Soil Release Polyesters For Use In Detergent Compositions

Abstract

Soil release polyesters for use in detergent compositions Polyesters are described comprising one or more structural units of the formula (I)

##STR00001##

and one or more structural units of the formula (II)

##STR00002##

and one or more terminal groups of the formula (III-a) or mixtures thereof

##STR00003##

wherein R.sup.1 is a linear or branched alkyl group comprising from 7 to 30 carbon atoms or a linear or branched alkenyl group comprising one or more double bonds and from 7 to 30 carbon atoms or mixtures thereof, a is, based on a molar average, a number from 1 to 200, and R.sup.2 is a linear or branched alkylene group (C.sub.mH.sub.2m) with m being a number from 2 to 10 or mixtures thereof.

The polyesters are particularly suited to be used as soil release agents.

Claims

1. A polyester comprising one or more structural units of the formula (I) ##STR00019## and one or more structural units of the formula (II) ##STR00020## and one or more terminal groups of the formula (III-a) or mixtures thereof ##STR00021## wherein R.sup.1 is a linear or branched, alkyl group comprising from 7 to 30 carbon atoms or a linear or branched, alkenyl group comprising one or more double bonds and from 7 to 30 carbon atoms or mixtures thereof, a is, based on a molar average, a number from 1 to 200, and R.sup.2 is a linear or branched alkylene group (C.sub.mH.sub.2m) with m being a number from 2 to 10 or mixtures thereof, .

2. The polyester according to claim 1, characterized in that R.sup.1 is selected from the group consisting of linear or branched C.sub.10-C.sub.15 alkyl, cocoyl, partially or totally hydrogenated variants of cocoyl, talloyl, partially or totally hydrogenated variants of talloyl and mixtures thereof.

3. The polyester according to claim 1, characterized in that R.sup.1 is a linear or branched, alkyl group comprising from 10 to 15 carbon atoms or mixtures thereof.

4. The polyester according to claim 1, characterized in that it further comprises one or more polyalkyleneglycol-derived structural units of the formula (IV-a) ##STR00022## or mixtures thereof, wherein f is, based on a molar average, a number from 2 to 200, and R.sup.3 is a linear or branched alkylene group (C.sub.nH.sub.2n), with n being a number from 2 to 10 or mixtures thereof, .

5. The polyester according to claim 1, characterized in that the amount of the one or more terminal groups of the formula (III-a) or mixtures thereof is at least 40 wt.-%, based on the total weight of the polyester.

6. The polyester according to claim 1, characterized in that the combined amount of the one or more structural units of the formula (I), and the one or more structural units of the formula (II), and the one or more terminal groups of the formula (III-a) or mixtures thereof, and, if present, the one or more polyalkyleneglycol-derived structural units of the formula (IV-a) or mixtures thereof, is at least 50 wt.-%, based on the total weight of the polyester.

7. The polyester according to claim 1, characterized in that its weight average molecular weight (M.sub.w) is from 5000 to 20000 g/mol.

8. The polyester according to claim 1, characterized in that the number of structural units of the formula (I) is, based on a molar average, from 2 to 60, .

9. The polyester according to claim 1, characterized in that it consists of a1) one or more structural units of the formula (I) and a2) one or more structural units of the formula (II) and a3) one or more terminal groups of the formula (III-a) or mixtures thereof.

10. A process for the preparation of a polyester comprising one or more structural units of the formula (I) ##STR00023## and one or more structural units of the formula (II) ##STR00024## and one or more terminal groups of the formula (III-a) or mixtures thereof ##STR00025## wherein R.sup.1 is a linear or branched, alkyl group comprising from 7 to 30 carbon atoms or a linear or branched, alkenyl group comprising one or more double bonds and from 7 to 30 carbon atoms or mixtures thereof, a is, based on a molar average, a number from 1 to 200, and R.sup.2 is a linear or branched alkylene group (C.sub.mH.sub.2m) with m being a number from 2 to 10 or mixtures thereof, comprising the steps of: heating one or more substances of the formula Q1—OOC—C.sub.6H.sub.4—COO—Q2, wherein Q1 and Q2, independently of one another, are selected from the group consisting of H and (C.sub.1-C.sub.4)-alkyl , and 1,2-propyleneglycol, and one or more substances of the formula R′—[O—R.sup.2].sub.a—OH or mixtures thereof, with the addition of a catalyst, to temperatures of from 160 to 220° C., and then continuing the reaction under reduced pressure at temperatures of from 160 to 240° C.

11. A soil release agent comprising one or more structural units of the formula (I) ##STR00026## and one or more structural units of the formula (II) ##STR00027## and one or more terminal groups of the formula (III-a) or mixtures thereof ##STR00028## wherein R.sup.1 is a linear or branched, alkyl group comprising from 7 to 30 carbon atoms or a linear or branched, alkenyl group comprising one or more double bonds and from 7 to 30 carbon atoms or mixtures thereof, a is, based on a molar average, a number from 1 to 200, and R.sup.2 is a linear or branched alkylene group (C.sub.mH.sub.2m) with m being a number from 2 to 10 or mixtures thereof.

12. A detergent composition, comprising Z1) one or more polyesters comprising one or more structural units of the formula (I) ##STR00029## and one or more structural units of the formula (II) ##STR00030## and one or more terminal groups of the formula (III-a) or mixtures thereof ##STR00031## wherein R.sup.1 is a linear or branched, alkyl group comprising from 7 to 30 carbon atoms or a linear or branched, alkenyl group comprising one or more double bonds and from 7 to 30 carbon atoms or mixtures thereof, a is, based on a molar average, a number from 1 to 200, and R.sup.2 is a linear or branched alkylene group (C.sub.mH.sub.2m) with m being a number from 2 to 10 or mixtures thereof and Z2) one or more surfactants.

13. The detergent composition according to claim 12, characterized in that it comprises the one or more polyesters of component Z1) in an amount of at least 0.1 wt.-%, based on the total weight of the detergent composition.

14. The detergent composition according to claim 12, characterized in that it comprises the one or more surfactants of component Z2) in an amount of at least 3 wt.-%, based on the total weight of the detergent composition.

15. A solution or dispersion comprising one or more polyesters comprising one or more structural units of the formula (I) ##STR00032## and one or more structural units of the formula (II) ##STR00033## and one or more terminal groups of the formula (III-a) or mixtures thereof ##STR00034## wherein R.sup.1 is a linear or branched, alkyl group comprising from 7 to 30 carbon atoms or a linear or branched, alkenyl group comprising one or more double bonds and from 7 to 30 carbon atoms or mixtures thereof, a is, based on a molar average, a number from 1 to 200, and R.sup.2 is a linear or branched alkylene group (C.sub.mH.sub.2m) with m being a number from 2 to 10 or mixtures thereof and one or more solvents selected from the group consisting of water, ethanol, propanol, butanol, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1 ,3-butylene glycol, 1,4-butylene glycol, butyl glycol, butyl diglycol, butyl polyglycol, and mixtures thereof, .

16. The polyester according to claim 1, characterized in that it consists of b1) one or more structural units of the formula (I) and b2) one or more structural units of the formula (II) and b3) one or more terminal groups of the formula (III-a) or mixtures thereof, and b4) one or more polyalkyleneglycol-derived structural units of the formula (IV-a) or mixtures thereof.

Description

EXAMPLES

[0126] The examples below are intended to illustrate the invention in detail without, however, limiting it thereto. Unless explicitly stated otherwise, all percentages given are percentages by weight (% by wt. or wt.-%).

[0127] Key to reactants used in the examples:

TABLE-US-00001 DMT dimethyl terephthalate EO ethylene oxide PG 1,2-propylene glycol IPT tetraisopropyl orthotitanate NaOAc sodium acetate Tallow-25EO Tallow alcohol (C16/18, C18 rich, saturated (hydrogenated)) ethoxylate with 25 EO (Genapol® T 250, Clariant) Tallow-50EO Tallow alcohol (C16/18, C18 rich, saturated (hydrogenated)) ethoxylate with 50 EO (Genapol® T 500, Clariant) Tallow-80EO Tallow alcohol (C16/18, C18 rich, saturated (hydrogenated)) ethoxylate with 80 EO (Genapol® T 800, Clariant) Tallow-120EO Tallow alcohol (C16/18, C18 rich, saturated (hydrogenated)) ethoxylate with 120 EO Lauryl-80EO Lauryl alcohol (C12/14, C12 rich) ethoxylate with 80 EO Isotridecyl-100EO Isotridecyl alcohol (C11-C14 iso alcohol, C13 rich) ethoxylate with 100 EO

Example 1: Polyester Preparation

[0128] General procedure for the preparation of the polyesters of the examples. The polyester synthesis is carried out by the reaction of dimethyl terephthalate (DMT), 1,2-propylene glycol (PG) and one or more poly(alkyleneglycol)monoalkylethers or one or more poly(alkyleneglycol)monoalkenylethers or mixtures thereof (collectively “Cap”), using sodium acetate (NaOAc) and tetraisopropyl orthotitanate (IPT) as the catalyst system. The synthesis is a two-step procedure. The first step is a transesterification and the second step is a polycondensation.

Inventive Polyester Example 1

[0129] 38.8 g (0.2 mol) of dimethyl terephthalate (DMT), 30.4 g (0.4 mol) of 1,2-propylene glycol (PG), 271.6 g (0.2 mol) of Tallow-25EO and 0.5 g of sodium acetate (anhydrous) (NaOAc) are weighed into a reaction vessel at room temperature. For the melting process and homogenization, the mixture is heated up to 70° C. 200 .Math.L (0.7 mmol) of tetraisopropyl orthotitanate (IPT) is added and the mixture is further heated up to 170° C. for 1 hour and then up to 210° C. for a further 1 hour sparged by a nitrogen stream. During the transesterification methanol is released from the reaction and is distilled out of the system (distillation temperature < 55° C.). After 2 hours at 210° C. nitrogen is switched off and the pressure is reduced to 400 mbar over 3 hours. Subsequently, the mixture is heated up to 230° C. At 230° C., the pressure is reduced to 1 mbar over 160 minutes. Once the polycondensation reaction has started, 1 ,2-propylene glycol is distilled out of the system. The mixture is stirred for 4 hours at 230° C. and a pressure of 1 mbar. The reaction mixture is cooled down to 140 - 150° C. Vacuum is released with nitrogen and the molten polymer is transferred out of the reactor.

[0130] Inventive polyester examples 2 to 14 are synthesized according to the general procedure as described above for inventive polyester example 1 with monomer type and dosage described below (see Table 1).

TABLE-US-00002 Inventive polyester examples 1 to 14 Inventive polyester example DMT [g] PG [g] Cap [type] Cap [g] Yield [g] MW [g/mol] 1 38.8 30.4 Tallow-25EO 271.6 308.2 6372 2 97.1 76.1 Tallow-25EO 271.6 371.8 5628 3 58.3 45.7 Tallow-25EO 271.5 328 6572 4 48.6 38.1 Tallow-50EO 351.3 398.5 8264 5 77.7 60.9 Tallow-50EO 245.6 354 6676 6 58.3 45.7 Tallow-50EO 245.6 304.7 8663 7 48.6 38.1 Tallow-80EO 378.1 428.2 10849 8 116.5 91.3 Tallow-80EO 378.1 502.9 9781 9 97.1 76.1 Tallow-80EO 378.1 478.1 10096 10 58.3 45.7 Tallow-120EO 275 336.1 10068 11 29.1 22.8 Lauryl-80EO 155.9 186.6 14284 12 77.7 60.1 Lauryl-80EO 155.9 235.2 10331 13.sup.a 93.2 73.1 Lauryl-80EO 498.8 594.8 12370 14 77.7 60.9 Isotridecyl-100EO 401.2 482.3 10631 .sup.a 400 .Math.L IPT and 1.0 g NaOAc were used

Example 2: Compositions Containing Polyesters and Their Viscosity

[0131] A series of exemplary liquid laundry detergent compositions containing no polyester (reference composition A), containing a comparative polyester (comparative composition B) or containing inventive polyester (inventive compositions C-M) were prepared according to Table 2.

[0132] Key to ingredients used in the compositions of Table 2

TABLE-US-00003 LAS is C.sub.12-14 linear alkylbenzene sulfonate, sodium salt SLES 2EO is sodium lauryl ether sulfate with 2 moles EO (Genapol® LRO, Clariant). Nl 7EO is C.sub.12-15 alcohol ethoxylate 7EO nonionic (Genapol® LA070, Clariant) Fatty Acid is a C.sub.12-18 stripped palm kernel fatty acid SRP is a polyester prepared according to examples from Table 1 Texcare® SRN 260 is a nonionic soil release polymer (Clariant)

TABLE-US-00004 Liquid laundry detergent compositions for performance testing Ingredient Composition A (reference) Composition B (comparative) Compositions C-M (inventive) wt.-% a.m. wt.-% a.m. wt.-% a.m. LAS 5.2 5.2 5.2 SLES 2EO 6.5 6.5 6.5 Nl 7EO 5.2 5.2 5.2 Fatty Acid 2.8 2.8 2.8 Glycerol 2.4 2.4 2.4 Ethanol 1.2 1.2 1.2 Sodium citrate 1.7 1.7 1.7 Sodium tetraborate decahydrate 2.0 2.0 2.0 Sodium chloride 1.0 1.0 1.0 Texcare® SRN 260 0 1.0 0 SRP 0 0 1.0 Demineralized water and NaOH to adjust pH ad 100 ad 100 ad 100 pH Value 8.4 8.4 8.4 a.m. active matter

[0133] The viscosities of the compositions of Table 2 were determined using a Malvern Kinexus equipped with a CP 4°/40 mm, at a temperature of 25° C. and at a shear rate of 200 s.sup.-1 and rounded to the nearest 5 mPas. The appearance of the compositions was determined visually. The results are summarized in Table 3.

TABLE-US-00005 Viscosity and appearance of liquid detergent compositions Composition Inventive polyester example Viscosity [mPas] Appearance at room temperature A (reference) - 580 Clear B (comparative) - 285 Clear C (inventive) 1 700 Clear D (inventive) 3 865 Clear E (inventive) 4 1075 Clear F (inventive) 6 1235 Clear G (inventive) 7 920 Clear H (inventive) 9 1215 Clear I (inventive) 10 1305 Clear J (inventive) 11 815 Clear K (inventive) 12 1020 Clear L (inventive) 13 1580 Clear M (inventive) 14 1340 Clear

Example 3: Soil Release Performance of Inventive Polyesters

[0134] Detergent compositions of Example 2 were tested for their soil release performance according to the “Dirty-Motor Oil” Test (DMO-Test) using a Lini Apparatus under the following conditions (see Table 4).

TABLE-US-00006 Conditions for testing of soil release performance Equipment Linitest Plus (SDL Atlas) Water hardness 14°dH Washing temperature 40° C. Washing time 30 minutes Detergent concentration 4.3 g/l liquid detergent Soiled Fabric : Liquor Ratio 1 : 40

[0135] As test fabric, white polyester standard swatches (WFK 30A from WFK Testgewebe GmbH) were used. The fabrics were prewashed three times with the liquid detergent compositions. The swatches were then rinsed, dried and soiled with 25 .Math.l of dirty motor oil. After 1 hour the soiled fabrics were washed again with the same stored laundry detergent compositions used in the pre-washing step. After rinsing and drying the washed swatches, a measurement of the remission of the stained fabric at 457 nm was made using a spectrophotometer (Datacolor 650).

[0136] The soil release performance is shown as an improvement in soil removal of the swatches washed with a composition containing an inventive polyester as additive compared with the same composition containing no additive (Composition A)

[00001]$\Delta R=R_{withaddictive}-R_{withoutadditive}$

[0137] The washing results obtained for the inventive laundry detergent compositions comprising the polyesters of the invention are expressed as ΔR along with the standard deviations (SD) (see Table 5).

TABLE-US-00007 Soil release test results Detergent composition Soil release test result ΔR SD I (inventive) 13.0 2.1 J (inventive) 15.4 2.1 K (inventive) 16.2 1.4 L (inventive) 17.6 1.0 M (inventive) 16.9 0.9

[0138] The results in Table 5 suggest that the inventive polyesters show a significant soil release effect.

[0139] Similar tests with Compositions C to H suggest that the polyesters provide a significant soil release effect.