EP1233994A2 - Composition for cleaning carpets, curtains and covering fabrics and/or for facilitating the removal of stains - Google Patents

Composition for cleaning carpets, curtains and covering fabrics and/or for facilitating the removal of stains

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Publication number
EP1233994A2
EP1233994A2 EP00980707A EP00980707A EP1233994A2 EP 1233994 A2 EP1233994 A2 EP 1233994A2 EP 00980707 A EP00980707 A EP 00980707A EP 00980707 A EP00980707 A EP 00980707A EP 1233994 A2 EP1233994 A2 EP 1233994A2
Authority
EP
European Patent Office
Prior art keywords
residues
parts
formula
units
sulfonated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00980707A
Other languages
German (de)
French (fr)
Inventor
Garry Embleton
Gladys Saliba Gabriel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay USA Inc
Original Assignee
Rhodia Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhodia Inc filed Critical Rhodia Inc
Publication of EP1233994A2 publication Critical patent/EP1233994A2/en
Withdrawn legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715Polyesters or polycarbonates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0031Carpet, upholstery, fur or leather cleansers
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507Polyesters
    • D06M15/5075Polyesters containing sulfonic groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds

Definitions

  • a subject matter of the present invention is an aqueous composition
  • aqueous composition comprising at least one sulfonated copolyester for cleaning carpets, including fitted carpets, curtains and covering fabrics at least partially made of hydrophobic synthetic polymer, in particular of polyester or polyamide, very particularly of polyamide, and/or for facilitating the removal of stains and dirt (soil release) therefrom.
  • Another subject matter of the invention is a process for cleaning carpets, including fitted carpets, curtains and covering fabrics at least partially made of hydrophobic synthetic polymer, in particular of polyester or polyamide, very particularly of polyamide, and/or for facilitating the removal of stains and dirt (soil release) therefrom by the nonpermanent deposition on these, by spraying, application by hand or application using a cleaning device, of an aqueous composition comprising at least one sulfonated copolyester.
  • an aqueous composition for the nonpermanent treatment of carpets including fitted carpets, curtains and covering fabrics, of at least one sulfonated copolyester as detergent agent and/or as agent which facilitates the removal of stains and dirt (soil release) .
  • a sulfonated copolyester as detergent agent and/or as agent which facilitates the removal of stains and dirt (soil release) .
  • terephthalic oligomers carrying sulfonated functional groups as antisoiling (soil release) agents in detergent compositions for washing laundry made of polyester or based on polyester (WO 95/32997, WO 92/04433 and US 4,877,796) .
  • the Applicant Company has found that some copolyesters exhibiting sulfonated units are particularly advantageous in aqueous compositions for the nonpermanent treatment of carpets, including fitted carpets, curtains and covering fabrics at least partially made of hydrophobic synthetic polymer, in particular of polyester or polyamide, very particularly of polyamide, as detergent (soil removal) agents and/or as agents which facilitate the removal of stains and dirt (soil release).
  • nonpermanent means that the active agent only remains temporarily on the fibers or surfaces and can be easily removed, unlike a permanent (finishing) treatment carried out at high temperature, where the active agent is intended to remain permanently on the fibers or surfaces.
  • a first subject matter of the invention is an aqueous composition for cleaning carpets, including fitted carpets, curtains and covering fabrics at least partially made of hydrophobic synthetic polymer, in particular of polyester or polyamide, very particularly of polyamide, and/or for facilitating the removal of stains and dirt (soil release) therefrom comprising at least one water-soluble or water-dispersible copolyester (SC) comprising sulfonated units, characterized in that said copolyester (SC) is composed essentially - of units of general formula (I)
  • NA nonionic mono- or polyarylene or nonionic alkylene residue
  • SA sulfonated mono- or polyarylene or sulfonated alkylene residue
  • A is a sulfonated residue (SA) , with respect to all the units of formula -C (0) -A-C (0) - in the units of formula (I), being of the order of 5 to 40, preferably of 7 to 35; and .
  • n is equal to 1 , 2 , 3 or 4 ,
  • a and n have the definitions given above .
  • Z represents a sulfonated C 2 -C 3i alkyloyl or aryloyl group carrying a sulfonate functional group, such as sulfobenzoyl M0 3 SC 6 H 4 C (0) -, where M is an alkali metal; the molar percentage of units of formula (0-CH 2 -CH 2 -) n where n is equal to 1, with respect to all the units of formula (0-CH 2 -CH 2 -) n where n is equal to 1, 2, 3 and 4 in the units of formula (I), (Hi) and (II 2 ), being of the order of 10 to 80, preferably of the order of 20 to 60; and the weight [lacuna] molecular mass of said copolyesters being less than 20,000, preferably less than 15,000, very particularly from 5000 to 10,000.
  • the weight [lacuna] molecular masses are measured by gel permeation chromatography in dimethyl
  • the nonionic residues (NA) of the units of formula (I) can be alike or different.
  • nonionic residues of nonionic C 6 -C ⁇ 4 mono- or polyarylene residues and nonionic C 1 -C 9 alkylene residues, such as the 1, 4-phenylene, 1, 3-phenylene, 1 , 6-naphthalene, 1 , 6-cyclohexylene, ethylene, trimethylene, tetra ethylene or hexamethylene residues.
  • SA sulfonated residues
  • SA sulfonated residues
  • Cg-C ⁇ 4 mono- or polyarylene residues and sulfonated C1-C9 alkylene residues carrying at least one sulfonic acid functional group preferably in the form of an alkali metal sulfonate, very particularly sodium sulfonate, such as the sodiooxysulfonylphenylene, sodiooxysulfonyl- naphthalene, sodiooxysulfonylbiphenylene or sodiooxy- sulfoethylene residues.
  • the nonionic residue (NA) is preferably a 1, 4-phenylene residue (NAl) or 1, 3-phenylene residue (NA2) and the sulfonated residue (SA) is preferably a 5-sodiooxysulfonyl-l, 3-phenylene residue .
  • the nonionic residues (NA) of the units of formula (I) are 1, 4-phenylene residues (NAl) or a mixture of 1, 4-phenylene residues (NAl) and 1, 3-phenylene residues (NA2), the molar percentage of the units of formula -C (0) -A-C (0) - where A is a residue (NAl), with respect to all the units of formula -C (O) -A-C (0) - where A is a nonionic residue (NA) , being of the order of 50 to 100, preferably of 70 to 90.
  • the chain-end groups are preferably groups of formula (Hi) .
  • Other units can additionally be present as chain ends in minor amounts, such as groups of formula (III)
  • sulfonated copolyesters exhibiting groups of formula (Hi) as chain ends can be obtained in a known way, for example by esterification and/or transesterification and polycondensation of a monomer composition composed essentially of: - a nonsulfonated diacid monomer (NAM) composed of at least one aromatic or aliphatic dicarboxylic acid or anhydride or their diesters in an amount corresponding to an (NAM) / (NAM) + (SAM) molar ratio of 95/100 to 60/100, preferably of the order of 93/100 to 65/100
  • a sulfonated diacid monomer composed of at least one sulfonated aromatic or sulfonated aliphatic dicarboxylic acid or anhydride or their diesters in an amount corresponding to an (SAM) / (NAM) + (SAM) molar ratio of the order of 5/100 to 40/100, preferably of the order of 7/100 to 35/100 - and a polyol monomer (P) composed of ethylene glycol and optionally of diethylene glycol according to an amount corresponding to a number of OH functional groups of the polyol monomer (P) /number of COOH functional groups or of COOH functional group equivalents of the diacid monomers (NAM) + (SAM) ratio of the order of 1.05 to 4, preferably of the order of 1.1 to 3.5 and very particularly of the order of 1.8 to 3.
  • SAM sulfonated diacid monomer
  • the basic unit considered in the definition of the mole of monomer (NAM) or (SAM) is the COOH functional group in the case of diacids or the COOH functional group equivalent in the case of anhydrides or diesters. Mention may be made, among nonsulfonated diacid monomers (NAM) , of terephthalic, isophthalic,
  • the nonsulfonated diacid monomer is preferably composed by 50 to 100 mol%, very particularly of 70 to 90 mol%, of terephthalic acid or anhydride or of one of its lower diesters (of methyl, ethyl, propyl, isopropyl or butyl) and of 0 to 50 mol%, very particularly of 10 to 30 mol%, of isophthalic acid or anhydride or of one of its lower diesters (of methyl, ethyl, propyl, isopropyl or butyl); the preferred diesters are those of methyl.
  • the sulfonated diacid monomer exhibits at least one sulfonic acid group, preferably in the form of an alkali metal sulfonate (preferably sodium sulfonate), and two acid functional groups or acid functional group equivalents (that is to say, one anhydride functional group or two ester functional groups) attached to one or more aromatic rings when said monomer is aromatic.
  • SAM sulfonated 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.
  • SAM sulfonated diacid monomers
  • aromatic or aliphatic dicarboxylic acids such as sulfoisophthalic, sulfoterephthalic, sulfoorthophthalic, 4-sulfonaphthalene-2 , 7- dicarboxylic, sulfodiphenyldicarboxylic or sulfosuccinic acids, their anhydrides or lower diesters.
  • the preferred sulfonated diacid monomers are sulfoisophthalic acids or anhydrides and their dimethyl esters and very particularly dimethyl 5- ( sodiooxysulfonyl) isophthalate .
  • Said sulfonated copolymers exhibiting groups of formula (III) as chain ends can be obtained by conventional esterification and/or transesterification and polycondensation processes, for example by an 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 at reduced pressure in the presence of a polycondensation catalyst .
  • said sulfonated copolyesters are obtained by carrying out the following successive stages:
  • the diesters of the nonsulfonated dicarboxylic acids (NAM) and sulfonated dicarboxylic acids (SAM) employed in the transesterification (interexchange) stage are preferably dimethyl esters.
  • the preferred sulfonated copolyesters can be obtained from - terephthalic acid (NAMl), in the diester form (preferably the dimethyl ester form) , optionally as a mixture with isophthalic and/or terephthalic acid (NAM2) in the diacid or anhydride form, according to an (NAMl) / (NAMl) + (NAM2) molar ratio of the order of 100/100 to 50/100, preferably of the order of 90/100 to 70/100
  • - monoethylene glycol They can be prepared by carrying out the following successive stages: - a stage of transesterification (interexchange) between, on the one hand, the diester (preferably the dimethyl ester) of terephthalic acid (NAMl) and the diester (preferably the dimethyl ester) of sulfoisophthalic acid (SAM) and, on the other hand, monoethylene glycol (P), the number of OH functional groups (P) /number of COOH functional group equivalents of (NAM1)+(SAM) ratio being of the order of 1.05 to 4, preferably of the order of 1.1 to 3.5 and very particularly of the order of 1.8 to 3
  • NAM2 isophthalic and/or terephthalic acid
  • P monoethylene glycol
  • P monoethylene glycol
  • the number of OH functional groups (P) /number of COOH functional groups of (NAM2) ratio being of the order of 1.05 to 4, preferably of the order of 1.1 to 3.5 and very particularly of the order of 1.8 to 3
  • Chain ends with a formula of the type (II 2 ) can be obtained by employing, preferably in the esterification stage, sulfonated monoacid monomers, such as m-sodiosulfobenzoic acid or methyl or 2-hydroxyethyl m-sodiosulfobenzoate .
  • Said aqueous compositions can comprise from 0.05 to 5 parts, preferably from 0.1 to 2 parts, very particularly from 0.2 to 1.5 parts, by weight of copolyester (SC) per 100 parts by weight of aqueous compositions .
  • Said composition can be an aqueous solution or an aqueous dispersion of said copolyester (SC) or can additionally comprise other additives, such as: * surface-active agents in amounts ranging from 0.5 to 10 parts, preferably from 1 to 5 parts, very preferably from 1 to 2 parts, by weight per 100 parts by weight of aqueous composition, surface-active agents such as - anionic surface-active agents, such as . alkyl ester sulfonates of formula R-CH (S0 3 M) -COOR' , where R represents a Cs- 2 o? preferably Cio-Ci ⁇ .
  • alkyl radical R 1 a C ⁇ -C 6 , preferably C ⁇ -C 3 , alkyl radical and M an alkali metal (sodium, potassium or lithium) cation, a substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl- or tetramethylammonium, dimethylpiperidinium, and the like) cation or a cation derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine, and the like) ; .
  • alkali metal sodium, potassium or lithium
  • a substituted or unsubstituted ammonium methyl-, dimethyl-, trimethyl- or tetramethylammonium, dimethylpiperidinium, and the like
  • alkanolamine monoethanolamine, diethanolamine, triethanolamine, and the like
  • alkyl sulfates of formula ROS0 3 M where R represents a C5-C24, preferably Cio-Cis, alkyl or hydroxyalkyl radical, M representing a hydrogen atom or a cation with the same definition as above, and their ethoxylenated (EO) and/or propoxylenated (PO) derivatives exhibiting an average of 0.5 to 30, preferably of 0.5 to 10, EO and/or PO units;
  • alkylamide sulfates of formula RCONHR'OS0 3 M where R represents a C 2 -C 22 , preferably C 6 -C 2 o/ alkyl radical, R' a C 2 -C 3 alkyl radical, M representing a hydrogen atom or a cation with the same definition as above, and their ethoxylenated (EO) and/or propoxylenated (PO) derivatives exhibiting an average of 0.5 to 60 EO and/or PO units; .
  • C 8 -C 24 preferably Ci4-C 20 , saturated or unsaturated fatty acids, C9-C20 alkylbenzenesulfonates, primary or secondary C ⁇ -C 22 alkylsulfonates, alkylglycerol sulfonates, the sulfonated polycarboxylic acids described in GB-A-1, 082 , 179, paraffin sulfonates, N-acyl-N-alkyltaurates, alkyl phosphates, isethionates, alkylsuccinamates, alkylsulfosuccinates, the monoesters or diesters of sulfosuccinates, N-acylsarcosinates, alkylglycoside sulfates or polyethoxycarboxylates the cation being an alkali metal (sodium, potassium or lithium) , a substituted or unsubstituted ammonium residue (methyl
  • non-ionic surface-active agents such as .
  • polyoxyalkylenated C 8 -C 22 aliphatic alcohols comprising from 1 to 25 oxyalkylene (oxyethylene or oxypropylene) units; mention may be made, by way of example, of Tergitol 15-S-9 or Tergitol 24-L-6 NMW, sold by Union Carbide Corp., Neodol 45-9, Neodol 23-65, Neodol 45-7 or Neodol 45-4, sold by Shell Chemical Co., Kyro EOB, sold by The Procter & Gamble Co., Synperonic A3 to A9 from ICI, or Rhodasurf IT, DB and B from Rhodia;
  • ethoxylated amines comprising from 5 to 30 ethoxylated units; . alkoxylated amidoamines comprising from 1 to 50, preferably from 1 to 25, very particularly from 2 to 20, oxyalkylene units (preferably oxyethylene units; . amine oxides, such as (Cio-Ci ⁇ alkyl ) dimethylamine oxides or (C 8 -C 22 alkoxy) ethyldihydroxyethylamine oxides;
  • alkoxylated terpene hydrocarbons such as ethoxylated and/or propoxylated a- or b-pinenes, comprising from 1 to 30 oxyethylene and/or oxypropylene units; . the alkylpolyglycosides which can be obtained 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, and the like) exhibiting a C 4 -C 2 o, preferably C 8 -C ⁇ 8 , alkyl group and a mean number of glucose units of the order [lacuna] 0.5 to 3, preferably of the order of 1.1 to
  • alkylpolyglycoside per mole of alkylpolyglycoside (APG) ; mention may in particular be made of those exhibiting a Cs-Ci 4 alkyl group and, on average, 1.4 glucose units per mole a C 12 -C 14 alkyl group and, on average, 1.4 glucose units per mole a C 8 -Ci4 alkyl group and, on average, 1.5 glucose units per mole a C 8 -C ⁇ o alkyl group and, on average, 1.6 glucose units per mole sold respectively under the names Glucopon 600 EC ® , Glucopon 600 CSUP ® , Glucopon 650 EC ® and Glucopon 225 CSUP ® by Henkel.
  • amphoteric surface-active agents such as alkyl betaines, alkyl dimethyl betaines, alkyl amidopropyl betaines, alkyl amidopropyldimethyl betaines, alkyl trimethyl sulfobetaines , imidazoline derivatives, such as alkyl amphoacetates, alkyl amphodiacetates, alkyl amphopropionates or alkyl amphodipropionates, alkyl sultaines or alkylamidopropyl hydroxysultaines, the condensation products of fatty acids and of protein hydrolysates, amphoteric derivatives of alkylpolyamines , such as Amphionic XL", sold by Rhodia, or Ampholac 7T/X ® and Ampholac 7C/X ® , sold by Berol Nobel, or proteins or protein hydrolysates;
  • * antiredeposition agents in amounts ranging from 0.1 to 3 parts, preferably from 0.5 to 1 part, by weight per 100 parts by weight of aqueous composition, such as water-soluble salts of carboxylic polymers or copolymers, for example salts of polyacrylic acid, or copolymers of acrylic acid and of maleic anhydride;
  • alcohols in amounts ranging from 0.5 to 10 parts, preferably from 1 to 5 parts, by weight per 100 parts by weight of aqueous composition, such as ethanol, propylene glycol, isopropanol or butylene glycol;
  • fragrances in amounts ranging from 0.05 to 0.2 part by weight per 100 parts by weight of aqueous composition;
  • polyester copolymers based on ethylene terephthalate and/or propylene terephthalate and polyoxyethylene and/or polyoxypropylene units are based on ethylene terephthalate and/or propylene terephthalate and polyoxyethylene and/or polyoxypropylene units.
  • Said aqueous compositions according to the invention can exhibit a level of dry matter of the order of 0.5 to 15%, preferably of the order of 0.5 to 7.5%, very preferably of 1 to 3%, of its weight.
  • Said compositions can exhibit a pH of 3 to
  • a second subject matter of the invention is a process for cleaning carpets, including fitted carpets, curtains and covering fabrics, in particular made of synthetic polymer, very particularly of polyamide, and/or for facilitating the removal of stains and dirt (soil release) therefrom by nonpermanent deposition on these, by spraying, application by hand or application using a device for cleaning textile surfaces, of the liquid aqueous composition comprising at least one copolyester (SC) as defined above.
  • SC copolyester
  • Said copolyester makes it possible to remove stains, in particular greasy stains (polish, ballpoint pen, lipstick, oil, and the like) or aqueous stains (coffee, and the like), and/or to facilitate the removal of said stains; it also makes it possible to remove dirt, in particular that transported by shoe soles (dust, clay, earth, and the like) , and/or to facilitate the removal of said dirt.
  • this is an operation for the pretreatment of the surfaces under consideration using said composition comprising at least one copolyester (SC) according to the invention, said composition being composed of an aqueous solution or suspension of at least one copolyester (SC) or additionally comprising other additives as mentioned above.
  • SC copolyester
  • This pretreatment operation makes it possible for the stains and dirt which will be deposited subsequently to be more easily removed during a following cleaning using an aqueous composition comprising or not comprising copolyester (SC) .
  • the amount of copolyester (SC) and the nature and the amounts of the other additives optionally present in said aqueous compositions, in order to carry out the cleaning process and/or to facilitate the removal of stains and dirt, have already been mentioned above .
  • aqueous composition employed correspond to a deposited amount of copolyester (SC), expressed as dry matter, of the order of 0.01 to 5, preferably of 0.05 to 3, g/m 2 of surface.
  • SC copolyester
  • compositions can optionally be diluted before use.
  • Said aqueous composition comprising the copolyester (SC) can be deposited on said surface to be treated by spraying, by application using a shampooer or by application using an injection-extraction device, or by simply pouring said liquid composition onto the surface to be treated, with optional rubbing using a sponge or brush.
  • a third subject matter of the invention is a process for improving the properties of compositions for cleaning carpets, including fitted carpets, curtains and covering fabrics, in particular made of synthetic polymer, very particularly of polyamide, by addition to said compositions of an effective amount of at least one copolyester (SC) as defined above as detergent (soil removal) agent and/or as agent for facilitating the removal of stains and dirt (soil release) .
  • Another subject matter of the invention is the use, in an aqueous composition for cleaning carpets, including fitted carpets, curtains and covering fabrics, in particular made of synthetic polymer, very particularly of polyamide, of at least one copolyester (SC) as defined above as detergent agent and/or as agent for facilitating the removal of stains and dirt (soil release) from said carpets, including fitted carpets, curtains and covering fabrics .
  • SC copolyester
  • Said copolyester (SC) can be employed according to amounts, expressed as dry matter, of the order of 0.01 to 5, preferably of 0.05 to 3, g/m 2 of surface .
  • Said compositions can optionally be diluted before use.
  • Said aqueous composition comprising the copolyester (SC) can be deposited on said surface to be treated by spraying, by application using a shampooer or by application using an injection-extraction device, or by simply pouring said liquid composition onto the surface to be treated, with optional rubbing using a sponge or brush.
  • Example 1 The following example is given by way of illustration .
  • Example 1 The following example is given by way of illustration .
  • the medium is subsequently preheated to 180°C and then brought to 220°C over approximately
  • reaction mixture is subsequently heated in order to reach 230°C over 30 minutes.
  • charge II the gradual introduction of the following charge II is begun:
  • lacuna molecular mass is 5100; this is 9300 by weight (measurements by gel permeation chromatography in dimethylacetamide comprising 10 ⁇ 2 N LiBr at 100°C; results expressed in polystyrene equivalents) .
  • This terephthalic copolymer comprises 15 mol% of sulfonate functional groups and exhibits, per 100 ether bonds of formula (0-CH 2 -CH 2 -) n ,
  • the fitted carpet is first of all cleaned from one side to the other, front and rear, using Rug Color detergent diluted according to the manufacturer's instructions (2 oz. per gallon, i.e. approximately 15 g/1), using a Bissel steam cleaning device. 2) After drying, the fitted carpet is cut up into
  • the oil stains are produced by using the micropipette; the waxy stains are firstly pressed onto the applicational sponge and subsequently applied to the fitted carpet samples.
  • the oil stains are applied at a dose of 0.12 ⁇ 0.05 g for each fitted carpet sample inside a 2" x 2" (approximately 5 x 5 cm 2 ) square mask using a spatula.
  • the waxes are applied at a dose by weight of 0.15 ⁇ 0.05 g.
  • the stains are cleaned by rubbing five times from the top of the stain through the center using a dry white absorbent paper towel; the paper towel is turned over in order to obtain a clean surface and rubbing is carried out a further five times from the bottom of the stain through the center.

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  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
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Abstract

Aqueous composition comprising at least one sulfonated copolyester, preferably a terephthalic copolyester, for cleaning carpets, including fitted carpets, curtains and covering fabrics at least partially made of hydrophobic synthetic polymer, in particular of polyester or polyamide, very particularly of polyamide, and/or for facilitating the removal of stains and dirt (soil release) therefrom.

Description

COMPOSITION FOR CLEANING CARPETS, INCLUDING FITTED
CARPETS, CURTAINS AND COVERING FABRICS AND/OR FOR
FACILITATING THE REMOVAL OF STAINS AND DIRT THEREFROM
A subject matter of the present invention is an aqueous composition comprising at least one sulfonated copolyester for cleaning carpets, including fitted carpets, curtains and covering fabrics at least partially made of hydrophobic synthetic polymer, in particular of polyester or polyamide, very particularly of polyamide, and/or for facilitating the removal of stains and dirt (soil release) therefrom. Another subject matter of the invention is a process for cleaning carpets, including fitted carpets, curtains and covering fabrics at least partially made of hydrophobic synthetic polymer, in particular of polyester or polyamide, very particularly of polyamide, and/or for facilitating the removal of stains and dirt (soil release) therefrom by the nonpermanent deposition on these, by spraying, application by hand or application using a cleaning device, of an aqueous composition comprising at least one sulfonated copolyester. It is also targeted at the use, in an aqueous composition for the nonpermanent treatment of carpets, including fitted carpets, curtains and covering fabrics, of at least one sulfonated copolyester as detergent agent and/or as agent which facilitates the removal of stains and dirt (soil release) . It is known to decrease the viscosity of stable aqueous emulsions of a mixture of at least one nonionic hydrophilic surface-active agent and of at least one nonionic hydrophobic surface-active agent by addition of an optionally sulfonated, terephthalic oligomer or polymer; these emulsions can be used as cleaning composition, for example for cleaning carpets (EP-A-629, 690) .
It is also known to use terephthalic oligomers carrying sulfonated functional groups as antisoiling (soil release) agents in detergent compositions for washing laundry made of polyester or based on polyester (WO 95/32997, WO 92/04433 and US 4,877,796) . The Applicant Company has found that some copolyesters exhibiting sulfonated units are particularly advantageous in aqueous compositions for the nonpermanent treatment of carpets, including fitted carpets, curtains and covering fabrics at least partially made of hydrophobic synthetic polymer, in particular of polyester or polyamide, very particularly of polyamide, as detergent (soil removal) agents and/or as agents which facilitate the removal of stains and dirt (soil release). The term "nonpermanent" means that the active agent only remains temporarily on the fibers or surfaces and can be easily removed, unlike a permanent (finishing) treatment carried out at high temperature, where the active agent is intended to remain permanently on the fibers or surfaces.
A first subject matter of the invention is an aqueous composition for cleaning carpets, including fitted carpets, curtains and covering fabrics at least partially made of hydrophobic synthetic polymer, in particular of polyester or polyamide, very particularly of polyamide, and/or for facilitating the removal of stains and dirt (soil release) therefrom comprising at least one water-soluble or water-dispersible copolyester (SC) comprising sulfonated units, characterized in that said copolyester (SC) is composed essentially - of units of general formula (I)
[-O-C(O) -A-C(O) - (0-CH2-CH2-)n-] (I), where . the symbol A represents
* a nonionic mono- or polyarylene or nonionic alkylene residue (NA) * or a sulfonated mono- or polyarylene or sulfonated alkylene residue (SA) carrying at least one sulfonic acid functional group, the molar percentage of the units of formula
-C (0) -A-C (0) - where A is a sulfonated residue (SA) , with respect to all the units of formula -C (0) -A-C (0) - in the units of formula (I), being of the order of 5 to 40, preferably of 7 to 35; and . n is equal to 1 , 2 , 3 or 4 ,
- as chain ends, of alike or different groups of formula
-A-CO-O- (CH2-CH2-0)n-H (11^ -A-CO-O- (CH2-CH2-0)n-Z (II2) in which formulae
. A and n have the definitions given above . Z represents a sulfonated C2-C3i alkyloyl or aryloyl group carrying a sulfonate functional group, such as sulfobenzoyl M03SC6H4C (0) -, where M is an alkali metal; the molar percentage of units of formula (0-CH2-CH2-) n where n is equal to 1, with respect to all the units of formula (0-CH2-CH2-) n where n is equal to 1, 2, 3 and 4 in the units of formula (I), (Hi) and (II2), being of the order of 10 to 80, preferably of the order of 20 to 60; and the weight [lacuna] molecular mass of said copolyesters being less than 20,000, preferably less than 15,000, very particularly from 5000 to 10,000. The weight [lacuna] molecular masses are measured by gel permeation chromatography in dimethylacetamide comprising 10~2N LiBr at 100°C. The results are expressed in polystyrene equivalents.
The nonionic residues (NA) of the units of formula (I) can be alike or different.
Mention may be made, as example of nonionic residues (NA) , of nonionic C6-Cι4 mono- or polyarylene residues and nonionic C1-C9 alkylene residues, such as the 1, 4-phenylene, 1, 3-phenylene, 1 , 6-naphthalene, 1 , 6-cyclohexylene, ethylene, trimethylene, tetra ethylene or hexamethylene residues. The sulfonated residues (SA) of the units of formula (I) can be alike or different.
Mention may be made, as example of sulfonated residues (SA), of sulfonated Cg-Cι4 mono- or polyarylene residues and sulfonated C1-C9 alkylene residues carrying at least one sulfonic acid functional group, preferably in the form of an alkali metal sulfonate, very particularly sodium sulfonate, such as the sodiooxysulfonylphenylene, sodiooxysulfonyl- naphthalene, sodiooxysulfonylbiphenylene or sodiooxy- sulfoethylene residues.
The nonionic residue (NA) is preferably a 1, 4-phenylene residue (NAl) or 1, 3-phenylene residue (NA2) and the sulfonated residue (SA) is preferably a 5-sodiooxysulfonyl-l, 3-phenylene residue . In a very preferred way, the nonionic residues (NA) of the units of formula (I) are 1, 4-phenylene residues (NAl) or a mixture of 1, 4-phenylene residues (NAl) and 1, 3-phenylene residues (NA2), the molar percentage of the units of formula -C (0) -A-C (0) - where A is a residue (NAl), with respect to all the units of formula -C (O) -A-C (0) - where A is a nonionic residue (NA) , being of the order of 50 to 100, preferably of 70 to 90.
The chain-end groups are preferably groups of formula (Hi) . Other units can additionally be present as chain ends in minor amounts, such as groups of formula (III)
-A-CO-OH (III) where A has the definition given above. Said sulfonated copolyesters exhibiting groups of formula (Hi) as chain ends can be obtained in a known way, for example by esterification and/or transesterification and polycondensation of a monomer composition composed essentially of: - a nonsulfonated diacid monomer (NAM) composed of at least one aromatic or aliphatic dicarboxylic acid or anhydride or their diesters in an amount corresponding to an (NAM) / (NAM) + (SAM) molar ratio of 95/100 to 60/100, preferably of the order of 93/100 to 65/100
- a sulfonated diacid monomer (SAM) composed of at least one sulfonated aromatic or sulfonated aliphatic dicarboxylic acid or anhydride or their diesters in an amount corresponding to an (SAM) / (NAM) + (SAM) molar ratio of the order of 5/100 to 40/100, preferably of the order of 7/100 to 35/100 - and a polyol monomer (P) composed of ethylene glycol and optionally of diethylene glycol according to an amount corresponding to a number of OH functional groups of the polyol monomer (P) /number of COOH functional groups or of COOH functional group equivalents of the diacid monomers (NAM) + (SAM) ratio of the order of 1.05 to 4, preferably of the order of 1.1 to 3.5 and very particularly of the order of 1.8 to 3. The basic unit considered in the definition of the mole of monomer (NAM) or (SAM) is the COOH functional group in the case of diacids or the COOH functional group equivalent in the case of anhydrides or diesters. Mention may be made, among nonsulfonated diacid monomers (NAM) , of terephthalic, isophthalic,
2, 6-naphthalenedicarboxylic, cyclohexanedicarboxylic, succinic, glutaric, adipic or suberic acids, their anhydrides or lower diesters . The nonsulfonated diacid monomer (NAM) is preferably composed by 50 to 100 mol%, very particularly of 70 to 90 mol%, of terephthalic acid or anhydride or of one of its lower diesters (of methyl, ethyl, propyl, isopropyl or butyl) and of 0 to 50 mol%, very particularly of 10 to 30 mol%, of isophthalic acid or anhydride or of one of its lower diesters (of methyl, ethyl, propyl, isopropyl or butyl); the preferred diesters are those of methyl. The sulfonated diacid monomer (SAM) exhibits at least one sulfonic acid group, preferably in the form of an alkali metal sulfonate (preferably sodium sulfonate), and two acid functional groups or acid functional group equivalents (that is to say, one anhydride functional group or two ester functional groups) attached to one or more aromatic rings when said monomer is aromatic.
In the case of a sulfonated aliphatic 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. Mention may be made, among sulfonated diacid monomers (SAM) , of sulfonated aromatic or aliphatic dicarboxylic acids, such as sulfoisophthalic, sulfoterephthalic, sulfoorthophthalic, 4-sulfonaphthalene-2 , 7- dicarboxylic, sulfodiphenyldicarboxylic or sulfosuccinic acids, their anhydrides or lower diesters. The preferred sulfonated diacid monomers (SAM) are sulfoisophthalic acids or anhydrides and their dimethyl esters and very particularly dimethyl 5- ( sodiooxysulfonyl) isophthalate . Said sulfonated copolymers exhibiting groups of formula (III) as chain ends can be obtained by conventional esterification and/or transesterification and polycondensation processes, for example by an 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 at reduced pressure in the presence of a polycondensation catalyst . According to a preferred method of preparation, said sulfonated copolyesters are obtained by carrying out the following successive stages:
- a stage of transesterification (interexchange) between, on the one hand, the sulfonated diacid monomer (SAM), in the diester form, and from 50 to 100 mol%, very particularly from 30 to 90 mol%, of the total amount of the nonsulfonated diacid monomer (NAM) , in the diester form, and, on the other hand, an amount of polyol monomer (P) corresponding to a number of OH functional groups of the polyol monomer (P) /number of COOH functional group equivalents of said monomers (NAM) and (SAM) in the form [lacuna] diesters ratio of the order of 1.05 to 4, preferably of the order of 1.1 to 3.5 and very particularly of the order of 1.8 to 3.0 - an optional stage of esterification between the optional remaining amount of the nonsulfonated diacid monomer (NAM) , in the diacid or anhydride form, and an amount of polyol monomer (P) corresponding to a number of OH functional groups of the polyol monomer (P) /number of COOH functional groups of the nonsulfonated diacid monomer (NAM) in the diacid or anhydride form ratio of the order of 1.05 to 4, preferably of the order of 1.1 to 3.5 and very particularly of the order of 1.8 to 3.0
- a polycondensation stage.
The diesters of the nonsulfonated dicarboxylic acids (NAM) and sulfonated dicarboxylic acids (SAM) employed in the transesterification (interexchange) stage are preferably dimethyl esters.
The preferred sulfonated copolyesters can be obtained from - terephthalic acid (NAMl), in the diester form (preferably the dimethyl ester form) , optionally as a mixture with isophthalic and/or terephthalic acid (NAM2) in the diacid or anhydride form, according to an (NAMl) / (NAMl) + (NAM2) molar ratio of the order of 100/100 to 50/100, preferably of the order of 90/100 to 70/100
- sulfoisophthalic acid, in the diester form (preferably the dimethyl ester form)
- monoethylene glycol. They can be prepared by carrying out the following successive stages: - a stage of transesterification (interexchange) between, on the one hand, the diester (preferably the dimethyl ester) of terephthalic acid (NAMl) and the diester (preferably the dimethyl ester) of sulfoisophthalic acid (SAM) and, on the other hand, monoethylene glycol (P), the number of OH functional groups (P) /number of COOH functional group equivalents of (NAM1)+(SAM) ratio being of the order of 1.05 to 4, preferably of the order of 1.1 to 3.5 and very particularly of the order of 1.8 to 3
- a stage of esterification between isophthalic and/or terephthalic acid (NAM2) and, on the other hand, monoethylene glycol (P) , the number of OH functional groups (P) /number of COOH functional groups of (NAM2) ratio being of the order of 1.05 to 4, preferably of the order of 1.1 to 3.5 and very particularly of the order of 1.8 to 3
- a polycondensation stage.
The operating conditions for the transesterification, esterification and condensation stages which can be employed are those disclosed in W095/32997.
Chain ends with a formula of the type (II2) can be obtained by employing, preferably in the esterification stage, sulfonated monoacid monomers, such as m-sodiosulfobenzoic acid or methyl or 2-hydroxyethyl m-sodiosulfobenzoate . Said aqueous compositions can comprise from 0.05 to 5 parts, preferably from 0.1 to 2 parts, very particularly from 0.2 to 1.5 parts, by weight of copolyester (SC) per 100 parts by weight of aqueous compositions .
Said composition can be an aqueous solution or an aqueous dispersion of said copolyester (SC) or can additionally comprise other additives, such as: * surface-active agents in amounts ranging from 0.5 to 10 parts, preferably from 1 to 5 parts, very preferably from 1 to 2 parts, by weight per 100 parts by weight of aqueous composition, surface-active agents such as - anionic surface-active agents, such as . alkyl ester sulfonates of formula R-CH (S03M) -COOR' , where R represents a Cs-2o? preferably Cio-Ciβ. alkyl radical, R1 a Cι-C6, preferably Cχ-C3, alkyl radical and M an alkali metal (sodium, potassium or lithium) cation, a substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl- or tetramethylammonium, dimethylpiperidinium, and the like) cation or a cation derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine, and the like) ; . alkyl sulfates of formula ROS03M, where R represents a C5-C24, preferably Cio-Cis, alkyl or hydroxyalkyl radical, M representing a hydrogen atom or a cation with the same definition as above, and their ethoxylenated (EO) and/or propoxylenated (PO) derivatives exhibiting an average of 0.5 to 30, preferably of 0.5 to 10, EO and/or PO units;
. alkylamide sulfates of formula RCONHR'OS03M, where R represents a C2-C22, preferably C6-C2o/ alkyl radical, R' a C2-C3 alkyl radical, M representing a hydrogen atom or a cation with the same definition as above, and their ethoxylenated (EO) and/or propoxylenated (PO) derivatives exhibiting an average of 0.5 to 60 EO and/or PO units; . salts of C8-C24, preferably Ci4-C20, saturated or unsaturated fatty acids, C9-C20 alkylbenzenesulfonates, primary or secondary Cβ-C22 alkylsulfonates, alkylglycerol sulfonates, the sulfonated polycarboxylic acids described in GB-A-1, 082 , 179, paraffin sulfonates, N-acyl-N-alkyltaurates, alkyl phosphates, isethionates, alkylsuccinamates, alkylsulfosuccinates, the monoesters or diesters of sulfosuccinates, N-acylsarcosinates, alkylglycoside sulfates or polyethoxycarboxylates the cation being an alkali metal (sodium, potassium or lithium) , a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl- or tetramethylammonium, dimethylpiperidinium, and the like) , or a residue derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine, and the like) ;
- with non-ionic surface-active agents, such as . polyoxyalkylenated (polyethoxyethylenated, polyoxypropylenated or polyoxybutylenated) alkylphenols, the alkyl substituent of which is C6-Cι2, comprising from 5 to 25 oxyalkylene units; mention may be made, by way of example, of Triton X-45, X-114,
X-100 or X-102, sold by Rohm & Haas Co., or Igepal NP2 to NP17 from Rhodia;
. polyoxyalkylenated C8-C22 aliphatic alcohols comprising from 1 to 25 oxyalkylene (oxyethylene or oxypropylene) units; mention may be made, by way of example, of Tergitol 15-S-9 or Tergitol 24-L-6 NMW, sold by Union Carbide Corp., Neodol 45-9, Neodol 23-65, Neodol 45-7 or Neodol 45-4, sold by Shell Chemical Co., Kyro EOB, sold by The Procter & Gamble Co., Synperonic A3 to A9 from ICI, or Rhodasurf IT, DB and B from Rhodia;
. the products resulting from the condensation of ethylene oxide or of propylene oxide with propylene glycol or ethylene glycol, with a weight [lacuna] molecular mass of the order of 2000 to 10,000, such as the Pluronics sold by BASF;
. the products resulting from the condensation of ethylene oxide or of propylene oxide with ethylenediamine, such as the Tetronics sold by BASF; . ethoxylated and/or propoxylated C8-Cι8 fatty acids comprising from 5 to 25 ethoxylated and/or propoxylated units; . Ce-C2o fatty acid amides comprising from 5 to 30 ethoxylated units;
. ethoxylated amines comprising from 5 to 30 ethoxylated units; . alkoxylated amidoamines comprising from 1 to 50, preferably from 1 to 25, very particularly from 2 to 20, oxyalkylene units (preferably oxyethylene units; . amine oxides, such as (Cio-Ciβ alkyl ) dimethylamine oxides or (C8-C22 alkoxy) ethyldihydroxyethylamine oxides;
. alkoxylated terpene hydrocarbons, such as ethoxylated and/or propoxylated a- or b-pinenes, comprising from 1 to 30 oxyethylene and/or oxypropylene units; . the alkylpolyglycosides which can be obtained 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, and the like) exhibiting a C4-C2o, preferably C8-Cι8, alkyl group and a mean number of glucose units of the order [lacuna] 0.5 to 3, preferably of the order of 1.1 to
1.8, per mole of alkylpolyglycoside (APG) ; mention may in particular be made of those exhibiting a Cs-Ci4 alkyl group and, on average, 1.4 glucose units per mole a C12-C14 alkyl group and, on average, 1.4 glucose units per mole a C8-Ci4 alkyl group and, on average, 1.5 glucose units per mole a C8-Cιo alkyl group and, on average, 1.6 glucose units per mole sold respectively under the names Glucopon 600 EC®, Glucopon 600 CSUP®, Glucopon 650 EC® and Glucopon 225 CSUP® by Henkel.
- and/or with amphoteric surface-active agents, such as alkyl betaines, alkyl dimethyl betaines, alkyl amidopropyl betaines, alkyl amidopropyldimethyl betaines, alkyl trimethyl sulfobetaines , imidazoline derivatives, such as alkyl amphoacetates, alkyl amphodiacetates, alkyl amphopropionates or alkyl amphodipropionates, alkyl sultaines or alkylamidopropyl hydroxysultaines, the condensation products of fatty acids and of protein hydrolysates, amphoteric derivatives of alkylpolyamines , such as Amphionic XL", sold by Rhodia, or Ampholac 7T/X® and Ampholac 7C/X®, sold by Berol Nobel, or proteins or protein hydrolysates;
* antiredeposition agents, in amounts ranging from 0.1 to 3 parts, preferably from 0.5 to 1 part, by weight per 100 parts by weight of aqueous composition, such as water-soluble salts of carboxylic polymers or copolymers, for example salts of polyacrylic acid, or copolymers of acrylic acid and of maleic anhydride; * alcohols, in amounts ranging from 0.5 to 10 parts, preferably from 1 to 5 parts, by weight per 100 parts by weight of aqueous composition, such as ethanol, propylene glycol, isopropanol or butylene glycol; * fragrances, in amounts ranging from 0.05 to 0.2 part by weight per 100 parts by weight of aqueous composition;
* other antisoiling agents, such as
. polyester copolymers based on ethylene terephthalate and/or propylene terephthalate and polyoxyethylene terephthalate units, optionally comprising sulfoisophthaloyl units in their chain
. polyester copolymers based on ethylene terephthalate and/or propylene terephthalate and polyoxyethylene and/or polyoxypropylene units.
Said aqueous compositions according to the invention can exhibit a level of dry matter of the order of 0.5 to 15%, preferably of the order of 0.5 to 7.5%, very preferably of 1 to 3%, of its weight. Said compositions can exhibit a pH of 3 to
12, preferably of 4 to 10, very preferably of 7 to 10.
A second subject matter of the invention is a process for cleaning carpets, including fitted carpets, curtains and covering fabrics, in particular made of synthetic polymer, very particularly of polyamide, and/or for facilitating the removal of stains and dirt (soil release) therefrom by nonpermanent deposition on these, by spraying, application by hand or application using a device for cleaning textile surfaces, of the liquid aqueous composition comprising at least one copolyester (SC) as defined above. Said copolyester (SC) makes it possible to remove stains, in particular greasy stains (polish, ballpoint pen, lipstick, oil, and the like) or aqueous stains (coffee, and the like), and/or to facilitate the removal of said stains; it also makes it possible to remove dirt, in particular that transported by shoe soles (dust, clay, earth, and the like) , and/or to facilitate the removal of said dirt.
When said process has more particularly the aim of facilitating the removal of stains and dirt (soil release) from carpets, including fitted carpets, curtains and covering fabrics, this is an operation for the pretreatment of the surfaces under consideration using said composition comprising at least one copolyester (SC) according to the invention, said composition being composed of an aqueous solution or suspension of at least one copolyester (SC) or additionally comprising other additives as mentioned above. This pretreatment operation makes it possible for the stains and dirt which will be deposited subsequently to be more easily removed during a following cleaning using an aqueous composition comprising or not comprising copolyester (SC) . The amount of copolyester (SC) and the nature and the amounts of the other additives optionally present in said aqueous compositions, in order to carry out the cleaning process and/or to facilitate the removal of stains and dirt, have already been mentioned above .
The amounts of aqueous composition employed correspond to a deposited amount of copolyester (SC), expressed as dry matter, of the order of 0.01 to 5, preferably of 0.05 to 3, g/m2 of surface.
Said compositions can optionally be diluted before use.
Said aqueous composition comprising the copolyester (SC) can be deposited on said surface to be treated by spraying, by application using a shampooer or by application using an injection-extraction device, or by simply pouring said liquid composition onto the surface to be treated, with optional rubbing using a sponge or brush. A third subject matter of the invention is a process for improving the properties of compositions for cleaning carpets, including fitted carpets, curtains and covering fabrics, in particular made of synthetic polymer, very particularly of polyamide, by addition to said compositions of an effective amount of at least one copolyester (SC) as defined above as detergent (soil removal) agent and/or as agent for facilitating the removal of stains and dirt (soil release) .
The amount of copolyester (SC) and the nature and the amounts of the other additives optionally present in said aqueous compositions have already been mentioned above.
Another subject matter of the invention is the use, in an aqueous composition for cleaning carpets, including fitted carpets, curtains and covering fabrics, in particular made of synthetic polymer, very particularly of polyamide, of at least one copolyester (SC) as defined above as detergent agent and/or as agent for facilitating the removal of stains and dirt (soil release) from said carpets, including fitted carpets, curtains and covering fabrics .
The amounts of copolyester (SC) and the nature and the amounts of the other additives optionally present in said aqueous compositions have already been mentioned above.
Said copolyester (SC) can be employed according to amounts, expressed as dry matter, of the order of 0.01 to 5, preferably of 0.05 to 3, g/m2 of surface . Said compositions can optionally be diluted before use. Said aqueous composition comprising the copolyester (SC) can be deposited on said surface to be treated by spraying, by application using a shampooer or by application using an injection-extraction device, or by simply pouring said liquid composition onto the surface to be treated, with optional rubbing using a sponge or brush.
The following example is given by way of illustration . Example 1
The following charge I is introduced, after several purges with nitrogen, into a stainless steel reactor with a capacity of 1 liter:
* Dimethyl terephthalate 310.4 g (1.598 mol)
* Ethylene glycol 339 g (5.47 mol)
* Dimethyl 5-(sodiooxy- 104.4 g (0.353 mol) sulfonyl) isophthalate
* Titanium aminotriethanolate 54 ppm of (catalyst) titanium
The medium is subsequently preheated to 180°C and then brought to 220°C over approximately
130 minutes, during which period of time the methanol resulting from the transesterification reaction is distilled off.
The reaction mixture is subsequently heated in order to reach 230°C over 30 minutes. When the reaction mass has reached this temperature, the gradual introduction of the following charge II is begun:
* Isophthalic acid 11.72 g (0.07 mol)
* Ethylene glycol 67.2 g (0.34 mol)
* Terephthalic acid 56.7 g (1.08 mol) over a period of time of one hour, while maintaining 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 off without retrogradation . A gradual vacuum is applied at this temperature in order to obtain a reduced pressure of 100 mbar over 22 minutes. The reaction mass is then poured. The product is redispersible in water.
Its number [lacuna] molecular mass is 5100; this is 9300 by weight (measurements by gel permeation chromatography in dimethylacetamide comprising 10~2N LiBr at 100°C; results expressed in polystyrene equivalents) .
This terephthalic copolymer comprises 15 mol% of sulfonate functional groups and exhibits, per 100 ether bonds of formula (0-CH2-CH2-) n,
. 55.7 "ethylene glycol" bonds (n=l) . 31.8 "diethylene glycol" bonds (n=2) . 10.2 "triethylene glycol" bonds (n=3) . 2.3 "tetraethylene glycol" bonds (n=4) This copolymer is tested with regard to its detergent properties in the cleaning of fitted carpets made of polyamide . DETERGENCY - Materials -
. fitted carpet made of polyamide, with an offwhite color
. source of stains
* dirty motor oil * lipstick (Vivid Red from Revlon)
* Kiwi black shoe polish from Kiwi
* coffee analytical balance micropipette . applicational sponge white paper towel stopwatch
"Dirt Devil" vacuum cleaner "Bissel" steam cleaner . "Rug Doctor" steam cleaning concentrate - Preparation of the fitted carpets -
1) The fitted carpet is first of all cleaned from one side to the other, front and rear, using Rug Color detergent diluted according to the manufacturer's instructions (2 oz. per gallon, i.e. approximately 15 g/1), using a Bissel steam cleaning device. 2) After drying, the fitted carpet is cut up into
4" x 4" (approximately 10 x 10 cm2) squares which are marked underneath in order to make sure that all the strands are oriented in the same direction from one square to another in order to obtain similar appearance characteristics (less reflectance) .
3) The fitted carpet samples are subsequently marked in order to indicate the tests and the products.
- Staining-cleaning test - 1) Two tests are carried out for each stain. The reflectance before staining, Rdl, of the fitted carpet samples is measured.
2) The oil stains are produced by using the micropipette; the waxy stains are firstly pressed onto the applicational sponge and subsequently applied to the fitted carpet samples.
The oil stains are applied at a dose of 0.12 ± 0.05 g for each fitted carpet sample inside a 2" x 2" (approximately 5 x 5 cm2) square mask using a spatula. The waxes are applied at a dose by weight of 0.15 ± 0.05 g.
3) The stains are left to dry overnight before cleaning. The reflectance of the stained fitted carpet samples, RD2 , before cleaning is measured. 4) The samples are dried four times (each time for
5 seconds), following the recommendations given on the label carried by the fitted carpet, using white absorbent paper towels.
5) The samples are subsequently treated by spraying at a distance of 4-6" (approximately 10-15 cm) with 4.0 ± 0.1 g of the following aqueous liquid cleaning product sodium lauryl sulfate 2% sodium polyacrylate 1% propylene glycol 3% . fragrance 0.05% water q.s. for 100% with a pH of 9, to which has been added from 0.25% to
1% of its weight of sulfonated copolymer prepared above . 6) The product is left to stand in order to allow the foam formed to penetrate into the stains.
7) The stains are cleaned by rubbing five times from the top of the stain through the center using a dry white absorbent paper towel; the paper towel is turned over in order to obtain a clean surface and rubbing is carried out a further five times from the bottom of the stain through the center.
8) Stages 5) to 7) are repeated an additional four times for each sample, for a total of five cleaning cycles. 9) The fitted carpets are dried and then vacuumed. The reflectance, Rd3, of the cleaned fitted carpet samples is then measured. The removal of the stains (soil removal), R", is calculated as follows:
Rd2 - Rd3
R' = x 100
Rd2 - Rdl
The results obtained (values of R" in %) are as follows:
(photometric measurements of the reflectance values made with a Datacolor Elrepho 2000 spectrophotometer at a wavelength of 680 mm, without UV, spot adjusted to
27)
The higher the value of R" obtained, the better the performance.

Claims

CLAIMS 1. Aqueous composition for cleaning carpets, including fitted carpets, curtains and covering fabrics at least partially made of hydrophobic synthetic polymer, in particular of polyester or polyamide, very particularly of polyamide, and/or for facilitating the removal of stains and dirt therefrom comprising at least one water-soluble or water-dispersible copolyester (SC) comprising sulfonated units, characterized in that said copolyester (SC) is composed essentially
- of units of general formula (I) t-O-C(O) -A-C(O) - (0-CH2-CH2-)n-] (I), where
. the symbol A represents * a nonionic mono- or polyarylene or nonionic alkylene residue (NA)
* or a sulfonated mono- or polyarylene or sulfonated alkylene residue (SA) carrying at least one sulfonic acid functional group, the molar percentage of the units of formula
-C (0) -A-C (0) - where A is a sulfonated residue (SA), with respect to all the units of formula -C (0) -A-C (0) - in the units of formula (I), being of the order of 5 to
40, preferably of 7 to 35; and . n is equal to 1, 2, 3 or 4,
- as chain ends, of alike or different groups of formula -A-CO-O- ( CH2-CH2-0 ) n-H ( H i )
-A-CO-O- ( CH2-CH2-0 ) n- Z ( I I 2 ) in which formulae
. A and n have the definitions given above . Z represents a sulfonated C2-C3ι alkyloyl or aryloyl group carrying a sulfonate functional group, such as sulfobenzoyl M03SC6H4C (0) -, where M is an alkali metal; the molar percentage of units of formula (0-CH2-CH2-) n where n is equal to 1, with respect to all the units of formula (0-CH2-CH2-) n where n is equal to 1, 2, 3 and 4 in the units of formula (I), (Hi) and (II2), being of the order of 10 to 80, preferably of the order of 20 to
60; and the weight [lacuna] molecular mass of said copolyesters being less than 20,000, preferably less than 15,000, very particularly from 5000 to 10,000.
2. Composition according to claim 1, characterized in that the alike or different nonionic residues (NA) are nonionic C6-C14 mono- or polyarylene residues or nonionic C1-C9 alkylene residues, such as the 1, 4-phenylene, 1 , 3-phenylene, 1 , 6-naphthalene, 1 , 6-cyclohexylene, ethylene, trimethylene, tetramethylene or hexamethylene residues.
3. Composition according to claim 1 or 2, characterized in that the alike or different sulfonated residues (SA) are sulfonated C6-C14 mono- or polyarylene residues or sulfonated C1-C9 alkylene residues carrying at least one sulfonic acid functional group, preferably in the form of an alkali metal sulfonate, very particularly sodium sulfonate, such as the sodiooxysulfonylphenylene, sodiooxysulfonylnaphthalene, sodiooxysulfonylbiphenylene or sodiooxysulfoethylene residues .
4. Composition according to any one of claims 1 to 3, characterized in that the alike or different nonionic residues (NA) are 1, 4-phenylene residues (NAl) or 1, 3-phenylene residues (NA2) and the sulfonated residue (SA) is a 5-sodiooxysulfonyl-1, 3- phenylene residue.
5. Composition according to any one of claims 1 to 4, characterized in that the nonionic residues (NA) of the units of formula (I) are 1 , 4-phenylene residues (NAl) or a mixture of 1 , 4-phenylene residues (NAl) and 1, 3-phenylene residues (NA2), the molar percentage of the units of formula -C (0) -A-C (0) - where A is a residue (NAl), with respect to all the units of formula -C (0) -A-C (0) - where A is a nonionic residue (NA) , being of the order of 50 to 100, preferably of 70 to 90.
6. Composition according to any one of claims 1 to 5, characterized in that the chain-end groups are groups of formula (Hi) .
7. Composition according to any one of claims 1 to 6, characterized in that said copolyester additionally comprises, as chain end, groups of formula (III)
-A-CO-OH (III) where A has the definition given above.
8. Composition according to any one of claims 1 to 7, characterized in that it comprises from 0.05 to 5 parts, preferably from 0,1 to 2 parts, very particularly from 0.2 to 1.5 parts, of its weight of copolyester (SC) .
9. Composition according to any one of claims 1 to 8, characterized in that it additionally comprises at least one other additive chosen from surface-active agents, antiredeposition agents, alcohols or fragrances.
10. Composition according to claim 9, characterized in that it comprises
- up to 10 parts, preferably from 1 to 5 parts, very preferably from 1 to 2 parts, of its weight of at least one surface-active agent - up to 3 parts, preferably from 0.5 to 1 part, of its weight of at least one antiredeposition agent
- up to 10 parts, preferably from 1 to 5 parts, of its weight of an alcohol
- up to 0.2 part of its weight of at least one fragrance.
11. Composition according to any one of claims 1 to 10, characterized in that it exhibits a level of dry matter of 0.5 to 15%, preferably of 0.5 to 7.5%, very preferably of 1 to 3%, of its weight.
12. Composition according to any one of claims 1 to 11, characterized in that it exhibits a pH of 3 to 12, preferably of 4 to 10, very preferably of 7 to 10.
13. Process for cleaning carpets, including fitted carpets, curtains and covering fabrics, in particular made of synthetic polymer, very particularly of polyamide, and/or for facilitating the removal of stains and dirt therefrom by nonpermanent deposition on these, by spraying, application by hand or application using a device for cleaning textile surfaces, of the liquid aqueous composition comprising at least one copolyester (SC) as defined in any one of claims 1 to 12.
14. Process according to claim 13, characterized in that the amounts of aqueous composition employed correspond to a deposited amount of copolyester (SC), expressed as dry matter, of the order of 0.01 to 5, preferably of 0.05 to 3, g/m2 of surface .
15. Process for improving the properties of compositions for cleaning carpets, including fitted carpets, curtains and covering fabrics, in particular made of synthetic polymer, very particularly of polyamide, by addition to said compositions of an effective amount of at least one copolyester (SC) as defined in any one of claims 1 to 7 as detergent agent and/or as agent for facilitating the removal of stains and dirt (soil release) .
16. Process according to claim 15, characterized in that the amount of copolyester (SC) employed represents from 0.05 to 5 parts, preferably from 0.1 to 2 parts, very particularly from 0.2 to 1.5 parts, of the weight of said composition.
17. Use, in an aqueous composition for cleaning carpets, including fitted carpets, curtains and covering fabrics, in particular made of synthetic polymer, very particularly of polyamide, of at least one copolyester (SC) as defined defined in any one of claims 1 to 7 as detergent agent and/or as agent for facilitating the removal of stains and dirt (soil release) from said carpets, including fitted carpets, curtains and covering fabrics .
18. Use according to claim 17, characterized in that the amount of copolyester (SC) employed represents from 0.05 to 5 parts, preferably from 0.1 to 2 parts, very particularly from 0.2 to 1.5 parts, of the weight of said composition.
EP00980707A 1999-11-29 2000-11-28 Composition for cleaning carpets, curtains and covering fabrics and/or for facilitating the removal of stains Withdrawn EP1233994A2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US16781899P 1999-11-29 1999-11-29
US167818P 1999-11-29
PCT/US2000/032149 WO2001038467A2 (en) 1999-11-29 2000-11-28 Composition for cleaning carpets, curtains and covering fabrics and/or for facilitating the removal of stains

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EP1233994A2 true EP1233994A2 (en) 2002-08-28

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JP (1) JP2003518148A (en)
CN (1) CN1402745A (en)
AU (1) AU1793401A (en)
BR (1) BR0015927A (en)
CA (1) CA2393947A1 (en)
WO (1) WO2001038467A2 (en)

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EP2534206B1 (en) * 2010-02-09 2014-04-02 Unilever PLC Dye polymers
CN103608380B (en) * 2011-06-15 2016-08-31 巴斯夫欧洲公司 There is the branched polyester of sulfonate groups
WO2017174258A1 (en) * 2016-04-08 2017-10-12 Unilever Plc Laundry liquid composition
US11739286B2 (en) * 2017-11-17 2023-08-29 Conopco, Inc. Soil release polymers and laundry detergent compositions containing them
CN111979056B (en) * 2020-09-01 2021-09-21 广州市盛邦化工科技有限公司 Washing liquid suitable for polyester fabric

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CA1190695A (en) * 1981-05-14 1985-07-16 George J. Stockburger Anionic textile treating compositions
ATE186324T1 (en) * 1993-06-09 1999-11-15 Procter & Gamble STABLE AQUEOUS NON-IONIC SURFACTANT EMULSIONS
EP0776965A3 (en) * 1995-11-30 1999-02-03 Unilever N.V. Polymer compositions
DE60022170T2 (en) * 1999-03-09 2006-02-23 Rhodia Chimie SULFONED COPOLYMER AND METHOD FOR CLEANING SURFACES AND / OR PREPARING STAIN-PROVING PROPERTIES OF SUCH SURFACES AND / OR REMOVING STAIN OR CONTAMINATION

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CA2393947A1 (en) 2001-05-31
AU1793401A (en) 2001-06-04
BR0015927A (en) 2002-08-06
WO2001038467A3 (en) 2001-10-25
JP2003518148A (en) 2003-06-03
WO2001038467A2 (en) 2001-05-31

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