JP2815883B2 - Aqueous suspension biocide composition - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to an aqueous suspension biocide composition, and more particularly to an aqueous suspension biocide composition having a melting point of 15 so that it does not crystallize during storage.
It relates to an aqueous suspension composition of a water-insoluble biocide at ~ 80 ° C.

[Conventional technology and its problems]

Conventionally, water-insoluble biocides have been used as emulsions or wettable powders, but recently, water-insoluble biocides have been used as suspensions (flowable formulations) in which fine particles of water-insoluble biocides are dispersed in water using an appropriate dispersant. More often. Various anionic or nonionic surfactants or water-soluble polymer surfactants have been proposed as dispersants, and stable suspension preparations have been obtained even under severe storage conditions.

However, as a water-insoluble biocide, the melting point is 15-80 ° C
In the case of using such a material, when it is stored under conditions of a large temperature difference, there is a problem that crystal displacement occurs in the emulsified particles, and crystal precipitation occurs together with emulsion breaking.

[Means for solving the problem]

Therefore, the present inventors have proposed a method of stabilizing an emulsion (suspension) by enhancing a hydrophilic protective colloid by forming an ion complex, providing a hydrophilic protective colloid by hydrophobic / hydrophobic interaction, and using a substance having slightly different dissolution parameters. The results of various investigations on methods such as surface modification by the bleed effect have shown that the use of a specific compound in the method described above under high-temperature (50 ° C) and low-temperature (-10 ° C) storage cycle tests under severe conditions Breaking of the emulsion during storage of the
The present inventors have found that a fluid suspension without crystal precipitation can be obtained, and completed the present invention.

That is, the present invention relates to an aqueous suspension biocide composition in which particles of a water-insoluble biocide having a melting point in the range of 15 to 80 ° C are suspended in water, and the following (i) or (ii): It is intended to provide an aqueous suspension biocide composition comprising a compound in a ratio of 0.1 to 2.0 by weight relative to the biocide.

(I) Lower alcohol ester of higher fatty acid (ii) Ester of adipic acid and linear or branched alcohol having 4 to 22 carbon atoms The higher fatty acid ester of (i) used in the present invention has 8 to 8 carbon atoms. Lower alcohol esters of 22 fatty acids are used. The alcohol forming the adipic acid ester (ii) is a straight-chain or branched-chain alcohol having 4 to 22 carbon atoms, and particularly preferably an alcohol having 10 to 18 carbon atoms. As the adipic acid ester (ii), a diester is preferably used.

The content of the carboxylic acid esters (i) and (ii) in the biocide composition of the present invention is 0.1% by weight relative to the biocide.
-2.0, preferably 0.2-1.0.

Specific examples of the biocide used in the present invention include, for example, dimethoate (mp 52 ° C, dimethyl-S-
(N-methylcarbamoylmethyl) phosphorothiol thionate), phosphorone (mp 48 ° C., S-[(6-chloro-2-oxo-3-benzoxazonyl) -methyl] diethyl phosphorothiol thionate), spliceside ( mp 40 ° C, S-[(5-methoxy-2-oxo-2,3
-Dihydro-1,3,4-thiadiazoyl- (3) -methyl] dimethylphosphorothiolthionate), tumaside (mp 76 ° C., m-trimethylcarbamate), and fungicide binapacacryl (mp 66 ° C., 2-secondary-butyl) -4,6-dinitrophenyl-3-methylcrotonate), fujiwan (mp 54 ° C, diisopropyl-1,
3-dithiolan-2-colidenamalonate), herbicides include phenothiol (mp 42 ° C, S-ethyl-[(4-chloro-o-tolyl) oxy] -thioacetate, nitrophen (mp 71 ° C, 2,4 -Dichlorophenyl-p-nitrophenyl ether), alachlor (m.
p.41 ° C., 2-chloro-2 ′, 6′-diethyl-N-methoxymethylacetanilide), trifluralin (mp49
° C, α, α, α-trifluoro-2,6-dinitro-N, N-
Dipropyl-p-toluidine), as acaricides, dymite (mp 70 ° C., 1,1-bis (p-chlorophenyl) ethanol), quelcene (m.
p.79.5 ° C, 2,2,2-trichloro-1,1-bis (p-chlorophenyl) ethanol), citrazone (mp 73 ° C, 5-
Chloro-α-ethoxyimino-2,5-dimethoxybenzylbenzoate).

These biocides are present in the aqueous suspension biocide compositions of the present invention.
10 to 60% by weight is blended.

The amount of the anionic or nonionic surfactant or polymer surfactant added as a dispersant to the aqueous suspension biocide composition of the present invention is 0.1 to 10% by weight.

The dispersant used in the present invention is selected from the group consisting of unsaturated carboxylic acids and monomers thereof.
A water-soluble or water-dispersible polymer containing at least one species or two or more as an essential component is particularly preferred.

Examples of the monomer used in the production of the polymer include unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid, unsaturated dicarboxylic acids such as maleic acid, and derivatives thereof such as alkyl esters (methyl ester) of the above-mentioned acids. ), Alkali metal salts (such as soda salts), ammonium salts and organic amine salts (such as triethanolamine salts),
There are these mixtures. In addition to these monomers, vinyl acetate, isobutylene, diisobutylene,
Copolymerizable monomers such as styrene can also be added.

The method of polymerizing these monomers is performed by a conventionally known method. The proportion of the monomer component and the degree of polymerization of the polymer are not particularly limited, but the polymer must be at least water-soluble or water-dispersible.

Specific examples include acrylic acid polymer, methacrylic acid polymer, copolymer of acrylic acid and methacrylic acid,
Copolymer of acrylic acid and polyoxyethylene methacrylate, copolymer of acrylic acid and methyl acrylate, copolymer of acrylic acid and vinyl acetate, copolymer of itaconic acid and vinyl acetate Or a saponified product thereof, a copolymer of acrylic acid and maleic acid, a copolymer of maleic acid and isobutylene, a copolymer of maleic acid and styrene, and salts of these with alkali metals, ammonia and organic amines. Can be Two or more of these polymers can be used.

The amount of the dispersant used in the present invention is preferably 0.001 to 1, more preferably 0.005 to 0.5, by weight based on the biocide.

Other nonionic or anionic surfactants that can be used as a dispersant include, for example, polyoxyalkylene alkyl ethers, polyalkylene oxide-based nonionic surfactants such as polyoxyalkylene alkylaryl ethers, and, for example, alkyl sulfates, Anionic surfactants such as oxyalkylene alkyl sulfates and polyoxyalkylene alkyl phosphates are exemplified. If necessary, it can be used in combination with the above-mentioned polymer surfactant.

Aqueous suspension biocide compositions of the present invention typically have a melting point of 15 to 80.
A mixture of a biocide at 1 ° C. and one or more of the compounds (i) and (ii) is heated and melted, and then added to an aqueous solution containing a dispersant by stirring with a homomixer or the like. Thus, a suspension having a particle diameter of usually about 5 to 20 μ is obtained.

〔The invention's effect〕

The aqueous suspension biocide composition of the present invention comprises (i) and (ii)
By bleeding the surface of the biocide with the compound of the above, surface modification is performed, and an emulsion having excellent storage stability can be obtained.

〔Example〕

Hereinafter, the present invention will be described with reference to Examples, but the present invention is not limited to these Examples. The compounds and biocides used in the examples are listed below.

(A) Crystal precipitation inhibitor compound Example 1 20 parts by weight of the compound (1) and 20 parts by weight of the biocide (III) were mixed and melted. While 2 parts by weight of acrylic acid and butyl acrylate was previously dissolved in 58 parts by weight of water, the above-mentioned mixed melt was gradually added with stirring with a homomixer to obtain a suspension preparation. .

Example 2 8 parts by weight of the compound (2) and 35 parts by weight of the biocide (IV) were mixed and melted. In advance, add 60 parts of acrylic acid polymer to 56 parts by weight of water.
% Sodium salt-neutralized product 0.5 part by weight and polyoxyethylene nonylphenol ether 0.5 part by weight were dissolved therein, and the above mixed solution was gradually added thereto with stirring with a homomixer to obtain a suspension preparation.

Comparative Example 1 While 2 parts by weight of a sodium salt of a copolymer of itaconic acid and vinyl acetate was previously dissolved in 68 parts by weight of water, a solution of 30 parts by weight of biocide (I) was stirred with a homomixer. The suspension was gradually added to obtain a suspension formulation.

Comparative Example 2 60% saponified vinyl acetate polymer in 69 parts by weight of water 1
A melt of 30 parts by weight of the biocide (II) was gradually added to the suspension while stirring with a homomixer to obtain a suspension formulation.

Test Example 1 The suspension preparations prepared in Examples 1 and 2 and Comparative Examples 1 and 2 were subjected to a storage test with -10 ° C for 3 days and 50 ° C for 3 days as one cycle. Changes in viscosity, presence or absence of crystal precipitation, changes in active ingredients, and changes in suspension stability were examined by the following methods.

 Table 1 shows the results.

(Measurement method) Particle size (μ): Measured with a Coulter counter.

Viscosity (cps): Measured with a B-type viscometer (30 rpm / 25 ° C.) Crystal precipitation (presence / absence): Observed by an optical microscope (× 400) Change in active ingredient (%): Measured by gas chromatography.

Suspension stability (%): Put into a cylinder having an inner diameter of 2 cm and a height of 10 cm, and determine the suspension ratio by the following formula.

Continued on the front page (58) Fields surveyed (Int.Cl. ⁶ , DB name) A01N 25/04 A01N 25/30 CA (STN) REGISTRY (STN) WPIDS (STN)

Claims (2)

(57) [Claims] 1. An aqueous suspended biocide composition comprising particles of a water-insoluble biocide having a melting point in the range of 15 to 80 ° C. suspended in water, wherein the compound is a compound of the following (i) or (ii): , In an amount of 0.1 to 2.0 by weight relative to the biocide. (I) Lower alcohol ester of higher fatty acid (ii) Ester of adipic acid with linear or branched alcohol having 4 to 22 carbon atoms 2. The aqueous suspension biocide composition according to claim 1, wherein one or more selected from the group consisting of unsaturated carboxylic acids and monomers thereof as a dispersant is an essential component. An aqueous suspension biocide composition comprising a water-soluble or water-dispersible polymer.