JPS5872501A - Liquid agricultural chemical - Google Patents

Abstract

PURPOSE:A liquid agricultural chemical, prepared by dispersing an active constituent of an agricultural chemical in an aqueous colloidal dispersion of a copolymer having a specific colloidal particle diameter, having a low viscosity and improved fluidity at a high concentration, improved storage stability, capable of being diluted easily, and having a great effect by the application in a small amount. CONSTITUTION:A liquid agricultural chemical prepared by dispersing an active constituent of an agricultural chemical in an aqueous colloidal dispersion of a copolymer having <=0.1mu, preferably <=0.05mu, colloidal particle diameter. The colloidal dispersion is required to contain at least 50% or more hydrosol having <=0.1mu particle diameter, and preferably a hydrosol consisting essentially of particles having <=0.05mu particle diameter is suitable. 100pt.wt. aqueous colloidal dispersion of the copolymer having <=0.1mu particle diameter adjusted to 10-50wt% concentration is stirred, and 20- 300pts.wt., preferably 20-150pts.wt., active constituent of an agricultural chemical is slowly added thereto. The resultant mixture is the stirred until the uniform mixing is possible to give the aimed agricultural chemical. The active constituent of the agricultural chemical may either one of the solid and liquid, but the solid is powdered to particles having preferably <=200mu particle diameter.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a liquid pesticide with improved fluidity, and the purpose thereof is to provide a novel dosage form of a good drug that can be sprayed as is or at a low dilution ratio, that is, with a high concentration of active ingredients. It's there to provide.

Conventional copper caps for agricultural chemicals can be broadly divided into four types: powders, powders, granules, wettable powders, and emulsions.

Powders contain about 2 to 5 active agricultural ingredients, and are mixed with, adhered to, and adsorbed with talc, clay, kaolin, diatomaceous earth, bentonite, calcium carbonate, white carbon, and inorganic carriers, and are usually sprayed as is.

Powder powder is granulated using a binder such as polyvinyl alcohol, ilpoquin methyl cellulose, starch, and lignin sulfonate, and the particle size is approximately 50 to 2.
It is a granule of about 00μ.

Wettable powders contain about 20 to 50 active agricultural ingredients, and are composed of an inorganic carrier, a dispersant, etc. used in powders, and are dispersed and diluted in water before being sprayed.

The emulsion consists of about 20 to 50 active agricultural ingredients, an organic solvent such as xylene, hexane, mineral oil, and an emulsifier, and is emulsified and diluted in water before being sprayed.

Of course, when spraying in the air using an aircraft, there is significant drift.
Its use has declined sharply in recent years.

Powder was developed to prevent this drift, and although it is in practical use, it is expensive, and its low concentration of active ingredients makes aerial spraying less efficient. Usage has been stagnant in recent years.

Since the wettable powder contains a large amount of inorganic carrier, the diluted dispersion is unstable and may cause sedimentation, which may clog the nozzle of the sprayer and the atomizer. In addition, if the dilution ratio is low, it will become a highly viscous slurry or paste, so 1.
This often causes inconvenience when spraying small amounts of liquid. Although emulsions are excellent in terms of workability, the biggest problem is the contamination and damage to the coating caused by the organic solvents they contain.

In addition, carbamate-based drugs, which are major insecticides, are insoluble in many organic solvents, making it difficult to form emulsions. 15111
degree.

Aerial spraying of pesticides has gone from the era of solid pesticide spraying, mainly powder, to the era of liquid pesticide spraying.

Among these, in recent years, there has been a sudden shift to spraying smaller amounts of liquids and small amounts of liquids, in view of the loading efficiency of aircraft.

In view of this current situation, the present inventors have developed a product that does not contain an inorganic carrier or organic solvent, contains the active ingredient at a high concentration, has low viscosity, and exhibits excellent fluidity, and can be used as it is or diluted at a low magnification. We also conducted extensive research on formulations that are suitable for spraying small amounts of liquid.

As a result, active agricultural ingredients are dispersed using a copolymer colloidal dispersion with a particle size of α1μ or less; when stabilized, it has low viscosity and excellent fluidity, and it also contains the active ingredient at a high concentration and is easy to dilute. The present invention was completed by discovering that a new one-dose type agricultural chemical can be obtained.

That is, in the present invention, the agricultural chemical active ingredient is colloidal particles 11a.
It is a liquid agricultural chemical that is dispersed in an aqueous copolymer colloid dispersion of 1p or less.

The agricultural chemical active ingredient that can be used in the present invention may be in either powder or liquid form.5 The powder preferably has a particle size of 200μ or less; if it is too large, the dispersion stability will be poor and sedimentation and deposition will occur easily. do not have.

represent

That is, CYAP (thiophosphoric acid op) is used as an organophosphorus insecticide.
- cyanophenyl = o, o-dimethyl), MBP (0-dimethyl to thiophosphate = O-4-ditro m-tolyl') = gcp (rho-2,4-di-l lorophenyl thiophosphate = Q, 0- diethyl), diazinon (, ao-diethyl thiophosphate rho-2-inpropyl-4-methyl-
6-117 midinyl), pyridafenthione (2,3-dihydro-5-oxo-2F phe2'-6-pyridazinyl-h0-diethyl thiophosphate), marathon [8-t2-bis(ethoxycarbonyl)ethyl dithiophosphate] = 0.0-dimethyl], dimethoate (0.0-dimethyl dithiophosphate = S-(N-medylcarbamoylmethyl)), inthioate [8-2-(inpropythio)ethyl dithiophosphate = 0.0-dimethyl] , DMTP
(8-2-methoxy-5-oxo-144 dithiophosphoric acid
-thiadiazolin-4-ylmethyl; Q, 0-')methyk), 1) DVP (1/acid 2,2--/chlorovinyl dimethyl), BPN (0-ethyl phenylphosphonothionate = 0-p Carbamate insecticides such as NkC (1+h 1-naphthyl carbamate)
, MTMC (m-)lyl methylcarbamate), BPM
C (0-sec-butylphenyl methylcarbamate)
, MPMC (44-xylyl methylcarbamate), virimicarp (2-dimethylamino-5,6-dimethylpyrimidin-4-yl dimethylcarbamate), natural insecticides, pyrethrin, lobone, etc., acaricides. as, CPCB8 (p-chlorophenyl p-chlorobenzenesulfonate), chlorpropylate (1), 1)'-
dilaa isopropyl benzylate), fenisop d molate (p,p'-isopropyl dibromobenzilate),
BPP8 [2-(p-ter@-butylphenoxy)cyclohexyl-propynyl sulfite], amitraz (N
-Methyl-bis(2,4-xylyliminomethyl)amino 1, etc., insecticides such as gnB (12-dibromoethane), EDC (t2-dichloroethane), DCIP (bis(2-chloro-1-methylethyl)) ether], sulfur fungicides such as maneb [ethylene bis(dithiocarbamic acid) manganese], polycarbamate [bis(dimethyldithiocarbamic acid) ethylene bis(dithiocarbamic acid) dizinc], thiram [bis(dimethylthiocarbamoyl) disulfide]. ], organic chlorine disinfectants, etc.
N (tetrachloroinphthalonitrile), fusaride (
45,47-titrachlorophthalide), IBP (S-benzyl thiophosphate = 0.0-diisopropyl), BDDP (low ethyl dithiophosphate =
S, S-diphenyl), etc., and other fungicides.
PcNB (pentachloronitrobenzene), equimezol (5-ethyl-5-triclo-a-methyl-1,2,
4-thiadiazole), cabtane (N-()lichloromethylthio)-4-cyclohexene-v2-dichal ximide], phenazine oxide (phenazine 5-oxide), CN^(2,II-dichloro-4-nitroaniline) , Anilazine [2,4-dichloroct-6-(0-taloloanilino)-1&5-triazine], Thiophanate methyl (4,4'-0-phenylenebis(5-thioallophonate) dimethyl), Isobrothiolane (t3 -dithiolane-2-ylidenemalonate (diisopropyl), fluorimide [N-(p-fluorophenyl)-di90
romaleimide], MCP (4-ri00
Nisder-0-ethyl fluoroxyacetate), DNBP
(2-see-methyl-4,6-sinitrophenol)
, NTP (2,4-dichlorophenylyl-nitrophenyl; ether), MCC (methyl 44-dichlorobenylide), vernalate (S-propyl dipropylthiocarbamate), molinate (hexahydro-1H
-azepine-1-carbothioate S-ethyl), DCPA
i', 4'-dif-loloprobionanilide), butachlor [2-chloro-26'-diethyl-N-(butoxymethyl)acetanilide, DCMU (5-(a4-dichlorophenyl)-11-dimethylurea)] , Simazine [
2-chloro-4,6-bis(ethylamino)-15,5
-) riazine], terbasil (5-ter*-butyl-)
5-chloro-6-methyluracil), DON (2,6-
cyclopenzonitrile), -DRA (6-dichloro-2-methoxybenzoic acid dimethylamine salt), ACN (
2-amino-5-chloro-14-naphthoquinone), acephenone (4'-1eft-butyl-2', 4'-
Dimethy A/-5'.

Warfarin (5-(a-acetonyl"-benzyl)-4-
Indolebutyric acid [4-(5-indolyl)butyric acid], -1-naphthylacetamide (1,1'-methylenebis(thiosemicarbazide)), etc. -su7taleneacetoa, 6-(N-benzylamino)purine, etc., repellents;
Eugenol (4-ori-2-methoxyphenol)
etc., and can be widely applied to hexa-bamate systems, etc., which have conventionally been difficult to emulsify.

These pesticide active ingredients can be used alone or in combination of two or more.

The copolymer aqueous colloid dispersion used in the liquid agricultural chemical of the present invention needs to have a particle size α1μ or less and be a so-called hydrosol. The difference between hydrosol and emulsion is
This is clearly determined by the particle size, with both having a ticL of 1μ or less, and the latter having a ticL of approximately 15 to 14μ. Furthermore, phase JI is also included in the stabilization mechanism of the dispersion system. In other words, emulsions usually contain a large amount of surfactant, whereas hydrosols contain only a small amount of surfactant 4 or none at all, and the stabilization is mainly due to the dissociation of carboxyl groups.

Copolymer aqueous colloid dispersion #i used in the present invention, particles s
It is necessary to contain a hydrosol of at least 50 μm or more, particularly preferably Jri701 or more, and preferably a hydrosol containing α05 μm or less is suitable.

An emulsion with a particle size of 15μ100 may disperse the pesticide active ingredient in the very early stages, but its retention stability is poor, and the powdery active ingredient will settle, accumulate, or float in a short period of time. Put it away. Furthermore, if a so-called water-soluble polymer solution in which the polymer is completely dissolved in water at the molecular level (generally particle size α005μ or less) is used, the dispersibility will be extremely poor, and the paste will become pudding-like and will not flow properly. It is not possible to obtain pesticides with specific properties.

The copolymer of the present invention may form an aqueous colloidal dispersion depending on the balance between the dissociation of hydrophobic groups and carboxyl groups, and there are no limitations on the copolymer composition, polymerization method, manufacturing method, etc.

- Introduction of carboxyl group with acrylic acid, methacrylic acid,
A method based on copolymerization of unsaturated carboxylic acids such as maleic acid, itaconic acid, and crotonic acid is easy and preferred.

Examples of the hydrophobic monomer include acrylic acid alkyl ester, meth, acrylic acid alkyl ester, vinyl acetate,
Examples include styrene, chlorine, nitrile, vinyl chloride, vinyl chloride, and olefins such as ethylene, funibirene, butadiene, and imbutylene. Furthermore, a suitable amount of a monomer having a hydroxyl group, a sulfone group, an amide group, or an alkylammonium group may be copolymerized.

The polymerization method is preferably emulsion polymerization or solution polymerization because it is simple.

For example, it can be produced by the four methods disclosed in Tokukai No. 49-56942, No. 52-5541, and No. 52-47489.

In the case of emulsion polymerization, an unsaturated carboxylic acid and a comonomer are polymerized in the presence of a small amount of an emulsifier, and the mixture is heated under mechanical shearing, if necessary, and a solvent is added. Partially or completely neutralized with potassium hydroxide, ammonium hydroxide, or an alkali such as an organic amine to form a colloidal dispersion. If a solvent is added, as necessary.
This is removed by distillation. The amount of unsaturated carboxylic acid suitable for making a colloidal dispersion varies depending on the unsaturated carboxylic acid, the type of neutralizing alkali, the composition of the comonomer, etc., but is generally 5 to 50% by weight (based on the monomer weight). In the case of a copolymer mainly composed of acrylic acid alkyl ester, the total weight is about 5 to 15 acrylic acid or methacrylic acid.

The degree of neutralization is preferably the minimum amount required to form a colloidal dispersion, with a suitable pH of 6 to 8, and preferably 7.5 or less within this range.

This is because many of the active ingredients of agricultural chemicals are classified as acids, alkalis, especially 'f' and alkalis.

The alkali is preferably sodium hydroxide or an organic amine with a relatively high boiling point, such as mono-, di-, or triethanolamine, morpholine, or the like. This is to make it easier to wash away pesticides from hands, protective clothing, sprayers, and the surface of coated bales that have drifted and adhered to them when spraying pesticides.

1 The copolymer used in the present invention can be similarly produced by solution polymerization, in which an unsaturated carboxylic acid and a comonomer are polymerized in a hydrophilic or hydrophobic organic solvent, and after neutralization, the solvent is washed with urine. When K is substituted, a colloid dispersion is obtained.

Also, as my father-in-law's manufacturing method, rosin, petroleum grade 11 under high temperature,
A colloidal dispersion is obtained by adding unsaturated cardanic acid such as maleic acid and neutralizing with alkali. Furthermore, lower alkyl esters such as methyl acrylate and ethyl acrylate can be saponified with a strong alkali such as sodium hydroxide or potassium hydroxide to form a colloidal dispersion.

These aqueous colloidal dispersions are stabilized by hydrophobic groups and caluns, and are considered to be a type of polymeric surfactant. It is presumed that the active pesticide ingredients, which have hydrophobic groups and parent wood groups, are attached to and adsorbed by colloidal particles, and move and move smoothly within the system together with the colloidal particles, resulting in a pesticide with excellent fluidity and low viscosity. .

The method for producing the agricultural chemical of the present invention will be briefly described below.

Particles 11 [11μ or less copolymer aqueous colloid dispersion
Adjust to a concentration of 0 to 50% by weight. For work purposes, if restrictions on the viscosity of 41 are acceptable, 50 weight upwind can be used. The viscosity at this time is preferably about 10 to IQ, 000 cp3, particularly about 10 to 1.000 cps from the viewpoint of workability. Pesticide active ingredients can be applied in either solid or liquid form, but
If it is solid, it is ground into powder, preferably with a particle size of 200 μm or less.

100 parts of the copolymer aqueous colloid dispersion is efficiently stirred to add 20 to 300 parts of the agricultural chemical active ingredient, particularly preferably 20 to 300 parts.
Gradually add 150 parts and continue stirring until uniformly mixed. In this case, an antifoaming agent may be added to the colloidal dispersion in advance, if necessary. Agrochemicals with excellent fluidity of 50 to 1[) and 0OOCPS can be obtained by stirring for about 50 minutes to 1 hour. If the viscosity is too high, adjust the concentration and amount of the copolymer aqueous colloid dispersion and the amount of the pesticide active ingredient to reduce the viscosity. Despite the high concentration of 15 to 60% by weight, the obtained pesticide exhibits excellent fluidity, good storage stability, and is easy to dilute with water.

In order to improve the storage stability of pesticides, K, polyacrylic acid, -d, ammonium polyacrylate, carboxylmethylcellulose, hydroxyethylcellulose, methylcellulose, lignin sulfone [7-t, , l-'
A small amount of water-soluble polymers such as lipinyl alcohol, polyethylene glycol, gelatin, starch, zein, sodium alginate, guar gum, locust bean gum, and xanthan gum may be added. If the amount added is too large, the stability of the system will be impaired, so care must be taken in this regard. Furthermore, a small amount of a surfactant, a polymer emulsion, or an organic solvent may be mixed according to IK requirements.

According to the present invention, it is possible to spray trace or small amounts of carbamate pesticides, etc., which were conventionally difficult to emulsify, avoid problems caused by organic solvents in emulsions, and have good adhesion to plants. It is possible to obtain a new formulation of agricultural chemicals that is
It can be said that its industrial value is extremely large.

Next, examples and comparative examples will be shown to specifically explain the present invention.

The copolymer colloid dispersions used in each example (Examples 1 to 24) were 5 of A, B, C-1D, and g shown in Table 1 below.
It is a kind.

,yo,''In 4. above, the shoulder number. Contents 1st. Pass 7, ah.

1) MMA: Methyl methacrylate EA: Ethyl methacrylate MAA: Methacrylic acid St: Styrene MLA: Maleic acid Et: Ethylene AA
Niacrylic acid 2) Weight ratio 3) Measure the particle size range in which 90 particles are distributed from an electron micrograph 4) Measure with a B-type viscometer at 5 Orpm and 25°C.

5) Copolymer non-volatile content (weight W#Cyro) Copolymer aqueous colloid dispersion A353F whose values at 25°C are shown in Table 1.
was transferred to a 51 beaker and water was added to make 1q. The concentration of the prepared aqueous solution is 25'l.

500 rpm with a stirrer equipped with 4 blades with a length of 7 scratches.
The mixture was stirred at a rotation speed of . While stirring, NAC (1-naphthyl methylcarbamate) powder 80011 was gradually added over 3 minutes. The NAC powder was smoothly dispersed and mixed, and a nearly homogeneous liquid mixture was obtained 10 minutes after the addition was completed. Stirring was further continued for 50 minutes after the addition was completed to obtain a white homogeneous liquid pesticide. Although the agricultural chemical FiNAC was contained at a high concentration of 44.4%, the viscosity was low at 2.500 cps, and the workability was good. The water dilutability and stability (see notes in Table 2) were also good, making it suitable as an agricultural chemical for aerial spraying.

Examples 2 to 24 Agricultural chemicals were produced according to Example 1 with the compositions shown in Table 2. When an antifoaming agent was added, the foam disappeared and the mixture could be mixed more smoothly. Agrochemicals with low viscosity and excellent fluidity were obtained, which can be applied to various types of agrochemical active ingredients in liquid and powder form. All of them had good water dilutability and stability, and were suitable as agricultural chemicals for aerial spraying.

(Note) The contents of the layer numbers in Table 2 are as follows.

1) See Table 1 2) Concentration of colloidal dispersion prepared by adding water to the copolymer in Table 1 (weight 1 5) 1407K (Sannobuco KK), amount added to colloidal dispersion (same) 4) Produced Amount of active ingredient in total amount of agricultural chemicals (same) 5) BM type viscosity needle, 50 rpm 25°C 6) 11 Put 700 I of water in a beaker and use 4 blades to
While stirring at ゜rpm, add 100N of pesticide and mix for 5 minutes.

O: Completely and uniformly mixed. ×: Not uniform.

7) Based on accelerated test stored at 50°C for 14 days. If no changes such as thickening, aggregation, or separation occur, it is rated as 1 'Good'.

Comparative Examples 1 to 6 Tests according to Example 1 were conducted using the liquids shown in Table 5 as solutions for dissolving or mixing agricultural chemical active ingredients. The results are shown in Table-3.

From this Table-5, the following can be said.

(Otori) Even when a completely dissolved aqueous polymer solution is used to disperse and mix the pesticide active ingredient (Comparative Examples 1 to 4), the viscosity increases during preparation, loses fluidity, and solidifies into a paste or pudding. However, the next day, the solidification progressed and it was found that it was unsuitable as a moxibustion drug.

(Ratio of pesticide active ingredients added to emulsion)
In Comparative Example 5, the dispersion had low viscosity and good mixability, and became a uniform white dispersion immediately after stirring, but the holding power was poor and the NAC sedimented and deposited on the next day, so it was not ideal. It's hard to say what a thing it is.

(2) When using a nonionic surfactant (Comparative Example 6)
Similarly to Comparative Examples 1 to 4, it solidified the next day and was inappropriate.

Patent applicant name Toagosei Chemical Industry Co., Ltd.

Claims (1)

[Claims] t, a waxy elixir in which an agrochemical active ingredient is dispersed in an aqueous copolymer colloid dispersion having a colloidal particle size of α1# or less.