹ and R ^{2 each} have 6 to ¹ carbon atoms.
8 hydrocarbon groups. Examples of such a hydrocarbon group include a hexyl group, an octyl group, a decanyl group, a dodecanyl group, a tetradecanyl group, a hexadecanyl group, an octadecanyl group, an 8-hexadecenyl group, and a 9-octadecenyl group. Is preferred.

In the formula 1, A ¹ and A ² are (poly) oxyalkylene groups composed of oxyalkylene units having 2 to 4 carbon atoms such as oxyethylene units, oxypropylene units and oxybutylene units. The oxyalkylene unit has an oxyethylene unit in a proportion of 50 mol% or more, preferably 100 mol%. The number of repeating oxyalkylene units constituting the (poly) oxyalkylene group is 1 to 10,
It is preferably 8.

In the formula 1, M ¹ is an alkaline earth metal such as beryllium, magnesium, calcium, etc.
Of these, magnesium is preferred.

The sulfosuccinates represented by the formula 2 used in the present invention include: 1) a sulfosuccinate having two (poly) oxyalkylene groups in the molecule when r and s in the formula 2 are 1; Acid alkali metal salt or ammonium salt, 2) Formula 2
Wherein one of r and s is 1 and the other is 0, wherein an alkali metal or ammonium sulfosuccinate having one (poly) oxyalkylene group in the molecule; When r and s of the above are 0, an alkali metal salt or ammonium sulfosuccinate having no (poly) oxyalkylene group in the molecule is included.

In the formula (2), R ³ and R ⁴ are the same as R ^{1 in} the formula ( ^1).
And R ² are the same as described above. Also, A ³ and A ⁴ are the same as described above for A ¹ and A ^{2 in} Equation 1.

In the formula (2), M ² is an alkali metal such as sodium, potassium or lithium, or ammonium, with sodium being preferred.

The sulfosuccinate represented by the above formula 1 and the sulfosuccinate represented by the above formula 2 can be synthesized by known methods. For example, maleic anhydride and an aliphatic alcohol and / or an aliphatic alkoxypolyalkylene glycol monool are subjected to an esterification reaction in the presence of an acid catalyst to obtain a corresponding maleic diester, which is then reacted with sodium bisulfite. Sulfonation gives the sulfosuccinate sodium salt. Further, sodium sulfosuccinate and an alkaline earth metal chloride undergo a metathesis reaction to obtain an alkaline earth metal sulfosuccinate.

The surfactant composition for agrochemical preparation of the present invention comprises:
Ester-type nonionic surfactant as described above,
A sulfosuccinate represented by the formula 1 and a sulfosuccinate represented by the formula 2, wherein the ester-type nonionic surfactant is 30 to 80% by weight, preferably 35 to 70% by weight. Wherein the sulfosuccinate represented by the formula 1 is 1
0-60% by weight, preferably 15-50% by weight and formula 2
Wherein the sulfosuccinate represented by the formula (1) comprises 5 to 55% by weight, preferably 10 to 50% by weight.

The surfactant composition for agrochemical preparation of the present invention comprises:
It does not particularly limit the form of the pesticide formulation to which it is applied, and is applicable to various forms of pesticide formulations such as emulsions, microemulsions, emulsions, suspensions, wettable powders, hydrated granules, and granules. Among them, it can be advantageously applied to emulsions, suspensions and hydrated granules. The present invention does not particularly limit the amount of the surfactant composition for agrochemical preparation of the present invention used when preparing the agrochemical formulation, and the usual amount of the agrochemical formulation can be applied. Usually, depending on the form of the pesticide formulation,
The surfactant composition for agrochemical formulation of the present invention in 100 parts by weight of agrochemical formulation, 2 to 20 parts by weight for emulsion, 5 to 40 parts by weight for microemulsion, 3 to 20 parts by weight for emulsion Ratio, 2 to 10 parts by weight for suspensions, 2 to 10 parts by weight for wettable powders, 2 to 30 parts by weight for hydrated granules, 1 to 10 parts by weight for granules It is used so that

The surfactant composition for agricultural chemicals of the present invention does not particularly limit the other components of the agricultural chemical to which the composition is applied. Such other components include solvents, carriers, and auxiliary agents such as a decomposition inhibitor and a thickener.

Further, the surfactant composition for agrochemical preparation of the present invention does not particularly limit the pesticidally active ingredient of the agrochemical formulation to which the composition is applied. Such pesticidally active ingredients include insecticides, fungicides, herbicides and the like.

As insecticides, 1) 1- (6-chloro-
3-pyridylmethyl) -N-nitroimidazolidin-2
Nitro-based insecticides such as ilideneamine (imidacloprid); 2) 1- [3,5-dichloro-4- (3-chloro-5-trifluoromethyl-2-pyridyloxy) phenyl] -3- (2,6- Difluorobenzoyl) urea (chlorofluazuron), 1- (3,5-dichloro-
Benzoylurea insecticides such as 2,4-difluorophenyl) -3- (2,6-difluorobenzoyl) urea (teflubenzuron); 3) carbamate insecticides such as o-sec-butylphenylmethylcarbamate (BPMC); 4) S-α-ethoxycarbonylbenzyl-
Organic phosphoric ester insecticides such as O, O-dimethylphosphorodithioate (fentoate), O, O-dimethyl-O-4-nitro-m-tolylphosphorothioate (Sumithion), 5) 3-phenoxybenzyl (I
RS) cis, trans-3- (2,2-dichlorovinyl) -2,2-dimethyl-cyclopropanecarboxylate (permethrin) and the like.

Examples of fungicides include 1) diisopropyl-1,3-dithiolan-2-ylidenemalonate (isoprothiolane) and dimethyl 4,4- (o-phenylene).
Organosulfur-based fungicides such as bis (3-thioallophanate) (Topzin M), 2) (Z) -2′-methylacetophenone = 4,6-dimethylpyrimidin-2-ylhydrazone (ferimzone), 3) 4 , 5,6,7-tetrachlorophthalide (fusaride), tetrachloro-isophthalonitrile (daconyl) and other organic chlorine-based fungicides;
4) Organophosphorus fungicides such as O-ethyl-S, S-diphenylphosphorodithioate (edifenfos);
5) Manganese ethylene bis (dithiocarbamate)
(Manneb) and the like.

Further, as herbicides, 1) 3- (4,6-
Dimethoxypyrimidin-2-yl) -1-[(2-methoxycarbonylbenzyl) sulfonyl] urea (bensulfuronmethyl), ethyl 5- [3- (4,6-dimethoxypyrimidin-2-yl) ureidosulfonyl] -1
-Methylpyrazole-4-carboxylate (pyrazosulfuron-ethyl), 1- (2-chloroimidazo [1,
2-a] pyridin-3-ylsulfonyl) -3- (4,
6-dimethoxypyrimidin-2-yl) urea (imazosulfuron), 1- (4,6-dimethoxypyrimidine-
2-yl) -3- (3-trifluoromethyl-2-pyridylsulfonyl) urea (furazasulfuron), methyl 3-chloro-5- (4,6-dimethoxypyrimidine-2
-Ylcarbamoylsulfamoyl) -1-methylpyrazole-4-carboxylate (halosulfuronmethyl) and other sulfonylurea herbicides; 2) 2-benzothiazol-2-yloxy-N-methyl-acetanilide (mefenacet); Anilide herbicides such as -chloro-2 ', 6'-diethyl-N- (2-propoxyethyl) acetanilide (pretilachlor); 3) 4-
(2,4-dichlorobenzoyl) -1,3-dimethylpyrazol-5-yloxytoluene-4-sulfone (pyrazolate), 2- [4- (2,4-dichlorobenzoyl) -1,3-dimethylpyrazole- 5-yloxy]
Pyrazole herbicides such as acetophenone (pyrazoxifen); 4) O-3-tert-butylphenyl-6-
Carbamate herbicides such as methoxy-2-pyridyl (methyl) thiocarbamate (pyributicarb) and S-4-chlorobenzyldiethylthiocarbamate (thiobencarb) 5) 1- (α, α-dimethylbenzyl) -3
Urea herbicides such as-(p-tolyl) urea (Dimron); and 6) amino acid herbicides such as N- (phosphonomethyl) glycine (glyphosate).

The surfactant composition for agrochemical preparation of the present invention comprises:
Since the application performance of the pesticidally active ingredient in the pesticide preparations of various forms prepared by using the same is not impaired, and particularly easily susceptible to biodegradation after application, environmental problems due to the residual can be remarkably reduced.

[0033]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the surfactant composition for agrochemical preparations of the present invention include the following 1) to 9). 1) The following ester-type nonionic surfactant (A-
1) a sulfosuccinate (C-5) represented by the formula 1 and a sulfosuccinate (D-4) represented by the formula 2, and the ester-type nonionic surfactant (A-1) is 60 % By weight, 15% by weight of the sulfosuccinate of the formula 1 (C-5) and 2% of the sulfosuccinate of the formula 2 (D-4)
A surfactant composition for agricultural chemicals comprising 5% by weight. Ester-type nonionic surfactant (A-1): polyoxyethylene (the number of oxyethylene units n = 20) sorbitan mixed fatty acid ester (mixed fatty acid: 9-octadecenoic acid 80% by weight, 9,12-octadecadienoic acid) A mixed fatty acid composed of 10% by weight, 5% by weight of tetradecanoic acid and 5% by weight of hexadecanoic acid) Sulfosuccinate (C-5) represented by Formula 1: R in Formula 1
Sulfosuccinate when ¹ and R ² are lauryl groups, p and q are 0, and M ¹ is magnesium Sulfosuccinate (D-4) represented by Formula 2: R in Formula 2
Sulfosuccinate when ³ and R ⁴ are octyl groups, r and s are 0, and M ² is sodium

2) The following ester-type nonionic surfactants (A-2) and ester-type nonionic surfactants (B-
1) comprising a sulfosuccinate (C-2) represented by the formula 1 and a sulfosuccinate (D-1) represented by the formula 2, wherein the ester-type nonionic surfactant (A-2) is 25 % By weight, and the ester-type nonionic surfactant (B-1) contained 25% by weight.
1% by weight of the sulfosuccinate (C-2) represented by the formula 1
5% by weight and a sulfosuccinate represented by the formula 2 (D-1)
Is a surfactant composition for agricultural chemicals comprising 35% by weight. Ester-type nonionic surfactant (A-2): polyoxyethylene (the number of oxyethylene units n = 30) sorbitan mixed fatty acid ester (mixed fatty acid: 50% by weight of 9-octadecenoic acid, 9,12-octadecadienoic acid) (A mixed fatty acid comprising 45% by weight and 5% by weight of hexadecanoic acid) Ester-type nonionic surfactant (B-1): polyoxyethylene (the number of oxyethylene units n = 60) castor oil Sulfosuccinic acid represented by Formula 1 Salt (C-2): R in Formula 1
¹ and R ² are 2-ethylhexyl groups, p and q are 1, A ¹
And sulfo A ² are represented by polyoxyethylene (number n = 6 oxyethylene units) (the number m = 2 of oxypropylene units) polyoxypropylene group, sulfosuccinates formula 2 where M ¹ is magnesium Succinate (D-1): R in Formula 2
³ and R ⁴ are octyl groups, r and s are 1, A ³ and A ⁴ are polyoxyethylene (the number of oxyethylene units n = 3)
Group, sulfosuccinate when M ² is ammonium

3) The following ester-type nonionic surfactant (A-3), a sulfosuccinate represented by the formula 1 (C-
2) and an ester type nonionic surfactant (A-3) comprising a sulfosuccinate (D-3) represented by the formula (2) and
Is 40% by weight of a sulfosuccinate represented by the formula (C-
2) 40% by weight of a sulfosuccinate (D-3) represented by Formula 2 and 20% by weight of a surfactant composition for agricultural chemicals. Ester-type nonionic surfactant (A-3): polyoxyethylene (number of oxyethylene units n = 30) polyoxypropylene (number m of oxypropylene units m = 5) sorbitan mixed fatty acid ester {mixed fatty acid: ester-type nonion Mixed fatty acids as in the case of the surfactant (A-1)} Sulfosuccinate (C-2) represented by the formula 1: Same as the sulfosuccinate (C-2) Acid salt (D-3): R in formula 2
³ and R ⁴ are lauryl groups, r and s are 1, A ³ and A ⁴ are polyoxyethylene (the number of oxyethylene units n = 8)
Group, sulfosuccinate when M ² is potassium

4) The following ester-type nonionic surfactant (B-1), sulfosuccinate (C-
1) and a sulfosuccinate (D-4) represented by the formula 2, and an ester type nonionic surfactant (B-1)
Is 70% by weight of a sulfosuccinate represented by the formula 1 (C-
A surfactant composition for agrochemical preparation comprising 1% by weight of 15) and 15% by weight of a sulfosuccinate (D-4) represented by the formula (2). Ester-type nonionic surfactant (B-1): Same as the above-mentioned ester-type nonionic surfactant (B-1) Sulfosuccinate (C-1) represented by the formula 1: R in the formula 1
¹ and R ² are octyl groups, p and q are 1, A ¹ and A ² are polyoxyethylene (the number of oxyethylene units n = 2)
Sulfosuccinate when the group, M ¹ is magnesium Sulfosuccinate (D-4) represented by Formula 2: Same as the above sulfosuccinate (D-4)

5) The following ester-type nonionic surfactant (B-2), a sulfosuccinate represented by the formula 1 (C-
1) and a sulfosuccinate (D-4) represented by the formula 2 and an ester type nonionic surfactant (B-2)
Is 65% by weight of a sulfosuccinate represented by the formula 1 (C-
A surfactant composition for agrochemical preparation comprising 1) 25% by weight and 10% by weight of a sulfosuccinate (D-4) represented by the formula (2). Ester-type nonionic surfactant (B-2): polyoxyethylene (the number of oxyethylene units n = 35) polyoxypropylene (the number of oxypropylene units m = 5) castor oil sulfosuccinate represented by Formula 1 (C-1): Same as the above sulfosuccinate (C-1) Sulfosuccinate (D-4) represented by the formula 2: Same as the above sulfosuccinate (D-4)

6) The following ester-type nonionic surfactant (B-3), a sulfosuccinate represented by the formula 1 (C-
4) and an ester-type nonionic surfactant (B-3) comprising a sulfosuccinate (D-3) represented by the formula 2
Is 60% by weight of a sulfosuccinate represented by the formula (C-
4) A surfactant composition for agrochemical preparation comprising 30% by weight of the sulfosuccinate (D-3) represented by the formula 2 and 10% by weight. Ester-type nonionic surfactant (B-3): polyoxyethylene (the number of oxyethylene units n = 30) rapeseed oil Sulfosuccinate (C-4) represented by Formula 1: R in Formula 1
¹ and R ² are octyl groups, p is 1, q is 0, A ¹ is a polyoxyethylene (the number of oxyethylene units n = 5) group, M
Sulfosuccinate when ¹ is magnesium Sulfosuccinate (D-3) represented by the formula 2: Same as the above sulfosuccinate (D-3)

7) The following ester-type nonionic surfactant (B-1), a sulfosuccinate (C-
2) and a sulfosuccinate (D-2) represented by the formula 2, and an ester type nonionic surfactant (B-1)
Is 35% by weight of a sulfosuccinate represented by the formula 1 (C-
2) A surfactant composition for agrochemical preparation, comprising 15% by weight of a sulfosuccinate (D-2) represented by the formula 2 and 50% by weight. Ester-type nonionic surfactant (B-1): Same as the above-mentioned ester-type nonionic surfactant (B-1) Sulfosuccinate (C-2) represented by the formula 1: Sulfosuccinate (C The sulfosuccinate (D-2) represented by the formula 2: R in the formula 2
³ and R ⁴ are 2-ethylhexyl groups, r and s are 1, A ³
And a sulfosuccinate wherein A ⁴ is a polyoxyethylene (number of oxyethylene units n = 3) polyoxypropylene (number m of oxypropylene units m = 2) group and M ² is sodium

8) The following ester-type nonionic surfactant (B-1), sulfosuccinate (C-
3) and an ester-type nonionic surfactant (B-1) comprising a sulfosuccinate (D-2) represented by the formula (2).
Is 35% by weight of a sulfosuccinate represented by the formula 1 (C-
3) A surfactant composition for agrochemical preparation comprising 25% by weight of a sulfosuccinate (D-2) represented by the formula 2 and 40% by weight. Ester-type nonionic surfactant (B-1): Same as the above-mentioned ester-type nonionic surfactant (B-1) Sulfosuccinate (C-3) represented by the formula 1: R in the formula 1
¹ is a lauryl group, R ² is an octyl group, p and q are 1, A ¹
And a sulfosuccinate in the case where A ² is a polyoxyethylene (the number of oxyethylene units n = 5) group and M ¹ is magnesium; a sulfosuccinate represented by Formula 2 (D-2): the above sulfosuccinic acid Same as salt (D-2)

9) The following ester-type nonionic surfactant (B-2), sulfosuccinate (C-
2) and a sulfosuccinate (D-5) represented by the formula 2, and an ester-type nonionic surfactant (B-2)
Is 40% by weight of a sulfosuccinate represented by the formula (C-
2) A surfactant composition for agricultural chemicals comprising 50% by weight of a sulfosuccinate (D-5) represented by the formula 2 and 10% by weight. Ester-type nonionic surfactant (B-2): Same as the above-mentioned ester-type nonionic surfactant (B-2) Sulfosuccinate (C-2) represented by Formula 1: Sulfosuccinate (C Same as -2) Sulfosuccinate (D-5) represented by Formula 2: R in Formula 2
³ is an octyl group, R ⁴ is a lauryl group, r and s are 0, M ²
Where sulphosuccinate is sodium

Hereinafter, the structure and effects of the present invention will be more specifically described with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following Examples and Comparative Examples, parts are parts by weight, and% is% by weight.
Means

[0043]

EXAMPLES Test Category 1 (Preparation of Surfactant Composition for Agrochemical Formulation) Examples 1 to 9 and Comparative Examples 1 to 14 Polyoxyethylene (the number of oxyethylene units n = 2)
0) 60 parts of sorbitan palm fatty acid ester, 21.4 parts of a 70% isopropyl alcohol solution of magnesium dilauryl sulfosuccinate and 35.7 of a 70% isopropyl alcohol solution of dioctyl sulfosuccinate sodium salt.
The isopropyl alcohol was distilled off under reduced pressure while heating and stirring at 60 to 80 ° C.
A surfactant composition (S-1) for agrochemical preparation was prepared.
Similarly, the surfactant compositions (S-2) to (S-9) and (r-) for pesticide preparations of Examples 2 to 9 and Comparative Examples 1 to 14 were prepared.
1) to (r-14) were prepared. Table 1 summarizes the compositions of the prepared surfactant compositions for agrochemical preparations of each example.

[0044]

[Table 1]

In Table 1, A-1 to A-3, a-1 to a-3: polyoxyalkylene sorbitan fatty acid esters B-1 to B-3, b-1 to b- 3: triglyceride derivatives summarized in Table 3 C-1 to C-5, c-1 to c-3: sulfosuccinates represented by Formula 1 summarized in Table 4, etc. D-1 to D- 5, d-1 to d-3: sulfosuccinates represented by the formula 2 summarized in Table 5 and the like

[0046]

[Table 2]

In Table 2, sorbitan, fatty acid, alkylene oxide: types of raw materials used for the synthesis of polyoxyalkylene sorbitan fatty acid esters and their molar numbers Mixed fatty acid A: 9-octadecenoic acid 80% by weight, 9.1
2-octadecadienoic acid 10% by weight, tetradecanoic acid 5
Mixed fatty acid consisting of 5% by weight of hexadecanoic acid and 5% by weight of hexadecanoic acid Mixed fatty acid B: 50% by weight of 9-octadecenoic acid, 9.1
Mixed fatty acid composed of 45% by weight of 2-octadecadienoic acid and 5% by weight of hexadecanoic acid EO: ethylene oxide (hereinafter the same) PO: propylene oxide (hereinafter the same)

[0048]

[Table 3]

In Table 3, fats, alkylene oxides: types of raw materials used for the synthesis of triglyceride derivatives and their mole numbers Fatty acids forming fatty acid residues of triglyceride, which is a main component of castor oil, fatty acids: ricinoleic acid 87% by weight, olein Mixed fatty acid comprising 8% by weight of acid and 5% by weight of linoleic acid Fatty acid forming fatty acid residue of triglyceride which is a main component of rapeseed oil: 62% by weight of oleic acid, 2% of linoleic acid
Mixed fatty acid comprising 4% by weight and 14% by weight of linolenic acid

[0050]

[Table 4]

[0051]

[Table 5]

In Tables 4 and 5, OP: number of oxypropylene units OE: number of oxyethylene units

Test Category 2 (Preparation of Agrochemical Formulation) Emulsions (EC-1) to (EC-5) and (ec-1)
Preparation of (ec-9) 11 parts of cypamethrin, 5 parts of the surfactant composition for agricultural chemicals (S-1), and 84 parts of non-xylene solvent Solvesso 150 (exxon aromatic petroleum fraction, trade name) at room temperature. To prepare a uniform emulsion (EC-1). Emulsions (EC-2) to (EC-5) and (ec-1) to
(Ec-9) was prepared. Table 6 shows the composition of each prepared emulsion.
Are shown together.

Microemulsion (ME-1)
Preparation of (ME-4) and (me-1) to (me-6) 10 parts of Trebon, a surfactant composition for agrochemical formulation (S-
2) 30 parts of butyl diglycol and 40 parts of water were mixed at room temperature to obtain a uniform microemulsion (ME-
1) was prepared. Similarly, microemulsions (ME-2) to (ME-4) and (me-1) to (me)
-6) was prepared. Table 7 summarizes the compositions of the prepared microemulsions.

Emulsions (EW-1) to (EW-)
3) and Preparation of (ew-1) to (ew-4) After adding and dissolving 7 parts of the surfactant composition for agrochemical formulation (S-2) to 50 parts of fentoate, 10 parts of propylene glycol and 33 parts of water Was added and mixed gently with stirring to obtain a mixture. The obtained mixture was transferred to a homomixer and stirred at 10,000 rpm for 15 minutes to prepare a milk-like emulsion (EW-1). Similarly, the emulsions (EW-2), (EW-3) and (ew)
-1) to (ew-4) were prepared. Table 8 summarizes the compositions of the prepared emulsion agents.

Preparation of Suspensions (SC-1) to (SC-3) and (sc-1) to (sc-5) 20 parts of Fusaride, a surfactant composition for agricultural chemicals (S-
4) 3 parts, 15 parts of a 1% aqueous solution of xanthan gum, 0.5 parts of montmorillonite, 5 parts of propylene glycol and 56.5 parts of water are mixed at room temperature, and further, a diameter of 1 to 1.
100 parts of 5 mm glass beads were added, and the mixture was pulverized with a four-cylinder sand grinder at 2000 rpm for 2 hours to prepare a uniform suspension (SC-1). Similarly, suspending agents (SC-2), (SC-3) and (sc-1) to (sc
-5) was prepared. Table 9 summarizes the compositions of the prepared suspensions.

Preparation of wettable powders (WP-1) to (WP-3) and (wp-1) to (wp-4) 72 parts of Topgin M, a surfactant composition for agricultural chemicals (S
-2) 5 parts, 5 parts of white carbon (trade name, Carplex # 80, manufactured by Shionogi & Co., Ltd.) and 18 parts of agricultural clay are mixed, and further pulverized and mixed with a coffee mill to obtain a wettable powder (W).
P-1) was prepared. Similarly, a wettable powder (WP-2),
(WP-3) and (wp-1) to (wp-4) were prepared. Table 10 summarizes the compositions of the prepared wettable powders.

-Hydrated granules (WG-1) to (WG-4)
And Preparation of (wg-1) to (wg-5) 72 parts of Topgin M, a surfactant composition for pesticide formulation (S
-2) After mixing 20 parts and 8 parts of agricultural clay, 7 parts of water was further added and kneaded sufficiently, and the screen opening was 0.7 mm.
Was granulated with a basket-type granulator. The obtained granules were dried to a water content of 0.5% or less, and then sized (grain length: about 3 mm) to prepare hydrated granules (WG-1). Similarly, hydrated granules (WG-2) to (WG-4) and (wg-1) to (wg-5) were prepared. Table 11 summarizes the compositions of the prepared hydrated granules.

Granules (G-1) to (G-3) and (g-
1) Preparation of (g-5) After mixing 10 parts of mefenacet, 4 parts of the surfactant composition for agricultural chemicals (S-3) and 86 parts of clay, 10 parts of water was further added and kneaded sufficiently. Granulation was performed with a basket-type granulator having a screen opening of 1 mm to obtain a granulated product. The obtained granules were dried to a water content of 0.5% or less and then sized (grain length: about 3 mm) to prepare granules (G-1). Similarly, granules (G-2), (G-3) and (g-1) to (g-5)
Was prepared. Table 12 summarizes the compositions of the prepared granules.

Test Category 3 (Evaluation of Application Performance for Pesticide Formulations) With respect to each of the agricultural chemical preparations prepared in Test Category 2, the application performance was evaluated according to the form by the following method, and the results were shown in Tables 6 to 12.
Are shown together.

Evaluation of Emulsification of Emulsions, Microemulsions and Emulsifiers 1 ml of the emulsion, microemulsions and emulsions prepared in Test Category 2 were fitted with 100 ml stoppers containing 99 ml of 3 ° C. hard water at 20 ° C. In addition to the cylinder,
After sealing, the cylinder was inverted 20 times at a rate of once every 2 seconds to emulsify, and then the emulsifying property was visually evaluated in the following four stages. Evaluation criteria 1: emulsified particles are fine and show very good emulsifying properties 2: show good emulsifying properties 3: emulsifying properties are unstable and there is a problem in practical use 4: emulsifying properties are poor and cannot be put to practical use

Evaluation of suspension stability of suspension, wettable powder and hydrated granules 1 g of the suspension, wettable powder and hydrated granules prepared in Test Category 2 1 with 99 ml of hard water
In addition to the 00 ml stoppered cylinder, after dispersing the cylinder by inverting it 20 times under the same conditions as above, the dispersion was transferred to a sedimentation tube, and the amount of sedimentation when left at 20 ° C. for 1 hour was measured. The suspension stability was evaluated in the following four stages. Evaluation criteria 1: The amount of sedimentation is very small and good suspension is exhibited. 2: The good suspension is exhibited. 3: The amount of sedimentation is large and there is a problem in practical use.

Evaluation of Suspension Formulation Stability 50 g of the suspension prepared in Test Category 2 was added at -5 ° C.
The test was performed for 6 cycles, with each cycle of standing at 24 ° C. and 54 ° C. for 24 hours, and then the appearance of the suspension was evaluated on the following four scales. Evaluation criteria 1: No caking was observed, and the liquid layer to be separated was within 10% of the total sample volume. 2: No caking was observed, and the liquid layer to be separated was within 20% of the total sample volume. There is a problem when the liquid layer to be separated and separated is 20% or more of the total sample volume. 4. Remarkable abnormalities such as caking are recognized and are not practical.

Evaluation of Diffusion Property of Granules 0.5 g of the granules prepared in Test Category 2 were gently placed in the center of a 25 cm diameter vinyl chloride vat containing 1200 ml of 3 ° C. hard water at 25 ° C. The diffusivity of the granules after 30 minutes was evaluated on the following four scales. Evaluation criteria 1: No prototype of the injected granules was observed, and very good diffusibility was exhibited. 2: No prototype of the injected granules was observed, showing good diffusibility. The prototype of the granule is recognized and the diffusivity is poor. 4: The prototype of the granule input is recognized and the diffusivity is extremely poor.

Test Category 4 (Evaluation of Biodegradability) For each of the surfactant compositions for agricultural chemicals used in Test Category 2, the BOD was determined in accordance with JIS-K0102-1993.
Was measured. Separately, the calculated total oxygen consumption (TOD) was calculated, the ratio of BOD / TOD was calculated, and the biodegradability was evaluated based on the following criteria. The results are summarized in Tables 6 to 12. Evaluation criteria 1: BOD / TOD ratio is 0.4 or more, excellent in biodegradability 2: BOD / TOD ratio is less than 0.1 to less than 0.4, biodegradability is somewhat poor 3: BOD Poor biodegradability when the ratio of / TOD is 0.1 or less

[0066]

[Table 6]

In Table 6, X-1: aromatic solvent (trade name: Solvesso 150, manufactured by Exxon Corporation) cypamethrin: (R, S) -α-cyano-3-phenoxybenzyl (1RS, 3RS)-(1RS, 3RS) )
-3- (2,2-Dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate Marathon: S-1,2-bis (ethoxycarbonyl) ethyl O, O-dimethylphosphodithioate diazinon: O, O- Diethyl O-2-isopropyl-6-methylpyrimidin-4-yl phosphorothioate BPMC, Sumithion: The above-mentioned pesticidally active ingredient r-15: Polyoxyethylene (the number of oxyethylene units n = 25) tristyryl phenyl ether 60 R-16: a mixture of 60 parts of polyoxyethylene (the number of oxyethylene units n = 22) tristyrylphenyl ether and 40 parts of calcium dodecylbenzenesulfonate

[0068]

[Table 7]

In Table 7, X-2: a mixture of 20 parts of butyldiglycol and 40 parts of water X-3: a mixture of 20 parts of butyldiglycol and 30 parts of water trebon: 2- (4-ethoxyphenyl)- 2-methylpropyl 3-phenoxybenzyl ether permethrin: the above-mentioned pesticidally active ingredient r-17: a mixture of 55 parts of polyoxyethylene (number of oxyethylene units n = 18) tristyrylphenyl ether and 45 parts of calcium dodecylbenzenesulfonate

[0070]

[Table 8]

In Table 8, X-4: a mixture of 10 parts of propylene glycol and 63 parts of water X-5: a mixture of 10 parts of propylene glycol and 33 parts of water fentoate, BPMC: the above-mentioned pesticidally active ingredient r-18: Polyoxyethylene (the number of oxyethylene units n = 57) polyoxypropylene (the number of oxypropylene units m = 43) copolymer

[0072]

[Table 9]

In Table 9, T-1: a mixture of 0.5 parts of montmorillonite, 0.15 parts of xanthan gum and 5 parts of propylene glycol T-2: 0.3 parts of montmorillonite, 0.05 parts of xanthan gum and 5 parts of propylene glycol Mixture of Fusaride and Topozin M: the above-mentioned pesticidally active ingredient r-19: polyoxyethylene (the number of oxyethylene units n = 15) tristyryl phenyl ether phosphate triethanolamine salt Evaluation 1: Suspension stability Evaluation 2: Formulation Stability

[0074]

[Table 10]

In Table 10, U-1: a mixture of 5 parts of white carbon (trade name: Carplex # 80 manufactured by Shionogi & Co., Ltd.) and 18 parts of agricultural clay U-2: White carbon (manufactured by Shionogi & Co., Ltd.) Mixture of 20 parts of trade name Carplex # 100 and 40 parts of agricultural clay Topazin M, Fusaride, Diazinon: The above-mentioned pesticidally active ingredient r-20: 90 parts of sodium salt of naphthalenesulfonic acid formalin condensate and polyoxyethylene (oxyethylene Number of units n = 10) mixture with 10 parts of nonylphenyl ether

[0076]

[Table 11]

In Table 11, V-1: Agricultural clay topzin M, fusaride, maneb: The above-mentioned pesticidally active ingredient

[0078]

[Table 12]

In Table 12, V-1: Agricultural clay mefenacet, Daimlon, pretilachlor: The above-mentioned pesticidally active ingredient r-21: Polyoxyethylene (the number of oxyethylene units n = 12) tristyryl phenyl ether sulfate ammonium salt 60 Mixture of 1 part with 40 parts of sodium dodecylbenzenesulfonate

[0080]

As is apparent from the above description, the present invention described above undergoes biodegradation promptly after application without impairing the application performance such as emulsification, dispersion and diffusion of the pesticidally active ingredient.
This has the effect of significantly reducing environmental problems due to the residue.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) // C08L 71/02 C08L 71/02

Claims (5)

[Claims] 1. An ester-type nonionic surfactant comprising the following ester-type nonionic surfactant, a sulfosuccinate represented by the following formula 1, and a sulfosuccinate represented by the following formula 2: For a pesticide formulation, characterized in that the ratio is from 30 to 80% by weight, the sulfosuccinate of the formula 1 is from 10 to 60% by weight and the sulfosuccinate of the formula 2 is from 5 to 55% by weight. Surfactant composition. Ester-type nonionic surfactant: One or two or more ester-type nonionic surfactants selected from the following polyoxyalkylene sorbitan fatty acid esters and the following triglyceride derivatives: Polyoxyalkylene sorbitan fatty acid ester: 12 to 22 carbon atoms A polyoxyalkylene sorbitan fatty acid ester obtained by reacting an alkylene oxide having 2 to 4 carbon atoms at a ratio of 5 to 40 moles with respect to 1 mole of an ester compound formed from a fatty acid and sorbitan, The ratio of ethylene oxide is 5
0 mol% or more of polyoxyalkylene sorbitan fatty acid ester triglyceride derivative: 9 to 1 alkylene oxide having 2 to 4 carbon atoms per 1 mol of fat or oil mainly containing triglyceride having a fatty acid residue having 12 to 22 carbon atoms.
A triglyceride derivative reacted at a ratio of 20 mol, wherein the ratio of ethylene oxide in the alkylene oxide is 50 mol% or more. (Equation 2) (In the formulas 1 and 2, R ¹ , R ² , R ³ , R ⁴ : a hydrocarbon group having 6 to 18 carbon atoms A ¹ , A ² , A ³ , A ⁴ : an oxyalkylene unit having 2 to ⁴ carbon atoms Wherein the number of repetitions of the oxyalkylene unit is 1 to 10 and the polyoxyalkylene group has at least 50 mol% of oxyethylene units as the oxyalkylene unit. , Q, r, s: 0 or 1 M ¹ : alkaline earth metal M ² : alkali metal or ammonium) 2. The method according to claim 1, wherein the ester type nonionic surfactant is 35%.
７０70% by weight, the sulfosuccinate represented by the formula 1 is 15〜
50% by weight and 10% of the sulfosuccinate of formula 2
The surfactant composition for agrochemical preparation according to claim 1, which comprises 50% by weight. 3. The polyoxyalkylene sorbitan fatty acid ester is a fatty acid having 12 to 22 carbon atoms containing 9-octadecenoic acid and 9,12-octadecadienoic acid in total of 5%.
The surfactant composition for agrochemical preparation according to claim 1 or 2, wherein a mixed fatty acid containing 0% by weight or more is used. 4. The sulfosuccinate according to claim 1, wherein the sulfosuccinate represented by the formula 1 is magnesium sulfosuccinate, and the sulfosuccinate represented by the formula 2 is sodium sulfosuccinate. A surfactant composition for agricultural chemical formulations. 5. The sulfosuccinate represented by the formula (1) is a compound wherein p and q in the formula (1) are 0, and the sulfosuccinate represented by the formula (2) is a compound represented by the formula (2) The surfactant composition for an agricultural chemical formulation according to claim 1, 2, 3 or 4, wherein 0 is 0.