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EP4244324A1 - Compositions aqueuses de polyester, détergents et agents de nettoyage les contenant et leur utilisation - Google Patents

Compositions aqueuses de polyester, détergents et agents de nettoyage les contenant et leur utilisation

Info

Publication number
EP4244324A1
EP4244324A1 EP21786086.5A EP21786086A EP4244324A1 EP 4244324 A1 EP4244324 A1 EP 4244324A1 EP 21786086 A EP21786086 A EP 21786086A EP 4244324 A1 EP4244324 A1 EP 4244324A1
Authority
EP
European Patent Office
Prior art keywords
formula
polyester
structural units
compositions according
formulas
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.)
Pending
Application number
EP21786086.5A
Other languages
German (de)
English (en)
Inventor
Daniel KÖNNING
Roman MORSCHHÄUSER
Judith Preuschen
Paul Kaufmann
Niklas DIEKHANS
Said Kchirid
Stefan RIEGELBECK
Bastian VIEL
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.)
Catexel GmbH
Original Assignee
Weylchem Performance Products GmbH
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 Weylchem Performance Products GmbH filed Critical Weylchem Performance Products GmbH
Publication of EP4244324A1 publication Critical patent/EP4244324A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/181—Acids containing aromatic rings
    • C08G63/183—Terephthalic acids
    • 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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/672—Dicarboxylic acids and dihydroxy compounds
    • 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
    • C08G63/6886—Dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/12—Soft surfaces, e.g. textile
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2006—Monohydric alcohols
    • C11D3/201—Monohydric alcohols linear
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2041—Dihydric alcohols
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2003—Alcohols; Phenols
    • C11D3/2065—Polyhydric alcohols
    • 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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers

Definitions

  • the invention relates to aqueous compositions of selected polyesters which are suitable as additives for detergents and cleaning agents and which are distinguished by very good dirt-removing power.
  • polyesters in detergents to improve soil removal from textiles, to reduce resoiling, to protect the fibers under mechanical stress and to finish the fabric with an anti-crease effect.
  • SRP soil-release polyester
  • polyesters can be found in US Pat. No. 4,702,857 A, US Pat. No. 4,427,557 A, US Pat. No. 4,721,580 A, US Pat , US 5,599,782 A, WO 94/22937 A1 , EP 1 966 273 B1 and EP 2 504 380 A1.
  • Polyesters with improved soil release properties can contain anionic groups and/or nonionic groups. These can occur as end groups in the polyester molecule or they are residues that occur in the groups that build up the polymer backbone.
  • anionic radicals are sulfonic acid groups; these can occur, for example, in 5-sulfoisophthalic acid residues or as end groups derived from isethionic acid.
  • nonionic residues are polyethylene glycol residues; these can occur, for example, in the polymer backbone of the polyester or as end groups.
  • Anionic polyesters usually cannot be stored dissolved in water. These polyesters are constructed in such a way that they can be drawn onto a polymer fiber from an aqueous medium, for example a washing liquor. To do this, the structure of these polyesters to be hydrophilic enough to be transported in water; on the other hand, this polyester must also be hydrophobic enough to be able to be drawn onto the fiber.
  • polyester molecule Because of these properties, the polyester molecule is likely to exist in an aggregated form in water even though it appears dissolved. A consequence of this "semi-solubility" is a crystallization of the polymer chains "in solution". Larger aggregates are formed, which scatter the light, making the dispersion opaque and appearing white. Unfortunately, as the crystallization progresses, the viscosity also increases because larger and larger aggregates are formed. This can lead to a firm consistency.
  • polyesters with dirt-removing properties it is important that they can be stored as aqueous compositions and that the increase in viscosity is kept within limits.
  • WO 2011/063945 A1 The fact that concentrates can be produced from SRP with a selected structure in organic/aqueous media is described in WO 2011/063945 A1, for example.
  • This document describes aqueous concentrates of special anionic polyesters that can be stored for a certain period of time.
  • the aim of the invention described in this document was to develop polyester structures based on sulfo-containing monomers which, on the one hand, show very good graying-inhibiting performance when used in liquid detergents and, on the other hand, show only a minimal tendency to crystallize in aqueous solution and are storage-stable as a solution.
  • These polymer solutions, referred to as concentrates should be suitable for use in liquid detergent formulations and should be as clear and low-viscous as possible.
  • the solution described in WO 2011/063945 A1 consists in using selected sulfo-containing polyesters with a certain ratio of propylene glycol to ethylene glycol units.
  • a further possible measure for stabilizing SRP compositions consists in adding small amounts of organic solvents. Such compositions are described, for example, in EP 3 517 597 A1. With anionic SRP, however, it has been shown that this measure is not always successful promises.
  • an aqueous composition of a polyester was investigated which has ethylene glycol terephthalate and propylene glycol terephthalate units and end groups derived from isethionic acid and from polyethylene glycol monomethyl ether.
  • Organic alcohols such as 1,2-propylene glycol or glycerol, were added to this aqueous composition. It was shown that after a few hours the viscosity at 25° C. increased from initially 400 mPas to over 45,000 mPas. In this form, this product cannot be handled or processed properly.
  • compositions of selected SRPs in organic/aqueous media are known, for example, from WO 2011/063945 A1. There, concentrates of anionic polyesters in water and/or in water-miscible organic solvents are described. However, there is no indication that other polymers can be used to stabilize the compositions in addition to anionic polyesters.
  • Combinations of anionic and nonionic SRPs have been used in detergents.
  • DE 10 2014218 952 A1 describes agents for treating textiles that contain surfactants and contain at least one anionic aromatic polyester and at least one nonionic aromatic polyester. It has been found that the primary detergency of the agent can be increased by combining two special SRPs. However, it has been found that providing the combination of the SRPs in a surfactant containing composition is difficult to accomplish. A combination of the SRP with surfactants in a clear liquid detergent leads to turbidity or the formation of deposits when the SRP is added or when the detergent is stored. This document therefore proposes providing the polyester combinations as storage-stable portions. In the examples, packaging is used in which the SRP are stored in different chambers and are only combined during the washing process.
  • Anionic SRPs are often solid or waxy at room temperature, while nonionic SRPs are often liquids. If anionic and nonionic SRP are combined with or without surfactants, solid or initially liquid compositions, the latter also solidifying after some time.
  • US 2014/0274860 A1 discloses granulated detergents which, in addition to builders, fillers, alkali carriers and surfactants, also contain synergistic combinations of anionic and nonionic SRPs. These detergents are in solid form, so that no cloudiness or deposits can form during storage.
  • the object of the present invention was to provide SRP compositions which are stable over a long period of time and whose viscosity does not increase or does not increase appreciably even after prolonged storage and which neither become cloudy nor form deposits during storage.
  • Another object of the present invention was to provide stable, low viscosity SRP compositions.
  • compositions according to the invention do not thicken and remain stable for several months even on warm storage, ie they neither become cloudy nor form deposits.
  • the present invention relates to compositions containing
  • A) at least one anionic polyester obtainable by polymerization of components a) one or more sulfo-free aromatic dicarboxylic acids and/or their salts and/or their anhydrides and/or their esters, b) optionally one or more sulfo-containing dicarboxylic acids, their salts and/or their Anhydrides and/or their esters, c) one or more aliphatic diols of the formula (1) H-(OC m H 2m )sOH (1), where m is a number from 2 to 10 and m can have different meanings within a molecule within the scope of the given definition, s is a number from 1 to 200, where s is at least 1 means and can additionally assume a value between 2 and 200, d) optionally one or more compounds of the formula (2)
  • R 2 is a (Me a+ ) b OOC- or (Me a+ ) b 'O 3 S- radical
  • R 1Q is hydrogen or Ci-C 6 -alkyl
  • Me is hydrogen or an a-valent cation
  • a is a number from 1 to 3
  • b is a number with the value 1/a
  • the proportion by weight of the total amount of polyesters A and B in the compositions according to the invention is usually 1 to 50%, preferably 5 to 40%, in particular 10 to 30% and very particularly preferably 15 to 25%, based on the total amount of the composition.
  • the proportion by weight of the total amount of (cyclo)aliphatic alcohols having 1-10 carbon atoms in the composition according to the invention is usually 20 to 95%, preferably 40 to 80%, in particular 60 to 70% and very particularly preferably 50 to 75%, based on the total amount the composition.
  • the proportion by weight of water in the composition according to the invention is usually 1 to 50%, preferably 2 to 30%, in particular 5 to 20% and very particularly preferably 7 to 15%, based on the total amount of the composition.
  • the composition according to the invention contains water-soluble or water-miscible (cyclo)aliphatic alcohols, water and optionally other additives such as water-miscible non-alcoholic organic solvents, e.g. acetone, surfactants, dyes, fragrances or buffer substances.
  • water-soluble or water-miscible (cyclo)aliphatic alcohols e.g. acetone, surfactants, dyes, fragrances or buffer substances.
  • the proportion by weight of the total amount of optional further additives in the composition according to the invention is usually 0 to 20%, preferably 0 to 10%, and very particularly preferably 0 to 5%, based on the total amount of the composition.
  • the proportion by weight of polyester A in the total mass of polyesters A and B in the compositions according to the invention is usually 1 to 99%, preferably 20 to 80%, particularly preferably 30 to 70% and very particularly preferably 40 to 60%.
  • the proportion by weight of polyester B in the total mass of polyesters A and B in the compositions according to the invention is usually 99 to 1%, preferably 80 to 20%, particularly preferably 70 to 30% and very particularly preferably 60 to 40%.
  • Monomer component a) is a sulfo-free aromatic dicarboxylic acid and/or its salt and/or its anhydride and/or its ester.
  • Preferred compounds of monomer component a) are terephthalic acid, in particular the Ci-C4-dialkyl esters of terephthalic acid, for example dimethyl terephthalate, and isophthalic acid and Ci-C4-dialkyl esters of isophthalic acid or naphthalenedicarboxylic acid and Ci-C 4 -dialkyl esters of naphthalenedicarboxylic acid.
  • the monomer component a) forms the backbone of the polyester used according to the invention.
  • the monomer component b) is a sulfo-containing dicarboxylic acid, its salts and/or its anhydrides and/or its esters.
  • Preferred compounds of monomer component b) are 5-sulfoisophthalic acid, in particular 5-sulfoisophthalic acid di(Ci-C 4 )alkyl esters and their alkali metal salts, for example alkali metal salts of 5-sulfoisophthalic acid and 5-sulfoisophthalic acid dimethyl ester sodium salt or lithium salt.
  • the monomer component b) forms the backbone of the polyester used according to the invention.
  • the monomer component c) is an aliphatic diol of the formula (1) defined above. These can be straight-chain or branched aliphatic diols. Diols of the monomer component c) are alkylene glycols which are optionally used together with polyoxyalkylene compounds. In the context of this description, polyoxyalkylene compounds are to be understood as meaning homo- or copolymers derived from alkylene oxides. With different alkylene oxide units in the molecule, for example units derived from ethylene oxide and from propylene oxide, the different units can be randomly distributed in the polymer or also in the form of blocks or there can be a gradual change in the monomer composition from predominantly one type of monomers to predominantly another type of monomers (gradient copolymer).
  • Index s is preferably a number from 1 to 50, in particular from 1 to 20, very particularly from 1 to 10 and most preferably 1.
  • Preferred compounds of monomer component c) are ethylene glycol, propylene glycol, especially 1,2-propylene glycol.
  • Polyoxyalkylene compounds used with preference are polyoxyethylene compounds having 2 to 20, in particular 2 to 10, ethyleneoxy repeat units or polyoxypropylene compounds having 2 to 20, especially 2 to 10 propyleneoxy repeat units.
  • monomer components c) are mixtures of ethylene glycol and ethylene oxide-propylene oxide block copolymers of the formula H-[(OCH 2 CH 2 ) q1 ]-[(OCH 2 CH(CH 3 )) P i ]-OH where q1 is a number from 12 to 120 and p1 is a number from 11 to 60, preferably from 15 to 50, and particularly preferably from 20 to 40. Polyesters derived from these monomer components are known, for example, from EP 2670786 B1.
  • the molar mixing ratio of alkylene glycols to polyoxyalkylene compounds is usually from 20:1 to 1:1, preferably from 10:1 to 5:1.
  • the monomer component c) forms the backbone of the polyester used according to the invention.
  • the monomer component d) is a compound of the formula (2) defined above. It can be straight-chain or branched aliphatic trade connections.
  • Preferred compounds of the monomer component d) are alkylene glycols with end caps on one end or polyoxyalkylene compounds with end caps on one end.
  • polyoxyalkylene compounds are to be understood as meaning homo- or copolymers derived from alkylene oxides. With different alkylene oxide units in the molecule, for example units derived from ethylene oxide and from propylene oxide, the different units can be randomly distributed in the polymer or also in the form of blocks or there can be a gradual change in the monomer composition from predominantly one type of monomers to predominantly another type of monomers (gradient copolymer).
  • An example of a block copolymer is an ethylene oxide/propylene oxide block copolymer. If different alkylene oxide units are present in the molecule, these are cases in which o within a molecule can assume different meanings within the scope of the given definition. Ethylene glycol monomethyl ether, polyoxyethylene monomethyl ether with average molecular weights of 200 to 2000 g/mol or poly[ethylene oxide-copropylene oxide] monomethyl ether with average molecular weights of 100 to 20,000 g/mol, preferably 500 to 10,000 g/mol, are preferred.
  • the monomer component d) forms end groups of the polyester used according to the invention.
  • Index o is preferably a number from 2 to 4 and in particular from 2 to 3.
  • Index p is preferably a number from 1 to 50, in particular from 1 to 20, very particularly from 1 to 10 and most preferably from 2 to 3.
  • monomer components d) are mixtures of ethylene glycol and ethylene oxide-propylene oxide block copolymers of the formula which are end-capped at one end
  • R 1 -[(OCH 2 CH 2 ) q1 ]-[(OCH 2 CH(CH 3 )) p i]-OH
  • R 1 has the meaning defined above, preferably Ci. 6 -alkyl, in particular methyl
  • q1 is a number from 12 to 120
  • p1 is a number from 11 to 60, preferably from 15 to 50, and more preferably from 20 to 40.
  • Polyesters derived from these monomer components are known, for example, from EP 2670786 B1.
  • the monomer component e) is a compound of the formulas (3) and/or (4) defined above.
  • the compounds of formula (3) can be straight-chain or branched aliphatic compounds.
  • Preferred compounds of the formula (3) are those of the formula H-(OCH 2 CH 2 ) r i-SO 3 X, where r 1 is a number from 1 to 4, particularly preferably 1 and 2, and X is hydrogen, sodium or potassium.
  • sulfobenzoic acid By the connections of forms! (4) are derivatives of sulfobenzoic acid. This can be the free sulfobenzoic acid, its salts or esters, in particular the free acid, its alkali metal or alkaline earth metal salts or its alkyl esters.
  • the sulfo group can be in the 2-, 3- or 4-position of the phenyl ring, preferably in the 3-position.
  • Preferred compounds of formula (4) are those of the formula XO3S-C6H4-COOY, where X and Y are independently hydrogen, sodium or potassium.
  • Index q is preferably a number from 2 to 4 and in particular from 2 to 3.
  • Index r is preferably a number from 1 to 5, in particular from 1 to 4 and very particularly from 1 to 3.
  • the monomer component e) forms end groups of the polyester used according to the invention.
  • Me in the formulas (3) and (4) is preferably hydrogen or a mono- to trivalent cation, preferably hydrogen, an alkali metal cation, an alkaline earth metal cation or an ammonium cation.
  • the monomer component f) is a crosslinking polyfunctional compound.
  • the monomer component f) forms the backbone of the polyester used according to the invention.
  • Preferred compounds of the monomer component f) are polyfunctional compounds with a crosslinking action at least 3, in particular 3 to 6, functional groups capable of the esterification reaction, for example acid, alcohol, ester, anhydride or epoxy groups. Different functionalities are also possible in one molecule.
  • Preferred examples thereof are citric acid, malic acid, tartaric acid and gallic acid, particularly preferably 2,2-dihydroxymethylpropionic acid.
  • Polymeric crosslinkers can also be used, for example polyacrylic acid, polymaleic acid or maleic acid-ethylene copolymers.
  • trihydric or higher alcohols such as pentaerythrol, glycerol, sorbitol and trimethylolpropane, as monomer component f).
  • Further preferred monomer components f) are tribasic or higher aliphatic and aromatic carboxylic acids, such as benzene-1,2,3-tricarboxylic acid (hemimellitic acid), benzene-1,2,4-tricarboxylic acid (trimellitic acid), particularly preferably benzene-1,3, 5-tricarboxylic acid (trimesitic acid).
  • benzene-1,2,3-tricarboxylic acid hemimellitic acid
  • benzene-1,2,4-tricarboxylic acid trimellitic acid
  • trimellitic acid particularly preferably benzene-1,3, 5-tricarboxylic acid (trimesitic acid).
  • polyesters A can also contain further structural units g) which are derived from monomers which are copolymerizable with the monomers a) to f), the monomers g) being derived from the monomers a) to f ) differentiate.
  • the molar proportion of these further structural units g) in polyester A is usually 0 to 10%, in particular 0 to 5%.
  • Polyesters A particularly preferably contain no further structural units g). Examples of monomers g) are diamines, bisphenols, polyester-forming phosphorus compounds or polyester-forming sulfur compounds.
  • polyesters A or B To prepare the polyesters A or B, individual monomer components or mixtures of different compounds corresponding to one monomer component can be used.
  • Polyester A contains at least one structural unit with an ionic group. These structural units are derived from the monomer units b) or e). At least one of these monomer units, if appropriate also both of these monomer units, are used for the production of polyester A. Polyester B does not contain a structural unit with an ionic group. In the production of polyester B, only monomer units a), c) and d) are used, and optionally crosslinkers f) and optionally other monomers g′).
  • polyesters B can also contain further nonionic structural units g′) which are derived from monomers which are copolymerizable with the monomers a), c), d) and f). , where the monomers g') differ from the monomers a), c), d) and f).
  • the molar proportion of these further structural units g′) in polyester B is usually 0 to 10%, in particular 0 to 5%.
  • Polyesters B particularly preferably contain no further structural units g′). Examples of monomers g') are diamines, bisphenols, polyester-forming phosphorus compounds or polyester-forming sulfur compounds.
  • the molar proportion of component a), based on the total polyester A, is generally from 20 to 50%, particularly preferably from 25 to 45% and very particularly preferably from 35 to 42%.
  • the molar proportion of component b), based on the total polyester A, is generally from 0 to 40%, particularly preferably from 5 to 25% and very particularly preferably from 10 to 20%.
  • the molar proportion of component c), based on the total polyester A, is generally from 20 to 60%, particularly preferably from 25 to 55% and very particularly preferably from 35 to 48%.
  • the molar proportion of component d), based on the total polyester A, is generally from 0.5 to 40%, particularly preferably from 1 to 20% and very particularly preferably from 4 to 10%.
  • the molar proportion of component e), based on the total polyester A is generally from 0 to 10%, particularly preferably from 1 to 8% and very particularly preferably from 2 to 5%.
  • the molar proportion of component f), based on the total polyester A is generally from 0 to 10%, particularly preferably from 0 to 5% and very particularly preferably from 0 to 3%.
  • Particularly preferred polyesters A are uncrosslinked.
  • the molar proportion of component a), based on the total polyester B, is generally from 30 to 50%, particularly preferably from 45 to 55% and very particularly preferably from 39 to 41%.
  • the molar proportion of component c), based on the total polyester B, is generally from 10 to 50%, particularly preferably from 15 to 40% and very particularly preferably from 25 to 35%.
  • the molar proportion of component d), based on the total polyester B, is generally from 1 to 40%, particularly preferably from 10 to 35% and very particularly preferably from 20 to 30%.
  • the molar proportion of component f), based on the total polyester B, is generally from 0 to 10%, particularly preferably from 0 to 5% and very particularly preferably from 0 to 3%.
  • Particularly preferred polyesters B) are uncrosslinked.
  • compositions contain polyesters A and/or B in which component a) is selected from the group consisting of terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, their alkali metal salts or alkaline earth metal salts or their dialkyl esters.
  • compositions contain polyesters A, in which component b) is selected from the group consisting of sulfoterephthalic acid, sulfoisophthalic acid, sulfonaphthalenedicarboxylic acid, their alkali metal salts or alkaline earth metal salts or their dialkyl esters.
  • Further preferred compositions contain polyesters A and/or B, in which component c) is selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol or mixtures of two or more thereof, preferably ethylene glycol, 1,2-propylene glycol or mixtures thereof and particularly preferred ethylene glycol.
  • compositions contain polyesters A and/or B in which component d) is a compound of formula (2a).
  • R 3 is a linear or branched alkyl group with 1 to 6 carbon atoms, in particular with 1 to 3 carbon atoms,
  • R 4 and R 5 independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms, and t is a number from 1 to 50, preferably from 12 to 30.
  • compositions contain polyester A in which component e) is a compound of formula (3a).
  • Me is hydrogen, a monovalent metal cation or an ammonium cation
  • R 6 and R 7 are independently hydrogen or an alkyl group having 1 to 4 carbon atoms
  • u is a number from 1 to 50, preferably from 1 to 5 and very particularly preferably 1 or 2.
  • compositions contain polyester A in which component e) is a compound of formula (3b).
  • Me is hydrogen, a monovalent metal cation or an ammonium cation, preferably hydrogen or a sodium cation, and
  • R 11 is hydrogen, a monovalent metal cation or an ammonium cation, preferably hydrogen or a sodium cation, and wherein the sulfonyl group is located in particular in the 3-position of the phenyl ring.
  • compositions contain polyester A in which component e) is a mixture of the compounds of formulas (3a) and (3b) defined above.
  • compositions contain polyesters A and/or B in which structural units derived from component f) have the formula (6) or are derived from polyacrylic acid, polymaleic acid or from maleic acid-ethylene copolymers where y is a number from 3 to 6,
  • R 8 is a tri- to hexavalent organic radical, preferably a tri- to hexavalent alkyl or aryl radical, and
  • Polyesters A used with particular preference are known from DE 10 2016 003 544 A1.
  • compositions according to the invention contain polyester A with recurring structural units of the formula Ia and with end groups of the formula II and the formula III or with end groups of the formula II and the formula IV or with end groups of the formula II, III and IV or the compositions contain polyester A with recurring structural units of the formula Ia and the formula Ib and with end groups of the formula II and the formula III or with end groups of the formula II and the formula IV or with end groups of the formula II, III and IV wherein RCC is 4 -alkyl,
  • M is hydrogen or a mono- or divalent cation
  • i is 1 or 2
  • x is 0.5 or 1 and the product i ⁇ x is 1, and
  • z is a number from 3 to 35
  • the compositions contain polyester B with recurring structural units of the formula Ia defined above and with end groups of the formula V or polyester B with recurring structural units of the formulas Ia and Ib defined above and with end groups of the formula V
  • R 9 O-(-CH 2 CH 2 o-)— (yj wherein R 9 is hydrogen or Ci-C4-alkyl, and c is a number from 1 to 50, preferably 1 to 35.
  • the proportion of recurring structural units of the formula Ia or of recurring structural units of the formulas Ia and Ib or of recurring structural units of the formulas Ia, Va and/or Vb and/or Via and/or Vlb or of recurring structural units of the formulas Ia, Ib, Va and /or Vb and/or Via and/or Vlb in the polyesters A is usually 80 to 100 mol%, preferably 90 to 100 mol%, based on the total amount of recurring structural units in polyester A.
  • the proportion of recurring structural units of the formula Ia or of recurring structural units of the formulas Ia and Ib in the polyesters B is usually 80 to 100 mol%, preferably 90 to 100 mol%, based on the total amount of the recurring structural units in polyester B.
  • the proportion of recurring structural units of the formulas Va and / or Via or the formulas Va and Vb and / or the formulas Via and Vlb in the polyesters A is usually 0 to 15 mol%, preferably 1 to 15 mol%, particularly preferably 3 to 10 Mol%, and most preferably 5 to 8 mol%, based on the total amount of repeating structural units in polyester A.
  • the proportion of recurring structural units of the formulas Va and / or Via or the formulas Va and Vb and / or the formulas Via and Vlb in the polyesters B is usually 0 to 15 mol%, preferably 1 to 15 mol%, particularly preferably 3 to 10 Mol%, and most preferably 5 to 8 mol%, based on the total amount of repeating structural units in polyester B.
  • the proportion of end groups of the formulas II and III or of the formulas II and IV or of the formulas II, III and IV in the polyesters A is usually 80 to 100 mol%, preferably 90 to 100 mol%, based on the total amount of the end groups in polyester A .
  • the proportion of end groups of V in the polyesters B is usually 80 to 100 mol%, preferably 90 to 100 mol%, based on the total amount of end groups in polyester B.
  • compositions according to the invention contain polyesters B of the formula below
  • 4 -alkyl groups are, preferably methyl or n-butyl, q1 is a number from 12 to 120, p1 is a number from 11 to 60, preferably from 15 to 50, and more preferably from 20 to 40, and n1 is a number from 2 to 10 is.
  • the block copolyesters B of the above formula are linear block copolyesters.
  • block copolyesters B of the above formula in which n is a number from 3 to 9, in particular from 3 to 5, very particularly preferably those derived from dimethyl terephthalate and 1,2-propylene glycol.
  • Block copolyesters B of the above formula in which p1 is a number from 11 to 50 and q1 is a number from 18 to 60 are also particularly preferred.
  • Block copolyesters B of the formula below are very particularly preferred
  • n2 is a number from 2 to 15, preferably from 2 to 12, more preferably from 3 to 9 and most preferably from 4 to 9, and die
  • CeFU residues are derived from terephthalic acid or its esters.
  • polyesters are known, for example, from EP 2670786 B1.
  • the compositions according to the invention contain polyesters A which are derived from dimethyl terephthalate, dimethyl 5-sulfoisophthalate sodium salt, ethylene glycol and/or 1,2-propylene glycol and its end groups are derived from isethionic acid sodium salt and from polyethylene glycol monomethyl ether, in particular from polyethylene glycol monomethyl ether with a molecular weight of 700 to 2000 g/mol. and polyesters B which are derived from dimethyl terephthalate, ethylene glycol and/or 1,2-propylene glycol and whose end groups are derived from polyethylene glycol monomethyl ether, in particular from polyethylene glycol monomethyl ether with a molecular weight of 700 to 2000 g/mol.
  • the polyesters A and B used according to the invention generally have number-average molecular weights in the range from 700 to 50,000 g/mol, preferably from 800 to 25,000 g/mol, in particular 1000 to 15,000 g/mol, particularly preferably 1200 to 12,000 g/mol.
  • the number average molecular weight is determined by size exclusion chromatography in aqueous solution using a calibration with polyacrylic acid sodium salt standards. Such standards are commercially available, for example from PSS, Mainz.
  • the molecular weight data in this description relate to the number-average molecular weight.
  • polyesters A and B used according to the invention can be synthesized by processes known per se by polycondensation of components a) to g).
  • the abovementioned components are first heated with the addition of a catalyst at temperatures of 160 to approx. 220° C. under normal pressure using an inert atmosphere, preferably in the presence of a salt of a CrC4-alkyl carboxylic acid, in particular a dehydrated or partially hydrated sodium acetate CH 3 COONa x (H 2 O) X , where x is a number in the range from 0 to 2.9, and where this salt is present in amounts by weight of from 0.5% to 30%, preferably from 1% to 15%, especially preferably from 3% to 8%, based on the total amount of the monomers used and the salt of the carboxylic acid.
  • a salt of a CrC4-alkyl carboxylic acid in particular a dehydrated or partially hydrated sodium acetate CH 3 COONa x (H 2 O) X , where x is a number in the range from 0 to 2.9
  • this salt is present in amounts by weight of from 0.5% to 30%, preferably from 1%
  • the required molecular weights are then built up in vacuo at temperatures from 160 to 240° C. by distilling off superstoichiometric amounts of the glycols used.
  • the known transesterification and condensation catalysts of the prior art such as, for example, are suitable for the reaction Titanium tetraisopropylate, dibutyltin oxide, alkali or alkaline earth metal alkoxides or antimony trioxide/calcium acetate.
  • a preferred process for preparing the polyesters A and B used according to the invention is characterized in that the condensation of the components is carried out in a one-pot process, with the transesterification and condensation catalysts being added before the heating.
  • polyesters A and B used according to the invention are readily soluble in water, show no tendency to hydrolysis at neutral or slightly acidic pH and form stable compositions which show little or no degradation and thus loss of performance even under more severe external conditions (storage at 45° C.).
  • polyesters used according to the invention show excellent dispersing power for grease and other soiling of fibers and thus counteract the graying of the textiles.
  • the performance in terms of increasing primary detergency, soil release activity and hydrophilization of nonionic polyesters is not inferior to solid anionic types.
  • polyester compositions according to the invention are prepared by dissolving the appropriate amount of polyester in a combination of water with water-miscible (/cyclo)aliphatic alcohols.
  • (Cyclo)aliphatic alcohols containing 1 to 20 carbon atoms are used as component C). Alcohols with one or more hydroxy groups can be used. The alcohols can be primary, secondary, or tertiary alcohols.
  • Aliphatic alcohols having one to four hydroxyl groups and one to ten, particularly preferably one to six, carbon atoms are preferred. Also preferred are cycloaliphatic alcohols having one or two hydroxy groups and five to six carbon atoms.
  • Examples of aliphatic alcohols having one to four hydroxyl groups and one to six carbon atoms are methanol, ethanol, propanol, butanol, pentanol, hexanol, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol , 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, ethylene glycol monomethyl ether , diethylene glycol, diethylene glycol monomethyl ether, triethylene glycol, trimethylolpropane, g
  • cycloaliphatic alcohols having one hydroxy group and five to six carbon atoms are cyclopropanol and cyclohexanol.
  • Preferred components C) are methanol, ethanol, n-propanol, isopropanol, glycerol, ethylene glycol, propanediol, diethylene glycol and triethylene glycol.
  • polyesters are added directly or in portions at temperatures of 10 to 90° C., preferably 30 to 70° C., particularly preferably 50 to 60° C., to the water/alcohol mixture initially taken for the solution and completely dissolved by stirring.
  • low molecular weight dispersants can also be added before or during the dissolving process.
  • Alkylbenzenesulfonates are preferably used here, such as sodium cumenesulfonate, sodium xylenesulfonate or sodium toluenesulfonate. It has proven useful to use these hydrotropes in an amount of 0.1 to 30% by weight, preferably 1 to 15% by weight, based on the total weight of the composition.
  • the polyester compositions according to the invention are stable for several months when stored at 5 to 45.degree.
  • the viscosities of the compositions according to the invention range from 15 to 15,000 mPas, preferably from 100 to 8,000 mPas, particularly preferably in the range from 300 to 1,000 mPas.
  • the viscosities are measured using a Brookfield viscometer at 100
  • the spindle used will vary depending on Viscosity range adjusted.
  • the dispersions according to the invention are approximately colorless to slightly yellowish and largely transparent to opaque.
  • polyester compositions according to the invention give textile fibers very good dirt-removing properties, they significantly support the dirt-removing ability of the other detergent ingredients to oily, greasy or pigmented soiling and prevent particles from the washing liquor (especially lime soap and dirt pigments) from being deposited on the textile (greying).
  • a further subject of the invention is the use of the polyester compositions according to the invention in detergents and cleaning agents, in after-treatment agents for laundry, in particular in a fabric softener, textile care agents and agents for finishing textiles.
  • Detergent and cleaning agent formulations containing the polyester compositions according to the invention can be in the form of paste, gel or liquid. Liquid detergents are particularly preferred.
  • Examples of this are heavy-duty detergents, delicate detergents, color detergents, wool detergents, curtain detergents or modular detergents.
  • the polyester compositions according to the invention are also distinguished by outstanding drainage behavior, in particular when rinsing plastic, ceramic and glass and metal surfaces. When cleaning hard surfaces, it reduces the tendency to form limescale deposits and reduces re-soiling of the treated surface, makes it difficult for oil and dirt to adhere and makes it easier to clean the surfaces again.
  • the use of the polyester compositions according to the invention in the drying of crockery and cutlery proved to be particularly advantageous.
  • polyester compositions according to the invention can thus also be used in household cleaning agents, for example all-purpose cleaners, dishwashing agents, Rinse aids, carpet cleaning and impregnating agents, cleaning and care products for floors and other hard surfaces, eg made of plastic, ceramic, glass, stone, metal or surfaces coated with nanoparticles are incorporated.
  • Examples of technical cleaning agents are plastic cleaning and care products, such as for housing and car fittings, as well as cleaning and care products for painted surfaces such as car bodies.
  • composition of the formulations should be adapted to the type of textiles to be treated or washed or to the surfaces to be cleaned.
  • the detergent and cleaning agent formulations can contain common ingredients such as surfactants, emulsifiers, builders, bleach catalysts and activators, sequestering agents, graying inhibitors, dye transfer inhibitors, dye fixatives, enzymes, optical brighteners, and softening components.
  • formulations or parts of the formulation can be specifically colored and/or perfumed by dyes and/or fragrances.
  • Polyester A (anionic component)
  • anionic polyester component A can be found in example 1 of patent EP 3222 647 B1.
  • This is, for example, a polyester which was produced by polycondensation of dimethyl terephthalate, dimethyl 5-sulfoisophthalate sodium salt, ethylene glycol and 1,2-propylene glycol and which had end groups derived from sodium salt of isethionic acid and from polyethylene glycol monomethyl ether Polyester B (nonionic component)
  • nonionic polyester components B are given in the table below. They are produced analogously to the anionic polyester component, with the difference that no monomers with ionic groups are used for the synthesis. The process of melt condensation is known to the expert.
  • polyesters B were used for the examples, the data being in moles:
  • ⁇ MPEG polyethylene glycol monomethyl ether with an average molecular weight of 750 and 2000, respectively
  • the anionic polyester component polyester A (for definition see above) is added in small portions as a powder (particle size ⁇ 1000 ⁇ m) to the solution in a nitrogen countercurrent over the course of 30 minutes. It initially forms within the Dissolves a slight opalescence that turns into a milky white composition within 30 minutes. After the addition is complete, the mixture is stirred at 55° C. for a further 60 minutes and then the composition is discharged into a suitable vessel via the bottom valve of the stirred autoclave.
  • the viscosity of the composition at 20° C. measured using a Brookfield viscometer (spindle 3, 100 rpm) is 400 mPa*s. After storage for three months, the viscosity of the suspension was determined to be 600 mPa*s (measured on a sample heated to 20° C.).
  • the anionic polyester component polyester A (for definition see above) is added in small portions as a powder (particle size ⁇ 1200 ⁇ m) to the solution in a nitrogen countercurrent over the course of 30 minutes. Initially, a slight opalescence develops within the solution, which changes to a milky white composition within 30 minutes. After the addition is complete, the mixture is stirred at 55° C. for a further 60 minutes and then the composition is discharged into a suitable vessel via the bottom valve of the stirred autoclave.
  • the viscosity of the composition at 20° C. measured using a Brookfield viscometer (spindle 3, 100 rpm) is 700 mPa*s. After 2 months of warm storage at 45°C, a viscosity of 1000 mPa*s was determined (measured at 20°C).
  • Example 3 350 g of 1,2-propanediol and 75 g of 1,2,3-propanetriol are placed in a heatable 1 liter Büchi autoclave equipped with an Intermig stirrer, internal thermometer and reflux condenser. 15 g of distilled water are added to the mixture of polyols, rendered inert with nitrogen and then heated to 50° C. with stirring. After the target temperature has been reached, 40 g of a 70% strength solution of the nonionic polyester B (Nio1) are added with stirring. A clear solution of the components forms.
  • a second nonionic polyester 2 (Nio3) are added as a 75% solution in water to the glycol/water mixture. The solution is heated to 52°C.
  • the viscosity of the composition at 20° C. measured using a Brookfield viscometer is 600 mPa*s. After storage for three months at 45° C., the viscosity rose to 900 mPa*s. The measurement was carried out after the sample had been heated to 20°C.
  • 35 g of the anionic polyester component polyester A (for definition see above) is added in small portions as a powder (particle size ⁇ 1200 ⁇ m) to the solution in a nitrogen countercurrent over the course of 30 minutes. A slight opalescence initially develops within the solution, which changes to a milky white composition within 30 minutes. After the addition is complete, the mixture is stirred at 55° C. for a further 60 minutes and then the composition is discharged into a suitable vessel via the bottom valve of the stirred autoclave.
  • the viscosity of the composition at 20° C. is 500 mPa*s directly after preparation. After two months of storage at 45°C in a closed vessel, the viscosity rose to 700 mPa*s. The measurement was carried out after the sample had been heated to 20°C.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne des compositions aqueuses de polyesters anioniques sélectionnés et de polyesters non ioniques sélectionnés. Ces compositions sont caractérisées par une bonne stabilité au stockage et une faible viscosité et peuvent être utilisées dans des détergents et des agents de nettoyage pour améliorer leur capacité d'élimination de salissures.
EP21786086.5A 2020-11-13 2021-09-30 Compositions aqueuses de polyester, détergents et agents de nettoyage les contenant et leur utilisation Pending EP4244324A1 (fr)

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DE102020006977.0A DE102020006977A1 (de) 2020-11-13 2020-11-13 Wässrig-alkoholische Polyesterzusammensetzungen, Wasch- und Reinigungsmittel enthaltend diese und deren Verwendung
PCT/EP2021/000114 WO2022100876A1 (fr) 2020-11-13 2021-09-30 Compositions aqueuses de polyester, détergents et agents de nettoyage les contenant et leur utilisation

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Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4321604A1 (fr) 2022-08-08 2024-02-14 The Procter & Gamble Company Tissu et composition de soins à domicile comprenant un tensioactif et un polyester
WO2024094800A1 (fr) 2022-11-04 2024-05-10 The Procter & Gamble Company Composition d'entretien textile et ménager
WO2024094803A1 (fr) 2022-11-04 2024-05-10 The Procter & Gamble Company Composition d'entretien textile et ménager
WO2024094802A1 (fr) 2022-11-04 2024-05-10 The Procter & Gamble Company Tissu et composition d'entretien ménager
EP4630526A1 (fr) 2022-12-05 2025-10-15 The Procter & Gamble Company Composition de soin textile et ménager comprenant un composé de carbonate de polyalkylène
EP4634352A1 (fr) 2022-12-12 2025-10-22 The Procter & Gamble Company Composition de soin textile et ménager
EP4386074B1 (fr) 2022-12-16 2025-12-03 The Procter & Gamble Company Composition de soin pour le linge et le domicile
EP4458932A1 (fr) 2023-05-04 2024-11-06 The Procter & Gamble Company Tissu et composition de soins à domicile
EP4458933A1 (fr) 2023-05-05 2024-11-06 The Procter & Gamble Company Composition de tissu et de soins à domicile comprenant un polyol propoxylé
EP4484536A1 (fr) 2023-06-26 2025-01-01 The Procter & Gamble Company Composition de soin pour le linge et le domicile
EP4549540A1 (fr) 2023-11-02 2025-05-07 The Procter & Gamble Company Composition de soin pour le linge et le domicile
EP4549541A1 (fr) 2023-11-02 2025-05-07 The Procter & Gamble Company Composition de soin pour le linge et le domicile
EP4553137A1 (fr) 2023-11-08 2025-05-14 The Procter & Gamble Company Composition de soin domestique et de tissu comprenant un polyester
EP4570892A1 (fr) 2023-12-15 2025-06-18 The Procter & Gamble Company Composition de détergent à lessive
EP4570893A1 (fr) 2023-12-15 2025-06-18 The Procter & Gamble Company Composition de soin pour le linge et le domicile
EP4610340A1 (fr) 2024-03-01 2025-09-03 The Procter & Gamble Company Composition de détergent à lessive comprenant un polyester
EP4624555A1 (fr) 2024-03-26 2025-10-01 The Procter & Gamble Company Compositions de soin pour tissus et maisons
EP4624554A1 (fr) 2024-03-26 2025-10-01 The Procter & Gamble Company Compositions d'entretien de tissus
EP4636063A1 (fr) 2024-04-19 2025-10-22 The Procter & Gamble Company Produit détergent à lessive à dose unitaire
EP4660287A1 (fr) 2024-06-06 2025-12-10 The Procter & Gamble Company Utilisation d'un ester de polysaccharide dans une composition de détergent pour lessive
EP4663733A1 (fr) 2024-06-10 2025-12-17 The Procter & Gamble Company Utilisation d'un polymère greffé dans un procédé de blanchissage
EP4663732A1 (fr) 2024-06-10 2025-12-17 The Procter & Gamble Company Utilisation de polymère greffé dans une composition de détergent pour lessive

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4427557A (en) 1981-05-14 1984-01-24 Ici Americas Inc. Anionic textile treating compositions
US4702857A (en) 1984-12-21 1987-10-27 The Procter & Gamble Company Block polyesters and like compounds useful as soil release agents in detergent compositions
US4721580A (en) 1987-01-07 1988-01-26 The Procter & Gamble Company Anionic end-capped oligomeric esters as soil release agents in detergent compositions
US4968451A (en) 1988-08-26 1990-11-06 The Procter & Gamble Company Soil release agents having allyl-derived sulfonated end caps
HUT64387A (en) 1990-09-07 1993-12-28 Procter & Gamble Improved contaminant removing agents for granulated detergents
CA2159982A1 (fr) 1993-04-07 1994-10-13 Randall Alan Watson Oligomeres d'esters sulfones, utiles comme agents dispersants dans des compositions detergentes
US5415807A (en) 1993-07-08 1995-05-16 The Procter & Gamble Company Sulfonated poly-ethoxy/propoxy end-capped ester oligomers suitable as soil release agents in detergent compositions
WO1996018715A2 (fr) 1994-12-14 1996-06-20 The Procter & Gamble Company Esters oligomeres convenant comme agents de lavage facilite dans des compositions detergentes
US5691298A (en) 1994-12-14 1997-11-25 The Procter & Gamble Company Ester oligomers suitable as soil release agents in detergent compositions
EP0776965A3 (fr) * 1995-11-30 1999-02-03 Unilever N.V. Compositions de polymères
US5700386A (en) 1996-08-08 1997-12-23 The Procter & Gamble Company Process for making soil release polymer granules
US5922663A (en) 1996-10-04 1999-07-13 Rhodia Inc. Enhancement of soil release with gemini surfactants
DE19906367A1 (de) 1999-02-16 2000-08-17 Clariant Gmbh Verwendung von Kammpolymeren als Schutzablösepolymere
DE102005061058A1 (de) 2005-12-21 2007-07-05 Clariant Produkte (Deutschland) Gmbh Anionische Soil Release Polymere
DE102007005532A1 (de) * 2007-02-03 2008-08-07 Clariant International Limited Wässrige Oligo- und Polyesterzubereitungen
EP2504379B1 (fr) 2009-11-27 2014-07-02 Clariant Finance (BVI) Limited Utilisation de concentrés de polyester ayant une grande stabilité de solution et un effet antiredéposition dans des compositions detergentes
EP2504380B1 (fr) 2009-11-27 2014-08-13 Clariant Finance (BVI) Limited Polymères facilitant le lavage ayant un effet antiredéposition et une grande stabilité en solution
CN103347927B (zh) 2011-01-31 2015-04-22 荷兰联合利华有限公司 去污聚合物
US20140274860A1 (en) 2011-10-27 2014-09-18 The Dial Corporation Synergistic effect of soil release polymers on wash performance of fabrics
EP2966160A1 (fr) 2014-07-09 2016-01-13 Clariant International Ltd. Compositions stables au stockage comprenant des polymères de libération de salissure
DE102014218952A1 (de) 2014-09-19 2016-03-24 Henkel Ag & Co. Kgaa Mittel für die Textilbehandlung, enthaltend mindestens einen anionischen, aromatischen Polyester und mindestens einen nichtionischen, aromatischen Polyester
DE102016003544A1 (de) 2016-03-22 2017-09-28 Weylchem Wiesbaden Gmbh Polyester, Verfahren zu deren Herstellung und deren Verwendung
DE102017003927A1 (de) * 2016-12-05 2018-06-07 Gertraud Scholz Anionische Soll Release Polyester und deren Verwendung
HUE065859T2 (hu) 2018-01-25 2024-06-28 Procter & Gamble Polimer összetétel

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