WO2001023512A1

WO2001023512A1 - Use in a detergent composition of a sulfo-functional copolyester as fragrance retainer

Info

Publication number: WO2001023512A1
Application number: PCT/EP2000/009340
Authority: WO
Inventors: Gladys Saliba Gabriel; Jeanne Chang
Original assignee: Rhodia Chimie SAS
Current assignee: Rhodia Chimie SAS
Priority date: 1999-09-28
Filing date: 2000-09-13
Publication date: 2001-04-05
Anticipated expiration: 2002-03-28
Also published as: AU7659100A

Abstract

Use, in a detergent composition comprising a fragrance an intended for the treatment of surfaces, especially for washing laundry or textiles, of a water-soluble or water-dispersible sulfo-functional copolyester as a retainer of fragrances on said treated surfaces.

Description

USE IN A DETERGENT COMPOSITION OF A SULFO-FUNCTIONAL COPOLYESTER AS FRAGRANCE RETAINER

The present invention relates to the use, in a detergent composition comprising a fragrance and intended for the treatment of surfaces, of a water- soluble or water-dispersible sulfo-functional copolyester of low molecular mass as a retainer for the fragrances on said treated surfaces, especially as a fragrance retainer on laundry or textiles after they have been washed using said detergent composition.

It is known to use water-soluble or water- dispersible sulfo-functional copolyesters of low molecular mass, especially sulfo-functional copolyesters having a numerical molecular mass of less than 20,000 and obtained from at least one nonsulfo- functional diacid monomer, at least one sulfo- functional diacid monomer and at least one polyol, especially those obtained from a diester of terephthalic acid, isophthalic acid, a diester of sulfoisophthalic acid and a diol as soil release agents in detergent compositions for laundry or textiles, based in particular on polyester (WO 95/32997).

The applicant has now found that the presence of a water-soluble or water-dispersible sulfo- functional copolyester of low molecular mass in a detergent composition comprising a fragrance and intended for the treatment of surfaces made it possible to increase the fragrance retention on said treated surfaces, especially on laundry or textiles after washing it or them using said composition. The invention first provides for the use, in a detergent composition comprising a fragrance and intended for the treatment of surfaces, especially for washing laundry or textiles, of a water-soluble or water-dispersible sulfo-functional copolyester essentially comprising units of general formula (I) [-0-C(0)-A-C(0)-(0-CH₂-CH₂-)_n-] (I) where . the symbol A represents

* a nonionic mono- or polyarylene or nonionic alkylene radical (NA) * or a sulfo-functional mono- or polyarylene or sulfo-functional alkylene radical (SA) which carries at least one sulfonic acid function, the molar percentage of the subunits of formula -C (0) -A-C (0) - in which A is a sulfo-functional radical (SA) relative to the sum of the subunits of formula

-C (0) -A-C (0) - in the units of formula (I) being of the order of from 5 to 40, preferably from 7 to 35; and . n is 1, 2, 3 or 4, the molar percentage of the subunits of formula (0-CH₂-CH₂-) _n iⁿ which n is 1 relative to the sum of the subunits of formula (0-CH₂-CH₂-) _n in which n is 1, 2, 3 and 4 in the subunits of formula (I) being of the order of from 10 to 80, preferably of the order of from 20 to 60 ; and the ponderal molecular mass of said copolyesters being less than 20,000, preferably less than 15,000, especially from 5000 to 10,000; as a retainer of fragrances on said treated surfaces, especially as a fragrance retainer on laundry or textiles after washing it or them using said composition. The ponderal molecular masses are measured by gel permeation chromatography in dimethylacetamide containing 10^"2 N of LiBr at 100°C. The results are expressed in polystyrene equivalents.

As examples of nonionic radicals (NA) , mention may be made of nonionic C₆-C₁₄ mono- or polyarylene radicals and nonionic C^-Cg alkylene radicals such as the radicals 1, 4-phenylene, 1, 3-phenylene, 1, 6-naphthalene, 1, 6-cyclohexylene, ethylene, trimethylene, tetramethylene and hexamethylene .

As examples of sulfo-functional radicals (SA), mention may be made of sulfo-functional C₆-Cι₄ mono- or polyarylene radicals and sulfo-functional C^C? alkylene radicals which carry at least one sulfomc acid function, preferably m the form of a sulfonate of an alkali metal, especially sodium, such as sodio- oxysulfonyiphenylene, sodio-oxysulfonylnaphthalene, sodio-oxysulfonylbiphenylene and sodio-oxysulfoethylene radicals,

Preferably, the nonionic radical (NA) is a 1, 4-phenylene (NA1) or 1, 3-phenylene (NA2) radical and the sulfo-functional radical (SA) a 5-sodio- oxysulfonyl-1 , 3-phenylene radical .

Very preferably, the radicals (NA) of the nonionic units of formula (I) are 1, 4-phenylene radicals (NA1) or a mixture of 1, 4-phenylene (NA1) and 1, 3-phenylene (NA2) radicals, the molar percentage of the subunits of formula -C (0) -A-C (0) - where A is a radical (NA1) relative to the sum of the subunits of formula -C (0) -A-C (0) - where A is a nonionic radical (NA) being of the order of from 50 to 100, preferably from 70 to 90.

Said sulfo-functional copolyesters can be obtained conventionally; for example, by esterification and/or transesterification and polycondensation of a monomer composition based: - on a nonsulfo-functional diacid monomer

(MNA) consisting of at least one aromatic or aliphatic dicarboxylic acid or anhydride, diesters thereof, in an amount corresponding to a molar ratio (MNA) / (MNA) + (MSA) of the order of from 95/100 to 60/100, preferably of the order of from 93/100 to 65/100

- on a sulfo-functional diacid monomer (MSA) consisting of at least one sulfo-functional aliphatic or sulfo-functional aromatic dicarboxylic acid or anhydride or diesters thereof, in an amount corresponding to a molar ratio (MSA) / (MNA) + (MSA) of the order of from 5/100 to 40/100, preferably of the order of from 7/100 to 35/100

- and on a polyol monomer (P) comprising ethylene glycol and optionally diethylene glycol, in an amount corresponding to a ratio of the number of OH functions of the polyol monomer (P) to the number of COOH functions or COOH-function equivalents of the diacid monomers (MNAr) + (MSAr ) of the order of from 1.05 to 4, preferably of the order of from 1.1 to 3.5, and especially of the order of from 1.8 to 3.

The elemental entity considered in the definition of the mole of monomer (MNA) or (MSA) is the COOH function in the case of diacids or the COOH- function equivalent in the case of anhydrides or diesters .

Among nonsulfo-functional diacid monomers (MNA) , mention may be made of terephthalic, isophthalic, 2, 6-naphthalenedicarboxylic, cyclohexanedicarboxylic, succinic, glutaric, adipic and suberic acid, and their anhydrides or lower diesters. The nonsulfo-functional diacid monomer (MNA) consists preferably of from 50 to 100 molar %, especially of from 70 to 90 molar %, of terephthalic acid or anhydride or of one of its lower diesters (methyl, ethyl, propyl, isopropyl or butyl diesters) and of from 0 to 50 molar %, especially from 10 to 30 molar %, of isophthalic acid or anhydride or of one of its lower diesters (methyl, ethyl, propyl, isopropyl or butyl diesters); the preferred diesters are those of methyl. The sulfo-functional diacid monomer (MSA) has at least one sulfonic acid group, preferably in the form of a sulfonate of an alkali metal (preferably sodium) and two acid functions or acid-function equivalents (that is, one anhydride function or two ester functions) attached to one or more aromatic rings when said monomer is aromatic.

In the case of an aliphatic sulfo-functional diacid monomer, the sulfonic acid group can be bonded to a carbon atom of an alkylene radical either directly or indirectly via an alkylene, alkoxyalkylene, oxyalkylene, arylalkylene, alkylarylalkylene or alkoxyarylene group. Among sulfo-functional diacid monomers (MSA) , mention may be made of aliphatic or aromatic sulfo-functional dicarboxylic acids such as sulfoisophthalic, sulfoterephthalic, sulfoorthophthalic, 4-sulfonaphthalene-2, 7-dicarboxylic, sulfodiphenyldicarboxylic and sulfosuccinic acids and their anhydrides or lower diesters. The preferred sulfo-functional diacid monomers (MSA) are sulfoisophthalic acids or anhydrides and their methyl diesters, and especially dimethyl 5-sodio-oxysulfonyl- isophthalate .

Said sulfo-functional copolyesters can be obtained by the usual processes of esterification and/or transesterification and polycondensation; for example, by esterification and/or transesterification reaction, in the presence of an esterification/ transesterification catalyst, of the polyol monomer (P) with the various diacid monomers, each diacid being in the acid or anhydride form or in the form of one of its diesters, and polycondensation of the polyol esters under reduced pressure in the presence of a polycondensation catalyst. In one preferred preparation method, said sulfo-functional copolyesters are obtained by conducting the following successive steps:

- a transesterification (interchange) step between, on the one hand, the sulfo-functional diacid monomer (MSA) , in diester form, and from 50 to 100 molar %, especially from 30 to 90 molar %, of the total amount of the nonsulfo-functional diacid monomer (MNA) , in diester form, and, on the other hand, an amount of polyol monomer (P) corresponding to a ratio of the number of OH functions of the polyol monomer (P) to the number of COOH-function equivalents of said monomers (MNA) and (MSA) , in diester form, of the order of from 1.05 to 4, preferably of the order of from 1.1 to 3.5, and especially of the order of from 1.8 to 3.0 - an optional step of esterification between the optional remaining amount of the nonsulfo- functional diacid monomer (MNA) , in diacid or anhydride form, and an amount of polyol monomer (P) corresponding to a ratio of the number of OH functions of the polyol monomer (P) to the number of COOH functions of the nonsulfo-functional diacid monomer (MNA) in diacid or anhydride form of the order of from 1.05 to 4, preferably of the order of from 1.1 to 3.5, and especially of the order of from 1.8 to 3.0

- a polycondensation step.

The sulfo-functional (MSA) and nonsulfo- functional (MNA) dicarboxylic diesters employed in the transesterification (interchange) step are preferably methyl diesters.

The preferred sulfo-functional copolyesters can be obtained from

- terephthalic acid (MNA1) in the form of a diester (preferably methyl diester) , optionally in a mixture with isophthalic acid (MNA2 ) in the form of its diacid or anhydride, in a molar ratio

(MNA1) / (MNA1)+(MNA2) of the order of from 100/100 to

50/100, preferably of the order of from 90/100 to

70/100 - sulfoisophthalic acid, in the form of a diester (preferably methyl diester)

- monoethylene glycol They can be prepared by conducting the following successive steps:

- a transesterification (interchange) step between, on the one hand, the diester (preferably methyl diester) of terephthalic acid (MNA1) and the diester (preferably methyl diester) of sulfoisophthalic acid (MSA) and, on the other hand, monoethylene glycol (P), the ratio of the number of OH functions (P) to the number of COOH-function equivalents of (MNA1)+(MSA) being of the order of from 1.05 to 4, preferably of the order of from 1.1 to 3.5, and especially of the order of from 1.8 to 3

- an esterification step between isophthalic acid (MNA2) and, on the other hand, monoethylene glycol (P), the ratio of the number of OH functions of (P) to the number of COOH functions of (MNA2) being of the order of from 1.05 to 4, preferably of the order of from 1.1 to 3.5, and especially of the order of from 1.8 to 3 - a polycondensation step.

The operating conditions for the transesterification, esterification and condensation steps that can be employed are those described in W095/32997. Said sulfo-functional copolyesters carry at the chain ends groups of formula

-A-C0-0-(X-0)_n-H (Hi) where A and n are as defined above and X is -CH₂-CH₂- .

Other subunits may additionally be present at the chain ends, and m minor amounts, such as groups of formula -A-CO-OH (II' i) where A is as defined above.

In one alternative embodiment, said sulfo- functional copolyesters carry at the chain ends identical or different groups selected from those of formula (Hi) to (II₄) of formula

-A-CO-0-(X-0)_n-Z (II₂)

-A-CO-Z' (II₃)

-A-CO-0-(X'-0)_p-Z" (II₄) m which . A, X and n are as defined above

. Z represents a C₂-C₃ι alkyloyl or aryloyl group, optionally carrying an amomc function, preferablv sulfonate, such as sulfobenzoyl M0₃SC₆H₄C (0) - where M is an alkali metal . Z' represents a polyalkoxysulfonate group, m particular of formula (M0₃S) (CH₂) _q (CH₂-CH₂-0) (RO)_r-, where M is an alkali metal, q is 0 or 1, R is an ethylene or propylene group, and r ranges from 0 to 2 . X' represents a C₂-C₈ alkylene group, Z" represents a Cι-C₃₀ alkyl or aryl group, and p ranges from 0 to 6. Chain ends of a formula of the type (II₂), (II₃) and (II₄) can be obtained by employing monoacid monomers for the chain ends of formula (II₂), a hydroxypolyalkoxy- alkylsulfonate for the chain ends of formula (II₃), and a polyalkylene glycol monoether or a monoacid for the chain ends of formula (II₄) . Said sulfo-functional copolyesters can be employed as retainers of fragrances on surfaces, especially on laundry or polyester-based textiles in particular, in detergent compositions for surface treatment, in particular for washing laundry and polyester-based textiles in particular, in a proportion of from 0.01 to 10%, preferably from 0 05 to 5%, especially from 0.1 to 1% of the weight of said detergent composition.

Among the odorant compounds which can form part of the composition of the fragrances present in the detergent compositions, especially for laundry, mention may be made of

- hexylcinnamaldehyde,

- 2-methyl-3- (p-tert-butylphenyl ) propion- aldehyde,

- 7-acetyl-l, 2,3,4, 5, 6, 7, 8-octahydro-l, 1, 6, 7- tetramethylnaphthalene,

- benzyl salicylate,

- 7-acetyl-l, 1,3,4,4, 6-hexamethyltetralin, - p-tert-butylcyclohexyl acetate,

- methyl dihydroj asmonate,

- β-naphthol methyl ether, - methyl β-naphthyl ketone,

- 2-methyl-2- (p-isopropylphenyl) propion- aldehyde,

- 1,3,4,6,7, 8-hexahydro-4, 6,6,7,8,8-

5 hexamethylcyclopenta-γ-2-benzopyran,

- dodecahydro-3a, 6, 6, 9a-tetramethylnaphtho-

[2, lb]bifuran,

- anisaldehyde,

- coumarin, 10 - cedrol,

- vanillin,

- ethylvanillin,

- heliotropin,

- ethylene brassylate, 15 - isobornylcyclohexanol,

- cyclopentadecanolide,

- isoamyl acetate,

- tricyclodecenyl acetate,

- tricyclodecenyl propionate, 20 - β-phenylethyl alcohol,

- terpineol,

- linalool,

- linalyl acetate,

- geraniol, 25 - nerol,

- 2- ( 1, 1-dimethylethyl) cyclohexanol acetate,

- benzyl acetate, - terpenes (orange)

- eugenol,

- diethyl phthalate,

- essential oils, resin oils or resinoid oils (orange oil, lemon oil, patchouli oil, Peru balsam oil, resinoid olibanum oil, styrax oil, coriander oil, lavender oil, laburnum oil, etc) . Said fragrances can be present in the detergent compositions in a proportion of from 0.05 to 1%, preferably from 0.1 to 0.5% by weight.

Said detergent compositions can be compositions for the treatment of hard surfaces, such as those of ceramic, glass, porcelain, formica or another hard polymer, especially for cleaning crockery, bathrooms, kitchens, etc. They further comprise at least one surfactant, preferably anionic, nonionic or amphoteric.

Preferably, the detergent compositions concerned are for the hand or machine washing of laundry or textiles.

Said detergent compositions for laundry or textiles in which said sulfo-functional copolyesters can be employed as fragrance retainers may further comprise customary constituents such as:

- surfactants, preferably anionic, nonionic or amphoteric, in an amount of the order of from 5 to 70%, preferably from 5 to 50% of the weight of said composition, surfactants such as: anionic surfactants, for instance

. alkyl ester sulfonates of formula R-CH ( S0₃M) -COOR' , where R' represents a C₈_₂₀, preferably Cι₀-C₁₆, alkyl radical, R' a

preferably Cι~C₃, alkyl radical and M an alkali metal cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, tπmethyl-, tetramethylammonium, dimethylpiperidmium, etc.) or a cation derived from an alkanolamme (monoethanolamme, diethanolamme, tπethanolamme, etc.);

. alkyl sulfates of formula ROS0₃M, where R represents a Cs^_C₂₄, preferably Cι₀-Cι₈, alkyl or hydroxyalkyl radical, M representing a hydrogen atom or a cation as defined above, and also ethoxylenated (EO) and/or propoxylenated (PO) derivatives thereof, having on average from 0.5 to 30, preferably from 0.5 to 10, EO and/or PO subunits; . alkyla ide sulfates of formula RCONHR'OS0₃M where R represents a C₂-C₂₂, preferably C₆-C₂₀, alkyl radical and R' a C₂-C₃ alkyl radical,

M representing a nydrogen atom or a cation as defined above, and also ethoxylenated (EO) and/or propoxylenated (PO) derivatives thereof, having on average from 0.5 to 60 EO and/or PO subunits; . saturated or unsaturated C₈-C₂₄, preferably Cι₄-C₂₀/ fatty acid salts, C₉-C₂₀ alkylbenzenesulfonates, primary or secondary C₈-C₂₂ alkylsulfonates , alkylglycerol- sulfonates, the sulfo-functional polycarboxylic acids described m GB-A-1 082 179, paraffmsulfonates, N- acyl-N-alkyltaurates, alkyl phosphates, lsethionates, alkylsuccmamates alkylsulfosuccmates, monoesters or diesters of sulfosuccmates, N-acylsarcosmates, alkylglycoside sulfates and polyethoxycarboxylates the cation being an alkali metal (sodium, potassium, lithium) , a substituted or unsubstituted ammonium radical (methyl-, dimethyl-, tπmethyl-, tetramethyl- ammonium, dimethylpiperidmium, etc.) or being derived from an alkanolam e (monoethanolamine, diethanolamme, triethanolam e, etc.);

. sophorolipids, such as those m acid or lactone form which are derived from 17-hydroxyoctadecenιc acid; nonionic surfactants, for instance . polyoxyalkylenated (polyethoxyethylenated, polyoxypropylenated, polyoxybutylenated) alkylphenols whose alkyl substituent is C₆-Cι₂ and which contain from 5 to 25 oxyalkylene subunits; by way of example, mention may be made of TRITON X-45, X-114, X-100 or X-102 marked by Rohm & Haas Cy. and IGEPAL NP2 to NP17 from RHONE-POULENC;

. polyoxyalkyenated C₈-C₂₂ aliphatic alcohols containing 1 to 25 oxyalkylene (oxyethylene, oxypropylene) units; by way of example, mention may be made of TERGITOL 15-S-9 and TERGITOL 24-L-6 NMW marketed by Union Carbide Corp., NEODOL 45-9, NEODOL 23-65, NEODOL 45-7, and NEODOL 45-4 marketed by Shell Chemical Cy, KYRO EOB marketed by The Procter & Gamble Cy, SYNPERONIC A3 to A9 from ICI, and RHODASURF IT, DB and B from RHONE- POULENC;

. products resulting from the condensation of ethylene oxide or propylene oxide with propylene glycol, ethylene glycol, having a ponderal molecular mass of the order of 2000 to 10,000, such as the PLURONICs marketed by BASF;

. products resulting from the condensation of ethylene oxide or propylene oxide with ethylenediamine, such as the TETRONICS marketed by BASF;

. ethoxylated and/or propoxylated C₈-C₁₈ fatty acids containing 5 to 25 ethoxylated and/or propoxylated units;

• C₈-C₂₀ fatty acid amides containing 5 to 30 ethoxylated units;

. ethoxylated amines containing 5 to 30 ethoxylated units ;

. alkoxylated amidoamines containing 1 to 50, preferably 1 to 25, especially 2 to 20 oxyalkylene (preferably oxyethylene units;

. amine oxides such as C₁₀-C₁₈-alkyldimethylamine oxides and C₈-C₂₂-alkoxyethyldihydroxyethylamine oxides; . alkoxylated terpenic hydrocarbons such as ethoxylated and/or propoxylated a- or b- pmenes containing 1 to 30 oxyethylene and/or oxypropylene units; . alkylpolyglycosides obtainable by condensation (for example, by acid catalysis) of glucose with primary fatty alcohols (US-A-3 598 865; US-A-4 565 647; EP-A-132 043, EP-A-132 046, etc.) having a C₄-C₂₀, preferably C₈-Cι₈, alkyl group and an average number of glucose units of the order from 0.5 to 3, preferably of the order of 1.1 to 1.8 per mole of alkypolyglycoside (APG) ; mention may be made particular of those having

* a C₈-Cι₄ alkyl group and on average 1.4 glucose unit per mole * a C₁₂-C₁₄ alkyl group and on average 1.4 glucose unit per mole

* a C₈-Ci₄ alkyl group and on average 1.5 glucose unit per mole

* a C₈-C₁₀ alkyl group and on average 1.6 glucose unit per mole marketed respectively under the names GLUCOPON 600 EC ®,

® ®

GLUCOPON 600 CSUP , GLUCOPON 650 EC , GLUCOPON 225 CSUP

, by HENKEL . amphot eric surfactant s , for inst ance alkylbetames , alkyldimethylbet a es , alkylamidopropylbetames , alkylamidopropyldimethylbeta es , alkyltrimethyl- sulfobetames , lmidazolme derivatives such as alkylamphoacetates, alkyla phodiacetates, alkylampho- propionates, alkylamphodipropionates, alkylsultames or alkylamidopropylhydroxysultames, condensation products of fatty acids and protein hydrolysates, amphoteric derivatives of alkylpolyammes such as Amphionic XL ®,

(Ϊ0 fio marketed by Rhodia, Ampholac 7T/X , and Ampholac 7C/X marketed by Berol Nobel, and proteins or protein hydrolysates;

- organic or inorganic detergency adjuvants (builders), an amount such that the total amount of detergency ad uvant is of the order of from 5 to 50% of the weight of said composition, detergency adjuvants such as

- polyphosphates ( tripolyphosphates, pyrophosphates, orthophosphates, hexametaphosphates ) of alkali metals, of ammonium or of alkanolammes

- tetraborates or borate precursors

- alkali metal or alkaline earth metal carbonates (bicarbonates, sesquicarbonates)

- silicates of alkali metals - cogranules of hydrated silicates of alkali metals and of carbonates of alkali metals (sodium or potassium) which are rich silicon atoms m Q2 or Q3 form, which are described m EP-A-488 868, for powder detergent compositions - crystalline or amorphous alummosilicates of alkali metals (sodium, potassium) or of ammonium, such as zeolites A, P, X, etc. - water-soluble polyphosphonates ( 1-hydroxyethane- 1, 1-dιphosphonates, salts of methylene diphosphonates, etc.)

- water-soluble salts of carboxylic copolymers or polymers such as water-soluble salts of polycarboxylic acids having a molecular mass of the order of from 2000 to 100,000, obtained by polymerization or copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, maleic acid or maleic anhydride, fumaric acid, ltacomc acid, mesacomc acid, citraconic acid, methylenemalonic acid, and especially polyacrylates having a molecular mass of the order of from 2000 to 10,000 (US-A-3 308 067), copolymers of acrylic acid and maleic anhydride having a molecular mass of the order of from 5000 to 75,000 (EP-A-66 915)

- polycarboxylate ethers (oxydisuccmic acid and its salts, tartrate monosuccinic acid and its salts, tartrate monosuccinic acid and its salts, tartrate disuccmic acid and its salts

- hydroxypolycarboxylate ethers

- citric acid and its salts, mellitic acid, succmic acid and salts thereof

- salts of polyacetic acids ( ethylenediam e- tetraacetates, mtrilotriacetates,

N- ( 2-hydroxyethyl ) nitrilodiacetates ) - C5-C20-alkyl-succmιc acids and salts thereof

( 2-dodecenylsuccmates , lauryl succmates , etc . )

- polyacetal carboxylic esters

- polyaspartic acid, polyglutamic acid and salts thereof

- polyimides derived from the polycondensation of aspartic acid and/or of glutamic acid

- polycarboxymethyl derivatives of glutamic acid [for instance, N, N-bis ( carboxymethyl) glutamic acid and its salts, especially sodium salts] or of other ammo acids

- ammophosphonates such as nitrilotπs (methylene- phosphonates)

- soil release agents, m amounts of the order of 0.01-10%, preferably of the order of from 0.1 to 5%, and especially of the order of 0.2-3% by weight, agents such as

- cellulose derivatives such as cellulose hydroxyethers, methylcellulose, ethylcellulose, hydroxypropylmethylcellulose and hydroxybutyl- methylcellulose

- polyvmyl esters grafted onto polyalkylene backbones such as polyvmyl acetates grafted onto polyoxyethylene backbones (EP-A-219 048) - polyvmyl alcohols

- polyester copolymers based on ethylene terephthalate and/or propylene terephthalate and polyoxyethylene terephthalate units, w th an ethylene terephthalate and/or propylene terephthalate (number of units) /poloxyethylene terephthalate (number of units) ratio of the order of from 1/10 to 10/1, the polyoxyethylene terephthalate units having polyoxyethylene subunits havmg a molecular weight of the order of from 300 to 10,000, with a molecular mass of the copolyester of the order of from 1000 to 100,000

- polyester copolymers based on ethylene terephthalate and/or propylene terephthalate and polyoxyethylene and/or polyoxypropylene units, with an ethylene terephthalate and/or propylene terephthalate (number of units) /polyoxyethylene and/or polyoxypropylene (number of units) molar ratio of the order of from 1/10 to 10/1, the polyoxyethylene and/or polyoxypropylene units having a molecular weight of the order of from 250 to 10,000, with a molecular mass of the copolyester of the order of from 1000 to 100,000 (US-A-3 959 230, US-A-3 962 152, TJS-A-3 893 929, US-A-4 116 896, US-A-4 702 847, US-A-4 770 666, EP-A-253 567, EP-A-201 124)

- ethylene or propylene terephthalate/polyoxyethylene terephthalate copolymers containing sulf oisophthaloyl units their chain (US-A-4 711 730 ; US-A-4 702 857 ; US-A-4 713 194 )

- sulfoaroyl, sulfo-functional polyalkyleneoxyalkyl- terminal terephthalic copolyester oligomers optionally containing sulfoisophthaloyl units m their chain (US-A-4 721 580; US-A-5 415 807; US-A-4 877 896; US-A-5 182 043; US-A-5 599 782; US-A-4 764 289; EP-A-311 342; WO92/04433; W097/42293) - polyester-polyurethanes obtained by reaction of a polyester having a numerical molecular mass of 300-4000 and obtained from a diester of terephthalic acid, optionally a diester of terephthalic acid, optionally a diester of sulfoisophthalic acid, and a diol with a prepolymer having terminal isocyanate groups obtained from a polyoxyethylene glycol having a molecular mass of 600-4000 and a dnsocyanate (US-A-4 201 824)

- sulfo-functional polyester oligomers obtained by sulfonation of an oligomer derived from ethoxylated allyl alcohol, dimethyl terephthalate and 1,2- propylenediol, having from 1 to 4 sulfo-functional groups (US-A-4 968 451) .

- antiredeposition agents m amounts of approximately 0.01-10% by weight for a powder detergent composition and approximately 0.01-5% by weight for a liquid detergent composition, agents such as

- carboxymethylcellulose

- sulfo-functional polyester oligomers obtained by condensation of isophthalic acid, dimethyl sulfosuccmate and diethylene glycol (FR-A-2 236 926) ; - bleaches m an amount of approximately 0.1-20%, preferably 1-10% of the weight of said powder detergent composition, such as

- perborates such as sodium perborate monohydrate or tetrahydrate

- peroxygenated compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide and sodium persulfate - percarboxylic acids and their salts (which are called "percarbonates" ) such as magnesium monoperoxyphthalate hexahydrate, magnesium metachloroperbenzoate, 4-nonylammo-4-oxo- peroxybutyric acid, 6-nonylammo-6-oxoperoxycaproιc acid, diperoxydodecanedioic acid, peroxysuccmic acid nonyl amide, and decyldiperoxysuccmic acid, preferably combined with a bleach activator which generates a carboxylic peroxy acid m situ m the washing medium; among these activators, mention may be made of tetraacetylethylenediamme, tetraacetyl- methylened amme, tetraacetylglycoluryl, sodium p-acetoxybenzenesulfonate, pentaacetyl glucose, octaacetyl lactose, etc.

- color transfer inhibitors n an amount of approximately 0.05 to 5% by weight, for instance . polyvmylpyrrolidones . copolymers of N-vmylpyrrolidone and N-vmylimidazole . polyamine N-oxides

- fluorescent whiteners in an amount of approximately

0.05-1.2% by weight, agents such as stilbene derivatives, pyrazoline, coumarin, fumaric acid, cinnamic acid, azoles, methinecyanines, thiophenes, etc. foam suppressants in amounts possibly ranging up to 5% by weight, agents such as

- Cι₀-C₂₄ monocarboxylic fatty acids or their alkali metal, ammonium or alkanolamine salts, and triglycerides of fatty acids

- saturated or unsaturated aliphatic, alicyclic, aromatic or heterocyclic hydrocarbons, such as paraffins and waxes - N-alkylaminotriazines

- monostearyl phosphates and monostearyl alcohol phosphates

- polyorganosiloxane oils or resins optionally combined with particles of silica - softeners in amounts of approximately 0.5-10% by weight, agents such as clays

- enzymes in an amount possibly ranging up to 5 mg by weight, preferably of the order of 0.05-3 mg of active enzyme/g of detergent composition, enzymes such as proteases, amylases, lipases, peroxydases, cellulase (US-A-3 553 139, US-A-4 101 457, US-A-4 507 219, US-A-4 261 868, US-A-4 , 435 , 307 , GB-A-2 075 028, GB-A-2 095 275, GB-A-1 368 599, WO 92/13057) and other additives such as

- alcohols (methanol, ethanol, propanol, isopropanol, propanediol, ethylene glycol, glycerol)

- buffers or fillers such as sodium sulfate and the carbonates or bicarbonates of alkaline earth metals .

- pigments Preferably, said detergent compositions are substantially devoid of polyorganosiloxane compounds which carry ammo functions.

The present invention also provides a process for cleaning surfaces, especially laundry or textiles, using a detergent composition comprising a fragrance and a water-soluble or water-dispersible sulfo- functional copolyester of formula (I) m an amount which is effective for prolonging the persistence of said fragrance on said surfaces after cleaning. Said detergent composition is substantially devoid of polyorganosiloxane compounds which carry ammo functions .

The invention more particularly provides a process for washing laundry or textiles using a washing meαium comprising a fragrance and a water-soluble or water-dispersible sulfo-functional copolyester of formula (I) m an amount which is effective for prolonging the persistence of said fragrance on said laundry or said textiles after washing. The washing operation can be conducted at a temperature of the order of from 20 to 90°C, preferably from 30 to 60°C. Said detergent composition is substantially devoid of polyorganosiloxane compounds which carry ammo functions .

The example below is given by way of illustration. Example

After a number of purges with nitrogen, the following charge I is introduced mto a stainless steel reactor having a capacity of 1 liter:

* dimethyl terephthalate 310.4 g (1.598 mol)

* ethylene glycol 339 g (5.47 mol)

* dimethyl ιsophatalate-5-sodιum 104.4 g (0.353 mol) sulfonate

* titanium ammotnethanolate 54 ppm of titanium ( catalyst ) The medium is subsequently preheated to 180 °C then brought to 220 °C over approximately 130 minutes, during which time the methanol resulting from the transesterification reaction is distilled. The reaction mixture is subsequently heated to reach 230°C m 30 minutes. When the reaction mass has reached this temperature, the progressive introduction of the following charge II is commenced:

* isophthalic acid 11.72 g (0.07 mol)

* ethylene glycol 67.2 g (1.08 mol)

* terephthalic acid 56.7 g (0.34 mol) for a duration of one hour, while holding the reaction mass at 230°C. Heating is subsequently continued in order to bring this reaction mass to 250°C over 60 minutes. During this period, a mixture of water and ethylene glycol distils without reflux. At this temperature, a progressive vacuum is applied to give a reduced pressure of 100 bar in 22 minutes. The reaction mass is then discharged. The product is redispersible in water. Its numerical molecular mass is 5100; its ponderal molecular mass is 9300 (measured by gel permeation chromatography in dimethylacetamide containing 10^"" N of LiBr at 100°C) .

The molar percentage of the units of formula (0-CH₂-CH₂-) _n where n is 1 relative to the sum of the units of formula (0-CH₂-CH₂-) _n where n is 1, 2, 3 and 4 is 55.7.

The sulfo-functional copolyester thus obtained is employed within the detergent composition for the machine washing of laundry, featuring in the following table. TABLE

Claims

1) Use, m a detergent composition comprising a fragrance and intended for the treatment of surfaces, especially for washing laundry or textiles, of a water-soluble or water-dispersible sulfo-functional copolyester essentially comprising units of general formula (I)

[-0-C(0)-A-C(0)-(0-CH₂-CH₂-)_n-] (I) where . the symbol A represents * a noniomc mono- or polyarylene or noniomc alkylene radical (NA)

* or a sulfo-functional mono- or polyarylene or sulfo-functional alkylene radical (SA) which carries at least one sulfomc acid function, the molar percentage of the subunits of formula

-C (0) -A-C (0) - m which A is a sulfo-functional radical (SA) relative to the sum of the subunits of formula -C (0) -A-C (0) - m the units of formula (I) being of the order of from 5 to 40, preferably from 7 to 35; and . n is 1, 2, 3 or 4, the molar percentage of the subunits of formula (0-CH₂-CH₂-)_n m which n is 1 relative to the sum of the subunits of formula (0-CH₂-CH₂-) _n m which n is 1, 2, 3 and 4 m the subunits of formula (I) being of the order of from 10 to 80, preferably of the order of from 20 to 60; and the ponderal molecular mass of said copolyesters being less than 20,000, preferably less than 15,000, especially from 5000 to 10,000; as a retainer of fragrances on said treated surfaces, especially as a fragrance retainer on laundry or textiles after washing it or them using said composition .

2) Use according to claim 1), characterized in that the nonionic radicals (NA) are nonionic C₆-C₁₄ mono- or polyarylene radicals and/or nonionic Cι-C₉ alkylene radicals and in that the sulfo-functional radicals (SA) are sulfo-functional C₆-C₁₄ mono- or polyarylene radicals and/or sulfo-functional Cι-C₉ alkylene radicals which carry at least one sulfonic acid function.

3) Use according to claim 2), characterized in that the nonionic radicals (NA) are 1, 4-phenylene (NAl) and/or 1, 3-phenylene (NA2) radicals and the sulfo-functional radicals (SA) are 5-sodio-oxysulfonyl- 1, 3-phenylene radicals.

4) Use according to claim 3), characterized in that the radicals (NA) of the nonionic units of formula (I) are 1, 4-phenylene radicals (NAl) or a mixture of 1, 4-phenylene (NAl) and 1, 3-phenylene (NA2) radicals, the molar percentage of the subunits of formula -C (O) -A-C (0) - where A is a radical (NAl) relative to the sum of the subunits of formula -C (0) -A-C (0) - where A is a noniomc radical (NA) being of the order of from 50 to 100, preferably from 70 to 90.

5) Use according to any one of claims 1) to 4), characterized m that said sulfo-functional copolyesters of formula (I) are employed m a proportion of from 0.01 to 10%, preferably from 0 05 to 5%, especially from 0.1 to 1% of the weight of said detergent composition. 6) Use according to any one of claims 1) to

5), characterized m that said composition further comprises at least one surfactant.

7) Use according to any one of claims 1) to 6), characterized m that said composition is substantially devoid of polyorganosiloxane compounds which carry ammo functions .

8) Process for cleaning surfaces, especially laundry or textiles, using a detergent composition comprising a fragrance and a water-soluble or water-dispersible sulfo-functional copolyester of formula (I) mentioned m claim (I) m an amount which is effective for prolonging the persistence of said fragrance on said surfaces after cleaning.

9) Process for washing laundry or textiles, using a washing medium comprising a fragrance and a water-soluble or water-dispersible sulfo-functional copolyester of formula (I) mentioned m claim 1) m an amount which is effective for prolonging the persistence of said fragrance on said laundry or said textiles after washing.

10) Process according to claim 8) or 9), characterized in that said sulfo-functional copolyester of formula (I) is present in a proportion of from 0.01 to 10%, preferably from 0 05 to 5%, especially from 0.1 to 1% of the weight, expressed as dry weight, of said detergent composition or of said washing medium. 11) Process according to any one of claims 8) to 10), characterized in that said detergent composition or said washing medium further comprises at least one surfactant.

12) Process according to any one of claims 8) to 11), characterized in that said detergent composition or said washing medium is substantially devoid of polyorganosiloxane compounds which carry amino functions.