CA2393947A1 - 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 Download PDFInfo
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- CA2393947A1 CA2393947A1 CA002393947A CA2393947A CA2393947A1 CA 2393947 A1 CA2393947 A1 CA 2393947A1 CA 002393947 A CA002393947 A CA 002393947A CA 2393947 A CA2393947 A CA 2393947A CA 2393947 A1 CA2393947 A1 CA 2393947A1
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3715—Polyesters or polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0031—Carpet, upholstery, fur or leather cleansers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/507—Polyesters
- D06M15/5075—Polyesters containing sulfonic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Detergent Compositions (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Aqueous composition comprising at least one sulfonated copolyester, preferab ly a terephthalic copolyester, for cleaning carpets, including fitted carpets, curtains and covering fabrics at least partially made of hydrophobic synthet ic 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).
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) [-0-C (0) -A-C (0) - (O-CH2-CHz-) 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(O)-A-C(O)- where A is a sulfonated residue (SA), with respect to all the units of formula -C(O)-A-C(O)-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-CHZ-O ) n-H ( I I1 ) -A-CO-O- (CH2-CH2-O) n-Z (IIZ) in which formulae A and n have the definitions given above . Z represents a sulfonated C2-C31 alkyloyl or aryloyl group carrying a sulfonate functional group, such as sulfobenzoyl M03SC6H9C (O) -, where M is an alkali metal;
the molar percentage of units of formula (O-CH2-CH2-)n where n is equal to l, with respect to all the units of formula (O-CH2-CH2-)" where n is equal to l, 2, 3 and 4 in the units of formula (I), (II1) and (IIZ), 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 Liar 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-C19 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, tetramethylene or hexamethylene residues.
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) [-0-C (0) -A-C (0) - (O-CH2-CHz-) 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(O)-A-C(O)- where A is a sulfonated residue (SA), with respect to all the units of formula -C(O)-A-C(O)-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-CHZ-O ) n-H ( I I1 ) -A-CO-O- (CH2-CH2-O) n-Z (IIZ) in which formulae A and n have the definitions given above . Z represents a sulfonated C2-C31 alkyloyl or aryloyl group carrying a sulfonate functional group, such as sulfobenzoyl M03SC6H9C (O) -, where M is an alkali metal;
the molar percentage of units of formula (O-CH2-CH2-)n where n is equal to l, with respect to all the units of formula (O-CH2-CH2-)" where n is equal to l, 2, 3 and 4 in the units of formula (I), (II1) and (IIZ), 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 Liar 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-C19 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, tetramethylene or hexamethylene residues.
5 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 C6-C14 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-1,3-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 (NA1) and 1,3-phenylene residues (NA2), the molar percentage of the units of formula -C(O)-A-C(0)- where A is a residue (NA1), 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 (II1) .
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 (IIl) 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 molo, very particularly of 70 to 90 molo, of terephthalic acid or anhydride or of one of its lower diesters (of methyl, ethyl, propyl, isopropyl or butyl) and of 0 to 50 molo, very particularly of 10 to 30 molo, 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.
Mention may be made, as example of sulfonated residues (SA), of sulfonated C6-C14 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-1,3-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 (NA1) and 1,3-phenylene residues (NA2), the molar percentage of the units of formula -C(O)-A-C(0)- where A is a residue (NA1), 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 (II1) .
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 (IIl) 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 molo, very particularly of 70 to 90 molo, of terephthalic acid or anhydride or of one of its lower diesters (of methyl, ethyl, propyl, isopropyl or butyl) and of 0 to 50 molo, very particularly of 10 to 30 molo, 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 (IIl) 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 molo, very particularly from 30 to 90 molo, 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 5 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 10 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 (NAM1), 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 (NAM1)/(NAM1)+(NAM2) molar ratio of the order of 100/100 to 50/100, preferably of the order of 90/100 to - sulfoisophthal~._c acid, in the diester form (preferably the dimethyl ester form) - monoethylene glycol.
They can be prepared by carrying out the following successive stages:
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 (IIl) 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 molo, very particularly from 30 to 90 molo, 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 5 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 10 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 (NAM1), 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 (NAM1)/(NAM1)+(NAM2) molar ratio of the order of 100/100 to 50/100, preferably of the order of 90/100 to - sulfoisophthal~._c 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 (IIZ) 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.
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 (IIZ) 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 C8_ZO, preferably Clo-C16, alkyl radical, R' a C1-C6, preferably C1-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 CS-C24, preferably Clo-C18, alkyl or hydroxyalkyl radical, M representing a hydrogen atom or a can on with the same definition as above, and their ethoxylenated (E0) 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 Cz-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 (E0) and/or propoxylenated (PO) derivatives exhibiting an average of 0.5 to 60 EO
and/or PO units;
. salts of Cg-C2g, preferably C14-C2o, saturated or unsaturated fatty acids, C9-CZO alkylbenzenesulfonates, primary or secondary C8-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-C12, 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 CB-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-C18 fatty acids comprising from 5 to 25 ethoxylated and/or propoxylated units;
C8-CZo fatty acid amides comprising from 5 to 30 ethoxylated units;
. ethoxylated amines comprising from 5 to 30 ethoxylated units;
5 . 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 (Clo-C18 alkyl) dimethylamine oxides or (Ce-C22 alkoxy)ethyldihydroxyethylamine 10 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 15 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 C9-C2o, preferably CB-Cla, 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 C8-C14 alkyl group and, on average, 1.4 glucose units per mole * a C1z-C19 alkyl group and, on average, 1.4 glucose units per mole * a C8-C14 alkyl group and, on average, 1.5 glucose units per mole * a C8-Clo 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 malefic anhydride;
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 C8_ZO, preferably Clo-C16, alkyl radical, R' a C1-C6, preferably C1-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 CS-C24, preferably Clo-C18, alkyl or hydroxyalkyl radical, M representing a hydrogen atom or a can on with the same definition as above, and their ethoxylenated (E0) 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 Cz-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 (E0) and/or propoxylenated (PO) derivatives exhibiting an average of 0.5 to 60 EO
and/or PO units;
. salts of Cg-C2g, preferably C14-C2o, saturated or unsaturated fatty acids, C9-CZO alkylbenzenesulfonates, primary or secondary C8-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-C12, 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 CB-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-C18 fatty acids comprising from 5 to 25 ethoxylated and/or propoxylated units;
C8-CZo fatty acid amides comprising from 5 to 30 ethoxylated units;
. ethoxylated amines comprising from 5 to 30 ethoxylated units;
5 . 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 (Clo-C18 alkyl) dimethylamine oxides or (Ce-C22 alkoxy)ethyldihydroxyethylamine 10 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 15 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 C9-C2o, preferably CB-Cla, 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 C8-C14 alkyl group and, on average, 1.4 glucose units per mole * a C1z-C19 alkyl group and, on average, 1.4 glucose units per mole * a C8-C14 alkyl group and, on average, 1.5 glucose units per mole * a C8-Clo 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 malefic 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 150, preferably of the order of 0.5 to 7.50, very preferably of 1 to 30, 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).
* 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 150, preferably of the order of 0.5 to 7.50, very preferably of 1 to 30, 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/mz 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 5 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 10 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, 15 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 20 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.
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/mz 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 5 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 10 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, 15 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 20 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-ZN
Liar at 100°C; results expressed in polystyrene equivalents).
This terephthalic copolymer comprises 15 molo of sulfonate functional groups and exhibits, per 100 ether bonds of formula (O-CH2-CHz-)", . 55.7 "ethylene glycol" bonds (n=1) . 31.8 "diethylene glycol" bonds (n=2) . 10.2 "triethylene glycol" bonds (n=3) . 2.3 "tetraethylene glycol" bonds (n=4) This copolymer is i;ested 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.
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-ZN
Liar at 100°C; results expressed in polystyrene equivalents).
This terephthalic copolymer comprises 15 molo of sulfonate functional groups and exhibits, per 100 ether bonds of formula (O-CH2-CHz-)", . 55.7 "ethylene glycol" bonds (n=1) . 31.8 "diethylene glycol" bonds (n=2) . 10.2 "triethylene glycol" bonds (n=3) . 2.3 "tetraethylene glycol" bonds (n=4) This copolymer is i;ested 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 5 4.0 ~ 0.1 g of the following aqueous liquid cleaning product . sodium lauryl sulfate 20 . sodium polyacrylate to . propylene glycol 30 10 . fragrance 0.050 . water q.s. for 1000 with a pH of 9, to which has been added from 0.250 to to of its weight of sulfonated copolymer prepared above.
15 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 20 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 25 cycles.
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 5 4.0 ~ 0.1 g of the following aqueous liquid cleaning product . sodium lauryl sulfate 20 . sodium polyacrylate to . propylene glycol 30 10 . fragrance 0.050 . water q.s. for 1000 with a pH of 9, to which has been added from 0.250 to to of its weight of sulfonated copolymer prepared above.
15 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 20 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 25 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:
R ~ - Rd2 - Rd3 X 10 0 Rd2 - Rdl The results obtained (values of R" in o) 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) Formulation Lipstick Dirty Coffee Shoe motor oil polish Standard 44 29 50 79 Standard + 0.250 53 31 of copolymer Standard + 0.5% 70 43 of copolymer Standard + 0.750 76 48 of copolymer Standard + 1o of 74 64 82 90 copolymer The higher the value of R" obtained, the better the performance.
The removal of the stains (soil removal), R", is calculated as follows:
R ~ - Rd2 - Rd3 X 10 0 Rd2 - Rdl The results obtained (values of R" in o) 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) Formulation Lipstick Dirty Coffee Shoe motor oil polish Standard 44 29 50 79 Standard + 0.250 53 31 of copolymer Standard + 0.5% 70 43 of copolymer Standard + 0.750 76 48 of copolymer Standard + 1o of 74 64 82 90 copolymer The higher the value of R" obtained, the better the performance.
Claims (18)
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) [-O-C(O)-A-C(O)-(O-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(O)-A-C(O)- where A is a sulfonated residue (SA), with respect to all the units of formula -C(O)-A-C(O)-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-O)n-H (II1) -A-CO-O-(CH2-CH2-O)n-Z (II2) in which formulae . A and n have the definitions given above . Z represents a sulfonated C2-C31 alkyloyl or aryloyl group carrying a sulfonate functional group, such as sulfobenzoyl MO3SC6H9C(O)-, where M is an alkali metal;
the molar percentage of units of formula (O-CH2-CH2-)n where n is equal to 1, with respect to all the units of formula (O-CH2-CH2-)n where n is equal to 1, 2, 3 and 4 in the units of formula (I), (II1) 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 molar percentage of units of formula (O-CH2-CH2-)n where n is equal to 1, with respect to all the units of formula (O-CH2-CH2-)n where n is equal to 1, 2, 3 and 4 in the units of formula (I), (II1) 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 (NA1) 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 (NA1) or a mixture of 1,4-phenylene residues (NA1) and 1,3-phenylene residues (NA2), the molar percentage of the units of formula -C(O)-A-C(O)- where A is a residue (NA1), with respect to all the units of formula -C(O)-A-C(O)- 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 (II1).
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.
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.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US16781899P | 1999-11-29 | 1999-11-29 | |
| US60/167,818 | 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 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2393947A1 true CA2393947A1 (en) | 2001-05-31 |
Family
ID=22608967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002393947A Abandoned CA2393947A1 (en) | 1999-11-29 | 2000-11-28 | Composition for cleaning carpets, curtains and covering fabrics and/or for facilitating the removal of stains |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP1233994A2 (en) |
| JP (1) | JP2003518148A (en) |
| CN (1) | CN1402745A (en) |
| AU (1) | AU1793401A (en) |
| BR (1) | BR0015927A (en) |
| CA (1) | CA2393947A1 (en) |
| WO (1) | WO2001038467A2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA201205562B (en) * | 2010-02-09 | 2013-09-25 | Unilever Plc | Dye polymers |
| MX338318B (en) * | 2011-06-15 | 2016-04-12 | Basf Se | Branched polyesters with sulfonate groups. |
| BR112018070484A2 (en) * | 2016-04-08 | 2019-01-29 | Unilever Nv | liquid laundry composition and packaging containing a |
| 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 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1190695A (en) * | 1981-05-14 | 1985-07-16 | George J. Stockburger | Anionic textile treating compositions |
| ES2137245T3 (en) * | 1993-06-09 | 1999-12-16 | Procter & Gamble | STABLE AQUEOUS EMULSIONS OF NON-IONIC SURFACTANTS. |
| EP0776965A3 (en) * | 1995-11-30 | 1999-02-03 | Unilever N.V. | Polymer compositions |
| EP1161516B1 (en) * | 1999-03-09 | 2005-08-24 | Rhodia Chimie | Sulphonated copolymer and method for cleaning surfaces and/or providing same with stain resistant properties and/or for facilitating stain and soil release |
-
2000
- 2000-11-28 WO PCT/US2000/032149 patent/WO2001038467A2/en not_active Application Discontinuation
- 2000-11-28 AU AU17934/01A patent/AU1793401A/en not_active Abandoned
- 2000-11-28 JP JP2001540222A patent/JP2003518148A/en active Pending
- 2000-11-28 CA CA002393947A patent/CA2393947A1/en not_active Abandoned
- 2000-11-28 CN CN 00816462 patent/CN1402745A/en active Pending
- 2000-11-28 BR BR0015927-1A patent/BR0015927A/en not_active IP Right Cessation
- 2000-11-28 EP EP00980707A patent/EP1233994A2/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| WO2001038467A2 (en) | 2001-05-31 |
| BR0015927A (en) | 2002-08-06 |
| CN1402745A (en) | 2003-03-12 |
| AU1793401A (en) | 2001-06-04 |
| EP1233994A2 (en) | 2002-08-28 |
| JP2003518148A (en) | 2003-06-03 |
| WO2001038467A3 (en) | 2001-10-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Discontinued |