SALTS OF ETHERAMINES AND POLYMERIC ACID

Abstract

The present invention relates to salts of etheramines and polymeric acid, and in particular to salts of etheramines and polycarboxylic acid and their manufacturing process.

Claims

1. (canceled)

2. (canceled)

3. A salt of a hydrophobic etheramine and of a polymeric acid, wherein the hydrophobic etheramine is selected from the group consisting of an etheramine of formula (I), an etheramine of formula (II), ##STR00006## and a mixture of etheramines of formula (I) and formula (II), and wherein R.sub.1-R.sub.12 are independently selected from H, alkyl, cycloalkyl, aryl, alkylaryl, or arylalkyl, at least one of R.sub.1-R.sub.6 and at least one of R.sub.7-R.sub.12 is different from H, A.sub.1-A.sub.9 are independently from each other linear or branched propylene or linear or branched butylene, the sum of x+y is in the range of from 2 to 200, x≧1 and y≧1, and x.sub.1+y.sub.1 is in the range of from 2 to 200, x.sub.1≧1 and y.sub.1≧1.

4. The salt according to claim 3, wherein each of A.sub.1-A.sub.9 is one of a linear or a branched propylene.

5. The salt according to claim 3, wherein R.sub.3 and R.sub.9 are each an ethyl group, R.sub.1, R.sub.2, R.sub.5 R.sub.6, R.sub.7, R.sub.8, R.sub.11, R.sub.12 are each H, and R.sub.4 and R.sub.10 are each a butyl group.

6. A salt of a hydrophobic etheramine and of a polymeric acid, wherein the hydrophobic etheramine is an etheramine of formula (IV), ##STR00007## wherein R═H or ethyl, k=0 or 1, A represents at least one of (a) one of a linear or a branched propylene and (b) one of a linear or a branched butylene group, wherein A may be the same as or different from one another, the sum of x, y and z lies in the range of 3 to 100, x≧1, y≧1 and z≧1.

7. A salt of a hydrophobic etheramine and of a polymeric acid, wherein the hydrophobic etheramine is selected from the group consisting of an etheramine of formula (V), an etheramine of formula (VI), ##STR00008## and a mixture of etheramines of formula (V) and formula (VI) and wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently selected from the group consisting of H and one of a linear or branched alkyl group with 2 to 16 carbon atoms; A.sub.1, A.sub.2, A.sub.3 and A.sub.4 are independently selected from at least one of (a) a linear or branched propylene and (b) one of a linear or branched butylene, the sum of x+y is in the range of 2 to 100 and x≧1 and y≧1.

8. The salt according to claim 7, wherein A.sub.1, A.sub.2, A.sub.3 and A.sub.4 are propylene.

9. The salt according to claim 7, wherein R.sub.1 is a linear alkyl group with 2 to 8 carbon atoms and R.sub.2, R.sub.3 and R.sub.4 are hydrogens.

10. The salt according to claim 7, wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently selected from the group consisting of H, a methyl group and an ethyl group and A.sub.1, A.sub.2, A.sub.3 and A.sub.4 are one of linear or branched butylene.

11. The salt according to claim 10, wherein the polymeric acid is one of a homopolymer of a carboxylic acid or a copolymer of acrylic acid and maleic acid.

12. The salt according to claim 3, wherein the polymeric acid is a polyacrylic acid with a molecular weight (Mw) of from 1,000 g/mol to 1,000,000 g/mol determined by gel permeation chromatography and referring to the free acid.

13. The salt according to claim 3, wherein the polymeric acid is a copolymer of acrylic acid and maleic acid with a molecular weight of from 1,000 g/mol to 1,000,000 g/mol.

14. A salt of a hydrophobic etheramine and of a polymeric acid obtainable by a process comprising the following steps: a) the reaction of 1,3-diols of formula (III) with at least one of propylene oxide and butylene oxide, wherein the molar ratio of 1,3-diol to propylene oxide and/or butylene oxide is in the range of 1:2 to 1:10, ##STR00009## with R.sub.1-R.sub.6 are independently of one another H, alkyl, cycloalkyl, aryl, alkylaryl, arylalkyl and at least one group selected from R.sub.1-R.sub.6 is different from H (compound A), b) the amination of the alkoxylated 1,3-diols (compound A) with ammonia in the presence of a catalysator (compound B), c) the mixing of compound B to an aqueous solution of a polymeric acid at 25° C., wherein the molar ratio of the polycarboxylic acid groups to amino groups in compound B lies in the range of 100:1 to 1:1, d) the removal of the water from the aqueous solution by one of spray-drying using a gas with an inlet temperature of at least 125° C. spray granulation using a gas with an inlet temperature of at least 125° C., distillation under reduced pressure, and phase separation followed by distillation.

15. A salt of a hydrophobic etheramine and of a polymeric acid obtainable by a process comprising the following steps: a) the reaction of glycerine or 1,1,1-trimethylolpropane with at least one of butylene oxide and propylene oxide, wherein the molar ratio of glycerine or 1,1,1-trimethylolpropane to butylene oxide and/or propylene oxide is in the range of 1:3 to 1: 10 (compound C), b) the amination of the alkoxylated glycerine or 1,1,1-trimethylolpropane (compound A) with ammonia in the presence of a catalysator (compound D), c) the mixing of compound D to an aqueous solution of a polymeric acid at 25° C., wherein the molar ratio of the polycarboxylic acid groups to amino groups in compound B lies in the range of 100:1 to 1:1, d) the removal of the water from the aqueous solution by one of spray-drying using a gas with an inlet temperature of at least 125° C. spray granulation using a gas with an inlet temperature of at least 125° C. distillation under reduced pressure, and phase separation followed by distillation.

16. A salt of a hydrophobic etheramine and of a polymeric acid obtainable by a process comprising the following steps: a) the reaction of 1,2-dialcohols of formula (VII) with at least one of propylene oxide and butylene oxide, wherein the molar ratio of 1,2-dialcohol to propylene oxide and/or butylene oxide is in the range of 1:2 to 1:100, ##STR00010## wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently selected from the group consisting of H and a linear or branched alkyl group with 2 to 16 carbon atoms (compound E), b) the amination of the alkoxylated 1,2-dialcohol (compound E) with ammonia in the presence of a catalysator (compound F), c) the mixing of compound F to an aqueous solution of a polymeric acid at 25° C., wherein the molar ratio of the polycarboxylic acid groups to amino groups in compound B lies in the range of 100:1 to 1:1, d) the removal of the water from the aqueous solution by one of spray-drying using a gas with an inlet temperature of at least 125° C. spray granulation using a gas with an inlet temperature of at least 125° C. by distillation under reduced pressure, and or by phase separation followed by distillation.

17. The salt of claim 14, wherein the process further comprises milling the resulting solid.

18. The salt of claim 15, wherein the process further comprises milling the resulting solid.

19. The salt of claim 16, wherein the process further comprises milling the resulting solid.

Description

SYNTHESIS EXAMPLES

Example 1

[0109] 2.5 g of a polyetheramine (2-Aminomethylethyl)-omega-(2-aminomethylethoxy)-poly(oxy (methyl-1,2-ethandiyl)), sold under the trade name Polyetheramine® D 230 (BASF) were added at room temperature to 10.0g of a 50wt % aqueous solution of a copolymer of acrylic acid and maleic acid. The copolymer of acrylic acid and maleic acid has an average molecular weight Mn of about 70000 g/mol (measured by gel permeation chromatography, calibrated with polysty-renesulfonate) and a molar ratio of acrylic acid to maleic acid of 4:1. The temperature was increased to 50° C. The mixture was stirred for additional 1 hour without external heating. Water was removed in vacuo (0.7 mbar). After milling, 4.5 g white odorless crystals were obtained. pH of a 10% solution in water:6.

Example 2

[0110] 25.0 g of a polyetheramine (2-Aminomethylethyl)-omega-(2-aminomethylethoxy)-poly(oxy (methyl-1,2-ethandiyl)), sold under the trade name Polyetheramine® D 230 (BASF) were added at room temperature to 100.0 g of a 50 wt % aqueous solution of the sodium salt of a homopolymer of acrylic acid. The sodium salt of the homopolymer of acrylic acid has a molecular weight of about 4000 g/mol (measured by gel permeation chromatography, calibrated with polystyrenesulfonate). The temperature was increased to 41° C. The mixture was stirred for additional 2 hours at 60° C. Water was removed in vacuo (0.7 mbar). After milling, 70.0 g light yellow crystals were obtained. The pH of a 10% solution in water was 6.

Example 3

[0111] 62.5g of a polyetherdiamine from 2-butyl-2-ethyl-1,3-propandiol, alkoxylated with 2.0 mol propylene oxide per OH, and aminated (amine value 278.2 mg KOH/g) were added at room temperature to 250.0 g of a 50 wt % aqueous solution of a copolymer of acrylic acid and maleic acid. The copolymer of acrylic acid and maleic acid has a molecular weight of about 70000 g/mol (measured by gel permeation chromatography, calibrated with polystyrenesulfonate) and a molar ratio of acrylic acid to maleic acid of 4:1. The temperature was increased to 50° C. The mixture was stirred for additional 2 hours at 60° C. Water was removed in vacuo (0.7 mbar). After milling, 85.0 g white odorless crystals were obtained. The pH of a 10% solution in water was 6, water content: 0.9%.

Example 4

[0112] 25.0g of a polyetherdiamine from 2-butyl-2-ethyl-1,3-propandiol, alkoxylated with 2.0 mol propylene oxide per OH, and aminated (amine value 278.2 mg KOH/g) were added at room temperature to 100.0 g of a 50 wt % aqueous solution of the sodium salt of a homopolymer of acrylic acid. The sodium salt of the homopolymer of acrylic acid has a molecular weight of about 4000 g/mol (measured by gel permeation chromatography, calibrated with polystyrenesulfonate). The temperature was increased to 42° C. The mixture was stirred for additional 2 hours at 60° C. A two-phase system was obtained and the waterphase was discarded. The organic phase was dried at 60° C. under vacuum (0.7 mbar). After milling, 71.0 g white odorless crystals were obtained. The pH of a 10% solution in water was 4.1, water content: 0.9%.

Example 5

[0113] 25g of a polyetherdiamine from 2-butyl-2-ethyl-1,3-propandiol, alkoxylated with 2.0 mol propylene oxide per OH, and aminated (amine value 278.2 mg KOH/g) were added at room temperature to 100.0 g of a 50 wt % aqueous solution of a copolymer of acrylic acid and maleic acid. The copolymer of acrylic acid and maleic acid has a molecular weight of about 3000 g/mol (measured by gel permeation chromatography, calibrated with polystyrenesulfonate) and a molar ratio of acrylic acid to maleic acid of 1.7:1.The temperature was increased to 39° C. The mixture was stirred for additional 2 hours at 60° C. Water was removed in vacuo (0.7 mbar). After milling, 71.5 g sticky yellow crystals were obtained. The pH of a 10% solution in water was 3.5, water content: 0.9%.

APPLICATION EXAMPLES

[0114] The inventive salt of a hydrophobic polyetheramine and a polymeric acid may be used in cleaning compositions which may include from about 0.1% to about 10%, in some examples, from about 0.2% to about 5%, and in other examples, from about 0.5% to about 3%, by weight of the composition, of the salt according to the invention.

[0115] The cleaning composition comprises one or more surfactants. The cleaning composition comprises one or more surfactants in an amount sufficient to provide desired cleaning properties. The cleaning composition may comprise, by weight of the composition, from about 1% to about 70% of one or more surfactants. The detergent composition may comprise, by weight of the composition, from about 2% to about 60% of one or more surfactants. The detergent composition may comprise, by weight of the composition, from about 5% to about 30% of one or more surfactants. The surfactant may comprise a detersive surfactant selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, zwitterionic surfactants, amphoteric surfactants, ampholytic surfactants, and mixtures thereof. Those of ordinary skill in the art will understand that a detersive surfactant encompasses any surfactant or mixture of surfactants that provide cleaning, stain removing, or laundering benefit to soiled material.

[0116] Anionic Surfactants

[0117] The one or more surfactants may consist essentially of, or even consist of, an anionic surfactants.

[0118] Specific, non-limiting examples of suitable anionic surfactants include any conventional anionic surfactant. This may include a sulfate detersive surfactant, for e.g., alkoxylated and/or non-alkoxylated alkyl sulfate materials, and/or sulfonic detersive surfactants, e.g., alkyl benzene sulfonates.

[0119] The cleaning composition may comprise a nonionic surfactant. In some examples, the cleaning composition comprises up to about 25%, by weight of the cleaning composition, of one or more nonionic surfactants, e.g., as a co-surfactant. In some examples, the cleaning composition comprises from about 0.1% to about 15%, by weight of the cleaning composition, of one or more nonionic surfactants. In further examples, the cleaning compositions comprise from about 0.3% to about 10%, by weight of the cleaning compositions, of one or more nonionic surfactants.

[0120] The surfactant system may comprise combinations of anionic and nonionic surfactant materials. In some examples, the weight ratio of anionic surfactant to nonionic surfactant is at least about 2:1. In other examples, the weight ratio of anionic surfactant to nonionic surfactant is at least about 5:1. In further examples, the weight ratio of anionic surfactant to nonionic surfactant is at least about 10:1.

[0121] The cleaning compositions of the invention may also contain adjunct cleaning additives. Suitable adjunct cleaning additives include builders, structurants or thickeners, clay soil removal/anti-redeposition agents, polymeric soil release agents, polymeric dispersing agents, polymeric grease cleaning agents, enzymes, enzyme stabilizing systems, bleaching compounds, bleaching agents, bleach activators, bleach catalysts, brighteners, dyes, hueing agents, dye transfer inhibiting agents, chelating agents, suds supressors, softeners, and perfumes.

[0122] Methods of Use

[0123] The present invention includes methods for cleaning soiled material. As will be appreciated by one skilled in the art, the cleaning compositions of the present invention are suited for use in laundry pretreatment applications, laundry cleaning applications, and home care applications. Such methods include, but are not limited to, the steps of contacting cleaning compositions in neat form or diluted in wash liquor, with at least a portion of a soiled material and then optionally rinsing the soiled material. The soiled material may be subjected to a washing step prior to the optional rinsing step.

[0124] For use in laundry pretreatment applications, the method may include contacting the cleaning compositions described herein with soiled fabric. Following pretreatment, the soiled fabric may be laundered in a washing machine or otherwise rinsed.

[0125] Machine laundry methods may comprise treating soiled laundry with an aqueous wash solution in a washing machine having dissolved or dispensed therein an effective amount of a machine laundry cleaning composition in accord with the invention. An “effective amount” of the cleaning composition means from about 20 g to about 300 g of product dissolved or dispersed in a wash solution of volume from about 5 L to about 65 L. The water temperatures may range from about 5° C. to about 100° C. The water to soiled material (e.g., fabric) ratio may be from about 1:1 to about 30:1. The compositions may be employed at concentrations of from about 500 ppm to about 15,000 ppm in solution. In the context of a fabric laundry composition, usage levels may also vary depending not only on the type and severity of the soils and stains, but also on the wash water temperature, the volume of wash water, and the type of washing machine (e.g., top-loading, front-loading, top-loading, vertical-axis Japanese-type automatic washing machine).

[0126] The cleaning compositions herein may be used for laundering of fabrics at reduced wash temperatures. These methods of laundering fabric comprise the steps of delivering a laundry cleaning composition to water to form a wash liquor and adding a laundering fabric to said wash liquor, wherein the wash liquor has a temperature of from about 0° C. to about 20° C., or from about 0° C. to about 15° C., or from about 0° C. to about 9° C. The fabric may be contacted to the water prior to, or after, or simultaneous with, contacting the laundry cleaning composition with water.

[0127] Another method includes contacting a nonwoven substrate impregnated with an embodiment of the cleaning composition with soiled material. As used herein, “nonwoven substrate” can comprise any conventionally fashioned nonwoven sheet or web having suitable basis weight, caliper (thickness), absorbency, and strength characteristics. Non-limiting examples of suitable commercially available nonwoven substrates include those marketed under the tradenames SON-TARA® by DuPont and POLYWEB® by James River Corp.

[0128] Hand washing/soak methods, and combined handwashing with semi-automatic washing machines, are also included.

[0129] Machine Dishwashing Methods

[0130] Methods for machine-dishwashing or hand dishwashing soiled dishes, tableware, silverware, or other kitchenware, are included. One method for machine dishwashing comprises treating soiled dishes, tableware, silverware, or other kitchenware with an aqueous liquid having dissolved or dispensed therein an effective amount of a machine dishwashing composition in accord with the invention. By an effective amount of the machine dishwashing composition it is meant from about 8 g to about 60 g of product dissolved or dispersed in a wash solution of volume from about 3 L to about 10 L.

[0131] One method for hand dishwashing comprises dissolution of the cleaning composition into a receptacle containing water, followed by contacting soiled dishes, tableware, silverware, or other kitchenware with the dishwashing liquor, then hand scrubbing, wiping, or rinsing the soiled dishes, tableware, silverware, or other kitchenware. Another method for hand dishwashing comprises direct application of the cleaning composition onto soiled dishes, tableware, silverware, or other kitchenware, then hand scrubbing, wiping, or rinsing the soiled dishes, tableware, silverware, or other kitchenware. In some examples, an effective amount of cleaning composition for hand dishwashing is from about 0.5 ml. to about 20 ml. diluted in water.

[0132] Packaging for the Compositions

[0133] The cleaning compositions described herein can be packaged in any suitable container including those constructed from paper, cardboard, plastic materials, and any suitable laminates. An optional packaging type is described in European Application No. 94921505.7.

[0134] Multi-Compartment Pouch Additive

[0135] The cleaning compositions described herein may also be packaged as a multi-compartment cleaning composition.

EXAMPLES

[0136] In the following examples, the individual ingredients within the detergent compositions are expressed as percentages by weight of the detergent compositions.

Example 1

[0137]

TABLE-US-00001 1 (wt %) Linear alkylbenzenesulfonate.sup.1 8.2 AE3S.sup.2 1.9 Zeolite A.sup.3 1.8 Citric Acid 1.5 Sodium Carbonate.sup.5 29.7 Silicate 1.6R (SiO.sub.2:Na.sub.2O).sup.4 3.4 Soil release agent.sup.6 0.2 Acrylic Acid/Maleic Acid Copolymer.sup.7 2.2 Carboxymethylcellulose 0.9 Protease - Purafect ® (84 mg active/g).sup.9 0.08 Amylase - Stainzyme Plus ® (20 mg active/g).sup.8 0.16 Lipase - Lipex ® (18.00 mg active/g).sup.8 0.24 Cellulase - Celluclean ™ (15.6 mg active/g).sup.8 0.1 Salt of Polyetheramine and Polymeric Acid.sup.10 2.0 TAED .sup.11 3.26 Percarbonate.sup.12 14.1 Na salt of Ethylenediamine-N,N′-disuccinic acid, 2.19 (S,S) isomer (EDDS).sup.13 Hydroxyethane di phosphonate (HEDP).sup.14 0.54 MgSO.sub.4 0.38 Perfume 0.38 Suds suppressor agglomerate.sup.15 0.04 Sulphonated zinc phthalocyanine (active).sup.16 0.0012 Sulfate/Water & Miscellaneous Balance .sup.1Linear alkylbenzenesulfonate having an average aliphatic carbon chain length C.sub.11-C.sub.12 supplied by Stepan, Northfield, Illinois, USA .sup.2AE3S is C.sub.12-.sub.15 alkyl ethoxy (3) sulfate supplied by Stepan, Northfield, Illinois, USA .sup.3Zeolite A is supplied by Industrial Zeolite (UK) Ltd, Grays, Essex, UK .sup.41.6R Silicate is supplied by Koma, Nestemica, Czech Republic .sup.5Sodium Carbonate is supplied by Solvay, Houston, Texas, USA .sup.6Soil release agent is Repel-o-tex ® PF, supplied by Rhodia, Paris, France .sup.7Acrylic Acid/Maleic Acid Copolymer is molecular weight 70,000 and acrylate:maleate ratio 70:30, supplied by BASF, Ludwigshafen, Germany .sup.8Savinase ®, Natalase ®, Stainzyme ®, Lipex ®, Celluclean ™, Mannaway ® and Whitezyme ® are all products of Novozymes, Bagsvaerd, Denmark. .sup.9Proteases may be supplied by Genencor International, Palo Alto, California, USA (e.g. Purafect Prime ®) or by Novozymes, Bagsvaerd, Denmark (e.g. Liquanase ®, Coronase ®). .sup.10Salt of Polyetheramine and Polymeric Acid of synthesis Examples 3, 4, or 5. .sup.11TAED is tetraacetylethylenediamine, supplied under the Peractive ® brand name by Clariant GmbH, Sulzbach, Germany .sup.12Sodium percarbonate supplied by Solvay, Houston, Texas, USA .sup.13Na salt of Ethylenediamine-N,N′-disuccinic acid, (S,S) isomer (EDDS) is supplied by Octel, Ellesmere Port, UK .sup.14Hydroxyethane di phosphonate (HEDP) is supplied by Dow Chemical, Midland, Michigan, USA .sup.15Suds suppressor agglomerate is supplied by Dow Corning, Midland, Michigan, USA .sup.16Fluorescent Brightener 1 is Tinopal ® AMS, Fluorescent Brightener 2 is Tinopal ® CBS-X, Sulphonated zinc phthalocyanine and Direct Violet 9 is Pergasol ® Violet BN-Z all supplied by Ciba Specialty Chemicals, Basel, Switzerland

Examples 2-7

[0138] Granular laundry detergent compositions designed for hand washing or top-loading washing machines may be added to sufficient water to form a paste for direct contact with the surface to be treated, forming a concentrated cleaning composition.

TABLE-US-00002 2 3 4 5 6 7 (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) Linear alkylbenzenesulfonate 20 22 20 15 20 20 C.sub.12-14 Dimethylhydroxyethyl 0.7 0.2 1 0.6 0.0 0 ammonium chloride AE3S 0.9 1 0.9 0.0 0.5 0.9 AE7 0.0 0.0 0.0 1 0.0 3 Sodium tripolyphosphate 5 0.0 4 9 2 0.0 Zeolite A 0.0 1 0.0 1 4 1 1.6R Silicate (SiO.sub.2:Na.sub.2O at 7 5 2 3 3 5 ratio 1.6:1) Sodium carbonate 25 20 25 17 18 19 Polyacrylate MW 4500 1 0.6 1 1 1.5 1 Random graft copolymer 0.1 0.2 0.0 0.0 0.0 0.0 Carboxymethyl cellulose 1 0.3 1 1 1 1 Stainzyme ® (20 mg active/g) 0.1 0.2 0.1 0.2 0.1 0.1 Bacterial protease (Savinase ® 0.1 0.1 0.1 0.1 0.1 32.89 mg active/g) Natalase ® (8.65 mg active/g) 0.1 0.0 0.1 0.0 0.1 0.1 Lipex ® (18 mg active/g) 0.03 0.07 0.3 0.1 0.07 0.4 Biotouch ® ROC (20 mg active/ 0.1 0.2 0.2 0.2 0.1 0.4 g) *Salt of Polyetheramine and 2.0 3.0 2.0 2.0 3.0 2.0 Polymeric Acid Fluorescent Brightener 1 0.06 0.0 0.06 0.18 0.06 0.06 Fluorescent Brightener 2 0.1 0.06 0.1 0.0 0.1 0.1 DTPA 0.6 0.8 0.6 0.25 0.6 0.6 MgSO.sub.4 1 1 1 0.5 1 1 Sodium Percarbonate 0.0 5.2 0.1 0.0 0.0 0.0 Sodium Perborate 4.4 0.0 3.85 2.09 0.78 3.63 Monohydrate NOBS 1.9 0.0 1.66 0.0 0.33 0.75 TAED 0.58 1.2 0.51 0.0 0.015 0.28 Sulphonated zinc phthalocyanine 0.0030 0.0 0.0012 0.0030 0.0021 0.0 S-ACMC 0.1 0.0 0.0 0.0 0.06 0.0 Direct Violet 9 0.0 0.0 0.0003 0.0005 0.0003 0.0 Acid Blue 29 0.0 0.0 0.0 0.0 0.0 0.0003 Sulfate/Moisture Balance

Examples 8-13

[0139] Granular laundry detergent compositions designed for front-loading automatic washing machines may be added to sufficient water to form a paste for direct contact with the surface to be treated, forming a concentrated cleaning compostion.

TABLE-US-00003 8 9 10 11 12 13 (wt %) (wt %) (wt %) (wt %) (wt %) (wt %) Linear alkylbenzenesulfonate 8 7.1 7 6.5 7.5 7.5 AE3S 0 4.8 0 5.2 4 4 C12-14 Alkylsulfate 1 0 1 0 0 0 AE7 2.2 0 3.2 0 0 0 C.sub.10-12 Dimethyl hydroxyethylammonium 0.75 0.94 0.98 0.98 0 0 chloride Crystalline layered silicate (δ- 4.1 0 4.8 0 0 0 Na.sub.2Si.sub.2O.sub.5) Zeolite A 5 0 5 0 2 2 Citric Acid 3 5 3 4 2.5 3 Sodium Carbonate 15 20 14 20 23 23 Silicate 2R (SiO.sub.2:Na.sub.2O at ratio 0.08 0 0.11 0 0 0 2:1) *Salt of Polyetheramine and Polymeric 2.0 3.0 2.0 3.0 3.0 2.0 Acid Soil release agent 0.75 0.72 0.71 0.72 0 0 Acrylic Acid/Maleic Acid Copolymer 1.1 3.7 1.0 3.7 2.6 3.8 Carboxymethylcellulose 0.15 1.4 0.2 1.4 1 0.5 Bacterial protease (84 mg active/ 0.2 0.2 0.3 0.15 0.12 0.13 g) Stainzyme ® (20 mg active/g) 0.2 0.15 0.2 0.3 0.15 0.15 Lipex ® (18.00 mg active/g) 0.05 0.15 0.1 0 0 0 Natalase ® (8.65 mg active/g) 0.1 0.2 0 0 0.15 0.15 Celluclean ™ (15.6 mg active/g) 0 0 0 0 0.1 0.1 Biotouch ® ROC (20 mg active/g) 0.2 0.1 0.2 0.2 0.2 0.2 TAED 3.6 4.0 3.6 4.0 2.2 1.4 Percarbonate 13 13.2 13 13.2 16 14 Na salt of Ethylenediamine-N,N′- 0.2 0.2 0.2 0.2 0.2 0.2 disuccinic acid, (S,S) isomer (EDDS) Hydroxyethane di phosphonate 0.2 0.2 0.2 0.2 0.2 0.2 (HEDP) MgSO.sub.4 0.42 0.42 0.42 0.42 0.4 0.4 Perfume 0.5 0.6 0.5 0.6 0.6 0.6 Suds suppressor agglomerate 0.05 0.1 0.05 0.1 0.06 0.05 Soap 0.45 0.45 0.45 0.45 0 0 Sulphonated zinc phthalocyanine 0.0007 0.0012 0.0007 0 0 0 (active) S-ACMC 0.01 0.01 0 0.01 0 0 Direct Violet 9 (active) 0 0 0.0001 0.0001 0 0 Sulfate/Water & Miscellaneous Balance

Raw Materials and Notes for Composition Examples 2-13

[0140] *Salt of Polyetheramine and Polymeric Acid of synthesis Examples 3, 4, or 5.

[0141] Linear alkylbenzenesulfonate having an average aliphatic carbon chain length C.sub.11-C.sub.12 supplied by Stepan, Northfield, Ill., USA

[0142] C.sub.12-14 Dimethylhydroxyethyl ammonium chloride, supplied by Clariant GmbH, Sulzbach, Germany

[0143] AE3S is C12-15 alkyl ethoxy (3) sulfate supplied by Stepan, Northfield, Ill., USA

[0144] AE7 is C12-15 alcohol ethoxylate, with an average degree of ethoxylation of 7, supplied by Huntsman, Salt Lake City, Utah, USA

[0145] AE9 is C.sub.12-13 alcohol ethoxylate, with an average degree of ethoxylation of 9, supplied by Huntsman, Salt Lake City, Utah, USA

[0146] HSAS is a mid-branched primary alkyl sulfate with carbon chain length of about 16-17 Sodium tripolyphosphate is supplied by Rhodia, Paris, France

[0147] Zeolite A is supplied by Industrial Zeolite (UK) Ltd, Grays, Essex, UK

[0148] 1.6R Silicate is supplied by Koma, Nestemica, Czech Republic

[0149] Sodium Carbonate is supplied by Solvay, Houston, Tex., USA

[0150] Polyacrylate MW 4500 is supplied by BASF, Ludwigshafen, Germany

[0151] Carboxymethyl cellulose is Finnfix® V supplied by CP Kelco, Arnhem, Netherlands

[0152] Suitable chelants are, for example, diethylenetetraamine pentaacetic acid (DTPA) supplied by Dow Chemical, Midland, Mich., USA or Hydroxyethane di phosphonate (HEDP) supplied by Solutia, St Louis, Miss., USA Bagsvaerd, Denmark

[0153] Savinase®, Natalase®, Stainzyme®, Lipex®, Celluclean™, Mannaway® and Whitezyme® are all products of Novozymes, Bagsvaerd, Denmark.

[0154] Biotouch® ROC is a product of AB Enzymes, Darmstadt, Germany.

[0155] Bacterial protease (examples 8-13) described in U.S. Pat. No. 6,312,936 B1 supplied by Genencor International, Palo Alto, California, USA

[0156] Bacterial protease (examples 14-20) described in U.S. Pat. No. 4,760,025 is supplied by Genencor International, Palo Alto, Calif., USA

[0157] Fluorescent Brightener 1 is Tinopal® AMS, Fluorescent Brightener 2 is Tinopal® CBS-X, Sulphonated zinc phthalocyanine and Direct Violet 9 is Pergasol® Violet BN-Z all supplied by Ciba Specialty Chemicals, Basel, Switzerland

[0158] Sodium percarbonate supplied by Solvay, Houston, Tex., USA

[0159] Sodium perborate is supplied by Degussa, Hanau, Germany

[0160] NOBS is sodium nonanoyloxybenzenesulfonate, supplied by Future Fuels, Batesville, Arkansas, USA

[0161] TAED is tetraacetylethylenediamine, supplied under the Peractive® brand name by Clariant GmbH, Sulzbach, Germany

[0162] S-ACMC is carboxymethylcellulose conjugated with C. I. Reactive Blue 19, sold by Megazyme,

[0163] Wicklow, Ireland under the product name AZO-CM-CELLULOSE, product code S-ACMC.

[0164] Soil release agent is Repel-o-tex® PF, supplied by Rhodia, Paris, France

[0165] Acrylic Acid/Maleic Acid Copolymer is molecular weight 70,000 and acrylate:maleate ratio 70:30, supplied by BASF, Ludwigshafen, Germany

[0166] Na salt of Ethylenediamine-N,N′-disuccinic acid, (S,S) isomer (EDDS) is supplied by Octel, Ellesmere Port, UK

[0167] Hydroxyethane di phosphonate (HEDP) is supplied by Dow Chemical, Midland, Mich., USA

[0168] Suds suppressor agglomerate is supplied by Dow Corning, Midland, Mich., USA

[0169] HSAS is mid-branched alkyl sulfate as disclosed in U.S. Pat. No. 6,020,303 and U.S. Pat. No. 6,060,443

[0170] C.sub.12-14 dimethyl Amine Oxide is supplied by Procter & Gamble Chemicals, Cincinnati, Ohio, USA

[0171] Liquitint® Violet CT is supplied by Milliken, Spartanburg, S.C., USA.

Example 14

Multiple Compartment Unit Dose Compositions

[0172] Multiple compartment unit dose laundry detergent formulations of the present invention are provided below. In these examples the unit dose has three compartments, but similar compositions can be made with two, four or five compartments. The film used to encapsulate the compartments is polyvinyl alcohol.

TABLE-US-00004 Base Composition 1 % Ingredients Glycerol 5.3 1,2-propanediol 10.0 Citric Acid 0.5 Monoethanolamine 10.0 Caustic soda — Hydroxyethane diphosphonic acid 1.1 Potassium sulfite 0.2 Nonionic Marlipal C24EO.sub.7 20.1 HLAS 24.6 Fluorescent Brightener 2 0.2 C12-15 Fatty acid 16.4 A compound having the following general structure: 2.9 bis((C.sub.2H.sub.5O)(C.sub.2H.sub.4O)n)(CH.sub.3)—N.sup.+—C.sub.xH.sub.2x—N.sup.+—(CH.sub.3)- bis((C.sub.2H.sub.5O)(C.sub.2H.sub.4O)n), wherein n = from 20 to 30, and x = from 3 to 8, or sulphated or sulphonated variants thereof Polyethyleneimine ethoxylate PEI600 E20 1.1 MgCl.sub.2 0.2 Solvents (1,2 propanediol, ethanol) To 100%

[0173] Multi-Compartment Formulations

TABLE-US-00005 Composition 1 2 Compartment A B C A B C Volume of each compartment 40 ml 5 ml 5 ml 40 ml 5 ml 5 ml Active material in Wt. % Perfume 1.6 1.6 1.6 1.6 Dyes <0.01 <0.01 <0.01 <0.01 TiO2 0.1 — 0.1 Sodium Sulfite 0.4 0.4 0.3 0.3 Salt of Polyetheramine and 4-40% 4-40% Polymeric Acid.sup.1 Acusol 305, Rohm&Haas 1.2 2 Hydrogenated castor oil 0.14 0.14 0.14 0.14 Solid non-active filler.sup.2 Add to Add to 100% 100% Base Composition 1 Add to Add to Add to Add to Add to 100% 100% 100% 100% 100% .sup.1Salt of Polyetheramine and Polymeric Acid of synthesis Examples 3, 4, or 5. .sup.2Solid non-active fillers include sodium sulfate, silica, silicates, zeolite.