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US-12624158-B2 - Polyesters comprising structural units with sulfonate groups, and polyalkoxy ether end groups, detergents, and cleaning agents comprising these and their use

US12624158B2US 12624158 B2US12624158 B2US 12624158B2US-12624158-B2

Abstract

Disclosed are polyesters containing structural units corresponding to formula (I) or to formula (II) or to formulae (I) and (II), structural units of formula (III) or of formula (IV) or of formulae (III) and (IV), and optionally structural units of the formula (V) —CO—R 1 —CO—O—C 2 H 4 —O—  (I), —CO—R 1 —CO—O—(C 3 H 6 —O)—  (II), —CO—R 2 —CO—O—C 2 H 4 —O—  (III), —CO—R 2 —CO—O—(C 3 H 6 —O)—  (IV), —CO—R 3 —CO—O—R 4 —O—  (V), as well as nonionic endgroups of the formula (VI), and optionally nonionic endgroups of the formula (VII) —CO—(O—C 2 H 4 —) n —OR 5 (VI), —CO—OR 6 (VII). In these structural units and endgroups R 1 to R 6 are selected organic radicals and n is a number between 30 and 500. The polyesters according to the invention are characterized by very good soil release properties, can be readily stored in detergent and cleaning agent formulations and can be used as soil-release polymers.

Inventors

  • Roman Morschhäuser
  • Judith Preuschen
  • Stefan Riegelbeck
  • Niklas Diekhans
  • Rolf Ludwig
  • Said Kchirid

Assignees

  • CATEXEL GMBH

Dates

Publication Date
20260512
Application Date
20230619
Priority Date
20220621

Claims (19)

  1. 1 . Polyesters, based on all the structural units and end groups in the molecule, comprising 4 to 30% by weight of structural units of formula (I) or of formula (II) or of formulae (I) and (II), 0.25 to 10% by weight of structural units of formula (III) or of formula (IV) or of formulae (III) and (IV), and 0 to 5% by weight of structural units of formula (V) Wherein the following structural units represent the formulae (I through VII): —CO—R 1 —CO—O—C 2 H 4 —O— (I), —CO—R 1 —CO—O—(C 3 H 6 —O)— (II), —CO—R 2 —CO—O—C 2 H 4 —O— (III), —CO—R 2 —CO—O—(C 3 H 6 —O)— (IV), —CO—R 3 —CO—O—R 4 —O— (V), 50 to 95% by weight of nonionic endgroups of formula (VI), and 0 to 5% by weight of nonionic endgroups of formula (VII) —CO—(O—C 2 H 4 —) n —OR 5 (VI), —CO—OR 6 (VII), and wherein further: R 1 is a divalent aromatic hydrocarbon radical without sulfo groups or without salts of sulfo groups, R 2 is a divalent aromatic hydrocarbon radical substituted with at least one sulfo group or with the salt of a sulfo group, R 3 is an alkylene, cycloalkylene or arylene radical, R 4 is an alkylene or cycloalkylene radical, provided that the structural unit of formula (V) is different from the structural units of formulae (I), (II), (III) and (IV), R 5 is C 1 -C 6 alkyl, cycloalkyl, aryl or aralkyl, R 6 is a monovalent organic radical, and n is a number between 55 and 500.
  2. 2 . Polyesters according to claim 1 , wherein R 1 is a phenylene or naphthylene radical.
  3. 3 . Polyesters according to of claim 1 wherein R 2 is a phenylene or naphthylene radical substituted by one or two sulfo groups or salts thereof.
  4. 4 . Polyesters according to claim 1 containing structural units of the formulae (II) and (IV) in addition to the end groups.
  5. 5 . Polyesters according to claim 1 containing structural units of the formulae (I), (II), (III) and (IV) in addition to the end groups.
  6. 6 . Polyesters according to claim 1 containing only end group of the formula (VI).
  7. 7 . Polyesters according to claim 1 , wherein n is a number between 55-140.
  8. 8 . Polyesters according to claim 1 , wherein R 5 is C 1 -C 6 -alkyl.
  9. 9 . Polyesters according to claim 1 having a melting range starting at 45° C. or higher.
  10. 10 . Polyesters according to claim 1 containing end groups of the formula (VI) and, in addition to the end groups, containing structural units of the formulae (I), (II), (III) and (IV).
  11. 11 . Polyesters according to claim 1 having structural units of formulae (Ia) and (Va) and end groups of formula (VI), the proportion of structural units of the formula (Ia) being 4 to 30% by weight and the proportion of structural units of the formula (Va) being 0.25 to 10% by weight and the proportion of end groups being 50 to 95% by weight, based on all structural units and end groups, or having structural units of formulae (Ib) and (Vb) and end groups of formula (VI), the proportion of the structural units of the formula (Ib) being from 4 to 30% by weight and the proportion of the structural units of the formula (Vb) being from 0.25 to 10% by weight and the proportion of the end groups being from 50 to 95% by weight, based on all the structural units and end groups, or having structural units of formulae (Ia), (Ib), (Va) and (Vb) and end groups of formula (VI), the proportion of the structural units of the formulae (Ia) and (Ib) together being 4 to 30% by weight and the proportion of the structural units of the formulae (Va) and (Vb) together being 0.25 to 10% by weight and the proportion of the end groups being 50 to 95% by weight, based on all structural units and end groups, the end groups of the formula (VI) being covalently bonded to carboxyl radicals of the polyester via an ester linkage wherein R 5 and n are as defined in claim 1 , M is hydrogen or a monovalent or divalent cation, i is 1 or 2 x is 0.5 or 1 and the product i·x=1.
  12. 12 . A detergent or cleaning composition comprising at least one polyester according to claim 1 .
  13. 13 . The detergent or cleaning composition according to claim 12 which is a liquid detergent.
  14. 14 . The detergent or cleaning composition according to claim 13 containing 10 to 40% by weight, based on the total amount of the liquid detergent, of anionic surfactant or of mixtures of anionic surfactants.
  15. 15 . The detergent or cleaning composition according to claim 12 which is a detergent and is in powder form or in the form of a tablet.
  16. 16 . The process of using the polyesters according to claim 1 as soil release polymers or as graying inhibitors in detergents and cleaning compositions, textile care compositions and compositions for finishing textiles.
  17. 17 . Polyesters according to claim 1 , wherein R 1 is a 1,3 radical.
  18. 18 . Polyesters according to claim 1 wherein R 2 is a 1,3-phenylene radical substituted in the 5-position by a sulfo group or the salt of a sulfo group.
  19. 19 . Polyesters according to claim 1 , wherein R 5 is methyl.

Description

CLAIM FOR PRIORITY This application is a national phase application of DE 10 2022 002 248.6 FILED Jun. 21, 2022. The priority of DE 10 2022 002 248.6 is hereby claimed and its disclosure incorporated herein by reference. TECHNICAL FIELD The invention relates to selected polyesters for use in detergents and cleaning agents, which are characterized by very good soil release properties, allow the preparation of storage-stable liquid and solid formulations, are readily soluble in water, have low hygroscopicity and a solid, non-sticky consistency. BACKGROUND OF THE INVENTION The use of polyesters in detergents to improve soil release from textiles, reduce resoiling, protect fibers under mechanical stress and provide fabrics with an anti-crease effect is well known. These polyesters are known as SRP grades. A large number of polyester types and their use in detergents and cleaning agents are described in the patent literature. In addition to polyesters built up from exclusively non-ionic assemblies, polyesters are also used, some of which have anionic units. These anionic polyesters are actually preferred for reasons of efficiency; however, such polyesters, especially in liquid formulations such as in liquid detergents, tend to form deposits during storage . . . . U.S. Pat. No. 4,702,857 A discloses block copolyesters with anionic groups as soil release polymers. U.S. Pat. No. 4,427,557 discloses further SRPs with anionic groups. These are capped with low molecular weight nonionic end groups. SRPs with nonionic and ionic groups in the polymer backbone and with nonionic end groups are known from several patent documents. For example, WO 2008/110318 A2 describes anionic SRPs that have a softening point above 40° C., are derived from terephthalic acid, sulfoisophthalic acid and glycols, such as ethylene glycol and/or propylene glycol, and have end groups derived from alkylene glycol ethers. These polyesters are readily soluble in water, exhibit good soil release properties and can be readily incorporated into solid detergents and cleaning agents. The chain length of the alkylene glycol ethers used ranges from 1 to 200 repeating units. However, the preference is in the lower range corresponding to 1 to 20 repeat units; this corresponds to an average molecular weight of up to about 1000 for polyalkylene glycol ethers. According to the execution examples, polyalkylene glycol ethers with three to eight repeat units are used and the proportion by weight of the end groups, based on the total weight of the polyester, is less than 30%. From WO 1995/02030 A1 detergent compositions are known which contain selected SRP. These SRPs contain terephthalic acid glycol units and sulfoisophthalic acid glycol units, with ethylene glycol and or propylene glycol as alkylene glycols and selected end groups. End groups include alkoxylated hydroxyethane sulfonates, sulfoaroyl units, poly(oxyethylene)oxy monoalkyl ethers or ethoxylated or propoxylated sulfophenyl units. Exemplary SRPs include an oligomer of terephthalic acid ethylene glycol, terephthalic acid propylene glycol, 5-sulfoisophthalic acid ethylene glycol and 5-sulfoisophthalic acid propylene glycol units, that contains end groups derived from an oligomeric poly(ethylene glycol) monomethyl ether of molecular weight 750 and about 80 mol %, based on the amount of all end groups, of sodium 2-(2-hydroxyethoxy)ethane sulfonate. These polyesters are also readily soluble in water, exhibit good soil release properties and can be readily incorporated into solid detergents and cleaning agents. Colored polyesters are known from WO 2011/120653 A1. These are obtained by copolymerization of sulfogroup-free aromatic dicarboxylic acids or their polyester-forming derivatives, optionally sulfogroup-containing aromatic dicarboxylic acids or their polyester-forming derivatives, diols, alkylene glycol ethers and/or alkylene glycol sulfonates in the presence of pigments. The polyesters are characterized by a very good soil release effect and show a homogeneously colored and at the same time transparent appearance. WO 2011/063945 A1 discloses polyester concentrates with high solvent stability and graying inhibiting activity. The aqueous polyester concentrates contain 12-60 wt. % of polyesters obtained by copolymerization of sulfogroup-free aromatic dicarboxylic acids or polyester-forming derivatives thereof, optionally sulfogroup-containing aromatic dicarboxylic acids or polyester-forming derivatives thereof, ethylene glycol, 1,2-propylene glycol, alkylene glycol ethers and optionally alkylene glycol sulfonates, wherein at least one component containing sulfo groups must be present and wherein the molar ratio of 1,2-propylene glycol to ethylene glycol is greater than 1.60. These polyesters are characterized by a very good soil release effect, show a good graying inhibiting effect when used in liquid detergents and have only a minimal tendency to crystallize in aqueous solution. SRPs with high solution