CZ248596A3

CZ248596A3 - Emulgator mixtures

Info

Publication number: CZ248596A3
Application number: CZ962485A
Authority: CZ
Inventors: Dirk Hoorne; Lodewijk Maria Rogiers
Original assignee: Ici Plc
Priority date: 1994-02-24
Filing date: 1995-02-22
Publication date: 1996-12-11
Also published as: CA2183857A1; PL316035A1; BR9506879A; HU9602318D0; AU1713595A; KR970701000A; HUT74772A; KR970701001A; CA2183858A1; SK109096A3; ZA951475B; BR9506873A; EP0746201A1; WO1995022896A1; PL316034A1; JPH09509660A; WO1995022897A1; HU9602319D0; HUT74607A; JPH09509362A

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

Invention 'containing s? emulsifiable water, and containing a chemical agent with an activity specific to the intended use of the concentrate; furthermore, the invention relates to dilute formulations containing the concentrate, and to methods, preparation or use of such emulsifier compositions, concentrates and diluted formulations containing the composition.

Background Art

Emulsifier compositions containing multiple 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 readily emulsifiable upon conversion to a diluted formulation. However, the effectiveness of such emulsifier compositions as emulsifiers and the extent to which the resulting compositions are readily emulsifiable in water to dilute formulations are usually limited to the specific combination of dispersed chemical agent and readily emulsifiable surfactants.

. A group of polyalkylene oxypolester esters of dicarboxylic acids has been developed which are described in published PCT Application No. WO 94/00508 A (PCT / GB 93/01335). Presented

The invention relates to the use of compounds of formulas I or II as set forth below:

Y. A ¹ . OC. (HR) C. C (HR ¹ ). CO. A. (C _m H ₂ mO) _n . R ² (I) one of R ¹ and R ¹ is an alkenyl or alkyl group of 6 to 22 carbon atoms each and the other is a hydrogen atom,

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

R is hydrogen or alkyl having 1 to 16, especially 1 to 6, carbon atoms;

A ¹ is -O-, -O or -NR ⁴ -, wherein R ⁴ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, especially methyl or ethyl, wherein when A ¹ -O, Y is a cation, in particular H ⁺ , and an alkali metal cation, in particular sodium or potassium cation, or an ammonium ion (especially NH 4, ammonium amine ion or ammonium alkanolamine ion), and when A ¹ is -O- or NR ⁴ -, then Y is an alkyl group with 1 to 6 carbon atoms (R ³ )

- or the axis of the pattern e (C _n H _2a O) _n . R ² , where m, on R ² independently of one another have the meanings given above, k '61

YA ^ OC. (HR) CC (HR ¹ ) .CO.A. (C _and H _2a O). C _P H _2p . AND WHAT . (HR ³ ) C. C (HR) CO. A ¹ . Y ° (II) where

-3n, m and R, R ¹ , A, A ¹ and Y each independently have the meanings given above, and p is 2 or 3.

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

Ha:

R ¹ -CH (CO-AY) -CHzCO.AZ (Ia) wherein T

Z is a radical of formula (C _m H ² mO) _n R ² where n, m and R ² are as defined in formula I above, wherein n is preferably 3 to 50,

R ² is hydrogen or alkyl of 1 to 16 carbon atoms and preferably 1 to 6 carbon atoms;

A and A ¹ are independently -O-, -O * or -NH-, wherein when A or A ¹ is -O, Y is a cation;

For example, H ⁺ or an alkali metal cation, and if A, or A is -O- or -NH-, then Y is a group R or (CmHzmO) _n R ', where m and R ² are as defined above and may be same or different from group Z

R ¹ is an alkyl or alkenyl group having from 6 to 22 carbon atoms and preferably from 13 to 20 carbon atoms;

-4or

R ¹ -CH (COA ¹ Y) -CH 2 -CO. ADA. OC-CH ₂ -CH (COA) -R ¹ (H a) where

D is a radical of formula (CMH ₂ Mo) _nCpH2 _£, _kdepje _._ 2_ .or .___

3, a

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

WO 94/00508 describes 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 that can be used in the preparation of concentrates containing a chemical having an activity specific to the intended use of the concentrate, wherein the concentrates are readily emulsifiable in water. These emulsions are generally applicable in the agrochemical industry, for example in compositions containing a chemical known in the agrochemical industry and having an appropriate effect and can be used to control weeds, fungi or insects.

SUMMARY OF THE INVENTION

The inventive principle of the first embodiment consists in that the emulsifier composition comprises

(a) at least one surfactant consisting of a polyalkylene oxypolo dicarboxylic acid ester of formula (I) or (II) as set forth above;

b) at least one additional surfactant.

A particularly suitable emulsifier composition according to the first embodiment comprises

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

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

The balance of the mixture may be carried out with a water-miscible liquid and / or a water-immiscible, for example organic, liquid. This may be desirable when the viscosity of the composition is otherwise inappropriately high. The components and their ratios are preferably selected such that, when some components are easy to use

available only as aqueous solutions, the mixture obtained by mixing the components is stable, despite the introduction of water.

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

Groups in the surfactants of formulas I or II used according to the invention are suitably linear alk (en) yl groups.

Other surfactants used may be those which, when using an emulsifier mixture in the preparation of a concentrate containing a chemical with an efficacy for the intended use of the concentrate, give a concentrate which:

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

(b) remains homogeneous when diluted with water to dilute.

Other surfactants suitable for their stability in use and storage of the concentrate may be anionic, cationic, amphoteric or non-ionic surfactants or mixtures thereof. Suitable anionic surfactants are salts of alkene sulfonates, such as salts of alkylbenzene sulfonates having 6 to 16 carbon atoms in a straight or branched alkyl chain, for example where alkyl is lauryl (dodecyl), or mixtures thereof, further selected from the group consisting of polysalkylated aryllaryl salts ) phosphates or sulphates, substances selected from the group consisting of alkaryl phosphate or sulphate salts, substances selected from the group consisting of salts of straight or branched alkyl and alkoxyalkyl phosphates or sulphates, substances selected from the group consisting of esters and salts thereof with 1 to 8 carbon atoms, preferably 12 to 18 carbon atoms, for example laurates, heptadecanoates, heptadecenoates, stearates and oleates, and those selected from the group consisting of salts of alkoxylated carboxylated alkaryl alcohols and fatty alcohols, for example the methylcarboxylates of the latter (ethylene oxide) alcohols having 12 to 15 carbon atoms. Examples of suitable salts include alkali metal cations such as sodium or potassium, alkaline earth metal salts, e.g.

And a salt with a cation of ammonium, aliphatic ammonium and alkanolammonium, wherein the aliphatic or alkanol moiety is, for example, C 1 -C 4 alkyl, which is straight or branched.

When used in particular for agrochemical purposes for the preparation of an emulsifiable concentrate containing an agrochemical with a specific action for the desired concentrate application, the preferred component (b) is an anionic surfactant selected from the group consisting of C 1 -C 16 alkylbenzene sulfonate salts, or a branched alkyl chain, for example, where the alkyl is lauryl. The preferred salt is calcium salt.

Suitable cationic surfactants include 3011 ¹¹ alkoxylated fatty amines having 8 to 24, preferably more than 12, carbon atoms, and especially 12 to 12 carbon atoms. 18 carbon atoms, the latter include, for example, C12-C15 alkylammonium salts (e.g., chlorides).

Nonionic surfactants are particularly useful in concentrates that are readily emulsifiable, particularly in agrochemical concentrates. They are non-ionic surfactants used in the agrochemical industry for the preparation of emulsifiable preparations, in particular compounds of the general formulas

R ^{21 is} O (X) R ²² - and / or R ²³ -N- (XH) ₂ where

R ²¹ is an alkyl group or an alkenyl group having up to 24, preferably 6 to 21, and especially 9 to 18, carbon atoms, an alkylphenol group having 6 to 12 carbon atoms in the alkyl moiety, a sorbityl group, or a general group

- R ⁴ CO, wherein R ⁴ is an alkyl group having 11 to 22 carbon atoms,

R 'is a hydrogen atom or an alkyl group, a carboxyalkyl group, for example a carboxyalkyl group having 2 to 4 carbon atoms, or a fatty acid residue having 10 to 22 carbon atoms,

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

R ²³ is an alkyl or alkenyl group having 10 to 22 'carbon atoms each.

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 the poles (homoalkylene- or mixed alkylene oxide) groups wherein the alkylene groups each have from 2 to 8, preferably from 2 to 4, for example 2 or 3, carbon atoms and when R ²¹ is sorbityl and R ²² is fatty residue acids having 10 to 22 carbon atoms, X is a direct bond.

Examples of suitable nonionic surfactants include poles (alkoxylated) fatty acids and alcohols having 8 to 24, preferably 12 to 18, carbon atoms in the remainder of the masses of alcohol or alcohol. alkaryl alcohols having 8 to 24, preferably 12 to 18, carbon atoms, as well as (alkoxylated) sorbityl- and sorbitol esters, poles (alkoxylated) triglycerides, including, for example, poles (alkoxylated) vegetable oils, such as poly (ethoxylated) linseed oil, mustard oil, neem oil,

-9oiticic oil, palm oil, palm kernel oil, peanut oil, peril oil, poppy oil, safflower oil, sesame oil or (especially) soybean oil, as well as (alkoxylated) allyl alcohols, poles (alkoxylated) poles (arylaryl) alcohols; polyalkylene oxides, including (block) (co) polymers, especially those wherein the alkylene groups each have 2 to 4 carbon atoms, and sorbityl esters up to 30 carbon atoms, such as sorbityl monooleate.

In the emulsifier compositions of the first embodiment of the invention, particularly those 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 ²¹ O (X) R ²² and / or R ²³ -N (-XH) ₂ as defined above as preferred nonionic surfactants.

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

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

a) at least one polyalkylene oxypolo 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

-1.0b) 1) at least one nonionic surfactant in an amount of from 10 to 90% by weight, preferably from 10 to 50% by weight, for example from 10 to 40% by weight, in particular from 10 to 35% by weight, and 2) optionally at least one anionic surfactant, in an amount of from 0 to 60% by weight, based on the weight of the surfactant. the entire mixture, 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 total.

One group of emulsifier compositions comprises mixtures 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 mixtures that do not contain an anionic surfactant. Examples of water-miscible liquids that can balance the composition and which are desirable when the viscosity of the composition is inappropriately high include alcohols, including glycols, for example, straight or branched chain alkyl chains of 1 to 8 carbon atoms. such as isobutanol and propylene glycol. This liquid may often contain water which is introduced into the mixture and may be present in an amount of up to 3% by weight, based on the total composition.

As examples of water-miscible liquids that can balance the composition and which are desirable when the viscosity of the composition is inappropriately high, preferably 5 to 18 atoms are preferred ^. carbon, including aromatic hydrocarbons, straight or branched chain alcohols, optionally hydrogenated vegetable oils, optionally hydrogenated cottonseed oil, linseed oil, mustard oil, neem oil, oiticic oil, olive oil, palm oil oil, palm kernel oil, peanut oil, peril oil, poppy oil, rapeseed oil, safflower oil, sesame oil or soybean oil, as well as esters (especially C 1 -C 6 esters) of C 8 -C 22 fatty acids, especially fatty acids C12 -C18 acids, for example selected from the group consisting of - methyl laurate, heptadecanoate, heptadecenoate, heptadecadienoate, stearate or oleate, especially methyl llaurate and methyl oleate, as well as N-methylpyrrolidone and isoparaffins or mixtures thereof. A preferred such liquid is xylene, any mixture of aromatic hydrocarbons and N-methylpyrrolidone.

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

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

For example, such a chemical may be an agrochemical or a metal corrosion inhibitor.

One or more t may be present as agrochemicals

phytoactive substances, for example plant growth regulators or herbicides, and / or pesticides, for example insecticides, fungicides or acaricides. 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 typically 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. and another agent is a phytotoxicity inhibitor for controlling phytoactivity, for example, regulating the growth or herbicidal efficacy of a concentrate or corresponding diluted formulation, or, for example, Safener (phytotoxicity inhibitor) so that the formulation is more selective, for example, in grassy and broadleaf kinds. This other chemical

Can be present in an amount of up to 15% by weight based on the total weight of the concentrate.

Preference is given to concentrates having a high chemical content with a specific activity and appropriate for the intended use of the composition. These form dispersions of specific chemicals such as Acetochlor and Alachlor herbicides, but also pesticides such as insecticides, fungicides or acaricides, which are well known in the agrochemical industry, and are usually difficult to emulsify.

Preferred emulsifiable concentrates according to the first embodiment comprise

a) at least one polyalkylene oxypolo dicarboxylic acid in an amount of from 0.1 to 15% by weight, based on the total concentrate, preferably from 0.15 to 10% by weight,

b). at least one additional surfactant in an amount of from about 25% by weight of the total;

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

A greater proportion of the concentrate balance has a water-miscible liquid and / or a water-insoluble organic solvent, whereby a chemical is dissolved with an efficiency specific to the intended use of the concentrate or the corresponding diluted formulation. This may also be desirable if the viscosity of the concentrate is inappropriately high.

The concentrate, particularly for use in the form of a formulation for agrochemical application, may contain one or more 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, e.g.

When administered from some growth regulators, herbicides, insecticides, fungicides or acaricides, it is preferred that the concentrate contain a significant amount of water, for example over 25% by weight, based on total. These concentrates are in fact concentrated emulsions which are further emulsifiable by dilution with water to form preparations for application to, for example, agricultural crops. The components and their proportions are preferably selected 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, for example, in agriculture for the preparation of crop treatments, the composition of an emulsifiable concentrate is as follows:

a) - at least one polyalkylene oxypolo 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,

b) at least one nonionic surfactant in an amount of from 1 to 25% by weight based on the total emulsifiable concentrate;

c) no anionic surfactant.

Each of these concentrates

a) dispersing specific chemicals such as Acetochlor and Alachlor, but also pesticides, such as insecticides, fungicides or acaricides, which are known; that it is usually not easily emulsifiable with known surfactants,

b) remains homogeneous when diluted with water in the preparation of the diluted composition of the invention for application of concentrate component c) without the need for additional substances for. dispersing the phase a. preventing deposition of the phase from the diluted concentrate,

-14c) exhibits excellent wetting properties in relation to the dispersed chemical in the concentrate and particularly in relation to the substrate being treated.

Preferred compositions of the present invention, particularly when used for concentrates and preparations of agrochemicals, may also have a high chemical content relative to component a) above, for example herbicides such as Acetochlor and Alachlor.

Suitable and preferred polyalkylene oxypoloesters of dicarboxylic acids and other surfactants in the concentrate are generally those described herein for the emulsifier compositions of the first embodiment of the invention.

Examples of suitable water-miscible liquids include alcohols, including glycols, for example, straight or branched chain alkyls having from 1 to 8 carbon atoms. Isobutanol and propylene glycol are preferred. These liquids can often contain water. . Examples of water-insoluble organic solvents that have a concentrate balance include hydrocarbons having preferably 5 to 18 carbon atoms, including aromatic hydrocarbons, straight or branched chain alcohols, optionally hydrogenated vegetable oils, such as hydrogenated cottonseed oil, flaxseed oil, mustard oil, non-ointment o "Ojn oitricdrkdvý olejj olive oil, palm oil? ^-: palm kernel oil, -mash oil, peril oil, poppy oil, rapeseed oil, safflower oil, sesame oil or soybean oil, - esters- (especially with 1 to - 6 carbon atoms) fatty acids with - ~ - ' C8-C22, especially C12-C18, for example selected from the group consisting of methyl laurate, heptadecanoate, heptadecenoate, heptadecadienoate, stearate or oleate, especially methyl laurate and oleate, N-methylpyrrolidone and isoparaffins or mixtures thereof. Preferred solvents are

For example xylene, mixtures of aromatic hydrocarbons and N-methylpyrrolidone.

An antifoam agent may also be present. Sufficient amounts of this agent should be used to achieve the antifoam effect for the intended use of the concentrate, but without separating the agent from the mixture. Usually 0.05 to 10%, preferably 0.2 to 6% by weight, based on the total, is used. Any compounds commonly used as antifoam agents in aqueous dispersed phase formulations can be used. One or more polysiloxanes, in particular having hydrophilic groups, are preferably used as anti-foaming agents. Are they? preferably the compounds of formula

R * ₃ SiO [SiOR * R **] _n SiR * 3 wherein R * groups are individually alkyl groups, preferably having up 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 to R.

The R groups preferably have a molecular weight in the range of 1000 to 20000 and in particular of 5000 to 15000. Examples of suitable polysiloxane antifoam agents are described in British Patent Nos. 1,533,610 and 1,554,736.

Other possible additives to the emulsifiable concentrates of the present invention include surfactant-free agents commonly used in surfactants such as viscosity / stabilizer modifiers and antimicrobial agents. One group of known viscosity modifiers of this type are one or more commercially available substances which are water-soluble or water-miscible, such as gums, for example xanthan gums, and celluloses such as carboxymethylcellulose, carboxyethylcellulose

-16 or carboxypropylcellulose. These substances are often present, for example, in agrochemical formulations, in particular in an amount of 0.01 to 1% by weight, based on the total concentrate.

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

The emulsifiable concentrates according to the invention can be prepared by a conventional method of mixing the individual components.

According to a third embodiment, the invention consists in mixing the components together to prepare the concentrate. 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 stirring until a homogeneous product is obtained.

For emulsifiable concentrates of the invention, which are concentrated emulsions, it may be necessary to mix the components in a certain order. These emulsifiable concentrates can be prepared by separate conventional mixing.

(a) liquid carriers;

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

The concentrate is p-RIP-r-yl-di- careful spergovánům phase ^ ^_ ~ CBS ahQj'íčíí components a), b) and c) - the second phase. It may therefore be desirable to carry out the addition of phases at a slightly elevated temperature using high-shear mixing. when it is an inadequately high - - - - concentrate viscosity. The concentrated emulsion is then allowed to cool to room temperature.

In most applications, the surfactant concentrates according to the second embodiment of the invention are used in their (more concentrated) form and converted to more diluted forms only when used. Good stability is still required

In a more concentrated form when used than is used for preparing a more dilute form in use. According to a fourth embodiment of the invention, there is provided a formulation which is a mixture of components a), b) and c) of a concentrate according to a second embodiment of the invention, with 10- to 100,000 times the amount of water than the total weight of components a), b) and c), e.g. up to 1000 times the amount. Of course, the composition of the fourth embodiment of the invention may contain other components and additives. These suitable and preferred components and additives have already been described above and are, for example, solvents and antifoam agents which may be referred to as components d).

The preparation can be prepared in various ways, for example

1) extending components a), b), c) and d) to form a concentrate, and then diluting the concentrate with water to form the formulation, or

(2) mixing components (a), (b) and (c) to form a concentrate and diluting this concentrate with water to form the preparation, while mixing the components (d) and diluting the mixture of these components with water to prepare the second mixture, whereupon the first formulation and the second mixture are mixed into the desired formulation according to a fourth embodiment of the invention.

This process for preparing the composition of the fourth embodiment of the invention forms a fifth embodiment of the invention.

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

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

This method includes

-18a) a method of treating vegetation by applying the composition of the fourth embodiment of the invention comprising a chemical, which is agrochemicals, to plants and / or soil,

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

In the process according to 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 includes -

1) a method for controlling or inhibiting vegetation by applying a composition comprising a special chemical that is one or more phytoactive substances, 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, which is one or more pesticides, for example insecticides, fungicides or acaricides.

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

Typically, the concentrates and compositions of the present invention which contain agrochemicals as component c) are one or more phytoactive substances. for example, growth regulators and / or herbicides or pesticides, for example insecticides, fungicides or acaricides. As examples

For example, one or more phytoactive agents, for example herbicides such as Acetochlor, Alachlor and Triflural, but also pesticides, such as insecticides such as Propargite and Fenitrothion, and fungicides such as Propiconazole may be mentioned as suitable for use in the formulation.

The concentrates and formulations of the invention which contain agrochemicals as component c) may also contain an agrochemical enhancer or inhibitor. If the agrochemical is one or more phytoactive substances, 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 concentrates and formulations of the invention contain a corrosion inhibitor as component c). These can be used in a metal processing process which involves applying the composition to metal. One group of known corrosion inhibitors suitable for virtually all relevant substrates to be treated are straight-chain or branched alkancarboxylic acids and their water-soluble salts, for example with an alkali metal cation, for example sodium or potassium, or with an alkanolammonium cation. In particular, they are, for example, water-soluble straight-chain or branched alkanolammonium alkanolammonium salts having 8 to 11 carbon atoms.

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

Exemplary Embodiments of the Invention

Example 1

Preparation of a mixture _{of t} ________ emulsifier emulsifier mixture listed in Table 1 were prepared by simple mixing procedure of mixing the respective components in the indicated amounts. The components of Table 1 are as follows:

H1 semi-derivative of the formula

YO ₂ .C. (HR) CC (HR ¹ ) .CO ₂ (C _n H _{2 m} O) _n R ² where Y is H, one of R and R ¹ is C 18 H 35 and the other is hydrogen, m is 2, n is about 23 (corresponding to PEG 1000) and R ² is H,

A is an anionic surfactant calcium dodecylbenzenesulfonate,

N is a non-ionic surfactant - Atlas G-5000 surfactant (ICI)

W is a water-miscible liquid - isobutanol,

S is Solvesso 100, a mixture of aromatic hydrocarbons (Exxon Chemicals)

-21Table 1

slouč. C. % w / w components H1 AND N WITH W . El 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, 2 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 E5ic - 37.8 38.0 8.0 16, 2 E61c 36, 4 39, 0 9.0 15, 6

Example 2 *

Preparation of the emulsifiable concentrate, and of the diluted preparation, of the preparation

The above-mentioned emulsifier mixtures E1 to E6 and E21c to E61c are adjusted to the corresponding concentrates listed in Tables 2, 4, 6 and ₄ , 8, and simply by mixing the components in said amounts with stirring.

The above concentrates are formulated into the corresponding diluted formulations by adding these concentrates to water with the parameters given in each case above the respective table for a given% w / v. the degree of dilution (appropriate for the use of the given (diluted) concentrate), at a given temperature and at a given

-22WHO standard hardness 342 and 500 ppm, and the products are allowed to stand for a given time.

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

Table 2

concentrate Cl Target component wt./obj. component Alachlor (herbicide) 480 g 480 g El 40 g E2 - 40 g xylene to 1 liter up to 1 liter

Table 3% w / v. dilution at 25 ° C - standard water hardness 342 and 500 ppm

preparation F1. Fll hardness cream separation (ml) 342 ppm NS 3.5 C 50 0-ppm - NS -.....— 3, 5- C - - - - -

NS = no emulsion separation

-23Table 4

concentrate C2 C3 C2c C3c component wt./obj. component Acetochlor (herbicide) activity 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 100 - 320 g - 320 g

Table 5

% w / v dilution 30 ° C - standard water hardness 342 ppm

preparation F2 F3 F2c F3c standing time (h) - cream separation (ml) 0.5. TC TC 0.25C 6C 1.0 0.25C 25C 0.5C 6C

TC = traces (<0.05%) of emulsion separation

Table 6

concentrate C4 C4c component components Fenitrothion 520 g 520 g E3 100 g - E31c - 100 g Solvesso 150 to 1 liter to 1 liter

Solvesso 150 = Aromatic Hydrocarbon Mixture (Exxon Chemicals)

-24Table 7% w / v 30 ° C - standard water hardness 20 and 500 ppm

preparation F4 F4c Hardness (ppm) 20, 0 500, 0 20, 0 500, 0 standing time (h) separation (ml) 0, 5 NS NS 90C 90C 2.0 NS NS 9C + TOC 5C + 3OC 24.0 . NS NS 1C + 70 8C

NS = no emulsion separation

OC = separation of oily cream from emulsion

C = separation of cream from emulsion

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

Table 8

concentrate C5 C6 C7 C51c C61c C71c component component weight (g) Propargite (Insecticide) 635, 0 635.0 635.0 635.0 635, 0 635.0 E4 80.0 - - - - E5 - 80, 0 - - - - E6- - - -8Q-rQ- ----- - E41c - - - 80, 0 - - E51c - - - - 80, 0 - E61c - - - - • - 80.0 xylene 322.0 322.0 322.0 322Ϊ0 322, '0 322.0

-25Table 9% w / v 30 ° C - standard water hardness 342 ppm

preparation F5 F6 F7 F51c F61c F71c standing time (h) separation (ml) 0, 5 NS NS NS 0.5C + TO 0.5C + TO 1C + TO 1.0 NS NS NS 0, 50 0.50 - TC + IO TC + 1.20 2.0 NS NS NS 0, 50 0.50 TC + IO TC + IO 4.0 NS NS NS 0.5C + 0.50 TC + IO TC + IO 24.0 NS NS NS TC NS 0.5C + 0.70

m ....

NS NS · = no emulsion separation

TC = track (<0.05%) of oilseed emulsion separation C = emulsion cream separation. _t TO = trace (<0.05%) of oil separation from the emulsion. Separating the oil from the emulsion

Example 3, Preparation of Emulsifier Mixtures

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

Y.0 ₂ C. (HR) CC (HR ¹ ). CO2 (CmH2nO) _n . R ²

Where Y is H, one of R and R ¹ is CH 2; and the other is hydrogen, m is 2, n is about 14 (corresponds to PEG 600) and R ² is H.

Table 10

mixture E7 E8 E9 component % wt / wt. component H2 75.0 50, 0 - Atlas G-5000 25.0 50, 0 100.0

Example 4

Preparation of emulsifiable concentrate / concentrated emulsion) and diluted preparation, product testing

The above-mentioned emulsifier mixtures E7 to E9 are formulated into the corresponding concentrates listed in Table 11 by mixing the components in the indicated amounts in the following mixing procedure: Aceto.chlor, Safener, poly (ethoxylated) soybean oil and E7, E8 emulsifier mixture E9 or as components on the one hand, and propylene glycol, and water on the other hand, are mixed separately at 50 ° C with stirring until each product thereby TlbrnogenníT ^- ~ is of ±-kajír- with two twin-to-bad-phase - (phase B and phase A).

Stage B is carefully dispersed into phase A by slowly adding to-phase-A-steady-state stirring and maintaining the temperature at -50 ° C. The resulting phase B and phase A mixture is then homogenized by high shear mixing and the resulting concentrated emulsion 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-mentioned emulsifier compositions E7 to E9 are also formulated into the corresponding concentrates listed in Tables 14 and 17 by mixing the components in the indicated amounts according to the mixing procedure as described above. The effectiveness of each emulsifier mixture used in these concentrates is shown in Tables 12, 15 and 18.

Table 11

concentrate CE1 CE2 CE3 component mass / vol component Acetochlor (herbicide) potency 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 - - ' ^l '. E8 - 50 g - E9 - -. 50 g propylene glycol 50 g 50 g 50 g Rhodopol 23 (viscosity modifier) ig 1 g ig water to 1 liter to 1 liter to 1 liter

Table 12

preparation CE1 , CE2 CE3 temperature (° C) time (weeks) separation ^{: =} '' - - o 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 formulations by adding these concentrates to water with the parameters given in each case above the respective table for a given% w / v. the degree of dilution (appropriate for the use of the given (diluted) concentrate), at a given temperature and at a given WHO ... _: standard. 342 ppm, and the compositions are allowed to stand for a given period of time.

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

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

preparation CF1 CF2 CF3 temperature (° C) time (weeks) separation (ml) 0 NS TC 0.15 C 22 4 TC TC 0.1 C 40 ..... 4 - TC TC 0.1 C

TC = trace (<0.05%) separation of the cream from the emulsion cream. z, _emu 1 se_________________________________________________ _

-29Table 14

concentrate CE4 CE5 CE6 component weight / volume ponent Trifluralin (herbicide) potency 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 to 1 liter to 1 liter to 1 liter

Table 15

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

NS = no emulsion separation

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

preparation CF4 CF5 CF6 temperature (° C) time (weeks) separation (ml) 0, ..... 0.25 C 0.45 C 0.6 C 22 4 0.25 C 0.6 C - 40 4 35 C 0.7 C -

C = separation of cream from emulsion

-30Table 17

concentrate CE7 CE8 CE9 component weight / obj com] oonent Propiconazole (fungicide) efficiency 60% 417 g 417 g 417 g E7 100 g - - 100 g E9 - - 100 g propylene glycol 100 g 100 g 100 g xylene 183 g 183 g 183 g water to 1 liter to 1 liter to 1 liter

Table 18

preparation 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

preparation CF1 CF2 CF3 temperature (° C) time (weeks) separation (ml) 0 NS NS 2 C - - - - - -2 2 - · ..... - - - - - - - —- - ~ 4 - - - - NS NS- - -. .I. 40 4 NS TC 1 c

C = Separation of cream from emulsion I = Inability to emulsify

-31Industrial usability

The emulsifier compositions of the present invention are useful for emulsifying substances such as agrochemicals to form stable emulsions.

Claims

PATENT CLAIMS

An emulsifier composition comprising

(a) at least one polyalkylene oxyploxy ester of a vicidicarboxylic acid polyalkylene oxide.

of formula I or II,

Y. A ¹ . OC. (HR) C. C (HR ¹ ). CO. A. (C _m H2mO) _n. R ² (I) wherein one of R and R ¹ is an alkenyl or alkyl group each having 6 to 22 carbon atoms and the other is hydrogen,

A is -O- or -NR ⁴ -, wherein R ⁴ is hydrogen or C 1 -C 6 alkyl, 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 is a hydrogen atom or an alkyl group having 1 to 16 carbon atoms,

A ¹ is -O-, -O or -NR ⁴ -, wherein R ⁴ is hydrogen or C 1 -C 6 alkyl, wherein when A ^{1 is} -O ', Y is a cation, and when A ¹ is -O- or NR ⁴ -, then Y is an alkyl group having 1 to 6 carbon atoms (R ³ ) or a group of the formula (CmH ₂ mO) _n . R ^2, wherein m, on R ² are independently of each other as defined above, or

Y. A ¹ .0C. (HR) C. C (HR ¹ ). WHAT. A. (C _m H ₂ m0) _n. C _p H2p. AND WHAT . (HR ¹⁾ C. C (HR) CO. A ¹ . Y (II)

-33 where n, m and all substituents R, R ¹ , A, A ¹ and Y are independently as defined above, and p is 2 or 3, and

b) at least one additional surfactant.

2. A composition according to claim 1, wherein the compound of formula I or II comprises at least one compound of formula Ia or IIa.

R ^l CH (CO-AY) -CHaCO.AZ u x 3 '' (Ia) wherein s second 2, ^R z is a group of formula (C _m H2mO) _n R, wherein n, m and R 'are as defined for formula I above, wherein n is preferably 3 to 50,

R ² is hydrogen or an alkyl group having 1 to 16 carbon atoms,

A and A ¹ are, independently of one another, -O-, -O 'or -NH- groups

wherein if A or A ¹ is -O then Y is a cation, for example H ⁺ or an alkali metal cation, and if A or A ¹ is -O- or -NH-, then Y is. R ^z or (Cm H2m O) _n R ^2, wherein m and R ² have the meanings stated previously and may be the same or different to the group Z,

f. ¹ is acyl or. alkenyl -carbonyl jyždy ₌ ^ is 6 to 22 and _T _and _s_! í preferably 13 to 20 carbon atoms, or H> ·

R ^CH (CHΟΟύ) -CH 2 -CO. ADA. OC-CH 2 -CH (COA ¹ Y) -R ¹ (Ha) wherein

-34D is a group of formula (CmlhmO) _n C _p H 2 _P , wherein p is 2 or 3, and

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

A composition according to claim 1 or 2, characterized in that e. ..t_.i m .. that contains - · - - - - - - -

(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 mixture, 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 contains 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 whole composition, a. rr.

(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 of the total composition.

Composition according to any one of claims 1 to 4, characterized in that it contains at least one of the further surfactants:

an anionic surfactant selected from the group consisting of alkarenesulfonate salt, poly (alkoxylated arylaryl) phosphate or sulfate salt, alkaryl phosphate or sulfate salt, straight or branched alkyl and alkoxyalkyl phosphate or sulfate salt, fatty acid salt of 8 to 24 carbon atoms, alkoxylated salt group and carboxylated alkaryl alcohols and

Ϊ33ί \

-35 fatty alcohols wherein the cation in the salt 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, cationic surface an active agent selected from the group consisting of salts of alkoxylated fatty amines having 8 to 24 carbon atoms, and / or a nonionic surfactant selected from the group consisting of compounds of the general formulas

R ²¹ .O (X) R ²² and / or R ²³ -N- (XH) ₂ wherein ⁴ R ²¹ is an alkyl or alkenyl group having up to 24 carbon atoms, an alkylphenol group having 6 to 12 carbon atoms in the alkyl a moiety, a sorbityl group or a group of formula R ²⁴ CO wherein R ²⁴ is an alkyl group having 11 to 22 carbon atoms, R ²² is a hydrogen atom or an alkyl group, a carboxyalkyl group, or a fatty acid residue having 10 to 22 carbon atoms; carbon atoms,

X is a polyalkylene oxide group containing an average of 2 to 2

40 alkylene oxide groups or mixed alkylene oxide groups • --......, and __ ₌ _____ _________

....... “·

R ²³ is an alkyl or alkenyl group having in each case 10 to 22

LZ · carbon atoms. ^{6 * * *}

6. An emulsifiable concentrate comprising

(a) at least one polyalkylene oxypolo ester of a vic-dicarboxylic acid of the formula I or II as defined in

-36 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 for the intended use of the concentrate in an amount of from 2.5 to 95% by weight, based on the total concentrate. AND

Concentrate according to claim 6, characterized in that it contains one or more herbicides or pesticides as a chemical with a specific activity. . ·. -. . . . .

ío

Concentrate according to claim 6 or 7, characterized in that the balance 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.