FR2720399A1 - Sulphonated polyester(s) soluble or dispersible in water - Google Patents

Abstract

Water soluble or dispersible sulphonated polyesters obtd. by esterification and/or transesterification and polycondensation of a monomer compsn. based on: (i) a non-sulphonated diacid monomer (A) comprising at least one dicarboxylic acid or anhydride chosen from terephthalic acid or anhydride, isophthalic acid or anhydride, naphthalene-2,6-dicarboxylic acid or their diesters in an amt. corresponding to a mol. ratio (A)/(A)+(SA) of 95/100 to 60/100, pref. 93/100 to 65/100; (ii) a sulphonated diacid monomer (SA) comprising at least one sulphonated aromatic or aliphatic dicarboxylic acid or anhydride or their diesters in an amt. corresponding to a mol. ratio (SA)/(A)+(SA) of 5/100 to 40/100, pref. 7/100 to 35/100, up to 50 mol.%, esp. up to 30 mol.% of the amt. of non-sulphonated diacid monomer (A) and/or of the sulphonated diacid monomer (SA) opt. being replaced by a hydroxylated diacid monomer comprising at least one monomeric hydroxylated aromatic or aliphatic dicarboxylic acid (HA) or a diester of this; and (iii) a polyol monomer (P) comprising at least one polyol chosen from ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerol, 1,2,4-butanetriol and 1,2,3-butanetriol in an amt. corresponding to a ratio of the number of OH functions of the polyol (P) to the number of functions and equiv. functions of the acids (A)+(SA)+(HA) of 1.05-4, pref. 1.1-3.5 and esp. 1.8-3; with the provisos that: (1) the monomer (SA) comprises at least one aromatic sulphonated dicarboxylic acid or anhydride or a mixt. of aromatic sulphonated dicarboxylic acid(s) or anhydride(s) and aliphatic sulphonated acid(s) or anhydride(s) or their diesters when the polyol monomer (P) contains no polyol other than a glycol or when the hydroxylated diacid (HA) is absent; and (2) the sulphonated polyester has a number ave. mol.wt. of less than 20,000, a sulphur content of 0.5-10 (1.2-8) wt.% and an OH content of greater than 0.2 OH equivs./kg polymer.

Description

 The present invention relates to new water-dispersible or water-soluble sulfonated polyesters, their preparation process and their use as anti-fouling and / or anti-redeposition agent and optionally detergent in detergent compositions, in rinsing, softening or treatment compositions. anti-fouling (wfinishing "), for washing with or without pretreatment, rinsing, softening or anti-fouling treatment of textiles, in particular based on polyesters.

According to the invention, these are water-dispersible or water-soluble sulfonated polyesters, characterized in that they are capable of being obtained by esterification / polycondensation of a monomer composition based on:
- a non-sulfonated diacid monomer (A) consisting of at least one dicarboxylic acid chosen from terephthalic, isophthalic and 2.6 naphthalene dicarboxylic acids, or their diesters, in an amount corresponding to a molar ratio (A) / (A ) + (SA) of the order of 92/100 to 60/100, preferably of the order of 90/100 to 85/100
- a sulfonated diacid monomer (SA) consisting of at least one sulfonated aromatic dicarboxylic acid or sulfonated aliphatic acid, or their diesters, in an amount corresponding to a molar ratio (SA) / (A) + (SA) of the order from 8/100 to 401100, preferably of the order of 10/100 to 15/100 up to 40 mol%, preferably up to 30 mol%, and very particularly of the order of 10 to 20 mol%, the quantity of unsulfonated diacid monomer (A) and / or of sulfonated diacid monomer (SA) which can be replaced by a hydroxylated diacid monomer (HA) consisting of at least one aromatic or aliphatic aromatic or aliphatic dicarboxylic acid or a diester of said aromatic or aliphatic dicarboxylic acid hydroxylated
- And a polyol monomer (P) consisting of at least one polyol chosen from ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycerol, glycerol, 1,2,4 butane triol and 1 , 2.3 butane triol, in an amount corresponding to a ratio of the number of OH functions of (P) / number of COOH functions of the diacids (A) + (SA) + (HA) of the order of 1.5 to 3 , preferably of the order of 1.8 to 2.2 in that the sulfonated diacid monomer (SA) consists of at least one sulfonated aromatic dicarboxylic acid or of a mixture of sulfonated aromatic acid (s) and sulfonated aliphatic acid (s), or their diesters, when the polyol monomer (P) does not contain a polyol other than a glycol or when the hydroxylated diacid (HA) monomer is absent and in that said polyesters sulfonated present. a number-average molecular mass of less than 15,000,. a sulfur content by weight of the order of 0.5 to 10%, preferably of the order of 1.2 to 8% and a content of hydroxyl functions expressed in OH equivalent / kg of polymer greater than 0.2
The contents of hydroxyl functions are estimated by proton NMR; the measurement is carried out in dimethyl sulfoxide.

 The molecular weights in number are measured by gel permeation chromatography, in dimethylacetamide containing 10-2 N of LiBr, at 25 ° C. The results are expressed in polystyrene equivalents.

The elementary entity considered in the definition of the mole of (A), (SA) or (HA) is the function COOH
The unsulfonated dicarboxylic acids (A) preferably consist of 50 to 100 mol% of terephthalic acid or one of its lower diesters (methyl, ethyl, propyl, isopropyl, butyl) and from 0 to 50% of isophthalic acid and / or 2.6-naphthalene dicarboxylic acid or one of their lower diesters (methyl, ethyl, propyl, isopropyl, butyl); the preferred diesters are those of methyl.

In addition, there may be present, alongside these dicarboxylic acids, minor amounts of other aromatic diacids such as orthophthalic acid, anthracene acids, 1,8-naphthalene, 1,4-naphthalene, biphenyl. dicarboxylic, or aliphatic diacids such as adipic, glutaric, succinic, trimethyladipic, pimelic, azelaic, sebacic, suberic, itaconic, maleic ... in acid, anhydride or lower diesters form (methyl, ethyl, propyl, isopropyl, butyl).

 The sulfonated dicarboxylic acids (SA) have at least one sulfonic acid group, preferably in the form of an alkali metal sulfonate (preferably sodium), and two acid functions attached to one or more aromatic rings.

in the case of aromatic dicarboxylic acids, or on the aliphatic chain, in the case of aliphatic dicarboxylic acids.

Among these sulfonated acids (SA), mention may be made of aromatic sulfonated dicarboxylic acids such as sulfoisophthalic, sulfoterephthalic, sulfophthalophthalic acids, sulto4 naphthalene dicaioxylic acid 2,7, sulfobis (hydroxycarbonyl) 4 , 4 'diphenylsulfones, suWo-dipherf dicarboxylic acids, sulfobis (hydroxycarbonyl) -4,4' diphenylmethanes, sulfo-5-phenoxy-isophthalic acids or their lower diesters (methyl, ethyl, propyl. Isopropyl, butyl). sulfonated aliphatic sulfonated dicarboxylic acids such as sulfo-succinic acids or their lower di esters (methyl, ethyl, propyl, isopropyl, butyl). The preferred sulfonated dicarboxylic acids (SA) are sulfoisophthalic and sulfo-succinic acids, and most particularly dimethyl sodio-oxysulfonyl-5 isophthalate.

 Hydroxy dicarboxylic acids (HA) have at least one hydroxyl group attached to one or more aromatic rings, in the case of aromatic dicarboxylic acids, or to the aliphatic chain, in the case of aliphatic dicarboxylic acids .

Among these acids (HA), mention may be made of 5-hydroxy isophthalic, 4-hydroxy isophthalic, 4-hydroxy phthalic, 2-hydroxysuccinic, hydroxymethylglutaric, hydroxyglutaric ..., or their lower di esters (methyl, ethyl, propyl, isopropyl , butyl).

 The polyol (P) preferably used is monoethylene glycol and / or glycerol.

 Said water-soluble and / or water-dispersible sulfonated polyesters can be obtained by the usual esterification / polycondensation processes, for example by esterification reaction, in the presence of an esterification catalyst, of the polyol (s) (P) with the various acids1 each acid being in the acid form or in the form of one of its diesters; and polycondensation of polyol esters at reduced pressure, in the presence of a polycondensation catalyst.

According to a preferred mode of preparation, said water-soluble and / or water-dispersible sulfonated polyesters are obtained by carrying out the following successive steps:
a transesterification step (interchange) between on the one hand a fraction of all of the non-sulfonated dicarboxylic acids and the sulfonated dicarboxylic acid (s) and on the other hand a fraction of the polyds (P), the ratio number of OH functions of (P) / number of COOH functions of the fraction of all of the non-sulfonated dicarboxylic acids and of the sulfonated dicarboxylic acid (s) being of the order of 1.1 to 3.5, preferably of in the range of 2.0 to 3.0
an esterification step between the remaining fraction of all the non-sulfonated dicarboxylic acids and the remaining fraction of the polyol (s) (P), the ratio number of OH functions of the remaining fraction of (P) / number of functions
COOH of the remaining fraction of all of the unsulfonated dicarboxylic acids being of the order of 1.1 to 3.5, preferably of the order of 2.0 to 3.0
- a polycondensation step
The non-sulfonated and sulfonated dicarboxylic acids used at the transesterification (interchange) stage are preferably present in the form of their methyl diesters.

The non-sulfonated dicarboxylic acid (s) used in the esterification step are preferably present in acid form.

 The interchange stage is carried out at a temperature greater than or equal to 130 "C, preferably of the order of 140 to 220" C and more particularly of ordering from 180 to 220 "C; at this temperature the methanol formed is eliminated of the reaction medium, preferably by distillation. This interchange operation is preferably carried out in the presence of a metal transesterification catalyst, in particular of a metal carboxylate, such as manganese acetate, zinc acetate, cobalt or calcium acetate, or an organic or inorganic titanate, such as butyl titanate, 2,2 ', 2 "-triethyl titanate (or titanium aminotriethanolate) or calcium titanate. Preferred catalysts are organic titanates; they are used in quantities of the order of at least 0.001% by weight expressed as titanium, preferably of the order of 0.002% to 0.02% by weight of titanium relative to the weight of reactants present.

The duration of the interchange operation is 1 to 4 hours; it is generally of the order of 2 to 3 hours.

When more than 90% of the theoretical amount of methanol has been distilled, the excess polyol is removed by bringing the temperature of the reaction medium to 230 ° C.

 The esterification operation is carried out by adding to the reaction medium, the remaining fraction of the unsulfonated aromatic dicarboxylic acids and the remaining fraction of the polyol (s), previously suspended, at a temperature corresponding to that of the end of the interchange temperature; the introduction period is around 1 hour.

This esterification operation is carried out at a temperature of the order of 230 to 280 "C, preferably of the order of 250 to 260" C, in the presence of a catalyst of the same type as that of transesterification; preferred catalysts are organic titanates; they are used in quantities of the order of at least 0.001% by weight expressed as titanium, preferably of the order of 0.002% to 0.02% by weight of titanium relative to the weight of reagents introduced into the 'esterification step; the reaction is carried out with elimination of water which is withdrawn from the reactor at the same time as the excess polyol.

 The polycondensation operation is preferably carried out at a temperature of the order of 230 to 280 "C, preferably of the order of 240 to 260" C, in another reactor previously brought to this temperature and gradually evacuated up to a pressure which can go up to 10 Pa; a pressure reduction up to approximately 10 millibar lasts on the order of 40 minutes.

The polycondensation operation takes place with elimination of polyol molecules, this operation is stopped when the motor torque of the stirring shaft indicates a value equivalent to approximately 0.5 to 5 meters.newton for a temperature of 250 "C reaction mass and a stirring speed of 80 revolutions / minute of an anchor-shaped mobile in a 7.5 liter reactor; the torque meter used is of the KYOWA type, the measurement range of which is between 0 and 100 meters.newton.

The vacuum is then broken with nitrogen, and the polymer is poured into an ingot mold; after cooling, the polymer is ground.

The preferred sulfonated polyesters can be obtained from
- terephthalic acid (Al) and isophthalic acid (A2), or terephthalic acid (Al) and a hydroxylated terephthalic acid or hydroxylated isophthalic acid (HA) optionally mixed with isophthalic acid (A2) , according to a molar ratio (A1) / (A2), (A1) / (HA) or (A1) / (HA) + (A2) of the order of 100/0 to 0/100, very particularly of the on the order of 100/0 to 50/50, the acids (Al) and (A2) preferably being in the form of their diesters, in particular in the form of methyl diester,
- a sulfoisophthalic acid (preferably in the form of its diesters, in particular in the form of methyl diester) as sulfonated dicarboxylic acid (SA)
- monoethylene glycol and / or glycerol as polyol (P)
They can be prepared according to the preferred method described above, by carrying out the following successive steps:
- a transesterification (inter-exchange) step between terephthalic acid (Al) and sulfoisophthalic acid (SA) on the one hand and monoethylene glycol and / or glycerol (P) on the other hand, the ratio number of functions OH of (P) / number of COOH functions of (A1) + (SA) being of the order of 1.1 to 3.5, preferably of the order of 2.0 to 3.0, the acids ( A1) and (SA) being preferably in the form of their diesters, in particular in the form of methyl diester
- an esterification step between isophthalic acid (A2) and / or iso or terephthalic hydroxyacid (HA) and on the other hand monoethylene glycol and / or glycerol (P), the number of functions ratio OH of (P) / number of COOH functions of (A2) + lou (HA) being of the order of 1.1 to 3.5, preferably of the order of 2.0 to 3.0 Diacid (A2 ) preferably in the form of one of its diesters, in particular in the form of methyl diester
- a polycondensation step
The sulfonated polyesters which are the subject of the invention are very particularly useful as anti-fouling and / or anti-redeposition agents and optionally detergents in detergent compositions, in rinsing, softening or anti-fouling treatment compositions (" finishing "), for washing with or without pretreatment, rinsing, softening or anti-fouling treatment of textiles, especially based on polyesters.

 The present invention also relates to detergent compositions containing on the order of 0.01 to 10%, preferably on the order of 0.1% to 5% and very particularly on the order of 0.2 to 3 %, relative to the weight of said compositions, of said sulfonated poyesters forming the subject of the invention.

Another subject of the invention consists in the reuse, as anti-fouling agents in detergent compositions for washing textile articles in particular based on polyester fibers, of hydrodispersallized or water-soluble sulfonated polyesters capable of being obtained by esterification I polycondensation of a monomer composition based on:
- a non-sulfonated diacid monomer (A) consisting of at least one dicarboxylic acid chosen from terephthalic, isophthalic acids and 2.6 naphthalene dicarboxylic acids, or their esters, in a quantity corresponding to molar ratio (A) / (A) + (SA) of the order of 92/100 to 601100, preferably of the order of 90/100 to 85/100
- a sulfonated diacid monomer (SA) consisting of at least one sulfonated aromatic dicarboxylic acid or sulfonated aliphatic acid, or their diesters, in an amount corresponding to a molar ratio (SA) I (A) + (SA) of the order from 8/100 to 40/100, preferably of the order of 101 100 to 15/100 up to 40 mol%, preferably up to 30 mol%, and very particularly of the order of 10 to 20 mol% , of the amount of unsulfonated diacid monomer (A) and / or of sulfonated diacid monomer (SA) which can be replaced by a hydroxylated diacid monomer (HA) consisting of at least one aromatic or aliphatic aromatic dicarboxylic acid or a diester of said aromatic dicarboxylic acid or aliphatic hydroxylated
- and a polyol monomer (P) consisting of at least one polyol chosen from ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerol, 1,2,4 butane triol and 1 , 2.3 butane triol, in an amount corresponding to a ratio of the number of OH functions of (P) / number of COOH functions of the diacids (A) + (SA) + (HA) of the order of 1.5 to 3 , preferably of the order of 1.8 to 2.2, said sulfonated polyesters having a number molecular mass of less than 15,000,. a sulfur content by weight of the order of 0.5 to 10%, preferably of the order of 1.2 to 8%. and a content of hydroxyl functions expressed in OH equivalent / kg of polymer greater than 0.2
Examples of monomers (A), (SA), (HA) and (P) have already been mentioned above; the operational conditions for preparing said sulfonated polyesters are those or equivalent to those also described above.

 In addition to the said sulfonated polyesters of the invention, other additives of the type described below can be present in the detergent compositions.

- SURFACTANTS, in amounts corresponding to about 340% by weight relative to the detergent composition, surfactants such as anionic surfactants. alkyl sulfonate esters of formula R-CH (SO3M) -COOR ', where R represents a Cg-20, preferably C10-C16 alkyl radical, R' a C1, preferably C1 3 alkyl radical and M a cation alkaline (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ...). Mention may very particularly be made of methyl ester sulfonates whose radicals R is C14-C16; the aikylsulphates of formula ROSO3M, in which R represents a C10-C24, preferably C12-C20, and very particularly C1 2-, alkyl or hydroxyalkyl radical
C18, M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated derivatives (OE) and / or propoxylenated (OP), having on average from 0.5 to 6 units, preferably from 0.5 to 3 OE etlou OP motifs; the alkylamide sulfates of formula RCONHR'OSO3M where R represents an alkyl radical in C2-C22, preferably in C6-C20, R 'an alkyl radical in C2-C3, M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated (OE) and / or propoxylenated (OP) derivatives, having on average from 0.5 to 60 EO and / or OP units; the salts of Cg-C24, preferably C14-C20 saturated or unsaturated fatty acids, Cg-C20 alkylbenzenesulfonates, C or C6 primary or secondary alkylsulfonates, alkylglycerol sulfonates, sulfonated polycarboxylic acids described in GOA-1,082 179, paraffin sulfonates, N-acyl N-alkylSurates, alkylphosphates, isethionates, alkylsuccinamates, alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates, alkylglycoside sulfates, polyethoxycarboxylates an alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ... ); nonionic surfactants polyoxyalkylenated (polyethoxyethylenated, polyoxypropylenated, polyoxybutylenated) alkylphenols in which the alkyl substituent is C6-C12 and containing from 5 to 25 oxyalkylene units; by way of example, mention may be made of the TRITON X-45, X-1 14, X-100 or
X-102 marketed by Rohm 8 Haas Cy .; glucosamide, glucamide, glycerolamide; polyoxyalkylenated Cg-C22 aliphatic alcohols containing from 1 to 25 oxyalkylene units (oxyethylene, oxypropylene); by way of example, mention may be made of
TERGITOL 15-S-9, TERGITOL 24-L-6 NMW marketed by Union Carbide Corp.,
NEODOL 459, NEODOL 23-65, NEODOL 457, NEODOL 454 marketed by
Shell Chemical Cy., KYRO EOB marketed by The Procter 8 Gamble Cy.

. the products resulting from the condensation of ethylene oxide the compound resulting from the condensation of propylene oxide with propylene glycol, such as the Pluronic sold by BASF; the products resulting from the condensation of ethylene oxide the compound resulting from the condensation of propylene oxide with ethylenediamine, such as TETRONIC sold by BASF; . amine oxides such as C1 01 8 dimethylamine alkyl oxides, C8-C22 alkoxy ethyl dihydroxy ethylamine oxides; . the alkylpolyglycosides described in US-A-4,565,647; . amides of C8-C20 fatty acids. ethoxylated fatty acids ethoxylated fatty amides ethoxylated amines cationic surfactants. alkyldimethylammonium halides amphoteric surfactants and zwlttenonlaues alkyldimethylbetaines, alkylamidoprnpyldimethylbetaines, alkyltrimethylsulfobetaines, islands of fatty acid condensation and protein hydrolysaS.

- BUILDERS, in amounts corresponding to about 5-50%, preferably about 5-30% by weight for liquid detergent formulas, or about 10-80%, preferably 15-50% by weight for detergent formulas in powders, builders such as inorganic builders. polyphosphates (tripolyphosphates, pyrophosphates, orthophosphates, hexametaphosphates) of alkali metals, ammonium or alkanolamines. tetraborates or borate precursors. silicates, in particular those having an SiO2 / Na20 ratio of the order of 1.611 to 3.2 / 1 and the lamellar silicates described in US-A4 664 839. alkali or alkaline earth carbonates (bicarbonates, sesquicarbonates). the cogranules of hydrated alkali metal silicates and alkali metal carbonates (sodium or potassium) rich in silicon atoms in Q2 or Q3 form, described in EP-A488 868. crystalline or amorphous aminosilicates of alkali metals (sodium, potassium ) or ammonium, such as zeolites A, P, X ...; Zeolite A with a particle size of the order of 0.1-10 micrometers is preferred as organic builders. water-soluble polyphosphonates (ethane 1-hydroxy-1, 1-diphosphonates, methylene salts diphosphonates ...). water-soluble salts of carboxylic polymers or copolymers or their water-soluble salts such as
polycarboxylate ethers (oxidisuccinic acid and its salts, monosuccinic acid tartrate and its salts, disuccinic acid tartrate and its salts
. hydroxypolycarboxylate ethers
. Citric acid and its salts, mellitic acid, succinic acid and their salts
. polyacetic acid salts (ethylenediaminetetraacetates, nitrilotriacetates, Ng2 hydroxyethyl) -nitrilodiacetates)
C5-C20 succinic alkyl acids and their salts (2-dodecenylsuccinates, lauryl succinates,)
. polycarboxylic esters
. polyaspartic acid, polyglutamic acid and their salts. polyimides derived from the polycondensation of aspartic acid and / or glutamic acid. polycarboxymethylated derivatives of glutamic acid or other amino acids - WHITENING AGENTS, in amounts of about 0.1-20%, preferably about 1-10% by weight, optionally combined with WHITENING ACTIVATORS, amounts of about 0.1-60%, preferably about 0.5-40% by weight, agents and activators such as bleaches. perborates such as sodium perborate monohydrate or tetrahydrate. peroxygenated compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, sodium persulfate preferably combined with a bleach activator generating in situ in the washing medium, a peroxyacid carboxylic acid; among these activators, mention may be made of tetraacetylethylene diamine, tetraacetyl methylene diamine, tetraacetyl glycoluryl, sodium p-acetoxybenzene sulfonate, pentaacetyl glucose, octaacetyl lactose. percarboxylic acids and their salts (called percarbonates ") such as magnesium monoperoxyphthalate hexahydrate, magnesium metachloroperberizoate, 4-nonylamino-4-oxoperoxybutyric acid, SnonylaminoR oxoperoxycaproic acid, diperoxydodecanedioic acid, nonylamide 'peroxisuccinic acid, I' decyldiperoxysuccinic acid.

These agents can be combined with at least one of the anti-fouling or anti-redeposition agents mentioned below.

Mention may also be made of non-oxygenated bleaching agents, acting by photoactivation in the presence of oxygen, agents such as sulphonated aluminum phthalocyanines and / or zinc - ANTI-FOULING AGENTS other, in amounts of about 0.01-10% , preferably about 0.1-5%, and very particularly of the order of 0.24% by weight, agents such as. cellulose derivatives such as cellulose hydroxyethers, methylcellulose,
Ethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose. polyvinyl esters grafted on polyalkylene trunks such as polyvinylacetates grafted on polyoxyethylene trunks (EP-A-219 048). polyvinyl alcohols. polyester copolymers based on ethylene terephthalate and / or propylene terephthalate and polyoxyethylene terephthalate units, with a molar ratio (number of units) ethylene terephthalate andlou propylene terephthalate / (number of units) polyoxyethylene terephthalate of the order of 1/10 to 10/1 , preferably of the order of 1/1 to 9/1, the polyoxyethylene terephthalates having polyoxyethylene units having a molecular weight of the order of 300 to 5000, preferably of the order of 600. aminocarboxylates such as ethylenediaminetetraacetates, hydroxyéyl ethylenediaminetriacetates, nitrilotriacetates. aminophosphonates such as nitrilotris (methylene phosphonates). polyfunctional aromatic compounds such as dihydroxydisunobenz8nes - POLYMERIC DISPERSING AGENTS, in an amount of the order of 0.1-7% by weight, to control the hardness of calcium and magnesium, agents such as. the water-soluble salts of polycarboxylic acids of molecular mass of the order of 2000 to 100,000, obtained by polymerization or copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, maleic acid or anhydride, fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and in particular polyacrylates of molecular mass of the order of 2,000 to 10,000 (US-A-3,308,067), copolymers of arylic acid and maleic anhydride of mass molecular of the order of 5,000 to 75,000 (EP-A-66,915). polyethylene glycols of molecular mass of the order of 1000 to 50,000 - FLUORESCENCE AGENTS (BRIGHTENERS), in an amount of about 0.05-1.2% by weight, agents such as stilbene derivatives, pyrazoline, coumarin, fumaric acid, cinnamic acid, azoles, methinecyanins, thiophenes ... ("The production and application of fluorescent brightening agents - M. Zahradnik, published by John Wiley & Sons, New York-1982-) - FOAM SUPPRESSORS, en amounts up to 5% by weight, agents such as. C1 024 monocarboxylic fatty acids or their alkali, ammonium or alkanolamine salts, fatty acid triglycerides, aliphatic, alicyclic, aromatic saturated or unsaturated hydrocarbons or heterocyclic, such as paraffins, waxes. N-alkylaminotriazines, monostearylphosphates, monostearyl alcohol phosphates, polyorganosiloxane oils or resins optionally combined with silica particles - SOFTENING AGENTS, in amounts of about 0.5-10% by weight, agents such as clays - ENZYMES in amounts up to 5mg by weight, preferably to order 0.05-3mg of active enzyme / g of detergent composition, enzymes such as. proteases, amylases, lipases, cellulases, peroxidases (US-A-3,553,139,
US-A-4 101 457, US-A4 507 219, US-Aç 261 868 - OTHER ADDITIVES such as alcohols (methanol, ethanol, propanol, isopropanol, propanedid, ethylene glycol, glycerin) buffering agents for pigment fragrances
The following examples are given by way of illustration.

Example 1
Preparation of a sulfone polyester
In a 7.5-liter stainless steel reactor, fitted with an anchor agitator rotating at 80 rpm connected to a KYOWA coupler, a double jacket for the circulation of a heat-transfer liquid and a column of distillation regulated by a solenoid valve, we introduce:
- 12.17 moles of dimethyl terephthalate (2363 g)
- 1.99 moles of sodium dimethyl-5-sulfonate isophthalate (590 g)
- 40.16 moles of ethylene glycol (2493g)
- 54 ppm (by weight) of titanium in the form of butyl orthotitanate
The mixture is preheated to 1300C.

 It is then brought to a temperature of 220 ° C. in about 130 minutes, to distill more than 90% of the theoretical amount of methanol.

The reaction mixture is then brought to 230 "C in 30 minutes. When the reaction mass has reached 230" C, the introduction of a suspension containing:
- 2.99 moles of isophthalic acid (497g)
- 8.00 moles of ethylene glycol (497g)
This introduction is carried out over a period of 60 minutes while maintaining the reaction mass at 230 "C.

Heating is then continued to bring the reaction mass to a temperature of 250 ° C. in 60 minutes.

During the period of introduction of the mixture of isophthalic acid and ethylene glycol and the period of heating to 250 ° C., a mixture of water and ethylene glycol is distilled without retrogradation.

The reaction mixture is then transferred to an autoclave preheated to 250ex, then put under reduced pressure to reach a value of 10 millibar in 38 minutes, which corresponds to a motor torque of 3 m.N.

The reaction mass is then poured; after cooling, a polyester dispersible in water is obtained having the following characteristics:. number molecular mass = 10480. rate of sulfonate functions: 11.6 mol%. rate of OH functions: 0.48 eq / kg
Example 2 Prenarabon of a Sulfon Polyester
The steps described in Example 1 are repeated under the same operating conditions, using
- 7.99 moles of dimethyl terephthalate (15519)
- 5.38 mol of sodium dimethyl-5-sulfonate isophthalate (15949)
- 37.5 moles of ethylene glycol (23259)
- 54 ppm (by weight) of titanium in the form of butyl orthotitanate (1.349) followed by the introduction at 230 "C of a suspension of
- 2.00 moles of isophthalic acid (332.6 g)
- 5.36 moles of ethylene glycol (33289)
The reaction mass is poured when the engine torque is 3 mN, which in this case corresponds to a reduced pressure of 100 millibar
A water-dispersible polyester with the following characteristics is obtained: number molecular mass = 9100. rate of sulfonate functions: 35 mol%. OH function rate: 0.39 eq / kg
Example 3
Preparation of a sulfone polyester
The steps described in Example 1 are repeated under the same operating conditions, using
- 9.04 moles of dimethyl terephthalate (1736g)
- 1.46 mole of sodium dimethyl-5-sulfonate isophthalate (433g)
- 29.4 moles of ethylene glycol (1825g)
- 54 ppm (by weight) of titanium in the form of titanium aminotriethanolate (1.349) followed by the introduction at 230 "C of a suspension of
- 2.40 moles of hydroxyisophthalic acid (4009)
- 19.33 moles of ethylene glycol (12009)
The reaction mass is poured when the engine torque is 3 mN, which in this case corresponds to a reduced pressure of 13 millibar
A water-dispersible polyester with the following characteristics is obtained: number average molecular mass = 13,310. rate of sulfonate functions: 11.3 mol%. OH function rate: 0.54 eq / kg
Example 4
Preparation of a sulfonated polyester
The steps described in Example 1 are repeated under the same operating conditions, using
- 12.17 moles of dimethyl terephthalate (2363 g)
- 1.99 moles of sodium dimethyl-5-sulfonate isophthalate (590 g)
- 40.16 moles of ethylene glycol (2493 g)
- 54 ppm (by weight) of titanium in the form of butyl orthotitanate followed by the introduction at 230 C of a suspension of
- 2.99 moles of isophthalic acid (497g)
- 2.99 moles of glycerol (275 g)
- 5.01 moles of ethylene glycol (2619)
The reaction mass is poured when the engine torque is 3 mN, which in this case corresponds to a reduced pressure of 13 millibar
A water-dispersible polyester with the following characteristics is obtained: number average molecular mass = 12,130. rate of sulfonate functions: 11.6 mol%. OH function rate: 0.41 eq / kg
Example 5
Formulation of a lavelino detergent composition
Composition of detergent parts by weight
- zeolite 4A 25
- light carbonate 15
- disilicate R2A 5
- SOKALAN CP5 (BASF) 5 acrylic / maleic copolymer
- Na sulfate 10.7
- carboxymethylcellulose 1
- perborate monohydrate 15
- tetraacetylethylenediamine 5
- linear dodecylbenzenesulfonate 6
- SYNPERONIC A3 (C12-C15 fatty alcohol ethoxylated with 3 EO 3
- SYNPERONIC A9 (C12-C15 fatty alcohol ethoxylated to 9 EO 9
- Esperase enzyme 4.0 T 0.3
- anti-fouling agent
Example 6
ANTI-FIT PROTECTION
The anti-fouling polymers tested are introduced into the detergent composition of Example 5, at a rate of 1% by weight of active polymer material.

Test
Prewash:
Squares in polyester or polyester / cotton (65/35) of dimension 10 × 10 cm, are prewashed in a TERGOTOMETER for 20 minutes at 400C, with the detergent formula containing 1% by weight of active material of polymer tested; the water used has a hardness of 30 HT; ; the amount of detergent used is 5g per 1 liter of water.

The tissue squares are then rinsed 3 times for 5 minutes in cold water (14 "C), then dried by two passages under ice-maker.

Staining:
4 drops of draining motor oil are deposited on 6 of the prewashed squares, and, in order to ensure good fixation of the stain, the tissues are placed in an oven at 60 ° C. for 1 hour. To allow good reproducibility of the results, the fabrics are washed within 24 hours.

Washing:
The washing is carried out under the same conditions as the prewash (at 40 "C for 20 minutes, using 59 detergent containing 1% of active material of anti-fouling polymer for 1 liter of water of 30" HT, then 3 5-minute rinses in cold water and 2 dryings under ice-cold)
Evaluation
The refection of the fabrics before and after washing is measured using the DR colorimeter.

LANGE / LUCI 100.

The effectiveness of the polymer tested as an anti-fouling agent is assessed by the% of stain removal calculated by the formula
Een% = 100 x (R3-R2) / (R1-R2) R1 representing the reflectance before washing the soiled fabric
R2 representing the reflectance, before washing, of the soiled fabric
R3 representing the reflectance, after washing, of the soiled fabric
For each product tested, the average of the% stain removal is calculated.

The results obtained are given in Table 1 below
polymer E in%
10
that of example 1 63
that of example 2 80
that of example 3 50
GEROL PS 32t 13 water-dispersible sulfonated polyester containing 11.62 mol% of sulfonate functions and number average molecular weight of 25,000, marketed by RHONE
POULENC
Example 7
PRIMARY DETERGENCE PROPERTIES
Test pieces of the standard fabrics produced by the following CFT (Center for test materials) - 10D sebum cotton - polyester / cotton (65/35) 20D sebum - 30D polyester sebum 10x10 cm test pieces are washed in a TERGOTOMETER for 20 minutes at 40 C, with the above washing formula to which is added 1% by weight of polymer active material; The water used has a hardness of 30 HT.

The fabrics are then rinsed 3 times for 5 minutes and dried on a freezer.

The reflectance of the test pieces is measured using a XENOCOLOR reflectometer (DR
LANGE), before washing, as well as after washing and drying, according to the "L"',"'a"'and' b system (scale from black to white, from green to red and from blue to yellow).

The hE value is calculated for each type of fabric by taking the geometric sum of the color differences hL, ha and Ab before and after washing on soiled fabrics, i.e. = = (AL2 + ha2 + Ab2) 1/2
The results obtained appear in the following polymer table
40
that of example 1 42
that of example 2 51.3
that of example 3 43.6
GEROL PS 32 46.2

Claims (14)

 1) Water-dispersible or water-soluble sulfonated pdyesters characterized in that they are capable of being obtained by polycondensal esterification of a monomer composition based on:  - a non-sulfonated diacid monomer (A) consisting of at least one dicarboxylic acid chosen from terephthalic, isophthalic and 2.6 naphthalene dicarboxylic acids, or their diesters, in an amount corresponding to a molar ratio (A) / (A ) + (SA) of the order of 92/100 to 60/100, preferably of the order of 90/100 to 85/100  - a sulfonated diacid monomer (SA) consisting of at least one sulfonated aromatic dicarboxylic acid or sulfonated aliphatic acid, or their diesters, in an amount corresponding to a molar ratio (SA) I (A) + (SA) of the order from 811 OC to 40/100, preferably of the order of 101100 to 15/100 up to 40 mol%, preferably up to 30 mol%, and very particularly of the order of 10 to 20 mol%, of the quantity of unsulfonated diacid monomer QV eVou of sulfonated diacid monomer (SA) which can be replaced by a hydroxylated diacid monomer (HA) consisting of at least one hydroxylated aromatic or aliphatic dicarboxylic acid or a diester of said aromatic or aliphatic aliphatic dicarboxylic acid  - and a polyol monomer (P) consisting of at least one polyol chosen from ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerol, 1,2,4 butane triol and 1 , 2.3 butane triol, in an amount corresponding to a ratio of the number of OH functions of (P) / number of COOH functions of the diacids (A) + (SA) + (HA) of the order of 1.5 to 3 , preferably of the order of 1.8 to 2.2 in that the sulfonated diacid monomer (SA) consists of at least one sulfonated aromatic dicarboxylic acid or of a mixture of sulfonated aromatic acid (s) ( s) and sulfonated aliphatic acid (s), or their diesters, when the polyol monomer (P) does not contain a polyol other than a glycol or when the hydroxylated diacid (HA) monomer is absent and in this that said sulfonated polyesters have. a number-average molecular mass of less than 15,000,. a sulfur content by weight of the order of 0.5 to 10%, preferably of the order of 1.2 to 8%. and a content of hydroxyl functions expressed in OH equivalent / kg of polymer greater than 0.2  2) Polyesters according to claim 1), characterized in that the non-sulfonated dicarboxylic acids (A) consist of 50 to 100% mobire of terephthalic acid or one of its lower diesters and from 0 to 50% of acid isophthalic and / or 216-naphthalene dicarboxylic acid or one of their lower diesters.  3) Polyesters according to claim 1) or 2), characterized in that the sulfonated acids (SA) are chosen from sulfoisophthalic, sulfo-terephthalic, suWo-orthophthalic acids, sulfo4 naphthalene dicarboxylic acid-2,7, sulfo - bis (hydroxycarbonyl) -4,4 'diphenylsulfones, suWo-diphenyl-dicarboxylic acids, sulfo-bis (hydrnxycarbonyl) -4,4' diphenylmethanes, 5-sulfophenoxy-isophthalic acids, sulfo-succinic acids, or their lower diesters.  4) Polyesters according to any one of Claims 1) to 3), characterized in that the hydroxylated dicarboxylic acids (HA) are chosen from 5-hydroxy isophthalic, 4-hydroxy isophthalic, 4-hydroxy phthalic, hydroxp2 methylsuccinic, hydroxymethylgl utanque, hydroxyglutarique, or their lower diesters.  5) Polyesters according to any one of claims 1) to 4), characterized in that the polyol (P) is monoethylene glycol and / or glycerol.  6) Polyesters according to any one of the preceding claims, characterized in that they are capable of being obtained from  - terephthalic acid (Al) and isophthalic acid (A2), or terephthalic acid (Al) and a hydroxylated terephthalic acid or hydroxylated isophthalic acid (HA) optionally mixed with isophthalic acid (A2) , according to a molar ratio (A1) / (A2), (A1) / (HA) or (A1) / (HA) + (A2) of the order of 100/0 to 0/100, very particularly of the on the order of 100/0 to 50/50, the acids (Al) and (A2) preferably being in the form of their diesters, in particular in the form of methyl diester,  - a sulfoisophthalic acid (preferably in the form of its diesters, in particular in the form of methyl diester) as sulfonated dicarboxylic acid (SA)  - monoethylene glycol and / or glycerol as polyol (P)  7) Process for preparing the polyesters which are the subject of any of the preceding claims, characterized in that the following successive steps are carried out:  a transesterification step (inter-exchange) between on the one hand a fraction of all the non-sulfonated dicarboxylic acids and the sulfonated dicarboxylic acid (s) and on the other hand a fraction of the polyol (s), the ratio number of OH functions of (P) I number of COOH functions of the fraction of all of the non-sulfonated dicarboxylic acids and of the sulfonated dicarboxylic acid (s) being of the order of 1.1 to 3.5, preferably of in the range of 2.0 to 3.0  an esterification step between the remaining fraction of all of the non-sulfonated dicarboxylic acids and the remaining fraction of the polyol (s) (P), the ratio number of OH functions of the remaining fraction of (P) / number of functions COOH of the remaining fraction of all of the unsulfonated dicarboxylic acids being of the order of 1.1 to 3.5, preferably of the order of 2.0 to 3.0  - a polycondensation step.  polycondensation operation taking place with elimination of polyol molecules, and being stopped when the motor torque of the stirring shaft indicates a value equivalent to approximately 0.5 to 5 meters.newton for a stirring speed of 80 revolutions / minute of an anchor-shaped mobile in a 7.5 liter reactor and a temperature of 250 C of the reaction mass.  8) Detergent compositions containing on the order of 0.01% to 10% by weight of the polyesters forming the subject of any one of claims 1) to 6), relative to the weight of said compositions.  9) Use, as anti-fouling agents in detergent compositions, of water-dispersible or water-soluble sulfonated polyesters capable of stretching obtained by esterification / polycondensation of a monomer composition based on:  - a non-sulfonated diacid monomer (A) consisting of at least one dicarboxylic acid chosen from terephthalic, isophthalic and 2.6 naphthalene dicarboxylic acids, or their esters, in an amount corresponding to molar ratio (A) / (A) + (SA) of the order of 92/100 to 60/100, preferably of the order of 90/100 to 8fi / 100  - a sulfonated diacid monomer (SA) consisting of at least one sulfonated aromatic dicarboxylic acid or sulfonated aliphatic acid, or their diesters, in an amount corresponding to a molar ratio (SA) / (A) + (SA) of the order from 8/100 to 40/100, preferably of the order of 10/100 to 15/100 up to 40 mol%, preferably up to 30 mol%, and very particularly of the order of 10 to 20 molar%, of the amount of non-sulfonated diacid monomer W and / or of sulfonated diacid monomer (SA) which can be replaced by a hydroxylated diacid monomer (HA) consisting of at least one aromatic or aliphatic aromatic dicarboxylic acid or a diester of said aromatic dicarboxylic acid or aliphatic hydroxylated  - And a polyol monomer (P) consisting of at least one polyol chosen from ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerol, 1,2,4 butane triol and 1 , 2,3 butane triol, in an amount corresponding to a ratio of number of OH functions of (P) / number of COOH functions of the diacids (A) + (SA) + (HA) of the order of 1.5 to 3 , preferably of the order of 1.8 to 2.2, said sulfonated polyesters having. a number-average molecular mass of less than 15,000,. a sulfur content by weight of the order of 0.5 to 10%, preferably of the order of 1.2 to 8%. and a content of hydroxyl functions expressed in OH equivalent / kg of polymer greater than 0.2  10) Use according to claim 9), characterized in that the unsulfonated dicarboxylic acids (A) consist of 50 to 100 mol% of terephthalic acid or one of its lower di esters and from 0 to 50% of isophthalic acid and / or 2,6-naphthalene dicarboxylic acid or one of their lower diesters.  11) Use according to claim 9) or 10), characterized in that the sulfonated acids (SA) are chosen from sulfoisophthalic, sulfo-terephthalic, sulfo-orthophthalic acids, sulfo4 naphthalene dicarboxylic acid-2,7, sulffr bis (hydroxycarbonyl) -4,4 'diphenyls ulfones, sulfo-diphenyl-dicarboxylic acids, suWo-bis (hydroxycarbonyl) -4,4' diphenylmethanes, 5-isophthalic sulfphenoxy acids, sulfosuccinic acids, or their lower diesters.  12) Use according to any one of claims 9) to 11), characterized in that the hydroxylated dicarboxylic acids (HA) are chosen from 5-hydroxy isophthalic, 4-hydroxy isophthalic, 4-hydroxy phthalic, 2-hydroxy acids methylsuccinic, hydroxymethylglutaric, hydroxyglutaric, or their lower diesters.  13) Use according to any one of claims 9) to 12), characterized in that the polyol (P) is monoethylene glycd and / or glycerol.  14) Use according to any one of claims 9) to 13), characterized in that said said water-soluble or water-dispersible sulfonated polyesters are capable of being obtained from  - terephthalic acid (A1) and isophthalic acid (A2), or terephthalic acid (A1) and a hydroxylated terephthalic acid or hydroxylated isophthalic acid (HA) optionally mixed with isophthalic acid (A2) , according to a molar ratio (A1) / (A2), (A1) / (HA) or (A1) / (HA) + (A2) of the order of 10010 to 0/100, very particularly of the order of 100 / 0 to 50/50, the acids (Al) and (A2) being preferably in the form of their diesters, in particular in the form of methyl diester,  - a sulfoisophthalic acid (preferably in the form of its diesters, in particular in the form of methyl diester) as sulfonated dicarboxylic acid (SA)  - monoethylene glycol and / or glycerol as polyol (P)