JP2850001B2 - Aqueous suspension biocide composition and method for producing the same - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to an aqueous suspension biocide composition, and more particularly to a water-insoluble biocide liquid at room temperature and a paste-like or solid water-insoluble biocide at room temperature. The present invention relates to an aqueous suspension biocide composition excellent in storage stability containing an agent. (Prior art and its problems) An aqueous suspension biocide composition containing a water-insoluble biocide that is liquid at room temperature and a paste-like or solid water-insoluble biocide at room temperature is a biocide that is liquid at room temperature. , Dissolved in a hydrophobic solvent or a mixture of a hydrophobic solvent and a hydrophilic solvent in order to obtain a stable emulsion over a long period of time, adding an emulsifier to form an emulsion in water, and forming a paste or solid at room temperature in the emulsion. The biocide is dispersed with the help of a dispersant. However, when stored at a high temperature for a long period of time, coalescence of the emulsified particles and the dispersed particles occurs, and an aggregated sediment is generated. [Means for Solving the Problems] Accordingly, the present inventor has conducted intensive studies in order to solve such disadvantages, and as a result, the following structure has excellent fluidity and can be stored at high temperature (60 ° C.) or high temperature. The present inventors have found that a stable aqueous suspension biocide composition which does not cause crystallization or gelation even under abusive conditions by a low-temperature (−10 ° C.) cycle test can be obtained and completed the present invention. That is, the present invention provides a mixed aqueous suspension biocide composition containing a water-insoluble biocide liquid at room temperature and a paste-like or solid water-insoluble biocide at room temperature. 5 to 35% by weight of the biocide is emulsified with 0.5 to 10% by weight of polyvinyl alcohol or a derivative thereof dissolved in 10 to 85% by weight of water. An aqueous suspension biocide composition stabilized by 35% by weight of 0.3 to 8% by weight of a specific dispersant and 0.001 to 10% by weight of a water-soluble thickener is provided. Specific examples of the water-insoluble biocide used in the present invention, which is liquid at room temperature, include pyrethrin-based insecticides, ethylphosphonate, DDVP (2,2-dichlorovinyldimethylphosphate), marathon (s- [1 , 2-bis (ethoxycarbonyl) ethyl] dimethyl phosphorothiolothionate), ethion (tetraethyl-s', s'-methylenebisphosphorothiolothionate), cystotox (diethyl-s- (2-ethylthioethyl) Aliphatic organophosphorus insecticides such as phosphorothiolate), estotux (s- (2-ethylsulfinyl-1-methylethyl) dimethylphosphorothiolate), and parathion (diethyl-
p-nitrophenyl phosphorothioate, sumithion (dimethyl-4-nitro-m-tolyl phosphorothioate), biteite (dimethyl-4-methylthio-m-tolyl phosphorothioate), EPN (ethyl-p Organophosphorus insecticides having an aromatic ring such as -nitrophenylethylphenylphosphorothionate), ersan (s- [α- (ethoxycarbonyl) benzyl] dimethylphosphorothiolothionate), diazinon (diethyl-2- Heterocycles such as isopropyl-4-methyl-6-pyrimidinyl phosphorothioate) and rubitox (s-[(6-chloro-2-oxo-3-benzoxazolinyl) -methyl] diethyl phosphorothiolothionate) And organic phosphorus insecticides having the formula Examples of herbicides include 2,4D ester (ethyl 2,4-dichlorophenoxyacetate), aletit (2-secondary-butyl-4,6-dinitrophenylacetate), and benthiocarb (sp-chlorobenzyldiethylthiocarbamate). ), Eptam (s-ethyldipropylthiocarbamate) and the like. Fungicides include, for example, chitazine P (s-benzyldiisopropyl phosphorothioate), EDDP (O-ethyldiphenyl phosphorodithiolate) and the like. Examples of the water-insoluble biocide which is a paste or solid at room temperature that can be used in the present invention include disinfectants such as dicene (ethylenebis (dithiocarbamate) zinc salt) and manebudacene (ethylenebis (dithiocarbamate) manganese salt). Organic sulfur agent, Fusaride (4,5,6,7-
Organochlorine fungicides such as tetrachlorophthalide) and daconyl (tetrachloroisophthalonitrile), and other captans (N- (trichloromethylthio) -4-cyclohexene-1,2-dicarboximide) and difortan (N- ( 1,1,2,2-tetrachloroethylthio) -4-cyclohexene-1,2-dicarboximide), thiophanate methyl (dimethyl-4,4'-o-phenylene-3,
3'-dithiodialophanate), penrate (methyl-1- (butylcarbamonyl) -2-benzimidazole carbamate), fujiwan (diisopropyl-1,3-)
Dithiolan-2-ylidene-malonate), binapacryl (2-sec-butyl-4,6-dinitrophenyl-3-methylcrotonate), tatigalen (3-hydroxy-s
-Methyl isoxazole) and the like, and examples of the insecticide include denafone (1-naphthylmethyl carbamate),
Carbamate insecticides such as mipsin (o-cumenylmethyl carbamate) and meovar (3,4-xylylmethyl carbamate); Examples of acaricides include tedeon (p-chlorophenyl-2,4,5-trichlorophenylsulfone), molestan (s, s-6-methylquinosaline-2,3-diyldithiocarbonate),
And herbicides such as Carmex D (3- (3,4-dichlorophenyl) -1,1-dimethylurea) and teupasan (1- (2-methylcyclohexyl)). Urea herbicides such as -3-phenylurea; triazine herbicides such as simazine (2-chloro-4,6-bis (ethylamino) -1,3,5-triazine); nip (2,4-
Dichlorophenyl-p-nitrophenyl ether), MO
Diphenyl ether-based herbicides such as (p-nitrophenyl-2,4,6-trichlorophenyl ether), and others such as promacil (5-bromo-3-sec-butyl-6).
-Methyluracil) and the like. The biocide which is liquid at room temperature used in the present invention is 5 to 35% by weight as an active ingredient in the composition, preferably as an active ingredient.
The biocide, which is 10 to 30% by weight, or a paste or solid at room temperature, is incorporated in the composition as an active ingredient in an amount of 5 to 35% by weight, preferably 10 to 30% by weight as an active ingredient. In practicing the present invention, combinations of the above-mentioned active ingredients, such as fungicides and fungicides, fungicides and insecticides, insecticides and insecticides, insecticides and herbicides, and herbicides, depending on the purpose, may be used. If a herbicide or the like is selected and formulated, an aqueous suspension biocide composition having a wide range of effects can be obtained. The polyvinyl alcohol used in the present invention has a degree of polymerization of 10.
The polymerization degree is from 0 to 5,000, preferably from 500 to 3,000. Further, the polyvinyl alcohol is obtained by oxidizing polyvinyl acetate, but of course, completely saponified,
It may be partially saponified. Examples of polyvinyl alcohol derivatives include so-called carboxyl group-modified poval in which a carboxyl group is introduced by a carboxylic acid such as acrylic acid, methacrylic acid, and itaconic acid, hydrophobic group-modified poval in which an alkyl group is introduced into a side chain, and alkyl group. Modified poval having both carboxyl groups in the molecule, cationic modified poval in which a cationic monomer is introduced into the molecule, and the like, and the method of introducing such a method by etherification, esterification, acetalization of a hydroxyl group in the poval, and the like Method by copolymerization with other monomers, or etherification, esterification of the copolymer,
Examples of the method include acetalization and the like, but needless to say, the method is not limited to these. The blending amount of polyvinyl alcohol or its derivative is
0.5 to 10% by weight. As the water-soluble thickener, any of natural, semi-synthetic and synthetic water-soluble thickeners can be used.For natural mucilage, microorganism-derived xanthan gum, xanflow, plant-derived pectin, gum arabic, guar gum, etc. Methylated, carboxyalkylated, hydroxyalkylated (including methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, etc.) of cellulose or starch derivatives in semi-synthetic mucilage, and polyacrylate, polymaleate, polyvinyl Specific examples include pyrrolidone. The amount of the water-soluble thickener varies depending on the type of the water-soluble thickener.
It is 0.001 to 10% by weight, preferably 0.01 to 10% by weight. Dispersants that can be used in the present invention include polyoxyethylene nonyl phenol ether, polyoxyethylene styrenated phenyl phenol ether, polyoxyethylene / polyoxypropylene butyl ether, polyoxyethylene tribenzyl phenyl phenol ether, and butyl naphthalene sulfone. It is selected from sodium acid salts, sodium alkylbenzenesulfonate salts, and sodium dialkylsulfosuccinate salts. These may be used in combination. The compounding amount of the dispersant is 0.3 to 8% by weight as an active ingredient in the composition. Also, as other than the essential components, it also depends on the type of the drug substance,
Common solvents can be used. For example, hydrophilic solvents include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, isopropyl alcohol, and butyl alcohol, and hydrophobic solvents include xylene, isophorone, methyl naphthalene, methyl ethyl ketone, and kerosene. A hydrophilic solvent is preferred, but a combined use with a hydrophobic solvent also gives favorable results. The aqueous suspension biocide composition of the present invention can be easily prepared by the following method. As this method, (1) polyvinyl alcohol or a derivative thereof 0.5
-10% by weight is dissolved in 10-85% by weight of water, and 5-35% by weight of a liquid biocide is added at room temperature to form an emulsion by stirring. 0.3 to 8% by weight of a dispersant, 5 to 35% by weight of a paste-like or solid biocide at room temperature, and 0.001 to 10% by weight of a water-soluble thickener are added to the emulsion and stirred to form an aqueous suspension. A process for obtaining a biocide composition. At this time, it is convenient for the operation to add the water-soluble thickener at the end so as to adjust the viscosity. (2) Polyvinyl alcohol or its derivative 0.5-1
0% by weight is dissolved in 10 to 85% by weight of water, and 5 to 35% by weight of a liquid biocide is added at room temperature to form an emulsion by stirring. (Solution A) Separately, 0.3 to 8% by weight of a dispersant, 5 to 35% by weight of a paste-like or solid biocide at room temperature and 0.001 to 10% by weight of a water-soluble thickener are added to water and stirred. (Solution B) A method for producing an aqueous suspension biocide composition by mixing and stirring Solution A and Solution B. At this time, as the liquid B, a water dispersion obtained by dispersing the biocide together with the dispersant in water except for the water-soluble thickener is prepared as the liquid B, and the mixture of the liquid A and the liquid B is mixed with the water-soluble thickener. It is convenient for the operation to add viscosity to adjust the viscosity. [Action / Effect] The mechanism of how the aqueous suspension biocide composition of the present invention can be stably suspended even under severe conditions is not always clear, but polyvinyl alcohol is a protective colloid. Thus, it is considered that the coalescence of the emulsified particles and the dispersed particles is prevented. According to the present invention, it is possible to produce an aqueous suspension biocide composition comprising a mixture of a liquid biocide at room temperature and a paste or solid biocide at room temperature, which is stable even under severe conditions for a long period of time. Natsuta [Examples] Next, the present invention will be described with reference to examples, but the present invention is not limited thereto. Parts in the examples are on a weight basis. Example 1 Polyvinyl alcohol (degree of polymerization 1500, degree of saponification 70
%), Add EDDP, a liquid biocide, mix and stir for 20 minutes with a Moho mixer to form an emulsion. Thereafter, the phthalide is added with a polyalkylene styrenated phenol ether, and the mixture is stirred again for 20 minutes with a homomixer. Thereafter, a thickener is added to adjust the viscosity. EDDP 15 parts Fusalide 20 Polyvinyl alcohol (degree of polymerization 1500, saponification degree 70%) 2 Polyalkylenestyrenated phenol ether 1 Thickener (carboxymethylcellulose) 2 Water 59 Defoamer 1 100 parts Prepared mixed aqueous suspension killing The viscosity of the agent is 400 c.p. Example 2 Polyvinyl alcohol (polymerization degree 1000, saponification degree 20)
%), And a liquid biocide, benthiocarb, is added and mixed and stirred with a homomixer for 20 minutes to form an emulsion. Then DCMU (Carmex D),
A formalin condensate of sodium naphthalene sulfonate is added, and the mixture is stirred again for 20 minutes with a homomixer, and then a thickener is added to adjust the viscosity. Benthiocarb 10 parts DCMU 30 Polyvinyl alcohol (polymerization degree 1000, saponification degree 20%) 1 Formalin condensate of sodium naphthalenesulfonate 3 Thickener (methylcellulose) 2 Water 54 100 parts Prepared mixed aqueous suspension biocide The viscosity is 340 c.p. Example 3 Polyvinyl alcohol (polymerization degree 500, saponification degree 10
%) Is dissolved, and Sumithion, a liquid biocide, is added thereto and mixed and stirred for 20 minutes with a homomixer to form an emulsion. (Solution A) Polyoxyethylene / polyoxypropylene butyl ether is dissolved in water, thiophanate methyl as a solid biocide is added, and the mixture is wet-pulverized with a sand grinder for 60 minutes. (Liquid B) Liquid A and liquid B prepared in advance are mixed, and a viscosity modifier is adjusted by adding a thickener. Sumithion 15 parts Thiophanate methyl 20 Polyvinyl alcohol (polymerization degree 500, saponification degree 10%) 2 Thickener (sodium polyacrylate) 3 Polyoxyethylene / polyoxypropylene butyl ether 1 Water 59 100 parts Prepared mixed aqueous suspension The viscosity of the turbid biocide is 600 c.p. Comparative Example 1 Polyoxyethylene styrenated phenol ether was dissolved in water, and a liquid biocide, EDDP, was charged and mixed and stirred for 20 minutes with a homomixer to form an emulsion. Then add Fusaride and use a homomixer again.
After stirring for minutes, the viscosity is adjusted by adding a thickener. EDDP 15 parts Fusaride 20 Polyoxyethylene styrenated phenol ether 5 Thickener (carboxymethylcellulose) 2 Water 57 Defoamer 1 100 parts The viscosity of the prepared mixed aqueous suspension biocide is 490 cp. Comparative Example 2 Benthiocarb and polyoxyethylene tribenzylated phenol ether were dissolved in xylene, water was added, and the mixture was mixed and stirred with a homomixer for 20 minutes to form an emulsion. Thereafter, DCMU and a formalin condensate of sodium naphthalenesulfonate are added, and the mixture is again stirred for 20 minutes with a homomixer, and then a thickener is added to adjust the viscosity. Benthiocarb 10 parts DCMU 30 Polyoxyethylene tribenzylated phenol ether 3 Formalin condensate of sodium naphthalenesulfonate 3 Xylene 6 Water 46 Thickener (methylcellulose) 2 100 parts The viscosity of the prepared mixed aqueous suspension biocide is 670 c. p. Stability test The aqueous suspension biocide composition prepared according to Examples 1 to 3 and Comparative Examples 1 and 2 was placed in a cylinder having an inner diameter of 3 cm and a height of 12 cm up to a height of 10 cm, and subjected to a 60 ° C storage test and 60 ° C,- A recycle test was performed every 7 days at each temperature of 10 ° C., and changes in viscosity, the presence or absence of crystal precipitation, and the presence or absence of the formation of a gel were observed. The suspension ratio was determined by the following equation. Table 1 shows the results
It was shown to.

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Claims (1)

(57) [Claims] 5 to 35% by weight of a water-insoluble biocide liquid at room temperature, 5 to 35% of a paste- or solid water-insoluble biocide at room temperature
Weight%, polyvinyl alcohol or its derivative 0.5-10 weight%, water-soluble thickener 0.001-10 weight%, polyoxyethylene nonyl phenol ether, polyoxyethylene styrenated phenyl phenol ether,
Polyoxyethylene / polyoxypropylene butyl ether, polyoxyethylene tribenzylphenylphenol ether, sodium butylnaphthalenesulfonate,
An aqueous biocide composition containing 0.3 to 8% by weight of a dispersant selected from sodium alkylbenzenesulfonate and sodium salt of dialkylsulfosuccinate and 10 to 85% by weight of water as essential components. 2. After preparing an emulsion containing polyvinyl alcohol or a derivative thereof, a water-insoluble biocide liquid at room temperature and water, polyoxyethylene nonylphenol ether, polyoxyethylenestyrenated phenylphenol ether, polyoxyethylene polyoxyethylene Dispersant selected from propylene butyl ether, polyoxyethylene tribenzylphenyl phenol ether, sodium butylnaphthalenesulfonate, sodium alkylbenzenesulfonate and sodium dialkylsulfosuccinate, a water-insoluble biocide paste or solid at room temperature and water-soluble 5 to 35% by weight of a water-insoluble biocide which is liquid at room temperature, and 5 to 35% by weight of a paste-like or solid water-insoluble biocide at room temperature, characterized by adding a thickener and stirring. Alcohol or its derivative 0.5 to 10% by weight, water-soluble thickener 0.001 to 10% by weight, polyoxyethylene nonylphenol ether, polyoxyethylene styrenated phenyl phenol ether, polyoxyethylene / polyoxypropylene butyl ether, polyoxyethylene tri Dispersant 0.3 to 8% by weight selected from benzylphenylphenol ether, sodium butylnaphthalenesulfonate, sodium alkylbenzenesulfonate and sodium salt of dialkylsulfosuccinate
And a method for producing an aqueous suspension biocide composition containing 10 to 85% by weight of water as an essential component. 3. The addition of a dispersant, a paste-like or solid water-insoluble biocide at room temperature and a water-soluble thickener, the aqueous dispersion containing the dispersant and a paste-like or solid water-insoluble biocide at room temperature are first added, followed by 3. The process according to claim 2, wherein the process is carried out by adding a water-soluble thickener.