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Publication numberUS3529923 A
Publication typeGrant
Publication dateSep 22, 1970
Filing dateSep 21, 1967
Priority dateSep 21, 1967
Also published asDE1794180A1, DE1794180B2, DE1794180C3
Publication numberUS 3529923 A, US 3529923A, US-A-3529923, US3529923 A, US3529923A
InventorsRonald O Baukol, Ronald L Jacobsen, Ronald A Perry
Original AssigneeProcter & Gamble
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Ultramarine benzyl quaternary ammonium compound mixture in a granular bluing composition
US 3529923 A
Abstract  available in
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Claims  available in
Description  (OCR text may contain errors)

United States Patent O ULTRAMARINE BENZYL QUATERNARY AMMO- NIUM COMPOUND MIXTURE IN A GRANULAR BLUING COMPOSITION Ronald A. Perry, Mexico City, Mexico, Ronald O. Baukol, Anoka, Minn., and Ronald L. Jacobson, Wyoming, Ohio, assignors to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Filed Sept. 21, 1967, Ser. No. 669,398

Int. Cl. C09c 1/32; D061 3/12 US. Cl. 8-77 7 Claims ABSTRACT OF THE DISCLOSURE A granular bluing composition having non-staining qualities comprising an inorganic particulate alkaline salt, ultramarine blue and a cationic quaternary ammonium compound, preferably in a form agglomerated with an adhesive agent and water. The bluing composition is particularly useful in admixture with white or lightly colored detergent granules to provide a speckled composition.

BACKGROUND OF THE INVENTION Granular bluing compositions are useful in offsetting the yellowing tendency of laundered fabrics and have particular utility when mixed with detergent granules. For example, when such a bluing composition is mixed with colorless or lightly colored granules as described in Canadian Pat. 577,479, issued June 9, 1959 to Britt, a speckled granular composition is obtained which not only provides bluing utility without the need for adding dye to all the granules, but also has a distinctive and attractive appearance. Various methods of production of granular bluing compositions are known in the art including an agglomeration process, as described in US. Pat. 3,035,301, issued May 22, 1962, and spray-drying.

When ultramarine blue is used as the pigment in agglomeration, or similar granules-forming processes, the resulting granules or bluing compositions, particularly when added to granular detergent composition, may cause staining of the fabrics that they come in contact with during the various Washing operations, particularly, in the hand washing of fabrics. Ultramarine blue is a particulate pigment which is a complex combination of silica, alumina, soda and chemically combined sulfur which exists naturally and can also be synthetically prepared. When a monoparticulate layer of ultramarine blue attaches to a fabric this results in a desired bluing effect. However, when the ultramarine blue particles first attach to each other and then to the fabric this may result in an undesired staining effect due to the plurality of layers of bluing material. As ultramarine blue is an excellent and highly desirable coloring material, i.e., stable to alkali, non-toxic and nonirritating, various methods of overcoming this staining problem have been investigated without a completely satisfactory solution of the problem.

It is, therefore, an object of this invention to provide novel granular bluing compositions which do not stain fabrics, particularly when utilized in detergent compositions.

Other objects and advantages of this invention will be apparent from the following description.

SUMMARY OF THE INVENTION The objects of this invention are achieved by a granular bluing composition containing an inorganic alkaline salt, ultramarine blue and a cationic quaternary ammonium compound of a specific class. Preferably the composition is in the form of an agglomerate.

The inorganic alkaline salt utilized in this invention is 3,529,923 Patented Sept. 22, 1970 a water-soluble hydratable salt which is compatible with the other ingredients of the composition and the usual hydrate of which is fairly stable against thermal decomposition at room temperature. The function of the inorganic alkaline salt is to serve as a carrier for the ultramarine blue and the specific cationic quaternary ammonium compound. The salt must be alkaline because ultramarine blue is sensitive to any acid. It is a preferred embodiment of this invention to employ an inorganic alkaline salt, such as sodium tripolyphosphate, in the bluing composition which contributes to its overall laundering effectiveness, particularly if it is used to speckle detergent compositions. Otherwise, the granular water-soluble hydratable inorganic alkaline salt can be any salt having the desired properties of compatability and hydrate stability.

Alkali metal tripolyphosphates, e.g., sodium tripolyphosphate, are the preferred inorganic alkaline salts but alkali phosphates, e.g., trisodium phosphate, alkali metal carbonates, e.g., sodium carbonate, alkali metal pyrophosphates, e.g., sodium pyrophosphate, and alkali metal tetraborates, e.g., anhydrous borax, can also be utilized. Corresponding potassium and lithium salts can likewise be used, but sodium salts are preferred. The inorganic alkaline salt comprises the bulk of the granular bluing composition and will comprise the balance of the composition after the ultramarine blue and the cationic compound and any other additives such as an adhesive agent and water are included. Generally the inorganic alkaline salt will comprise from about 60% to about by weight of the bluing composition.

Ultramarine blue is used to give the granular bluing composition its distinctive color and bluing utility. The ultramarine blue comprises from about 0.1% to about 15% by weight of the granular bluing composition. If less than about 0.1% by Weight is used the desired bluing effect is not achieved and if more than about 15% by weight is used then an undesirable level of bluing and staining may occur even with the usage of the specific cationic quaternary ammonium compounds of this invention. A preferred range of ultramarine blue of from about 3% to about 8% by weight will yield the best results of this invention.

The specific cationic quaternary ammonium compounds which can be utilized in this invention are of the formula:

wherein from 1 to 3 of the R groups are long chain alkyl groups having from about 10 to about 20 carbon atoms, and mixtures thereof, and wherein one of the R groups is wherein n is from 1 to about 3 and wherein remaining R groups are alkyls having from 1 to about 3 carbon atoms; X is selected from the group consisting of chloride, bromide, iodide, alkyl sulfate and alkyl phosphate anions wherein the alkyl groups contain from 1 to about 3 carbon atoms.

Examples of preferred cationic quaternary ammonium compounds are: dicoconut alkyl methylbenzylammonium chloride and coconut alkyl dimethylbenzylammonium chloride, wherein coconut alkyl is a mixture of alkyls with the following chain distribution: 2%C 66%C 23 %-C and 9%-C Examples of other suitable cationic quaternary ammonium compounds are:

decyl dimethylbenzylammonium bromide, di-undecyl propylbenzylammonium iodide,

dodecyl diethyl-Z-phenylethylammonium chloride, tridecyl methylethylbenzylammonium methylsulfate, tri-tetradecyl 3-phenylpropylammonium bromide, pentadecyl dipropylbenzylammonium methylphosphate, di-hexadecyl methyl-Z-phenylethylammonium propylphosphate, heptadecyl dipropylbenzylammonium ethylsulfate, tri-octadecyl benzylammonium chloride, di-nonadecyl ethyl-3-phenylpropylammonium ethylphosphate, eicosyl ethylpropylbenzyl ammonium propyl sulfate, tallow alkyl methylpropylbenzylammonium bromide, ditallow alkyl ethyl-2-phenylethylammonium iodide, ditallow alkyl methylbenzylammonium chloride, tritallow alkyl benzylammonium chloride, tallow alkyl dimethylbenzylammonium chloride,

and mixtures thereof.

The desired cationic quaternary ammonium compound comprises from about .004% to about 5% by weight of the granular bluing composition. If less than about .004% by weight of the cationic quaternary ammonium compound is used then the staining problem may not be ade quately solved. More than about 5% by weight is unnecessary and may adversely affect other ingredients in the composition such as an adhesive agent which might be used. A preferred range is from about 0.1% to about 1% by weight.

In order to overcome the staining problem and achieve the desired bluing effects with the ultramarine blue, the specific cationic quaternary ammonium compounds of this invention must be utilized. Anionic and nonionic surfactants and cationic quaternary ammonium compounds other than the class described above will not effectively meet the ultramarine blue staining problem. While not wishing to be bound by theory, it is believed that the cationuic compound somehow prevents the undesired grouping of ultramarine blue particles which causes staining and encourages the desired monoparticulate layering on the fabric.

While the best mode contemplated for preparing the granular bluing composition of the present invention is set forth below, any equivalent method can likewise be used. The granular bluing composition can be made, for example, by agglomeration, spray-on, spray drying processes, mechanical mixing, and the like.

The preferred method of preparing the granular bluing composition is agglomeration which utilizes a pan agglomerator in generally the following manner: the inorganic particulate alkaline salt as described above, which is initially comprised of a particle size such that it passes through a and is retained on an 80 Tyler mesh screen is sprayed with an adhering mixture containing an adhesive agent as described below, ultramarine blue and a cationic quaternary ammonium compound selected from those described above and water. The salt particles tumble around and over themselves on a revolving pan tilted between 40 and 50 from the vertical. The revolving pan agglomerator has a peripheral lip or weir which ex: tends 4 to 6 inches above the surface of the pan and normal to it. As the pan rotates on its tilted position, the granules are forced to tumble over one another and are not permitted to jump the weir until they have achieved sufficient size, i.e., particles which pass through a 10 and are retained on a 20 mesh Tyler mesh screen. The build-up in particle size is achieved by the particles agglomerating with themselves because of the sticky adhesive mixture being sprayed on them. The resulting particle size is determined by several factors, e.g., the angle of the pan from the vertical, the speed of rotation of the pan, the total throughput of inorganic alkaline salt to adhesive spray, the composition of the adhesive agent and the initial particle size of the inorganic alkaline salt. In accordance with the present invention, all of these features can be properly selected and controlled,

The water-soluble adhesive agents which can be used in agglomerating the granular bluing composition are any materials which act as an adhesive or binding agent and afford an easy method of building up the particulate inorganic alkaline salt to a desired size containing the ultramarine blue and the specific cationic quaternary ammonium compound.

The water-soluble adhesive agent is employed with water and can be an organic material, e.g., various starches such as corn starch and tapioca starch, dextrin and other partially hydrolyzed or so-called water-soluble starches; gums, such as gum tragacanth and other water-soluble gums and water-soluble glues; or an inorganic material, e.g., silicates.

The water-soluble adhesive agent, when used, comprises from about 5 %to about 20% by weight of an agglomerated form of the granular bluing composition. If less than about 5% by weight of the water-soluble adhesive agent is used, then the desired binding and adhesive effects would not be achieved and if more than 25% by weight is used then the water used therewith would present a drying problem. Preferably from about 6% to about 12% by weight of the water-soluble adhesive agent will best realize the objects of this invention.

The water-soluble adhesive agent can optionally also contain minor additives such as small amounts of sodium metaborate (Na B O -8H O), borax (Na B O -5H O) and Dowicide A. These components can comprise up to about 10% by weight of the adhesive agent. The sodium metaborate is used as a pH buffer and the borax is used to increase the viscosity of the adhesive agent. Dowicide A is a trade name of an antimicrobial agent of the formula C H (C H )ONa-4H O marketed by the Dow Chemical Company. Other similar antimicrobial agents can also be used.

The percentage of water in an agglomerated form of the granular bluing composition is from about 5% to about 30% by weight. Water is employed along with the adhesives to effect the desired agglomeration. If less than about 5% by weight is used an effective adhesive mixture will not be formed for agglomeration purposes and if more than about 30% by Weight is utilized a drying problem would result. A preferred range is from about 7% to about 20% by weight of water for best results.

The granular bluing compositions of this invention can also be prepared by typical spray drying operations. It is well known to those skilled in the art that in a typical spray drying operation, an aqueous mixture is first prepared in a flowing condition which is referred to as a crutcher mix. This mix, containing about 25% to 50% water, preferably about 38% to 45% water, is then pumped to the top of a drying tower and provided with sufiicient energy for atomization by a low pressure pump and a high pressure pump. The mix is delivered to the spray nozzles at the top of the spray tower at pressures between 500 and 1800 p.s.i. where it is atomized into the upper part of the chamber or tower. This tower contains a column of air which has been heated to a temperature in the range of from about 220-500 F. and which may pass in either concurrent or countercurrent direction to the sprayed mixture to evaporate the water from the falling atomized particles. As the particles descend through the tower, drying takes place. The finished granules collect in the cone at the bottom of the tower and pass out of the tower through a feeder valve into a rotating drum. Eventually the product is conveyed to the packing area by belt.

The granular bluing compositions of this invention can also be prepared by a typical spray-on operation. A sprayon process generally involves the formation of a slurry at room temperature which is then sprayed onto the particu late inorganic alkaline salt. The particulate salt can be in a. vessel under agitation, e.g., a ribbon blender, falling through an open zone, e.g., a drying tower, or being passed on a belt exposed to the fine spray of the slurry. Other techniques can likewise be used.

The granular bluing composition of the present invention is desirably comprised of granules coming within the range of 0.2 millimeter up to 1.5 millimeters in size. Preferably, the granules should be of a reasonably uniform size averaging about 1 millimeter. A satisfactory particle size distribution can be obtained by having less than 1% be retained on a Tyler 14 mesh, about 40% being retained on 48 Tyler mesh and having less than about pass through 65 Tyler mesh.

The granular size distribution should especially be adhered to when the bluing composition is to be employed with and distributed throughout a granular detergent composition. In such an application, it is especially important to be free of fine, powdery materials for the reason that they tend to segregate in a carton and the desired aesthetic appearance would be lost. In addition, fine bluing powders, i.e., less than 0.2 millimeter, tend to blend into the background and present a diffused or pastel appearance when employed in detergent compositions. Particle sizes greater than 1.5 millimeters also tend to detract from the desired distinctive appearance. As a precautionary measure, the fines can be screened out either before coloring or after, by using screens of 35 Tyler mesh or even finer.

Even apart from the consideration of employing the bluing composition in combination with granular detergent compositions, the particle size distribution given above aifords best results of imparting a desired bluing effect without the risk of an attendant staining problem.

When the granular bluing composition is utilized with a granular detergent composition, e.g., a white granular detergent composition, the bluing composition should be used in an amount of from 2% up to about 30% by weight of the combined composition; the balance to 100% being the detergent composition. The teachings of the Britt patent infra in this regard are incorporated herein by reference. It has been found that with this proportion of bluing granules thoroughly mixed with a balance ,of detergent granules of roughly the same general characteristics of size, density or specific gravity, the mixture is permanent in the sense that the bluing granules do not tend to segregate upon handling, jogging and the like. Preferably, the bluing granules of the present invention and the bulk of the detergent composition granules should have approximately the same screen analysis, i.e., particle size distribution.

The following examples illustrate in detail the manner in which the invention may be practiced. However, the invention is not confined to the specific limitations set forth in the individual examples but rather, to the scope of the appended claims.

PREFERRED EMBODIMENTS Example I The following granular bluing composition was prepared in a 12 pound yield by an agglomeration process utilizing a pan agglomerator which revolved tilted 45 from the vertical. The revolving pan had a peripheral lip 6 inches above the surface of the pan and normal to it. Nine pounds of sodium tripolyphosphate having a particle size 90% of which passed through a 28 and are retained on an 80 Tyler mesh screen were sprayed with an adher ing mixture containing 1.1 pounds of an adhesive agent comprised of dextrin, Dowicide A, sodium metaborate and borax; .65 pound of ultramarine blue, .05 pound of dicoconut alkyl methylbenzylammonium chloride and 2.2 pounds of water. The particles were then tumbled over one another and were not permitted to jump the weir until they had achieved the desired size which was such that particles passed through a 10 mesh and were retained on a 20 Tyler mesh screen. About one pound of water was lost to the atmosphere.

The adhesive agent contained about 91% dextrin and about 9% of the other components, i.e., Dowicide A, sodium metaborate and borax. The adhesive agent, ultramarine blue and dicoconut alkyl methylbenzylammonium chloride were mixed in cool water F.) and then heated for about 25 minutes at a temperature of about 190 F. to achieve hydrolysis. The adhering mixture was then cooled down to about F. to increase the viscosity and with continuous agitation was sprayed on the sodium tripolyphosphate particles.

The following composition was thus prepared, all amounts being expressed as parts by weight:

The pH of this composition at a conventional washing concentration of about 5 grams per gallon in water at F. was 9.6. The color of the composition was blue.

Three swatches, one each of cotton muslin, resin-treated cotton muslin and Dacron were tested in the following manner: about 5 grams of the granular bluing composition were weighed out and put. into a container. The swatches of cloth, approximately 12 inches square, were folded to one quarter of their original size and placed in rectangular dishpans. One gallon of soft water at 100 F. made up to 7 grain hardness was poured slowly over the swatches in the dishpan. The measured amount of the blue granular detergent additive was then poured slowly into the solution and the solution with the swatches was then left undisturbed for 30 minutes. At the end of this period the swatches were removed, the excess Water was squeezed out by hand and the swatches were then put through an automatic rinse cycle in an upright top-loading washing machine.

As a control and as a basis for comparison identical swatches Were prepared and tested except that no dicoconut alkyl methylbenzylammonium chloride was present in the composition and a minor amount of Pluronic L- 64 was present. Pluronic L-64 is a condensate of ethylene oxide with a hydrophobic base formed by condensing propylene oxide with propylene glycol with a molecular Weight of about 2900 and acts as a wetting agent.

The composition of this control sample, all amounts being expressed as parts by weight, was as follows:

Sodium tripholyphosphate 75.00 Pluronic L-64 0.16 Ultramarine blue 5.40 Adhesive agent as defined above 9.20 Water 10.24

Resin-treated muslin Muslin Dacron Granular bluing composition with dicoconut alkyl methylbenzylamrnonium chloride 0 0 0 Granular bluing composition without dicoconut alkyl methylbenzylammonium chloride 5 5 3 These results clearly show that the swatches laundered with the granular bluing composition of this invention displayed a definite and significant reduction and almost total absence of staining when compared with the corresponding swatches laundered with the detergent additive without dicoconut alkyl methylbenzylammonium chloride present therein. Thus, the granular bluing composition of this invention olfers desired bluing effects without the attendant staining problems previously incurred.

Substantially the same results are obtained in bluing compositions of Example I when any of the following cationic compounds are substituted on an equal weight basis for dicoconut alkyl methylbenzylammonium chloride in Example I:

and mixtures of any of these.

When particulate trisodium phosphate, sodium carbonate, sodium pyrophosphate and anhydrous borax are substituted for sodium tripolyphosphate on an equal weight basis as the inorganic alkaline base granule of Example I substantially equivalent results are obtained in that excellent bluing effects are obtained with a definite and significant reduction of staining observed.

Example II The following granular bluing composition is prepared according to the process and other conditions of Example I; all amounts being expressed as parts by weight:

Sodium tripolyphosphate 78.5 Ultramarine blue 5.4 Coconut alkyl dimethylbenzylammonium chloride 0.5 Adhesive agent of Example I 9.0 Water 6.6

The pH of this composition at a conventional washing concentration of about grams per gallon in water at 130 F. is about 9.6. The coconut alkyl is derived from middlecut coconut fatty alcohol of the following chain distribution: 2%-C10, 66%C12, %C14 and 9% C15.

When this granular bluing composition is tested according to the procedure of Example I on swatches corresponding to those utilized in Example I there is a desirable level of bluing obtained with a significant reduction in staining in comparison to the same composition except containing no coconut alkyl dimethylbenzylammonium chloride.

Example III The composition of Example I was added to a granular detergent composition prepared by standard spray drying methods having a particle size 90% of which passed through a 10 and was retained on a 100 Tyler mesh screen, to give the following formulation; all amounts being expressed as parts by weight:

Sodium straight chain alkylbenzene sulfonate wherein the alkyl averages about 12 carbon This distinctively speckled detergent composition had bluing utility and was compared, according to the staining test procedure outlined in Example I, with an identical detergent composition except that no dicoconut alkyl methylbenzylammonium chloride was present in the bluing composition. The results of these staining tests are expressed in the following table:

Resiu-treated muslin Muslin Dacron Detergent composition with dicoconut alkyl methylbenzylammonium chloride 1 1. 5 1 Detergent composition without dicoconut alkyl methylbenzylammonium chloride 4 4 4 These results show significant differences in staining. Since identical compositions except for the dicoconut alkyl methylbenzylammonium chloride were utilized, the differences are due to the use of the specific quaternary ammonium compound, i.e., dicoconut alkyl methylbenzylammonium chloride.

Example IV A slurry is prepared by mixing together at room temperature the following components, all parts by weight:

Sodium tripolyphosphate 80.0 Water 57.0

Ultramarine blue n 5.0

which is then spray dried in a tower with an inlet temperature of about 180 F. and under about 500 p.s.i. pressure and an outlet temperature of about 200 F. A granular bluing composition of particle size which passes through a 10 mesh and is retained on a 100 mesh Tyler screen is produced with the composition as follows, all parts by weight:

Dicoconut alkyl methylbenzylammonium chloride Sodium tripolyphosphate 80.0 Water 14.0 Ultramarine blue 5.0 Dicoconut alkyl methylbenzylammonium chloride 1.0

This granular bluing composition used alone or in a detergent composition imparts a desired bluing effect to fabrics treated thereby without any staining problems.

Example V A slurry is prepared by mixing together at room tem perature the following components, all parts by weight:

Ultramarine blue 5 .0 Dicoconut alkyl methylbenzylammonium chloride 1.0 Water 14.0

which is then sprayed onto parts particulate sodium tripolyphosphate under constant agitation in a ribbon blender. A granular bluing composition of particle size which passes through a 10 mesh and is retained on a mesh Tyler screen is produced with the composition as follows, all parts by weight:

Sodium tripolyphosphate 80.0 Ultramarine blue 5.0

Coconut alkyl dimethylbenzyl ammonium methyl sulfate 1.0

Water 14.0

When this granular bluing composition is used in a detergent composition a desired bluing results without staining problems.

White fabrics immersed in an aqueous solution of this granular bluing composition having a concentration of grams per gallon acquire an effective bluing treatment without any staining problem.

In addition to the preferred embodiments descriibed herein, other arrangements and variations within the spirit and scope of the invention and the appended claims will occur to those skilled in the art.

What is claimed is:

1. A granular bluing composition consisting essentially of a water-soluble inorganic alkaline hydratable salt, from about 0.1% to about 15% ultramarine blue, from about .004% to about 5% of a cationic quaternary ammonium compound of the formula wherein from 1 to 3 of the R groups are long chain alkyl groups having from about to about 20 carbon atoms, and mixtures thereof, and wherein one of the group is wherein n is from 1 to about 3 and wherein remaining R groups are alkyl having from 1 to about 3 carbon atoms and wherein X is selected from the group consisting of chloride, bromide, iodide, alkyl sulfate and alkyl phosphate anions wherein the alkyl groups contain from 1 to about 3 carbon atoms.

2. The composition of claim 1 in agglomerate form wherein the inorganic salt, the ultramarine blue and the cationic compound are agglomerated with from about 5% to about 20% of a water-soluble adhesive agent and about 5% to about 30% water.

3. The composition of claim 2 wherein the inorganic salt is sodium tripolyphosphate.

4. The composition of claim 3 wherein the cationic quaternary ammonium compound is dicoconut alkyl methylbenzylammonium chloride.

5. The composition of claim .3 wherein the cationic quaternary ammonium compound is coconut alkyl dimethylbenzylammonium chloride.

6. The composition of claim 4 wherein the cationic quaternary ammonium compound is present in amount of from about 0.1% to about 1.0%.

7. A process for the preparation of the composition of claim 2 which comprises agglomerating an inorganic alkaline salt, ultramarine blue and from about .004% to about 5% of the cationic quaternary ammonium compound of claim 1 with an adhesive agent and water.

DONALD LEVY, Primary Examiner US. Cl. XJR.

Patent Citations
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Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3931037 *Nov 1, 1973Jan 6, 1976The Procter & Gamble CompanySubstantially uncolored detergent products containing coloring materials
US4097418 *Jan 10, 1977Jun 27, 1978The Procter & Gamble CompanyGranular colored speckles
US4632768 *Jun 6, 1985Dec 30, 1986The Procter & Gamble CompanyClay fabric softener agglomerates
US5605883 *Nov 8, 1995Feb 25, 1997Iliff; Robert J.Agglomerated colorant speckle exhibiting reduced colorant spotting
US7645729Jul 20, 2005Jan 12, 2010The Procter & Gamble CompanyDetergent compositions comprising coloured particles
US8470760Mar 4, 2011Jun 25, 2013Milliken 7 CompanyColored speckles for use in granular detergents
US8476216Mar 4, 2011Jul 2, 2013Milliken & CompanyColored speckles having delayed release properties
US8921301Jun 4, 2013Dec 30, 2014Milliken & CompanyColored speckles for use in granular detergents
US9506015Nov 21, 2014Nov 29, 2016Ecolab Usa Inc.Compositions to boost fabric softener performance
US20060019860 *Jul 20, 2005Jan 26, 2006The Procter & Gamble CompanyDetergent compositions comprising coloured particles
DE2632367A1 *Jul 17, 1976Feb 17, 1977Procter & GambleGranulierte gefaerbte partikel
DE19826632C1 *Jun 17, 1998Feb 3, 2000Henkel KgaaVerfahren und Stoffgemisch zum Behandeln von Wäsche einer im wesentlichen einheitlichen nichtweißen Farbe
EP1627909A1 *Jul 22, 2004Feb 22, 2006The Procter & Gamble CompanyDetergent compositions comprising coloured particles
EP2118256A1Jan 18, 2008Nov 18, 2009Unilever PLCShading composition
EP2118256B1 *Jan 18, 2008Sep 7, 2011Unilever PLCShading composition
EP2248884A1 *Jul 22, 2004Nov 10, 2010The Procter and Gamble CompanyDetergent Compositions Comprising Coloured Particles
WO2006020162A1 *Jul 15, 2005Feb 23, 2006The Procter & Gamble CompanyDetergent compositions comprising coloured particles
WO2007006357A1 *Apr 27, 2006Jan 18, 2007Unilever PlcDye delivery granules
Classifications
U.S. Classification8/648, 510/349, 510/515, 106/414, 510/444
International ClassificationC11D3/40, C11D1/62, F27B9/36
Cooperative ClassificationC11D3/046, C11D1/62, C11D3/06, C11D3/40, F27B9/36
European ClassificationC11D3/06, C11D3/04S, F27B9/36, C11D3/40, C11D1/62