Aqueous Polyester Compositions, Detergents, and Cleaning Agents Containing Them and Their Use

Abstract

Disclosed are aqueous compositions of selected anionic polyesters and of selected nonionic polyesters.

These compositions are characterized by good storage stability and low viscosity and can be used in detergents and cleaning agents to improve soil release.

Claims

1. Compositions containing A) at least one anionic polyester obtainable by polymerization of the components a) one or more aromatic dicarboxylic acids which are free from sulfo groups and/or salts thereof and/or anhydrides thereof and/or esters thereof, b) optionally one or more dicarboxylic acids containing sulfo groups, their salts and/or their anhydrides and/or their esters, c) one or more aliphatic diols of the formula (1)
H(OC.sub.mH.sub.2m).sub.sOH(1), wherein m is a number from 2 to 10 and m can assume 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 and can additionally assume a value between 2 and 200, d) optionally one or more compounds of the formula (2)
R.sup.1O(C.sub.oH.sub.2oO).sub.pH(2) wherein R.sup.1 is a linear or branched alkyl group containing 1 to 22 carbon atoms, is a number from 2 to 10 and o can assume different meanings within a molecule within the scope of the given definition, p is a number from 1 to 200, e) optionally one or more compounds of the formula (3) and/or of the formula (4)
R.sup.2(C.sub.qH.sub.2qO).sub.rH(3),
(Me.sup.a+).sub.b.sup.O.sub.3SC.sub.6H.sub.4COOR.sup.10(4), wherein q is a number from 2 to 10, r is a number from 1 to 10, and R.sup.2 is a radical (Me.sup.a+).sub.b.sup.OOC or (Me.sup.a+).sub.b.sup.O.sub.3S, R.sup.10 is hydrogen or C.sub.1-C.sub.6-alkyl, Me is hydrogen or an a-valent cation, a is a number from 1 to 3, b is a number having the value 1/a, and f) optionally one or more crosslinking polyfunctional compounds, with the proviso that at least one of components b) or e) is present, B) at least one nonionic polyester obtainable by polymerization of components a), c), d) and optionally f) defined above, C) one or more aliphatic or cycloaliphatic alcohols containing 1-20 carbon atoms, and D) water.

2. Compositions according to claim 1, wherein the proportion by weight of the polyesters A) and B) in the composition is 1 to 50%, preferably 5 to 40%, in particular 10 to 30% and very preferred 15 to 25%.

3. Compositions according to at least one of claims 1 or 2, wherein the proportion by weight of polyester A) in the total mass of polyesters A) and B) is 20 to 80%, preferably 40 to 60%.

4. Compositions according to at least one of claims 1 to 3, characterized in that the proportion by weight of polyester B) in the total mass of polyesters A) and B) is 80 to 20%, preferably 60 to 40%.

5. Compositions according to at least one of claims 1 to 4, wherein component a) is selected from the group consisting of terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, alkali metal salts or alkaline earth metal salts thereof or dialkyl esters thereof.

6. Compositions according to at least one of claims 1 to 5, wherein component b) is selected from the group consisting of sulfoterephthalic acid, sulfoisophthalic acid, sulfonaphthalene dicarboxylic acid, their alkali metal salts or alkaline earth metal salts or their dialkyl esters.

7. Compositions according to at least one of claims 1 to 6, wherein component c) is selected from the group consisting of ethylene glycol, propylene glycol or mixtures thereof, preferably ethylene glycol, 1.2-propylene glycol or mixtures thereof.

8. Compositions according to at least one of claims 1 to 7, characterized in that component d) is a compound of formula (2a)
R.sup.3O(CHR.sup.4CHR.sup.5O).sub.sH(2a) wherein R.sup.3 represents a linear or branched alkyl group with 1 to 6 C atoms, in particular with 1 to 3 C atoms, R.sup.4 and R.sup.5 independently of one another represent hydrogen or an alkyl group having 1 to 4 carbon atoms, and s is a number from 1 to 50, preferably from 12 to 30.

9. Compositions according to at least one of claims 1 to 8, wherein component e) is a compound of the formula (3a)
MeO.sub.3S(CHR.sup.6CHR.sup.7O).sub.tH(3a) wherein Me is hydrogen, a monovalent metal cation or an ammonium cation, R.sup.6 and R.sup.7 independently of one another represent hydrogen or an alkyl group having 1 to 4 carbon atoms, and t is a number from 1 to 50, preferably from 1 to 5 and most preferred from 1 or 2.

10. Compositions according to at least one of claims 1 to 8, wherein component e) is a compound of the formula (3b)
MeO.sub.3SC.sub.6H.sub.4COOR.sup.11(3b) wherein Me is hydrogen, a monovalent metal cation or an ammonium cation, preferably hydrogen or a sodium cation, and R.sup.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.

11. Compositions according to claims 9 and 10, wherein component e) is a mixture of the compounds of the formulae (3a) and (3b).

12. Compositions according to at least one of claims 1 to 11, wherein the polyesters A and B are non-crosslinked.

13. Compositions according to at least one of claims 1 to 12, wherein polyester A) contains recurring structural units of the formula Ia and end groups of the formula II and of the formula III or end groups of the formula II and of the formula IV or end groups of the formula II, III and IV or contains recurring structural units of the formula Ia and of the formula Ib and end groups of the formula II and of the formula III or end groups of the formula II and of the formula IV or end groups of the formula II, III and IV. ##STR00005## wherein R is C.sub.1-C.sub.4-alkyl, M is hydrogen or a monovalent or divalent cation i is 1 or 2 x is 0.5 or 1 and the product i.Math.x=1, and z is a number from 3 to 35, and wherein polyester B) contains recurring structural units of the formula Ia defined above and end groups of the formula V or contains recurring structural units of the formula Ia and of the formula Ib defined above and end groups of the formula V ##STR00006## wherein R.sup.9 is hydrogen or C.sub.1-C.sub.4alkyl, and c is a number from 1 to 35.

14. Compositions according to claim 13, wherein polyester A) contains, in addition to the recurring structural units of the formula Ia or of the formulae Ia and Ib and the end groups of the formulae II and III or of the formulae II and IV or of the formulae II, III and IV, the structural units of the formula Va and/or of the formula VIa or the structural units of the formulae Va and Vb and/or of the formulae VIa and VIb ##STR00007## wherein M is hydrogen or a monovalent or divalent cation, i is 1 or 2 x is 0.5 or 1, and the product i.Math.x=1.

15. Compositions according to claim 13 or 14, wherein the proportion of recurring structural units of the formula Ia or of recurring structural units of the formulae Ia and Ib or of recurring structural units of the formulae Ia, Va and/or Vb and/or VIa and/or VIb or of recurring structural units of the formulae Ia, Ib, Va and/or Vb and/or VIa and/or VIb in polyester A) is from 80 to 100 mol %, based on the total amount of recurring structural units in polyester A), and wherein the proportion of recurring structural units of the formula Ia or of recurring structural units of the formulae Ia and Ib in polyester B) is from 80 to 100 mol %, based on the total amount of recurring structural units in polyester B).

16. Compositions according to claim 13, 14 or 15, wherein the proportion of end groups of the formulae II and III or of the formulae II and IV or of the formulae II, III and IV in polyester A) is 80 to 100 mol %, based on the total amount of end groups in polyester A), and wherein the proportion of end groups of formula V in polyester B) is 80 to 100 mol %, based on the total amount of end groups in polyester B).

17. Compositions according to at least one of claims 1 to 16, wherein polyesters A) are derived from terephthalic acid dimethyl ester, 5-sulfoisophthalic acid dimethyl ester sodium salt, ethylene glycol and/or 1, 2-propylene glycol and wherein their end groups are derived from isethionic acid sodium salt and from polyethylene glycol monomethyl ether, and wherein polyesters B are derived from terephthalic acid dimethyl ester, ethylene glycol and/or 1,2-propylene glycol and wherein their end groups are derived from polyethylene glycol monomethyl ether.

18. Compositions according to at least one of claims 1 to 17, wherein component C) is selected from the group consisting of methanol, ethanol, n-propanol, isopropanol, glycerol, ethylene glycol, propanediol, diethylene glycol, triethylene glycol and mixtures of two or more thereof.

19. Detergents and cleaning agents comprising a composition according to at least one of claims 1 to 18.

20. Use of a composition according to any one of claims 1 to 18 for washing textiles or for drying and cleaning hard surfaces.

21. Use according to claim 20, wherein the composition is used to improve soil release from textiles, to reduce resoiling, to protect fibers under mechanical stress and to provide fabrics with an anti-creasing effect.

Description

EXAMPLES

[0173] The following examples illustrate the invention without limiting it.

[0174] Polyester A (Anionic Component)

[0175] The preparation and composition of the anionic polyester component A can be taken from Example 1 of patent EP 3 222 647 B1. This is, for example, a polyester prepared by polycondensation of terephthalic acid dimethyl ester, 5-sulfoisophthalic acid dimethyl ester sodium salt, ethylene glycol and 1,2-propylene glycol, and which had end groups derived from isethionic acid sodium salt and from polyethylene glycol monomethyl ether

[0176] Polyester B (Non-Ionic Component)

[0177] The composition of the nonionic polyester components B is indicated in the following table. Their preparation is analogous to that of the anionic polyester component, with the difference that no monomers with ionic groups are used for synthesis. The melt condensation process is known to the expert.

[0178] The following polyesters B were used for the examples, the data being in mol:

TABLE-US-00001 terephthalic 1,2-propane 1,2-ethane MPEG*.sup.) MPEG*.sup.) acid diol diol 750 2000 Nio 1 3 2 2 Nio 2 5 4 2 Nio 3 6 4 1 2 Nio 4 3 2 1 1 *.sup.)MPEG = polyethylene glycol monomethyl ether with an average molecular weight of 750 or 2000

Example 1

[0179] In a heatable 1 liter Bchi autoclave equipped with an impeller stirrer, internal thermometer and reflux condenser, 300 g of 1.2-propanediol and 60 g of 1,2,3-propanetriol are introduced. To the mixture of polyols, 16 g of distilled water is added, inerted with nitrogen, and then heated to 50 C. with stirring. After reaching the target temperature, 80 g of a 70% solution of non-ionic polyester B (Nio 1) is added with stirring. A clear solution of the components is formed. The solution is tempered to 55 C.

[0180] 44 g of the anionic polyester component polyester A (for definition see above) is added in small portions as powder (particle size <1000 m) to the solution in nitrogen countercurrent within 30 minutes. A slight opalescence initially forms within the solution, which changes to a milky white composition within 30 minutes. Once the addition is complete, stirring is continued for an additional 60 minutes at 55 C. and then the composition is drained into a suitable vessel via the bottom valve of the stirred autoclave.

[0181] The viscosity of the composition at 20 C. measured with a Brookfield viscometer (spindle3, 100 rpm) is 400 mPa*s. After three months of storage, the viscosity of the suspension was determined to be 600 mPa*s (measured on a sample tempered to 20 C.).

Example 2

[0182] In a heatable 1 liter Bchi autoclave equipped with an Intermig stirrer, internal thermometer and reflux condenser, 310 g of 1.2-propanediol and 85 g of 1,2,3-propanetriol are introduced. To the mixture of polyols, 18 g of distilled water is added, inerted with nitrogen, and then heated to 50 C. with stirring. After reaching the target temperature, 70 g of a 75% solution of nonionic polyester B (Nio2) is added with stirring. A clear solution of the components is formed. The solution is tempered to 52 C.

[0183] 52.5 g of the anionic polyester component polyester A (see above for definition) is added in small portions as a powder (particle size <1200 m) to the solution in nitrogen countercurrent within 30 minutes. A slight opalescence initially forms within the solution, which changes to a milky white composition within 30 minutes. After completion of the addition, stirring is continued for a further 60 minutes at 55 C. and then the composition is drained into a suitable vessel via the bottom valve of the stirred autoclave.

[0184] The viscosity of the composition at 20 C. measured with a Brookfield viscometer (spindle3, 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

[0185] In a heatable 1 liter Bchi autoclave equipped with an Intermig stirrer, internal thermometer and reflux condenser, 350 g of 1.2-propanediol and 75 g of 1,2,3-propanetriol are introduced. To the mixture of polyols, 15 g of distilled water is added, inerted with nitrogen, and then heated to 50 C. with stirring. After reaching the target temperature, 40 g of a 70% solution of nonionic polyester B (Nio1) is added with stirring. A clear solution of the components is formed.

[0186] In addition, 40 g of a second nonionic polyester 2 (Nio3) is added as a 75% solution in water to the glycol/water mixture. The solution is tempered to 52 C.

[0187] 47.5 g of the anionic polyester component Polyester A (see above for definition) is added in small portions as a powder (particle size <1200 m) to the solution in nitrogen countercurrent within 30 minutes. A slight opalescence initially forms within the solution, which changes to a milky white composition within 30 minutes. Once the addition is complete, stirring is continued for an additional 60 minutes at 55 C. and then the composition is drained into a suitable vessel via the bottom valve of the stirred autoclave.

[0188] The viscosity of the composition at 20 C. measured with a Brookfield viscometer (spindle3, 100 rpm) is 600 mPa*s. After three months of storage at 45 C., the viscosity increased to 900 mPa*s. The measurement was made after the sample had been tempered to 20 C.

Example 4

[0189] In a heatable 1 liter Bchi autoclave equipped with an Impeller stirrer, internal thermometer and reflux condenser, 200 g of 1.2-propanediol, 100 g of 1.2-ethanediol and 70 g of 1,2,3-propanetriol are introduced. To the mixture of polyols, 16 g of distilled water is added, inerted with nitrogen, and then heated to 50 C. with stirring. After reaching the target temperature, 40 g of a 70% solution of nonionic polyester B (Nio1) is added with stirring. A clear solution of the components is formed. In addition, a second nonionic polyester B (Nio4) is added to the solution. The solution is tempered to 50 C.

[0190] 35 g of the anionic polyester component polyester A (see above for definition) is added in small portions as a powder (particle size <1200 m) to the solution in nitrogen countercurrent within 30 minutes. A slight opalescence initially forms within the solution, which changes to a milky white composition within 30 minutes. After completion of the addition, stirring is continued for a further 60 minutes at 55 C. and then the composition is drained into a suitable vessel via the bottom valve of the stirred autoclave.

[0191] The viscosity of the composition at 20 C. measured with a Brookfield viscometer (spindle3, 100 rpm) is 500 mPa*s immediately after preparation. After two months of storage at 45 C. in a closed vessel, the viscosity increased to 700 mPa*s. The measurement was made after the sample had been tempered to 20 C.