JPH03206002A - Dispersing agent for suspended insecticide - Google Patents

Abstract

PURPOSE:To provide a dispersing agent giving an insecticidal aqueous suspension having sufficient storage stability, low viscosity and good flowability by incorporating a specific compound such as a polyethylene glycol styrene oxide adduct into the dispersing agent. CONSTITUTION:A dispersing agent for suspending insecticides comprises a compound of formula I [Z is the residue of a p valent active hydrogen-containing compound; p is 1-8; A is 2-4C alkylene; Y is group of formula II (R, R' are H, alkyl or halogen), III (R'' is alkyl) or V; n is 0-1000, but at least one of the n among p kinds of n is >=1 and three or more of the Y exist in the molecule]. A suspended insecticide composition contains 0.1-40wt.% of the dispersing agent, 5-70wt.% of an insecticide and 20-80wt.% of an aqueous medium as essential components. The composition has good flowability even at a high concentration.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to dispersants and compositions for suspended biocides.

[Conventional technology co-dispersion stabilizers include water-soluble or water-insoluble thickeners, such as xanthan gum, Xanflo Vectin, gum arabic, guar gum, methylated cellulose, methylated starch derivatives, carboxyl alkylated products, polyacrylates] , borimaleate, holivinyl alcohol, polyvinylpyrrolidone, and smectite clay minerals.

[Problems to be Solved by the Invention] However, when dispersing with the above-mentioned dispersion stabilizer, the biocide to be dispersed may aggregate or precipitate, resulting in insufficient storage stability, and the dispersion may have a high viscosity. do.

[Means for Solving the Problems] The present inventors have conducted intensive studies on dispersants with sufficient storage stability and low viscosity of dispersion, and cloudy biocide compositions containing the same, and have developed the present invention. reached.

That is, the present invention provides a general formula Z[(AO)m(YO),Hco, (1) (wherein Z is a residue of a p-valent active hydrogen-containing compound, and p is 1 to 8
, A is an alkylene group having 2 to 4 carbon atoms, R and R' are hydrogen atoms, alkyl groups, or halogen atoms, R
# is an alkyl group having 3 or more carbon atoms, m is an integer of 1 to too many, and n is an integer of 0 or 1 to 1,000. However, p
At least one of these n is 1 or more, and 3 or more Ys exist in the molecule.

) A dispersant for a biocidal aqueous suspension consisting of a compound represented by;
Furthermore, it is a suspended biocide composition characterized by containing the dispersant (▲), biocide (B), and aqueous medium (C) as essential components.

In the general formula (1), examples of the alkyl group for R and R' include alkyl groups having 1 to 4 carbon atoms (methyl, ethyl group, etc.), and examples of the halogen atom include chlorine, bromine, etc. Of R and R', preferred are a hydrogen atom and a methyl group. It is preferable that at least one of R1R' is a hydrogen atom.

Examples of the active hydrogen-containing compound constituting the residue of the active hydrogen-containing compound having a p value of 2 include alcohols, phenols, amines, carboxylic acids, and mercabutanes. Alcohols include aromatic xts 1 m alcohols (penzyl alcohol, phenylethyl alcohol, etc.), aliphatic monohydric alcohols (alcohols with 1 to 20 carbon atoms, such as methyl alcohol and 2-ethylhexyl alcohol), aliphatic diols (ethylene glycol ,
diethylene glycol, propylene glycol, dipropylene glycol, 1,3- or 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, etc.), trivalent to octavalent aliphatic polyols (glycerin, trimethylolpropane, trimethylolethane, hexanetriol,
pentaerythritol, diglycerin, α-methylglucoside, nrubitol, xylitol, mannitol, glucose, fructose, sucrose, etc.), alicyclic diols (alicyclic polyols having 3 to 15 carbon atoms, such as cyclohexane-1. 4-dimethanol), and their anolekylene oxides [ethylene oxide and/or
Or adducts such as propylene oxide may be mentioned.

Phenols include bisphenols [bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenylene)propane (bisphenol A), bis(4-hydroxyphenyl)sulfone, (bisphenol S), 2. 2-bis(4-hydroxy-3,5-
dibromophenyl) propane, etc.], polyhydric phenols (
hydroquinone, catechol, resorcinol, etc.).

Examples of amines include ammonia, alkanolamines (monogy or triethanolamine, n- or isopropanolamine, n-propanolamine, etc.), alkylamine with 1 to 2 (1) 7 carbon atoms, and 20 carbon atoms.
6 alkylene diamine (ethylene diamine, hexamethylene diamine, etc.), polyanolekylene polyamine (
diethylenetriamine, triethylenetetramine, etc.)
, aromatic amines (aniline, phenylene diamine, diaminotoluene, xylylene diamine, methylene dianiline, diethyltolylene diamine, diphenyl ether diamine, etc.), alicyclic amines (inphorone diamine, cyclohexynolemethane diamine, cyclohexylene diamine, etc.) ), heterocyclic amines (biverazine, aminoethylpiperazine), and amino group-containing polyhydric alcohols to which alkylene oxide is added.

Carboxylic acids include monocarboxylic acids (acetic acid, probionic acid, lauric acid, stearic acid, oleic acid, etc.)
, dicarboxylic acids (succinic acid, maleic acid, fumaric acid,
itaconic acid, azelaic acid, mesaconic acid, citraconic acid, sebacic acid, glutaconic acid, adipic acid, malonic acid,
Phthalic acid, isophthalic acid, terephthalic acid, cyclohexanedicarboxylic acid, nadic acid, methylnadic acid, octylsuccinic acid, dodecenylsuccinic acid, etc.), tricarboxylic acids (tricarballylic acid, benzenetricarboxylic acid, etc.), and the like. As mercaptans,
Alkyl mercabutane having 1 to 20 carbon atoms, such as cetyl menolecabutane, may be mentioned. These can be used alone or as a mixture of two or more.

Among the active hydrogen-containing compounds, preferred are aliphatic diols.

In general formula (1), examples of the alkylene group of A include alkylene groups having 2 to 4 carbon atoms (ethylene, propylene, butylene groups, etc.).

The alkylene group A and the group Y together with the oxygen atom O form an oxyalkylene group (AO) and a group (YO).

Multiple oxyalkylene groups (AO) and (YO)
may be the same or different, and the addition format may be block addition type, random addition type, or a mixture of both.

m is an integer of 1 to 1000, preferably 100 to 600
, particularly preferably from 300 to 500. m is 1000
If it exceeds this amount, the reactivity with (YO) becomes poor and it becomes difficult to obtain a compound having the desired performance.

n is 0 or an integer of 1 to 1000, preferably 1 to 30
0, particularly preferably 20-100.

At least one of the p n's is 1 or more. p
If all n's are O, dispersion stability is insufficient. Y
There are three or more in the molecule. When Y is 2 or less, dispersion stability is insufficient.

In the general formula, the bonding order of m pieces of (AO) and n pieces of (YO) is not particularly limited, and block AO1 block Y
Whether it is in the order of O or in the order of block Y01 block AO,
AO and YO may be random.

The molecular weight of the compound represented by general formula (1) is usually 500
~300,000 preferably 1,000-100
,000, more preferably 1,000 to 40,00
It is 0.

If necessary, other dispersants can be added to the emulsifier of the present invention comprising the compound of general formula (1). Other dispersants that may be added as necessary include anionic surfactants and nonionic surfactants.

Examples of the anionic surfactant include sodium polystyrene sulfonate, sodium alkylbenzene sulfonate, sodium lignin sulfonate, and polyoxyethylene alkyl sulfate. Examples of nonionic surfactants include polyoxyethylene alkylaryl ether, polyoxyethylene alkyl ether, and polyoxyethylene phosphoryoxypropylene glycol.

Preferred are sodium polystyrene sulfonate, sodium dodecylbenzenesulfonate and sodium ligninsulfonate polyoxyethylene alkylaryl ether and polyoxyethylene polyoxypropylene glycol.

In the dispersant of the present invention, the amount of the compound of general formula (1) is usually 5% or more, preferably 50% or more.

Obtainable.

The suspension biocide composition consists of a dispersing agent (A), a biocide (B) and an aqueous medium (C).

As the biocide (B), the herbicide [2-chloro-4-ethylamino-6-isopropylamino-1.3.5-triazine (atrazine) N 2 ], which is usually solid at room temperature, is used.
, 6-dichlorobenzonitrinole (dichlobenil),
2.4-bis(isoprobylamino)-6-methylthiol, 3,5-triazine (prometon), 2-chloro4,6-bis(ethynoleamino)-1.3.5-}riazine (simazine), etc.] , insecticide [l-naphthyl methyl carbamate (carbanyl), dimethyl (E)-1-
Methyl-2-methylcarbamoyl vinyl phosphate (monocrotophosphate), 0.0-dimethyl-S-methylcarbamoylmethylphosphorodithioate (dimethoate), etc., fungicides [sulfur powder, 1,2,3
．． Acaricides such as 6-tetrahydride-N-(}lichloromethylthio)phthalimide (cabutane), acaricides [isobrovir-4,4-dichlorobenzilate (chlorobrovirate), 2-SEC-butyl-4,6-dinitro phenol (Dinocep), ethyl-4,4-dichlorobenzilate (chlorobenzilate), etc.] and combinations of two or more of these.

Examples of the aqueous medium (C) include water and diols (ethylene glycol, propylene glycol, 1,3-propanediol, etc.). Among these, water is preferred.

Moreover, an adjuvant can be used as necessary. These adjuvants include preservatives (sodium dehydroacetate,
lactic acid, paraformaldehyde, etc.), colorants (Blue L, etc.), stabilizers, antifoaming agents, thickeners (water-soluble or water-insoluble thickeners, such as xanthan gum, xanthan gum, xanthan gum, gum arabic, guar gum, cellulose). Methylated products, methylated starch derivatives, carboxyl alkylated products, polyacrylates, polymaleates, polyvinyl alcohol, clay minerals such as clay minerals and smectite, mineral powders and water-soluble powders) and antifreeze agents (such as ethylene glycol) can be mentioned. The mineral powders mentioned above include waxite, talc, kaolin, calcium carbonate, bentonite, silica powder, limestone powder, acid clay, silica powder, gypsum, pumice powder, shellfish powder, mica powder, and amorphous powder. Examples include hydrated sodium silicate (white carbon), and water-soluble powders include lactose, fructose, glucose, and the like.

The amounts of each component are as follows based on the weight of the suspended biocide composition.

The amount of the dispersant (A) of the present invention is usually 0.1 to 40%, preferably 2.0 to 30%. If the amount of the dispersant (A) is less than 0.1%, no effect can be expected, and if the amount exceeds 40%, undesirable problems such as deterioration of the suspension state and economic disadvantage will occur, which outweigh the advantages of increasing the amount.

The biocide (B) is usually 5 to 70%, preferably 15 to 60%.
%. The content of the aqueous medium (C) is usually 20 to 80%, preferably 30 to 70%. The amount of adjuvant is usually 0 to 30%, preferably 0.5 to 1.0%. Thickener is usually 0-1
．． 0%, preferably 0-0.5%. The amount of antifreeze is usually 0 to 0.5%, preferably 0 to 0.5%.

The method for producing the suspended biocide composition may be the same as the conventional method, and the solid drug substance (biocide) is previously pulverized using a pulverizer such as a jet-o-mizer, and the dispersant of the present invention, After blending the aqueous medium and, if necessary, a thickener, an antifreeze agent, etc. in the above-mentioned amounts, the mixture is stirred and mixed using a homogenizer or an atomizer to obtain a uniform suspended biocide composition.

Note that some thickeners may form a "mamato" when directly dissolved in the composition, so they are dissolved in water in advance and added to a thickener aqueous solution premix (concentration is usually 5%).
(preferably 1% or less) and incorporate it into the composition.

The suspended biocide composition of the present invention is diluted by adding it to water to prepare a spray solution for use. The amount of the suspended biocide composition added to water is arbitrary, but is preferably about 0.5 to 20% by weight. The application method of the spray liquid is to spray it on fields etc. in a form depending on the biocide component.

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

Parts in Examples indicate parts by weight.

Examples 1 to 3 and Comparative Examples 1 to 3 Dispersants of the present invention and dispersion stabilizers of comparative examples are shown in Table 1 below, respectively.

Parts in Examples indicate parts by weight.

Table 1 SO: Styrene oxide EO: Ethylene oxide PEG: Polyethylene glycol PPG: Polypropylene glycol Examples 4-8 and Comparative Examples 4-8 Suspended biocide compositions were formulated as shown in Tables 2 and 3. Obtained.

Other dispersants, biocides (B), solvents (C), and preservatives used in Examples 4 to 8 and Comparative Use Examples 4 to 8 are as follows.

Biocide I Carbanyl 2 Atrazine 3 Cabtane 4 Dimethoate and others 1 Polyoxyethylene (9) nonilf dispersant Enyl ether 2 Sodium polystyrene sulfonate 3 Sodium alkylnaphthalene sulfonate Formalin synthesis aqueous medium Water preservative Sodium dehydroacetate Table 2 Units are % by weight (based on the weight of the composition as 100).

table 3 The unit is % by weight (the weight of the composition is 100).

Test Example 1 Physical properties of Examples 4 to 8 and Comparative Use Examples 4 to 8 were evaluated by the following method.

(1) Viscosity of the Composition The suspended biocide composition was measured using a BL viscometer (20°C. No. 3).
Viscosity is measured using a rotor). Lower viscosity is better (unit: centivoise).

(2) Storage stability Appearance of biocidal aqueous emulsion composition at room temperature (1 month after preparation)
Observe. It is preferable that the biocide does not precipitate or form separated precipitates.

(3) Persistence 100ml of 3 degree and 19.2 degree hard water at 20℃ for 300m
Into a beaker, 0.5 g of the hydration preparation prepared in advance by the above method is gently added, and the time until the powder is submerged is measured. The shorter the time, the better.

(4) Self-dispersing 200℃ of 3 degree hard water at 20℃ in a 250ml cylinder with a stopper.
Sample 1 prepared by the above method. Gently add 0g.

The cylinder was left standing and the self-dispersibility was evaluated according to the following evaluation criteria.

4: Immediately disperses without forming secondary aggregates.

3: No secondary agglomerates are formed, but 1 level below the cylinder water surface
It starts to disperse below 72.

2: Forms flocs on the water surface without self-dispersion.

1: Forms secondary aggregates and does not self-disperse.

4 is the best.

(5) Precisely weigh 1.0g of the suspension stability sample into a beaker, and
Add 0+al and mix and disperse well. 250m
1 Transfer to a cylinder with a stopper, add 3 degree hard water at 20°C to make 25 hl, let stand for 15 minutes, shake vigorously 30 times per minute, and let stand for 5 minutes. Next, place a 25ml pipette into the liquid, keep its tip in the center of the liquid, carefully take 25ml of the test liquid, filter it using a glass filter, dry the remaining portion at 105°C for 4 hours, and use the following formula to calculate the suspension rate. seek.

BXIO Suspension rate (X) XIOO A A: Weight of the sample accurately weighed at the beginning B: Dry residue weight of collected test solution The higher the suspension rate (%), the better.

(6) Foaming sample 1. Weigh 0 g accurately in a beaker, add 5 hl of 3 degree hard water at 20°C, and mix and disperse well. 250 liters of it
The mixture was transferred to a cylinder with a stopper, and 3 degrees hard water at 20°C was added thereto to make a total volume of 25 HL.The mixture was allowed to stand for 15 minutes, and then vigorously shaken 30 times per minute, and the foam height (am) was immediately measured. The lower the height of the bubbles, the better.

All evaluation results are shown in Table-4 and Table-5.

Table-4 Table-5 A: 3rd degree hard water B: IO degree indicates hard water.

[Effects of the Invention] The dispersant of the present invention has low viscosity and excellent storage stability. Furthermore, the biocidal aqueous emulsion composition of the present invention has good fluidity despite its high concentration, and is excellent in all aspects of improving the fluidity of biocide suspensions.

Claims (1)

[Claims] 1. General formula Z[(AO)_m(YO)_nH]_p(1) (in the formula,
Z is the residue of a p-valent active hydrogen-containing compound, p is an integer from 1 to 8, A is an alkylene group having 2 to 4 carbon atoms, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ Numerical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ R and R' are hydrogen atoms, alkyl groups, or halogen atoms, R
" is an alkyl group having 3 or more carbon atoms, m is an integer of 1 to 1000, and n is 0 or an integer of 1 to 1000. However, p
At least one of these n is 1 or more, and 3 or more Ys exist in the molecule. ) A dispersant for a suspended biocide consisting of a compound represented by: 2. A biocide suspension composition comprising the dispersant (A), biocide (B), and aqueous medium (C) according to claim 1 as essential components. 3. 0.1-40% of (A) based on the weight of the composition;
The composition according to claim 2, containing 5 to 70% of (B) and 20 to 80% of (C). 4. The composition according to any one of claims 1 to 3, wherein the biocide is selected from the group consisting of herbicides, insecticides, fungicides, and acaricides.