AU625160B2 - Granular laundry detergent compositions having improved solubility - Google Patents

Description

AUSTRALIA

Patents Act COMPLETE SPECIFICATION

(ORIGINAL)

6251 0 Class Int. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority Related Art: Applicant(s): The Procter Gamble Company One Procter Gamble Plaza, Cincinnati, Ohio 45202, UNITED STATES OF

AMERICA

Address for Service ist PHILLIPS ORMONDE FITZPATRICK Patent and Trade Mark Attorneys 367 Collins Street Melbourne 3000 AUSTRALIA Complete Specification for the invention entitled: GRANULAR LAUNDRY DETERGENT COMPOSITIONS HAVING IMPROVED SOLUBILITY Our Ref 182812 POF Code: 44135/44135 The following statement is a full description of this invention, including the best method of performing it known to applicant(s): 1- 6006 i I t i j

-IA-

GRANULAR LAUNDRY DETERGENT COMPOSITIONS HAVING IMPROVED SOLUBILITY Jeffrey E. Boucher Eugene J. Pancheri FIELD OF THE INVENTION The present invention relates to granular detergent compositions having improved solubility. More particularly, it 5 relates to granular detergent laundry compositions and additives containing sodium carbonate and sodium phosphate and low levels of potassium salt for improved cold water solubility. Processes for improving solubility of granular detergent compositions are also included.

BACKGROUND OF THE INVENTION This invention was made during a search for a way to improve solubility of granular laundry detergent products and prevent clumps of detergent from remaining in the washer and on washed clothes. Such clumps, which may appear as solid white masses ranging from about 5 to 40 millimeters in diameter and about 2 to 4' ,t 10 millimeters in length, have occurred during cold water washes ,when the order of addition to the washing machine is laundry detergent product first, clothes second, and water last. It has been found that the primary contributors to this solubility 20 problem are the sodium carbonate and sodium phosphate in the granular laundry detergent. It has been discovered that surprisingly low levels of potassium salts can be included in the granular detergent composition to improve solubility and eliminate or reduce this clumping problem.

Sodium carbonate and sodium pyrophosphate have been used in granular detergent compositions (for example, U.S. Patent 4,299,717, Cottrell et al, issued November 10, 1981). Potassium salt has been substituted for sodium salt to eliminate giant micelles of sodium salt of washed fatty acid in the washing liquid (Japanese Patent Application 61164000). The solubility of a solid is lower in a solution of a salt containing a common ion than in pure water (Chemical Principles, 4th ed., Masterton Slowinski, W.B. Saunders Co. 1977, pg. 435). Lastly, a water-softening composition comprising tetrasodiur pyrophosphate and an alkaline material selected from the group consisting of trisodium Irr~ a-

I

~-LIII-~II~LL-~-I~ ii-i-- CIUI~_ 2 a phosphate, sodium hydroxide, sodium carbonates, potassium hydroxide, potassium carbonates, soap and sodium silicate is disclosed in U.S. Patent 2,381,960, Johnson, patented August 14, 1945. However, it has not been disclosed that low levels of potassium salt can be added to a granular laundry detergent composition or additive containing sodium carbonate and sodium phosphate to improve solubility of the composition in water.

SUMMARY OF THE INVENTION The instant invention presents a granular laundry detergent composition comprising: from about 5 to 70 weight detergent surfactant selected from the group consisting of anionics, nonionics, zwitterionics, ampholytics, cationics, and mixtures thereof; from about 5 to 70 weight sodium phosphate; from about 5 to 70 weight sodium carbonate; and from about 0.1 to 10 weight potassium salt.

A process for improving solubility of a granular laundry detergent composition according to the above is also presented.

DESCRIPTION OF THE INVENTION ii This invention covers a granular laundry detergent composition or additive which is soluble in cold or cool water, i.e. the composition or additive readily dissolves/disperses in water at a temperature between about 32*F and 90'F (32.2'C), preferably between about 35'F and 50"F Because of S the incorporation of a surprisingly low level of potassium salt in the product, no significant amount of product remains bound in the clothes or in the bottom of the washing machine tub after a typical cold water wash cycle, even with a product first, clothes \second, water last order of addition. A process for improving solubility or dispersibility of a granular detergent composition is also included in the invention.

The claimed granular laundry detergent composition or additive comprises: nonionics, zwitterionics, ampholytics, cationics, and mixtures thereof; S(b) from about 5 to 70 weight sodium phosphate; from about 5 to 70 weight sodium carbonate; and from about 0.1 to 10 weight potassium salt.

A. Detergent Surfactant The first ingredient, present at a level of from about 5 to 1 70 weight preferably about 10 to 30 weight is detergent surfactant selected from the group consisting of anionics, nonionics, zwitterionics, ampholytics, cationics, and mixtures thereof. Preferred is from about 10 to 30 weight most preferably from about 12 to 20 weight detergent surfactant selected from the group consisting of anionics, nonionics, cationics, and mixtures thereof.

Water-soluble salts of the higher fatty acids, "soaps", are useful anionic surfactants in the compositions herein. This includes alkali metal soaps such as the sodium, potassium, S ammonium, and alkylolammonium salts of higher fatty acids containing from about 8 to about 24 carbon atoms, and preferably from about 12 to about 18 carbon atoms. Soaps can be made by direct saponification of fats and oils or by the neutralization of free fatty acids. Particularly useful are the sodium and S potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, sodium or potassium tallow and coconut soap.

Useful anionic surfactants also include the water-soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts, of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants are the 4 sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 1 2-C18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 10 to about 16 carbon atoms, in straight chain or branched chain configuration, see U.S.

Patents 2,220,099 and 2,477,383. Especially valuable are linear 1 straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14, abbreviated as C11-14 LAS.

Especially preferred is from about 12 to 20 weight of a mixture of C10-16 linear alkylbenzene sulfonate and C1 2 18 alkyl sulfate. These are preferably in a weight ratio of between 50:50 and 80:20, preferably 70:30, sodium C10-16 (preferably C11-14) LAS:sodium C12-18 (preferably C14-16) alkyl sulfate.

Other anionic surfactants herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain from about 8 to about 12 carbon atoms; and sodium or potassium salts of alkyl ethylene oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.

Other useful anionic surfactants herein include the water-soluble salts of esters of alpha-sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; t water-soluble salts of 2-acyloxyalkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin and paraffin sulfonates containing from about 12 to carbon atoms; and beta-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to carbon atoms in the alkane moiety.

Water-soluble nonionic surfactants are also useful in the instant detergent granules. Such nonionic materials include compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which may be aliphatic or alkyl aromatic in nature. The length of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.

Suitable nonionic surfactants include the polyethylene oxide condensates of alkyl phenols, the condensation products of alkyl phenols having an alkyl group containing from about 6 to carbon atoms, in either a straight chain or branched chain I| configuration, with from about 3 to 80 moles of ethylene oxide per mole of alkyl phenol.

Included are the water-soluble and water-dispersible condensation products of aliphatic alcohols containing from 8 to 22 carbon atoms, in either straight chain or branched configuration, with from 3 to 12 moles of ethylene oxide per mole of alcohol.

Semi-polar nonionic surfactants include water-soluble amine oxides containing one alkyl moiety of from abut 10 to 18 carbon atoms and two moieties selected from the group of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon atoms; Swater-soluble phosphine oxides containing one alkyl moiety of about 10 to 18 carbon atoms and two moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups j,l containing from about 1 to 3 carbon atoms; and water-soluble sulfoxides containing one alkyl moiety of from about 10 to 18 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to 3 carbon atoms.

I.

6- Preferred nonionic surfactants are of the formula Rl(OC2H4)nOH, wherein R 1 is a C10-C 1 6 alkyl group or a C8-C12 alkyl phenyl group, and n is from 3 to about Particularly preferred are condensation products of C 12

-C

1 alcohols with from about 5 to about 20 moles of ethylene oxide per mole of alcohol, C12-C13 alcohol condensed with about moles of ethylene oxide per mole of alcohol.

Ampholytic surfactants include derivatives of aliphatic or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and at least one aliphatic substituent contains an anionic water-solubilizing group.

Zwitterionic surfactants include derivatives of aliphatic, quaternary, ammonium, phosphonium, and sulfonium compounds in S which one of the aliphatic substituents contains from about 8 to 18 carbon atoms.

i, Cationic surfactants can also be included in the present detergent granules. Cationic surfactants comprise a wide variety of compounds characterized by one or more organic hydrophobic groups in the cation and generally by a quaternary nitrogen associated with an acid radical. Pentavalent nitrogen ring compounds are also considered quaternary nitrogen compounds.

I Halides, methyl sulfate and hydroxide are suitable. Tertiary amines can have characteristics similar to cationic surfactants at washing solution pH values less than about 8.5. A more complete disclosure of these and other cationic surfactants useful herein can be found in U.S. Patent 4,228,044, Cambre, issued October 14, 1980, incorporated herein by reference.

Cationic surfactants are often used in detergent compositions to provide fabric softening and/or antistatic benefits.

Antistatic agents which provide some softening benefit and which are preferred herein are the quaternary ammonium salts described r 1 7 in U.S. Patent 3,936,537, Baskerville, Jr. et al., issued February 3, 1976, which is incorporated herein by reference.

Useful cationic surfactants also include those described in U.S. Patent 4,222,905, Cockrell, issued September 16, 1980, and in U.S. Patent 4,239,659, Murphy, issued December 16, 1980, both incorporated herein by reference.

B. Sodium Phosphate The second required ingredient, present in the instant granular detergent composition at a level of from about 5 to weight preferably from about 10 to 40 weight most preferably about 15 to 35 weight is sodium phosphate.

Sodium phosphates for use herein may be sodium orthophosphate (Na3P04), sodium pyrophosphate (Na4P207), sodium tripolyphosphate (Na5P3010), and/or sodium metaphosphate (NaP03) and amorphous phosphate glasses. Tripolyphosphate generally has better detergency than pyrophosphate, which is better than orthophosphate. Metaphosphate and many of the phosphate glasses (supercooled solutions) are equal to or better than tripolyphosphate in detergency, but they are undesirable in that they can be unstable at normal crutcher pH and they may form sticky product.

Sodium tripolyphosphate is an especially good builder and, along with sodium pyrophosphate, is preferred for use herein.

Sodium tripolyphosphate is formed by condensing together three 25 orthophosphate molecules with elimination of water, yielding a straight chain molecule. It may be anhydrous or hydrated. Some hydrolysis (reversion) occurs during processing of the sodium tripolyphosphate (STPP). Therefore the actual builder ratio (versus formulated ratio) may consist of a higher ratio of STPP to pyrophosphate.

The instant granular detergent composition preferably comprises from about 1 to 10 weight sodium tripolyphosphate (STPP). It is preferred that this granular laundry detergent composition have a phosphate builder system comprising: i.

t -8crutched phosphate builder selected from STPP and TSPP and mixtures thereof; wherein the crutched builder is in spray-dried detergent granules; and admixed phosphate builder selected from STPP and TSPP and mixtures thereof; and wherein and have a ratio of from about 1:25 to about 25:1; the phosphate builder system having from 0 to about 50% of the admixed TSPP by weight of the phosphate builder system, according to pending U.S. Patent Application Serial No. 231,108, Beerse et al, filed August 11, 1988.

Most useful herein are sodium pyrophosphate salts, which can be obtained commercially or can be formed by neutralization of the corresponding pyrophosphoric acids or acid salts. Readily available commercially are tetrasodium pyrophosphate (TSPP) Na4P207 and its decahydrate Na4P207 10H20, sodium acid pyrophosphate or "acid pyro" Na2H2P207 and its hexahydrate t, Na 2

H

2

P

2 0 7 .6H 2 0, and pyrophosphoric acid H4P207. The generic formula for the anhydrous forms of these compounds can be expressed as NaxHyP207, where x and y are integers having the sum of 4.

The sodium pyrophosphate herein can be tetrasodium pyrophosphate (TSPP; preferred), trisodium pyrophosphate, disodium pyrophosphate, monosodium pyrophosphate, or mixtures thereof.

These may be anhydrous (preferred) or hydrated.

C. Sodium Carbonate The third required ingredient in the instant granular detergent composition is present at a level of from about 5 to weight preferably from about 8 to 50 weight most preferably from about 11 to 30 weight and is sodium carbonate. Sodium carbonate (Na2C03) can easily be obtained commercially.

D. Potassium Salts ,i The fourth required ingredient herein, which is present at a level of from about 0.1 to 10 weight preferably from about to 5 weight most preferably from about 1 to 3 weight is -9potassium salt. When the potassium salt is sprayed on the sodium carbonate rather than being crutched or admixed in the granular detergent composition (see below), the preferred amount of potassium salt is from about 0.1 to 2 weight preferably from about 0.2 to 1 weight Of the potassium salts, inorganic potassium salts are preferred, and are more preferably selected from the group consisting of potassium chloride (KC1), potassium carbonate

(K

2 C03), potassium sulfate (K2S04), and mixtures thereof. These are commercially available. Potassium carbonate is most preferred.

Inorganic potassium salts may include dehydrated (preferably) or hydrated tetrapotassium pyrophosphate (K4P207; preferred), tripotassium pyrophosphate (HK 3

P

2 07), dipotassium pyrophosphate (H2K2P207), and monopotassium pyrophosphate (H3KP 2 07). Of the hydrates, those which are stable up to about 120"F (48.9'C) are preferred.

Other potassium salts for use herein are dehydrated (preferably) or hydrated pentapotassium tripolyphosphate (K5P3010), tetrapotassium tripolyphosphate (HK 4

P

3 010), tripotassium tripolyphosphate (H2K 3 P301 0 dipotassium tripolyphosphate (H3K 2

P

3 0 1 and monopotassium tripolyphosphate (H4KP3010); potassium hydroxide (KOH); potassium silicate; and Spotassium neutralized surfactant such as linear potassium 25 alkylbenzene sulfonate, potassium alkyl sulfate, and/or potassium alkylpolyethoxylate.

Also suitable for use herein are salts of film forming polymers as described in U.S. Patent 4,379,080, Murphy, issued April 5, 1983, column 8, line 44 to column 10, line 37, incorporated herein, which are either partially or wholly neutralized with potassium. Particularly preferred are the potassium salts of copolymers of acrylamide and acrylate having a molecular weight between about 4,000 and 20,000.

I.-

10 It is preferred that the potassium salts herein have a mean particle size of less than about 200 microns, more preferably between about 1 and 100 microns, most preferably between about 1 and 10 microns.

E. Other Ingredients Additional detergent ingredients suitable for inclusion in a granular detergent composition may be added to the instant composition. These include other detergency builders, bleaches, bleach activators, suds boosters or suds suppressors, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smectite clays, enzymes, enzyme-stabilizing agents and perfumes. See U.S. Patent 3,936,537, issued February 3, 1976 to Baskerville, Jr. et al., incorporated herein by reference.

oBleaching agents and activators are described in U.S. Patent 4,412,934, Chung et al., issued November 1, 1983, and in U.S.

Patent 4,483,781, Hartman, issued November 20, 1984, both of which are incorporated herein by reference. Chelating agents are also described in U.S. Patent 4,663,071, Bush et al., from Column 17, 0, line 54 through Column 18, line 68, incorporated herein by reference. Suds modifiers are also optional ingredients and are described in U.S. Patents 3,933,672, issued January 20, 1976 to Bartoletta et al., and 4,136,045, issued January 23, 1979 to Gault 0o« o 25 et both incorporated herein by reference.

Suitable smectite clays for use herein are described in U.S.

Patent 4,762,645, Tucker et al, issued August 9, 1988, Column 6, .o line 3 through Column 7, line 24, incorporated herein by reference. Suitable additional detergency builders for use herein are enumerated in the Baskerville patent, Column 13, line 54 through Column 16, line 16, and in U.S. Patent 4,663,071, Bush et 0 o al, issued May 5, 1987, both incorporated herein by reference.

S- 11 F. Process Also included in the instant invention is a process for improving solubility or dispersibility of a granular detergent composition as described above. The process comprises: producing detergent granules comprising detergent surfactant selected from the group consisting of anionics, nonionics, zwitterionics, ampholytics, cationics, and mixtures thereof; and sodium phosphate; and admixing with said detergent granules sodium carbonate and potassium salt; wherein the final detergent composition comprises from about 5 to weight of the detergent surfactant, from about 5 to 70 weight sodium phosphate, from about 5 to 70 weight sodium carbonate, and from about 0.1 to 10 weight of the potassium salt.

Preferably, this process comprises: forming a paste comprising sodium linear C10-1 6 alkylbenzene sulfonate and sodium C12-18 alkyl sulfate in a ratio between 50:50 and 80:20; 0 crutching the paste with sodium pyrophosphate; spray drying the mixture of step to form detergent granules; and admixing the detergent granules with sodium carbonate and inorganic potassium salt selected from the group consisting of potassium chloride, potassium carbonate, potassium sulfate, and mixtures thereof, and having a mean particle size of less than about 200 microns; Swherein the final detergent composition comprises from about 12 to weight sodium linear C10- 16 alkylbenzene sulfonate and sodium 1 2 18 alkyl sulfate, from about 15 to 30 weight sodium pyrophosphate, from about 15 to 30 weight sodium carbonate, and from about 0.5 to 5 weight of the inorganic potassium salt.

It is preferred that step above additionally comprise crutching the paste with sodium tripolyphosphate so that the final 12 detergent composition comprises from about I to 10 weight sodium tripolyphosphate.

Although the potassium salt and sodium carbonate are preferably admixed, step in any order, they may be added in the crutcher, step Bleach and bleach activator and/or C12_13 alkylpolyethoxylate are preferably also admixed in step Polyethylene glycol, preferably of a molecular weight between about 6,000 and 12,000, sodium silicate, sodium sulfate and/or brightener are preferably 10 added in the crutcher, step Instead of admixing or directly crutching the potassium salt, an aqueous solution of the potassium salt is distributed on the sodium carbonate in a preliminary step before admixing (preferred) or crutching the coated sodium carbonate. The potassium salt may (less preferably) be agglomerated with the sodium carbonate in, for example, a Schugi agglomerator using an aqueous solution of the potassium salt at levels sufficient to cause agglomeration.

The distribution of the potassium salt may be by coating or, preferably, by spraying an aqueous solution on the surface of the sodium carbonate. Spraying on may be done in a Schugi agglomerator with the blades down and minimal residence time so the sodium carbonate is coated but not agglomerated. A rotating spray drum may alternatively be used to spray an aqueous solution of the potassium salt onto the sodium carbonate.

If the potassium salt (preferably inorganic salt, most preferably potassium carbonate, potassium chloride or potassium sulfate), is sprayed on, the percentage of it in the finished product can be lower than if it is admixed (or directly crutched), without losing effectiveness. From about 0.1 to 10 weight preferably from about 0.1 to 2 weight most preferably from about 0.2 to 1 weight potassium salt may be sprayed on the sodium carbonate. The potassium salt can be mixed in water, at a concentration at less than saturation for a given temperature, for subsequent distribution over the surfaces of the sodium carbonate 13 particles. The coated sodium c-.rbonate is the the granular detergent composition.

Certain ratios of sodium carbonate, s and/or potassium salt are preferred, as potassium salt is admixed: More Preferred Preferred -licauar n incorporated into odium pyrophosphate follows, when the Most Preferred Potassium salt: 2:1 to 1:140 1:2 to 1:40 1:5 to 1:20 sodium pyrophosphate Potassium salt: 2:1 to 1:140 1:2 to 1:50 1:5 to 1:30 sodium carbonate Sodium pyrophosphate: 15:1 to 1:15 5:1 to 1:6 1:1 to 1:2 sodium carbonate Certain rLtios of the above are preferred when the potassium salt is sprayed on the sodium carbonate: More Preferred Most Preferred Preferred Potassium salt: 3:1 to 1:280 1:2 to 1:80 1:5 to 1:20 sodium pyrophosphate Potassium salt: 3:1 to 1:280 1:2 to 1:110 1:5 to 1:25 sodium carbonate Sodium pyrophosphate: 14:1 to 1:14 5:1 to 1:6 1:1 to 2:1 sodium carbonate The following examples illustrate the compositions and processes of the present invention. All parts, percentages, and ratios herein are by weight unless otherwise specified.

EXAMPLE I A granular laundry detergent composition of the present invention is as follows: Component Active Weight Sodium C12.3 linear alkylbenzene sulfonate 8.66 Sodium C14-15 alkyl sulfate 4.14 Sodium tripolyphosphate 2.09 Tetrasodium pyrophosphate 17.44 i i:: ,i -14 Sodium silicate 7.04 Pentasodium diethylenetriamine pentaacetate 0.30 Polyethylene glycol 0.25 Sodium polyacrylate 0.88 Brightener 0.11 Moisture 4.61 Sodium perborate monohydrate 4.32 Nonanoyloxybenzene sulfonate 5.04 Sodium carbonate 20.72 Potassium carbonate 4.80 Sodium sulfate/Miscellaneous 19.60 The process used to make this composition is as follows: Stock Material Weight Step 1 Sodium C12.3 linear alkylbenzene 6.51 Sulfuric acid 5.47 Sodium C14-15 fatty alcohol 2.77 Sulfuric acid 2.57 Sodium hydroxide 4.39 Water 17.18 Sodium polyacrylate 2.14 Step, Polyethylene glycol 0.58 Tetrasodium pyrophosphate 17.16 Sodium tripolyphosphate 4.54 Sodium silicate 16.01 Sodium sulfate 12.51 Brightener 0.17 Pentasodium diethylenetriamine pentaacetate 1.05 Step 3 Sodium perborate monohydrate 4.32 Nonanoyloxybenzene sulfonate 6.47 SSodium carbonate 20.72 Potassium carbonate 4.80 'f 4:.

i i 15 ft I I (I fI (t 'It The ingredients listed in step 1 are added together to form a paste. This paste is then crutched with the ingredients listed in step 2. This mixture is then spray dried to evaporate the excess moisture and form detergent granules. The ingredients listed in step 3 are then admixed to form the finished granular detergent composition.

The composition ("product") is evaluated in a washing machine test designed to simulate consumer wash conditions that promote insoluble clump formation (cold water, product/clothes/water order of addition, normal cycle, large load). Visually, the insoluble clumps appear as solid, white masses, about 5 to 40 millimeters in diameter and about 2 to 10 millimeters in length, which remain bound in the washed clothes or can be seen at the bottom of the washing machine tub after the clothes are removed. In this test, the composition containing potassium carbonate has little to no product remaining while the same composition without potassium carbonate has a significant amount of product remaining as insoluble clumps. Consumer complaint information suggests that insoluble clumps remaining after washing are unacceptable.

Product Remaining* (at the end of wash/rinse) Standard Deviation Product without potassium carbonate 7.5% 1.4 25 Product with potassium carbonate 0.7% 0.6 *These numbers represent the average across 3 replicates.

EXAMPLE II A granular laundry detergent composition of the present invention is as follows: Component Active Weight Sodium C12.

3 linear alkylbenzene sulfonate 8.92 Sodium C14- 1 5 alkyl sulfate 4.26 Sodium tripolyphosphate 2.15 Tetrasodium pyrophosphate 17.96 ''I~t

(II

1 a

I

((I

r -16- Sodium silicate 7.25 Pentasodium diethylenetriamine pentaacetate 0.31 Polyethylene glycol 0.26 Sodium polyacrylate 0.91 Brightener 0.12 SMoisture 4.74 Sodium perborate monohydrate 4.44 Nonanoyloxybenzene sulfonate 5.19 Sodium carbonate 21.34 10 Sodium sulfate/Miscellaneous 20.20 Potassium chloride 1.98 The process used to make this composition is as follows: Stock Material Weight SteD 1 Sodium C12.3 linear alkylbenzene 6.51 Sulfuric acid 5.47 Sodium C14-15 fatty alcohol 2.77 Sulfuric acid 2.57 Sodium hydroxide 4.39 Water 17.18 Sodium polyacrylate 2.14 Step 2 Polyethylene glycol 0.58 STetrasodium pyrophosphate 17.16 Sodium tripolyphosphate 4.54 Sodium silicate 16.01 Sodium sulfate 12.51 Brightener 0.17 Pentasodium diethylenetriamine pentaacetate 1.05 Step 3 Sodium perborate monohydrate 4.32 Nonanoyloxybenzene sulfonate 6.47 Sodium carbonate 21.34 Potassium chloride* 1.98 ii.. 17 *Micronized to mean particle size of 1.5 microns.

The ingredients listed in step 1 are added together to form a paste. This paste is then crutched with the ingredients listed in step 2. This mixture is then spray dried to evaporate the excess moisture and form detergent granules. The ingredients listed in step 3 are then admixed to form the finished granular detergent composition.

The composition ("product") is evaluated in a washing machine test designed to simulate consumer wash conditions that promote insoluble clump formation (cold water, product/clothes/water order of addition, normal cycle, large load). Visually, the insoluble clumps appear as solid, white masses which remain bound in the washed clothes or can be seen at the bottom of the washing machine tub after the clothes are removed. In this test, the composition containing potassium chloride has significantly fewer insoluble clumps than the same composition with no potassium chloride.

Product Remaininq* Standard (at the end of wash/rinse) Deviation Product without potassium chloride 7.5% 1.4 Product with potassium chloride 1.0% 1.7 *These numbers represent the average across 3 replicates.

EXAMPLE III A granular laundry detergent composition of the present invention is as follows: Component Active Weight Sodium C12.3 linear alkylbenzene sulfonate 8.92 Sodium C14-15 alkyl sulfate 4.26 Sodium tripolyphosphate 2.15 Tetrasodium pyrophosphate 17.96 Sodium silicate 7.25 Pentasodium diethylenetriamine pentaacetate 0.31 Polyethylene glycol 0.26 Sodium polyacrylate 0.91 Brightener 0.12 c (I 18 Water 4.74 Sodium perborate monohydrate 4.44 Nonanoyloxybenzene sulfonate 5.19 Sodium carbonate 21.34 Sodium sulfate/Miscellaneous 20.20 Potassium sulfate 1.98 The process used to make this composition is as follows: Stock Material Weight Step 1 Sodium C12.

3 linear alkylbenzene 6.51 Sulfuric acid 5.47 Sodium C14-15 fatty alcohol 2.77 Sulfuric acid 2.57 Sodium hydroxide 4.39 Water 17.18 Sodium polyacrylate 2.14 t Step 2 Polyethylene glycol 0.58 Tetrasodium pyrophosphate 17.16 Sodium tripolyphosphate 4.54 Sodium silicate 16.01 Sodium sulfate 12.51 Brightener 0.17 Pentasodium diethylenetriamine pentaacetate 1.05 Ste 3 Sodium perborate monohydrate 4.32 Nonanoyloxybenzene sulfonate 6.47 Sodium carbonate 21.34 Potassium sulfate* 1.98 *Micronized to mean particle size of 1.5 microns.

The ingredients listed in step 1 are added together to form a paste. This paste is then crutched with the ingredients listed in step 2. This mixture is then spray dried to evaporate the excess moisture and form detergent granules. The ingredients listed in i 1- -19i.

J.-

1*

I

*1 i

I

i

I

step 3 are then admixed to form the finished granular detergent composition.

The composition ("product") is evaluated in a washing machine test designed to simulate consumer wash conditions that promote insoluble clump formation (cold water, product/clothes/water order of addition, normal cycle, large load). Visually, the insoluble clumps appear as solid, white masses which remain bound in the washed clothes or can be seen at the bottom of the washing machine tub after the clothes are removed. In this test, the composition containing potassium sulfate had little to no product remaining while the same composition with no potassium sulfate had a significant amount of product remaining as insoluble clumps.

Product Remaininq* Standard (at the end of wash/rinse) Deviation 15 Product without potassium sulfate 7.5% 1.4 Product with potassium sulfate 1.0% 0 *These numbers represent the average across 3 replicates.

EXAMPLE IV A granular laundry detergent composition of the present invention is as follows: Component Active Weight Sodium C12.

3 linear alkylbenzene sulfonate 9.10 Sodium C 1 4-1 5 alkyl sulfate 4.35 Sodium tripolyphosphate 2.19 25 Tetrasodium pyrophosphate 18.32 Sodium silicate 7.39 Pentasodium diethylenetriamine pentaacetate 0.31 Polyethylene glycol 0.27 Sodium polyacrylate 0.92 Brightener 0.12 Water 4.84 Sodium perborate monohydrate 4.53 Nonanoyloxybenzene sulfonate 5.29 Potassium sulfate coated sodium carbonate 21.77 Sodium sulfate/Miscellaneous 20.59 The process used to make this composition is as follows: Stock Material Weight Step 1 Sodium C12.3 linear alkylbenzene 6.51 j Sulfuric acid 5,47 Sodium C14-15 fatty alcohol 2.77 Sulfuric acid 2.57 Sodium hydroxide 4.39 Water 17.18 Sodium polyacrylate 2.14 SStep 2 Polyethylene glycol 0.58 Tetrasodium pyrophosphate 17.16 1 Sodium tripolyphosphate 4.54 Sodium silicate 16.01 S Sodium sulfate 12.51 IBrightener 0.17 SPentasodium diethylenetriamine pentaacetate 1.05 1 20 Step 3 Potassium sulfate* 0.41 Water 1.22 Sodium carbonate 20.14 Step 4 2 Sodium perborate monohydrate 4.32 Nonanoyloxybenzene sulfonate 6.47 *Micronized to mean particle size of 1.5 microns.

The ingredients listed in step 1 are added together to form a paste. This paste is then crutched with the ingredients listed in step 2. This mixture is then spray dried to evaporate the excess moisture and form detergent granules. The first two ingredients listed in step 3 are then mixed together and sprayed onto the sodium carbonate. This sodium carbonate along with the r 21 ingredients listed in step 4 are then admixed to form the finished product.

The product is evaluated in a washing machine test designed to simulate consumer wash conditions that promote insoluble clump formation (cold water, product/clothes/water order of addition, normal cycle, large load). Visually, the clumps are white solid masses which can be found bound up in the clothes or in the bottom of the washer after the clothes are removed. In this test, the product with potassium sulfate coated sodium carbonate showed little to no product remaining while the same product with uncoated sodium carbonate had a significant amount of product remaining as insoluble clumps.

Product Remaining* Standard (at the end of wash/rinse) Deviation Product without potassium sulfate 7.5% 1.4 Product with potassium sulfate 0.7% 1.2 *These numbers represent the average across 3 replicates.

EXAMPLE V A granular laundry detergent composition is as follows: Component Active Weight Sodium C12.3 linear alkylbenzene sulfonate 12.01 Sodium C14-15 alkyl sulfate 5.59 Sodium tripolyphosphate 33.73 Tetrasodium pyrophosphate 7.70 Sodium silicate 8.00 Sodium carbonate 9.17 Potassium carbonate 2.00 Sodium perborate monohydrate 0.40 Sodium polyacrylate 1.52 Enzyme 0.84 Silicone 0.16 Brightener 0.28 Polyethylene glycol 0.61 C12-13 alkylpolyethoxylate 0.10 j i Y- ~I 22 Sodium sulfate 8.95 Perfume 0.40 Water 7.34 Miscellaneous 1.20 The process used to make this composition is as follows: SteD 1 Sodium C12.3 linear alkylbenzene, sodium C14-15 fatty alcohol, sulfuric acid, sodium hydroxide, sodium polyacrylate, and water are added together to form a paste. This paste is then crutched with the ingredients in step 2.

Step 2 Polyethylene glycol, tetrasodium pyrophosphate, sodium tripolyphosphate, sodium silicate, sodium sulfate, and brightener are then crutched with the paste formed in step 1. This mixture is then spray dried to evaporate the excess moisture and form detergent granules.

Step 3 Sodium perborate monohydrate, sodium carbonate, potassium carbonate, silicone, C12-13 alkylpolyethoxylate, and enzyme are admixed to form the finished product. Perfume is sprayed on.

The product is evaluated in a washing machine test designed to simulate consumer wash conditions that promote insoluble clump formation (cold water, product/clothes/water order of addition, normal cycle, large load). In this test, the product with potassium carbonate showed a significant reduction in insoluble clumps product remaining) compared to the same product without potassium carbonate.

Product Remaininq* (at the end of wash/rinse) Standard Deviation Product without potassium carbonate 32.3% 2.4 Product with potassium carbonate 3.5% i; i i I t 23 Note: The number associated with the no-potassium product is an average of 2 replicates. The number associated with the potassium product is an average of 3 replicates.

EXAMPLE VI A granular laundry detergent composition is as follows: SComponent Active Weight Sodium C12.3 linear alkylbenzene sulfonate 9.49 Sodium C14-15 alkyl sulfate 4.06 Tetrasodium pyrophosphate 8.67 Crutched sodium tripolyphosphate 16.07 Admixed sodium tripolyphosphate 5.86 Sodium silicate 8.18 Sodium carb6nate 20.04 Potassium carbonate 2.00 Sodium perborate monohydrate 4.18 0 o 0. Nonanoyloxybenzene sulfonate 5.91 Pentasodium diethylenetriamine pentaacetate 0.49 S° Enzyme 0.63 o Sodium polyacrylate 1.10 o 20 Brightener 0.19 Polyethylene glycol 0.34 Sodium sulfate 9.72

C

1 2- 13 alkylpolyethoxylate .Perfume 0.25 25 Water 2.00 Miscellaneous 0.32 The process used to make this composition is as follows: SteD 1 Sodium C12.3 linear alkylbenzene, sodium C14-15 fatty 30 alcohol, sulfuric acid, sodium hydroxide, sodium polyacrylate, and water are added together to form a paste. This paste is then crutched with the ingredients in step 2.

L .I 24 Step 2 Polyethylene glycol, tetrasodium pyrophosphate, crutched sodium tripolyphosphate, sodium silicate, sodium sulfate, brightener, and pentasodium diethylenetriamine pentaacetate are crutched with the paste formed in step 1. This mixture is then spray dried to evaporate the excess moisture and form detergent granules.

Step 3 Oxygen bleach, bleach activator, sodium carbonate, potassium carbonate, admixed sodium tripolyphosphate, and C 12 13 alkylpolyethoxylate, and enzyme are then admixed to form the finished product. Perfume is sprayed on.

The product is evaluated in a washing machine test designed to simulate consumer wash conditions that promote insoluble clump formation (cold water, product/clothes/water order of addition, normal cycle, large load). In this test, the product with potassium carbonate showed a significant reduction in insoluble clumps product remaining) compared to the same product without potassium carbonate.

Product Remaininq* (at the end of wash/rinse) Standard Deviatioq Product without potassium carbonate 8.2% Product with potassium carbonate 1.9% 3.4 Note: These numbers represent the average across 3 replicates.

EXAMPLE VII A I A granular laundry detergent of the present invention is as follows: Component Active Weight Alkylpolyethoxylate 7.52 Sodium tripolyphosphate 21.42 Sodium carbonate 51.90 Sodium silicate 4.95 Oxygen bleach 2.03 Enzyme (Protease) 0.85 Brightener 0.26 Carboxymethyl cellulose 0.29 Perfume 0.24 Sodium sulfate/miscellaneous 1.31 Moisture 4.48 Potassium sulfate 4.76 This composition is based on laboratory analysis of a representative sample of a competitive granular laundry detergent product. The product is evaluated in a washing machine test designed to simulate consumer wash conditions that promote insoluble clump formation (cold water, product/clothes/water order of addition normal cycle, large load). Visually, the clumps are white solid masses which can be found bound up in the clothes or in the bottom of the washer after the clothes are removed. In 15 this test, the product with potassium sulfate showed a significant S'reduction in insoluble clumps compared to the same product without potassium sulfate.

Product Remaining* (at the end of wash/rinse) Standard Deviation Product without potassium sulfate 5.8 Product with potassium sulfate 0.7 1.2 These numbers represent the average across 6 replicates.

SITARxxd*kt&fixtx

Claims (15)

1. A granular laundry detergent composition or additive, comprising: from 5 to 70 weight detergent surfactant selected from the group consisting of anionics, nonionics, zwitterionics, ampholytics, cationics, and mixtures thereof; from 5 to 70 weight sodium phosphate; and from 5 to 70 weight sodium carbonate; and from 0.1 to 10 weight potassium salt.

2. A granular laundry detergent composition according to Claim 1, comprising from 10 to 30 weight detergent surfactant selected from the group consisting of anionics, nonionics, cationics and mixtures thereof.

3. A granular laundry detergent composition according to Claim 2, comprising from 12 to 20 weight detergent surfactant.

4. A granular laundry detergent composition according to Claim 3, comprising from 10 to 40 weight sodium pyrophosphate and from 8 to 50 weight sodium carbonate. 'I ''4

5. A granular comprising from 11 to 30 weight laundry detergent composition according to Claim 4, 15 to 35 weight tetrasodium pyrophosphate and from sodium carbonate.

6. A granular laundry detergent composition according to Claim wherein said potassium salt has a mean particle size of less than 200 microns.

7. A granular comprising from

8. A granular comprising from laundry detergent composition according to Claim 6, 0.5 to 5 weight inorganic potassium salt. laundry detergent composition according to Claim 1, 0.1 to 2 weight potassium salt. sl -r r n~n a Ann -27- &ab base quu4 I i

9. A granular laundry detergent composition according to Claim 7, wherein the inorganic potassium salt is selected from the group consisting of potassium chloride, potassium carbonate, potassium sulfate, and mixtures thereof; and has a mean particle size of between 1 and 10 microns. A granular laundry detergent composition according to Claim 9, comprising from 1 to 3 weight potassium carbonate.

11. A granular laundry detergent composition according to Claim 9, further comprising from 1 to 10 weight sodium tripolyphosphate.

12. A granular laundry detergent composition according to Claim 9, comprising: from 12 to 20 weight sodium linear C10-16 alkylbenzene sulfonate and sodium C12-18 alkyl sulfate in a ratio between 50:50 and 80:20; from 15 to 35 weight tetrasodium pyrophosphate; from 11 to 30 weight sodium carbonate; from 0.5 to 5 weight inorganic potassium salt selected from the group consisting of potassium chloride, potassium carbonate, potassium sulfate, and mixtures thereof, and having a mean particle size of less than 200 microns. -Vhe o r c-oA VJQ -P-C-

13. A process for improving solubility or dispersibility of a granular laundry detergent composition according to Claim 1, wherein an aqueous solution of said potassium salt is distributed on said sodium carbonate prior to incorporation into said granular laundry detergent composition.

14. A process for improving solubility or dispersibility of a granular laundry detergent composition according to Claim 7, wherein an aqueous solution of said potassium salt is sprayed onto said sodium carbonate prior to incorporation into said granular laundry detergent composition. qj RA"-* 0))r n' P&G Case 4004 S-28- q. the. or" co\iA \Ncater A process for improving solubility or dispersibility of a granular laundry detergent composition according to Claim 1, which comprises: producing detergent granules comprising detergent surfactant selected from the group consisting of anionics, nonionics, zwitterionics, ampholytics, cationics, and mixtures thereof; and sodium phosphate; and admixing with said detergent granules sodium carbonate and potassium salt; wherein the final detergent composition comprises from 5 to weight detergent surfactant, from 5 to 70 weight sodium phosphate, from 5 to 70 weight sodium carbonate, and from 0.1 to weight potassium salt. coo\ \NMOeA~

16. A process for improving ,solubility or dispersibility of a granular laundry detergent composition according to Claim 12, which comprises: forming a paste comprising sodium linear C10-16 alkylbenzene sulfonate and sodium C12-18 alkyl sulfate in a ratio between 50:50 and 80:20; crutching the paste with sodium pyrophosphate; spray drying the mixture of step to form detergent granules; and admixing the detergent granules with sodium carbonate and inorganic potassium salt selected from the group consisting of potassium chloride, potassium carbonate, potassium sulfate, and mixtures thereof, and having a mean particle size of less than 200 microns; AL wherein the final detergent composition comprises from 12 to weight sodium linear C10-16 alkylbenzene sulfonate and sodium C12-18 alkyl sulfate, from 15 to 35 weight sodium pyrophosphate, from 11 to 30 weight sodium carbonate, and from 0.5 to 5 weight inorganic potassium salt.

17. A process for improving solubility or dispersibility of a granular laundry detergent composition according to Claim 16, which further comprises in step crutching said paste with sodium r r ,z~~R r; i- 1 ;~l~--_~ulurrrarr.;rrr~*~-;-ul6- ~Ll;i .41 -29- tripolyphosphate so that the final detergent composition comprises from 1 to 10 weight sodium tripolyphosphate. A compositon or additive according to any one of claims 1 to 12 substantially as herein described with reference to any one of the Examples. A process according to any one of claims 13 to 17 substantially as herein described with reference to any one of the Examples. DATED: 6 March 1992 PHILLIPS ORMONDE FITZPATRICK Attorneys for: THE PROCTER GAMBLE COMPANY D--ka r-"Lb I .s [j 39 9843S