BR112020019253A2 - DETERGENT COLORING GRANULE, DETERGENT GRANULAR LAUNDRY COMPOSITION, PROCESS TO PROVIDE A DETERGENT GRANULAR LAUNDRY COMPOSITION AND METHOD OF TREATING A FABRIC - Google Patents

Abstract

the present invention provides a detergent coloring granule comprising a blue or violet tinting dye, alkyl ether carboxylate surfactant, a solid carrier and a binder, a method for making such a coloring granule as well as a laundry detergent composition comprising such a coloring granule.

Description

DESCRIPTION PATENT REPORT GRANULATE DETERGENT DYE, GRANULAR LAUNDRY DETERGENT COMPOSITION, PROCESS TO PROVIDE A

DETERGENT COMPOSITION OF GRANULAR LAUNDRY AND METHOD OF

TREATMENT OF A FABRIC Field of the Invention

[0001] The invention relates to coloring granules, a laundry composition comprising coloring granules and a method for preparing said granules and said composition.

Background of the Invention

[0002] Many garments are white, but over the life of these garments, whiteness is affected by reducing the aesthetic value of the garment. There is a need to maintain the white appearance of such garments so that the aesthetic value is maintained as long as possible.

[0003] WO2005 / 003274 describes a fabric washing treatment composition comprising a surfactant and from 0.0001 to 0.1% by weight of a dye combination that together has a visual effect on the human eye as a dye unique having a peak absorption wavelength in cotton from 540 nm to 650 nm, preferably from 570 nm to 630 nm, the combination comprising a photostable dye which is substantive in cotton. Such a dye or combination of dyes can be referred to as a toning dye.

[0004] WO2005 / 003275 teaches that such a toning dye can be incorporated into a treatment composition in a variety of ways. For example, dyes that are not heat sensitive can be included in a paste and spray dried. Alternatively, the dye can be incorporated into granules which are subsequently dosed to a detergent powder. However, it has been found that at higher concentrations of toning dye in granules of this type there could be a danger of stains and damage by dye on clothing. WO2005 / 003275 suggests that these problems can be avoided if the concentration of dye in the granules is less than 0.1% by weight.

[0005] EP 1814974 discloses dye granules comprising nonionic surfactant and a solid carrier, wherein the nonionic surfactant has 0.0001 to 5% by weight of dye dissolved therein.

[0006] EP3081625A1 discloses a solid free flowing particulate laundry detergent composition comprising: (a) from 0.1% by weight to 5% by weight of matting agent particle comprising: (i) 2% in weight at 10% by weight of matting agent, wherein the matting agent is a specific structure azothiophene dye polymer; and (ii) from 60% by weight to 98% by weight of clay; (b) from 35% by weight to 80% by weight of spray dried particle comprising: (a) from 8% by weight to 24% by weight of anionic alkyl benzene sulfonate surfactant; (b) from 5% by weight to 18% by weight of silicate salt; (c) from 0% by weight to 10% by weight of sodium carbonate; and (d) from 0% by weight to 5% by weight of carboxylate polymer.

[0007] When surfactants (non-ionic), which are solid at 293 K are used, poor distribution of dye in the solution or fabric can result when washing at low temperatures, such as below 40 ° C.

[0008] There is a need for detergent toner dye granules that provide improved dye distribution when used during low temperature washing.

Summary of the Invention

[0009] A detergent granule comprising a blue or violet tinting dye and an alkyl carboxylate ether has been found to provide improved dye deposition.

[0010] In addition to providing improved dye deposition, it has been found that the combination of alkyl ether carboxylate (AEC) and binder reduces staining by direct contact (stains); that is, staining that occurs when the granule is in direct contact with wet tissue.

[0011] Thus, the present invention relates to a detergent dye granule comprising: (i) from 0.005 to 5% by weight of blue or violet tinting dye; (ii) from 5 to 60% by weight of alkyl ether carboxylate surfactant, wherein the alkyl ether carboxylate surfactant is of the following structure: R1- (OCH2CH2) n-OCH2-COOH where R1 is selected from straight or branched C alkyl chains 10 to C 18 saturated or mono-unsaturated, where n is 5 to 40, and where the alkyl ether carboxylate surfactant is a solid at 293 degrees Kelvin at 1 bar pressure; (iii) 20 to 90% by weight of a solid vehicle; (iv) from 1 to 10% by weight of a binder.

[0012] In a second aspect, the present invention relates to a process for providing a granular laundry detergent composition comprising the step of mixing dye granules comprising (i) from 0.005 to 5% by weight of blue or violet toning dye; (ii) from 5 to 60% by weight of alkyl ether carboxylate surfactant, wherein the alkyl ether carboxylate surfactant is of the following structure: R1- (OCH2CH2) n-OCH2-COOH where R1 is selected from straight or branched C alkyl chains 10 to C 18 saturated or mono-unsaturated, where n is 5 to 40, and where the alkyl ether carboxylate surfactant is a solid at 293 degrees Kelvin at 1 bar pressure; (iii) 20 to 90% by weight of a solid vehicle; with other detergent granules to provide a granular laundry detergent composition.

[0013] A method for treating a fabric, the method comprising the steps of: (i) treating a fabric with an aqueous solution of granular laundry detergent composition according to the present invention, the aqueous solution comprising from 1 ppb to 5 ppm of dye toner and 0.2 g / L to 3 g / L of surfactant; and (ii) rinse and dry the fabric.

Detailed Description of the Invention

[0014] In a first aspect, the present invention relates to a detergent dye granule comprising: (i) from 0.005 to 5% by weight of blue or violet tinting dye; (ii) from 5 to 60% by weight of alkyl ether carboxylate surfactant, wherein the alkyl ether carboxylate surfactant is of the following structure: R1- (OCH2CH2) n-OCH2-COOH where R1 is selected from straight or branched C alkyl chains 10 to C 18 saturated or mono-unsaturated, where n is 5 to 40, and where the alkyl ether carboxylate surfactant is a solid at 293 degrees Kelvin at 1 bar pressure; (iii) 20 to 90% by weight of a solid vehicle; (iv) from 1 to 10% by weight of a binder, wherein the binder is a polymer.

[0015] The term 'comprising' as used herein should be understood as 'including' but not necessarily 'consisting of' or 'composed of'. In other words, the steps or options listed need not be exhaustive.

[0016] Unless otherwise specified, numerical ranges expressed in the form 'from x to y' or 'x-y' must be understood to include x and y. When, for a specific characteristic, multiple preferred ranges are described in the format 'from x to y' or 'x-y', it should be understood that all ranges combining different end points are also included. For the purposes of the present invention, room temperature is defined as a temperature of about 20 ° C.

[0017] Unless otherwise stated, percentages by weight (% by weight) are based on the total weight of the formulation.

[0018] In the context of the present invention, "granule" is to be understood as a particle having a size of 50 to 1800 micrometers. The granule size is determined by passing through a mesh sieve. Preferably the size is in the range of 100 to 800 micrometers.

[0019] In the context of the present invention, "toning dye" means an anionic blue or violet dye that is deposited on polyester, cotton or poly cotton fabrics under domestic washing conditions.

[0020] In the context of the present invention, "solid vehicle" means any solid material (at 293 degrees Kelvin at 1 bar pressure) in particulate form suitable for mixing in a laundry detergent formulation.

[0021] The term "particulate" in the context of the present invention in relation to a material, refers to a material consisting of discrete particles, preferably the discrete particles having a weighted average particle size in the range of 5-200 µm.

[0022] In the context of the present invention, "binder" is to be understood as a material used to bind two or more other materials together in the dye granule.

Alkyl ether carboxylate

[0023] The alkyl ether carboxylate according to the present invention is of the form R1- (OCH2CH2) n-OCH2-COOH.

The alkyl chain R1 is selected from straight or branched C 10 to C 18 saturated or mono-unsaturated alkyl chains preferably selected from: C 12 linear alkyl chain; C 14; C 16 and C 18. The alkyl chain is most preferably selected from CH3 (CH2) 15, CH3 (CH2) 17 and mixtures thereof.

[0025] The alkyl ether carboxylic acid has n selected from 5 to 40, preferably 7 to 35, more preferably 8 to 30, even more preferably 10 to 25. Preferably the value of n is selected so that the protonated form of the alkyl ether carboxylate is a solid at 293 K / 1 bar.

[0026] Masses of alkyl ether carboxylic acid are calculated in the protonated form, R1- (OCH2CH2) n-OCH2-COOH. They can be used in the form of salt for example sodium salt or amine salt.

[0027] Alkyl carboxylic acid is available from Kao (Akypo®), Huntsman (Empicol®) and Clariant (Emulsogen®).

[0028] Synthesis of alkyl ether carboxylic acids is discussed in Organic Chemistry of Anionic Surfactants edited by H.W. Stache (Marcel Dekker, New York 1996).

[0029] They can be synthesized via the reaction of the corresponding alcohol ethoxylate with chloroacetic acid or sodium acetate monochloride in the presence of NaOH: R1- (OCH2CH2) n-OH + NaOH + ClCH2COONa → R1- (OCH2CH2) n-OCH2COOH + NaCl + H2O

[0030] In this synthesis residual R1- (OCH2CH2) n-OH may be present, 1 preferably R - (OCH2CH2) n-OH levels are from 0 to 10% by weight in the alkyl ether carboxylic acid. Low levels of diglycolic acid and glycolic acid may be present as by-products.

[0031] NaCl from the synthesis may be present in the liquid laundry detergent composition. Additional NaCl can be added to the composition.

[0032] The alkyl carboxylic acid can also be synthesized via the oxidation reaction: R1- (OCH2CH2) n-OCH2CH2OH → R1- (OCH2CH2) n-OCH2COOH.

[0033] Oxidation is typically conducted using oxygen as an oxidizer under basic conditions in the presence of metallic catalyst such as Pd / Pt, as described in DE3135946; DE2816127 and EP0304763.

Toning dye

[0034] Toning dyes are present in the formulation at a level of 0.0001 to 0.25% by weight. Depending on the nature of the toning dye, there are preferred ranges depending on the effectiveness of the toning dye which is class-dependent and particularly effective within any particular class.

[0035] Dyes are discussed in K. Hunger (ed) Industrial dyes:

Chemistry, properties, applications (Weinheim: Wiley-VCH 2003). Organic dyes are listed in the color index (Society of Dyes and Colorists and American Association of Chemicals and Fabric Colorists).

[0036] Toning dyes for use in laundry detergents preferably have an extinction coefficient at maximum absorption in the visible range (400 to 700 nm) of more than 5000 L mol-1cm-1, preferably more than 10000 L mol-1cm- 1. Toning dyes are blue or violet in color.

Preferred toning dye chromophores are azo, azine, anthraquinone, phthalocyanine and triphenylmethane.

[0038] Azo, anthraquinone, phthalocyanine and triphenylmethane dyes preferably carry a liquid anionic charge or are unloaded. Azine dyes preferably carry a liquid cationic or anionic charge.

[0039] Toning dyes are deposited on fabric during the washing or rinsing step of the washing process providing a visible shade to the fabric. In this sense, the dye gives a blue or violet color to a white outfit with a tint angle of 240 to 345, more preferably 260 to 320, even more preferably 270 to 300. The white fabric used in this test is nonwoven cotton sheet mercerized target.

[0040] Toning dyes are discussed in WO2005 / 003274, WO2006 / 032327 (Unilever), WO2006 / 032397 (Unilever), WO2006 / 045275 (Unilever), WO2006 / 027086 (Unilever), WO2008 / 017570 (Unilever), WO2008 / 141880 (Unilever), WO2009 / 132870 (Unilever), WO2009 / 141173 (Unilever), WO2010 / 099997 (Unilever), WO2010 / 102861 (Unilever), WO2010 / 148624 (Unilever), WO2008 / 087497 (P&G), WO2011 / 011799 ( P&G), WO2012 / 054820 (P&G), WO2013 / 142495 (P&G) and WO2013 / 151970 (P&G).

[0041] The toning dye chromophoto is most preferably selected from mono-azo, bis-azo, anthraquinone and azine.

[0042] In one embodiment, a mixture of toning dyes can be used. Preferably, at least two, at least three or at least four toning dyes are used in combination.

[0043] In a preferred embodiment, the toning dye is a monozo dye. Mono-azo dyes preferably contain a heterocyclic ring and are most preferably thiophene dyes. The mono-azo dyes are preferably alkoxylated and are preferably uncharged or anionically charged at pH = 7. Alkoxylated thiophene dyes are discussed in WO2013 / 142495 and WO2008 / 087497.

[0044] In a preferred embodiment, the toner dye belongs to the class of thiophene dyes. An example of a thiophene dye has the following structure:.

[0045] In another preferred embodiment, the toning dye is a bis-azo dye. Bis-azo dyes are preferably sulfonated bis-azo dyes. Preferably the toning dye is of the following structures: n (NaO3S)

Y

D N O R4 N NH NR1R2 R5

N

X NaO3S or n (NaO3S)

Y

D N O R4 N E NH NR1R2 R5

N NaO3S SO3Na where: D and E rings can be independently naphthyl or phenyl as shown; R1 is selected from: hydrogen and C 1-C4-alkyl, preferably hydrogen; R2 is selected from: hydrogen, C 1 -C4-alkyl, substituted or unsubstituted phenyl and substituted or unsubstituted naphthyl, preferably phenyl; R3 and R4 are independently selected from: hydrogen, C 1 -C4-alkyl, preferably hydrogen or methyl; X and Y are independently selected from: hydrogen, C 1-C4-alkyl and C 1-C4-alkoxy; preferably the dye has X = methyl; and, Y = methoxy and n is 0, 1 or 2, preferably 1 or 2.

[0046] Preferred examples of sulfonated bis-azo compounds are direct violet 7, direct violet 9, direct violet 11, direct violet 26, direct violet 35, direct violet 40, direct violet 41, direct violet 51, direct violet 66, direct violet 99 and alkoxylated versions thereof. Alkoxylated bis-azo dyes are discussed in WO2012 / 054058 and WO2010 / 151906.

[0047] Preferably, the toning dye has the following structure:

[0048] In yet another preferred embodiment, the toning dye is an azine dye. Azine dyes typically have the following core structure:

N

The Rc Ra

N N N Rb Rd

B where Ra, Rb, Rc and Rd are selected from: H, and straight or branched C 1 to C 7 alkyl chain, benzyl, phenyl and naphthyl; the dye is replaced with at least one SO3- or –COO- group; ring B does not carry a negatively charged group or salt therefrom; and ring A can be further substituted to form a naphthyl; the dye is optionally substituted by groups selected from: amine, methyl, ethyl, hydroxyl, methoxy, ethoxy, phenoxy, Cl, Br, I, F and NO2.

[0049] Preferably, the azine dyes have the following general structure:

N HN N N (CH2CH2Y2) 2 X4 X3 where: X3 is selected from: -H; -F; -CH3; -C2H5; -OCH3; and –OC 2H5; X4 is selected from: -H; -CH3; -C 2H5; -OCH3; and –OC 2H5; Y2 is selected from: -OH; -OCH2CH2OH; -CH (OH) CH2OH; -OC (O) CH3; and C (O) OCH3.

[0050] Azine dyes are preferably selected from sulfonated phenazine dyes and cationic phenazine dyes. Preferred examples are acid blue 98, acid violet 50, dye with CAS-No 72749-80-5, acid blue 59 and phenazine dye selected from:

[0051] Preferably, the coloring dyes are of the following structure:

[0052] In another embodiment, the toning dye is a reactive blue anthraquinone dye. An example of an anthraquinone dye has the following structure:

[0053] In a preferred embodiment, the toning dye is a reactive anthraquinone blue dye covalently linked to an alkoxylated polyethyleneimine. Alkoxylation is preferably selected from ethoxylation and propoxylation, more preferably propoxylation. Preferably 80 to 95 mol% of the N-H groups in the polyethylene imine are replaced with isopropyl alcohol groups by propoxylation. Preferably the polyethylene imine prior to reaction with the dye and propoxylation has a molecular weight of 600 to 1800.

[0054] An example structure of a reactive anthraquinone covalently linked to a preferred propoxylated polyethyleneimine is the following structure:

Solid vehicle

[0055] The solid vehicle can be a water-soluble / surfactant or water-insoluble / surfactant vehicle. The solid carrier can be a solid material in particulate form, preferably having a weighted average particle size in the range of 5 to 500 micrometers, preferably 10 to 200 micrometers.

[0056] Preferably, the solid vehicle is insoluble in water / surfactant. In a preferred embodiment, the solid vehicle is a clay or zeolite. Zeolites are crystalline or amorphous water-insoluble aluminosilicates, examples being type zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite X, zeolite Y and also zeolite P as described in EP-A-0384070. In a preferred embodiment, the solid carrier is a crystalline aluminum silicate, preferably an alkali metal aluminum silicate, more preferably a sodium aluminum silicate.

[0057] In another embodiment, the solid vehicle is a clay. Typically, clay is a phyllosilicate clay with a 2: 1 layer structure, where the definition includes pyrophyllite clay, smectite or montmorillonite clay, saponites, vermiculites and micas. Preferably, the clay is of bentonite origin, bentonites being primarily montmorillonite clays together with various impurities, the level and nature of which depends on the source of the clay material. In a preferred embodiment, the solid carrier is Montmorillonite clay, preferably bentonite.

[0058] In yet another embodiment, the solid vehicle is water-soluble / surfactant. In a preferred embodiment, the solid carrier is a carbonate salt, a sulfate salt, a chloride salt or a citrate salt.

[0059] Preferably, the solid carrier is a carbonate salt. A preferred carbonate salt is sodium carbonate and / or sodium bicarbonate. Alternatively, the carbonate material can be potassium carbonate and / or potassium bicarbonate. A highly preferred carbonate material is sodium carbonate.

[0060] The carbonate salt can also be a double salt, like burqueíta. Burqueíta is a double congruent salt with chemical formula, Na6 (SO4) 2 (CO3), and complex sodium salts of the aqueous salt solution. Alternatively, the carbonate salt may be a sesquicarbonate or modified crystal growth carbonate as usual modified carbonate or modified crystal growth burqueite.

[0061] In a preferred embodiment, the carbonate salt is selected from the group of sodium carbonate, sodium sulfate, sodium chloride and sodium citrate.

[0062] The carbonate salt is, at least part of it, typically in particulate form, typically having a weighted average particle size in the range of 80 to 500 micrometers. However, it may be preferred for the carbonate material, or at least part of it, to be in micronized particulate form, typically having a weighted average particle size in the range of 4 to 40 micrometers.

[0063] In a preferred embodiment, the solid carrier comprises one or more of sodium carbonate, clays and zeolites, more preferably comprises sodium carbonate and even more preferably comprises at least 50% by weight of sodium carbonate, based on the total weight of the solid vehicle as comprised by the coloring granule.

[0064] Preferably, the solid vehicle comprises at least 60% by weight, more preferably at least 70% by weight, even more preferably at least 80% by weight of sodium carbonate, based on the total weight of the solid vehicle.

Binder

[0065] The dye granule comprises a binder. A binder is a material used to bond two or more materials together in the dye granule. Its two main properties are adhesion and cohesion. The ligand is other than a nonionic surfactant.

[0066] Preferably the dye granule comprises, based on the total weight of the dye granule, 0.5 to 10% by weight of binder, more preferably 0.75 to 8% by weight, even more preferably 1 to 7% by weight and even more preferably 1.5 to 5% by weight of binder.

[0067] The binder is a polymeric material. Preferably, the binder has a melting point above 30 ° C.

[0068] Polymers suitable for use in the present invention are soluble in water. By water-soluble, it should be understood that polymers have a greater solubility of 5 g / L at 20 ° C in demineralized water. The binder is preferably an acidic polymer. By acidic polymer, it is to be understood that a 1% solution of said polymer has a pH of less than 7, preferably less than 5.5.

[0069] Preferably the binder is selected from the group consisting of a polyacrylate, polyethylene glycol, polyacrylate / maleate copolymer and a combination thereof.

[0070] In a preferred embodiment, the binder is a copolymer,

preferably comprising groups of acrylic acid and more preferably it is a copolymer of maleic acid and acrylic acid.

[0071] The average molecular weight, MM, is preferably from 2000 to 100000. Preferably, the polymer is an acrylic / maleic with an acrylic to maleic segment ratio of about 30: 1 to about 1: 1.

[0072] Polymers suitable for use in the present invention have a molecular weight in the range of 1000 to 280,000, preferably 1500 to 150,000. Typically, the binder has an average molecular weight (MM) 2000 to 100000 Dalton, more preferably 5000 to 80000 Dalton, even more preferably from 10,000 to 50000 Dalton.

Suitable linkers which are, therefore, particularly useful in the present invention, include those having the following empirical formula I: R1 Yp (X CR3) R2 (I) CO2 M n where X is 0 or CH2; Y is a comonomer or mixture of comonomers; R1 and R2 are bleach-stable polymer end groups; R3 is H, OH or C 1-4 alkyl; M is H, and mixtures thereof with alkali metal, alkaline earth metal, ammonium or substituted ammonium; p is 0 to 2; and n is at least 10, and mixtures thereof.

[0074] The preferred polycarboxylate polymers fall into several categories. A first category belongs to the class of copolymeric polycarboxylate polymers which, formally at least, are formed from an unsaturated polycarboxylic acid such as maleic acid, citraconic acid, itaconic acid and mesaconic acid as the first monomer, and an unsaturated monocarboxylic acid such as acrylic acid or an alpha-C1-C4 alkyl acrylic acid as the second monomer. Referring to formula I, therefore, preferred polycarboxylate polymers of this type are those where X is CHO, R 3 is H or C 1-4 alkyl, especially methyl, p is about 0.1 to about 1.9, preferably from about 0.2 to about 1.5, n is on average from about 10 to about 1500, preferably from about 50 to about 1000, more preferably from 100 to 800, especially from 120 to 400 and Y comprises monomeric units of formula II

H H

C C (II) CO2 M CO2 M ®

[0075] Such polymers are available from BASF under the brand name Sokalan CP5 (neutralized form) and Sokalan ® CP45 (acid form).

[0076] Binding materials are commercially available. Water-soluble polymers of the Sokalan® type sold by BASF® are preferred.

[0077] The following are a list of such suitable products: Sokalan CP 10; Sokalan CP 10 S; Sokalan CP 12 S, Sokalan CP 13 S; Sokalan CP 45; Sokalan CP 5; Sokalan CP 7; Sokalan CP 9; Sokalan DCS; Sokalan HP 165; Sokalan HP 22 G; Sokalan HP 25; Sokalan HP 50; Sokalan HP 53; Sokalan HP 53 K; Sokalan HP 56; Sokalan HP 59; Sokalan HP 60; Sokalan HP 66; Sokalan PA 110 S; Sokalan PA 15; Sokalan PA 15 CL; Sokalan PA 20; Sokalan PA 20 PN; Sokalan PA 25 CL; Sokalan PA 30; Sokalan PA 40; Sokalan PM 70 and Sokalan SR 100.

[0078] Preferred examples of binders are Sokalan CP 5, Sokalan CP 7, Sokalan CP 9, Sokalan CP 10 S, Sokalan CP 10, Sokalan CP 12 S, Sokalan CP 13 S, available from BASF. Maleic acid-acrylic acid copolymers are most preferred.

Dye granule

[0079] The dye granule preferably has a size of 180 to 1000 micrometers based on the ability to pass through a graduated sieve. Preferably, the dye granule is 250-800 micrometers in size based on the ability to pass through a graduated sieve.

[0080] The coloring granules are preferably formed by drying a liquid paste or solution of the materials, for example by vacuum drying, freeze drying ®, drum dryer drying, Spin Flash (Anhydro), but more preferably by spray drying . Most preferably the liquid is an alkyl ether carboxylate surfactant and the coloring dye and mixed before combining with the carrier and binder.

[0081] Preferably, the dye granules have an average particle size, APS, of 0.1 to 300 micrometers, preferably 10 to 100 micrometers. This is preferably as measured by a laser diffraction particle size analyzer, preferably a Malvern HP with 100 mm lenses.

[0082] The coloring granules are preferably dosed afterwards into a laundry detergent powder composition.

Laundry composition

[0083] The laundry composition preferably comprises a surfactant selected from anionic or non-ionic surfactants (which includes a mixture thereof) in addition to the alkyl carboxylate ether of the dye granule.

[0084] Suitable anionic detergent compounds that can be used are generally water-soluble alkali metal or amine salts of fatty acids (soaps), organic sulfates and sulfonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the alkyl term being used to include the alkyl portion of higher alkyl radicals.

[0085] Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulfates, especially those obtained by sulphating higher C 8 to C 18 alcohols, produced for example from tallow or coconut oil, C 9 to C 20 alkyl benzene sodium and potassium sulfonates,

particularly secondary linear alkyl C 10 to C 15 sodium benzene sulfonates; and alkyl glyceryl ether sodium sulfates, especially those ethers of higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum.

[0086] The anionic surfactant is preferably selected from: linear alkyl benzene sulfonate; alkyl sulfates; alkyl ether sulfates; soaps; alkyl (preferably methyl) sulfonate ester, and mixtures thereof.

[0087] The most preferred anionic surfactants are selected from: linear alkyl benzene sulfonates; alkyl sulfates; soaps; alkyl ether sulphates and mixtures thereof. Preferably the alkyl ether sulfate is a n-C 12 -C 14 alkyl ether sulfate with an average of 1 to 3 EO units (ethoxylate). Sodium lauryl ether sulfate is particularly preferred (SLES). Preferably the linear alkyl benzene sulfonate is a C 11 to C 15 alkyl sodium benzene sulfonate (LAS). Preferably, the alkyl sulfate is a linear or branched C 12 to C 18 alkyl sulfate. Sodium dodecyl sulfate is particularly preferred (SDS, also known as primary alkyl sulfate). Soaps are preferably saturated fatty acids C 12 to C 18, preferably they are present in levels of less than 3% by weight of the formulation.

[0088] The level of anionic surfactant in the laundry composition is (i) 10 to 40% by weight. It is preferable in the composition that LAS is the predominant anionic surfactant present.

[0089] In powder detergent based on carbonate, it is preferable that> 90% by weight of anionic surfactant present is LAS.

[0090] Nonionic surfactant may be present in the mixture of surfactants.

[0091] Suitable non-ionic detergent compounds that can be used include, in particular, the reaction products of compounds having an aliphatic hydrophobic group and reactive hydrogen atom, for example, aliphatic alcohols, acids or amides, especially ethylene oxide both alone or with propylene oxide. Preferred nonionic detergent compounds are the condensation products of primary or secondary C 8 to C 18 aliphatic linear or branched alcohols with ethylene oxide.

[0092] Preferably the non-ionic surfactant is a non-ionic alkyl ethoxylated surfactant and is a C 8 to C 18 primary alcohol, more preferably a C 12-C 16 primary alcohol, with an ethoxylation average of 7 to 9 EO units.

[0093] Preferably additional (non-ionic) surfactants that are solid at 293 degrees Kelvin at 1 bar pressure, are, if present, predominantly formulated not in the coloring granule of the invention, but in other parts of the laundry detergent composition.

[0094] Preferably, the total weight amount of the additional (non-ionic) surfactants present in the granular laundry detergent composition as a whole, maximum 50% by weight, 40% by weight, 35% by weight, 30% by weight, 25 % by weight, 20% by weight, 15% by weight, 10% by weight, 5% by weight is comprised of the coloring granule according to the invention.

[0095] Preferably, the dye granule according to the invention comprises at most 50% by weight of additional (non-ionic) surfactants which are solid at 293 degrees Kelvin at 1 bar pressure, preferably at most 30% by weight, more preferably at most 25% by weight, even more preferably at most 10% by weight, even more preferably at most 1% by weight.

[0096] Preferably the dye granule according to the invention comprises less than 10% by weight of additional non-ionic surfactants which are solid at 293 degrees Kelvin at 1 bar pressure, preferably less than 5% by weight, more preferably less than 1 % by weight.

Complexing or sequestering agents

[0097] Sequestering materials can be selected from 1) calcium sequestering materials, 2) precipitating materials, 3) calcium ion exchange materials and 4) mixtures thereof.

[0098] Examples of complexing calcium-scavenging materials include alkali metal polyphosphates, such as sodium tripolyphosphate and organic scavengers, such as ethylene diamine tetraacetic acid.

[0099] Examples of precipitating sequestering materials include sodium orthophosphate and sodium carbonate.

[0100] Examples of sequestering calcium ion exchange materials include the various types of crystalline or amorphous water-insoluble aluminosilicates, of which zeolites are the most well-known representatives, eg zeolite A, zeolite B (also known as zeolite P), zeolite C , zeolite X, zeolite Y and also the zeolite type P as described in EP-A-0384070.

[0101] The composition may also contain 0-65% by weight of a scavenger or complexing agent such as ethylene diaminetetraacetic acid, diethylene triamino-pentaacetic acid, alkyl- or alkenyl succinic acid, nitrilotriacetic acid or other sequestrants mentioned below. Many hijackers are also bleach-stabilizing agents because of their ability to complex metal ions.

[0102] Zeolite and carbonate (including bicarbonate and sesquicarbonate) are preferred scavengers for powder detergents.

[0103] The composition may contain as a scavenger a crystalline aluminum silicate, preferably an alkali metal aluminum silicate, more preferably a sodium aluminum silicate. This is typically present at a level of less than 5% by weight. Aluminosilicates are materials having the general formula: 0.8-1.5 M2O.Al2O3.0.8-6 SiO2 where M is a monovalent cation, preferably sodium. These materials contain some bound waters and need to have a calcium ion exchange capacity of at least 50 mg CaO / g. Preferred sodium aluminosilicates contain 1.5-3.5 units of SiO2 in the above formula. They can be prepared easily by reacting between sodium silicate and sodium aluminate, as widely described in the literature.

[0104] Alternatively, or in addition to aluminosilicate scavengers, other forms of scavenger include silicates, such as silicates, metasilicates, silicates with soluble layers (e.g. Hoescht SKS-6).

[0105] Spray drying of the detergent powder is preferred.

Polymers

[0106] The composition can comprise one or more additional polymers. Examples are carboxymethylcellulose, poly (ethylene glycol), polyvinyl alcohol, polycarboxylates such as polyacrylates, maleic acid / acrylic copolymers and lauryl methacrylate / acrylic acid copolymers.

Enzymes

[0107] One or more enzymes are preferably present in a laundry composition of the invention and when carrying out a method of the invention.

[0108] Preferably the level of each additional enzyme laundry composition of the invention is 0.0001% by weight to 0.1% by weight of protein.

[0109] The additional enzyme is preferably selected from: amylases, mannanases, lipases and cellulases, more preferably amylases and lipases. Suitable lipases include those sold under the brand name lipex®, lipoclean® and lipolex® by Novozymes, Bagsvaerd Denmark.

[0110] An enzyme present in the composition can be stabilized using conventional stabilizing agents, eg, a polyol such as propylene glycol or glycerol, a sugar or sugar alcohol, lactic acid, boric acid or boric acid derivative, eg, a borate ester aromatic, or a phenyl boronic acid derivative such as 4-formylphenyl boronic acid, and the composition can be formulated as described in eg WO92 / 19709 and WO92 / 19708.

perfume

[0111] Preferably, the composition comprises a perfume. The perfume is preferably in the range of 0.001 to 3% by weight, more preferably 0.1 to 1% by weight. Many suitable examples of perfumes are provided in the Guide

1992 International Buyer Association of CTFA (Cosmetics, Hygiene and Fragrance Articles Association), published by CTFA Publications and the 80th Annual Edition of the 1993 Chemicals Buyers Directory of OPD, published by Schnell Publishing Co.

[0112] It is common for a plurality of perfume components to be in a formulation. In the compositions of the present invention it is anticipated that there will be four or more, preferably five or more, more preferably six or more or even seven or more different perfume components.

[0113] In perfume mixtures, preferably 15 to 25% by weight are head notes. Head notes are defined by Poucher (Journal of the Society of Chemical Cosmetics 6 (2): 80 [1955]). Preferred top notes are selected from citrus oils, linalool, linalyl acetate, lavender, dihydromyrcenol, rose oxide and cis-3-hexanol.

[0114] Perfume and head notes can be used to signal the cleansing and whitening benefits of the invention.

Fluorescent agent

[0115] The composition preferably comprises a fluorescent agent (optical brightener). Fluorescent agents are well known and many such fluorescent agents are commercially available. Generally, these fluorescent agents are supplied and used in the form of their alkali metal salts, for example, the sodium salts. The total amount of the fluorescent agent or agents used in the composition is generally from 0.005 to 2% by weight, more preferably 0.01 to 0.1% by weight. Preferred classes of fluorescents are: biphenyl di-styryl compounds, eg Tinopal (brand) CBS-X, di-amino stilbene sulfonic acid compounds, eg Tinopal DMS pure Xtra and Blankophor (brand) HRH and pyrazoline compounds, eg Blankophor SN . Preferred fluorescents are: 2- (4-styryl-3-sulfophenyl) -2H-naphthol [1,2-d] sodium triazole, 4,4'-bis {[4-anilino-6- (N-methyl-N -2-hydroxyethyl) amino-1,3,5-triazin-2-yl)] amino} disodium styrene-2,2'-disulfonate and disodium 4,4'-bis (2-sulfo-styryl) biphenyl.

[0116] It is preferred that the aqueous solution used in the method has a fluorescence present. When a fluorescent is present in the aqueous solution used in the method, it is preferably in the range of 0.0001 g / L to 0.1 g / L, preferably 0.001 to 0.02 g / L.

Additional dyes

[0117] Preferred non-toning dyes are selected from blue dyes, more preferably anthraquinone dyes carrying sulfonate groups and triphenylmethane dye carrying sulfonate groups. Preferred compounds are acid blue 80, acid blue 1, acid blue 3, acid blue 5, acid blue 7, acid blue 9, acid blue 11, acid blue 13, acid blue 15, acid blue 17, acid blue 24, acid blue 34 , acid blue 38, acid blue 75, acid blue 83, acid blue 91, acid blue 97, acid blue 93, acid blue 93: 1, acid blue 97, acid blue 100, acid blue 103, acid blue 104, acid blue 108 , acid blue 109, acid blue 110 and acid blue 213. Under dissolution granules with non-toning dyes provide a color that is attractive to the washing liquid.

[0118] In a preferred embodiment, the granular laundry detergent composition comprises: a) coloring granules as defined in the present invention in an amount so as to provide 0.0005 to 0.5% by weight of dye based on the total weight of the granular laundry detergent composition, b) 2 to 70% by weight of surfactant, based on the total weight of the granular laundry detergent composition, c) 5 to 50% by weight of scavenger, based on the total weight of the laundry detergent composition granular, d) 0.05 to 50% by weight of water soluble solid vehicle, based on the total weight of the granular laundry detergent composition, where the sum of ingredients a), b), c) and d) is at least 80% by weight based on the total weight of the composition.

[0119] Preferably, the granule containing dye is contained in the laundry detergent composition in an amount such that the level of granule dye in the total detergent composition is between 0.001 to 0.025% by weight, more preferably between 0.0015 to 0.025% in weight.

[0120] Preferably, the detergent granules comprise a maximum of 10% by weight of the total amount of dye and a maximum of 25% by weight of the total amount of alkyl ether carboxylate surfactant.

[0121] In a second aspect, the present invention provides a process for preparing a dye granule comprising the step of combining a toning dye with a binder, solid carrier and an alkyl ether carboxylate surfactant, wherein the alkyl ether carboxylate surfactant is as follows structure: R1- (OCH2CH2) n-OCH2-COOH where R1 is selected from saturated or mono-unsaturated C 10 to C 18 straight or branched alkyl chains, where n is 5 to 40.

[0122] The description of components of the dye granule applies mutatis mutandis to the components used in the method to prepare the dye granule as defined here.

[0123] Preferably, the toner dye is pre-mixed with the alkyl ether carboxylate before combining with the binder and the solid carrier. Typically, the alkyl ether carboxylate is heated to at least 5 ° C, preferably at least 10 ° C, more preferably at least 20 ° C above its melting point before mixing with the toner dye.

[0124] Preferably, the melting point of the alkyl ether carboxylate is in the range of from 313K to 353K.

[0125] In a third aspect, the present invention provides a process for providing a granular laundry detergent composition comprising the step of mixing the coloring granules according to the present invention with other detergent granules to provide a granular laundry detergent composition as defined on here. Preferably, the coloring granules are mixed dry with the other detergent granules.

[0126] The description of the components of the granular laundry detergent composition applies mutatis mutandis to the components used in the method for preparing a granular laundry detergent composition as defined here.

[0127] In a fourth aspect, the present invention provides a method of treating a fabric, the method comprising the steps of: (i) treating a fabric with an aqueous solution of granular laundry detergent composition as defined herein, the aqueous solution comprising from 1 ppb to 5 ppm of toning dye and from 0.2 g / L to 3 g / L of surfactant; and (ii) rinse and dry the fabric.

[0128] In one embodiment, the maximum temperature of the aqueous solution in step (i) is 50 degrees Celsius, preferably 45 degrees Celsius and more preferably 40 degrees Celsius.

[0129] Preferably, the maximum temperature of the aqueous solution in step (i) is between 15 and 40 degrees Celsius, more preferably between 20 and 35 degrees Celsius.

[0130] In a preferred embodiment, the temperature of the aqueous solution used for rinsing does not exceed the temperature of step (i).

Examples Example 1 - granulation

[0131] Alkyl ether carboxylate (or Na salt of cetearyl with 20 moles of ethoxylation) was melted at 60 ° C and 0.3 wt% toning dye mixed with that of the alkyl ether carboxylate. The toning dye used was a cationic azine dye of the following structure:

[0132] Sodium carbonate was added to a food processor using a blade shovel to mix. The mixture of liquid alkyl ether carboxylate and liquid dye was then slowly added until the mixture just started to form a mass. The binder, Sokalan CP5 (maleic acid-acrylic acid copolymer, sodium salt) was then added and granules resulted. These granules were placed in an oven at 50 ° C to dry and a fraction of a 0.5 to 1.8 mm sieve collected and used for further experiments.

[0133] The composition of the alkyl ether carboxylate granule was: Table 1 1 Sodium carbonate 68% by weight 69.9% by weight 68% by weight Alkyl ether carboxylate 23% by weight - 28% by weight Sokalan CP5 8, 93% by weight 7.33% by weight - T48 toning dye 0.07% by weight 0.07% by weight 0.07% by weight Nonionic surfactant: nonionic fatty alcohol - 22.7% by weight - (cetearyl with 20 moles of ethoxylation)

[0134] The formulation in the absence of a binder (Sokalan CP5) did not form granules.

[0135] A complete matching of the levels of the different components is not possible due to the different properties of non-ionic fatty alcohol and alkyl ether carboxylate.

Example 2 - Dye distribution

[0136] A basic laundry detergent powder was created as follows:

Table 2 Ingredient% by weight Linear alkyl benzene sulfonate 14.5 Sodium carbonate 20.0 Sodium sulfate 50.0 Sodium silicate 6.0 Zeolite 2.5 Speckled with blue and red salt 1.8 Perfume 0.3 Carboxymethylcellulose of sodium 0.1 Sokalan CP5 0.1 Minority components (inc. humidity) Up to 100%

[0137] The granules of example 1 were added to the base laundry powder so that it contained 0.01% by weight of toner dye.

[0138] 4 g / L of this detergent powder was then used to wash 3 pieces of 65:35 white braided poly cotton in a 30: 1 liquid to fabric ratio in water with 26 ° French hardness for 30 minutes at 20 ° C. Washings were performed in a plastic bottle placed on an orbital shaker at 150 RPM. After washing the fabrics were removed, rinsed, dried, the color of the fabric measured using a reflectometer and expressed as CIE Lab values. The degree of dye deposition was measured as Δb, where: Δb = b (control powder without toning dye) - b (powder with toning dye)

[0139] The results are given in the table below, next to the calculated 95% confidence limits of the 3 tissues.

Table 3 Dye granule Δb 95% 1 1.9 0.1 A 0.0 0.1

[0140] The alkyl ether carboxylate granule effectively distributes the toning dye, as demonstrated by an Δb = 1.9, the equivalent non-ionic granule does not.

Example 3 - Dye stain on the fabric

[0141] The alkyl ether granules of example 1 were produced again, but with different levels of the CP5 linker. In these granules 0.2% by weight of toner dye was mixed with the alkyl ether carboxylate. The granules were added to the laundry detergent powder base to give 0.005% by weight of dye. 3g of the powder sprinkled on a 10 by 10 cm square of polyester fabric that was placed on a wet support. The square of fabric and dust was left for 2 hours at 20 ° C, rinsed, dried and then the number of visible stains was counted. The experiment was repeated with cotton, poly-cotton and nylon-elastane fabrics and the total number of stains across the 4 fabrics was calculated as the numerical sum. The granule composition and staining results are given in the table below: Table 4 Granule Number of points 9.9% by weight of Sokalan CP5 69.3% by weight of sodium carbonate 20.8% by weight of alkyl ether mixture carboxylate / dye 13 toning (0.042% by weight of tinting dye in the granule) 9.9% by weight of Sokalan CP5 66.5% by weight of sodium carbonate 23.6% by weight of a mixture of alkyl ether carboxylate / dye 6 (0.047% by weight of toner dye in the granule)

6.2% by weight of Sokalan CP5 71.9% by weight of sodium carbonate 21.9% by weight of alkyl ether carboxylate / colorant 12 toner (0.044% by weight of colorant dye in the granule)

4.5% by weight of Sokalan CP5 64.9% by weight of sodium carbonate 30.7% by weight of alkyl ether carboxylate / dye 2 toner (0.061% by weight of tint dye in the granule)

1.7% by weight of Sokalan CP5 64.5% by weight of sodium carbonate 33.8% by weight of alkyl ether carboxylate / 0 coloring agent (0.068% by weight of coloring agent in the granule)

Claims (15)

Claims 1. Detergent coloring granule characterized by comprising: (i) from 0.005% to 5% by weight of a blue or violet tinting dye; (ii) from 5% to 60% by weight of alkyl ether carboxylate surfactant, wherein the alkyl ether carboxylate surfactant is of the following structure: R1- (OCH2CH2) n-OCH2-COOH where R1 is selected from straight or branched alkyl chains C 10 to C 18 saturated or mono-unsaturated, where n is 5 to 40, and where the alkyl ether carboxylate surfactant is a solid at 293 degrees Kelvin at 1 bar pressure; (iii) from 20% to 90% by weight of a solid vehicle; (iv) from 0.5% to 10% by weight of a binder. Dye granule according to claim 1, characterized in that R1 is selected from linear saturated C 12, C 14, C16 and C 18 alkyl chains and preferably R1 is selected from C 16 and C 18 alkyl chains. Dye granule according to claim 1 or 2, characterized in that the n of the alkyl ether carboxylate surfactant is 7 to 35, preferably 10 to 25. Dye granule according to any one of claims 1 to 3, characterized in that the amount of dye in the dye granule is from 0.01% to 0.1% by weight. Dye granule according to any one of claims 1 to 4, characterized in that the dye is a tinting dye with a chromophore selected from azo, azine, anthraquinone, phthalocyanine, triphenylmethane and combinations thereof, preferably selected from azo, azine dyes and combinations thereof. Dye granule according to any one of claims 1 to 5, characterized in that the solid carrier comprises one or more of sodium carbonate, clays and zeolites, more preferably it comprises sodium carbonate and even more preferably it comprises at least 50% by weight of sodium carbonate based on the total weight of the solid carrier as comprised by the coloring granule. Dye granule according to any one of claims 1 to 6, characterized in that the binder has an average molecular weight (MM) of 2000 to 100000 Dalton and preferably the dye granule comprises from 1% to 5% by weight of binder. Dye granule according to any one of claims 1 to 7, characterized in that the binder is a copolymer, preferably comprising acrylic acid groups and more preferably being a copolymer of maleic acid and acrylic acid. Dye granule according to any one of claims 1 to 8, characterized in that the dye granule has a size of from 180 to 1000 micrometers as based on the ability to pass through a graduated sieve. Dye granule according to any one of claims 1 to 9, characterized in that the total amount of alkyl ether carboxylate is 10% to 40% by weight and the total amount of dye is from 0.001% to 0.1 % by weight. 11. Granular laundry detergent composition characterized by comprising: a) coloring granules as defined in any one of claims 1 to 10 in an amount so as to provide 0.0005% to 0.5% by weight of dye based on the total weight of the granular laundry detergent composition, b) 2% to 70% by weight of surfactant, based on the total weight of the granular laundry detergent composition, c) 5% to 50% by weight of the binder, based on the total weight of the composition granular laundry detergent, d) 0.05% to 50% by weight of water soluble solid vehicle, based on the total weight of the granular laundry detergent composition, where the sum of ingredients a), b), c) and d ) is at least 80% by weight based on the total weight of the composition. Process for providing a granular laundry detergent composition characterized in that it comprises the step of mixing the dye granules, as defined in any one of claims 1 to 10, with detergent granules to provide a granular laundry detergent composition. Process according to Claim 12, characterized in that the detergent granule comprises a maximum of 10% by weight of the total amount of dye and a maximum of 25% by weight of the total amount of alkyl surfactant ether carboxylate. 14. Method of treating a fabric, characterized by the method comprising the steps of: (i) treating a fabric with an aqueous solution of granular laundry detergent composition, as defined in claim 11, the aqueous solution comprising from 1 ppb to 5 ppm toning dye and 0.2 g / L to 3 g / L of surfactant; and (ii) rinse and dry the fabric. Method for treating a fabric according to claim 14, characterized in that the maximum temperature of the aqueous solution in step (i) is 50 degrees Celsius, preferably 45 degrees Celsius and more preferably 40 degrees Celsius.