AU646915B2

AU646915B2 - Plant-protection compositions

Info

Publication number: AU646915B2
Application number: AU10073/92A
Authority: AU
Inventors: Jean-Francois Fiard
Original assignee: Rhone Poulenc Chimie SA
Current assignee: Rhodia Chimie SAS
Priority date: 1991-04-09
Filing date: 1992-01-06
Publication date: 1994-03-10
Anticipated expiration: 2012-01-06
Also published as: CA2065567A1; FR2675014B1; EP0508022A1; FR2675014A1; AU1007392A; JPH0597601A

Description

646915 1-

AUSTRALIA

PATENTS ACT 1990 CO0MPLT1F.T 9 P F Q TFVT QA TT N FOR A STANDARD PATENT 0 R I G I NA L C.

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egg of Applicant: *fee Actual Inventor: RHONE-POULENC CHIMIE Jean-Francois Fiard SHELSTON WATERS 55 Clarence Street SYDNEY NSW 2000 "PLANT-PROTECTION COMPOSITIONS" C. S

C.

Address for Service: Invention Titcle: 0@ The following statement is a full description of this invention, including the best method of performing it known to us:la PLANT-PROTECTION COMPOSITIONS The present invention relates to new plantprotection compositions and to their use for the treatment of plants.

Plant-protection active substances, such as insecticides, germicides, herbicides, fungicides, acaricides, nematicides, molluscicides, rodenticides, attractants, repellents and combinations of several of these compounds, are generally insoluble in water.

There are, however, some plant-protection active substances which are water-soluble. They are generally salt derivatives of active substances.

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Other compounds can also be present in plant protection compositions th.y are micronutrients. They are generally metallic 15 salts or chelates, which are soluble in water, By convenience, in this text the expression "plant-protection active substance" or simply "active substance" encompasses also these water-soluble micronutrients.

In the present text, water-soluble active e 20 substance is understood to mean a plant-protection active substance having a solubility in water at room temperature (approximately 20*C) of not less than grams per litre.

Despite their solubility in water, these active substances need, for better utilisation and for greater efficacy, to be employed in the form of aqueous compositions containing one or more formulation additives, and more especially one or more surfactants.

The increasingly earnest attention being paid to the various problems of pollution of the environment is leading to a search for plant-protection compositions of increasingly lower toxicity.

The present invention contributes to this trend by the use of a surfactant system consisting at fee e o** 00

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2 least partially of non-toxic, non-irritant and biodegradable compounds.

The emulsifying and dispersant character of sucroglycerides is known, for preparing aqueous dispersed systems of fats.

Sucroglycerides are mixtures of products obtained by transesterification of natural or synthetic triglycerides with sucrose. These mixtures essentially contain monoglycerides, diglycerides, small amounts of non-transesterified triglycerides and sucrose *0* S' o" monoesters and diesters.

0 Patent EP-A-0,091,331, which describes a process for preparing fluid sucoglycerie-i, also *points out that the said sucroglycerides have too**: 15 surfactant properties which may be used, in particular, for the preparation of emulsions of essential oils or refatted low-fat milk. Lecithins and fluid oils may *e also be combined with the sucroglycerides.

Patent CH 423,442 describes a process for 20 preparing emulsions of oils or of solid fats in water, using sucroglycerides and a lecithin as an emulsifying system.

The present invention consists in using this emulsifying power of sucroglycerides for obtaining compositions of plant-protection active substances, as well as the capacity of sucroglycerides to modify the bioavailability of the active substances.

More specifically, the present invention 3 hence relates, in the first place, to aqueous compositions of water-soluble plant-protection active substance, characterised in that they contain at least one water-soluble plant-protection active substance, sucroglycerides, at least one surfactant and water.

Among water-soluble plant-protection active substances, the following may be mentioned by way of non-limiting examples: glyphosate, in the form of its isopropylamine salt or its sodium salt, glufosinate, in the frm of its ammonium S' salt, 2,4-D, in the form of its 2-hydroxyethylammonium, dimethylammonium or tris(2-hydroxyethyl- 15 ammonium) salt, 2,4-DES, in tho form of its sodium salt, guazatine, in the form of its triacetate, MCPA, in the form of its sodium, potassium or dimethylammonium salt, 20 m4coprop, in the form of its sodium or potassium salt, 9 acifluorfen, in the form of its sodium or potassium salt, clopyralid, in the form of a 2-hydroxyethylammonium or potassium salt, MSMA, in the form of its sodium salt, paraquat, in the form of its dichloride or its bis(methyl sulphate).

It is naturally possible, without departing from the scope of the invention, to use other soluble salts of the various parent substances mentioned above, which are obtained, generally speaking, by neutralising the acid functions of the parent substances with an alkali metal hydroxide, an amine or an alkanolamine, or by neutralising the amine functions of the parent substances using an inorganic acid such as hydrochloric acid or sulphuric acid or an organic acid such as acetic acid.

As an example of water-soluble plant-protection active substances, there can be also mentioned micronutrients such as manganese sulphate, magnesium sulphate, 15 the manganese complex of the disodium salt of ethylenediamine tetraacetic acid (EDTA), the copper complex of the disodium salt of EDTA, the zinc complex of the disodium salt of EDTA, the cobalt complex of the disodium salt of EDTA, 20 the manganese complex of the dipotassium salt of EDTA.

It is possible to use several different water-soluble plant-protection active substances in the plant-protection s compositions according to the present invention.

As stated above, the sucroglycerides originate from transesterification of triglycerides with sucrose.

In the present text, the term "sucroglycerides" will be used in the plural, in order to indicate that they do nat consist of one single chemical compound.

As triglycerides employed for the preparation of the sucroglycerides, triglycerides of saturated or unsaturated aliphatic acids having at least 4 carbon atoms are generally used. Preferably, the acids from which the triglycerides are derived have 10 to carbon atoms.

The preparation of the sucroglycerides may be accomplished using synthetic triglycerides obtained by the reaction of glycerol and fatty acids. However, it is more advantageous from an economic standpoint to make use of natural triglycerides. These natural *e

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triglycerides are mixtures of triglycerides.

As an example of such natural triglycerides, there may be mentioned lard, tallow, groundnut oil, butter oil, cotton seed oil, linseed oil, olive oil, palm oil, grape pip oil, fish oil, soybean oil, castor oil, rapeseed oil, copra oil and coconut oil.

In the present invention, the sucroglycerides used originate, in particular, from palm oil, lard, copra oil, tallow, rapeseed oil or castor oil.

They take either liquid form, such as the sucroglycerides of rapeseed oil or of castor oil, or the form of more or less consistent pastes, differentiated from one another, in particular, by their melting point: lard sucroglycerides t 47 to tallow sucroglycerides 50 to palm oil sucroglycerides 55 to 58'C S" copra oil sucroglycerides 30 to 32'C.

A procedure for preparing the sucroglycerides 20 is described in Patent FR-A-2,463,512.

It is possible to use several different sucroglycerides in the aqueous emulsion in order, in particular, to employ their different specific properties.

Generally, the compositions of the invention contain from 0.1 to 40 by weight of sucroglycerides relative to the total weight of the composition, and preferably from 1 to 30 weight/weight.

6 The surfactants which participate in the composition of the invention with the sucroglycerides can be ionic and/or nonionic.

Although sucroglycerides are surf actant compounds, the term surfactant in the present text will be resorved for surfactants other than the said sucroglycerides.

Among ionic surf actants, there may be mentioned anionic surfactants such as, in particula-: phosphoric esters of alkoxylated fatty alcohols, of alkoxylated fatty acids, of alkoxylated alkyiphenols, of alkoxylated bis (1-phenyle'thyl )phenols, of alkoxylated tris -phenylethyl )phenols; -sulphuric esters of alkoxylated fatty alcohols, of *bb 15 alkoxylated alkyiphenols, of alkoxylated bis(phenylethyl)phenols, of alkoxylated tris(1phenylethyl )phenols; the unesterifiqd function or functions of the phosphoric acid or sulphuric acid can be in acid, form 4!20 or in the form of a sodium, potassium, amnmonium, amine or alkanolamine sait; -alkylarylsulfonates such as al kyl benzene- sul fonates and ~alkylnaphtalene-sulfonates of sodium, potassl'.iM., calcium, ammonium, amine or alkanolamine alkylsulfates of sodium, potassium, ammonium, amine or alkanolamine; alkyl (polyoxyalkylene)sulfates of sodium, potassium, ammonium, amine or alkanolamine.

The alkoxy units of these anionic surfactants are oxyethylene (OE) and/or oxypropylene (OP) units.

They usually vary in number from 2 to 100 according to the desired HL.B (hydrophilic-lipophilic Preferably, the number of alkoxy units lies between 4 and 50, without these values having acritical significance.

The alkoxylated fatty alcohols from which the above phosphoric and sulphuric esters are derived generally have from 6 to 22 carbon atoms, the alkoxy units being excluded from these numbers.

The alkoxylated alkylphenols from which the above phosphoric and sulphuric esters are derived generally contain 1 or 2 linear or branched alkoxy groups having from 4 to 12 carbon atoms, in particular octyl, nonyl or dodecyl groups.

S' When the unesterified functions of the phosphoric acid or sulphuric acid of the above esters are salified, they are most often salified in the form of sodium, potassium, ammoni'-n, butylamine, 15 isopropylamine, N-methylcyclohexylamine or triethanolamine salts, without these examples being limiting.

By way of particular examples of anionic oo* surfactants, the following may be mentioned, in particular: the triethanolamine salts of the phosphoric monoester and diester of ethoxylated tris(1-phenylethyl)phenol with 16 OE units, the potassium salts of the phosphoric monoester and diester of ethoxylated tris(1-phenylethyl)phenol with 16 OE units, the acid sulphate of ethoxylated bis(1-phenylethyl)phenol with 11 OE units, the potassium salt of the sulphuric monoester of eth'3xylated bis(1-phenylethyl)phenol with 15 OE units, the triethanolanine salt of the sulphuric monoester of ethoxylated bis(l-phenylethyl)phenol with 11 OE units, the amnmonium salt of the sulphuric monoester of ethoxylated tris(l-phenylethyl)phenol with 16 OE units, the acid phosphate of ethoxylated noriylphenol with 9 OE units,, the dodecylbenzene sulfonate of sodium, the methylnaphtalene sulfonate of sodium, the lauryl sulfate of sodium, the lauryl ether sulfate of sodium with 3 OE units.

~*Among ionic surfactants, cationic or *So, 15 amphoteric surfactants such as betaines and imidazolines may also be mentioned.

The betaines are aznphoteric surfactants of 00 the following formulae:

II

Ri N CH 2

COO-

CH2 COONa

R

1 NH- CH2 -CH2COO-

I

R2 in which: RI represents a linear or branched alkyl group having 3 to 18 carbon atoms, such as, for example, propyl, dodecyl or hexadecyl, or an alkanamido group such as, for example, dodecanamide,

R

2 represents a hyarogen atom or a propionate group.

The imidazolines are compounds derived from imidazoline containing a linear or branched alkyl or alkenyl substituent having 6 to 20 carbon atoms on the 10 carbon at the 2-position of the imidazoline ring and containing on the nitrogen atom at the 1-position one or more substituents such as hydroxyl, sodium alkanolate, (for example -CHzCHzONa), hydroxyalkyl (for example 2-hydroxyethyl), sodium alkylcarboxylate (for 15 example -CH 2 COONa), sodium alkoxyalkylcarboxylate (for example -C 2

HO-CH

2 COONa) or sodium hydroxyalkyl- 6 sulphonate (for example -CH 2

CHOH-CH

2 SONa).

The above betaines and imidazolines are often mixtures of compounds for which the hydrophobic alkyl or alkenyl substituents originate from natural compounds such as, for example, copra oil.

The betaines are marketed, in particular, under the brand name ALKATERIC, the ilidazolineF under the brand names ALKAZINE and MIRANOL.

Among nonionic surfactants, the following may be mentioned: alkoxylated triglycerides, alkoxylated sorbitan esters, alkoxylated fatty acids, alkoxylated fatty alcohols, alkoxylated fatty amines, alkoxylated bis(l-phenylethyl)phenols, alkoxylated tris(l-phenylethyl)phenols, alkoxylated alkylphenols.

The alkoxy units of these various surfactants are oxyethylene (OE) and/or oxypropylene (OP) units, most frequently OE units.

They usually vary in number from 2 to 100 15 according to the desired HLB (hydrophilic/lipophilic balance). This HLB will generally be not less than 11.

Preferably, the number of alkoxy units lies between 4 and The alkoxylated triglycerides can be triglycerides of vegetable or animal origin (such as lard, tallow, groundnut oil, butter oil, cotton seed oil, linseed oil, olive oil, palm oil, grape pip oil, S* fish oil, soybean oil, castor oil, rapeseed oil, copra oil, coconut oil), preferably ethoxylated.

The alkoxylated fatty acids are esters of fatty acids (such as, for example, oleic acid, stearic acid), preferably ethoxylated.

The alkoxylated sorbitan esters are cyclised 11 sorbitol esters of C, 1 to C 20 fatty acids such as lauric acid, stearic acid or oleic acid, preferably ethoxylated.

The term ethoxylated triglyceride relates, in the present invention, both to the products obtained by ethoxylation of a triglyceride with ethylene oxide and to those obtained by transesterification of a triglyceride with a polyethylene glycol.

Similarly, the term ethoxylated fatty acid includes both the products obtained by ethoxylation of a fatty acid with ethylene oxide and those obtained by esterification of a fatty acid with a polyethylene glycol.

The alkoxylated fatty amines generally have 15 from 10 to 22 carbon atoms, the alkoxy units being excluded from these numbers, and are preferably ethoxylated.

The alkoxylated fatty alcohols generally have from 6 to 22 carbon atoms, the alkoxy units being 20 excluded from these numbers and are preferably ethoxylated.

The alkoxylated alkylphenols generally have 1 or 2 linear or branched alkyl groups having 4 to 12 carbon atoms, in particular octyl, nonyl or dodecyl groups, and are preferably ethoxylated.

By way of examples of nonionic surfactants of the group comprising alkoxylated alkylphenols, alkoxylated bis(l-phenylethyl)phenols and alkoxylated 12 tris(l-phenylethyl)phenols, the following may be mentioned: ethoxylated ethoxylated units, ethoxylated units, ethoxylated units, ethoxcylated units, ethoxylated units, bis(I-phenylethyl)phenol with 5 OE 'units, bis(1-phenylethyl)phenol with 10 OE tris(l-phenylethyl)phenol with 16 OE tris(l-phenylethyl)phenol with 20 OE tris(1-phenylethyl)phenol with 25 OE tris(I-phenylethyl)phenol with 40 OE too b too* 009 .b C C 6 Ob PCbC lb be C

C

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be ethoxy/propoxylated 25 OE OP units, ethoxy/propoxylated units, ethoxy/prcopoxylated units, 20 ethoxy/propoxylated units, ethoxy/propoxylated units, ethoxy/propoxylated units.

tris -phenylethyl )phenols with nonyiphenols with 25 OE bP nonylphenols with 30 OE OP nonylphenols with 40 oE op nonylphenols with 55 OE OP nonyiphenols with 80 OE OP The compositions of the invention can naturally comprise several ionic and/or nonionic surf actants.

13 In order to have plant-protection compositions which are as satisfactory as possible from the standpoint of biodegradability, it will be preferable to use, among the ionic surfactants described above, phosphoric esters of ethoxylated fatty alcohols in acid form or in the form of their salts, sulphuric esters of ethoxylated fatty alcohols in acid form or in the form of their salts, phosphoric esters of ethoxylated fatty acids in acid form or in the form of their salts, betaines and imidazolines, and among the nonionic surfactants described above, ethoxylated triglycerides, ethoxylated sorbitan esters, ethoxylated fatt, alcohols and ethoxylated fatty acids.

4 The amount of surfactant used in the 4 15 compositions according to the invention may be 4 expressed as the weight ratio surfactant/sucroglycerides (the term surfactant in the present text not including the sucroglycerides).

e4 The ratio is generally not less than 0.8, and is preferably from 1 to The compositions can contain, apart from the active substance, sucroglycerides, surfactants and water, various other constituents such ass an antifreeze, an antifoam such as organopolysiloxanes, for example, a wetting agent, a thickening agent, water soluble compounds, 14 and auxiliary additives.

As wetting agents, the following may be mentioned, for example: surfactant compounds based on silicone, such as copolymers of polydimethylsiloxane and of either a homopolymer of ethylene glycol or a copolymer of ethylene glycol and propylene glycol; fluorinated surfactant compounds such as compounds containing a hydrophobic and oleophobic linear perfluorocarbon chaAn and a hydrophilic portion containing, Zor example, an acidic or neutralised sulphonic group, a carboxyl group or an ethoxylated alcohol residue.

Conventonal antifreezes such as ethy eno a Of, 15 glycol, propylene glycol, glycerol, diethylene *'ycol, triethylene glycol, tetraethylene glycol or urea may be used.

The antifreeze usually represents from 0 to 20 by weight, relative to the weight of the 0* 20 composition.

Water-soluble organic thickening ag ,tr, or those capable of swelling in water, such as polysaccharides of the xanthan gum type, alginates, carboxylated or hydroxylated methylcelluloses or synthetic macromolecules of the polyacrylate, polymaleate, polyvinylpyrrolidone, polyethylene glycol or polyvinyl alcohol type, or inorganic thickening agents such as bentonites or silicas, may be used.

As water-soluble compounds, there can be mentioned in particular salts such as sodium sulphate or ammonium sulphate.

Urea and its derivatives can also be mentioned.

The auxiliary additives which can be present are agents protecting again oxidation, UV rays or pH changes, colourings or bactericides.

The proportions, expressed in weight relative to the total weight of the composition, of the main constituents of the aqueous compositions of plantprotection active substances of the invention are generally as follows: from 1 to 50 and preferably from 2 to 40 of plant-protection active substance, from G~l to 40 and preferably from 1 to 30 of sucroglycerides, from 0.1 to 40 and preferably from 1 to 30 of ionic and/or nonionic surfactant, 15 and water q.s.

The compositions of the invention may be prepared by mixing their various constituents with stirring.

It is, more often than not, preferable, on the one hand to dissolve the plant-protection active Ssubstance in water, and on the other hand to prepare a mixture of the sucroglycerides, the ionic and/or n~nionic aurfactant or surfactants and the possible other additives in water wi'" stirring.

The antifreeze, when present, is then added with stirring to the emulsion of sucroglycerides, and the Solution of active substance is thereafter introduced in its turn.

16 In order to obtain a better homogeneity of the composition, the latter may then be transferred to an ultrasonic apparatus for one to a few minutes.

The compositions of the invention are stable for several months in a temperature range from -5°C to both at a given temperature and when they are subjected to temperature cycles. No recrystallisation, sedimentation or coalescence phenomenon has been ouserved on storage.

They are used for the treatment of plants, where appropriate after dilution with water or after

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mixing with aqueous suspensions, aqueous emulsions or aqueous suspo-emulsions of other active substances.

They occupy a very good position from the 15 ecotoxicological standpoint, since they do not contain an organic solvent, and the aucroglycerides they contain are especially non-toxic and biodegradable compounds which enable, in addition, the bioavailability of the active substances to be 20 increased.

The examples which follow illustrate the invention.

EXAMPLE 1 Composition based on ilvyhosate isopropylamine salt.

The isopropylamine salt of glyphosate is a herbicide obtained by neutralisation of one of the free acid functions of glyphosate of formula: 0 OH

II/

HO CO CH2 NH CH2 P-OH 200 g of a 60 weight/weight aqueous solution of glyphosate isopropylamine salt are introduced into a first container.

In a second container, a mixture of: 125 g of ethoxylated fatty alcohol containing 10 OE units and having an HLB of 14 75 g of rapeseed oil sucroglycerides 510 g of demineralised water is prepared.

S* 10 The mixture obtained is stirred and 90 g of monopropylene glycol are added. While stirring is continued, the 200 g of aqueous solution of glyphosate isopropylamine salt are then introduced.

The composition thereby obtained is transferred for 1 minute to an ultrasonic apparatus at maximum power in order to improve the homogeneity.

The composition has a pH of The compisition was stable: for more than 2 months at for more than 2 months in temperature cycles: 24 h at 24 h at EXAMPLE 2 Composition based on glyphosate isopropylamine salt.

Using the procedure described in Example 1, the following composition is prepared: 18 glyphosate isopropylamine salt (aqueous solution containing 60 by weight) :200 g phosphate of ethoxylated fatty alcohol, neutralised with butylamine 75 g ethoxylated fatty alcohol containing OE units (HLB =14) Sg rapeseed oil sucroglycerides 100 g monopropylene glycol 90 g demineralised water :485 g The compocition has r pH of The composition was stable: for more than 2 months at for more than 2 months in temperature cycles: 24 h at 24 h at EXAM'PLE .j Composition based on gly-phosate iso-orop-vlamine salt.

a *~Using the procedure described in Example 1,, the following composition is prepared: glyphosate isopropylaznine salt (aqueous solution containing 60 by weight) :200 g ethoxylated fatty alcohol cont&ining OE units (HLAi a 14) 200 g rapeseed oil suoroglycerides t 150 g monopropylene glyc~ol 1 110g demineralised water :340 g The composition has a pHI of The composition was stable: 19 for more than 2 months at for more than 2 months in temperature cycles: 24 h at -5 0

C

24 h at +45 0

C.

EXAMPLE 4 Composition based on glyphosate isopropylamine salt.

Using the procedure described in Example 1, the following composition is prepared: glyphosate isopropylamine salt (aqueous solution containing 60 by weight) 100 g S. phosphate of ethoxylated fatty alcohol, neutralised with potassium hydroxide 50 g rapeseed oil sucroglycerides 50 g xanthan gum (aqueous solution containing 15 2 by weight) 80 g 0 demineral.-ed water 720 g The composition has a pH of 5.3.

The composition was stable: 9* for more than 2 months at for more than 2 months in temperature cycles: 24 h at 24 h at *0 Composition based on alyphosate isopropylamine slt,.

Using the procedure described in Example 1, the following composition is prepared: glyphosate isopropylamine salt (aqueous solution containing 60 by weight) 182 g phosphate of ethoxylated fatty alcohol, neutralised with butylamine 75 g ethoxylated fatty alcohol containing OE units (HLB 14) 45 g rapeseed oil sucroglycerides 75 g demineralised water 623 g The composition has a pH of The composition was stable: for more than 2 months at 45 0

C

for more than 2 months, in temperature cycles: 24 h at 24 h at +450C.

EXAMPLE 6 S Composition based on glyphosate isopropylamine salt.

000* 15 Using the procedure described in Example 1, 0 the f';Towing composition is prepared: glyp 4-sate isopropylamine salt (aqueous solution containing 60 by weight) 230 g *I phosphate of ethoxylated fatty alcohol, neutralised with potassium hydroxide 80 g rapeseed oil sucroglycerides 58 g xanthan gum (aqueous solution containing 2 by weight) 74 g demineralised water 558 g The composition has a pH of The composition was stable: for more than 2 months at for more than 2 months in temperature cycles: 24 h at 24 h at +45 0

C.

EXAMPLE 7 Composition based on calv-Phosate-isoprgpvlam,,ne salIt.

Using the procedure described in Example 1, the following composition is prepared: glyphosate isopropylamine salt (aqueous solution containing 60 by weight) :200 g phosphate of ethoxylated fatty alcohol, neutralised with isopropylamine 50 g ethoxyrlated fatty alcohol cortaining OE units (HB =14) 50 g fe%- rapeseed oil sucroglycerides 75 g 0004 monopropylene glycol 94 g -derninexalised wAter :531 g The composition has a pH of The co'mpo sition was stable: -for more than 2 months at 450C -for more than 2 months in temperature 20 cycles: 24 hi at 24 h at +450C.

EXAMPLE 8 Composition based on clyvphoate isopro~ylamine-salt.

Using the procedure described in Example 1, the following composition is prepared: glyphosate isopropylamine salt (aqueous solution containing 60 by weight) :195 g phosphate of ethoxylated fatty alcohol, I I 22 neutralised with isopropylamine 73 g ethoxylated fatty alcohol containing OR units (HLB 14) 73 g copra oil sucroglycerides 73 g monopropylene glycol 88 g deminera3ised water 498 g The composition has a pH of The composition was stable: for more than 2 months at 450C for more than 2 months in temperature cycles: 24 h at 24 h at SXAMPLE 9 Composition based on glyphosate isopropylamine salt.

15 Using the procedure described in Example 1,

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the following composition is prepared: glyphosate isopropylamine salt (aqueous solution containing 60 by weight) 190 g phosphate of ethoxylated fatty alcohol, neutralised with butylamine 57 g ethoxylated fatty alcohol containing OE units (HLB 14) 57 g copra oil sucroglycerides 72 g monopropylene glycol 133 g demineralised water 491 g The composition has a pH of The composition was stable: for more than 2 months at 23 for more than 2 months in temperature cycles: 24 h at 24 h at EXAMPLE Composition based on glyphosate isopropylamine salt.

Usingr the procedure described in Example 1, the following composition is prepared: glyphosate isopropylamine salt (aqueous solution containing 60 by weight) 200 g ethoxylated castor oil containing 54 OE units 200 g

S

rapeseed oil sucroglycerides 100 g monopropylene glycol 90 g demineralised water 410 g 15 The composition has a pH of 0 The composition was stable: for more than 2 months at for more than 2 months in temperature k, 9cycles: 24 h at 24 h at +456C.

EXAMPLE 11 Composition based on clvyhosate isopropylamine salt.

Using the procedure described in Example 1, the following composition is prepared: glyphosate isopropylamine salt (aqueous solution containing 60 by weight) 190 g ethoxylated sorbitan monooleate containing 20 OE units (HLB 15) 238 g 24 rapeseed oil sucroglycerides 143 g monopropylene glycol 95 g demineralised water .334 g The composition has a pH of The composition was stable: for more than 2 months at 45 0

C

for more than 2 months in temperature cycles: 24 h at 24 h at +450C.

EXAMPLE 2 Composition based on glvyot isoropylamine salt.

Phoat iso Using the procedure describ'ed in Example 1, the following composition is p~repared: glyphosate isopropylauine salt (aqueous solution containing 60 by weight) :190 g ethoxylated sorbitan monooleate containing OE units (HLB 15) Sg phosphate of ethoxylated fatty alcohol, *.neutralised with isopropylamine 60 g rapesez~d oil sucroglycerir~s 75 g monopropylene glycol 90 g demineralised water :525 g 6 The composition has a pH of The composition was stable: *~for more than 2 months at -for more than 2 months in temperature cycles: 24 h at -S*C 24 h at +454C.

EXAMPLE 13 Composition based on alvohcItsatc isopropylamine salt.

Using the procedure described in Example 1, the following composition is prepared: glyphosate isopropylamine salt (aqueous solution containing 60 by woight) 190 g ethoxylated sorbitan monooleate containing OE units (HLB 15) :190 g phosphate of ethoxylated fatty alcohol, neutralised with butylamine 48 g rapeseed oil sucroglycerides :143 g monopropylene glycol 2 95 g 1- demineralised water 1 334 g *too eve The composition has a pH of The composition was stable: for more than 2 months at 450C for more than 2 months in temperature cycles: 24 h at 24 hi at +450C.

EXAMPLE 14 Comnosition based on-guazatine triacetate.

Guazatine triacitate is a fungicide obtained 0 by neutralisation using-acetic acid of guazatine of formula: R NH (CH 2 5 N C(CH2) 5 N] 1

H

R R witht n 1 or 2 $I I I R H (17 to 23 or -C=NH (77 to 83

NH

z Using the procedure described in Example 1, the following composition is prepared: guazatine triacetate (aqueous solution containing 70 by weight) 300 ethoxylated copra oil containing 28 OE units 58 ethoxylated castor oil containing 18 OE units 58 disodium 2-undecyl-l-hydroxy-1- (carboxylatomethyl)-1- [2-(carboxylatomethoxy)ethyl]imidazoline 175 rapeseed oil sucroglycerides 58 demineralised water 351 The composition has a pH of The composition was stable: for more than 2 months at for more than 2 months in temperature cycles: 24 h at 24 h at g g g 6 S6gO So 6O 0 6 e *o *S A *0 g g EXAMPLE Composition based on clyphosate isopropylamine salt and acifluorfen sodium salt.

The sodium salt of acifluorfen is a herbicide obtained by neutralisation with sodium hydroxide of acifluorfen of formula:

COOH

CF3 -0 N02 Using the procedure described in Example 1, the following composition is prepared: glyphosate isopropylamine salt (aqueous solution containing 60 S by weight) 175 g acifluorfen sodium salt (aqueous solution containing 21 by weight) 75 g phosphate of ethoxylated fatty alcohol, neutralised with butylamine 75 g S* ethoxylated fatty alcohol containing 10 10 OE units (HLB 14) 50 g rapeseed oil sucroglycerides 100 g monopropylene glycol 90 g @*fee: demineralised water 435 g The composition has a pH of The composition was stable: S for more than 2 months at for more than 2 months in temperature cycles: 24 h at 24 h at S*

O

EXAMPLE 16 Composition based on qlyphosate isopropylamine salt Using the procedure described in Example 1, the following composition is prepared glyphosate isopropylamine salt 80 g (expressed in the acid form of glyphosate) ethoxylated fatty alcohol containing 10 OE units (HLB 14) 45 g phosphate of ethoxylated fatty alcohol, 0 neutralised with isopropylamine 75 g

*,I

copra oil sucroglycerides 80 g demineralised water quantity for 1000 cm 3 The composition has un pH of 4.8.

The composition was stable for more than 2 months at for more than 2 months in temperature cycles 24 h at S* 24 h at The composition was homogeneous and did not separate 20 into different phases on storage during a long time. By dilution with water it gave a stable opalescent solution.

EXAMPLE 17 Composition based on glyphosate isopropvlamine salt Using the procedure described in Example 1, the following composition is prepared glyphosate isopropylamine salt 90 g (expressed in the acid form of glyphosate) ethoxylated fatty alcohol containing 10 OE units (HLB 14) 120 g copra oil sucroglycerides 90 g monopropylene glycol 150 g demineralised water quantity for 1000 cm 3 The composition has un pH of 5.1.

The composition was stable for more than 2 months at for more than 2 months in temperature cycles 24 h at 24 h at 10 The composition was homogeneous and did not separate into different phases on storage during a long time. By dilution with water it gave a stable opalescent solution.

EXAMPLE 18 Composition based on qlyphosate isopropylamine salt Using the procedure described in Example 1, the following composition is prepared glyphosate isopropylamine salt 90 g

•O

(expressed in the acid form of glyphosate) ethoxylated fatty alcohol containing 10 OE units (HLB 14) 60 g phosphate of ethoxylated fatty alcohol, neutralised with isopropylamine 60 g copra oil sucroglycerides 90 g urea 300 g demineralised water quantity for 1000 cm 3 The composition has un pH of 6.3.

The composition was stable for more than 2 months at for more than 2 months in temperature ,0 It cycles 24 h at 24 h at 450C.

The composition was homogeneots and did not separate into dilfferent phases on storage during a long time. By dilution wit "er it gave a stable opalescent solution.

EXI. 19 .Ccj LOc based on qlyphosate isopropylamine salt Using the procedure described in Example 1, the followirti composition is prepared 10 glyphosate isopropylamine salt 110 g 0* S" (expressed in the acid form of glyphosate) ethoxylated fatty alcohol containing 10 OE units (HLB 14) 75 g phosphate of ethoxylated fatty alcohol, neutralised with isopropylamine 75 g copra oil sucroglycerides 110 g S. monopropylene glyco 180 g demineralised water quantity for 1000 cm 3 The compositioiv has un pH of 5.8.

The composition was stable for more than 2 months at for more than 2 months in temperature cycles 24 h at 24 h at The composition was homogeneous and did not separate into different phases on storage during a long time. By dilution with water it gave a stable opalescent solution.

I I I 31 EXAMPLE Composition based on qlyphosate isopropylamine salt Using the procedure described in Example 1, the following composition is prepared glyphosate isopropylamine salt 90 g (expressed in the acid form of glyphosate) ethoxylated fatty alcohol containing 10 OE units (HLB 14) 90 g phosphate of ethoxylated fatty alcohol, 10 neutralised with isopropylamine 90 g S• copra oil sucroglycerides 126 g urea 300 g S demineralised water quantity for 1000 cm 3 to**: The composition has un pH of The compostibC, was stable for more than 2 months at f more than 2 months in temperature cycles 24 h at 24 h at The composition was homogeneous and did not separate into different phases on storage during a long time. By dilution with water it gave a stable opalescent solution.

EXAMPLE 21 Comoosition based on alvphosate isoproovlamine salt Using the procedure described in Example 1, the following composition is prepared glyphosate isopropylamine salt 90 g (expressed in the acid form of glyphosate) 1 t 32 ethoxylated fatty alcohol containing 10 OE units (HLB 14) 60 g phosphate of ethoxylated fatty alcohol, neutralised with isopropylamine rapeseed oil su;roglycerides urea demineralised water The composition has un pH of The composition was stable 10 for more than 2 months at 4 for more than 2 months in t cycles 24 h at 24 h at S60 g 90 g S 300 g quantity for 1000 cm 3 o*

S

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C

O 5.9.

emperature The composition was homogeneous and did not separate into different phases on storage during a long time. By dilution with water it gave a stable opalescent solution.

EXAMPLE 22 ComDosition based on manganese sulfate Using the procedure described in Example i (with replacing the glyphosate isopropylamine salt by manganese sulfate), the following composition is prepared (the percentages are in weight by weight) aqueous solution of manganese sulfate at 34 in weight by weight (corresponding to 11 of Mn) 59 copra oil sucroglycerides 6 sodium lauryl sulfate 6 demineralised water 29 The composition has a pH of 5.7.

33 The composition was ':table for more than 2 months at for more than 2 monthi in temperature cycles 24 h at O'C 24 h at The composition was homogeneous and did not separate into different phases on storage during a long time. By dilution with water it gave a stable opalescent solution.

EXAMPLE 23 Composition based on manganese sulfate Using the procedure described in Example 1 (with replacing the glyphcsate isopropylamine salt by manganese sulfate), the following composition is prepared (the percentages are in weight by weight) aqueous solution of manganese sulfate at 34 in weight by weight (corresponding to 11 of Mn) 54 copra oil sucroglycerides 7 sodium lauryl sulfate 4 monopropylene glycol 10 demineralised water 25 The composition has a pH of 5.7.

The composition was stable for more than 2 months at for more than 2 months in temperature cycles 24 h at O'C 24 h at .0 I I 34 The composition was homogeneous and did not separate into different phases on storage during a long time. By dilution with water it gave a stable opalescent solution.

EXAMPLE 24 Composition based on manoanese sulfate Using the procedure described in Example 1 (with replacing the glyphosate isopropylamine salt by manganese sulfate), the following composition is prepared (the percentages are in weight by weight) <n 10 aqueous solution of manganese sulfate at 34 in weight by weight (corresponding to 11 of Mn) 50 copra oil sucroglycerides 3 sodium lauryl sulfate 1.5 sodium lauryl ether sulfate (with 3 OE units) 1.5 mot propylene glycol 12 demineralised water 32 "a The composition has a pH of 5.7.

The composition was stable for more than 2 months at for more than 2 months in temperature cycles 24 h at O'C 24 h at The composition was homogeneous and did not separate into different phases on storage during a long time. By dilution with water it gave a stable opalescent solution.

EXAMPLE Composition based on manganese sulfate Using the procedure described in Example 1 (witn replacing the glyphosate isopropylamine salt by manganese sulfate), the following composition is prepared (the percentages in weight by weight) aqueous solution of manganese sulfate at 34 in weight by weight (corresponding to 11 of Mn) 44 copra oil sucroglycerides 5 S 10 sodium lauryl ether sulfate (with 3 OE units) 5 monopropylene glycol 9 *r 0 demineralised water 37 The composition has a pH of 5.6.

The composition was stable for more than 2 months at for more than 2 months in temperature cycles 24 h at 0*C 24 h at The composition was homogeneous and did not separate into different phases on storage during a long time. By dilution with water it gave a stable opalescent solution.

EXAMPLE 26 Composition based on manganese Using the procedure described in Example 1 (with replacing the glyphosate isopropylamine salt by manganese disodium salt of EDTA), the following composition is prepared (the percentages are in weight by weight) aqueous solution of manganese disodium salt of EDTA at 35 in weight by weight (corresponding to 5 of Mn) copra oil sucroglycerides phosphate of ethoxylated fatty alcohol (with 6 OE) neutralised with potassium hydroxide phosphate of ethoxylated fatty alcohol (with 6 OE) demineralised water S

C

9 00 S 0 r* 00 *0 The composition has a pH of 4.4.

The composition was stable for more than 2 months at for more than 2 months in temperature cycles 24 h at O'C 24 h at 15 The composition was homogeneous and did not separate into different phases on storage during a long time. By dilution with water it gave a stable opalescent solution.

EXAMPLE 27 Composition based on manganese Using the procedure described in Example 1 (with replacing the glyphosate isopropylamine salt by manganese disodium salt of EDTA), the following composition is prepared (the percentages are in weight by weight) aqueous solution of manganese disodium salt of EDTA at 35 in weight by weight (corresponding to 5 of Mn) 60 copra oil sucroglycerides 6 0 I 37 phosphate of ethoxylated fatty alcohol (with 6 OE) neutralised with potassium hydroxide 5 phosphate of ethoxylated fatty alcohol (with 6 OE) 5 demineralised water 24 The composition has a pH of 4.7.

The composition was stable for more than 2 months at for more than 2 montht in temperature cycles 24 h at O"C 10 24 h at *0 The composition was homogeneous and did not separate 00** into different phases on storage during a long time. By dilution with water it gave a stable opalescent solution.

94006e 4 EXAMPLE 28 Composition based on manganese Using the procedure described in Example 1 *i (with replacing the glyphosate isopropylamine salt by manganese *4 disodium salt of EDTA), the following composition is prepared (the percentages are in weight by weight) aqueous solution of manganese disodium salt of EDTA at 35 in weight by weight (corresponding to 5 of Mn) 72 copra oil sucroglycerides 3,6 phosphate of ethoxylated fatty alcohol (with 6 OE) neutralised with potassium hydroxide 3 phosphate of ethoxylated fatty alcohol (with 6 OE) 3 monopropylene glycol 5 demineralised water 13,4 38 The composition has a pH of 4.9.

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Claims

1. Aqueous compositions of water-soluble plant-protection active substance, characterised in that they contain at least one water-soluble plant- protection active substance, sucroglycerides, at least one surfactant and water.

2. Compositions according to claim 1, characterised in that the water-soluble plant- protection active substance is selected from the 10 soluble salts of the various parent substances mentioned below, obtained by neutralising the acid functions of glyphosate, of glufosiLnate of 2,4-D, of o 2,4-DES, of MCPA, of m6coprop, of acifluorfen, of clopyralid or of MSMA with an alkali metal hydroxide, an amine or an alkanolamine, or by neutralising the amine functions of guazatine or of paraquat using an inorg nic acid such as hydrochloric acid or sulphuric C acid or an organic acid such as acetic acid.

3. Compositions according to one of claims 1 and 2, characterised in that the water-soluble plant- protection active substance is selected from: glyphosate, in the form of its isopropylamine salt or its sodium salt, glufosinate, in the form of its ammonium salt, 2,4-D, in the form of its 2-hydroxyethyl- ammonium, dimethylammonium or tris(2-hydroxyethyl- ammonium) salt, 2,4-DES, in the form of its sodium salt, guazatine, in the form of its triacetate, MCPA, in the form of its sodium, potassium or dimethylammonium salt, m6coprop, in the form of its sodium or potassium salt, acifluorfen, in the form of its sodium or potassium salt, clopyralid, in the form of a 2-hydroxy- 10 ethyl/ammonium or potassium salt, MSMA, in the form of its sodium salt, paraquat, in the form of its dichloride or its bis(methyl sulphate).

4. Compositions according to claim 1, characterised in that the water-soluble plant-protection active substance is selected from micronutrients in the form of water-soluble metallic salts or chelates. Compositions according to one of claims 1 or 4, characterised in that the water-soluble plant-protection active substance is selected from manganese sulphate, magnesium sulphate, the manganese complex of the disodium salt of ethylenediamine tetraacetic acid (EDTA), the copper complex of the disodium salt of EDTA, the zinc complex of the disodium salt of EDTA, the cobalt complex of the disodium salt of EDTA, the manganese complex of the dipotassium salt of EDTA.

6. Compositions according to one of claims 1 to 5, characterised in that the sucroglycerides originate from the transesterification of triglycerides, preferably natural triglycerides, with sucrose.

7. Compositions according to one of claims 1 to 6, characterised in that the triglycerides employed for the preparation of the sucroglycerides are selected from natural triglycerides ouch as lard, tallow, groundnut oil, butter oil, cotton seed oil, linseed oil, olive oil, palm eil, grape pip oil, fish 15 oil, soybean oil, castor oil, rapeseed oil, copra oil S and coconut oil.

8. Compositions according to one of claims 1 to 7, characterised in thet they contain from 0.1 to 40 by weight of sucroglycerides relative to the total weight of the composition, and preferably from 1 to 30 weight/weight.

9. Compositions according to one of claims 1 to 8, characterised in that the surfactants~ which they contain are ionic and/or nonionic. Compositions according to claim 9, characterised in that the ionic surf actants are anionic surf actants such ast phosphoric esters of alkoxylated fatty alcohols, of alkoxylated fatty acids, of alkoxylated alkyiphenols, of alkoxylated bis(l-phenylethyl)phenols, of alkoxylated tris -phenylethyl.) phenols; -sulphuric esters of alkoxylated fatty alcohols, of alkoxylated alkylphenols, of alkoxylated bis(1- phenylethyl)phenols, of alkoxylated tris(l- phenylethyl )phenols; the unesterified function or functions of the :phosphoric acid or sulphuric acid can be in acid foim 96400 20 or in the form of a sodium, potassium, amnmonium, amine or alkanolamine saltj -alkylarylsulfonates such as al kyl benzene- sul fonates and alkylnaphtalene-sulfonates of sodium, potassium, calcium, *::,ammoniumn, amine or alkanolamine alkylsulfates of sodium, potassium, ammonium, amine or alkanolamine alkyl(polyoxyalkylene)sulfates of sodium, potassium, ammonium, amine or alkanolamine.

11. Compositions according to claim characterised in that the alkoxy units of the anionic surfactants are oxyethylene and/or oxypropylene units, which vary in number from 2 to 100 and preferably from 4 to

12. Compositions according to one of claims to and ii, characterised in that the anionic surf actants are selected from: the triethanolam~ine salts of the phosphoric monoester and diester of ethoxylated tris(l-phenylethyl)phenol with 16 CE units, the potassium~ salts of the phosphoric monoester and diester of ethoxylated tris(1-phenylethyl)phenol with 16 OE units, the zacid sulphate of ethoxylated bis(l-phenylethyl)- phenol with 11 OE units, 6 010 the potassium salt of the sulphuric monoester of too* 0ethoxylated bis(l-phenylethyl)phenol with 15 OE units, -the triethcinolamine salt of the sulphuric monoester of ethoxylated bis(1-phenylethyl)phenol with 11 CE units, :15 the amomonium salt of,the sulphuric monoester of e thoxylated tris(1-phenyletikyl)phenol with 16 OE units, the'acid phosphate of ethoxylated nonyipheno. with 9 OE unitst the dodecylbenzene sulfonate of sodium, the me-thylnaphtalene sulfonate of sodium, the lauryl sulfate of sodium, the lauryl ether sulfate of sodium with 3 OE units.

13. Compositions according to claim 9, characterised in that the ionic surfactants are cationic or amphoteric surfactants such as betaines and imidazolines.

14. Compositions according to claim 13# chavacterised in that the betaines are axphotoric surfactants of the following formulae: Ii U~ 44 CH3 RI N CH2COO- CH 3 CH2 RI N+ CH 2 COO- CH2 -COONa RI -SH-N HCO S.2 in whch Rrpeet ina rbace akl.ophvn 3.o1 aro tm, uha, o x.le rpl *oey orhxdcl ra laaiogopsc s ease xape ddc*aie R rerset NH hyroe atom or aCH2COogrup opoiinsacrin ocli 4 chrceie nta h iiaoie r opud deie frmiidzlnecnanigaliero brnce alyRrakny usiu hvn o2 cabo atm ntecro t h -oiino h imidazoline ringj and containing on the nitrogen atom at the 1-positiOn one or more subutituents such as hydroxyl, sodiiun alkanolate, hydroxyalkyl, sodium alkylcarboxylate, sodium alkoxyalkylcarboxylate or sodium hydroxyalkylsuiphonate.

16. Compositions according to claim 9, characterised in that the nonlonic surfactants are selected from: alkoxylated triglycerides, alkoxylated sorbitan esters, alkoxylated fatty acids, 4*4 alkoxylated fatty alcohols, 0e00 alkoxylated fatty amines, -0loyae i~-peyehlpaos alkoxylated bis -phenylethyl )phnols, alkoxylated alkylphenols.

17. Compositions according to claim 16, characterised in that the alkoxy units of the nonionic surfactants are oxyethylene and/or oxypropylene units, which vary ia number from 2 to 100 and preferably from 4 to 1e. Composit~ons according to one rf claims 16 and 17f characterised in that: the alkoxylated triglycerides are ethoxylated triglycerides of vegetable or animal origin, such as lard, tallow, groundnut oil, butter oil, cotton seed oil, linseed oil, olive oil, palm oil, grape pip oil, fish oil# soybean oil, castor oil, rapeseed oil, copra oil, coconut oil; the alkoxylated fatty acids are ethoxylated esters of fatty acids such as oleic acid, s~earic acid; the alkoxylated sorbitan esters are ethoxylated cyclised sorbitol esters of CIO to C 20 fatty acids such as lauric acid, stearic acid or oleic acid; the alkoxylated fatty amines have from 10 to 22 carbon atoms; the alkoxylated fatty alcohols have from 6 to 22 carbon atoms; the alkoxylated alkylphenols have 1 or 2 linear or #too branched alkyl groups having 4 to 12 carbon atoms,

19. Compositions according to one of claims 16 and 17, characterised in that the nonionic surfactants are selected from: ethoxylated bis(1-phnylethyl)phenol with 5 O units, 0 0 4 ethoxylated bia(I-phnylethyl)phenol with 10 OS 06 4units, 06006: ethoxylated tris(1-phenylethyl)phenol with 16 OE units, ethoxylated tris(1.-phenylethyl)phenol with 20 OE units, ethoxylated tris(1-phenylethyl)phnol with 25 OE units# ethoxylated tris(1-phenylethyl)phenol with 40 OE units, ethoxy/propoxylated tris(1-phenylethyl)phenols with OE OP units, ethoxy/propoxylated nonylphenola with 25 OE OP units, ethoxy/propoxylated nonylphenols with 30 OE OP units, ethoxy/propoxylated nonylphenols with 40 OE OP units, ethoxy/propoxylated nonylphenols with 55 OE OP units, ethoxy/propoxylated nonylphenols with 80 OE OP 10 units.

20. Compositions according to one of claims t- 12~ characterised in that the amount of surfactant used is such that the weight ratio surfactant/sucroglycerides is not less than 0.8 and is preferably from 1 to

21. Compositions according to one of claims 1 to 20 characterised in that they contain, apart from 9 the active substance, sucroglycerides, surfactants and Swater, various other constituents such as. an antifreeze, an antifoarm such as organopolysiloxanes, for example, a wetting agent, a thickening agent, and auxiliary additives.

22. Compositions according to one of claims 1 to 21, characterised in that the proportions of their main constituents, in weight relative to the total I 48 weight of the composition, are as follows: from 1 to 60 and preferably from 2 to 40 of plant-protection active substance, from 0.1 to 40 and preferably from 1 to 30 of sucroglycerides, from 0.1 to 40 and preferably from 1 to 30 of ionic and/or nonionic surfactant, and water q.s.

23. Process for preparing the compositions 10 according to one of claims 1 to 22, characterised in that: *00*a on the one hand, the plant-protection active substance is dissolved in water, on the other hand, a mixture of the sucroglycerides, the ionic and/or nonionic surfactant or surfactants and the possible other additives in water is prepared with stirring, the antifreeze, when present, is added with stirring to the emulsion of sucroglycerides, the solution of active substance is thereafter introduced into the emulsion of sucroglycerides. 2,4, Use of compositions according to one of claims 1 to 22 for the treatment of plants, where appropriate after dilution with water or after mixing with aqueous suspensions, aqueous emulsions or aqueous suspo-emulsions of other active substances. 11 An aqueous composition of water-soluble plant.-protection active substance substantially as herein described with reference to the examples. DATED this 6th Day of January, 1992 RHONE-POULENC CHIMIE Attorney:' IAN ERNS'T Fellow Institute of Patent Attorneys of Airv-Pz' of SHELSTON WATERS 1 0"- ABSTRACT The present invention relates to new plant- protection compositions and to their use for the treatment of plants. **e More specifically, it hence relates in the 5 first place, to aqueous compositions of water-soluble plant-protection active substance, characterised in that they contain a least one water-soluble plant- protection active substance, sucroglycerides, at least 9494 one surfactant and water. 10 These compositions are used for the treatment of plants, where appropriate after dilution with water or after mixing with aqueous suspensions, aqueous 9* 4 9 emulsions or aqueous suspo-emulsions of other active substances.