COMPOSITIONS COMPRISING BRANCHED SULFONATED SURFACTANTS

Abstract

Compositions, such as surfactant and/or detergent compositions, that include branched sulfonated surfactants. Related methods.

Claims

1. A surfactant composition comprising: from about 5% to about 75%, by weight of the surfactant composition, of a surfactant system, the surfactant system comprising: (a) a branched surfactant of the formula:
XY wherein X is a hydrophobic branched saturated alkyl moiety, the alkyl moiety comprising: (1) from about 9 to about 18 total carbons, on average, in the moiety; (2) a longest linear carbon chain attached to the Y moiety, the longest linear carbon chain having, from about 8 to about 17 carbon atoms, on average; and (3) one or more, on average, alkyl moieties (branch moieties) branching from the longest linear carbon chain, the branch moieties having from about 1 to about 3 carbon atoms, on average; and wherein Y is a sulfonate moiety; and (b) a non-sulfonated detersive surfactant; wherein the weight ratio of (a):(b) is from about 5:95 to about 95:5.

2. A surfactant composition according to claim 1, wherein the longest linear carbon chain in the -X moiety has from about 10 to about 17 carbons.

3. A surfactant composition according to claim 1, wherein the longest linear carbon chain in the -X moiety has an average number of carbons that is from 12 to 13, from 14 to 15, or from 16 to 17.

4. A surfactant composition according to claim 1, wherein the branch moieties have from about 1 to about 2.5.

5. A surfactant composition according to claim 1, wherein a majority of the branch moieties are methyl groups.

6. A surfactant composition according to claim 1, wherein at least one of the branch moieties is attached directly to a carbon of the longest linear carbon chain located at position 2 or greater, wherein the carbon at position 1 is the carbon of the longest linear carbon chain attached to the -Y moiety.

7. A surfactant composition according to claim 6, wherein at least one of the branch moieties is attached directly to a carbon of the longest linear carbon chain located at a position in the range of from position 2 to position (2), wherein the terminal carbon of the longest linear carbon chain is at positon .

8. A surfactant composition according to claim 1, wherein the X- moiety is not substituted with a sulphonate group.

9. A surfactant composition according to claim 1, wherein at least 30% of the branched surfactant includes branching moieties.

10. A surfactant composition according to claim 1, wherein Y is a non-alkoxylated sulfonate moiety.

11. A surfactant composition according to claim 1, wherein the non-sulfonated detersive surfactant is selected from the group consisting of anionic surfactant, nonionic surfactant, amphoteric surfactant, zwitterionic surfactant, and mixtures thereof.

12. A surfactant composition according to claim 1, wherein the non-sulfonated detersive surfactant is selected from the group consisting of alkyl alkoxylated sulfate surfactant, ethoxylated alcohol surfactant, amine oxide surfactant, quaternary ammonium surfactant, betaine surfactant, and mixtures thereof.

13. A surfactant composition according to claim 1, wherein the surfactant system further comprises alkyl benzene sulfonate surfactant.

14. A surfactant composition according to claim 1, the composition comprising from about 5% to about 50%, preferably from about from about 8% to about 30%, by weight of the surfactant composition, of the surfactant system.

15. A surfactant composition according to claim 1, the composition further comprising at least one detergent adjunct.

16. A surfactant composition according to claim 15, wherein the at least one detergent adjunct is selected from the group consisting of fatty acids and/or salts thereof, enzymes, encapsulated benefit agents, soil release polymers, hueing agents, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzyme stabilizers, catalytic materials, bleaching agents, bleach catalysts, bleach activators, polymeric dispersing agents, soil removal/anti-redeposition agents, polymeric dispersing agents, polymeric grease cleaning agents, brighteners, suds suppressors, dyes, hueing agents, perfume, structure elasticizing agents, fabric softeners, carriers, fillers, hydrotropes, solvents, anti-microbial agents and/or preservatives, neutralizers and/or pH adjusting agents, processing aids, opacifiers, pearlescent agents, pigments, anti-corrosion agents, anti-tarnishing agents, and mixtures thereof.

17. A surfactant composition according to claim 1, wherein the surfactant composition is a hard surface cleaning composition or a fabric care composition.

18. A process of treating a fabric, the process comprising the step of contacting a fabric with the composition of claim 1, preferably in the presence of water.

19. A process of making a surfactant composition, the process comprising the steps of: providing surfactants (a) and (b) as listed below, where (a) is a branched surfactant of the formula:
XY wherein X is a hydrophobic branched alkyl moiety, the alkyl moiety comprising: (1) from about 9 to about 18 total carbons, on average, in the moiety; (2) a longest linear carbon chain attached to the Y moiety, the longest linear carbon chain having from about 8 to about 17 carbon atoms, on average; and (3) one or more alkyl moieties (branch moieties) branching from the longest linear carbon chain, the branch moieties having from about 1 to about 3 carbon atoms, on average; and wherein Y is a sulfonate moiety; and where (b) is a non-sulfonated detersive surfactant; and combining (a) and (b) in a weight ratio of from about 5:95 to about 95:5.

20. A process of making a surfactant composition according to claim 30, the process further comprising the step of combining at least one detergent adjunct with (a) and/or (b) to form the surfactant composition.

Description

EXAMPLES

[0247] The examples provided below are intended to be illustrative in nature and are not intended to be limiting. Ingredients are provided as weight percent of the composition, unless indicated otherwise.

Synthesis Example 1

Synthesis of Branched C12/13 Alkyl Chloride from C23 Alcohol

[0248] A 2 L 3 neck 24/40 RBF is equipped w a thermometer in side neck, reflux condenser in center neck and an addition funnel in side neck. The system is equipped with positive nitrogen pressure inlet at top of addition funnel and outlet at the top of condenser. The gas effluent is run through a 1 L trap which is connected to a caustic bath/acid scrubber which is externally cooled.

[0249] The flask is charged with anhydrous DMF (100 ml) and the contents cooled to 0-10C. To this is added thionyl chloride (357 g, 3 moles) followed by Safol-23 Alcohol (485 g, 2.5 moles) at rate to maintain temperature at 0-10 C. Gas evolution is noted during the last of alcohol addition. The reaction temperature is slowly increased. At 50-60 C gas evolution is noted. The temperature is maintained at 50-60 C until no further gas is evolved (1hr). The temperature is slowly increased until gentle gas evolution is noted at 115-120 C. This temp is maintained for 5 hrs. The reaction is cooled to ambient temperature. 200 ml H.sub.2O is added to the crude reaction over 5 min with rapid stirring. The aqueous phase is separated from the organic. The organic phase is washed with 200 ml saturated aqueous sodium bicarbonate followed by 200 ml 10% aqueous sodium chloride. 452 grams of crude brown organic phase resulted.

[0250] The crude product is distilled through a short path set-up yielding 450 grams of light yellow product oil at 91-94 C & 0.50 Torr. The H and C13-NMR's conformed to product.

Synthesis Example 2

Synthesis of Branched C16/17 Alkyl Chloride from N67 Alcohol

[0251] The procedure in Synthesis Example 1 is followed using anhydrous DMF (75m1), thionyl chloride (238g, 2.0 moles), N67 Alcohol (427 g, 1.7 moles). The final reaction temperature of 130-135 is maintained for 7 hrs. Distillation yielded 330 grams light yellow product oil at 118-125C & 0.3 Torr. The H and C13-NMR's conformed to product.

Synthesis Example 3

Synthesis of Branched C12/13-Sodium Sulfonate from Branched C12/13 Alkyl Chloride

[0252] A 1 gallon Parr reactor is charged with branched C12/13 alkyl chloride (450 g, 2.13 moles) from Synthesis Example 1, anhydrous sodium sulfite (338 g, 2.65 moles) & water (2 L). The reactor is sealed, purged 3150 PSI nitrogen, charged 100 PSI nitrogen and the contents heated to 180 C for 10hrs with maximum stirring (650 RPM). The reactor is cooled and the crude product removed. The crude product is stripped of water.

[0253] H-NMR analysis of the crude product showed the organic portion to be a mixture of 35:65 Safol-23 Alcohol:Na Sulfonate. The crude product is ground and the alcohol is extracted by refluxing in 2L acetone 1 hr, filtering out the crude product and rinsing 2500 ml fresh acetone.

[0254] This extraction procedure is repeated 2 additional times.

[0255] The product is extracted from the crude filter cake using a soxhlet extractor with ethanol for 20 hrs. Stripping and drying of the ethanol extract yielded 395 g white product powder. The H and C13-NMR's conformed to product. The product is determined to be 87.6% active by CAT SO3 titration.

Synthesis Example 4

Synthesis of Branched C16/7-Sodium Sulfonate from Branched C16/17 Alkyl Chloride

[0256] The procedure in Synthesis Example 3 is followed using branched C16/17 alkyl chloride (300 g, 1.2 moles) from Synthesis Example 2, anhydrous sodium sulfite (189 g, 1.5 moles) & water (1.2 L) yielding 141 grams of white product powder. The H and C13-NMR's conformed to product. The product is determined to be 85.3% active by CAT SO3 titration.

Synthesis Example 5

Synthesis of Branched C12 Sodium Sulfonate from Branched C12 Alpha Olefin

[0257] Deoxygenated, deionised water (300 ml), isopropanol (400 ml), mid chain branched C12 alpha olefin (52.1 g, 0.31 mol) and t-butyl perbenzoate (1 g, 0.005 mol) are placed in a 1 litre alkyd flask fitted for reflux and equipped with a hook stirrer, thermometer, and a calibrated high temperature glass pH probe (Radiometer model G202CH), which is connected to a pH meter (Radiometer pH M28)-titrator (Radiometer TTT 11) assembly. An addition tube which protrudes into the flask is connected via a titrator controlled magnetic valve (Radiometer MNVI) to an addition funnel for the bisulphite solution. The whole system is protected from atmospheric oxygen by use of a static nitrogen atmosphere. After the contents of the flask are heated to reflux with stirring an aqueous solution containing 0.36 g ion sodium in a sodium bisulphite to sodium sulphite mole ratio of 7:2 is added to the mixture in sufficient quantity to obtain the desired pH of 7.3. The tendency of the pH to rise during the reaction is countered by addition of more of the bisulphite/sulphite solution until it has all been added. Subsequent control of pH is then effected by addition of sulphur dioxide gas until the reaction system can no longer sustain a pH of 7.3. The reaction is then complete. After the reaction mixture has been allowed to cool unchanged olefin is extracted with light petroleum ether (40-60). The residual aqueous isopropanol layer containing the product is evaporated to give a white solid which is dried in a vacuum oven at 80 C. The reaction product comprises 85% by weight sodium branched dodecyl-1-sulfonate and 15% by weight disodium branched dodecyl-2-sulphinate-1-sulphonate 15 w/w.

Example 1

Branched Sulfonate Surfactant and AES

[0258] To demonstrate the benefits of surfactant systems including the branched alkyl sulfonates of the present disclosure vs. reference surfactant systems, Dynamic Oil-water Interfacial Tension (DIFT) analysis is performed. Samples having surfactant systems as shown in Table 1 are prepared as follows.

[0259] Samples containing a total at 200 ppm surfactant in water with a hardness (3:1 Ca:Mg) of 7 grains per gallon (gpg) and at pH 8.2-8.5 at 22 C. are prepared with compositions specified in the table below. Each sample is analyzed as described above. Density settings for 22 C. are set at 0.917 g/ml for Canola Oil and 0.998 g/ml for aqueous surfactant phase. The density of the aqueous surfactant phase is assumed to be the same as water since it is a dilute solution. 1.50 mL of 1 (wt/wt) surfactant solution in deionized water is added to a 100 ml volumetric flask to which 3.5 mL of deionized water is added and the volumetric flask is then filled to the mark with a hardness solution of 7.37 gpg water, (3:1 CaCl2:MgCl2 solution) and mixed well.

[0260] The solution is transferred to a beaker and the pH is adjusted to 8.2-8.5 by adding a few drops of 0.1N NaOH or 0.1N H.sub.2SO4. The solution is then loaded into the tensiometer measurement cell and analyzed. The total time from mixing the surfactant solution with the hardness solution to the start of analysis is five minutes.

[0261] The surfactant systems and DIFT values for each sample are shown below in Table 1. Each group (A-F) of the data set includes surfactants in a different ratio. Percentages are provided by combined weight of the listed surfactants in the sample (i.e., by weight of the surfactant system). Based on instrument reproducibility, Min IFT differences greater than 0.1 mN/m are significant for interfacial tension values of less than 1 mN/m. For higher values of Min IFT, differences are 10% are greater than are significant. Typically, surfactant systems characterized by lower Min IFT values correlate with superior grease cleaning performance.

TABLE-US-00001 TABLE 1 Min IFT Sam- % N67- % N67- % % (mN/m), Group Ratio ple Sulfate.sup.a Sulfonate.sup.b LAS.sup.c AES.sup.d 1 uL/min A 100:0 1 100 0 0 0 0.360 2 0 100 0 0 0.981 3 0 0 100 0 1.065 4 0 0 0 100 2.010 B 90:10 5 90 0 0 10 0.270 6 0 90 0 10 0.708 7 0 0 90 10 0.759 C 70:30 8 70 0 0 30 0.340 9 0 70 0 30 0.333 10 0 0 70 30 0.478 D 50:50 11 50 0 0 50 0.361 12 0 50 0 50 0.289 13 0 0 50 50 0.495 E 30:70 14 30 0 0 70 0.629 15 0 30 0 70 0.583 16 0 0 30 70 0.832 F 10:90 17 10 0 0 90 1.265 18 0 10 0 90 1.481 19 0 0 10 90 1.497 .sup.aN67-Sulfate is mid-branched alkyl sulfate as disclosed in U.S. Pat. No. 6,020,303 and U.S. Pat. No. 6,060,443. N67 alcohol is obtained from Shell Chemicals, Houston, TX, USA. .sup.bAccording to Synthesis Example 4 .sup.cLAS is linear alkylbenzenesulfonate having an average aliphatic carbon chain length C.sub.11-C.sub.12 supplied by Stepan, Northfield, Illinois, USA. .sup.dAES is C.sub.12-15 alkyl ethoxy (1.8) sulfate, supplied by Shell Chemicals, Houston, TX, USA.

[0262] The results provided in Table 1 show that surfactant systems that include N67-Sulfonate in combination with AES in ratios from 90:10 to 10:90 are characterized by a lower minimum interfacial tension compared to similar surfactant systems that include LAS and AES. The results in Table 1 also show that surfactant systems that include N67-Sulfonate in combination with AES at particular ratios (70:30 to 30:70) are characterized by a lower minimum interfacial tension compared to similar surfactant systems that include N67-Sulfate and AES.

Example 2

Branched Sulfonate Surfactant and Nonionic Surfactant

[0263] Samples having surfactant systems shown in Table 2 are prepared and analyzed as described in Example 1. The surfactant systems and DIFT values for each sample are shown below in Table 2. Each group (G-J) of the data set includes surfactants in a different ratio.

[0264] Percentages are provided by combined weight of the listed surfactants in the sample. Based on instrument reproducibility, Min IFT differences greater than 0.1 mN/m are significant for interfacial tension values of less than 1 mN/m. Typically, surfactant systems characterized by lower Min IFT values correlate with superior grease cleaning performance Note that Samples 20 and 21 are the same as Samples 1 and 2 in Table 1.

TABLE-US-00002 TABLE 2 Min IFT Sam- % N67- % N67- % Nonionic (mN/m), Group Ratio ple Sulfate.sup.a Sulfonate.sup.b (NI 24-7.sup.e) 1 uL/min G 100:0 20 100 0 0 0.360 21 0 100 0 0.981 22 0 0 100 7.915 H 70:30 23 70 0 30 0.806 24 0 70 30 0.528 I 50:50 25 50 0 50 1.213 26 0 50 50 0.740 J 30:70 27 30 0 70 1.598 28 0 30 70 1.481 .sup.aN67-Sulfate is mid-branched alkyl sulfate as disclosed in U.S. Pat. No. 6,020,303 and U.S. Pat. No. 6,060,443. N67 alcohol is obtained from Shell Chemicals, Houston, TX, USA. .sup.bAccording to Synthesis Example 4 .sup.eNI 24-7 is C.sub.12-14 with an average degree of ethoxylation of 7 supplied by Huntsman, Salt Lake City, Utah, USA

[0265] The results provided in Table 2 show that surfactant systems that include N67-Sulfonate and nonionic surfactant (NI 24-7) in ratios from 70:30 to 30:70 are characterized by a lower minimum interfacial tension compared to similar surfactant systems that include N67-Sulfate and nonionic surfactant.

Example 3

Branched Sulfonate Surfactant, Amphoteric Surfactant, and Cationic Surfactant

[0266] Samples containing a total at 200 ppm surfactant in water with a hardness (3:1 Ca:Mg) of 3 grains per gallon (gpg) and at pH 8.2-8.5 at 22 C. are prepared with compositions specified in Table 3 below. Each sample is analyzed as described above. Density settings for 22 C. are set at 0.917 g/ml for Canola Oil and 0.998 g/ml for aqueous surfactant phase. The density of the aqueous surfactant phase is assumed to be the same as water since it is a dilute solution. 1.50 mL of 1 (wt/wt) surfactant solution in deionized water is added to a 100 ml volumetric flask to which 3.5 mL of deionized water is added and the volumetric flask is then filled to the mark with a hardness solution of 3.16 gpg water, (3:1 CaCl2:MgCl2 solution) and mixed well. The solution is transferred to a beaker and the pH is adjusted to 8.2-8.5 by adding a few drops of 0.1N NaOH or 0.1N H2504. The solution is then loaded into the tensiometer measurement cell and analyzed. The total time from mixing the surfactant solution with the hardness solution to the start of analysis is five minutes.

TABLE-US-00003 TABLE 3 % C.sub.12-14 % Lauryl % N67- dimethyl Trimethyl Sulfate.sup.a % N67- Amine Ammonium Min IFT Group Ratio Sample (comp.) Sulfonate.sup.b Oxide.sup.f Chloride.sup.g (mN/m), 1 uL/min K 100:0 29 100 0 0 0 0.218 30 0 100 0 0 0.778 31 0 0 100 0 1.225 32 0 0 0 100 11.655 L 75:25 33 75 0 25 0 1.450 34 0 75 25 0 0.886 35 75 0 0 25 2.558 36 0 75 0 25 1.243 .sup.aN67-Sulfate is mid-branched alkyl sulfate as disclosed in U.S. Pat. No. 6,020,303 and U.S. Pat. No. 6,060,443. N67 alcohol is obtained from Shell Chemicals, Houston, TX, USA. .sup.bAccording to Synthesis Example 4. .sup.fC.sub.12-14 dimethyl Amine Oxide is supplied by Procter & Gamble Chemicals, Cincinnati, USA .sup.gLauryl Trimethyl Ammonium Chloride is supplied by Evonik, Essen, Germany

[0267] The results show that in combination with an amphoteric surfactant, such as C.sub.12-14 dimethyl amine oxide, or a cationic surfactant, such as Lauryl Trimethyl Ammonium Chloride, compositions comprising N67-Sulfonate have a lower minimum interfacial tension than compositions having N67-Sulfate.

Example 4

Chemical Stability of Branched Sulfonates

[0268] To demonstrate the chemical stability of the benefits of the branched alkyl sulfonates of the present disclosure vs. reference surfactants, a chemical stability test is performed. In this test, a 25% active surfactant concentrates of C23 branched sulfate and C23 branched sulfonate, each derived from Safol 23 alcohol (ex Sasol) are created. The pH of the 25% surfactant concentrates are both adjusted to pH 8 using citric acid. The samples are divided in two and one portion of each sample is stored in an oven at 80 C. for 48 hours. Both samples are visually clear and isotropic at 80 C., indicating that they are in the micellar phase. Dynamic Oil-water Interfacial Tension (DIFT) analysis is performed on all four samples.

[0269] Samples containing a total at 400 ppm surfactant in water with a hardness (3:1 Ca:Mg) of 7 grains per gallon (gpg) and at pH 8.2-8.5 at 22 C. are prepared with compositions specified in the table below. Each sample is analyzed as described above. Density settings for 22 C. are set at 0.917 g/ml for Canola Oil and 0.998 g/ml for aqueous surfactant phase. The density of the aqueous surfactant phase is assumed to be the same as water since it is a dilute solution. 1.50 mL of 1 (wt/wt) surfactant solution in deionized water is added to a 100 ml volumetric flask to which 3.5 mL of deionized water is added and the volumetric flask is then filled to the mark with a hardness solution of 3.16 gpg water (3:1 CaCl2:MgCl2 solution) and mixed well. The solution is transferred to a beaker and the pH is adjusted to 8.2-8.5 by adding a few drops of 0.1N NaOH or 0.1N H.sub.2SO4. The solution is then loaded into the tensiometer measurement cell and analyzed. The total time from mixing the surfactant solution with the hardness solution to the start of analysis is approximately five minutes. The Min IFT value obtained at this time is the fresh measurement. Samples are then stored for forty-eight hours at 80 C. to simulate long-term and/or stressed storage conditions, and Min IFT is measured again. Results are shown below in Table 4.

[0270] Based on instrument reproducibility, Min IFT differences greater than 0.1 mN/m are significant for interfacial tension values of less than 1 mN/m. For higher values of Min IFT, differences are 10% are greater than are significant. Typically, surfactant systems characterized by lower Min IFT values correlate with superior grease cleaning performance.

TABLE-US-00004 TABLE 4 Min IFT Surfactant (mN/m), Sample (25 wt % active) 1 uL/min 37 Branched C23 sulfate.sup.h (fresh) 2.978 (comp.) 38 Branched C23 sulfate.sup.h (after 48 hrs at 80 C.) 12.216 (comp.) 39 Branched C23 sulfonate.sup.i (fresh) 8.038 40 Branched C23 sulfonate.sup.i (after 48 hrs at 80 C.) 8.589 .sup.hBranched sulfate derived from Safol 23 alcohol, obtained from Sasol North America Houston, TX, USA .sup.iAccording to Synthesis Example 3

[0271] The results in Table 4 show that the Min IFT of the Branched C23 Sulfate significantly increases after heating while the Min IFT of the Branched C23 Sulfonate does not change as significantly by comparison. Without being bound by theory, it is believed that the Branched C23 Sulfate is less chemically stable upon heating and is more susceptible to hydrolysis than the Branched C23 Sulfonate. This indicates that product compositions formulated with branched sulfonates according to the present disclosure are likely to be more stable and maintain a more consistent performance profile and/or stability upon transport/storage over time compared to comparable formulations that include branched sulfates. It is expected that this stability difference will hold true at higher surfactant concentrations as well (e.g, in concentrated compositions comprising approx. 95wt% branched sulfonate surfactant).

Example 5

Heavy Duty Liquid Laundry Detergent Compositions

[0272] Heavy duty liquid laundry detergent compositions are made by mixing together the ingredients listed in the proportions shown in Table 5.

TABLE-US-00005 TABLE 5 Raw Material A B C D E F G H I J K L Branched Sulfonate 6.9 6.7 1.9 2.6 16.9 4.8 7.6 3.4 1.2 4.4 7.9 3.5 AES 11.2 14.6 7.7 4.8 13.3 7.2 1.4 7.4 7.4 14.6 4.8 7.0 LAS 0.0 2.2 0.0 7.9 0.0 4.8 2.5 1.1 3.7 4.4 2.6 3.5 AE 0.0 0.0 0.0 4.8 8.7 4.7 6.1 0.2 0.7 3.7 4.8 7.0 C.sub.12-14 dimethyl Amine 0.7 2.0 0.6 0.5 1.2 0.0 0.5 0.0 0.5 0.9 0.0 0.0 Oxide Lauryl Trimethyl 0 0 0 0.25 0 0.5 0 1 0 0 0 0 Ammonium Chloride Sodium formate 2 0.09 1.2 0 1.6 0 0.2 1.6 0.09 1.2 0 1.6 Calcium formate 0 0 0 0.04 0 0.2 0 0.1 0 0 0.04 0 Calcium Chloride 0.01 0.08 0 0 0 0 0.001 0.01 0.08 0 0 0 Monoethanolamine 1.4 1 4 0.5 0 To 2 1.4 1 2.6 0.5 0.5 pH 8.2 Diethylene glycol 5.5 0 4.1 0 0.7 0 0 3 0 2 0 0 Chelant 0.15 0.15 0.11 0 0.5 0.11 0.8 0.15 0.15 0.11 0.07 0.15 Citric Acid 2.5 3.96 1.88 1.98 0.9 2.5 0.6 2.5 4 0 1.98 1.7 Fatty Acid 0.8 3.5 0.6 0.99 1.2 0 15 0.76 2.6 2.6 0.7 0.7 Borax 1.43 2.1 2 0.75 0 1.07 0 1.43 2.1 1.1 0.75 2.1 Ethanol 1.54 2 1.15 0.89 0 3 7 1.54 2 1.15 0.89 2 Ethoxylated 0 1.4 0 3 0 0 0.8 0 2 0 0 1 Polyethylenimine Zwitterionic 2.1 0 0.7 1.6 0.3 1.6 0 0.6 0.6 0 0.6 0 ethoxylated quaternized sulfated hexamethylene diamine PEG-PVAc Polymer 0.1 0.2 0 4 0.05 0 1 1.1 1.1 1.1 2.2 0 Grease Cleaning 1 2 0 0 1.5 0 0 0 4 0 0 1 Alkoxylated Polyalkylenimine Polymer Soil Release Agent 0 0 1 2 0 1.5 0 0 0.5 0 0 1 1,2-Propanediol 0 2.6 0 3.3 0.5 2 8 0 6.6 0 3.3 4 Sodium Cumene 0 0 0.5 1 5 0 0 2 0 0.5 1 0 sulphonate Fluorescent 0.2 0.1 0.05 0.3 0.15 0.3 0.2 0.2 0.1 0 0.3 0.02 Brightener Hydrogenated castor 0.1 0 0.4 0 0 0 0.1 0.1 0 0.4 0 0 oil derivative structurant Perfume 1.6 1.1 1 0.1 0.9 1.5 1.6 1.6 1.1 1 0.1 0.1 Core Shell Melamine- 0.5 0.05 0 0.02 0.1 0.05 0.1 0.5 0.05 0 0.02 0 formaldehyde encapsulate of perfume Protease (40.6 mg 0.8 0.6 0 0.9 0.7 0.2 1.5 0.01 0.6 0.7 0.9 0.9 active/g) Mannanase: (25 mg 0.07 0.05 0 0.06 0.04 0.001 0.1 0.07 0.05 0 0.06 0.07 active/g) Amylase: (15 mg 0.3 0 0.3 0.1 0 0.6 0.01 0.3 0 0.3 0.1 0.3 active/g) Xyloglucanase (20 mg 0.2 0.1 0 0 0.05 0.01 0.2 0.2 0.1 0 0 0 active/g) Lipase: (18 mg 0.4 0.2 0.3 0.1 0.2 0 0 0.4 0.001 0.3 0.1 0 active/g) Suds Suppressor 0.21 0 0.21 0 0 0 0 0.21 0 0.21 0 0.1 Hueing Agent 0 0 0 0 0.05 0 0 1 0 0 0 0.001 *Water, dyes & Balance minors

[0273] 14652M 49

Example 6

Compact/Unit Dose Compositions

[0274] Compact or unit dose laundry detergent formulations are made by mixing together the ingredients listed in the proportions shown in Table 6. The formulations may be encapsulated in a water-soluble film, such as M8630 (ex MonoSol LLC) to form a unit dose article. Such unit dose articles can comprise one or multiple compartments.

TABLE-US-00006 TABLE 6 Raw Material M N O P Q R Branched Sulfonate 18.0 24.0 5.0 4.0 6.0 12.0 AE 14.0 2.0 14.0 2.0 1.0 2.0 LAS 0.0 0.0 14.0 14.5 17.0 12.0 AES 9.0 15.0 8.0 7.5 16.0 14.0 Citric Acid 2.0 0.6 1.6 1.6 0.6 0.6 Fatty Acid 4.0 10.0 4.5 16.0 4.5 4.5 Enzymes 1.0 0.5 0.8 0.01 2.0 1.5 Ethoxylated 1.4 1.4 4.0 7.0 4.0 4.0 Polyethylenimine Chelant 0.6 0.3 2.0 1.2 3.0 3.0 PEG-PVAc Polymer 4.0 2.5 1.0 2.5 1.5 1.5 Fluorescent Brightener 0.2 0.4 0.3 0.3 0.1 0.3 1,2 propanediol 10.0 15.0 18.0 14.8 13.0 13.8 Glycerol 13.0 4.0 6.1 6.1 6.1 6.1 Monoethanolamine 9.8 10.0 6.7 8.0 9.8 9.8 TIPA 2.0 Sodium Cumene 2.0 2.0 sulphonate Cyclohexyl dimethanol 2.0 Water 12.0 10.0 9.0 10.0 10.0 10.0 Structurant 0.1 0.14 0.14 0 0.2 0.14 Perfume 0.2 1.9 1 1.9 1.9 1.9 Hueing Agent 0 0.1 0.001 0.0001 0 0 Buffers To pH 8.0 (monoethanolamine) Solvents (1,2 To 100% propanediol, ethanol) All enzyme levels are expressed as % enzyme raw material.

Example 7

Granular Laundry Detergent Compositions

[0275] Granular laundry detergent compositions are made by mixing together the ingredients listed in the proportions shown in Table 7.

TABLE-US-00007 TABLE 7 Ingredient S T U V W X Y Z AA AB AC AD AE Branched Sulfonate 2 2 0.5 20 5 9 1 7.1 0.5 10 7.5 2 5 LAS 24 6 20 0 15 2 8 7.1 5 1 0 7.5 2 AES 1.5 1 0.9 0 3 0.9 0 4.8 1 5 4 4 0 AS 0 1 2 0 1 0 1 0 1 0 0 0 0 AE 0.5 0 0 2 1 4 2.2 0 2.2 0 1 0.5 6.5 C.sub.10-12 Dimethyl- hydroxyethylammonium 0 0 0 0 0 0 0.5 1 4 1 0 0 0 chloride C.sub.12-14 Dimethyl- 2 0.2 1 0.6 0 0 0 0 0 0 0 0 0 hydroxyethylammonium chloride Sodium 5 0 4 10 2 0 0 0 0 0 0 0 0 tripolyphosphate Crystalline layered 0 0 0 0 0 0 4 0 5 0 10 0 0 silicate (Na.sub.2Si.sub.2O.sub.5) Silicate 2R 0 0 0 0 0 0 2 0 1 0 10 0 0 (SiO.sub.2:Na.sub.2O at ratio 2:1) 1.6R Silicate 10 5 2 3 3 5 0 0 0 0 0 0 0 (SiO.sub.2:Na.sub.2O at ratio 1.6:1) TAED 0 3.2 2 4 1 0 0 3.2 2 1 1 0 0 NOBS 0 0 2 0 1 0 0 0 2 0 1 0 0 Percarbonate 0 14.1 15 20 10 0 0 14.1 15 10 10 0 0 Zeolite A 0 1 0 1 4 1 5 0 5 0 2 2 0.5 Sodium carbonate 25 20 25 15 18 30 15 20 4 20 23 30 23 Acrylate Polymer 1 0.5 4 1 1.5 1 1.1 3.7 1 3.7 2.6 3.8 4 Soil release agent 3 0 0 0 0 0 2 0.72 1 0.72 0 0 0 Carboxymethylcellulose 0.5 0 0 0 0 0 0.15 1.4 0.2 2 1 0.5 0.5 PEG-PVAc Polymer 0.1 0.2 0 4 0.05 0 0 0 0 0 0 0 0 Protease (32.89 mg 0.1 0.1 0.1 0.1 0.4 0 0.2 0.2 1 0.15 0.01 0.13 0.13 active/g) Amylase(8.65 mg 0.3 0 0.1 0 0.1 0.1 0.2 0.001 0.2 0.4 0.15 0.15 0.15 active/g) Lipase(18 mg active/ 0.03 0.07 0.3 0.1 0 1 0.05 0.15 0.1 0 0.001 0 0 g) Cellulase(15.6 mg 0 0 0 0 0 0 0 0 0 0.001 0.1 0.1 0.2 active/g) Fluorescent Brightener 0.06 0 0.18 0.4 0.1 0.06 0 0.1 0.2 0 0.3 0 0 Chelant 0.6 2 0.6 0 0.6 0.6 0.2 0.5 2 0 0.2 0.4 0.2 MgSO.sub.4 0.3 1 1 0.5 1 1 0.42 0.42 4 0.42 0.4 0.2 0.4 Perfume 0.1 0.6 0.5 1.6 0.6 0.6 0.1 0.6 0.5 0.6 0.6 0.6 1 Suds suppressor 0.05 0.1 0 0.1 0.06 0.05 0.05 0.1 0 0.1 0.06 0.05 0.05 agglomerate Soap 0.45 0.45 0.45 1 0 0 0.25 0.45 0.45 1 0 0 0 Sulphonated zinc 0.1 0 0.0012 0.01 0.0021 0 0.0007 0.0012 0.0007 0.1 0.001 0 0 phthalocyanine Hueing Agent 0 0 0.0003 0.001 0.01 0.1 0 0.03 0.0001 0.0001 0 0 0.1 Sulfate/Water & Balance Miscellaneous All enzyme levels are expressed as % enzyme raw material.

Example 8

Liquid Bleach & Laundry Additive Detergent Formulations

[0276] Liquid bleach and/or laundry additive detergent compositions are made by mixing together the ingredients listed in the proportions shown in Table 8.

TABLE-US-00008 TABLE 8 Ingredients AF AG AH AI AJ AK Branched Sulfonate 15 5.5 2 5.5 4 10 AES 11.3 6 15.4 12 8 10 LAS 10.6 6 2.6 16 AE 2 Chelant 2.5 1.5 4.0 1,2-propandiol 10 15 Soil release agent 2.0 Ethoxylated Polyethylenimine 1.8 Acrylate Polymer 2.9 Acusol 880 (Hydrophobically 2.0 1.8 2.9 Modified Non-Ionic Polyol) Protease (55 mg/g active) 0.1 0.1 Amylase (30 mg/g active) 0.02 Perfume 0.2 0.03 0.17 0.15 Fluorescent Brightener 0.21 0.15 0.18 Water, other optional to 100% to 100% to 100% to 100% to 100% to 100% agents/components* balance balance balance balance balance balance *Other optional agents/components include suds suppressors, structuring agents such as those based on Hydrogenated Castor Oil (preferably Hydrogenated Castor Oil, Anionic Premix), solvents and/or mica pearlescent aesthetic enhancer. All enzyme levels are expressed as % enzyme raw material.

Example 9

Powder Bleach & Laundry Additive Detergent Formulations

[0277] Powder bleach and/or laundry additive detergent compositions are made by mixing together the ingredients listed in the proportions shown in Table 9.

TABLE-US-00009 TABLE 9 Ingredients AL AM AN AO Branched Sulfonate 1 2 5 10 AES 1 1 LAS 0.5 1 10 AE 0.25 1 2.5 2 Chelant 1 0.5 TAED 10 5 12 15 Sodium Percarbonate 33 20 40 30 NOBS 7.5 5 10 0 Protease (32.89 mg active/g) 0.1 0.1 0.01 0 Amylase - (8.65 mg active/g) 0.3 0 0.001 0 Mannanase (4 mg/g active) 0.2 0.02 Cellulase (15.6 mg/g active) 0.2 0.02 Perfume 0.2 0.03 0.17 Fluorescent Brightener 0.21 0.1 Sodium Sulfate to 100% to 100% to 100% to 100% balance balance balance balance All enzyme levels are expressed as % enzyme raw material.

Example 10

Hand Dish Washing Detergent Formulations

[0278] Liquid bleach and/or laundry additive detergent compositions are made by mixing together the ingredients listed in the proportions shown in Table 10.

TABLE-US-00010 TABLE 10 Level (as 100% active) AP AQ AR AS Sodium alkyl ethoxy sulfate 20.0 (C1213EO0.6S) Sodium alkyl ethoxy sulfate 18.7 10.3 16.7 (C1014EO2S) Branched Sulfonate of Invention 2.9 5.0 8.0 2.7 C.sub.12-14 dimethyl Amine Oxide 7.6 5.35 Cocamido propyl betaine 4.5 6 Lutensol XP80 - 3-propyl 0.45 0.8 heptanol EO8 AE-Neodol 91EO7 0.4 PEI600-EO10-PO7 block polymer 0.3 Sodium Chloride 1.2 1.0 0.8 0.8 Poly Propylene Glycol (MW 2000) 1 0.4 0.8 1.1 Ethanol 2 2.5 5 2 Sodium Hydroxide 0.24 0.2 0.25 0.18 Minors (perfume, preservative, to 100% to 100% to 100% to 100% dye) + water balance balance balance balance pH (@ 10% solution) 9.0 9.0 9.2 8.8

Raw Materials for Examples

[0279] LAS is linear alkylbenzenesulfonate having an average aliphatic carbon chain length C.sub.11-C.sub.12 supplied by Stepan, Northfield, Ill., USA or Huntsman Corp. HLAS is acid form.

[0280] AES is C.sub.12-14 alkyl ethoxy (3) sulfate, C.sub.12-15 alkyl ethoxy (1.8) sulfate or C.sub.14-15 alkyl ethoxy (2.5) sulfate, supplied by Stepan, Northfield, Ill., USA or Shell Chemicals, Houston, Tex., USA.

[0281] AE is selected from C.sub.12-13 with an average degree of ethoxylation of 6.5, C.sub.12-14 with an average degree of ethoxylation of 7, C.sub.14-15 with an average degree of ethoxylation of 7, C.sub.12-14 with an average degree of ethoxylation of 9 or C.sub.9-11 with an average degree of ethoxylation of 7, all supplied by Huntsman, Salt Lake City, Utah, USA or Shell Chemicals, Houston, Tex., USA.

[0282] AS is a C.sub.12-14 sulfate, supplied by Stepan, Northfield, Ill., USA.

[0283] C.sub.10-12 and C.sub.12-14 Dimethylhydroxyethyl ammonium chloride are supplied by Clariant GmbH, Germany.

[0284] C.sub.12-14 dimethyl Amine Oxide is supplied by Procter & Gamble Chemicals, Cincinnati, USA.

[0285] Sodium tripolyphosphate is supplied by Rhodia, Paris, France.

[0286] Zeolite A is supplied by Industrial Zeolite (UK) Ltd, Grays, Essex, UK.

[0287] 1.6R and 2.0R Silicate are supplied by Koma, Nestemica, Czech Republic.

[0288] Sodium Carbonate is supplied by Solvay, Houston, Tex., USA.

[0289] Acrylate Polymer is a polyacrylate molecular weight 4500 or Acrylic Acid/Maleic Acid Copolymer molecular weight 70,000 and acrylate:maleate ratio 70:30, supplied by BASF, Ludwigshafen, Germany.

[0290] PEG-PVAc polymer is a polyvinyl acetate grafted polyethylene oxide copolymer having a polyethylene oxide backbone and multiple polyvinyl acetate side chains. The molecular weight of the polyethylene oxide backbone is about 6000 and the weight ratio of the polyethylene oxide to polyvinyl acetate is about 40 to 60 and no more than 1 grafting point per 50 ethylene oxide units. Available from BASF (Ludwigshafen, Germany).

[0291] Ethoxylated Polyethylenimine is a 600 g/mol molecular weight polyethylenimine core with 20 ethoxylate groups per NH. Available from BASF (Ludwigshafen, Germany).

[0292] Zwitterionic ethoxylated quaternized sulfated hexamethylene diamine is described in WO 01/05874 and available from BASF (Ludwigshafen, Germany).

[0293] Grease Cleaning Alkoxylated Polyalkylenimine Polymer is a 600 g/mol molecular weight polyethylenimine core with 24 ethoxylate groups per -NH and 16 propoxylate groups per -NH. Available from BASF (Ludwigshafen, Germany).

[0294] Carboxymethyl cellulose is Finnfix V supplied by CP Kelco, Arnhem, Netherlands.

[0295] Amylases (Natalase, Stainzyme, Stainzyme Plus) may be supplied by Novozymes, Bagsvaerd, Denmark.

[0296] Lipases (Lipex), Cellulases(Celluclean), Mannanases (Mannaway) and Xyloglycanases (Whitezyme) may be supplied by Novozymes, Bagsvaerd, Denmark.

[0297] Proteases may be supplied by Genencor International, Palo Alto, Calif., USA (e.g. Purafect Prime) or by Novozymes, Bagsvaerd, Denmark (e.g. Liquanase, Coronase).

[0298] Suitable Fluorescent Brighteners are for example, Tinopal TAS, Tinopal AMS, Tinopal CBS-X, Sulphonated zinc phthalocyanine, available from BASF, Ludwigshafen, Germany.

[0299] Chelant is selected from, diethylenetetraamine pentaacetic acid (DTPA) supplied by Dow Chemical, Midland, Mich., USA, hydroxyethane di phosphonate (HEDP) supplied by Solutia, St Louis, Mo., USA; Ethylenediamine-N,N-disuccinic acid, (S,S) isomer (EDDS) supplied by Octel, Ellesmere Port, UK, Diethylenetriamine penta methylene phosphonic acid (DTPMP) supplied by Thermphos, or 1,2-dihydroxybenzene-3,5-disulfonic acid supplied by Future Fuels Batesville, Ark., USA.

[0300] Hueing agent is Direct Violet 9 or Direct Violet 99, supplied by BASF, Ludwigshafen, Germany. Soil release agent is Repel-o-tex PF, supplied by Rhodia, Paris, France.

[0301] Suds suppressor and suds suppressor agglomerate are supplied by Dow Corning, Midland, Mich., USA

[0302] Acusol 880 is supplied by Dow Chemical, Midland, Mich., USA.

[0303] TAED is tetraacetylethylenediamine, supplied under the Peractive brand name by Clariant GmbH, Sulzbach, Germany.

[0304] Sodium Percarbonate and Sodium Carbonate are supplied by Solvay, Houston, Tex., USA.

[0305] NOBS is sodium nonanoyloxybenzenesulfonate, supplied by Future Fuels, Batesville, Ark., USA.

[0306] Sulphonated zinc phthalocyanine is available from BASF (Ludwigshafen, Germany).

[0307] 1,2 propanediol, Monoethanolamine (MEA), Triethanolamine (TEA), Triisopropanolamine (TIPA) and Cyclohexyl dimethanol can be supplied by Dow Chemical Midland, Mich., USA

[0308] Diethylene glycol can be supplied by ME-Global (Dubai, United Arab Emirates)

[0309] Glycerol is supplied by Procter & Gamble Chemicals, Cincinnati, USA.

[0310] Sodium Cumene Sulfonate can be supplied by Stepan, Northfield, Ill., USA

[0311] C.sub.12-18 Fatty Acid can be supplied by Wilmar, Singapore.

[0312] Citric Acid and Ethanol can be supplied by Tate and Lyle, London, England.

[0313] Borax can be supplied by US Borax Valencia, Calif., USA.

[0314] Lauryl Trimethyl Ammonium Chloride can be supplied by Evonik, Essen, Germany.

[0315] Sodium Formate and Calcium Formate can be supplied by Perstorp, Toledo, Ohio, USA.

[0316] Magnesium Sulfate can be supplied by PQ Corporation, Valley Forge, Pa., USA.

[0317] Calcium Chloride can be supplied by Tetra Technologies Woodlands, Tex., USA.

[0318] Crystalline layered silicate (Na.sub.2Si.sub.2O.sub.5) can be supplied as SKS-6 Layer Silicate by Essential Ingredients Lawrenceville, Ga., USA.

[0319] Soap can be supplied as Soap Noodles and can be obtained from KLK, Malaysia.

[0320] Sodium Sulfate can be supplied by Searles Valley Minerals, Overland Park, Kans.

[0321] The dimensions and values disclosed herein are not to be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a dimension disclosed as 40 mm is intended to mean about 40 mm.

[0322] Every document cited herein, including any cross referenced or related patent or application and any patent application or patent to which this application claims priority or benefit thereof, is hereby incorporated herein by reference in its entirety unless expressly excluded or otherwise limited. The citation of any document is not an admission that it is prior art with respect to any invention disclosed or claimed herein or that it alone, or in any combination with any other reference or references, teaches, suggests or discloses any such invention. Further, to the extent that any meaning or definition of a term in this document conflicts with any meaning or definition of the same term in a document incorporated by reference, the meaning or definition assigned to that term in this document shall govern.

[0323] While particular embodiments of the present invention have been illustrated and described, it would be obvious to those skilled in the art that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.