JPS6032701A - Biocidal aqueous suspension composition - Google Patents

Abstract

PURPOSE:To provide the titled composition having excellent storage stability, suspension stability in dilution, and resistance to agglomeration in the combined use with other emulsifiable concentrate, wettable powder, etc., by using a thickening and dispersing agent comprising a water-soluble polymer compound having a specific chemical structure. CONSTITUTION:A biocide storable stably for a long period at a viscosity of 100-500cps is prepared by compounding (A) 1-70(wt)% biocide insoluble in water and solid or pasty at normal temperature, (B) 0.1-40%, especially 1-20% water-soluble polymer compound having an average molecular weight of 1,000- 10,000,000 and containing one or more basic or cationic N-atom in the recurring unit, and (C) 0.1-20%, especially 1-10% nonionic and/or anionic surface active agent. The component B is a homopolymer or copolymer of the salt or quaternary ammonium salt of the nitrogen-containing monomer of formula I -formula V(A is O or NH; n1 is 1-3; R1 is H or CH3; R2 and R3 are H, CH3 or C2H5).

Description

[Detailed description of the invention] The present invention relates to aqueous suspension biocide compositions.

Most biocides such as insecticides, fungicides, herbicides, and acaricides are virtually insoluble in water, and when used, they must be used as an aqueous suspension, for example by using a hydrating powder. However, there are disadvantages such as caking during storage or when exposed to high temperatures, and the inability to spray undiluted solution or concentrated dilution (4 times, 8 times, 30 times) when spraying in the air. There are restrictions in terms of usage.

On the other hand, if the biocide is made fluid, it becomes a dosage form suitable for aerial spraying and there is no risk of caking, but on the other hand, it is difficult to obtain an aqueous suspension that is stable over a long period of time.

Therefore, conventionally, in order to obtain a stable aqueous suspension, water-soluble polymer compounds such as homosaccharide, 7"p saccharide, and polyacrylates are used alone or in combination as thickening stabilizers, and as dispersing and wetting agents, for example, dialkyl sulfosuccinates are used. acids, anionic surfactants such as alkylbenzene sulfonates, naphthalene sulfonates, polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene styrenated phenol ethers, polyoxyethylene tribenzyl phenol ethers, etc. Nonionic surfactants have been used alone or in combination.In some cases, hydrophilic or hydrophobic solvents have also been used to improve suspension stability.However, the above-mentioned Even when a stabilizer and a dispersion/wetting agent were used in combination, the storage stability of aqueous suspension preparations was not satisfactory.That is, when an appropriate formulation viscosity was given as an aqueous suspension preparation (
Even at room temperature or high temperature (40 to 50° C.) (500 to 1500 centivoids), there were disadvantages such as poor suspension stability, gelation during storage, and formation of aggregates when diluted with water.

The present inventors have attempted to eliminate such drawbacks (as a result of intensive research), by using a water-soluble polymer compound with a specific chemical structure as a thickening dispersant, storage stability and dilution can be improved regardless of the type of biocide. It has been discovered that an aqueous suspension biocide composition can be obtained which exhibits excellent performance in terms of suspension stability and prevention of aggregate formation when used in combination with other emulsions or wettable powders, and has thus arrived at the present invention.

5-Q That is, the present invention comprises (&) 1 to 70 weight percent of a biocide that is insoluble in water and solid or pasty at room temperature; (b) one basic nitrogen atom or one cationic nitrogen atom in the repeating unit; or more, and its average molecular weight is 10
0.1 to 40 weight percent of a water-soluble polymer compound ranging from 0.00 to 10,000,000, and (0) 0.1 to 20 weight percent of a nonionic surfactant or/and an ionic surfactant. The present invention provides an aqueous suspension biocide composition containing %.

The water droplet-forming polymer compound of the present invention can be used not only as an agricultural biocide but also as an industrial biocide such as a slime control agent and a fungicide.

The water droplet-forming polymer compound according to the present invention is one that contains one or more basic II1 monoatoms or one or more cationic nitrogen atoms in the repeating unit and has an average molecular weight of 1000 to 10,000.
It is a water-soluble polymer compound in the range of 0,000, and specifically, a water-soluble polymer compound selected from the group consisting of the following (+) and (閤) is exemplified.

(1) Homopolymers of salts or quaternary ammonium salts of silicon-containing monomers represented by the following general formulas (11 to M), or copolymers of 2i1 or more thereof.

4 [In the formula, A represents 10- or -NH-, nl represents an integer of 1 to 3, R4 represents H or OH, R2 and R5 represent H,
OHs or O, H, t, 3] R1 [In the formula, R1, R2, R,, nl are the same as formula (I)]
[In the formula, R1 is the same as in formula (I). The substitution value of pyridine is 2
or 4th position] [In the formula, R1 and R2 are the same as in formula (I). The substitution value of piperidine is at the 2 or 4 position] [In the formula, R,, R,, R, are the same as in formula (I)] (1)
One or more salts or quaternary ammonium salts of silicon-containing monomers represented by the general formulas (I) to M, and '
I'-A vinyl monomer selected from the group consisting of unsaturated carboxylic acids or salts thereof or derivatives thereof, sulfonic acid group-containing vinyl compounds or salts thereof, acrylonitrile, vinylpyrrolidone, and aliphatic olefins having 2 to 20 carbon atoms. Copolymer of one type or two or more types.

Conventional thickening stabilizers include natural, semi-synthetic, and synthetic water-soluble thickeners, such as natural thickeners such as xanthan gum and zunfuro derived from microorganisms, pectin derived from plants, gum arabic, and guar gum; Thickeners include methylated, carboxyalkylated, and hydroxyalkylated products (including methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, etc.) of cellulose or starch derivatives, and synthetic products include polyacrylates,
Specific examples include polymaleate and polyvinylpyrrolidone. However, since these thickening stabilizers do not have sufficient dispersion stability against water-insoluble biocides, it has been necessary to use large amounts and, as a result, stabilize flowable formulations by increasing the viscosity. However, by using the water fII polymer compound of the present invention in combination with a conventionally known nonionic surfactant or anionic surfactant, the formulation viscosity of about 100 to 5007 inches can be maintained for a long period of time. A formulation with good suspension stability can be obtained. In addition, even when it was difficult to formulate a formulation when the concentration of biocide exceeded 50% by weight, it was possible to obtain a good flowable formulation by using the water-soluble polymer compound of the present invention.

The content of the water-soluble polymer compound of the present invention in the composition is from 0.1 to
40 weight percent, preferably 1 to 20 weight percent.

By using the water-soluble polymer compound of the present invention, any biocide that is insoluble in water and solid or paste at room temperature can be used regardless of the type of biocide, or even if two or more biocides with different structures are combined. Can be stably dispersed and suspended,
A biocide composition with good flowability can be obtained.

Biocides that are insoluble in water and solid or paste-like at room temperature include copper agents, mercury agents, organic tin agents, organic arsenic agents, sulfur, Daisen (zincified ethylene bis(dithiocarbamate)), etc. ), organic sulfur agents such as Chiku2mu (bis(dimethylthiocarbazyl)disulfite), Daconyl (tetrachloroisophthalonitrile), Rabcide (4,5,d,7-titrachlorophthalide)
Other organic chlorine agents such as cabtane (N-(trichloromethylthio)-4-cyclohexene-1,2-dicarboximide), difortan (N-(1,1,2,
2-tetrachloroethylthio)-4-cyclohexene-
1,2-dicarboximide), acridide (2-secondary-butyl-4,6-dinitrophenyl-5-methylcrotonate), Topzine M (dimethyl 4゜4
I-o-phenylene-3,3/-cythiodiallophanate], benlate (methyl-1-(butylcarbamoyl)-2-benziidazolecarbame) L-takegalen (3-hydroxy-5-methylinxazole), etc. ,
The insecticide is nDT(1,t,1-)dichlor-
Organophosphorus insecticides such as Kayaace (para-dimethylsulfamylphenyl diethyl phosphorothionate), Guardside (2-chloro-1-(2,4 , 5-)dichlorophenyl)-vinyl dimethyl phosphate], Bunabon (Tumaside (m-)lyl methyl carbamate containing 1-naphthyl-methyl carbamate), Macbar (5,5- Carbamate insecticides such as xylyl methyl carbamate), sepsin (O-cumenyl methyl carbamate), and Sancide (0-impp-boxyphenyl methyl carbamate), as well as metaldehyde (acetaldehyde tetramer), )
Herbicides such as (S-methyl-H-(methylcarbamyloxy)-thioacetate), nip (2S4-dichlorophenyl-p-nido-phenyl ether), no(
p-Nitrophenyl-2,4,6-) dichlorophenyl ether) Sudo diphenyl ether herbicides, Stam (3/, 4/-dichloropropionanilide), Daimid (N, H-dimethyl-2,2- Acid amide herbicides such as diphenylacetamide), sulfa (Mesol-6)
．． Carbamate herbicides such as 4-dichlorophenylate), urea herbicides such as Carmex n (s-(5A-dichlorophenyl)-1,1-diethylurea), simazine (2-chlor-4,6 -bis(ethyl-aino)-1,5,5-)riazine), gezaflim (2-chloro-4-ethylaino-6-imbrovirazeno-1)
, 5.5-) triazine herbicides such as riazine),
Acaricides include Saraviran (p-chlorophenyl p-chlorobenzenesulfonate) and Tedeon (p-ri p-ruphenyl-2,4,5-)! J Chlorphenylsulfone]
, Kelsene (2,2,2-trichlor-1,1-bis(
p-chlorophenyl)ethanol), omai)(2-(
p-tert-butylphenoxy)cyclohexylpropynylsulfite)nato.

There are also other industrial biocides such as diimide control agents, such as methylene bisthiocyanate, which are used as fungicides in paper manufacturing processes.

The content of the insecticide in the composition is 1 to 70% by weight
, preferably 10 to 60 weight percent.

15,, s In addition, as the nonionic surfactant and/or anionic surfactant according to the present invention, for example, polyoxyethylene (hereinafter referred to as pom) alkyl (carbon number 6 to 22) ether, POE alkyl ( Non-ionic compounds such as carbon atoms 4-18) phenol ether, polyoxypropylene polyoxyethylene (brotu/mata) ``!9ndum) purkyl ether, pog phenyl phenol ether, rom styrenated phephenol ether OW) ribenzyl phenol ether, etc. surfactant, lignin sulfonate, alkylbenzene sulfonate, alkyl sulfonate,
pog alkyl sulfonate, pot alkyl phenyl ether sulfonate, PO alkylphenyl ether phosphate salt, pom phenylphenol ether sulfone m salt, pog phenylphenol ether phosphate salt, naphthalene sulfonate, naphthalene sulfonate formalin M compound, POI) Ribenzylphenol ether sulfone salt, pox') Benzyl 1
Examples include anionic surfactants such as 4-phenylphenol ether phosphate ester salt. These can be used alone or in combination. Its content is 0.1-20% by weight in the composition, preferably 1-10% by weight.

An example of the aqueous suspension biocide composition of the present invention having good storage stability and excellent fluidity is as follows.

(A) Biocide 10-70 weight per hint (BJ Water-soluble polymer compound of the present invention 0.1-40 (DJ) Anti-foaming agent 0.1-51 (K) Antifreeze agent 1-101 (F) Water 10-40 801 Furthermore, the order of addition of each component in preparing an aqueous suspension is not limited.

Next, the present invention will be explained with reference to Examples, Comparative Examples, and Test Examples, but the present invention is not limited to these Examples.

In Examples and Comparative Examples, "parts" are parts by weight, and each component was adjusted by the following method to prepare a flowable formulation.

Flowable formulation preparation method> Weigh each ingredient in a wet grinding container, then
Add equal weight of glass beads and heat for 1 hour (10,000r).
pm/s++in) Wet grinding.

Example 1 Example 3 Sulfur 52 parts by weight Water-soluble polymer compound 8 Polyoxyethylene alkyl ether 2 Ethylene glycol 1 Water 37 Example 4 17- Water-soluble polymer compound 20 Ethylene glycol 2 Water 5B Example 5 Highly water-soluble Molecular compound @ 4 Alkyl sulfate 1 Ethylene glycol S Water 55 Example 6 18- Water-soluble polymer compound 5 Ethylene glycol 2 Water 3B Example 7 Water-soluble polymer compound 1° Ethylene glycol 2 Water 54 parts by weight Example 8 MBTO (12 parts by weight of methylenebisthiocyanate) Water-soluble polymer compound 1°P, O, E/P, 0. P block polymer 2 Ethylene glycol 2 Water 74 Comparative example 1 Sodium polyacrylate 2 Ethylene glycol 2 Water 52 Comparative example 2 Guardside 52 parts by weight Guar gum 1 Ethylene glycol 2 Water 42 Comparative example 5 Sulfur 52 parts by weight Carboxymethylcellulose 2 Ethylene glycol 1 Water 45 Comparative Example 4 Topgin M 42 parts by weight hylyloxymethyl heptalulose 2 Ethylene glycol 2 Water 5! I Comparative example 5 DOPA 37 parts by weight 20 - Polyvinylpyrrolidone 2 parts by weight Alkyl sulfate ring 1 Ethylene glycol 3 Water 57 Comparative example 6 Simazine 62 parts by weight Gum arabic 2 Ethylene glycol 2 Water 38 Comparative example 7 Nip 62 parts by weight Xanthan gum α5 Ethylene glycol 2 Water 645 Comparative Example 8 MBτ0 12 parts by weight Polymaleate 5 P O@E/P, O, P polymer 2 Ethylene glycol 2 Water 79 Test Example Fluidity adjusted according to Examples 1 to B and Comparative Examples 1 to 8 A sample of the biocide was placed in a cylinder with an inner diameter of 5QII and a height of 121)I to a height of 101)l, and stored at 25℃ and 45℃ for 4 weeks. Values measured using a viscosity needle), particle size measurements, and the presence or absence of redispersibility were investigated.

The results are shown in Table 1.

Evaluation of redispersibility> After storage at 25°C and 45°C for 4 weeks, invert the cylinder containing the fluid biocide and observe the presence or absence of hard cake at the bottom of the cylinder, and check for any hard cake that has formed at the bottom of the cylinder. investigated the number of times a cylinder was inverted to produce a uniform suspension.

B: 1 to 5 times 0-6 to 10 times D: 10 times or more As is clear from Table 1, by using the water-soluble polymer compound of the present invention, no hard cake was formed. The viscosity is low, and a flowable preparation with no change in physical properties after storage can be obtained.

Such good physical properties cannot be obtained with existing water-soluble polymers.

Applicant's agent: Furuya L. 26- 8-

Claims (1)

[Claims] t (a) 1 to 70% by weight of a biocide that is insoluble in water and solid or pasty at room temperature; (b) 1 basic silicon atom or cationic silicon atom in the repeating unit; or more, and the average molecular weight is 10
0.1 to 40 weight percent of a water-soluble polymer compound in the range of 0.0 to 10,000,000, and (0) a nonionic surfactant or/and an anionic surfactant of 0.1 to 40%. An aqueous suspension biocide composition comprising 20 weight percent. 2, (b) The water-soluble polymer compound is the following (1) and (b)
The aqueous suspension biocide composition according to claim 1, which is a polymeric compound selected from the group consisting of: (1) Homopolymers of salts or quaternary ammonium salts of monomers containing monomers represented by the following general formulas (I) to (to), or copolymers of two or more thereof. [In the formula, M represents 10- or -H, n represents an integer from 1 to black, R4 represents H or OH, R2 and B represent H, OR
or O
In the formula, R1 is the same as in formula (I). The substitution position of pyridine is the 2nd or 4th position] R1 2- [wherein, R1 and R2 are the same as in formula (I). The substitution position of piperidine is the 2 or 4 position] [In the formula, R1,, R,, R, are the same as in formula (I)] (1)
One or more salts or quaternary ammonium salts of fluorine-containing monomers represented by the general formulas (I) to (■), and an α,β-unsaturated carboxylic acid or a salt thereof or a derivative thereof, A copolymer with one or more vinyl monomers selected from the group consisting of sulfonic acid group-containing vinyl compounds or salts thereof, acrylonitrile, vinylpyrrolidone, and aliphatic olefins having 2 to 20 carbon atoms.