JPS58131902A - Liquid agricultural chemical - Google Patents

Abstract

PURPOSE:A liquid agricultural chemical having low viscosity and improved flow properties, containing an active ingredient in high concentration, capable of being diluted easily, by using an aqueous solution of polyvinyl alcohol modified by introducing a sulfone group to it, dispersing the active ingredient of agricultural chemical into it. CONSTITUTION:An aqueous solution of polyvinyl alcohol modified by introducing a sulfone group to it is used and an active ingredient of agricultural chemical (e.g., organophosphorus insecticide, carbamate-based insecticide, etc.) is dispersed into it, to give a liquid agricultural chemical. The modified polyvinyl alcohol is obtained by copolymerizing a sulfone group-containing monomer such as vinylsulfonic acid, etc. with vinyl acetate, followed by saponifying it. The prepared agricultural chemical has a high concentration of 15-60wt%.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a liquid agricultural chemical with improved fluidity,
The objective is to provide a new formulation of agricultural chemicals that can be sprayed at low dilution rates, ie, at high doses of active ingredients.

Conventional pesticide formulations can be broadly divided into powders, powders, granules, wettable powders, and emulsions.

Test M contains approximately 2 to 5 active pesticide ingredients, and is mixed with, adhered to, and adsorbed on a carrier such as talc, clay, kaolin, diatomaceous earth, bentonite, calcium carbonate, and white carbon, and is usually sprayed as is. .

Powder and granules are made by granulating powder using polyvinyl alcohol, carboxymethyl cellulose, lees 1), and bangu such as lJ gninosul heptaonic acid sodium, and the particle size is approximately 50~
200j141! It has become granules.

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

The emulsion consists of about 20 to 50 Is of agrochemical active ingredients, organic 111M such as xylene, hexane, mineral oil, and an emulsifier, and is emulsified and diluted in water before being sprayed.

Agriculture in a pharmaceutical form! The biggest drawback of powder agents is that they produce dust during handling and spraying, and drift is significant not only during normal spraying, but also during aerial spraying by aircraft, and their use has decreased dramatically 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. Also, if the dilution ratio is low, high viscosity slurry 1
7- Since it becomes a paste, it is often inconvenient to spray small amounts of liquid by aircraft.

Emulsions are excellent in terms of workability, but the biggest problem is the contamination and damage to the coating caused by the organic solvents they contain. In addition, carbamate drugs, which are viable insecticides, are soluble or insoluble in many organic solvents, making it difficult to emulsify them49. It is.

Aerial spraying of pesticides has gone from the era of solid pesticide spraying, mainly powder, to the era of liquid pesticide spraying, and in recent years there has been a sudden shift to small-volume and small-volume spraying of liquid pesticides due to the loading efficiency of aircraft. .

In view of these current circumstances, the present inventors have developed a product that does not contain an inorganic carrier or organic solvent, contains an active ingredient at a high concentration, has a 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, due to the introduction of sulfone group! 7 using a modified polyvinyl alcohol aqueous solution.

The present invention was completed by discovering that by dispersing and stabilizing the active ingredients of agricultural chemicals, it is possible to obtain a new formulation of agricultural chemicals that has low viscosity and excellent fluidity, contains the active ingredients at high concentrations, and is easily diluted.

That is, the present invention is a liquid agricultural chemical in which a good drug active ingredient is dispersed in a modified polyvinyl alcohol aqueous solution modified by the introduction of a sulfone group.

The agrochemical active ingredient that can be used in the present invention described above may be in either powder or liquid form. The particle size of the powder is preferably 00 μm or less; if the particle size is too large, the dispersion stability is poor and sedimentation and deposition tend to occur, which is not preferable.

There are a wide variety of pesticide active ingredients, but examples are as follows. The symbol or name before 0 or 00 is the general name of the agricultural chemical substance, and the symbol or name before 0 or 0 represents the chemical name.

That is, as an organophosphorus insecticide, CYAP (thiophosphate
-cyanophenyl 2 units, 0-dimethyl), MgP(?#
phosphoric acid 0.0-di) fk = 0-4-nitro-m-1 lyl), gcp (thiophosphoric acid 0-2.4-dichlorophenyl = 0.0-diethyl), diazinon (thiophosphoric acid @qO
-diethyl20-2-improvir-4-methyl-6-
pyrimidinyl), pyridafenthione (thiophosphoric acid 0-
2,3-dihydro-3-oquino-2-phenyl-6-pyridazinyl = 0.0-diethyl), Marathon [8-12-bis(ethoxycarbonyl)ethyl dithiophosphate = Q
, 0-dimethyl], dimethoate [dithiophosphoric acid qO-
7 dimethyl=S-(N-methylcarbamoylmethyl),
Isothioate (8-2-(isopropylthio)ethyl dithiophosphate = 0.0-dimethyl), DMT P (dithiophosphate III!5-2-methoxy-5-okino 1
．． 3.4-Thiadiazolin-4-ylmethyl=0.0-
dimethyl), DDVP (2,2-dicpropinyl dimethyl phosphate), EPN (phenylphosphonothionic acid 0-
Carbamate insecticides such as NAC (methylcarbamide @ 1-naphthyl), MTMC (m-)lyl methylcarbamate), BP
MC (methylcarbamide 1iQ-sec-butylphenyl), MPMC (4-xylyl to methylcarbamate)
, Virimicarp (2-dimethylamine-5,6-dimethylpyrimidin-4-yl dimethylcarbamate), etc.
Natural insecticides such as pyrethrin and rotinone; acaricides such as CPCB8 (p-chlorophenyl p-chlorobenzenesulfonate) and chlorpropylate (pop'
-improvil dichlorobenzilate), fenisopromole) (p*p-isopropyl dibromobenzilate),
BPPS (2-(p-tcrt-7'tylphenoxy)cyclohexyl-propynyl sulfite), amitraz (N-methyl-bis(2,4-xylyliminomethyl))
amine], EDB (12-dibromoethane), EDC (1,2-dichloroethane), DCIP as nematicides.
(bis(2-chloro-1-methylethyl) ether), manneb [ethylene bis(dithiocarbamic acid) manganese], polycarbamate [bis(dimethyldithiocarbamide II) ethylene bis(dithiophosphoric acid (mide acid) ) dizinc], thiram [bis(dimethylthiocarbamoyl) disulfide], organic chlorine disinfectants such as TPN (tetrachloroisophthalonitrile), fusaride (4,5,6,7-titrachlorophthalide), etc. IBP (thiophosphoric acid 1IS-benzyl-he0-diisopropyl), gDDP (dithiophosphoric acid 0-diisopropyl) as a fungicide
-Ethyl=3. PCNB (pentachloronitrobenzene), eclomesol (5-ethoxy-6-trichloromethyl-
1,2,4-thiadiazole), cabtane (N-()
(dichloromethylthio)-4-cyclohexene-t2-dicarboximide], phenazine oxide (phenazine 5
-oxide), CNA (2,6-dichloro-4-nitroaniline), anisidine [2,4-dichloro-6-(0
-chloroanilino) -1,3,5-triazine], thio77*-1-methyl (4,4'-0-phenylenebis(6-thioallophanic acid) dimethyl), isobrothiolane (t5-dithiolane-2-ylidenemalone) diisopropyl acid), fluorimide [N-(p-fluorophenyl)-dichloromaleimide], and MCP
(4-chloro0-0-tolylox/acetic acid ethyl ester)
.

DNBP (2-see-butyl-4,6-sinitrophenol), NIP (2,4-dichlorophenyl-nitrophenyl ether), MCC ('zh, methyl 4-cyclohelubanilide), Vernalate (diglo Pylthiocarno (S-provyl midate), Mori*-) (S-ethyl hexahydro-IH-azepine-1-carbothioate), ]) CPA (3',4'-dichloropropionanilide), butachlor [2- Chrollo-Otsu 6' 9
Ethyl-N-(butoxymethyl)acetanilide, DC
MUlj-(5,4-dichlorophenyl)-1,1-dimethyl JiR], simazine (2-chloro-4,6-bis(ethylamino)-t45-triazine), terbacil (3-1crt-butyl-5- chloro-6-methyluracil), D13N (2,6-cyclopenzonitrile), MDBA (melon 6-dichloroC1-2-methoxybenzoic acid dimethylamine salt), ACN (2-amino-6-chloro-1 , 4-t-phthoquinone), acephenone (4'-
1crt-butyl-21,61-dimethyl-5'.

5″-dinitroacetophenone), warfarin [3-(α-acetonylbenzyl)-4-hydroxycoumarin] as a rodenticide, bisthiosemi [11′-methylenebis(thiosemicarbazide)], etc., and indolebutyric acid [as a plant growth regulator]. 4-(5-indolyl)butyric acid], a-
Naphthylacetamide (1-naphthaleneacetamide)
, 6-(N-benzylamino)purine, etc., and repellents and attractants such as β-naphthol, cycloheximide, tetrahydrothiophene, diallyl sulfide, and eugenol (4-allyl-2-methoxyphenol). It can be widely applied to carbamate systems, etc., which have been difficult to apply.These agricultural chemical active ingredients can be applied alone or in a mixture of two or more.

The polyvinyl alcohol used in the present invention is originally water-bathable (hereinafter simply referred to as modified polyvinyl alcohol) that has been modified by introducing a sulfone group. There are no particular limitations on the copolymerization composition, polymerization method, manufacturing method, etc.

A preferred method for introducing a sulfono group into polyvinyl alcohol is to copolymerize a monomer having a sulfone group because it is simple. Examples of such monomers include: nyl sulfonic acid, allyl sulfonic acid, methalylsulfonic acid, styrene sulfonic acid, acrylamide-2-methylpropanosulfonic acid, and its alkali salts, i.e., sodium salts; There are potassium salts, lithium salts, etc.

Particularly preferred are sodium salts. The copolymerization ratio of these sulfonic group-containing monomers is preferably 0.5 to 20 mol, more preferably 1 to 10 mol, thereby providing a liquid agricultural chemical with low viscosity and excellent fluidity.

For the production of modified polyvinyl alcohol, a method of copolymerizing the above-mentioned sulfone group-containing monomer and vinyl acetate and saponifying the copolymer by a conventional method is industrially advantageous and preferred. Regarding the degree of saponification of modified polyvinyl alcohol, there is no limit to the percentage, and either partial saponification or complete saponification may be used, but the saponification degree is usually 70 mol or more, preferably 80 mol or more. suitable.

The modified polyvinyl alcohol aqueous liquid applied to the agricultural chemical of the present invention is within a range that does not impair water solubility.

Alternatively, a modified polyvinyl alcohol aqueous solution obtained by copolymerization with a hydrophobic monomer may be used. Examples of such hydrophobic monomers include acrylic acid alkyl esters, methacrylic acid alkyl esters, styrene, vinyltoluene, acrylonitrile, vinyl chloride, vinylidene chloride, and olefins such as ethylene, propylene, butadiene, and imbutylene. In addition, hydrophilic monomers having hydroxyl groups, carboxyl groups, ether groups, amide groups, etc. can also be used.

In the present invention, the action of the above-mentioned modified polyvinyl alcohol is thought to be to form a hydration layer within the capsule of the agricultural chemical active ingredient due to the strong dissociative group -8OP and the nonionic group -0H4C, thereby stabilizing the dispersion. This stabilizing energy H-so
It is presumed that this is caused by the electrical repulsion of ; and the steric repulsion of polyvinyl alcohol.

For this reason, as mentioned above, it is thought that there is a preferable content range for VC-sop. In addition, in order to provide steric repulsion, a polymer having a degree of polymerization of 50 or more is usually suitable.

As the polymerization method, a bath-free method or a solution polymerization using an alcohol or the like is simple and preferable. For example, JP-A-51-3385, JP-A-51-3385,
It can also be produced by the method disclosed in No. 6-98205.

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

A modified polyvinyl alcohol aqueous solution having a sulfone group is prepared to have a concentration of 10 to 50 dichloromethane.

For work purposes, if restrictions on viscosity are acceptable, it may be 50% by weight or more. The viscosity at this time is 10-10,
000 cps, I￥fK about 10 to 1,000 cps is preferable in terms of workability. The agricultural chemical active ingredient can be applied in either solid or liquid form, but if it is solid, it is ground by Ifi to powder, preferably to a particle size of F1200μ or less.

If there is an appropriate pH range depending on the active ingredient of the pesticide, the pH of the modified polyvinyl alcohol aqueous solution is adjusted in advance with an acid or alkali.

100 parts of a modified polyvinyl alcohol aqueous solution (the same applies below 2 parts by weight) is efficiently stirred, and 20 to 300 parts of the agricultural chemical active ingredient is added.
1, preferably 120 to 150 parts of F, are gradually added and stirring is continued until uniform mixing is achieved. In this case, an antifoaming agent may be added in advance if necessary. Agrochemicals with excellent fluidity of 50 to 10,000 Cps can be obtained by stirring for about 60 minutes to 1 hour. If the viscosity is too high, adjust the concentration of the denatured polyvinyl alcohol aqueous solution, violet, and the active ingredient of the pesticide to reduce the viscosity.

Despite the high concentration of 15 to 60% by weight, the resulting pesticide exhibits excellent fluidity, good storage stability, and is easy to dilute with water.

In order to determine the storage stability of agricultural chemicals, sodium polyacrylate, ammonium polyacrylate, carboxyl methyl cellulose, hydroxyethyl cellulose, methyl cellulose, sodium lignin sulfonate, polyvinyl alcohol, polyethylene glycol, gelatin, starch, casein, alginate , guar gum, locust bean gum, xanthan gum, and other water bathing polymers may be added in small amounts. 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 in if necessary.

The present invention makes it possible to spray trace or small amounts of carbamate pesticides, which were conventionally difficult to emulsify, avoids problems caused by organic solvents in emulsions, and has good adhesion to plants. A new form of pesticide can be obtained,
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 modified polyvinyl alcohol aqueous liquid used in each example (Examples 1 to 12) was A, 33. as shown in Table 1 below. C,
This is the 4 cypress species of D.

(Note) The contents of the layer numbers in Table 1 above are as follows.

1) VAC: Vinyl acetate MMA: Methyl 1) 1-tacrylate 2) Copolymer composition molar ratio before saponification.

5) Measured with a B-type viscometer at 5 Orpm and 25°C 4) Modified polyvinyl alcohol non-volatile content weight 5) Value at 25°C 6) Adjustment with ammonia water Example 1 Modified polyvinyl alcohol aqueous liquids 1 to 1 shown in Table IK The mixture was transferred to a No. 31 beaker and stirred at a rotation speed of 500 rpm using a stirrer equipped with 4 blades of 7 aa length. Under stirring, NAC (methyl carbamide l11-naphthyl) powder 7
00Ii was added gradually over 3 minutes. The NAC powder was dispersed and mixed smoothly, and a nearly uniform mixture was obtained 10 minutes after the addition was completed. Stirring was continued for 60 minutes after the addition was completed to obtain a white homogeneous liquid pesticide. Although this pesticide contains K at a high concentration of 411% NAC, 2.
It had a low viscosity of 100 cps and good workability. Ruritomo has good water dilutability and stability (see notes in Table 2 below), making it suitable as a pesticide for aerial spraying.

Examples 2 to 12 Agrochemicals were manufactured 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 have good water dilutability and stability and are suitable as agricultural chemicals for aerial spraying.13- (Note) The contents of the layer numbers in Table 2 are as follows.

1) See Table-1 2) 1407K (San Nopco KK), amount added to modified polyvinyl alcohol aqueous liquid (weight S) s>
Amount of active ingredient in total amount of agricultural chemicals produced (same) 4) BM type viscosity needle, 30 rpm 25℃ 5) 1 ton beaker with water 70
Add 0I, and while stirring with 4 blades of 20 OrIlfn, add Pesticide 1001 and mix for 5 minutes.

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

6) According to 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 4 As a liquid for dissolving or mixing agricultural chemical active ingredients, 1! -3K
A companion test was conducted according to Example 1 using the following. The results are shown in Shishi-5.

14- From this Table-6, the following can be said.

(1) Using a polyvinyl alcohol aqueous liquid that does not have a sulfono group, dispersion-mixing of pesticide active ingredients (Comparative Examples 1 to 3)
Even with 3), the viscosity increases during preparation, loses fluidity and solidifies into a paste, and further assimilation progresses the next day, making it unsuitable for use as a rigid agricultural chemical.

(1) Other water-soluble copolymers containing sulfone groups (acrylamide copolymer Comparative Example 4) 4b Similar to Comparative Examples 1 to 6, it solidified the next day and was inappropriate.

Patent applicant name Toagosei Chemical Industry Co., Ltd.

Claims (1)

[Claims] A liquid agricultural chemical in which the active drug ingredient is modified by introducing a sulfone group and dispersed in an aqueous container of nine-denatured polyvinyl alcohol.