JPH035403A - Dispersing agent for biocidal granule - Google Patents

Abstract

PURPOSE:To obtain a dispersing agent for biocidal granule, composed of a copolymer of a sulfone group-containing monomer. hydrophobic monomer and hydrophilic monomer at a specific molar ratio and excellent in disintegrating and extending properties in water and also in disintegration ratio, i.e., granule hardness. CONSTITUTION:A dispersion agent for biocidal granule composed of a copolymer containing 5-98mol% sulfone group-containing monomer [e.g. styrenesulfonic acid (salt)], 1-50mol% hydrophobic monomer (e.g. an alkyl unsaturated monocarboxylate or chain or cyclic olefin) and 1-80mol% hydrophilic monomer (e.g. an unsaturated monocarboxylic acid or unsaturated dicarboxylic acid) as essential constituent units. The above-mentioned dispersing agent is used as dispersing agent for biocidal granule compositions containing a biocide, such as insecticide, germicide acaricide or herbicide, and inorganic mineral fine powder as constituent ingredients. The dispersing agent has sufficient disintegrating and extending properties in water.

Description

[Detailed description of the invention] [Industrial application fields] The present invention relates to a dispersant for biocide granules.

[Prior Art] Conventionally, as a dispersant for biocide granules, a dispersant consisting of a polymer of sodium styrene sulfonate alone or a copolymer of methacrylic acid triethanolamine salt has been known (for example, JP-A-58 -131904 Publication, JP-A-03-0
6101, etc.).

[Issues that the invention aims to solve] However, this material is not sufficient in terms of underwater disintegration and expansion.

[Means for Solving the Problems] The present inventors have conducted intensive studies on a dispersant for biocide granules that has sufficient disintegration and spreading properties in water, and as a result, they have arrived at the present invention.

That is, the present invention is a copolymer comprising a sulfonic group-containing monomer (a), a hydrophobic monomer (b), and a hydrophilic monomer (c) as essential constituent units, and the total number of moles of the entire copolymer is Based on (a) 5-98%, (b) 1-50%,
This is a dispersant for biocide granules in which (C) is 1 to 80%.

In the present invention, the sulfonic acid (salt) group moiety can be obtained by polymerizing essential components excluding the sulfonic acid (salt) moiety to form a copolymer and then sulfonating (to form a salt); It can be introduced by a method such as polymerizing essential constituent components having a moiety to form a copolymer, but the former is preferred.

Details are described in Japanese Patent Application No. 82-288709.

Specific examples of the sulfonic group-containing monomer (a) in the present invention include aliphatic hydrocarbon vinyl monomer sulfonic acids (salts) such as vinyl sulfonic acid (salts) and (meth)allylsulfonic acid (salts); styrene sulfone acids (salts), aromatic hydrocarbon vinyl monomer sulfonic acids (salts) such as α-methylstyrene sulfonic acid 1); sulfopropyl (meth)
Acrylate, 2-hydroxy-3-(meth)acryloxypropylsulfonic acid (salt), 2-(meth)acryloylamino-2,2-dimethylethanesulfonic acid (salt)
(meth)acrylic sulfone l'1f2 (salts) such as;
(meth)acryloyloxy(hydroxy)alkanesulfonic acid (salt) such as 3-(meth)acryloyloxyethanesulfonic acid (salt), 3-(meth)acryloyloxy-2-hydroxypropanesulfonic acid (salt), etc.72-
Examples include (meth)acrylamido(hydroxy)alkanesulfonic acids (10) such as (meth)acrylamido-2-methylpropanesulfonic acid (salt) and l-(meth)acrylamido-2-hydroxypropanesulfonic acid (salt). .

Among these, preferred is styrene sulfonic acid (salt)
It is.

Among the above sulfonate salts, the salts include sodium salt,
Examples include alkali metal salts such as potassium salts and lithium salts, alkaline earth metal salts such as calcium salts and magnesium salts, and amine salts such as ethanolamine salts and triethanolamine salts. Preferred are sodium, potassium, lithium, calcium, and magnesium salts. Issliln th'a'tk day L leeret.

Examples of the hydrophilic monomer (C) in the present invention include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, amide group-containing monomers, and hydroxyl group-containing monomers.

Examples of unsaturated monocarboxylic acids include acrylic acid and methacrylic acid, and examples of unsaturated dicarboxylic acids include maleic acid, fumaric acid, and itaconic acid.

Further, as the salts of the above acids, for example, alkali metal salts (such as sodium), ammonium salts, organic amine salts (triethanolamine salts), and mixtures thereof can also be used.

Examples of the amide group-containing monomer include (meth)acrylamide, t, or N,N-di(hydroxy)alkyl(meth)acrylamide.

Hydroxyethyl (meth) as a hydroxyl group-containing monomer
Examples include hydroxy lower alkyl (meth)acrylates such as acrylates.

Other polyethylene glycol (meth)acrylates such as triethylene glycol (meth)acrylate;
Unsaturated alcohols such as (meth)allylic alcohol are also used as hydrophilic monomers.

Among these, preferred are unsaturated monocarboxylic acids and unsaturated dicarboxylic acids.

Hydrophobic monomers (b) in the present invention include unsaturated monocarboxylic acid alkyl esters, unsaturated dicarboxylic acid alkyl esters, conjugated dienes, chain olefins and cyclic olefins, vinyl ester monomers, nitriles, 21 (containing monomers, etc.). It will be done.

Specific examples of unsaturated monocarboxylic acid alkyl esters and unsaturated dicarboxylic acid alkyl esters include the aforementioned alkyl esters of unsaturated (mono- or alkyl) carboxylic acids (the number of carbon atoms in the alkyl group is usually 1 to 20). Specific examples of alkyl groups include methyl, ethyl, propyl, n-, sea-.

tert-butyl, pentyl, hexyl, dodecyl,
Examples include eicosyl and 2-ethylhexyl groups.

Examples of the conjugated diene include butadiene.

Examples of chain olefins include ethylene, propylene, and isoprene.

Examples of the cyclic olefin include styrene and alkyl group-substituted styrene (α-methylstyrene, p-methylstyrene, vinyltoluene, etc.).

Vinyl ester monomers include vinyl acetate, vinyl propionate, and vinyl phthalate.

Examples of the nitrile group-containing monomer include (meth)acrylonitrile.

Among these, preferred are unsaturated carboxylic acid alkyl esters, cyclic olefins and hydroxyl group-containing monomers.

The dispersant of the present invention is a copolymer comprising a sulfonic group-containing monomer (a), a hydrophobic monomer (b) and a hydrophilic monomer (c) as essential constituent units.

The average molecular weight of the copolymer is usually 1,000 to 2,000.
000, preferably 5,000 to 500,000. When the average molecular weight is m months and 000, the dispersibility in water is insufficient, and when it exceeds 2,000.000, the dispersibility in water becomes poor. The viscosity is usually to-ioo, o when expressed as a 30% by weight aqueous solution viscosity.

Ocps, preferably about 20~I,000cp
It is s.

Based on the total number of moles of the entire copolymer, (a) is usually 5 to 0.
8%, preferably 20-50%; (b) usually 1-50%
%, preferably 10-20%; (C) is 1-80%, preferably 30-70%.

Biocides for which the dispersant for biocidal granules of the present invention can be used include insecticides, fungicides, acaricides, herbicides, and the like, and include, for example, the following.

Insecticides include 0.0-dimethyl-5-(tomethylcarbamoylmethyl)sothiophosphate (dimethoate), 3.5-xylyl-tomethylcarbamate (I
MC), etc., and 3-allyloxy-1,2 as a bactericidal agent.
-benzoylthiazole-1,1-dioxide (probenazole), etc.; Herbicides include 2, 4. B-) dichlorophenyl-4-ditrophenol (-ship name GNP),
Examples include, but are not limited to, 2-chloro-2', G'-diethyl to N-(butoxymethyl)acetanilide (butachlor), and the like. These biocides can be used alone or in combination of two or more.

The dispersant of the present invention is used as a dispersant for a biocide granule composition containing the above biocide and an inorganic mineral fine powder as constituent components.

Examples of inorganic mineral fine powders include bentonite, clay talc, kaolin, calcium carbonate, and diatomaceous earth.

In addition to the above-mentioned copolymer, the dispersant of the present invention may include, for example, a granulation improver [such as a monovalent salt of carboxymethylcellulose (details are described in Japanese Patent Application No. 13-298945),
Blend binders (sodium lignin sulfonate, polyethylene glycol, etc.), penetrants (dioctyl sulfosuccinate sodium salt, polyoxyethylene alkylphenyl ether sulfate sodium salt, etc.) and other dispersants (polyoxyethylene alkylphenyl ether, etc.). be able to.

Based on the weight of the biocide granule composition, the dispersant is typically 0.5
~IO%, preferably 1-3%.

The Lt of the inorganic mineral fine powder is usually 99 to 80%, preferably 8 to 85%.

The biocide is usually 1-15%, preferably 3-10%.

The manufacturing method of the biocide granule composition is the same as the conventional method (
For example, a slurry containing a biocide and a dispersant contains 11!
(After adding and kneading the organic mineral fine powder and auxiliary agents as necessary, the mixture is extruded through a screen, molded with a granulator, dried, and sieved with a sifter to obtain the biocide granules of the present invention of the desired particle size. A composition is obtained.

The biocide granule composition of the present invention is applied directly to fields and the like.

[Examples] The present invention will be further described below with reference to Examples, but the present invention is not limited thereto.

Examples 1 to 8 and Comparative Examples 1 to 5 Table 11 Dispersants for biocide granules were obtained with the formulations shown in Table 2.

The abbreviations in the table are as follows.

aC styrenesulfonic acid a2: 2-acrylamido-2-methylpropanesulfonic acid bl: butyl methacrylate b2: p-methylstyrene cI nialic acid C2: maleic acid dl: methacrylic acid dl: methacrylic acid triethanolamine salt d3: styrene ( Numbers in ) indicate mol%.

Molecular weight is in thousands (for example, in the table, 14 indicates 14,000).

The numbers in the salt column indicate molar ratios.

Table 2 Use Examples 1 to 5 and Comparative Use Examples 1 to 5 Inorganic mineral fine powder (B), biocide (C), and dispersant (II) used in Use Examples 1 to 5 and Comparative Use Examples 1 to 5.
) is as follows.

biocide ! Dithianone 2 Dimethoate 　　1PC Inorganic mineral fine powder (carrier) l bentonite 2 Clay 3 Talc Unit is weight% (Patent featuring the total weight of the composition Table 4 The unit is % by weight (the total weight of the composition is 100).

Test Example 1 Physical properties of Usage Examples 1 to 5 and Comparative Usage Examples 1 to 5 were evaluated by the following method.

Add 20 parts of water to 100 parts of the composition in Table 3.4 and knead it,
Granules with a diameter of 0.9 square meters were made using a granulator and used in the following tests.

(1) Underwater disintegration spreading test method 3 degree hard water is poured into a Petri dish with a diameter of 10 cm to a depth of ICl11, and the temperature is maintained at 20°C. One granule (particle size: 0.9 mm, length: 2 mm) was gently dropped into the center of this petri dish, and the length (m) of disintegration and expansion of the granule in water after 30 minutes was measured.

The longer the expansion length, the better.

(2) Disintegration rate test method 4. 'It? Use a 500μ l/l mesh sieve until the residue that has remained on the sieve has hardly fallen off any longer.

■Precisely weigh 100g of sample, diameter 30±2mm% mm3
Place in a ball mill porcelain pot (inner diameter 100 wm x inner depth 10 hm) containing three 5±3 g magnetic balls.

■Place this ball mill porcelain pot on a variable roller ball mill and rotate it at 100 revolutions/minute for 10 minutes.

■Thoroughly sift the contents through a standard 500μ sieve and accurately weigh the weight of the sample remaining on the sieve (A g).

The disintegration rate (%) was determined using a zero-order equation.

+00-A 0G The smaller the value of the disintegration rate (%), the higher the hardness of the granule.

The evaluation results are shown in Table 5.

Table [Effects of the Invention] The biocide granule composition of the present invention is a dispersant with excellent disintegration and spreadability in water, and is also excellent in disintegration rate (granule hardness).

Claims (1)

[Claims] 1. Sulfonic group-containing monomer (a), hydrophobic monomer (b)
) and a hydrophilic monomer (c) as essential constituent units, based on the total number of moles of the entire copolymer (
a) 5-98%, (b) 1-50%, (c) 1-98%
A dispersant for biocidal granules that is 80%. 2. The dispersant according to claim 1, wherein the hydrophobic monomer is an unsaturated monocarboxylic acid alkyl ester, an unsaturated dicarboxylic acid alkyl ester, a conjugated diene, a chain olefin, a cyclic olefin, a vinyl ester monomer, or a nitrile group-containing monomer. . 3. The dispersant according to claim 1 or 2, wherein the hydrophilic monomer is an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, a sulfo group-containing monomer, an amide group-containing monomer, or a hydroxyl group-containing monomer. 4. The weight average molecular weight of the copolymer is 1,000 to 2,00
The dispersant according to any one of claims 1 to 3, which has a molecular weight of 0,000. 5. The dispersant according to any one of claims 1 to 4, wherein the biocide is selected from the group consisting of insecticides, fungicides, acaricides, and herbicides.