POLYESTERS

Abstract

Summary

The present invention relates to specific polyesters which are particularly suitable for use in fabric treatment applications, such as in fabric care and laundry detergent products. In such applications, the polyesters exhibit improved freshness performance, and especially good anti-malodor performance.

Claims

1. A polyester comprising A) one or more structure units of the formula (I) ##STR00010## wherein R.sub.1 is H or SO.sub.3.sup.− 1/p MP.sup.+, and 1/p MP.sup.+ is a cation, and B) one or more structure units of the formula (II)
—O—R.sub.2—O—  (II) wherein R.sub.2 is a linear or branched alkylene group represented by the formula (C.sub.mH.sub.2m) wherein m is an integer from 2 to 10, and C) one or more structure units selected from the group consisting of the formulae (III-a), (III-b), (III-c) and combinations thereof, ##STR00011## wherein R.sub.3 and R.sub.4 are, independently of one another, selected from linear or branched alkylene groups represented by the formula (C.sub.nH.sub.2n) wherein n is 2, 3 or 4, R.sub.5 is a group of the formula —(C.sub.jH.sub.2jO).sub.k—R.sub.98, wherein j is 2, 3 or 4, k is, based on a molar average, a number from 0 to 10, and R.sub.98 is selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, phenyl alkyl, phenyl alkenyl, alkyl phenyl, and alkenyl phenyl, wherein the alkyl and alkenyl groups, either as such or as a part of the aforementioned hydroxyalkyl, hydroxyalkenyl, phenyl alkyl, phenyl alkenyl, alkyl phenyl or alkenyl phenyl groups, contain 6 or more than 6 carbon atoms, R.sub.6 is a group of the formula —(C.sub.j1H.sub.2j1O).sub.k1—R.sub.99, wherein j1 is 2, 3 or 4, k1 is, based on a molar average, a number from 0 to 10, and R.sub.99 is selected from the group consisting of hydrogen, alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, phenyl alkyl, phenyl alkenyl, alkyl phenyl, and alkenyl phenyl, wherein the alkyl groups, either as such or as a part of the aforementioned hydroxyalkyl, phenyl alkyl or alkyl phenyl groups, contain from 1 to 30 carbon atoms, and wherein the alkenyl groups, either as such or as a part of the aforementioned hydroxyalkenyl, phenyl alkenyl or alkenyl phenyl groups, contain from 2 to 30 carbon atoms, a and b are, based on a molar average, independently of one another, numbers from 1 to 200, and 1/z X.sup.z− is an anion.

2. A polyester according to claim 1, characterized in that R.sub.1 is H.

3. A polyester according to claim 1, characterized in that R.sub.2 is selected from the group consisting of (C.sub.2H.sub.4), (C.sub.3H.sub.6) and mixtures thereof.

4. A polyester according to claim 1, characterized in that R.sub.3 and R.sub.4 are (C.sub.2H.sub.4).

5. A polyester according to claim 1, characterized in that a and b are 1.

6. A polyester according to claim 1, characterized in that R.sub.98 is selected from the group consisting of alkyl, alkenyl and mixtures thereof and wherein the alkenyl groups comprise one or more double bonds.

7. A polyester according to claim 1, characterized in that R.sub.99 is a linear or branched.

8. A polyester according to claim 1, characterized in that it further comprises one or more terminal groups (IV) derived from polyalkyleneglycol monoalkylethers.

9. A polyester according to claim 1, characterized in that it further comprises one or more polyalkyleneglycol-derived structure units (V).

10. A polyester according to claim 1, characterized in that the combined amount of the one or more structure units of the formula (I), and the one or more structure units of the formula (II), and the one or more structure units selected from the group consisting of the formulae (IIIa), (III-b), (III-c) and combinations thereof, and furthermore, if present, the one or more terminal groups (IV) derived from polyalkyleneglycol monoalkylethers, and, if present, the one or more polyalkyleneglycol-derived structure units (V), is at least 50 wt.-%, based on the total weight of the polyester.

11. A polyester according to claim 1, characterized in that it consists exclusively of one or more structure units of the formula (I), and of one or more structure units of the formula (II), and of one or more structure units selected from the group consisting of the formulae (III-a), (III-b), (III-c) and combinations thereof, and furthermore, if present, of one or more terminal groups (IV) derived from polyalkyleneglycol monoalkylethers, and, if present, of one or more polyalkyleneglycol-derived structure units (V).

12. A polyester according to claim 8, characterized in that the amount of the one or more terminal groups (IV), based on the total weight of the polyester, is at least 40 wt.-%.

13. A polyester according to claim 1, characterized in that its weight average molecular weight (Mw) is from 2000 to 20000 g/mol.

14. A process for the preparation of a polyester comprising the steps of: heating one or more substances of the formula Q.sub.1-OOC—C.sub.6H.sub.3R.sub.1—COO-Q.sub.2, wherein Q.sub.1 and Q.sub.2, independently of one another, are selected from the group consisting of H and (C.sub.1-C.sub.4)-alkyl and R.sub.1 is H or SO.sub.3.sup.− 1/p MP.sup.+, and one or more glycols of the formula HO—R.sub.2—OH, wherein R.sub.2 is a linear or branched alkylene group represented by the formula (C.sub.mH.sub.2m) wherein m is an integer from 2 to 10, and one or more amine alkoxylates of the formula H—(O—R.sub.3).sub.a—N(R.sub.5)—(R.sub.4—O).sub.b—H, wherein R.sub.3 and R.sub.4 are, independently of one another, selected from linear or branched alkylene groups represented by the formula (C.sub.nH.sub.2n) wherein n is 2, 3 or 4, R.sub.5 is a group of the formula —(C.sub.jH.sub.2jO).sub.k—R.sub.98, wherein i is 2, 3 or 4, k is, based on a molar average, a number from 0 to 10, and R.sub.98 is selected from the group consisting of alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl, phenyl alkyl, phenyl alkenyl, alkyl phenyl, and alkenyl phenyl, wherein the alkyl and alkenyl groups, either as such or as a part of the aforementioned hydroxyalkyl, hydroxyalkenyl, phenyl alkyl, phenyl alkenyl, alkyl phenyl or alkenyl phenyl groups, contain 6 or more than 6 carbon atoms, and a and b are, based on a molar average, independently of one another, numbers from 1 to 200, with the addition of a catalyst, to temperatures of 160 to 220° C., and then continuing the reaction under reduced pressure at temperatures of from 160 to 240° C.

15. A solution or dispersion comprising one or more polyesters according to claim 1, 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. A solution or dispersion comprising one or more polyesters according to claim 1, in an amount of from 25 to 70 wt.-%, based on the total weight of the solution or dispersion, 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, and butyl polyglycol and mixtures thereof in an amount of from 25 to 75 wt.-% based on the total weight of the solution or dispersion.

17. A polyester according to claim 1, characterized in that it further comprises one or more terminal groups (IV) derived from polyalkyleneglycol monoalkylethers, according to the formula (IV-a)
—O—[C.sub.2H.sub.4—O].sub.c—[C.sub.6—O].sub.d—[C.sub.4H.sub.8—O].sub.e—R.sub.7  (IV-a) wherein R.sub.7 is linear or branched (C.sub.1-C.sub.30)-alkyl, c, d and e are, based on a molar average, independently of one another, numbers from 0 to 200, the sum of c+d+e is from 2 to 500, the [C.sub.2H.sub.4—O], [C.sub.3H.sub.6—O]and [C.sub.4H.sub.8—O] groups of the terminal group (IV-a) may be arranged blockwise, alternating, periodically and/or statistically, preferably blockwise and/or statistically, and either of the [C.sub.2H.sub.4—O], [C.sub.3H.sub.6—O] and [C.sub.4H.sub.8—O] groups of the terminal group (IV-a) can be linked to —R.sub.7 and/or —O.

18. A polyester according to claim 1, characterized in that 1/p MP.sup.+ is selected from the group consisting of H.sup.+, Li.sup.+, Na.sup.+, K.sup.+, ½ Mg.sup.2+, ½ Ca.sup.2+, ⅓ Al.sup.3+, NH.sub.4.sup.+ and R.sup.aR.sup.bR.sup.cR.sup.dN.sup.+, wherein R.sup.a, R.sup.b, R.sup.c and R.sup.d, independently of one another, are H, linear or branched, and wherein in the cations R.sup.aR.sup.bR.sup.cR.sup.dN.sup.+ at least one of R.sup.a, R.sup.b, R.sup.c and R.sup.d is not H.

19. A polyester according to claim 1, characterized in that 1/z X.sup.z− is selected from the group consisting of Cl.sup.−, Br.sup.−, CH.sub.3—SO.sub.4.sup.−, C.sub.2H.sub.5—SO.sub.4.sup.−, HCOO.sup.−, ⅓ C(OH)(COO.sup.−)(CH.sub.2COO.sup.−).sub.2, CH.sub.3—COO.sup.−, NO.sub.3.sup.−, ½ CO.sub.3.sup.2−, ½ SO.sub.4.sup.2−, and ⅓ PO.sub.4.sup.3−.

20. A polyester according to claim 1, characterized in that it further comprises one or more polyalkyleneglycol-derived structure units (V), selected from the formula (V-a)
—O—[C.sub.2H.sub.4—O].sub.f—  (V-a) wherein f is, based on a molar average, a number from 2 to 500.

Description

EXAMPLES

[0116] 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.-%).

Example 1: Polyester Preparation

[0117] General procedure for the preparation of the polyesters of the examples. The polyester synthesis is carried out by the reaction of dimethyl terephthalate (DMT), one or more alkylene glycols, one or more amine ethoxylates and one or more alkyl capped polyalkylene glycols, using sodium acetate (NaOAc) and tetraisopropyl orthotitanate (IPT) as the catalyst system. The synthesis is a two-step procedure. The first step is a trans-esterification and the second step is a polycondensation. Subsequently, the obtained polyester can be quaternised or N-oxidised.

[0118] Key to reactants used in the examples: [0119] AES is alcohol ethoxysulfate [0120] DMT is dimethyl terephthalate [0121] EO is —CH.sub.2CH.sub.2O— or —OCH.sub.2CH.sub.2— [0122] Genamin® C 020 is coconut fatty amine ethoxylate with 2 EO (Clariant) [0123] Genamin® C 050 is coconut fatty amine ethoxylate with 5 EO (Clariant) [0124] Genamin® C 100 is coconut fatty amine ethoxylate with 10 EO (Clariant) [0125] Genamin® C 200 is coconut fatty amine ethoxylate with 20 EO (Clariant) [0126] Genamin® CH 020 is cyclohexylamine ethoxylate with 2 EO (Clariant) [0127] Genamin® 3920 is caprylamine ethoxylate with 2-4 EO (Clariant) [0128] IPT is tetraisopropyl orthotitanate [0129] LAS is linear alkyl benzene sulphonate [0130] MEA is monoethanolamine [0131] mPEG750 is mono hydroxyl-functional polyethylene glycol monomethyl ether, average molecular weight 750 Da (Polyglykol M 750, Clariant) [0132] mPEG1000 is mono hydroxyl-functional polyethylene glycol monomethyl ether, average molecular weight 1 kDa (Polyglykol M 1000, Clariant) [0133] mPEG2000 is mono hydroxyl-functional polyethylene glycol monomethyl ether, average molecular weight 2 kDa (Polyglykol M 2000, Clariant) [0134] mPEG3000 is mono hydroxyl-functional polyethylene glycol monomethyl ether, average molecular weight 3 kDa (Polyglykol M 3000, Clariant) [0135] mPEG4000 is mono hydroxyl-functional polyethylene glycol monomethyl ether, average molecular weight 4 kDa (Polyglykol M 4000, Clariant) [0136] mPEG5000 is mono hydroxyl-functional polyethylene glycol monomethyl ether, average molecular weight 5 kDa (Polyglykol M 5000, Clariant) [0137] NaCS is sodium cumene sulfonate [0138] Na-DTPA is sodium salt of diethylenetriamine-pentaacetate [0139] NaOAc is sodium acetate [0140] NBDEA is N-butyldiethanolamine [0141] NI 7EO is nonionic surfactant alkyl alkoxylate with on average 7 EO [0142] NI 9EO is nonionic surfactant alkyl alkoxylate with on average 9 EO [0143] NMDEA is N-methyldiethanolamine [0144] PG is 1,2-propylene glycol [0145] Texcare® SRN 240 is a nonionic soil release polymer (Clariant) [0146] Texcare® SRN 260 is a nonionic soil release polymer (Clariant) [0147] Tinosan HP100 is 30 wt.-% 4.4′-dichloro 2-hydroxydiphenyl ether dissolved in 1,2- propylene glycol [0148] TSA is Tryptic Soy agar, purchased from Merck

Inventive Polyester Example 1

[0149] 194 g (1 mol) of Dimethyl terephthalate (DMT), 143 g (1.88 mol) of 1,2-propylene glycol (PG), 71.2 g (0.25 mol) of Genamin® C 020, 456 g (0.23 mol) of mPEG2000 and 1.25 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. 1.65 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 polyester is transferred out of the reactor.

Inventive Polyester Example 2

[0150] 103.47 g of polyester example 1 was suspended in 126.1 mL of water at 60° C. To this suspension 10.4 μL (0.0146 mmol) diethylenetriaminepentaacetic acid (DTPA) and 0.2214 g NaHCO.sub.3 (2.6 mmol) were added. Now, 2.52 mL (29.3 mmol, 1.0 eq., based on the amine number of the polyester) H.sub.2O.sub.2 was added dropwise over a period of 30 minutes. The reaction mixture was stirred for 6 hours at 60° C. Based on NMR-analysis additional 2.52 mL H.sub.2O.sub.2 were added dropwise and the reaction mixture was stirred for additional 7 hours at 80° C. After the addition of 0.2232 g NaHCO.sub.3 (2.6 mmol) and further 4 hours at 80° C. the reaction mixture was cooled down and transferred out of the vessel.

Inventive Polyester Example 3

[0151] 100.64 g of polyester example 1 was heated to 60° C. and 2.65 mL (0.028 mol, 0.98 eq. based on the amine number of the polyester) dimethylsulphate was added dropwise over a period of 10 minutes. The reaction mixture was heated to 80° C. and stirred for additional 6 hours. During this period 11.57 g of isopropanol was added to keep the reaction mixture stirrable. After a negative Preussmanntest the reaction mixture was cooled down and the quaternised polyester was transferred out of the vessel.

[0152] Inventive polyester examples 4 to 17 are synthesized according to the general procedure as described above for inventive polyester example 1 with monomer type and dosage described below (see Table 1-1).

TABLE-US-00001 TABLE 1-1 Inventive polyester examples 4 to 17 Inventive mPEG polyester DMT [molecular mPEG PG amine ethoxylate IPT NaOAc example [g] weight] [g] [g] Type [g] [μL] [g] 4 97 2000 250 62 Genamin ® 3920 19 200 0.50 5 97 2000 250 55 Genamin ® 3920 38 200 0.50 6 97 2000 250 62 Genamin ® CH 020 19 200 0.50 7 31 2000 72 23 Genamin ® C 020 5 75 0.19 8 28 2000 65 20 Genamin ® C 020 16 75 0.19 9 78 2000 182 53 Genamin ® C 020 60 200 0.50 10 28 2000 66 21 Genamin ® C 050 15 75 0.19 11 27 2000 62 19 Genamin ® C 100 22 75 0.19 12 24 2000 56 17 Genamin ® C 200 33 75 0.19 13 30 750 67 22 Genamin ® C 020 11 75 0.19 14 30 1000 68 22 Genamin ® C 020 11 75 0.19 15 29 3000 69 21 Genamin ® C 020 11 75 0.19 16 29 4000 69 21 Genamin ® C 020 11 75 0.19 17 29 5000 69 21 Genamin ® C 020 11 75 0.19

[0153] Comparative polyester examples 1 to 4 are synthesized according to the general procedure as described above for inventive polyester example 1 with monomer type and dosage described below (see Table 1-2).

TABLE-US-00002 TABLE 1-2 Comparative polyester examples 1 to 4 mPEG Comparative DMT [molecular mPEG PG amine ethoxylate IPT NaOAc polyester [g] weight] [g] [g] Type [g] [μL] [g] 1 31 2000 73 21 NMDEA 10 75 0.19 2 31 2000 73 21 NBDEA 13 75 0.19 3 31 2000 73 23 NMDEA 5 75 0.19 4 31 2000 73 23 NBDEA 7 75 0.19

Example 2: Polyester Structure and Smell

[0154] The structure of the inventive and comparative polyesters of Table 2 below can be described using the following formula.

##STR00009##

[0155] The values of p and q mentioned in Table 2 below are obtained by NMR measurements.

TABLE-US-00003 TABLE 2 Polyester structures and odour R.sub.5 p q Polyester odour Comparative methyl 5.9 1.5 Strong amine smell polyester 1 Comparative n-butyl 4.3 3.2 amine smell polyester 2 Comparative methyl 7.0 0.6 Strong amine smell polyester 3 Comparative n-butyl 6.2 1.5 amine smell polyester 4 Inventive cocoyl 3.5 4.0 No obvious amine smell polyester 9 Inventive cocoyl 5.1 2.1 No obvious amine smell polyester 1 Inventive n-octyl 5.8 1.0 No obvious amine smell polyester 4 Inventive cyclohexyl 5.6 1.3 No obvious amine smell polyester 6

[0156] It was found that inventive polyesters have no obvious amine smell, which makes them suitable for use in detergent compositions as malodor control polyesters. The comparative polyesters are not suitable for use as malodor control polyesters because of their amine smell.

Example 3: Method of Evaluating Malodor and Freshness Benefit

[0157] Malodor and freshness of compositions comprising inventive or comparative polyesters are evaluated using the method described below.

[0158] Step 1: ‘Strip’ Wash

[0159] The desired range of fabrics for test are sourced from commercial suppliers. On receipt they are ‘strip’ washed twice to remove finishes applied by the garment/fabric manufacturer. Typically, a detergent which does not contain inventive polyester is used. Example detergent compositions not containing inventive polyester are composition A, composition B and composition C.

[0160] Step 2: Pre-Conditioning

[0161] After ‘strip’ washed, the test fabrics are preconditioned for additional 4 cycles using composition comprising inventive polyester and composition not comprising inventive polyester. If the weight of the test fabric is lower than the standard load size of the washing machine, additional ballast may be added into the washing machine and washed together with the test fabrics.

[0162] Step 3: Malodour Development

[0163] After pre-conditioning, standard size swatches (17.8 cm×17.8 cm) are cut from the preconditioned fabrics, and labelled, to provide 2 repetitions. The fabric swatches are then washed together with a series of malodour generation fabrics, including around 2.2 kg consumer dirty garment (sourced from consumer), 4 pieces WfK SBL 2004 sheets (sourced from Center for Testmaterials B.V.), 2 pieces 45 cm×45 cm CFT PC-S-33 Sebum/Carbon Black (sourced from Center for Testmaterials B.V.) sheets, 6 ml Technical (Artificial) Body Soil (sourced from Lubrizol) applied on 10 cm×5 cm polycotton fabric. If the weight of the test fabric and malodour generation fabric is lower than the standard load size of the washing machine, additional ballast may be added into the washing machine and washed together with the test fabrics. The test swatches are then left to allow malodour to develop after wash for further panellist assessment.

[0164] The fabric swatches with different pre-conditioning are washed all together in a single washing machine, using a detergent which does not contain inventive polyester or other soil release polyester. After wash, the swatches are left overnight in the washing machine, then removed from the washing machine into individual glass jars and stored for additional 3 days before panellist assessment.

[0165] Step 4: Malodour and Freshness Assessment.

[0166] The fabric swatches after malodour development are evaluated via a panel of 3 expert human graders, who grade each swatch for malodour intensity on a Monadic scale. The following 0-10 scales are used for malodour assessment (see Table 3-1). Malodour difference versus reference is usually reported. The malodour results given in the tables below are calculated as follows: malodour value of the reference minus malodour value of the sample.

TABLE-US-00004 TABLE 3-1 Scales used for malodour assessment Scale Description 0 No malodor 2 I think there is malodor 4 There is definitely malodor 6 Strong malodor 8 Very strong malodor 10 Eye-watery strong malodor

[0167] The freshness is evaluated against a reference using the following scales (see Table 3-2). The freshness results given in the tables below are calculated as follows: freshness value of the sample minus freshness value of the reference.

TABLE-US-00005 TABLE 3-2 Scales used for freshness evaluation Scale Description 0 No difference in freshness +2.5 Slightly more freshness +5 Clearly more freshness +7.5 Very clearly more freshness

Example 4. Malodor Benefit

[0168] Malodor Benefit of Inventive Polyester Versus No Polyester:

[0169] Liquid detergent composition containing inventive polyester example 1 (composition 1), 2 (composition 2), 3 (composition 3) and liquid detergent composition A comprising no inventive polyester are prepared by means known to those of ordinary skill in the art by mixing the listed ingredients (see Table 4-1).

TABLE-US-00006 TABLE 4-1 Compositions 1, 2 and 3 comprising inventive polyester and composition A comprising no inventive polyester Composition Composition Composition Composition 1 [wt.-%] 2 [wt.-%] 3 [wt.-%] A [wt.-%] LAS 13.4 13.4 13.4 13.4 AES 9.7 9.7 9.7 9.7 NI 7EO 6.4 6.4 6.4 6.4 Fatty Acid 3.0 3.0 3.0 3.0 Citric Acid 3.7 3.7 3.7 3.7 PEG-PVAc 1.5 1.5 1.5 1.5 graft polymer.sup.1 Amphiphilic 1.0 1.0 1.0 1.0 cleaning polymer.sup.2 Solvents 12.0 12.0 12.0 12.0 Inventive 0.2 — — — polyester 1 Inventive — 0.2 — — polyester 2 Inventive — — 0.2 — polyester 3 Enzymes.sup.3 0.06 0.06 0.06 0.06 Perfume 1.4 1.4 1.4 1.4 Water/minors Balance Balance Balance Balance .sup.1PEG-PVAc graft polymer is a polyvinyl acetate grafted polyethylene oxide copolymer having polyethylene oxide backbone and multiple polyvinyl acetate side chains. .sup.2bis(HOCH.sub.2CH.sub.2(OCH.sub.2CH.sub.2).sub.n)(CH3)N.sup.+—C.sub.xH.sub.2xN.sup.+—(CH3)bis((CH.sub.2CH.sub.2O).sub.nCH.sub.2CH.sub.2OH), wherein n = from 20 to 30, and x = from 3 to 8, or sulphated or sulphonated variants thereof. .sup.3Including protease, mannanase, amylase, pectate lyases

[0170] The malodour and freshness of compositions 1, 2 and 3 (comprising inventive polyester) and composition A (not comprising inventive polyester) were evaluated using the method as described above. The malodour and freshness results are summarized in Table 4-2 below. Clear improvement on malodour and freshness can be observed from inventive polyesters.

TABLE-US-00007 TABLE 4-2 Malodour and freshness results Composition Composition Composition Composition fabric 1 2 3 A Malodor Cotton +1.0s +0.8s 0 Reference versus Polycotton +0.8s +1.8s +0.2 Reference composition A polyester +0.5 +0.3s −0.2 Reference Freshness Cotton 0 0 −0.4 Reference versus Polycotton +2.1s +4.2s +0.8s Reference composition A Polyester +1.7s +2.1s +1.7s Reference s: statistically significant

[0171] Malodor benefit of inventive polymer versus comparative polymer (Texcare© SRN 240)

[0172] Liquid detergent composition containing inventive polyester 1 (composition 4) and liquid detergent compositions B and C not comprising inventive polyester are prepared by means known to those of ordinary skill in the art by mixing the listed ingredients (see Table 4-3).

TABLE-US-00008 TABLE 4-3 Composition 4 comprising inventive polyester and compositions B and C not comprising inventive polyester Composition Composition Composition 4 [wt.-%] B [wt.-%] C [wt.-%] LAS 8.5 8.5 8.5 AES 5.3 5.3 5.3 NI 7EO 2.8 2.8 2.8 NI 9EO 1.5 1.5 1.5 Fatty Acid 2.9 2.9 2.9 Citric Acid 5.5 5.5 5.5 PEG-PVAc graft polymer.sup.1 1.1 1.1 1.1 Amphiphilic cleaning polymer.sup.2 0.6 0.6 0.6 Solvents 5.3 5.3 5.3 Perfume 1.4 1.4 1.4 Enzyme System 0.1 0.1 0.1 Inventive polyester 1 1.0 0 0 Texcare ® SRN 240 0 1.0 0 Water/minors balance Balance Balance .sup.1PEG-PVAc graft polymer is a polyvinyl acetate grafted polyethylene oxide copolymer having polyethylene oxide backbone and multiple polyvinyl acetate side chains. .sup.2bis(HOCH.sub.2CH.sub.2(OCH.sub.2CH.sub.2).sub.n)(CH.sub.3)N.sup.+—C.sub.xH.sub.2xN.sup.+—(CH.sub.3)bis((CH.sub.2CH.sub.2O).sub.nCH.sub.2CH.sub.2OH), wherein n = from 20 to 30, and x = from 3 to 8, or sulphated or sulphonated variants thereof.

[0173] The malodour of composition 4 comprising inventive polyester and compositions B and C not comprising inventive polyester was evaluated using the method as described above. The malodour results are summarized in Table 4-4 below. Clear improvement on malodour can be observed from inventive polyester.

TABLE-US-00009 TABLE 4-4 Malodour results Composition Composition Composition fabric 4 B C Malodor versus Polycotton +1.3 0 Reference composition C Polyester +2.0s +1.25 Reference s: statistically significant

Example 5: Soil Release Performance of Inventive Polyesters

[0174] Liquid detergent compositions containing polyesters of the invention and liquid detergent compositions containing no inventive polyester are prepared by means known to those of ordinary skill in the art by mixing the listed ingredients (see Table 5-1).

TABLE-US-00010 TABLE 5-1 Compositions comprising inventive or no inventive polyester and used for evaluation of cleaning performance Detergent with Detergent with inventive no polyester polyester [wt.-%] [wt.-%] LAS 13.4 13.4 AES 9.7 9.7 NI 7EO 6.4 6.4 Fatty Acid 3.0 3.0 Citric Acid 3.7 3.7 Enzymes 0.06 0.06 PEG-PVAc graft polymer.sup.1 1.5 1.5 Amphiphilic cleaning polymer.sup.2 1.0 1.0 Solvents 12.0 12.0 Inventive polyester 1.0 0 Perfume 1.4 1.4 Water/minors Balance Balance .sup.1PEG-PVAc graft polymer is a polyvinyl acetate grafted polyethylene oxide copolymer having polyethylene oxide backbone and multiple polyvinyl acetate side chains. .sup.2bis(HOCH.sub.2CH.sub.2(OCH.sub.2CH.sub.2).sub.n)(CH.sub.3)N.sup.+—C.sub.xH.sub.2xN.sup.+—(CH.sub.3)bis((CH.sub.2CH.sub.2O).sub.nCH.sub.2CH.sub.2OH), wherein n = from 20 to 30, and x = from 3 to 8, or sulphated or sulphonated variants thereof.

[0175] The detergent compositions 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 5-2).

TABLE-US-00011 TABLE 5-2 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 g/l liquid detergent Soiled Fabric:Liquor Ratio 1:40

[0176] 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 μl 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).

[0177] The soil release performance is shown as an improvement in soil removal of the swatches washed with a composition containing a polyester of the invention (“with additive”) compared with the same composition containing no soil release polyester (“without additive”):

ΔR=R.sub.with additive−R.sub.without additive

[0178] The washing results obtained for the laundry detergent compositions comprising the polyesters of the invention are expressed as ΔR along with the standard deviations (SD) (see Table 5-3).

TABLE-US-00012 TABLE 5-3 Soil release test results Soil release test result Polyester ΔR SD Inventive polyester example 1 14.6 0.9 Inventive polyester example 2 16.7 0.4 Inventive polyester example 3 15.6 0.4 Inventive polyester example 4 11.8 1.6 Inventive polyester example 5 22.2 1.6 Inventive polyester example 6 27.9 3.2 Inventive polyester example 7 30.6 1.9 Inventive polyester example 8 16.8 4.0 Inventive polyester example 10 23.4 2.5 Inventive polyester example 11 18.5 3.2 Inventive polyester example 12 17.1 2.3 Inventive polyester example 14 15.7 2.5 Inventive polyester example 17 20.7 2.8

[0179] The results suggest that inventive polyesters show very good soil release efficacy (see results in Table 5-3 for inventive polyesters 1-8, 10-12, 14 and 17).

Example 6: Method of Measuring Bacteria Adhesion

[0180] Bacteria adhesion benefits of compositions comprising inventive polyester or comparative polyester are evaluated using the method described below.

[0181] Step 1: Preparation

[0182] Detergent solutions for fabric pre-treatment are prepared by adding polyester stock solution comprising inventive polyester or comparative polyester into 1000 ppm solution of base detergent in de-ionized (DI) water. Solution of 1000 ppm base detergent and 5 ppm inventive or comparative polyester are used in this specific test.

[0183] Step 2: Pre-Treat of Fabrics

[0184] 3 pieces of fabric (1 cm disks, polyester or cotton) are sterilized and placed into a 50 ml centrifuge tube using sterilized tweezers, then filled with 30 ml detergent solutions prepared above. After agitating in the centrifuge for 20 minutes at 40 RPM (rounds per minute), the wash liquor was poured out and replaced with sterile DI water and rinsed for 5 minutes.

[0185] The same fabric disks are washed/rinsed following the above process for another 3 times, each time using a freshly made detergent solution prepared following step 1.

[0186] Step 3: Inoculation and Extraction of Bacteria

[0187] The treated fabric disks were placed in 12 well microtitre plate (one disk per individual well) and let dry for 1 hour. 20 μl of the 10.sup.8 cfu/ml bacterial suspension (such as Klebsiella pneumonia) are added into each well that contains a fabric disk and incubated at 32° C. for 20 minutes.

[0188] Then the fabric disks are washed and rinsed again once following the wash/rinse process described in Step 2, using a freshly made detergent solution prepared following Step 1.

[0189] After wash, each fabric disk is moved into labelled vials of neutralizer broth (9 ml) and vortex for 30 seconds at speed setting 7 to extract the bacteria into broth. This suspension is labeled as 1× diluted suspension.

[0190] Take 1 ml of each of above 1× diluted suspension and dilute with another 9 ml of neutralizer broth, the diluted suspension is labeled as 2× diluted suspension.

[0191] Take 1 ml of each of above 2× suspension and dilute with another 9 ml of neutralizer broth, the diluted suspension is labeled as 3× diluted suspension.

[0192] Pipette 100 μl of each 1×, 2×, 3× diluted suspension onto a 55 mm agar plate containing TSA (Tryptic Soy agar, purchased from Merck), thoroughly spread across the plate using a spreader. Incubate the plates overnight at 32° C. Count the number of colonies on each plate, recording “too many too count” (Tmtc) where the mass of bacterial cells have formed a continuous lawn.

[0193] Bacteria Adhesion Test

[0194] Base detergent formulations below are prepared by means known to those of ordinary skill in the art by mixing the listed ingredients for the bacteria adhesion test (see Table 6-1).

TABLE-US-00013 TABLE 6-1 Base detergent formulation active [wt.-%] LAS 10.2 AES 1.4 NI 7EO 6.1 C.sub.12-C.sub.14 alkyl dimethyl amine oxide 0.5 C.sub.12-C.sub.18 Fatty Acid 2.5 Citric acid 1.2 Ethanol 1.7 NaCS 4.4 Na-DTPA 0.18 Alkoxylated Polyethyleneimine.sup.a 1.1 Alkoxylated Polyethyleneimine.sup.b 0.8 MEA 1.3 Tinosan HP100 0.05 Calcium chloride 0.03 Perfume 0.12 Hydrogenated castor oil derivative 0.12 structurant Water/minors Balance .sup.aPolyethylenimine (MW = 600) with 20 ethoxylate groups per —NH on average, .sup.bPolyethylenimine (MW = 600) with 24 ethoxylate groups and 16 propoxylate group per —NH on average.

[0195] The bacteria adhesion of inventive polyesters and comparative polyester (Texcare© SRN 260) are tested according to the method of this Example. Surprisingly, inventive polyesters provide much better bacteria adhesion prevention benefit versus the comparative polyester. Such bacteria adhesion reduction effect is shown for Klebsiella pneumoniae in the following Table 6-2.

TABLE-US-00014 TABLE 6-2 results of bacteria adhesion tests Plate Count (Klebsiella pneumoniae) Polyester 1X 2X 3X Texcare ® Tmtc Tmtc Tmtc SRN260 Inventive Tmtc 97 7 polyester 4 Inventive Tmtc 146 17 polyester 6 Inventive Tmtc 119 15 polyester 1 Inventive Tmtc 139 24 polyester 9