SK109096A3 - Emulsifier compositions - Google Patents

Abstract

Emulsifier compositions include surfactant vic-dicarboxylic acid polyalkyleneoxy half ester derivative of the formula (I) Y.A<1>.OC.(HR)C.C(HR<1>).CO.A.(CmH2mO)n.R<2> or (II) Y.A.<1>.OC.(HR)C.C(HR<1>).CO.A.(CmH2mO)n.CpH2p.A.CO.(HR<1>)C.C(HR)CO.A<1>.Y, where the substituents have defined meanings, and at least one other surfactant are effective in emulsifying materials such as agrochemicals to give stable emulsions. The emulsifier can also be formed as a concentrate that can contain a specifically effective chemical and typically an organic liquid or solvent so that the concentrate forms an emulsion directly on dilution with water.

Description

Technical field

The invention relates to emulsifier compositions, in particular compositions comprising a plurality of surfactants, further to emulsifiable concentrates which are readily emulsifiable in water and comprising an emulsifier composition, in particular a concentrate having a high chemical reagent content with an activity specific for the intended use of the concentrate. compositions containing the concentrate, and methods for preparing or using the emulsifying compositions, concentrates, and dilute compositions containing the composition.

BACKGROUND OF THE INVENTION

Emulsifier compositions containing a plurality of surfactants are generally known in the agrochemical industry. These can be used to prepare concentrates containing a chemical agent with an activity specific to the intended use of the concentrate, and these concentrates are easily emulsifiable upon conversion to a diluted formulation. However, the efficacy of such emulsifier compositions as emulsifiers and the extent to which the resulting compositions can be readily emulsified in water to dilute formulations are usually limited to a specific combination of a dispersible chemical agent and readily emulsifiable surfactants.

A group of polyalkylene oxypoloesters of vic-dicarboxylic acids has been developed, as described in PCT Publication No. WO 94/00508 A (PCT / GB 93/01335). The present invention relates to the use of compounds of formulas I or II as set out below:

YA ¹ OC (HR) CC (HR ¹ ) COCO. (C 1 H ³ O ³ ) R ³ (I) wherein one of R 1 and R ¹ is alkenyl or alkyl of 6 to 22 carbon atoms and the other is hydrogen,

A is -O- or -NR * -, wherein R ^-4 is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, especially methyl or ethyl, n is 2 to 100 (and may not be an integer on average), m is 2 or 3 (and may vary according to the polyoxyalkylene chain),

R ² is H or alkyl of 1 to 16, particularly 1 to 6 carbon atoms,

A ^x is -O-, -O or -NR ⁴ -, wherein R * is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, especially methyl or ethyl, and when A ¹ is -O ", Y is a cation, especially H *, and an alkali metal cation, in particular a sodium or potassium cation, or an ammonium ion (especially NH ₄ * _{from an} ammonium ion of an amine or an ammonium ion of an alkanolamine), and if A ¹ is -O- or -NR *, then Y is an alkyl group of 1 to 6 carbon atoms (R ³⁾ or a group of formula (CH 0), R ^2, wherein m, n and R ² are independently as defined above, or

YA ^X .OC. (HR) CC (HR ¹⁾ .co.il. (C ^ H ^ O) ^ H ^ .C .A.CO. (HR ^and -) CC (HR) CO.A ¹ .Y (II) wherein n, m and all substituents R, R ¹ , A, A ¹ and Y are independently as defined above, and p is 2 or 3.

As described in WO 94/00508, the compounds of formulas I and II in the free acid form are defined such that Y is an H * cation, including the ionized and non-ionized forms of the free acids. The compounds of formulas Ia and II are typical mixtures of isomers corresponding to the two explanations of the anhydride ring opening reaction used for their synthesis. It is believed that the alk (en) yl chain has less steric effect on the ratio of isomers (usually about 60:40), the major isomer being formed by nucleophilic attack on the anhydride carbonyl group distant from the alk (en) yl group. Thus, in particular, compounds of formulas I and II include compounds of formulas Ia and IIa:

R ¹ -CH (CO-AY) -CH ₂ CO.AZ (1a) wherein

Z is of the formula (CHO) ^R2, wherein n '', it mma 2 m ^and R are as described for formula I above, wherein n is preferably 3 to 50,

R ³ is hydrogen or C 1 -C 16 alkyl and preferably C 1 -C 6 alkyl,

A and A ¹ are independently -O-, -O "or -NH-, wherein when A or A ^x is -O", then Y is a cation, for example H * or an alkali metal cation, and when A or A ^x is -O- or -NH-, then Y is R ² or (CHO) R ^a , where R ^a is as defined above and may be the same or different from Z,

R ^x is an alkyl or alkenyl group each having from 6 to 22 and preferably from 13 to 20 carbon atoms, or

R ¹ -CH (COA ¹ Y) -CH _and -CO.ADA.OC-CH _and -CH (COA ¹ Y) -R ¹ (Ha) where

D is a group of the formula wherein p is or 3, a

R ¹ , A, A ¹ , m and n are as defined above for formula Ia.

WO 94/00508 discloses various uses of these compounds, including use as emulsifiers for invert polymerization of acrylamide and as wool scouring agents. It has now been found that these compounds can be used in multi-surfactant emulsifier compositions which can be used in the preparation of concentrates containing a chemical with an activity specific for the intended use of the concentrate, these concentrates being easily emulsifiable in water. These emulsions are generally applicable in the agrochemical industry, for example in preparations which contain a chemical known in the agrochemical industry and have the appropriate effect and can be used to control weeds, fungi or insects.

SUMMARY OF THE INVENTION

According to a first embodiment, the emulsifier composition comprises

(a) at least one polyalkylene oxypoloester of a vicidicarboxylic acid polyalkylene oxypoloester of the general formula I or II as mentioned above, and

b) at least one additional surfactant.

A particularly suitable emulsifier composition according to the first embodiment comprises

(a) at least one compound of the formula I or II as above, in an amount of from 5 to 90% by weight, based on the total composition, preferably from 10 to 75% by weight, and

b) at least one additional surfactant in an amount of from 10 to 90% by weight, preferably 10 to 70% by weight, based on the total composition.

The composition may be balanced with a water-miscible liquid and / or a water-immiscible, for example, organic, liquid. This may be required if the viscosity of the composition is otherwise unsuitably high. The components and their ratios are preferably selected such that, if some components are readily available only as aqueous solutions, the composition obtained by mixing the components is unstable, apart from the introduction of water into it.

The composition often comprises a semi-ester containing anionic groups and / or in particular anion-ionizable groups. Such preferred ester derivatives are generally described in WO 94/00508, but preferred surfactants of this type include the mono- and di-esters of formulas I or II, in which the alk (en) yl substituent on the succinyl moiety preferably has 8. up to 20 carbon atoms. This is particularly the case in the agrochemical industry in the preparation of emulsifiable concentrates containing a chemical with an activity specific for the intended use of the concentrate. Ester derivatives of this type include, in particular, those compounds in which the alk (en) yl substituent has 10 to 17 carbon atoms, preferably 12 to 14 carbon atoms, and in particular those in which the substituent is an alkenyl group. Such preferred polyalkylene polyol esters of vic-dicarboxylic acids also include those compounds wherein Z (in general formula Ia) is an alkylene oxide (block) (co) polymer of formula (CHO) R ³ as defined above, wherein n is preferably 7 to 13 and m are 2 and / or 3. As described in WO 94/00508, alk (en) yl groups in surfactants of the formulas

I or II used according to the invention are suitably linear alk (en) yl groups.

Other surfactants used may be those which, when used as an emulsifier composition in the preparation of a concentrate containing a chemical with an activity specific for the intended use, provide a concentrate which:

(a) is stable and homogeneous for at least 24 hours after mixing; and

(b) remains homogeneous when diluted with water to the diluted preparation.

Other surfactants suitable for their stability in use and storage of the concentrate may be anionic, cationic, amphoteric or nonionic surfactants or mixtures thereof. Suitable anionic surfactants are alkarene sulfonate salts, such as straight chained or branched chain alkylbenzene sulfonate salts, for example, wherein the alkyl is lauryl (dodecyl), or mixtures thereof, and selected from the group consisting of poly (alkoxylated) salts. arylaryl) phosphates or sulphates, substances selected from the group consisting of alkaryl phosphates or sulphates, substances selected from the group consisting of straight or branched chain alkyl or alkoxyalkylphosphates or sulphates, substances selected from the group consisting of salts of C 8 to C 24 fatty acids, preferably 12 up to 18 carbon atoms, for example laurates, heptadecanoates, heptadecenoates, stearates and oleate, and substances selected from the group consisting of salts of alkoxylated and carboxylated alkaryl alcohols and fatty alcohols, the latter being, for example, methyl carboxylates of poly (ethylene oxide) alcohols of 12 to 15 at carbon atoms. Examples of suitable salts include salts with an alkali metal cation such as sodium or potassium, alkaline earth metal salts such as calcium, and salts with an ammonium, aliphatic ammonium and alkanolammonium, wherein the aliphatic or alkanol moiety is e.g. up to 4 carbon atoms that are straight or branched.

When the composition is used primarily for agrochemical purposes to prepare an emulsifiable concentrate containing an agrochemical with a specific effect for the desired concentrate applications, the preferred component b) is an anionic surfactant selected from the group consisting of C1 -C16 alkylbenzene sulfonate salts in straight or branched chain alkyl. chains, for example, wherein the alkyl is lauryl. A preferred salt is a calcium salt.

Suitable cationic surfactants include salts of alkoxylated fatty amines containing from 8 to 24, preferably more than 12 carbon atoms and in particular from 12 to 18 carbon atoms, the latter including, for example, poly (ethylene oxide) alkyl ammonium salts of 12 to 15 carbon atoms, for example chlorides .

Nonionic surfactants can be used, in particular, in concentrates which are readily emulsifiable, especially in agrochemical concentrates. They are nonionic surfactants used in the agrochemical industry for the preparation of emulsifiable preparations, in particular compounds of the general formulas

R ³¹ .O (X) R ³³ and / or R ^a3 N _{(H), and} wherein

R ³¹ is an alkyl or alkenyl group having up to 24, preferably 6 to 21, and in particular 9 to 18, carbon atoms, an alkylphenol group having 6 to 12 carbon atoms in the alkyl moiety, a sorbityl group or a group of formula R ³⁴ CO wherein R ³⁴ is an alkyl group having 11 to 22 carbon atoms,

R ³³ is a hydrogen atom or an alkyl group, a carboxyl group, for example a C 2 -C 4 carboxyl group, or a C 10 to C 10 fatty acid residue,

X is a polyalkylene oxide group containing on average 2 to 40, preferably 2 to 13, and in particular from 2 to 10 alkylene oxide or mixed alkylene oxide groups, and

R ²³ is an alkyl or alkenyl group containing from 10 to 22 carbon atoms.

Examples of suitable R ²¹ groups are, for example, sorbityl and lauryl, heptadecyl, heptadecenyl, heptadecadienyl, stearyl and oleyl. Examples of suitable R ²² groups are, for example, carboxymethyl, carboxyethyl or carboxypropyl or salts thereof, and laurate, heptadecanoate, heptadecenoate, heptadecadienoate, stearate or oleate. Examples of suitable X groups are poly (homoalkylene or mixed alkylene oxide) groups wherein the alkylene groups each have 2 to 8, preferably 2 to 4, for example 2 or 3, carbon atoms and when R ²¹ is sorbitol and R ²² is a fatty acid moiety containing 10 up to 22 carbon atoms, X is a direct bond.

Examples of suitable nonionic surfactants include poly (alkoxylated) fatty acids and alcohols containing 8 to 24, preferably 12 to 18, carbon atoms in the fatty acid or alcohol moiety, and poly (alkoxylated) alkaryl alcohols containing 8 to 24, s. preferably 12 to 18, carbon atoms, further poly (alkoxylated) sorbityl and sorbitol esters, poly (alkoxylated) triglycerides, including, for example, poly (alkoxylated) vegetable oils such as poly (ethoxylated rope oil, mustard oil, non-oil, oiticic oil, palm oil, palm kernel oil, peanut oil, pearl oil, poppy oil, safflower oil, sesame oil or (in particular) soybean oil, poly (alkoxylated) allyl alcohols, poly (alkoxylated poly (arylaryl) alcohols, and polyalkylene oxides, including (block) (co) polymers, especially those in which the alkylene groups each have 2 to 4 carbon atoms and sor 9 bityl esters of up to 30 carbon atoms a medicament such as sorbityl monooleate.

In emulsifier compositions according to the first embodiment of the invention, in particular used for formulations used for agrochemical purposes, component b) (at least one other surfactant) is

1) at least one nonionic surfactant and optionally

2) at least one anionic surfactant.

A preferred nonionic surfactant as component b) comprises compounds of the general formulas

R ^{aa and} O (X) R ^aa and / or R ^a3 -N- (XH) _and as defined above as preferred nonionic surfactants.

A preferred surfactant as component b) includes salts of C 6 -C 16 alkylbenzene sulfonates in a straight or branched alkyl chain, for example wherein the alkyl is lauryl. Calcium salts are preferred.

Preferred emulsifier compositions according to the first embodiment of the invention comprise

(a) at least one polyalkylene oxypoloester of vic-dicarboxylic acid in an amount of from 5 to 90% by weight, based on the total concentrate, preferably from 10 to 75% by weight, and

b) 1) at least one non-ionic surfactant in an amount of from 10 to 90% by weight, based on the total, preferably from 10 to 50% by weight, for example from 10 to 40% by weight, in particular from 10 to 35% by weight;

2) optionally at least one anionic surfactant in an amount of from 0 to 60% by weight, based on the total composition, preferably from 0 to 40% by weight, for example from 15 to 40% by weight, in particular from 25 to 40% by weight, based on the total .

One group of emulsifier compositions are compositions comprising at least one anionic surfactant in an amount of 15 to 40% by weight, in particular 25 to 40% by weight, of the composition. Another group consists of compositions which do not contain an anionic surfactant. Examples of water-miscible liquids that can balance the composition and which are required when the viscosity of the composition is unsuitably high include alcohols, including glycols, for example, straight or branched (C 1 -C 8) alkyl chain such as isobutanol and propylene glycol. This liquid can often contain water which is thereby introduced into the composition and can be present in an amount of up to 3% by weight, based on the total composition.

Examples of water-immiscible liquids that can balance the composition and are required when the viscosity of the composition is unsuitably high include hydrocarbons, preferably those containing 5 to 18 carbon atoms, including aromatic hydrocarbons, straight-chain or straight-chain alcohols. branched chain, optionally hydrogenated vegetable oils such as optionally hydrogenated cottonseed oil, rope oil, mustard oil, neem oil, oitic oil, olive oil, palm oil, palm kernel oil, peanut oil, pearl oil, poppy oil, rapeseed oil, safflower oil oil, sesame oil or soybean oil; esters (especially C 1 -C 6 esters) of C 8 -C 22 fatty acids, especially C 12 -C 18 fatty acids, for example selected from the group consisting of methyl laurate, heptadecanoate, heptadecenoate, heptadecadienoate, stearate or oleate, especially methyl llaurate and methyl oleate; N-methylpyrrolidone and isoparaffins or mixtures thereof. Such a preferred liquid is xylene, any mixture of aromatic hydrocarbons and N-methylpyrrolidone.

According to a second embodiment, the emulsifiable concentrate comprises an emulsifier composition according to the first embodiment of the invention, and

(c) at least one chemical with efficacy according to the intended use of the concentrate.

Such a chemical may be, for example, an agrochemical or a metal corrosion inhibitor.

One or more phytoactive substances, for example plant growth regulators or herbicides, and / or pesticides, for example insecticides, fungicides or acaricides, may be present as agrochemicals. These concentrates may contain another chemical to form a concentrate in which the efficacy of the first chemical is much more specific or selective in the intended use of the concentrate or the corresponding diluted formulation. These concentrates generally include, for example, concentrates in which the first chemical is a substance with one or more phytoactivities, for example plant growth regulators or herbicides and / or pesticides, for example insecticides, fungicides or acaricides, and another is a phytotoxicity inhibitor for regulating phytoactivity, for example growth or herbicidal efficacy of the concentrate or the corresponding diluted formulation, or, for example, Safener (a phytotoxicity inhibitor), so that the formulation is more selective, for example, in grass and broadleaf weeds. This chemical may be present in an amount of up to 15% by weight based on the total weight of the concentrate.

Preferred are high chemical concentrates having activity specific and appropriate to the intended use of the composition. These form dispersions of specific chemicals, such as the herbicides Acetochlor and Alachlor, but also pesticides, such as insecticides, fungicides or acaricides, which are known in the agrochemical industry and these dispersions are not readily emulsifiable.

Preferred emulsifiable concentrates according to the first embodiment of the invention comprise

(a) at least one polyalkylene oxypoloester of vic-dicarboxylic acid in an amount of from 0.5 to 15% by weight based on the total concentrate, preferably from 0.15 to 10% by weight, and

(b) at least one additional surfactant in an amount of from 1 to 25% by weight of the total; and

c) at least one chemical specific for the intended use of the concentrate in an amount of from 2.5 to 95% by weight, based on the total, preferably from 10 to 50% by weight.

The water-miscible liquid and / or the water-insoluble organic solvent has a greater share in the concentration of the concentrate, thereby dissolving the chemical with an activity specific to the intended use of the concentrate or the corresponding diluted preparation. This may also be required if the viscosity of the concentrate is unsuitably high. The concentrate, especially after use as a formulation for agrochemical application, may contain one or more of such liquids and / or solvents in an amount of from 0 to 97% by weight, and in particular from 5 to 90% by weight, based on the total concentrate. In some uses of the concentrate, for example when applied to a formulation of some of the growth regulators, herbicides, insecticides, fungicides or acaricides, it is preferred that the concentrate contains a significant amount of water, for example more than 25% by weight, based on the total. These concentrates are in fact concentrated emulsions that can be further emulsified by dilution with water to form preparations for application to, for example, agricultural crops. The components and their proportions are preferably chosen such that the concentrates formed by mixing the components are stable, irrespective of the water introduced therein. If the concentrate is a concentrated emulsion suitable for use in agriculture, for example, in the preparation of crop treatment products, the composition of an emulsifiable concentrate is as follows:

(a) at least one polyalkylene oxypoloester of vic-dicarboxylic acid in an amount of from 0.1 to 15% by weight, preferably from 0.2 to 10% by weight, based on the total concentrate, and

(b) at least one non-ionic surfactant in an amount of from 1 to 25% by weight, based on the total emulsifiable concentrate; and

(c) no anionic surfactant.

Each of these concentrates

(a) form a dispersion of specific chemicals, such as the herbicides Acetochlor and Alachlor, but also pesticides, such as insecticides, fungicides or acaricides, which are known not to be readily emulsifiable by known surfactants;

b) remains homogeneous in dilution with water in the preparation of the diluted formulation of the invention for application of the ingredient

(c) concentrate, without the need to add additional substances to disperse the phase and prevent phase deposition from the diluted concentrate;

(c) exhibits excellent wetting properties in relation to the dispersed chemical in the concentrate and in particular in relation to the substrate to be treated.

Preferred compositions of the present invention, particularly when used for concentrates and formulations of agrochemicals, may also have a high content of chemicals relative to component a) above, for example herbicides such as Acetochlor and Alachlor. Suitable and preferred polyalkylene oxypolo esters of vicidicarboxylic acids and other surfactants in the concentrate are generally those described herein for emulsifier compositions according to the first embodiment of the invention.

Examples of suitable water-miscible liquids include alcohols, including glycols, for example, straight or branched chain alkyl having 1 to 8 carbon atoms. Isobutanol and propylene glycol are preferred. These liquids can often contain water.

Examples of water-insoluble organic solvents which contribute to the concentration of the concentrate include hydrocarbons, preferably having 5 to 18 carbon atoms, including aromatic hydrocarbons, straight or branched chain alcohols, optionally hydrogenated vegetable oils such as optionally hydrogenated cottonseed oil, rope oil, mustard oil, neem oil, oitic oil, olive oil, palm oil, palm kernel oil, peanut oil, pearl oil, poppy oil, rapeseed oil, safflower oil, sesame oil or soybean oil, esters (especially esters of 1 to 1) Selected from the group consisting of methyl laurate, heptadecanoate, heptadecenoate, heptadecadienoate, stearate or oleate, especially methyllaurate and oleate, N-methylpyrrolidone and isoparafines or mixtures thereof. Preferred solvents are, for example, xylene, mixtures of aromatic hydrocarbons and N-methylpyrrolidone.

An antifoaming agent may also be present. Sufficient amounts of this agent need to be used to provide an antifoaming effect for the intended use of the concentrate, but without separating the agent from the composition. Usually 0.05 to 10%, preferably 0.2 to 6% by weight, based on the total, is used. Any compound commonly used as an antifoaming agent in aqueous preparations with a high dispersed phase content may be used. One or more polysiloxanes, preferably containing hydrophilic groups, are preferably used as antifoams. They are preferably compounds of the general formula

R * ₃ SiO [SiOR * R **] _n SiR * ₃ wherein R * are individually alkyl groups, preferably 1 to 3 carbon atoms and most preferably methyl groups, one or more R ** groups may be polyalkylene glycol residues and others have the meaning given for R *.

The R * groups preferably have a molecular weight ranging from 1,000 to 20,000, and in particular from 5,000 to 15,000. Examples of suitable polysiloxane antifoams are described in British Patent Specifications 1,533,610 and 1,554,736.

Other possible additives to the emulsifiable concentrates of the invention include non-surfactants commonly used in surfactants, such as viscosity modifiers, stabilizers, and antimicrobial agents. One group of known viscosity modifiers of this type are one or more commercially available water-soluble or water-miscible substances such as gums, for example xanthan gums, and celluloses, for example carboxymethylcellulose, carboxyethylcellulose or carboxypropylcellulose. These substances are often present, for example, in agrochemical formulations, in particular in an amount of from 0.01 to 1% by weight, based on the total concentrate.

The emulsifier concentrates described may have a pH in the range, for example, from 5 (acidic) to 9 (alkaline), such as from 6 to 8.

The emulsifiable concentrates of the invention may be prepared by conventional mixing of the individual components.

According to a third embodiment, the invention consists in a process for the preparation of this concentrate by mixing the ingredients together. This can be achieved, for example, by mixing components a),

b) and c) and any other components, for example solvents and / or other additives, and mixing until a homogeneous product is obtained.

For the emulsifiable concentrates of the invention that are concentrated emulsions, it may be necessary to mix the ingredients in a particular order. These emulsifiable concentrates may be prepared by separate conventional mixing

(a) liquid carriers; and

(b) components (a), (b) and (c) and other possible components, to form two separate liquid phases, with stirring being continued until each product is homogeneous.

The concentrate is prepared by carefully dispersing the phase containing components a), b) and c) into a second phase. It may therefore be required that the addition of the phases be carried out at a slightly elevated temperature using high shear mixing when the viscosity of the concentrate is unsuitably high. The concentrated emulsion is then allowed to cool to room temperature.

In most applications, the surfactant concentrates of the second embodiment of the invention are used in their (more concentrated) form and are converted to more dilute forms only when used. Good storage stability of the more concentrated form is still required while it is used to prepare the more dilute form in use. According to a fourth embodiment of the invention, a composition is prepared which is a mixture of components a), b) and c) of a concentrate according to the second embodiment of the invention with 10 to 10,000 times the amount of water, based on the total weight of components a), with 30 to 1000 times the amount. The formulation according to the fourth embodiment of the invention may, of course, contain other ingredients and additives. These suitable and preferred components and additives have been described above and are, for example, solvents and antifoams which may be referred to as components d).

The composition can be prepared in various ways, for example

(1) mixing components (a), (b), (a) and (d) to form a concentrate and then diluting the concentrate with water to form a preparation, or

2) mixing components a), b) and c) to form a concentrate and diluting the concentrate with water to form a formulation, while mixing components d) to prepare a second mixture, then mixing the first formulation and the second mixture to the desired formulation according to the fourth embodiment.

This preparation process of the fourth embodiment of the invention forms a fifth embodiment of the invention.

In all of these processes for preparing the formulation of the invention, the ratio of the weight of water used to the total weight of components a), b) and c) in the formulation of the second embodiment of the invention is, of course, adjusted to obtain the final formulation of components a), b) and c) is defined above.

According to a sixth embodiment, the invention also relates to a method of applying the composition of the fourth embodiment to a substrate.

This method includes

(a) a method of treating vegetation by applying to a plant and / or soil a composition according to a fourth embodiment of the invention comprising a chemical, which is an agrochemical,

b) a method of treating a metal comprising applying a composition according to the invention, optionally containing a special chemical, which is a metal corrosion inhibitor, to said metal.

In the process of (a), the agrochemicals may be one or more phytoactive substances, for example growth regulators and / or herbicides and / or pesticides, for example insecticides, fungicides or acaricides. Thus, the method of applying the composition of the fourth embodiment of the invention comprises

(1) a method of controlling or inhibiting vegetation by administering a composition comprising a special chemical that is one or more phytoactive agents, for example, growth regulators and / or herbicides; and

(2) a method for controlling or inhibiting plant pests by applying a composition comprising a special chemical that is one or more pesticides, for example insecticides, fungicides or acaricides.

In carrying out the process of paragraph 1), the effect of the agrochemical, whether one or more phytoactive substances, for example growth regulators and / or pesticides, for example insecticides, fungicides or acaricides, can be enhanced by the use of surfactants. In carrying out the process of (2), the metal treatment may include, for example, cutting or abrasion.

The concentrates and preparations according to the invention which contain agrochemicals as component c) are usually one or more phytoactive substances, for example growth regulators and / or herbicides or pesticides, for example insecticides, fungicides or acaricides. Examples of agrochemicals suitable for use in the formulation include one or more phytoactive agents, for example herbicides such as Acetochlor, Alachlor and Trifluralin, but also pesticides, for example insecticides such as Propargit and Fenitrothion, and fungicides such as Propiconazole.

The concentrates and formulations of the invention which contain agrochemical as component c) may also contain an enhancer or inhibitor of agrochemical action. When the agrochemical is one or more phytoactive agents, for example, growth regulators or herbicides, and the composition further comprises an agrochemical inhibitor, the inhibitor is usually a phytotoxicity inhibitor. An example of such a substance is Safener.

Some of the concentrates and compositions of the invention contain a corrosion inhibitor as component c). These can be used in a metal working method which comprises applying the composition to the metal. One group of known corrosion inhibitors suitable for virtually all the relevant substrates to be treated are straight-chain or branched alkanecarboxylic acids and their water-soluble salts, for example with an alkali metal cation, for example sodium or potassium, or with an alkanolammonium cation. They are in particular the water-soluble straight-chain or branched alkanolammonium salts of alkanecarboxylic acids having 8 to 11 carbon atoms.

The present invention is illustrated by the following examples. All parts and percentages are by weight unless otherwise indicated. The example numbers supplemented by the letter c are used for comparison.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

Preparation of emulsifier compositions

The emulsifier compositions listed in Table 1 are prepared with mixing by a simple mixing procedure from the respective ingredients in the amounts indicated. The components of Table 1 are as follows:

H1 semi-ester of a derivative of the general formula

YO .C. (HR) CC (HR ¹⁾ .CO (CHO), R ^and A '''' 2 M and m n wherein

Y is H, one of R and R ¹ is a C _s H _e and the other is hydrogen, m is

2, n is about 23 (corresponds to PEG 1000) and R ² is H,

A is an anionic surfactant - calcium dodecylbenzenesulfonate,

N is a nonionic surfactant - Atlas G-5000 surfactant (ICI)

W is a water miscible liquid - isobutanol,

S is a solvent - Slovesso 100, a mixture of aromatic hydrocarbons (Exxon Chemicals)

Table 1

compound no. % w / w. ingredients hl A N WITH W E1 30.0 30.8 13.0 13.0 13.2 E2 10,0 28.0 35.0 15.0 12.0 E3 25.0 33.6 16.0 11.0 14.4 E4 10,0 39.2 27.0 7.0 16.8 E5 10,0 37.8 28.0 8.0 16.2 E6 10,0 36.4 29.0 9.0 15.6 Ellc - 30.8 43.0 13.0 13.0 E21c - 28.0 45.0 15.0 12.0 E31c - 33.6 41.0 11.0 14.4 E41c - 39.2 37.0 7.0 16.8 E51c - 37.8 38.0 8.0 16.2 E61c 36.4 39.0 9.0 15.6

Example 2

Preparation of emulsifiable concentrate and diluted formulation, formulation testing

The above emulsifier compositions E1 to E6 and E21c to E61c are made into the corresponding concentrates listed in Tables 2, 4, 6 and 8 by simply mixing the ingredients in the indicated amounts with mixing.

* The above concentrates are formulated into the corresponding diluted preparations by adding these concentrates to water with the parameters listed in each case above the respective table for the given% w / w. degree of dilution (suitable for a given use of the (dilute) concentrate) at a given temperature and at a given WHO standard hardness of 342 and 500 ppm, and the formulations are allowed to stand for the indicated time.

The efficacy of each emulsifier composition used in the concentrates is shown in Tables 2, 4, 6 and 8, and the formulations corresponding to these concentrates are shown in Tables 3, 5, 7 and 9, where the numbering of each formulation corresponds to the numbering of each concentrate and (which comprises components a), b) and c)) which is separated from the remaining phase.

Table 2

concentrate Cl CLL component materials. / vol. ingredients Alachlor (herbicide) 480 g 480 g E1 40 g E2 - 40 g xylene up to 1 liter up to 1 liter

Table 3% w / v dilution at 25 CC - standard water hardness of 342 and 500 ppm

agent F1 fll hardness cream separation (ml) 342 ppm (herbicide) NS 3,5 C 500 ppm NS 3,5 C

NS = no separation

Table 4

concentrate C2 C3 c2c C3c component materials. / vol. ingredients Acetochlor (herbicide) efficiency 94% 920 g 530 g 920 g 530 g Safener (phytotoxicity inhibitor) - 70 g - 70 g E2 80 g - - - E3 - 80 g - - E21C - - 80 g - E31C - - - 80 g Solvesso - 320 g - 320 g

Table 5% w / v dilution 30 CC - standard water hardness 342 ppm

agent F1 F3 F2C F3C time of standing cream separation (ml) 0.5 TC TC 0,25C 6C 1/0 0,25C 0,25C 0.5C 6C

TC = traces (<0.05%) of emulsion separation

Table 6

concentrate C4 C4C component ingredients Fenitrithion 520 g 520 g E3 100 g - E31c - 100 g Solvesso 150 up to 1 liter up to 1 liter

Solvesso 150 = aromatic hydrocarbon mixture (Exxon Chemicals)

Table 7% w / v 30 'C - standard water hardness of 20 and 500 ppm

agent F4 F4c hardness (ppm) 20.0 500.0 20.0 500.0 time of standing separation (ml) 0/5 NS NS 90C 90C 2.0 NS NS 9C-TOC 5C-30C 24.0 NS NS 1C-70 8C

NS = no emulsion separation

OC = separation of the oily cream from the emulsion

C = separation of cream from emulsion

TOC = traces (<0.05%) separation of oily cream from emulsion O = separation of oil from emulsion

Table 8

concentrate C5 C6 C7 C51C C61c C71c component weight of components (g) Propargite (insecticide) 635.0 635.0 635.0 635.0 635.0 635.0 E4 80.0 - - - - - E5 - 80.0 - - - - E6 - - 80.0 - - - E41c - - - 80.0 - - E51c - - - - 80.0 - E61c - - - - - 80.0 xylene 322.0 322.0 322.0 322.0 322.0 322.0

Table 9% w / v 30 ´C - standard water weight 342 ppm

agent F5 F6 F7 F51C F61C F71c standing time (h) separation (ml) 0.5 NS NS NS 0.5C + IT 0.5C + IT 1C-IT 1.0 NS NS NS 0.5C 0.50 TC-10 TC + 1.20 2.0 NS NS NS 0.5C 0.50 TC + 1O TC + 100 00 4.0 NS NS NS 0.5C-0.50 TC-10 TC-10 24.0 NS NS NS TC NS 0.5C-0.70

NS = no emulsion separation

TC = trace (<0.05%) emulsion separation of oily cream C = emulsion separation of cream

TO = trace (<0.05%) of oil separation from emulsion

O = oil separation from emulsion

Example 3

Preparation of emulsifier compositions

The emulsifier compositions listed in Table 10 are prepared under agitation by a simple agitation procedure from the respective ingredients in the indicated amounts. The semi-ester H2 component in Table 10 has the following formula:

YO _and C (HRC.CÍHR ¹⁾ _{.CO, and} (C _e H _ain O) _n ^{R, and} wherein Y is H, one of R and ^R1 is and the other is hydrogen, m is 2, n is about 14 (corresponding to PE6 600) and R ^a is H.

Table 10

composition E7 E8 E9 component % w / w. ingredients H2 75.0 50.0 - Atlas G-5000 25.0 50.0 100.0

Example 4

Preparation of emulsifiable concentrate (concentrated emulsion) and diluted formulation, formulation testing

The above emulsifier compositions E7 to E9 are formulated into the corresponding concentrates listed in Table 11 by mixing the ingredients in the indicated amounts in the following blending procedure: the components on the one hand and the propylene glycol and the water on the other hand, are mixed separately at 50 ° C with stirring until each product is homogeneous, thereby obtaining two separate liquid phases (phase B and phase A).

Phase B is carefully dispersed into Phase A by slowly adding to Phase A while stirring and maintaining the temperature at 50 ° C. The resulting mixture of phase B and phase A is then homogenized by high shear mixing and the resulting concentrated emulsion is allowed to cool to room temperature with gentle stirring. The viscosity modifier is then dispersed into the emulsion under high shear mixing to form a concentrated emulsion.

The above emulsifier compositions E7 to E9 are also formulated into the corresponding concentrates listed in Tables 14 and 17 by mixing the ingredients in the indicated amounts according to the mixing procedure as above. The efficacy of each emulsifier composition used at these concentrations is shown in Tables 12, 15 and 18.

Table 11

concentrate CE1 CE2 CE3 mass component / vol. ingredients Acetochlor (herbicide) efficiency 93% 538 g 538 g 538 g safener (phytotoxicity inhibitor) 52 g 52 g 52 g poly (ethoxylated) soybean oil 15 g 15 g 15 g E7 50 g - - E8 - 50 g - E9 - - 50 g propylene glycol 50 g 50 g 50 g Rhodopol 23 (viscosity modifier) 1 g i g i g Water up to 1 liter to 1 liter up to 1 liter

Table 12

agent CE1 CE2 CE3 temperature (’C) time (weeks) separation 0 NS NS NS 22 4 NS NS NS 40 4 NS NS NS

NS = no emulsion separation

The above concentrates are formulated into the corresponding diluted preparations by adding these concentrates to water with the parameters given in each case above the respective table for the given% by weight. the degree of dilution (suitable for the given use of the (dilute) concentrate) at a given temperature and at a given WHO standard hardness of 342 ppm, and the formulations are allowed to stand for a given time.

The efficacy of each emulsifier composition used in the concentrates is shown in Tables 11, 14 and 17, and the formulations corresponding to these concentrates are shown in Tables 13, 16 and 19, where the numbering of each formulation corresponds to the numbering of each concentrate and a), b) and c)), which is separated from the remaining phase.

Table 13% w / v dilution 22 ´C - standard water hardness 342 ppm

agent CF1 CF2 CF3 temperature (* C) time (weeks) separation 0 NS TC 0.15 C 22 4 TC TC 0.1 C 40 4 TC TC 0.1 C

TC trace (<0.05%) of emulsion cream separation C = emulsion cream separation

Table 14

concentrate CE4 CE5 CE6 component w / v ingredients Trifluralin (herbicide) efficiency 96% 500 g 500 g 500 g E7 50 g - - E8 - 50 g - E9 - - 50 g propylene glycol 20 g 20 g 20 g xylene 205 g 205 g 205 g Water up to 1 liter up to 1 liter up to 1 liter

Table 15

agent CE4 CE5 CE6 temperature (* C) time (weeks) separation 0 NS NS NS 22 4 NS NS - 40 4 NS NS -

Table 16% w / v dilution 22 ´C - standard water hardness 342 ppm

agent CF4 CF5 CF6 temperature (’C) time (weeks) separation (ml) 0 0,25C 0,45C 0.6C 22 4 0,25C 0.6C - 40 4 0,25C 0,7C -

C = separation of cream from emulsion

Table 17

concentrate CE7 CE8 CE9 component materials. / vol. ingredients Propiconazole (fungicide) efficiency 60% 417 g 417 g 417 g E7 100 g - - E8 - 100 g - E9 - - 100 g propylene glycol 100 g 100 g 100 g xylene 183 g 183 g 183 g Water up to 1 liter up to 1 liter up to 1 liter

Table 18

agent CE7 CE8 CE9 temperature (‘C) time (weeks) separation 0 NS NS NS 22 4 NS NS NS 40 4 NS NS NS

NS = no emulsion separation

Table 19% w / v dilution 22 * C - standard water hardness 342 ppm

agent CF1 CF2 CF3 temperature (* C) time (weeks) separation (ml) 0 NS NS 2C 22 4 NS NS I 40 4 NS TC 1C

C = separation of cream from emulsion I = impossibility to emulsify

Industrial usability

The emulsifier compositions of the invention can be used to emulsify substances such as agrochemicals to form stable emulsions.

Claims (2)

An emulsifier composition comprising (a) at least one polyalkylene oxypolo ester of a vicidicarboxylic acid of the formula I or II, YA ^ .OC. (HR) CC (HR ¹⁾ .co.il. (I) wherein one of R 1 and R ¹ is an alkenyl or alkyl group having from 6 to 22 carbon atoms and the other is a hydrogen atom, A is -O- or -NR * -, wherein R * is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, n is 2 to 100 (and may not be an integer on average), m is 2 or 3 (and may be vary by polyoxyalkylene chain), R ^a is a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, is -O-, -O or -NR * -, wherein R * or an alkyl group having 1 to 6 wherein when A ¹ is -0 ", Y or - NR *, then Y is hydrogen, is a cation, and when A ¹ is -O-C 1 -C 6 alkyl (R ³ ) or a group of formula (C 1 H 6 O ³ ) R ³ , where m, na R ^a independently of one another have the meaning given above, or YA ^X .OC. (HR) CC (HR ^X) .co.il. («ΖΗ ^ Ο) ^. . AND WHAT. ^(X HR) CC (HR) CO.AT ^X .Y (II) wherein n, m and all of the substituents R, R ^1, A, ^A1 and Y are independently as defined above, and p is 2 or 3, and b) at least one additional surfactant. Composition according to claim 1, characterized in that it contains as a compound of the formulas I and II at least one compound of the formulas Ia and IIa: R ¹ -CH (CO-AY) _and CH CO.AZ (Ia) wherein Z is a group of formula (CHO) R ³ wherein n, m and R ³ are as defined in formula I above, wherein n is preferably 3 to 50, R ³ is a hydrogen atom or an alkyl group having 1 to 16 carbon atoms, A and A ¹ are independently -O-, -O or -NH-, wherein when A or A ¹ is -O ", then Y is a cation, for example H * or an alkali metal cation, and when A or A ¹ is -O- or -NH-, then Y is a group R ³ or (CHO) R ³ wherein m and R ³ are as defined above and may be the same or different from the group Z, R ¹ is an alkyl or alkenyl group each having from 6 to 6 carbon atoms 22 and preferably 13 to 20 carbon atoms; R ¹ -CH (COA ¹ Y) -CH ₂ -CO. ADA. OC-CH ₂ -CH (COA'-Y) -R ¹ (IIIa) • wherein ¹ D is a group of formula (CHO) c H where m 2 mnp 2p p is 2 or 3, and R ¹ , A, A ¹ , m and n are as defined above. Composition according to claim 1 or 2, characterized in that it comprises (a) at least one compound of the formula I or II as defined in claims 1 or 2, in an amount of from 5 to 90% by weight, based on the total composition, and b) at least one additional surfactant in an amount of from 10 to 90% by weight of the total composition. Composition according to any one of claims 1 to 3, characterized in that it comprises at least one compound of the formula I or II as defined in claims 1 or 2 in an amount of from 5 to 90% by weight, based on the total composition, and (1) at least one non-ionic surfactant in an amount of from 10 to 90% by weight of the total; and 2) optionally at least one anionic surfactant in an amount of 0 to 60% by weight based on the total composition. A composition according to any one of claims 1 to 4, characterized in that it contains at least one further surfactant: an anionic surfactant selected from the group consisting of alkarene sulphonate salt, poly (alkoxylated-arylaryl) phosphate or sulphate salt, alkaryl phosphate or sulphate salt, straight or branched alkyl alkoxyalkyl phosphate or sulphate salt, fatty acid salt of 8 to 24 carbon atoms, and carboxylated alkaryl alcohols and fatty alcohols wherein the salt cation is an alkali metal, an alkaline earth metal, and / or an ammonium cation, an aliphatic ammonium cation or an alkanolammonium cation, wherein the aliphatic or alkanol moiety is a C 1 -C 4 alkyl group, and mixtures thereof a cationic surfactant selected from the group consisting of salts of alkoxylated fatty amines containing from 8 to 24 carbon atoms and / or a non-ionic surfactant selected from the group consisting of compounds of the general formulas R ^a1 .O (X) R ^aa and / or R ^a3 -N- (XH) _and wherein R ^x is an alkyl or alkenyl group having up to 24 carbon atoms, an alkylphenol group of 6 to 12 carbon atoms in the alkyl moiety, a sorbityl group or a group of formula R ³ * CO, wherein R ³⁴ is an alkyl group of 11 to 22 atoms alkyl, R ³² is a hydrogen atom or an alkyl, carboxyl, or C 10 -C 22 fatty acid residue; ; X is a polyalkylene oxide group containing an average of from 2 to 40, alkylene oxide groups or mixed alkylene oxide groups, and R ³³ is an alkyl or alkenyl group containing in each case 10 to 22 carbon atoms. 6. An emulsifiable concentrate comprising (a) at least one polyalkylene oxypoloester of a vic-dicarboxylic acid of the formula I or II as defined in claim 1 in an amount of from 0.1 to 15% by weight, based on the total concentrate; « (b) at least one additional surfactant in an amount of from 1 to 25% by weight based on the total concentrate; and (c) at least one chemical with an activity specific to the intended use of the concentrate in quantities from 2.5 to 95% by weight, based on the total concentrate. Concentrate according to claim 6, characterized in that it contains one or more herbicides or pesticides as a chemical with specific activity for the intended use. Concentrate according to claim 6 or 7, characterized in that the concentration of the concentrate is carried out with one or more water-miscible organic liquids selected from the group consisting of alcohols and glycols, and / or one or more water-immiscible liquids selected from the group comprising hydrocarbons, straight or branched chain alcohols, optionally hydrogenated vegetable oils, esters of 1 to 6 carbon atoms of 8 to 22 carbon atoms, N-methylpyrrolidone and isoparaffins, or mixtures thereof.