JPS61126001A - Aqueous suspension of biocide composition, and production thereof - Google Patents

Abstract

PURPOSE:To produce the titled composition having excellent storage stability and fluidity, and storable at a high temperature without causing crystallization and gelation, by mixing a water-insoluble biocide having low melting point, polyvinyl alcohol, and a water-soluble thickener at specific ratios and using the mixture as an essential component. CONSTITUTION:A pasty or solid water-insoluble biocide having a melting point of 38-110 deg.C, especially 38-90 deg.C, such as dimethyl-2,2,2-trichloro-1-hydroxyethyl phosphonate, etc. is added in an amount of 5-50wt% under agitation to an aqueous solution of a polyvinyl alcohol having a polymerization degree of 100-5,000 and a concentration of 0.1-10wt%, and stirred and mixed sufficiently. The objective stable composition can be produced by adding 0.001-10wt% water-soluble thickener such as carboxymethyl cellulose, etc., to the mixture. EFFECT:The composition is resistant to crystallization and gelation and is stable under severe conditions such as storage at a high temperature (60 deg.C) or in cycling test between a high temperature and a low temperature (-10 deg.C).

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an aqueous suspension biocide composition, and further relates to an aqueous suspension biocide composition. Most of the biocides, such as the A dispersion system (@turbidity) that combines two or more species, or an emulsion system that partially uses an organic solvent and consists of a nonionic surfactant or anionic surfactant alone or in combination of two or more of them.
emulsion).

However, for formulations containing water-insoluble biocides with melting points below 110°C, especially below 90°C, they may be exposed to high temperatures (temperatures near or above the melting point of the biocide) or to high temperatures during long-term storage. When the growth of the dispersed particles,
Agglomeration and destruction of emulsion particles occur, resulting in crystal precipitation and gelation.

[Means for solving problems]

Therefore, the inventor of the present invention has conducted extensive research to solve these drawbacks, and has found that by adopting the following configuration, it has excellent fluidity, and has been confirmed by high-temperature storage (60°C) or high-temperature and low-temperature (-10°C) cycle tests. The present invention was completed by discovering that it is possible to obtain a stable aqueous suspension biocide composition that does not cause crystal precipitation or gelation even under abusive conditions.

That is, the present invention uses 5 to 50% by weight of a pasty or solid water-insoluble biocide having a melting point of 38 to 110°C.

The present invention provides an aqueous suspension biocide composition containing as essential ingredients 0.1 to 10% by weight of polyvinyl alcohol and 0.001 to 10% by weight of a water-soluble thickener.

If the melting point of the biocide is lower than 38°C, a stable suspended biocide composition may not be obtained during formulation. Specific examples of the biocide used in the present invention include:

Insecticides include trichlorfon (m, p, a 4℃, dimethyl-2,2,2-) dichloro-1-hydroxyethylphosphonate), dimethoether) (m, p, 52℃, dimethyl-8-(N-methylcarbamoyl) methyl) phosphorothiolthionate), hamidothion (m, p, ao℃,
Dimethyl-8-(2-(1-methylcarpamoylethylthio)ethyl]phosphorothiolate), Phosvel (m,
p, 7'5°C.

4-bromo-2,5-dichlorophenylmethylphenylphosphonothionate), Ronnel (m, p.

41°C, dimethyl-2,4,5-) +J chlorophenyl phosphorothionate), guard side (m, p.

98°C, 2-chloro-1-(2,4,5-trichloro
.

lophenyl)-vinyl dimethyl phosphate).

Phosaron (m, p, 48℃+day-[(6-chloro-2-
oxo-5-penzoxazonyl)-methyl]diethylphosphorothiolthionate)% spracide (m, p,
40°C for 2 days - [5-methoxy-2-oxo-2,3-dihydro-1,3',4-thiadiazoyl-(3)-methylcudimethylphosphorothiolthionate), Tumaside (m, p, 76 ℃.

m-)lyl methyl carpamate), mibucin (m.

p, 96°C, 0-cumenyl methyl carbamate)% Meopal (m, p, 80°C, 3.4-xylyl methyl carbamate); fungicides include binapacryl (m, p, 66
°C, 2-secondary-butyl-4,6-dinito I-+phenyl-3-methylchloro)*-)), hydroxyinxazole (m, p, aa °C, 3-hydroxy-5-methylinxazole), Fujiwan (m, p, 54°C, diisopropyl-1,3-dithiolane-2-colibunamalonate); herbicides include phenothiol (m, p, 42°C,
S-ethyl [(4-chloro-0-tolyl)oxyph-thioacetate), Primage (m, p, 39°C, triisocropanolamine salt of 2-secondary-butyl-4,6-sinitrophenol), Nitrofen (m, p,
71°C, 2,4-dichlorophenyl-p-nitrophenyl ether), chlorpropham (m.

p, 39°C, isoyropyru-m-chlorocarpanylate).

Propanil (m, p, 92°C, s', l-dichlorocropionanilide), alachlor (m, p, a1°C, 2
-Chloro-2/, 6/ -diethyl-N-methoxymethylacetanilide), triflurali:/(m, p, 4
9°C, α,α,α-trifluoro2,6-sinitroN,N-dipropyl-p-toluidine)% ametrine (
m, p, 86°C, 2-ethylamino-4-ing apyramino-6-methylthio-1,3,5-triazine);
Chlorpherane (m, p, 86.
5°C, p-chlorophenyl-p-chlorobenzenesulfonate), dymite (m-p-70°C, 1,1-his(p-chlorophenyl)ethanol), Kelsen (m-p-70°C,
, p, 79.5°C, 2,2.2-trichloro-1,
1-bis(p-chlorophenyl)ethanol).

Citrazine (m, p, 75°C, 5-chloro-α-ethoxyimino-2,5-dimethoxybenzylbenzoate)
Examples include.

The biocide used in the present invention is 5 to 50% by weight in the composition.
, preferably 10 to 40% by weight.

The polyvinyl alcohol used in the present invention has a polymerization degree of 10.
0-5000, preferably polymerization degree 500-30000
It is 4. Further, although the polyvinyl alcohol is obtained by saponifying polyvinyl acetate, it may be completely saponified or partially saponified.

The blending amount of polyvinyl alcohol is 0.1 to 10% by weight,
Preferably it is 0.5 to 10% by weight.

Natural, semi-synthetic and synthetic water-soluble thickeners can be used as water-soluble thickeners. Natural mucilages include xanthan gum and xanfro derived from microorganisms, pectin derived from plants,
Gum arabic, guar gum, etc. are semi-synthetic mucilages that contain methylated, carboxyalkylated, and hydroxyalkylated products (including methylcellulose, carboxymethylcellulose, hydroxymethylcellulose, etc.) of cellulose or starch derivatives, and synthetic mucilages that contain polyacrylic acid. Specific examples of water-soluble thickeners include salts, polymaleates, polyvinylpyrrolidone, etc. The amount of the water-soluble thickener varies depending on the type of thickener, but it is usually 0.0% in the composition.
001-10% by weight, preferably 0.01-10% by weight
It is.

The aqueous suspension biocide composition of the present invention can be easily prepared by the following method.

First, dissolve polyvinyl alcohol in water.

Add and mix the biocide that has been heated and dissolved in advance while stirring with a homomixer or the like. After sufficient stirring and mixing, a water-soluble thickener is added.Accordingly, the present invention is based on the following two steps: Adding a biocide that has been heated and dissolved in advance to water in which polyvinyl alcohol has been dissolved, while stirring; 5-50% by weight of a pasty or solid water-insoluble biocide with a melting point of 3°8-110°C, characterized by adding a water-soluble thickener after thorough stirring and mixing, and 0.1-50% polyvinyl alcohol.
10% by weight and water-soluble thickener '0.001-10
In carrying out the present invention, in addition to the essential ingredients, dispersants, anti-foaming agents, decomposition inhibitors, etc. are provided. can be added as necessary. A nonionic surfactant and/or anionic surfactant is used as the dispersant. Further, it is also possible to use an organic solvent within a range of 20% by weight, if necessary.

[Action/Effect]

The mechanism of how the aqueous suspension biocide composition of the present invention is able to keep a suspension composition of a water-insoluble biocide with a low melting point stably suspended even under severe conditions is not necessarily clear. However, polyvinyl alcohol becomes a protective colloid,
It is believed that the water-soluble thickener protects the cotton biocide particles in both liquid and solid form and prevents them from settling. In any case, according to the present invention, a water-insoluble biocide with a melting point of 38 to 110°C, particularly 38 to 90°C, which has been difficult to formulate as an aqueous suspension biocide composition, can be prepared in an aqueous suspension. [Example] Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these. is based on weight.

Example 1 Polyvinyl alcohol (degree of polymerization 1500) in water.

(Saponification degree: 70%) was dissolved, trichlorfon raw material which had been heated and dissolved in advance was added, and the mixture was mixed and stirred for 20 minutes using a homo mixer to form an emulsion. After that, a thickener is added to adjust the viscosity.The viscosity of the prepared emulsion is approximately 2500. P deral 0 Example 2 Add polyvinyl alcohol to water (polymerization degree 500, saponification degree 2
0%), and added the Tumaside raw material which had been heated and dissolved in advance, and mixed and stirred for 20 minutes in a homomixer to form an emulsion. A thickener is then added to adjust the viscosity.

100 copies The viscosity of the prepared emulsion was approximately 4000. 0 which is P Example 3 Polyvinyl alcohol (degree of polymerization 2400) in water.

(Saponification degree: 50%) was added, and the Fujiwan raw material which had been heated and dissolved in advance was added thereto, and the mixture was mixed and stirred for 5 minutes using a homo mixer to form an emulsion. Thereafter, sodium alkylnaphthalene sulfonate and a thickener are added to adjust the viscosity.

The viscosity of the emulsion prepared in 100 parts was approximately 2100.2. It is.

Example 4 Polyvinyl alcohol (degree of polymerization 1500) in water.

(Saponification degree: 90%) is dissolved, and the triclefone raw material which has been heated and dissolved in advance is added, and the mixture is mixed and stirred for 30 minutes using a homo mixer to form an emulsion. Then, the viscosity was adjusted by adding polyoxyethylene (20 mol) as a styrenated phenol nitrate thickener.The viscosity of the prepared emulsion was approximately 4200! , P, is 0. Comparative Example 1 Polyoxyethylene (25 mol), styrenated phenol ether, alkylbenzene sulfonic acid calcium salt, and trichlorfone raw material were dissolved in xylene, and this homogeneous mixture was poured into water and then mixed in a homomixer for 20 minutes. Mix and stir;
Perform emulsion formation. After that, a thickener is added to adjust the viscosity.

The viscosity of the prepared emulsion was approximately 5200. P, is 0 Comparative Example 2 Polyoxyethylene (18 mol) nonylphenol ether, alkylbenzene sulfonic acid calcium salt, and Tumaside raw material were dissolved in xylene, and this homogeneous mixture was poured into water and then mixed and stirred in a homomixer for 20 minutes. Perform emulsion formation. After that, a thickener is added to adjust the viscosity.The viscosity of the prepared 100 parts emulsion is about 5200. P.

Comparative Example 3 Diethylene glycol monobutyl ether, polyoxyethylene (12 mol) tribenzylphenol ether, alkylbenzene sulfonic acid calcium salt, and 7-dione raw material were dissolved in diethylene glycol monobutyl ether and xylene, and this homogeneous mixture was poured into water and mixed in a homomixer for 30 minutes. Stir to form an emulsion. A thickener is then added to adjust the viscosity.

The viscosity of 100 parts of the emulsion prepared was approximately 3900. P, is 0 Comparative Example 4 Polyoxyethylene (40 mol) sorbitol oleyl ester, alkylbenzene sulfonic acid calcium salt, and trifluralin ester were dissolved in xylene, and this homogeneous mixture was poured into water and then mixed and stirred in a homomixer for 20 minutes. death,
Form an emulsion. A thickener is then added to adjust the viscosity.

The viscosity of the v4I emulsion is approximately 4200. P.

Test Examples The aqueous suspension biocide compositions prepared according to Examples 1 to 4 and Comparative Examples 1 to 4 were placed in a cylinder with an inner diameter of 3e and a height of 12 to a height of 10 and heated at 50°C, -5°C and 50°C. 7 at each temperature
A daily recycling test was conducted to evaluate changes in viscosity and the presence or absence of crystal precipitation. In addition, the suspension ratio was determined using the following formula. The results are shown in Table 1.

Claims (1)

[Scope of Claims] 1. 5-50% by weight of a pasty or solid water-insoluble biocide with a melting point of 38-110°C, 0.1-10% by weight of polyvinyl alcohol, and 0.001-10% by weight of a water-soluble thickener. % of an aqueous suspension biocide composition containing as an essential ingredient. 2. A biocide having a melting point of 38 to 110°C, characterized by adding a biocide that has been heated and dissolved in advance to water in which polyvinyl alcohol has been dissolved under stirring, and then adding a water-soluble thickener after stirring and mixing thoroughly. Paste or solid water-insoluble biocide 5-50% by weight, polyvinyl alcohol 0.1-1
A method for producing an aqueous suspension biocide containing 0% by weight and 0.001 to 10% by weight of a water-soluble thickener as essential components.