JPS61212326A - Macroparticle emulsion - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel macro atrmlsion containing active compounds from the class comprising phosphates and/or carbamates, a method for the preparation of said macroatrmls, and a method for controlling pests thereof. ).

A large number of aqueous solutions of active compounds of agricultural chemicals are already known. Preparations of this type are made, for example, by dissolving the generally water-insoluble active compound in an amount of an organic solvent and adding a sufficient amount of emulsifier to form a sufficiently stable emulsion when the formulation is diluted with water to the working concentration. It can be produced by adding. However, the presence of solvents often results in concentrates having disadvantages regarding flammability, toxicity, plant tolerance and malodor.

In the case of active compounds of agrochemicals that are not hydrolysed in water at a certain pH value or are insensitive in nature to hydrolysis, organic solvents or mixtures of organic solvents are used in the production of formulations of plant protection agents. It can be completely or at least partially replaced by water. By adding a suitable emulsion, a macroemulsion is obtained, i.e. the oil phase is added to the aqueous phase by 0.1
An oil/water emulsion is obtained which is dispersed in the form of droplets of submicron diameter (see European Patent Publication No. 0.062,1).
No. 81, No. 0, 10th No. 009 and No. 0.107.02
No. 5).

The disadvantage of these macroemulsions is that the active compounds present are generally released very quickly and as a result the toxicity of the preparations is less favorable than in the case of concentrates where large amounts of organic solvent are present. It is often undesirable. Furthermore, macroemulsion concentrates of this type are often stable against phase separation only within a narrow temperature range.

Macroemulsions of active compounds in agricultural chemicals are known, ie oil/water emulsions in which the oil phase is dispersed in the aqueous phase in the form of droplets with an average diameter of 0.5 μm or more. In known macroemulsions, thickeners are added for stabilization (see US Pat. No. 4,303,640). However, due to the thickeners present, the viscosity of these macroemulsions is so high that it is difficult to weigh the preparation and substantial residual amounts of plant protection agent remain in the empty container.

Finally, oil/water emulsions of certain agricultural chemical active compounds which contain 4-vinyl alcohol as a stabilizer in addition to the usual emulsifiers are also known (see European Patent Publication No. 0.111). , No. 580). However, the toxicity of such emulsions with an average droplet size of 1 μm is no more favorable than that of corresponding emulsions in which only polyvinyl alcohol is present as stabilizer. Undesirable irritating effects on the skin and mucous membranes occur in some cases, especially during the application of spray liquids diluted to the working concentration.

This time at least one active compound α001-60 from the class comprising phosphates and/or carbamates
wt%, aromatic diluent 0-50 wt%, average molecular weight s, ooo~150,000 and acetate)
Polyvinyl alcohol α00 to fund t2~50mol
1 to 20% by weight, and/or the formula [wherein, X is an integer of 10 to 50, and Y is 15 to
is an integer of 65] nonylphenol/propylene oxide/ethylene oxide adduct 0.001 to 20% by weight, and/or average molecular weight 2,000 to 8. OOO and HLB value 8~
30 ethylene oxide/f robylene oxide/ethylene oxide block copolymer 0.001 to 20% by weight,
and a new macroemulsion has been discovered, containing water and, if appropriate, additives, in which the oil phase is dispersed in the aqueous phase in the form of droplets with an average particle diameter of 0.1 to 50 μm. .

Furthermore, the macroemulsion according to the invention comprises polyvinyl alcohol from 1 to 25 with an average molecular weight s of ooo to 150,000 and an acetate group content of 2 to 30 mol.
and/or an aqueous solution containing 1 to 30% by weight of a nonylphenol/propylene oxide/ethylene oxide adduct of the formula: and/or an average molecular weight of 2,000 to 8,000 and an HLB value of 8 to 3.
0 ethylene oxide/propylene oxide/ethylene oxide block copolymer 1 to 30 weights! % containing at least one active compound from the class including phosphates and/or carbamates at a temperature of 10 to 30 °C, if appropriate in the presence of an aromatic diluent. and then the resulting emulsion is heated to 10 to 70°C by using suitable equipment, if appropriate after pre-introducing the additives.
It has now been discovered that the emulsifier can be produced by a process in which the emulsifier is homogenized at a temperature of 100 mL, and if appropriate then additives are introduced and the emulsifier is worked up to the desired concentration with water.

Finally, it has been found that the macroemulsions according to the invention are very suitable for controlling pests.

It must be regarded as very surprising that the macroemulsions according to the invention have a less irritating effect on the skin and mucous membranes than corresponding previously known emulsions containing organic solvents and conventional emulsions. . Also surprising is the fact that the formulations according to the invention are stable over a relatively wide temperature range with regard to decomposition of the active compound, crystallization of the active compound and separation.

The macroemulsion according to the invention is characterized by a number of advantages.

That is, they can be prepared in a simple manner by using readily available auxiliaries. Addition of thickeners and emulsifiers is unnecessary. Furthermore, the macroemulsion according to the present invention has a low viscosity and can be weighed without difficulty.

It should also be pointed out that the emulsions according to the invention have advantageous toxicity properties at low and high temperatures, good dispersibility in water and good material stability.

In the macroemulsion according to the invention, one or more insecticide, acaricide and/or nematicide substances from the class comprising phosphates and/or carbamates are present as active ingredients. Suitable active ingredients are both substances that are liquid at room temperature and substances that are solid at room temperature. The following may be mentioned as individual examples of active compounds of this type: O-ethyl 0-(3-methyl-4-methylthiophenyl) inglobilamide phosphate, 0-ethyl S,
S-diphenylzothiophosphate, 0.0-tumethyl 0-(4-methylthio-3-methylphenyl)thionophosphate, O-ethyl S-zorobyl 0-(2,4-sochlorophenyl)thionophosphate, 0.0--/ethyl 0-(4-nitrophenyl)thionophosphate, o-methyl 0-(4-nitrophenyl)thionophosphate, 〇-ethyl 0-(4-methylthiophe=h)S -Globylzothiophosphate, (0,0-diethyl-thionophosphoryl)-α-oximino-phenylacetonitrile, 0.0-diethyl 0-
(3-chloro-4-methyl-7-coumarinyl)thionophosphate, S-1:1.2-bis-(ethoxycarbonyl)-ethyl]01O-tumethyldithiophosphate, 0-ethyl 0-(2-iso propoxycarbonyl-phenyl)-N-inpropylthionophosphoramide, 2-isopropoxyphenyl N-methylcarbamate, 2-ethylthiomethyl-phenyl N-methyl-carbamate, 2,3-dihydro-2,2-tumethyl -7-Benzofuranylmethyl-carbamate, 3.5-tmethyl-(4-methylthiophenyl)N-methylcarbamate.

All customary aromatic solvents or solvent mixtures boiling between 100 and 290° C. can be present in the macroemulsions according to the invention. Toluene, ethylbenzene, chlorobenzene, xylene, alkylated benzenes having an average number of carbon atoms of 9, e.g. the solvent species known under the name of Tsurpetz (5oL-νeaao), and naphthalene optionally substituted with alkyl having 1 to 3 carbon atoms. suitable.

The macroemulsion according to the invention may be made of polyvinyl alcohol of the above-mentioned type, or a nonylphenol/propylene oxide/ethylene oxide adduct of the formula (■), or an ethylene oxide/globylene oxide/ethylene oxide block copolymer of the above-mentioned type, or of the above-mentioned components. Contains one or more mixtures.

The preferred polyvinyl alcohol has an average molecular weight of 20,000
~125,000 and an acetate group content of 2 to 30 moles.

The following may be mentioned as examples of polyvinyl alcohols of this type: Average molecular weight 47. Polyvinyl alcohol with OOO and acetate group content 12 mol, average molecular weight 99,000
and polyvinyl alcohol with an acetate group content of 12 mol, average molecular weight 81.000 and an acetate group content of 12
Polyvinyl alcohol in moles, average molecular weight 25,00
0 and acetate group content 12 mol, average molecular weight 82,000 and acetate group content 1
7 mol of 4-rivinyl alcohol, average molecular weight 85,0
Vinyl alcohol with an average molecular weight of 2000 and an acetate group content of 23 mm, an average molecular weight of 2000 and an acetate group content of 2
9 moles of polyvinyl alcohol, and an average molecular weight of 75
,000 and an acetate group content of 4 mol.

In each case, the acetate group content is a measure of the degree of hydrolysis of the polyvinyl alcohol made from polyvinyl acetate.

A preferred nonylphenol/propylene oxide/ethylene oxide adduct is one in which X represents an integer of 20 to 45 and 1
A compound of formula (I) in which Y represents an integer of 20 to 60.

Suitable ethylene oxide/propylene oxide/ethylene oxide block copolymers have an average molecular weight of 2,500 to
S000 and HLB value (=hydrophilic-lipophilic balance) 9~
There are 27 such compounds.

The HLB value is a measure of the hydrophilicity or lipophilicity of the substance used.

Suitable additives that may be present in the macroemulsifier of the invention are:
dyes, preservatives, antifoaming agents, antifreeze agents, crystallization inhibitors, odor improvers and acids.

In this connection, anthraquinone dyes, azo dyes and polyphthalocyanine dyes may be mentioned as examples of dyes.

2-hydroxybiphenyl, norbic acid, '7'-hydroxybenzaldehyde, methyl p-hydroxybenzoate, benzaldehyde, benzoic acid, propyl p-
Hydroxybenzoate, p-nitrophenol and the preservatives commercially available under the trade names Priventol CP degva-ntol (2) and Ditruxmin (2) may be mentioned as examples of preservatives.

A suitable antifoam agent is silicone oil.

Glycols, glycerol, urea, sugars and polyethylene glycols may be mentioned as examples of antifreeze agents. Examples of crystallization inhibitors i. Alkylphenols condensed with 1 to 8 moles of ethylene oxide and 1 mole. In this connection, nonylphenol condensed with 2 mol 1 mol of ethylene oxide may be particularly mentioned.

Aromatic oils can be used as odor modifiers.

Examples of acids which can be present as additives in the macroemulsifiers according to the invention are inorganic and organic acids such as phosphoric acid, citric acid and benzoic acid.

The macroemulsion according to the invention contains water as a continuous phase. In the case of concentrates, the amount of water is relatively small. In highly dilute emulsions, substantial amounts of water are present.

In the case of the macroemulsions according to the invention, the oil phase (=dispersed phase) is dispersed in the form of droplets in the aqueous phase. The size of this oil droplet can vary within certain limits.

In general, the average particle diameter is α1-5.0 μm, preferably 0.2-2.5 μm.

In the macroemulsions according to the invention, the percentages of the components present can vary within a relatively wide range. The amount of active compound from the class comprising phosphates and carbamates is generally from 0.001 to 60% by weight, preferably from 0.01 to 50% by weight. The amount of aromatic diluent is generally from 0 to 50% by weight, preferably from 0 to 40% by weight.

When polyvinyl alcohol is present, the amount of this component generally ranges from 0.001 to 20%, preferably from Q.
It is 15% by weight. If the nonylphenol/propylene oxide/ethylene oxide adduct of formula (I) is present, the amount of this component is generally from 0.001 to 20% by weight, preferably from 0.01 to 10% by weight. If the polyethylene oxide/propylene oxide/ethylene oxide block copolymer is present, the amount of this component will generally be 0.00
It is 1 to 20% by weight, preferably 0.01 to 10% by weight. Additives are 01-20% by weight, preferably 02-15%
May be present in amounts by weight.

The percentage of water in the macroemulsions according to the invention is in each case the difference between 100% by weight and the total weight of the remaining components.

In the preparation of the macroemulsions according to the invention, it is preferred to use all the components already mentioned as preferred or by way of example in connection with the description of the macroemulsions according to the invention.

If an active compound which is liquid at room temperature is used in the process of the invention, this active compound is generally used in that state. However, it is also possible to use solutions of particularly active compounds in aromatic diluents.

If an active compound which is solid at room temperature is used in the process of the invention, a solution of this substance in an aromatic diluent is used.

,/IJ When carrying out the process of the invention using vinyl alcohol, this component is used in the form of an aqueous solution.

The concentration of this solution can vary within certain limits. Generally, an aqueous solution containing 1 to 25% by weight X1, preferably 2 to 20% by weight of polyvinyl alcohol is used.

Nonylphenol of formula (I)/7'ropylene oxide/
When carrying out the process according to the invention with ethylene oxide adducts, this component is used in the form of an aqueous solution. The concentration of this solution can vary within a range. In general, the formula (
The nonylphenol/propylene oxide/ethylene oxide adduct of I) is used in an aqueous solution of 1 to 30% by weight, 5 to 25% by weight.

When carrying out the process of the invention using ethylene oxide/propylene oxide/ethylene oxide block copolymers, this component is used in the form of an aqueous solution. The concentration of this solution can vary within certain limits. Generally 1 to 30% by weight of block copolymer, preferably 5 to 25% by weight
An aqueous solution containing .

In the first step of the process of the invention, a preliminary emulsion is produced, which is then homogenized in the second step.

In the first and second stages of the process according to the invention, the reaction temperature can be varied within certain limits. The first stage is generally carried out at a temperature of 10-30°C, preferably 15-25°C. The second stage is generally 10-70°C, preferably 1
It is carried out at a temperature of 5-65°C.

The homogenization in the second stage of the process of the invention is preferably carried out using a high-pressure homogenizer or a jet diffuser with a pressure drop across the dispersing nozzle of 10 to 50 bar.
et disparstr). Jet dispersers of this type are already known (see European Patent Publication No. 101,007).

When carrying out the process of the invention, the method used is generally as follows: in a first step, a solution of one or more liquid active compounds or solid and/or liquid active compounds is first prepared in an aromatic diluent. and/or an aqueous polyvinyl alcohol solution and/or an aqueous solution of a nonylphenol/propylene oxide/ethylene oxide adduct of formula (■) and/or an ethylene oxide/propylene oxide/
The aqueous solution of the ethylene oxide block copolymer and, if appropriate, additives are added with stirring at a temperature of 10 to 30°C, and then in a second stage the pre-emulsion obtained is heated to 10 to 70°C using suitable equipment. Homogenization is carried out at a temperature of 0.degree. C. and, if appropriate, then additives are introduced and the emulsion is brought to the desired consistency with water.

The amounts of each component are selected such that the macroemulsion contains each component in concentrations within the ranges described above.

The macroemulsion according to the invention has very good insecticidal, acaricidal and/or nematocidal properties. It can therefore be used in agriculture, in horticulture, in the household and hygiene sector and in the veterinary sector for combating suitable animal pests such as insects, mites and/or nematodes.

The macroemulsifiers according to the invention can be applied in prepared form or after predilution. The amount used depends on the concentration of active compound in the formulation and on the intended use.

The macroemulsions according to the invention can be prepared in the usual manner, eg by spraying, atomizing, if appropriate after dilution beforehand.
omtsing) and spraying (water fLy)K
Therefore, it is applied.

The following example illustrates a method for making a macroemulsion according to the invention.

Preparation Examples Example 1 A solution of 6 parts by weight of an ethylene oxide/propylene oxide/ethylene oxide block copolymer with an average molecular weight of 6500 and an HLE value of 15.0 in 59 parts of demineralized water was
It was added to 25 parts by weight of o-dimethyl 0-('5-methyl-4-methylthiophenyl)thiophosphate at room temperature with gentle stirring. The pre-emulsion obtained was homogenized at 20° C. using a jet disperser with a pressure drop of 40 bar across the dispersion nozzle. Next, 10 parts by weight of glycerol was added, and stirring was continued for an additional 5 minutes. A macroemulsion was thus produced in which the oil phase was dispersed in the aqueous phase in the form of droplets with an average particle diameter of 1 μm.

The resulting macroemulsion remained stable even after storage in a thermal cycling chamber at temperatures between -15° and +30°C and for 8 weeks at +50°C.

Example 2 A solution of 6 parts by weight of an ethylene oxide/propylene oxide/ethylene oxide block copolymer having an average molecular weight of 3000 and an HLB value of 15.0 in 49 parts of demineralized water was
A solution of 825 parts by weight of ethyl 〇-(3-methyl-4-methylthiophenyl)isoprobylamide-phosphate in 20 parts by weight of an aromatic solvent known under the trade name Tsurupez 100 is added at room temperature with gentle stirring. Added. The pre-emulsion obtained was homogenized at 50 DEG C. using a jet disperser with a pressure drop of 40 bar over the dispersion nozzle. Next, 10 parts by weight of glycerol was added, and stirring was continued for an additional 5 minutes. A macroemulsion was thus produced in which the oil phase was dispersed in the aqueous phase in the form of droplets with an average particle diameter of 1 μm.

The resulting macroemulsion remained stable even after storage in a thermal cycling chamber at temperatures between -15° and +30°C and for 8 weeks at +50°C.

Example 3 Approximate Formula % Formula % 2.4 parts by weight of ren oxide adduct, 45.6 parts by weight of demineralized water
The solution in parts by weight was converted into
parts by weight at room temperature with gentle stirring. The pre-emulsion obtained was homogenized at 50 DEG C. using a jet disperser with a pressure drop of 40 bar per dispersing nozzle. Then 10 parts by weight of glycerol and 1 part of demineralized water
94 parts by weight were added and stirring was continued for an additional 5 minutes. A macroemulsion was thus produced in which the oil phase was dispersed in the aqueous phase in the form of droplets with an average particle diameter of 1 μm.

The resulting macroemulsion was stable 11 even after storage for 8 weeks in a thermal cycling chamber at temperatures between -15° and +30°C and at +50°C.

Claims (1)

Claims: 1. At least one active compound from the class comprising phosphates and/or carbamates from 0.001 to 60%
% by weight, aromatic diluent 0-50% by weight, polyvinyl alcohol with average molecular weight 5,000-150,000 and acetate group content 2-30 mol% 0.00
1 to 20% by weight, and/or formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) [In the formula, X is an integer of 10 to 50, and Y is 15 to
an integer of 65] 0.001 to 20% by weight of a nonylphenol/propylene oxide/ethylene oxide adduct, and/or an average molecular weight of 2,000 to 8,000 and an HLB value of 8 to 3
0.001 to 20% by weight of ethylene oxide/propylene oxide/ethylene oxide block copolymer of macroemulsion, which is dispersed in the form of droplets. Macroemulsion according to claim 1, wherein 2,O,O-dimethyl O-(3-methyl-4-methylthiophenyl)thiophosphate is present as active compound from the phosphate-comprising class. 3. O-ethyl O-(3-methyl-4-methylthio-phenyl)isopropylamide phosphate is present as an active compound from the phosphate-comprising class;
A macroemulsion according to claim 1. 4, O-ethyl O-(2,4-dichlorophenyl)S-
Macroemulsion according to claim 1, wherein n-propyldithiophosphate is present as the active compound from the class comprising phosphates. 5. Toluene, ethylbenzene, chlorobenzene, xylene, alkylated benzene having an average carbon number of 9 and/or naphthalene optionally substituted with an alkyl having 1 to 3 carbon atoms are present as aromatic diluents. Macro emulsion according to item 1. 6. Polyvinyl alcohol with an average molecular weight of 20,000-125,000 and an acetate group content of 2-30 moles
．． 01 to 15% by weight, and/or nonylphenol/propylene oxide adduct 0.01 of formula (I), where X represents an integer of 20 to 45, and Y represents an integer of 20 to 60.
~10% by weight, and/or average molecular weight 2,500-7,000 and HLB value 9-2
The macroemulsion according to claim 1, containing 0.01 to 10% by weight of the ethylene oxide/propylene oxide/ethylene oxide crock copolymer of No. 7. 7. Dyes, preservatives, antifoaming agents, antifreeze agents, anticrystallization agents,
The macroemulsifier according to claim 1, wherein an odor improver and/or an acid are present as additives. 8. Macroemulsifier according to claim 1, wherein the oil phase is dispersed in the aqueous phase in the form of droplets with an average particle diameter of 0.2 to 2.5 μm. 9. Polyvinyl alcohol 1 to 1 with an average molecular weight of 5,000 to 150,000 and an acetate group content of 2 to 30 mol%
An aqueous solution containing 25% by weight, and/or a formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) [In the formula, X represents an integer from 10 to 50, and Y represents an integer from 15 to 65] an aqueous solution containing 1 to 30% by weight of a nonylphenol/propylene oxide/ethylene oxide adduct of
an aqueous solution containing 1 to 30% by weight of ethylene oxide/propylene oxide/ethylene oxide clock copolymer containing phosphate and/or carbamate at a temperature of 10 to 30°C, if appropriate in the presence of an aromatic diluent. at least one active compound from the following types, with stirring, and the emulsion obtained, if appropriate, after pre-introduction of additives, by using suitable equipment. ℃
A method for producing a macroemulsion, which comprises homogenizing the macroemulsion at a temperature of , and if appropriate then introducing additives and working up the emulsifier to the desired concentration with water. 10. Use of the macroemulsion according to claim 1 for controlling pests.