MX2008009491A - Laundry care compositions with thiazolium dye - Google Patents

Abstract

The present invention relates to thiazolium dyes, laundry care compositions comprising one or more thiazolium dyes, processes of making such dyes and laundry care compositions and methods of using same. The dyes, compositions and methods of the present invention are advantageous in providing improved hueing of fabric, including whitening of white fabric, while avoiding significant build up of bluing dyes on the fabric.

Description

additional impractical in the laundry process. In addition, a chlorine treatment is expensive and damaging to the fabric, which contributes to increasing the degradation of the fabric. Accordingly, there is a need for improved clothing care products that can counteract the undesirable discoloration of the fabrics, including the yellowish color of the white fabrics.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to thiazolium dyes, laundry care compositions comprising one or more thiazolium dyes, processes for making these dyes and laundry care compositions, and methods of using them. The dyes, compositions and methods of the present invention are advantageous to provide better tonalization of the fabric, including bleaching of the white fabric, while avoiding significant accumulation of bluing dyes in the fabric.

DETAILED DESCRIPTION OF THE INVENTION Definitions As used herein, the term "laundry care composition" includes, unless otherwise indicated, washing agents and / or compositions for the treatment of fabrics in granular form, powder, liquid, gel, paste, bar and / or scales.

As used herein, the term "fabric treatment composition" includes, unless otherwise indicated, fabric softening compositions, fabric improver compositions, fabric freshening compositions and combinations thereof. These compositions may, but do not necessarily have to be, compositions that are used in the rinse. As used herein, the articles, including "the", "the" "an" "a" when used in a claim, should be understood to mean one or more of what is claimed or described. As used herein, the terms "include", "includes" and "including" are not limiting. As used herein, the term "polyether" is defined as at least two units of repeating ether that are chemically linked through the oxygen atoms of the ethers. These polyethers may be derived from materials including, but not limited to, ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, glycidol, epichlorohydrin, pentaerythritol, glucose or combinations thereof. As used herein, "capped polyether" refers to a polyether terminating in an alkyl or aryl moiety, including, but not limited to, a moiety selected from a methyl, ethyl, butyl, isopropyl, tertiary butyl, amyl, benzyl moiety , pentyl, and acetyl. As used herein, "EO" represents an ethylene oxide moiety.

As used herein, "PO" represents a propylene oxide moiety. The test methods described in the Test Methods Section of the present application should be used to determine the use of respective values of the parameters of the applicants' inventions. Unless indicated otherwise, all levels of the component or composition refer to the active portion of that component or composition and exclude impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions. All percentages and proportions are calculated by weight, unless indicated otherwise. All percentages and proportions are calculated based on the total composition, unless indicated otherwise. It should be understood that any maximum numerical limit given in this specification shall include any lower numerical limit, as if the lower numerical limits had been explicitly annotated herein. Any minimum numerical limit given in this specification shall include any major numerical limit, as if the larger numerical limits had been explicitly annotated herein. Any numerical range given in this specification shall include any smaller numerical range that falls within the larger numerical range, as if all minor numerical intervals had been explicitly annotated herein.

All the cited documents are incorporated herein in their relevant part as reference. The mention of any document should not be construed as an admission that it corresponds to a prior industry with respect to the present invention.

Garment care compositions In one aspect, a garment care composition is described which may comprise a laundry care ingredient and a suitable thiazolium dye. Suitable thiazolium dyes include thiazolium dyes that exhibit good coloring efficiency during a laundry cycle without exhibiting excessive undesirable accumulation after washing. In this way, the undesirable blueing is prevented after repeated washing with the detergent compositions of the invention and unnecessary chlorine treatments are unnecessary and damaging to the fabrics. Suitable thiazolium dyes include the thiazolium dyes that are described under the heading "Suitable thiazolium dyes" of the present specification. In one aspect, the laundry care compositions described in the present specification can employ the thiazolium dyes described in the present specification as listed in Formulas V through VIII of the present specification.

In one aspect, suitable thiazolium dyes include the thiazolium dye molecules numbers 1-80 as listed in Tables 1 and 2 of the present specification. In one aspect, suitable thiazolium dyes include the thiazolium dye molecules numbers 1, 4, 5, 7, 8, 12, 13, 15, 16, 17, 21, 24, 25, 26, 30, 31, 33 , 36, 38, 40, 45 and 48 as listed in Tables 1 and 2 of this specification. In one aspect, suitable thiazolium dyes include the thiazolium dye molecules numbers 12, 13, 15, 16, 24, 25, 26, 30, 31, 33, 36, 38, 40, 45 and 48 as listed in Tables 1 and 2 of the present specification. In one aspect, the laundry care compositions described in the present specification can employ combinations of any of the suitable thiazolium dyes described in the present specification. In one aspect, the laundry care compositions described in the present specification may employ a non-tint dye in combination with the thiazolium dye. The non-tinting dye may be selected from non-tinting dyes described in U.S. Pat. no. 2005/028820 A1, U.S. Pat. num. 4,137,243, 4,601, 725 and 4,871, 371. Without being limited to theory, it is believed that the combination of a thiazolium dye with a non-tinting dye allows flexibility in mixing the color to achieve a desired shade.

In one aspect, the laundry care compositions described in the present specification may employ a non-tinting dye, which may be non-substantive in nature, in combination with the thiazolium dye. The combination of both a thiazolium dye and a non-tinting dye can allow the personalization of the product color and the hue of the fabric. In one aspect, Acid Blue 7 can be used as a non-tint and non-bluish dye. In one aspect, any of the components in encapsulated form, including suitable thiazolium dyes, can be employed in the laundry care compositions. These encapsulates may comprise one or more such components. In one aspect, laundry care compositions comprising a thiazolium dye and a laundry care ingredient are described, which have a tonality efficiency of greater than 10 but less than 40, from about 15 to about 35, or even of about 15 to about 30, and a wash removal capacity of from about 30% to about 85%, from about 40% to about 85%, from about 50% to about 85%. Suitable ingredients for the care of clothing include, but are not limited to, the materials described in the present specification as useful aspects of the present invention, including additional materials as described in the present specification.

Liquid Laundry Detergent Compositions In one aspect, the laundry care compositions described herein may take the form of liquid laundry detergent compositions. In one aspect, these compositions can be a high performance liquid composition. Such compositions may comprise a sufficient amount of a surfactant to provide the desired level of one or more cleaning properties, generally by weight of the total composition, from about 5% to about 90%, from about 5% to about 70% or even from about 5% to about 40%, and a sufficient amount of a suitable thiazolium dye which is described under the heading "suitable thiazolium dyes" of the present specification to provide an effect as described under the heading "Suitable thiazolium dyes. "of the present specification, to provide a coloring effect to the washed fabric in a solution containing the detergent, generally by weight of the total composition, from about 0.0001% to about 0.05%, or even about 0.001% to approximately 0.01%. The liquid detergent compositions comprise a non-surfactant liquid aqueous carrier. Generally, the amount of non-surfactant liquid aqueous carrier employed in the compositions herein will be effective to solubilize, suspend or disperse the components of the composition. For example, the compositions may comprise, by weight, from about 5% to about 90%, of about 10% a about 70%, or even from about 20% to about 70% of a non-surfactant aqueous liquid carrier. The most cost-effective type of non-surfactant aqueous liquid carrier can be water. Accordingly, the aqueous non-surfactant liquid carrier component, generally, can be for the most part, if not all, water. Although other types of water miscible liquids, such as alkanols, diols, other polyols, ethers, amines, and the like, have been added to the liquid detergent compositions as cosolvents or stabilizers, for the purposes of the present invention, the use of such miscible liquids in water to reduce the cost of the composition. Accordingly, the aqueous liquid carrier component of the liquid detergent products herein, will generally comprise water present in concentrations ranging from about 5% to about 90%, or even from about 20% to about 70%, by weight of the composition. The liquid detergent compositions herein may take the form of an aqueous solution or uniform dispersion or suspension of surfactant, thiazolium dye, and certain other optional ingredients, some of which, typically, may be in solid form, which have been combined with the normally liquid components of the composition, such as the liquid non-ionic alcohol ethoxylate surfactant, the aqueous liquid carrier, and any other normally liquid optional ingredient. This solution dispersion or suspension will be of acceptable stable phase and, in general, will have a viscosity that varies from about 0.1 to 0.6 Pa.s (about 100 to 600 cps), more preferably, about 0.15 to 0.4 Pa.s (about 150 to 400 cps). For purposes of the present invention, the viscosity is measured with a Brookfield LVDV-II + viscometer apparatus which employs an axle no. twenty-one . Suitable surfactants can be anionic, nonionic, cationic, zwitterionic, and / or amphoteric surfactants. In one aspect, the detergent composition comprises anionic surfactant, nonionic surfactant, or mixtures thereof. Suitable anionic surfactants can be any of the types of conventional anionic surfactants, generally used in liquid detergent products. These surfactants include alkylbenzenesulfonic acids and their salts, as well as alkoxylated or non-alkoxylated alkylsulphate materials. Exemplary anionic surfactants are the alkali metal salts of C-10-16 alkylbenzenesulfonic acids, preferably C-n.-u alkylbenzenesulfonic acids. In one aspect, the alkyl group is linear. These linear alkylbenzene sulphonates are known as "LAS" (for its acronym in English). These surfactants and their preparation are described, for example, in U.S. Pat. num. 2,220,099 and 2,477,383. Especially preferred are the straight-chain sodium and potassium alkyl benzene sulfonates, in which the average number of carbon atoms in the alkyl group is from about 1 to 14 C. Sodium Ci iC 4, for example C 12, LAS is a specific example of such surfactants.

Another illustrative type of ammonium surfactant comprises ethoxylated alkyl sulfate surfactants. Said materials, also known as alkyl ether sulfate or polyethoxylated alkyl sulfates, are those corresponding to the formula: R'-0- (C2H40) n-S03M, where R 'is a C8-C20 alkyl group, n has a value of about 1 to 20, and M is a salt forming cation. In a specific embodiment, R 'is a C10-C18 alkyl, n has a value of about 1 to 15, and M is sodium, potassium, ammonium, alkylammonium or alkanolammonium. In more specific embodiments, R 'is a C-I 2-C-I 6, n has a value of about 1 to 6, and M is sodium. Alkylether sulfates will be used, generally, in the form of mixtures that include lengths of variable R 'chains and varying degrees of ethoxylation. Frequently, such mixtures will, inevitably, also contain some non-ethoxylated alkyl sulphate materials, ie, surfactants of the above ethoxylated alkyl sulfate formula, where n = 0. The non-ethoxylated alkyl sulfates can also be added separately to the compositions of this invention and used as or in any anionic surfactant component that could be present. Specific examples of non-ethoxylated components, for example, alkyl ether sulfate surfactants, are those produced by the sulfation of fatty alcohols higher than C8-C2o. Conventional primary alkylsulfate surfactants have the general formula: ROS03"M +, wherein R is, generally, a linear hydrocarbyl group of C8-C2o, which may be straight or branched chain, and is a cation which It dissolves in water. In specific embodiments, R is a Ci0-Ci5 alkyl) and is an alkali metal, more specifically, R is Ci2-C14 and M is sodium. Specific non-restrictive examples of anionic surfactants useful herein include: a) alkylbenzene sulfonates (LAS) of C-C18; b) C10-C20 branched chain random alkylsulphates (AS); c) (2,3) Ci0-C18 secondary alkyl sulfates having Formulas (I) and (II): (I) (I ") wherein M in formulas (I) and (II) is hydrogen or a cation that provides charge neutrality, and all M units, if associated with a surfactant or an additional ingredient, can be a hydrogen atom or a cation which depends on the form isolated by the technician or the relative pH of the system in which the compound is used, with non-limiting examples of preferred cations including sodium, potassium, ammonium, and mixtures thereof, and x is an integer of at least about 7, preferably, at least about 9, and is an integer of at least 8, preferably, at least about 9; d) Ci0-Ci8 alkyl alkoxysulfates (AEXS) wherein, preferably, x is 1-30; e) Ci0-Ci8 alkyl alkoxy carboxylates preferably comprising 1 -5 ethoxy units; f) alkyl sulfates branched medium chain, as described in U.S. Pat. num. 6,020,303 and 6,060,443; g) medium chain branched alkyl alkoxysulfates as described in U.S. Pat. num. 6,008,181 and 6,020,303; h) modified alkylbenzene sulfonate (MLAS) as described in patents WO 99/05243, WO 99/05242, WO 99/05244, WO 99/05082, WO 99/05084, WO 99/05241, WO 99/07656, WO 00/23549, and WO 00/23548; i) methyl ester sulfonate (MES); and j) alpha-olefin sulfonate (AOS). Suitable nonionic surfactants useful herein may comprise any of the types of conventional nonionic surfactants commonly used in liquid detergent products. These include the surfactants of alkoxylated fatty alcohols and amine oxide. Preferred for use in the liquid detergent products herein are those nonionic surfactants which are normally liquid. Nonionic surfactants suitable for use herein include the nonionic surfactants of alkoxylated alcohols. The alkoxylated alcohols are materials of the following formula: R1 (CmH2mO) nOH, wherein R1 is an alkyl group of C8-Ci6, m is from 2 to 4, and n ranges from about 2 to 12. Preferably, R1 is an alkyl group which may be primary or secondary, containing from about 9 to 15 atoms carbon, more preferably, from about 10 to 14 carbon atoms. In one embodiment, it is also preferred that the alkoxylated fatty alcohols are ethoxylated materials containing about to 12 ethylene oxide moieties per molecule and, with a greater preference, from about 3 to 10 ethylene oxide moieties per molecule. The alkoxylated fatty alcohol materials useful in the liquid detergent compositions herein will often have a hydrophilic-lipophilic balance (HLB) ranging from about 3 to 1 7. Most preferably, the HLB of this material will vary from about 6 to 15, more preferably, from about 8 to 1. The non-ionic alkoxylated fatty alcohol surfactants have been marketed under the tradename Neodol® by Shell Chemical Company. Another suitable type of nonionic surfactant useful herein comprises the amine oxide surfactants. Amine oxides are materials that are often known in the industry as non-ionic "semipolar". The amine oxides have the formula: R (EO) x (PO) and (BO) zN (O) (CH2R ') 2. qH2O. In this formula, R is a relatively long chain hydrocarbyl portion which may be saturated or unsaturated, linear or branched, and may contain from 8 to 20 and, preferably, from 10 to 16 carbon atoms, and which, more preferably, is a primary alkyl of C- | 2-C-16. R 'is a short chain portion which is preferably selected from hydrogen, methyl and -CH2OH. When x + y + z is different than 0, EO is ethyleneoxy, PO is propyleneoxy and BO is butyleneoxy. The amine oxide surfactants are illustrated by alkyl dimethylamine oxide of C-i2.i. Non-limiting examples of anionic surfactants useful herein include: a) Ci2-C18 alkyl ethoxylates, such as surfactants not ionic NEODOL® from Shell; b) C6-C-i2 alkylphenol alkoxylates, wherein the alkoxylate units are a mixture of ethyleneoxy and propyleneoxy units; c) C1 2-Ci8 alcohol and C6-C-2 alkylphenol condensates with block polymers of ethylene oxide / propylene oxide, such as Pluronic® from BASF; d) medium chain branched alcohols of C- | 4-C22, BA, as described in U.S. Pat. no. 6, 150,322; e) Ci4-C22 medium chain branched alkyl alkoxylate, BAEX, wherein x 1 -30, as described in US Pat. UU num. 6, 1 53,577, 6,020,303 and 6,093,856; f) alkylpolysaccharides as described in U.S. Pat. no. 4,565,647 of Llenado, granted on January 26, 1986; specifically, alkyl polyglycosides as described in U.S. Pat. num. 4,483,780 and 4,483,779; g) fatty acid polyhydroxyalmides as described in U.S. Pat. no. 5,332,528, WO 92/06162, 93/19146, 93/19038, and 94/09099; and h) poly (oxyalkylated alcohol) surfactants capped with ether as described in U.S. Pat. num. 6,482,994 and the patent 01/42408. In the laundry detergent compositions herein, the detergent surfactant component may include combinations of anionic and nonionic surfactant materials. When this is the case, the weight ratio of anionic to nonionic will vary, generally, from 10:90 to 90:10, more generally, from 30:70 to 70:30. Cationic surfactants are well known in the industry and non-limiting examples thereof include ammonium surfactants quaternary, which have up to 26 carbon atoms. Additional examples include a) quaternary ammonium alkoxylate surfactants (AQA), such as those set forth in U.S. Pat. no. 6,136,769; b) dimethyl hydroxyethylammonium quaternary as described in U.S. Pat. no. 6,004,922; c) cationic polyamine surfactants, as described in patents WO 98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006; d) cationic ester surfactants, such as those described in U.S. Pat. num. 4,228,042, 4,239,660 4,260,529 and 6,022,844; and e) amino surfactants, such as those set forth in U.S. Pat. no. 6Lu. , 221, 825 and in the patent WO 00/47708, specifically amido propyl dimethyl amine (APA). Non-limiting examples of zwitterionic surfactants include: derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See U.S. Pat. no. 3,929,678 to Laughlin et al. , granted on December 30, 1975 in column 19, line 38 to column 22, line 48, for examples of zwitterionic surfactants; betaine, including alkyl dimethylbetaine and coconut dimethylamidopropyl betaine, amine oxides from Ce to C-ie (preferably, C12 to C18) and sulfo and hydroxy betaines, such as N-alkyl-N, N-dimethylamino-1-propane sulfonate, where the alkyl group may be from C8 to Cie, preferably, C0 to d4.

Non-limiting examples of ampholytic surfactants include: the aliphatic derivatives of secondary or tertiary amines, or the aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight or branched chain. One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water solubilizing group, eg, carboxy, sulfonate, sulfate . See column 19, lines 18-35 of U.S. Pat. no. 3,929,678 issued to Laughlin et al., December 30, 975, examples of ampholytic surfactants.

Granular Laundry Detergent Compositions In one aspect, the laundry care compositions described herein, may take the form of granular laundry detergent compositions. These compositions may comprise a sufficient amount of thiazolium dye which is described under the heading "suitable thiazolium dyes" of the present specification, to provide a coloring effect to the washed fabrics in a solution containing the detergent, generally in weight of the total composition, from about 0.0001% to about 0.05%, or even from about 0.001% to about 0.01%. The granular detergent compositions of the present invention can include any number of detergent ingredients conventional For example, the surfactant system of the detergent composition may include anionic, nonionic, zwitterionic, ampholytic and cationic classes, and compatible mixtures thereof. Detergent surfactants for granular compositions are described in U.S. Pat. no. 3,664,961 to Norris, issued May 23, 1972; and 3,919,678 to Laughlin et al., Issued December 3, 1975. Cationic surfactants include those described in U.S. Pat. num. 4,222,905 of Cockrell, granted on September 16, 1980, and 4,239,659 of Murphy, granted on December 16, 1980. Non-limiting examples of surfactant systems include the conventional C 8 -C 8 alkylene ketones ("LAS") and the primary alkyl sulfates , branched and randomized of C 0 -C 2o ("AS"), the secondary alkyl sulfates of C 10 -C 18 (2.3) of the formula CH 3 (CH 2) x (CHOSO 3"M +) CH 3 and CH 3 (CH 2) and (CHOSO 3" M +) CH2CH3, wherein xy (y + 1) are integers of at least about 7, preferably, at least about 9, and M is a cation of solubilization in water, especially sodium, unsaturated sulfates such as oleyl sulfate, alkoxysulfates of Ci0-C18 alkyl ("AEXS", especially EO 1 -7 ethoxysulfates), C 0-Ci8 alkyl alkoxy carboxylates (especially EO 1 -5 ethoxycarboxylates), glycerol ethers of C10-18, alkyl polyglycosides of Ci0- Ci8 and its corresponding sulfated polyglycosides, and alpha fatty acid esters sulfonated C-i2-C-i8. If desired, conventional non-ionic and amphoteric surfactants, such as alkyl ethoxylates, may also be included in the surfactant system. of C-12-C18 ("AE") including narrow peak alkyl ethoxylates and C6-Ci2 alkylphenol alkoxylates (especially mixed ethoxylates and ethoxy / propoxy), betaines and sulfobetaines ("sultaines") of C12-C -18, Ci0-C18l amine oxides and the like. The C10-C18 N-alkyl polyhydroxyl fatty acid amides can also be used. See the patent 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxyalmides of fatty acids, such as C10-C18 N- (3-methoxypropyl) glucamide. The glucamides of N-propyl to N-hexyl C 2 -Ci 8 can be used for low foam formation. Conventional C10-C20 soaps can also be used. If a high foaming is desired, the branched-chain C-io-Ci6 soaps can be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in the standard texts. The detergent composition can and, preferably, it includes a detergent additive. The additives, generally, are selected from the various water soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, polyhydroxysulfonates, polyacetates, carboxylates, and polycarboxylates. The alkali metals are preferred, especially the sodium salts of the foregoing. Preferred for use herein are phosphates, carbonates, silicates, C10-18 fatty acids. polycarboxylates, and mixtures thereof. More preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, mono- and di-succinate tartrate, sodium silicate, and mixtures thereof.

Specific examples of inorganic phosphate additives are sodium potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of about 6 to 2, and orthophosphates. Examples of polyphosphonate additives are the sodium and potassium salts of ethylene diphosphonic acid, the sodium salts of ethane-1-hydroxy-, 1-diphosphonic acid, and the sodium and potassium salts of ethane-1, 2, 2- triphosphonic Other phosphorous additive compounds are described in U.S. Pat. num. 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148. Examples of non-phosphorus inorganic additives are sodium and potassium carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate, and silicates having a weight ratio of SiO2 to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0. to approximately 2.4. The water-soluble non-phosphorous organic additives useful in the present invention include the various polyacetates, carboxylates, polycarboxylates and polyhydroxysulfonates of substituted ammonium, ammonium and alkali metals. Examples of polyacetate and polycarboxylate additives are the salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids of sodium, potassium, lithium, ammonium and substituted ammonium, and citric acid. Polycarboxylate polymeric additives are described in U.S. Pat. no. 3,308,067 of DiehI, issued May 7, 1967. These materials include the water soluble salts of homopolymers and copolymers of aliphatic carboxylic acids, such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylenemalonic acid. Some of these materials are useful as the water-soluble anionic polymer described hereafter, but only if they are intimately mixed with the non-soap anionic surfactant. Other polycarboxylates suitable for use herein are the polyacetal carboxylates described in U.S. Pat. num. 4,144,226, issued March 1, 1979 to Crutchfield et al., And 4,246,495, issued March 1, 979 to Crutchfield et al. The water soluble silicate solids represented by the formula SiO2.M2O, M is an alkali metal, with a weight ratio SiO2: M2O of from about 05 to about 40, are useful salts in the detergent granules of the invention at levels of about 2% to about 15% by weight of anhydrous base. The anhydrous or hydrated particulate silicate can also be used. Any number of additional ingredients may also be included as components in the granular detergent composition. These include other detergent additives, bleaches, bleach activators, foam boosters or foam suppressors, antifog agents and anticancers, soil suspending agents, soil release agents, germicides, pH adjusting agents, alkalinity sources non-additives, chelating agents, smectite clays, enzymes, enzyme stabilizing agents and perfumes. See U.S. Pat. no. 3,936,537, issued February 1, 1976 by Baskerville, Jr. et al.

Bleaching agents and bleach activators are described in U.S. Pat. num. 4,412,934, Chung et al., Issued November 1, 1983, and 4,483,781, Hartman, issued November 20, 1984. Chelating agents are also disclosed in U.S. Pat. no. 4,663,071, Bush et al., From column 17, line 54 to column 18, line 68. Also optional ingredients are foam modifiers and are described in U.S. Pat. num. 3,933,672, granted on January 20, 1976 to Bartoletta et al., And 4,136,045, granted on January 23, 1979 to Gault et al. Smectite clays suitable for use herein are described in U.S. Pat. no. 4,762,645 to Tucker et al., Issued August 9, 1988, column 6, line 3 to column 7, line 24. Additional detergent additives suitable for use herein are listed in the Baskerville patent, column 13, line 54 to column 16, line 16, and in U.S. Pat. no. 4,663,071 of Bush et al., Issued May 5, 1987.

Fabric conditioner compositions that are used in the rinse In one aspect, the laundry care compositions described herein may take the form of fabric conditioning compositions that are used in the rinse. These compositions may comprise a fabric softening active and a sufficient amount of suitable thiazolium dye, which are described under the heading "suitable thiazolium dyes" of the present specification, to provide a coloring effect to the fabric treated with the composition, generally, from about 0.00001% by weight (0.1 ppm) to about 1% by weight (10,000 ppm), or still from about 0.0003% by weight (3 ppm) to about 0.03% by weight (300 ppm) based on the total weight of the fabric conditioning composition that is used in the rinse. In another specific embodiment, the compositions are fabric conditioning compositions that are used in the rinse. Examples of a typical conditioning composition that is used in the rinse can be found in the US provisional patent application. with no. series 60/687582, filed October 8, 2004. In one embodiment of the invention, the active fabric softener (hereinafter "FSA") is a quaternary ammonium compound suitable for softening fabrics in one step of rinsing. In one embodiment, the FSA is formed by the reaction product of a fatty acid and an aminoalcohol obtaining mixtures of mono, di and, in one mode, triester. In another embodiment, the FSA comprises one or more quaternary ammonium softening compounds, such as, but not limited to, a monoalkyl quaternary ammonium compound, a diammonium quaternary compound and a diester quaternary ammonium compound, or a combination thereof. In one aspect of the invention, the FSA comprises a diester quaternary ammonium compound composition (hereinafter forward, DQA, for its acronym in English). In certain embodiments of the present invention, the compositions of DQA compounds also comprise a description of the FSA diamido and FSA with combined linkages of amido and ester and also the diester linkages mentioned above, all mentioned herein as DQA. A first type of DQA (DQA (1)) suitable as FSA in the CFSC herein includes a compound comprising the formula: . { R4-m-N + - [(CH2) n -Y-RW X- wherein each R substituent is hydrogen, a short-chain hydroxyalkyl group of Ci-C6, preferably CrC3, for example, methyl (more preferred), ethyl , propyl, hydroxyethyl, and the like, poly (C2-C3 alkoxy), preferably, a polyethoxy, benzyl group, or mixtures thereof; each m is 2 or 3; each n is from 1 to about 4, preferably, 2; each Y is -O- (O) C-, -C (O) -O-, -NR-C (O) -, or -C (O) -NR- and it is acceptable for each Y to be the same or different; the sum of carbons in each R, plus one when Y is -O- (O) C- or -NR-C (O) -, is C2-C22, preferably, Ci4-C2o, and each R is a hydrocarbyl or substituted hydrocarbyl group; it is acceptable that R1 is unsaturated or saturated and branched or linear and, preferably, is linear; it is acceptable that each R1 1 is the same or different and, preferably, these are equal; and X "can be any anion compatible with the softener, preferably, chloride, bromide, methyl sulfate, ethyl sulfate, sulfate, phosphate, and nitrate, more preferably, sulfate chloride. methyl. In general, the preferred DQA compounds are made by reacting alkanolamines, such as MDEA (methyldiethanolamine) and TEA (triethanolamine) with fatty acids. Some materials that result, in general, from these reactions include N, N-di (acyl-oxyethyl) -N, N-dimethylammonium chloride or N, N-di (acyl-oxyethyl) -N, N-methylhydroxyethylammonium methylsulfate. , wherein the acyl group is derived from animal, unsaturated and polyunsaturated fats, fatty acids, for example, tallow, hardened sebum, oleic acid or partially hydrogenated fatty acids, derived from vegetable oils or partially hydrogenated vegetable oils, such as canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soy bean oil, resin oil , rice bran oil, palm oil, etc. Non-limiting examples of suitable fatty acids are listed in U.S. Pat. no. 5,759,990 in column 4, lines 45 to 66. In some modalities the FSA includes other assets in addition to DQA (1) or DQA. In yet another embodiment, the FSA comprises only DQA (1) or DQA and is free or virtually free of any other quaternary ammonium compound or other active ingredients. In yet another embodiment, the FSA comprises the amine precursor that is used to produce DQA. In another aspect of the invention, the FSA comprises a compound, identified as DTTMAC, which comprises the formula: [R4-m - N (+) - R1 m] A " wherein each m is 2 or 3, each R1 is a C6-C22, preferably, C14-C20, but not more than one is less than about C2 and the other is, then, at least about 16, hydrocarbyl or substituent of hydrocarbyl substituted, preferably, alkyl or alkenyl (unsaturated alkyl, including polyunsaturated alkyl, sometimes referred to as "alkylene") of C10-C20, most preferably, alkyl or alkenyl of C- | 2-Ci8, branched or non-branched branched In one embodiment, the iodine value (IV) of the FSA is from about 1 to 70; each R is H or a short chain alkyl or hydroxyalkyl group of C C6, preferably C1-C3, for example, methyl (more preferred), ethyl, propyl, hydroxyethyl, and the like, benzyl, or (R2 O) 2 -4H, wherein each R 2 is an alkylene group of C C 6; and A 'is an anion compatible with the softener, preferably, chloride, bromide, methyl sulfate, ethyl sulfate, sulfate, phosphate, or nitrate; more preferably, chloride or methyl sulfate. Examples of these FSAs include dialkyldimethylammonium salts and dialkylenediimethylammonium salts, such as dimethylammonium diphosphate and methylsulfate dimethylammonium diphosphate. Examples of commercially available dialkylenedimethylammonium salts useful in the present invention are dihydrogenated tallow dimethyl ammonium chloride and ditallow dimethyl ammonium chloride, available from Degussa under the tradenames Adogen® 442 and Adogen® 470 respectively. In one modality, the FSA comprises other assets in addition to DTTMAC. In yet another embodiment, the FSA comprises only DTTMAC compounds and is free or essentially free of any other quaternary ammonium compound or other active compounds.

In one embodiment, the FSA comprises an FSA described in U.S. Pat. no. 2004/0204337 A1, published October 14, 2004 by Corona et al., Of paragraphs 30-79. In another embodiment, the FSA is described in U.S. Pat. no. 2004/0229769 A1, published November 18, 2005, by Smith et al., In paragraphs 26-31; or the U.S. patent no. 6,494,920, in column 1, line 51 et seq., Which detail an esterquat or ester salt of quaternized triethanolamine fatty acid. In one embodiment, the FSA is chosen from at least one of the following: dimethyl ammonium chloride of oleylxyethyl dichloroethylammonium dihydrogenated tallow dimethylammonium chloride, dimethylammonium ditallow chloride, dimethylammonium dimethylammonium methylisulfate dimethylammonium tallow dihydrogenated oxyloxyethylchloride , dihydrogenated tallow dimethyl ammonium dimethyl ammonium chloride and mixtures thereof. In one embodiment, the FSA may also include compositions of amide-containing compounds. Some examples of compounds comprising diamide may include, but are not limited to, methylisulfate methyl bis (tallowamidoethyl) -2-hydroxyethylammonium (distributed by Degussa under the tradenames of Varisoft 1 10 and Varisoft 222). An example of a compound containing amide and ester is N- [3- (stearoylamino) propyl] -N- [2- (stearoyloxy) ethoxy) ethyl)] - N -methylamine. Another specific embodiment of the invention provides a fabric care composition that is used in rinsing and that further comprises a cationic starch. Cationic starches are described in U.S. Pat. no. 2004/0204337 A1. In one embodiment, the fabric care composition comprises from about 0.1% to about 7% cationic starch by weight of the laundry care composition. In one embodiment, the cationic starch is HCP401 from National Starch.

Suitable thiazolium dyes Suitable thiazolium dyes include azo dyes which may have the following Formula (I): Formula I wherein: R3 and R4 may be identical or different and are, independently of one another, hydrogen, a saturated or unsaturated alkyl group (C1-C22), an alkyl group (C22 C22) substituted by a halogen atom, a hydroxyalkyl group (C2-C22) optionally interrupted by oxygen, a polyether group derived from ethylene oxide, propylene oxide or butylene oxide, an alkylamino group (CrC22), a substituted or unsubstituted phenyl group or a benzyl group, a group (C1-C22) alkyl terminated sulfonate, sulfate, or carboxylate, or the radical groups R3 and R4, together with the remaining molecule, can form a saturated or unsaturated, substituted or unsubstituted carbocyclic or heterocyclic ring system optionally substituted by halogen, sulfate, sulfonate, phosphate, nitrate, and carboxylate; X may be a radical group of the phenol series or a heterocyclic radical group or aniline series or m-toluidine series which may have the following Formula I I; Formula II wherein R5 and R6 may be identical or different and are, independently of one another, a straight or branched chain, sutured or unsaturated alkyl group (Ci-C22) > an alkyl ether group (C C22) > a hydroxyalkyl group (C2-C22) optionally interrupted by oxygen, a polyether group derived from ethylene oxide, propylene oxide, butylene oxide, glycidyl or combinations thereof, an alkylamino group (Ci-C22), a substituted phenyl group or unsubstituted or a benzyl group, a linear or branched (C1-C22) alkyl group terminated in a linear or branched alkyl group (Ci-C22), hydroxyl, acetate, sulfonate, sulfate, or carboxylate, or R5 and R6 or R5 and R7 or R6 and R7, together with the nitrogen atom, form a ring system of 5 members to 6 members, which they can comprise another heteroatom; or R5 and [¾ or R5 and R7 or R6 and R7, form with a carbon atom of the benzene ring a heterocycle containing five or six members optionally containing oxygen or containing nitrogen which may be substituted with one or more alkyl groups ( C-1-C-22); R7 can be identical or different and are, independently of one another, hydrogen, a halogen atom an alkyl group saturated or unsaturated, an alkyl ether group (C1-C22). a hydroxyl group, a hydroxy (C1-C22), a (C1-C22) alkoxy group, a cyano group, a nitro group, an amino group, an alkylamino group (C1-C22), a dialkylamino group (Ci-C22) ) > a carboxylic acid group, a C (O) O- (C1-C22) alkyl group, a substituted or unsubstituted C (O) O-phenyl group; Q 'can be an anion that provides the total charge balance of the compound of Formula I, and the index q can be 0 or 1. Suitable anions include chlorine, bromine, methosulfate, tetrafluoroborate, and acetate anions. RT can be an alkyl radical (Ci-C22) > Alkylaromatic, or an alkyl sulfonate having the following Formula (III); where R2 is hydrogen, methyl, ethyl, acetate, or a hydroxyl group; m and p are integers from 0 to (n-1), n is an integer from 1 to 6 and m + p = (n-1); with the proviso that the heterocycle of Formula (I) comprises at least two and, at most, three heteroatoms, wherein the heterocycle has at most one sulfur atom; In one aspect, a suitable thiazolium dye can have the following Formula IV: Formula IV wherein Rs and Rg may be identical or different and may be, independently of each other, a saturated or unsaturated (C1-C22) alkyl group, a (C1-C22) alkyl group, a hydroxyalkyl (C2-C22) optionally interrupted group by oxygen, a polyether group derived from ethylene oxide, propylene oxide or butylene oxide, an alkylamino group (C C22), a substituted or unsubstituted phenyl group or a benzyl group, a (C1-C22) alkyl group terminated by sulfonate, sulfate, or carboxylate, or R8 and Rg, together with the nitrogen atom, can form a 5-membered, 5-membered ring system, which may comprise another heteroatom; or R8 or Rg can form, with a carbon atom of the benzene ring, a heterocycle containing five or six members optionally containing oxygen or containing nitrogen which may be substituted with one or more alkyl groups (C1-C22), and mixtures thereof, and R 0 is hydrogen or methyl. For Formula IV, Q 'is as described for Formula I above.

In one aspect, suitable thiazolium dyes may have Formula (V); Formula V R1 may be selected from a branched or unbranched alkyl portion (C1-C22), an aromatic alkyl portion, a polyalkylene oxide moiety or a moiety having the following Formula (VI); Formula VI where (i) R 2 may be selected from hydrogen, methyl, ethyl, propyl, acetate or a hydroxyl portion; m and p can be, independently, integers from 0 to (n-1), with the proviso that n is an integer from 1 to 6 and m + p = (n-1) (¡i) Y can be selected from a hydroxyl, sulfonate , sulfate, carboxylate or acetate; b. ) R3 and R4: i.) Can be independently selected from hydrogen; a saturated or unsaturated (C 1 -C 22) alkyl moiety; a hydroxyalkyl (C2-C22) moiety; a hydroxyalkyl (C2-C22) moiety comprising, in addition to the hydroxyl oxygen, an oxygen atom; a polyether portion; an alkylamino (C1-C22) moiety; a substituted or unsubstituted phenyl portion; a substituted or unsubstituted benzyl moiety; an alkyl portion (C-1-C22) terminated in sulfonate, sulfate, acetate, or carboxylate; or i.) when taken together to form a saturated or unsaturated carbocyclic or heterocyclic moiety; or iii.) when taken together to form a saturated or unsaturated carbocyclic or heterocyclic moiety and substituted by sulfate, sulfonate, phosphate, nitrate, and carboxylate; c. ) X may be a portion having the following Formula VII; Formula VII where R5 and 6: (a) can be independently selected from hydrogen; a saturated or unsaturated alkyl portion (C-1-C22); a hydroxyalkyl (C2-C22) moiety; a hydroxyalkyl (C2-C22) moiety comprising, in addition to the hydroxyl oxygen, an oxygen atom; a finished or non-finished polyether portion; an alkylamino (C1-C22) moiety; a substituted or unsubstituted phenyl portion; a substituted or unsubstituted benzyl moiety; a (C 1 -C 22) alkyl portion comprising a terminal portion of C 1 -C 4 alkyl ether, sulfonate, sulfate, acetate or carboxylate; a thiazole or (b) when taken together to form a saturated or unsaturated heterocyclic moiety; or (c) when taken together form a saturated or unsaturated heterocyclic portion and substituted by one or more alkoxylate, sulfate, sulfonate, phosphate, nitrate, and / or carboxylate moieties; (d) when taken in conjunction with R7 > R8) or R7 and R8 form one or more saturated or unsaturated heterocyclic portions, optionally substituted by one or more alkoxylate, sulfate, sulfonate, phosphate, nitrate, and / or carboxylate moieties; or (e) when taken together they form a thiazole moiety; ii.) R7 and R8 can be independently selected from hydrogen or a saturated or unsaturated alkyl moiety; d.) Q "may be an anion that provides the total charge balance of the compound of Formula I, and the index q is 0 or 1.

Suitable anions include chlorine, bromine, methosulfate, tetrafluoroborate, and acetate anions. In one aspect, for Formula V: a. ) Ri can be a methyl portion; b. R3 and R4 can be hydrogen; and c. ) X can have the following Formula VIII: Formula VIII wherein (i) R5 and R6 can be as defined for Formula VII above; (ii) R7 can be hydrogen or a methyl portion; and (iii) R8 can be hydrogen. In one aspect, for Formula VII R5 and R6 each independently comprises from 1 to 20 alkylene oxide units and, independently, a portion selected from the group comprising styrene oxide, glycidyl methyl ether, isobutyl glycidyl ether, isopropyl glycidyl ether, tert-butyl glycidyl ether, 2-ethylhexylglycidyl ether, or glycidylhexadecyl ether. In one aspect, suitable thiazolium dyes are set forth in the following Table 1 and are defined as thiazole dyes in Table 1. The chemical names are as determined as determined by the ChemFinder LevelPro software; Version 9.0 available from CambridgeSoft, Cambridge, Massachusetts, USA, for such dyes are provided respectively in the following Table 2. These dyes are associated, as necessary to balance the molecular charge, with a Q anion. "This anion does not it is shown in the following structures, but for the purposes of the present specification it is presumed that it is present as required.This anion is as described above for Formula (I).

TABLE 1 8fr TABLE 2 In one aspect, suitable thiazolium dyes include the thiazolium dye molecules numbers 1, 4, 5, 7, 8, 12, 13, 15, 16, 7.21, 24, 25, 26, 30, 31, 33, 36, 38, 40, 45 and 48, as listed in Tables 1 and 2 of this specification. In one aspect, suitable thiazolium dyes include the thiazolium dye molecules numbers 12, 13, 15, 16, 24, 25, 26, 30, 31, 33, 36, 38, 40, 45 and 48, as listed in Tables 1 and 2 of the present specification. Suitable thiazolium dyes described herein may be made by methods known in the industry and / or according to the examples of the present specification.

Additional materials Although not essential for the purposes of the present invention, the non-limiting list of additional ingredients illustrated hereinafter is suitable for use in laundry care compositions and may be desirably incorporated into certain embodiments of the invention. , for example, to help or improve performance, to treat the substrate to be cleaned, or to modify the aesthetic characteristics of the composition as in the case with perfumes, dyes, dyes, or the like. It is understood that these additional ingredients are in addition to the components previously listed for any particular embodiment. The total amount of these additional ingredients may vary from about 0.1% to about 50%, or even from about 1% to about 30%, by weight of the laundry care composition.

The precise nature of these additional components and the levels of incorporation of these will depend on the physical form of the composition and the nature of the operation for which they will be used. Suitable auxiliary materials include, but are not limited to, polymers, for example, cationic polymers, surfactants, additives, chelating agents, dye transfer inhibiting agents, dispersants, enzymes and enzyme stabilizers, catalytic materials, bleach activators, agents polymer dispersion agents, clay / antiredeposit removal agents, brighteners, foam suppressors, dyes, other perfumes and perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, process aids or pigments. In addition to the following disclosure, suitable examples of additional components and levels of use are found in U.S. Pat. num. 5,576,282, 6,306,812 B1 and 6,326,348 B1 which are incorporated by reference. As indicated, the additional ingredients are not essential for the applicants' laundry and cleaning compositions. Thus, certain embodiments of applicants' compositions do not contain one or more of the following additional materials: Bleach activators, surfactants, additives, chelating agents, dye transfer inhibiting agents, dispersants, enzymes and enzyme stabilizers, complexes metallic catalysts, polymeric dispersing agents, agents for the removal / re-blocking of clay and dirt, brighteners, suppressants foam, dyes, additional perfumes and perfume delivery systems, agents for elasticizing the structure, fabric softeners, carriers, hydrotropes, process assistants or pigments. However, when the composition contains one or more additional components, that or those components must be present as specified below: Surfactants: the compositions according to the present invention may comprise a surfactant or surfactant system, wherein the surfactant may be selected of non-ionic or anionic or cationic surfactants or ampholytic or amphoteric or semi-polar non-ionic surfactants. The surfactant is generally present at a level of about 0.1%, about 1% or even about 5% by weight of the cleaning compositions at about 99.9%, to about 80%, to about 35% Or even about 30% by weight of the cleaning compositions. Additives: the compositions of the present invention may comprise one or more additives or additive systems. When present, the compositions will generally comprise at least about 1% additive or from about 5% or 10% to about 80%, 50% or even 30% by weight of said additive. The additives include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphates, alkali metal silicates, alkaline earth metal and alkali metal carbonates, aluminosilicate additives, polycarboxylate compounds, hydroxypolycarboxylate ethers, maleic anhydride copolymers with ethylene or methyl ether vinyl, 1, 3,5-trihydroxybenzene-2,4,6-trisulphonic acid and carboxymethyl-oxysuccinic acid, the different alkali metals, ammonium and substituted ammonium salts of polyacetic acids such as tetraacetic acid ethylenediamine and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof. Chelating agents: the compositions herein may also optionally comprise one or more copper, iron or manganese chelating agents. If used, the chelating agents will generally comprise from about 0.1% by weight of the compositions herein to about 15% or even from about 3.0% to about 15% by weight of the compositions herein. Dye transfer inhibiting agents: the compositions of the present invention may, in addition, include one or more dye transfer inhibiting agents. Suitable polymeric dye transfer inhibiting agents include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. When present in the compositions herein, the dye transfer inhibiting agents are present at levels from about 0.0001%, to about 0.01%, of about 0.05% by weight of the cleaning compositions at about 10%, about 2% or even about 1% by weight of the cleaning compositions. Dispersants: the compositions of the present invention may further comprise dispersants. Suitable water-soluble organic materials are the homo or copolymeric acids or their salts, in which the polycarboxylic acid can contain at least two carboxyl radicals separated from each other by not more than two carbon atoms. Enzymes: the compositions may comprise one or more detergent enzymes that provide cleaning performance or fabric care benefits. Examples of suitable enzymes include, but are not limited to, hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tanases. , pentosanas, malanases, ß-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase and amylases, or mixtures thereof. A typical combination is a cocktail of conventional applicable enzymes such as protease, lipase, cutinase or cellulase in conjunction with amylase. Enzyme Stabilizers: Enzymes for use in compositions, for example, detergents can be stabilized by various techniques. The enzymes employed herein can be stabilized by the presence of water-soluble magnesium or calcium ion sources in the finished compositions that provide the ions for the enzymes.

Catalytic metal complexes: applicants' compositions can include catalytic metal complexes. - A type of metal-containing decolorizing catalyst is a catalyst system comprising a transition metal cation of defined decolorizing catalyst activity., such as copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese cations, an auxiliary metal cation having little or no decolorizing catalyst activity, such as zinc or aluminum cations, and a part having stability constants defined for catalytic and auxiliary metal cations, particularly, ethylenediaminetetracetic acid, ethylenediaminetetra (methylenephosphonic acid) and water soluble salts thereof. Such catalysts are described in U.S. Pat. no. 4,430,243. If desired, the compositions herein can be catalyzed by means of a manganese compound. Such compounds and levels for use are known in the industry and include, for example, manganese-based catalysts described in U.S. Pat. no. 5,576,282. Cobalt bleaching catalysts useful herein are known, and are described, for example, in U.S. Pat. num. 5,597,936 and 5,595,967. Said cobalt catalysts are prepared by known methods, such as those described in U.S. Pat. num. 5,597,936 and 5,595,967. The compositions herein may also conveniently include a transition metal complex of a rigid macropolycyclic ligand (abbreviated MRL). For an issue practical and not limiting, the cleaning compositions and processes herein can be regulated to provide in the order of at least one part per one hundred million MRL species of the beneficial agent in the aqueous washing medium, and can provide from about 0.005 ppm to about 25 ppm, from about 0.05 ppm to about 10 ppm, or even from about 0.1 ppm to about 5 ppm of the MRL in the wash liquor. Preferred transition metals in the transition metal bleach catalyst include manganese, iron and chromium. Preferred MRLs herein are a special type of ultra rigid ligand which is a bridge, such as 5,12-diethyl-, 5,8,2-tetraazabicyclo [6,6,2] hexadecane. Suitable MRLs of transition metals are prepared rapidly by known procedures such as those described, for example, in WO 00/32601 and in U.S. Pat. no. 6,225,464.

Processes for making the laundry care compositions The laundry care compositions of the present invention can be formulated in any suitable form and prepared by any process chosen by the formulator, non-limiting examples of which are described in the patents of the inventors. USA num. 5,879,584; 5,691, 297; 5,574,005; 5,569,645; 5,565,422; 5,516,448; 5,489,392; and 5,486,303.

In one aspect, the liquid detergent compositions described herein can be prepared by combining the components of these in any convenient order and mixing, for example, by stirring, the resulting combination of components to form a phase-stable liquid detergent composition. In one aspect, a liquid matrix is formed that contains at least a higher, or even substantially total, proportion of the liquid components, for example, nonionic surfactant, non-surfactant liquid carriers and other optional liquid components, the liquid components being fully mixed imparting shear stress to this liquid combination. For example, a mechanical agitator can be used to achieve rapid agitation. While the shear agitation is maintained, practically all of any anionic surfactant and solid ingredients can be added. The mixture is continued to stir and, if necessary, at this point said agitation can be intensified to form a solution or a uniform dispersion of solid phase insoluble particulates within the liquid phase. After adding some or all of the solid materials in this stirred mixture, the particles of the preferred enzyme material are incorporated, for example, enzymatic granules. As a variation of the method of preparing the composition described above, one or more of the solid components can be added to the stirred mixture as a solution or slurry of premixed particles with a minor portion of one or more of the liquid components. After adding all the components of the composition are continued stirring the time necessary to form the compositions with the appropriate characteristics of viscosity and phase stability. Frequently, this will involve stirring approximately 30 to 60 minutes. In another aspect for producing liquid detergents, the thiazolium dye is first combined with one or more liquid components to form a premix of thiazolium dye, and this premix of thiazolium dye is added to the composition formulation containing a substantial portion. , for example, more than 50% by weight, more than 70% by weight, or even more than 90% by weight, of the components balance of the laundry detergent composition. For example, in the methodology described above, both the thiazolium dye premix and the enzyme component are added in a final step of the component additions. In another aspect, the thiazolium dye is encapsulated before being added to the detergent composition, the encapsulated dye is suspended in a structured liquid, and the suspension is added to a composition formulation containing a substantial portion of the balance of the components of the laundry detergent composition. Various techniques for forming detergent compositions in such a solid form are well known in the industry and can be used herein. In one aspect, when the laundry care composition is in the form of a granular particle, the thiazolium dye is provided in particulate form, optionally including additional components, but not all, of the laundry detergent composition. The thiazolium dye particulate is combined with one or more additional particulates which contain a balance of components of the laundry detergent composition. In addition, the thiazolium dye, which optionally additional, but not all, additional components of the laundry detergent composition, can be provided in encapsulated form, and the thiazolium dye encapsulate is combined with particles containing a substantial balance of components of the composition laundry detergent.

Methods for using the laundry care compositions The laundry care compositions described in the present specification can be used to clean or treat a fabric. Generally, at least a portion of the fabric is contacted with an embodiment of the laundry care compositions mentioned above, in pure form or diluted in a liquid, for example, a washing liquid and then the fabric optionally wash and / or rinse In one aspect, a fabric is optionally washed and / or rinsed, contacted with an embodiment of the laundry care compositions mentioned above and then optionally washed and / or rinsed. For the purposes of the present invention, washing includes but is not limited to scrubbing and mechanical agitation. The fabric can comprise almost any cloth capable of being washed or treated. The laundry care compositions described in the present specification can be used to form aqueous solutions of washing for use in washing fabrics. Generally, an effective amount of the compositions in the water, preferably in a conventional automatic washing machine, is added to form these aqueous washing solutions. The aqueous washing solution formed in this way then comes into contact with the fabrics to be washed, preferably by means of agitation. An effective amount of the laundry care composition, such as the liquid detergent compositions described in the present specification, can be added to the water to form aqueous laundry solutions which may comprise from about 500 to about 7000 ppm or even from about 1000 to approximately 3000 pm of the composition for the care of clothes. In one aspect, one or more of the thiazolium dyes described in the present specification can be delivered, for example, via a laundry care composition, such that during the wash cycle or the rinse cycle the concentration of the one or more colorants may be from about 0.5 parts per billion (ppb) to about 5 parts per million (ppm), from about 1 ppb to about 600 ppb, from about 5 ppb to about 300 ppb, or even about 10 ppb a approximately 100 ppb of thiazolium dye. In one aspect, these concentrations can be achieved during the wash cycle, and / or the rinse cycle, of a 17 gallon automatic washing machine.

In one aspect, the laundry care compositions may be employed as a laundry additive, a pretreatment composition and / or a post-treatment composition.

Test methods I. Method to determine the tonalizing efficiency for detergents a. ) Two 25 cm x 25 cm fabric samples of interwoven 16 oz cotton fabric (270 g / square meter, polished with fluorescent brightening agent Uvitex BNB, from Test Fabrics, PO Box 26, Weston, PA, 18643). b. ) Two one liter aliquots of tap water are prepared with 1.55 g high performance liquid (HDL) standard AATCC as shown in Table 3. c. ) A sufficient amount of dye to be tested is added to one of the aliquots of Step b.) Above to produce an absorbance of the 1 AU aqueous solution. d. ) A sample of a.) Above is washed in one of the aliquots of water containing 1.55 g of high performance liquid test (HDL) detergent standard AATCC and the other sample is washed in the other aliquot . This washing step should be carried out for 30 minutes at room temperature atmosphere with agitation. After this washing step, the samples are rinsed separately and dried, e.) After rinsing and drying each sample, the tonalizing efficiency, DE * etf, of the dye is evaluated by determining the L *, a * value measurements , and b * of each sample using a Hunter LabScan XE reflectance spectrophotometer with D65 illumination, 10 ° excluding the observer and the UV filter. Then the tonalizing efficiency of the dye is calculated using the equation: FROM * eff = ((? - L%) 2 + (a * c - a%) 2 + (b * c - b * s) 2) 1/2 wherein the subscripts c and s, respectively, refer to the values L *, a * and b * measured in the control, that is, the sample of cloth washed in the detergent without colorant, as well as the sample of cloth washed in the detergent that contains the dye to be identified.

II. Method to determine the removal capacity a.) Prepare two separate aliquots of 150 ml of the HDL solution shown in Table 1, according to the AATCC Test Method 61 -2003, Test 2A and with 1.55 g / Liter of the formula of high performance liquid AATCC HDL in distilled water. b. ) A 15 cm x 5 cm sample of each fabric sample from the Method to determine the tonalizing efficiency for the detergents described above was washed in a Launderometer laboratory washer for 45 minutes at 49 ° C in 150 ml of the high performance liquid detergent solution prepared according to Step II. a.) previous. c. ) The samples are rinsed with separate aliquots of rinse water and air dried in the dark, the amount of residual coloration is evaluated by measuring the DE * s of the dye, and the L *, a *, and b * values of each sample using the Hunter LabScan XE reflectance spectrophotometer with D65 illumination, 10 ° excluding the observer and the UV filter. Then the tonalizing efficiency of the dye is calculated using the following equation: DE \ es = ((L * c - L%) 2 + (a * c - a * s) 2 + (b * c - b%) 2) 1/2 wherein the subscripts c and s, respectively, refer to the values L *, a * and b * measured in the control, that is, the fabric sample initially washed in the detergent without colorant, as well as the fabric sample initially washed in the detergent that contains the dye to be identified. The wash removal value of the colorant is then calculated according to the formula:% removal = 100 x (1 - DE * res / DE * eff).

TABLE 3 Formula pH adjusted to 8.5 Diethylenetriamine pentamethylene phosphonic acid, pentasodic salt EXAMPLES The following examples illustrate the compositions of the present invention, but do not limit or in any other way define the scope thereof.

EXAMPLE 1 The following liquid formulas are within the scope of the present invention: 1 Diethylenetriaminepentaacetic acid, sodium salt ^ Diethylenetriamine pentamethylene phosphonic acid, sodium salt ^ Diethylenetriaminepentaacetic acid, sodium salt 4 A non-staining dye used to adjust the color of formula 5 Compact formula, packaged as a unit dose on polyvinyl alcohol film 6 Acusol OP 301 EXAMPLE 2 The following granular detergent formulations are within the scope of the present invention: Formulated as a particle containing 0.5% dye, 99.5% PEG 4000 Formulated as a layered particle containing 2% dye according to U.S. Pat. no. 2006 252667 A1 Formulated as a particle containing 0.5% dye according to U.S. Pat. no. 4,990,280 Formulated as a particle containing 0.5% dye with zeolite EXAMPLE 3 The following fabric conditioning formulas that are used in the rinse are within the scope of the present invention. a N, N-di (tallowoyloxyethyl) -N, N-dimethyl ammonium chloride. b Cationic starch based on potato starch or common corn starch, containing 25% to 95% amylose and a degree of substitution of 0.02 to 0.09 and having a viscosity measured as water fluidity with a value of 50 to 84 c Copolymer of ethylene oxide and terephthalate with the formula described in U.S. Pat. no. 5, 574,179 in col. 15, lines 1-5, where each X is methyl, each n is 40, u is 4, each R1 is practically phenylene 1, 4, each R2 is practically ethylene, propylene 1, 2, or mixtures of these. d Diethylenetriaminepentaacetic acid. e KATHON® CG available from Rohm and Haas Co. Silicone antifoam agent available from Dow Corning Corp. under the tradename DC2310. 9,4,4-bis- (2-sulphotrisyl) biphenyl disodium, available from Ciba Specialty Chemicals. n Ethoxylated cocometyl ammonium chloride [15], available from Akzo Nobel EXAMPLE 4 Synthesis of mtol-10EO methylthiazolium Five hundred forty-nine grams of 85% phosphoric acid 75 grams of 98% sulf acid and 9 drops of 2-ethyl hexanol defoamer are added to a 100 milliliter three-mouth flask equipped with a thermometer, cooling bath, and mechanical stirrer. The mixture is cooled and 30.9 grams of 2-aminothiazole are added to the flask. The mixture is further cooled to below 0 ° C after which 105 grams of 40% nitrosyl sulf acid are added while maintaining the temperature below 5 ° C. After three hours, the mixture provides a positive nitrite test and 25 grams of sulfamic acid are slowly added while the temperature is maintained below 5 ° C. After one hour a negative nitrite test is evident. A 2000-milliliter beaker is loaded with 190 grams of m-toluidine 10 EO intermediate, 200 grams of water, 200 grams of ice and 12 grams of urea. The mixture is cooled to 0 ° C. The diazo solution is added dropwise to the beaker for about 30 minutes, while keeping the temperature below 10 ° C. The resulting mixture is stirred for several hours and left to stand overnight, after which 780 grams of 50% sodium hydroxide to neutralize the excess acid to a pH of about 7 while the temperature is kept below 20 ° C. The bottom salt layer is removed and the product is washed with 200 milliliters of a 10% sodium sulfate solution. The each aqueous is removed and the desired product is obtained as an orange liquid (240 grams, 70% active). One hundred grams of the above orange liquid and 28.40 grams of dimethyl sulfate are placed in a 500 milliliter flask equipped with a reflux condenser, thermometer, heating mantle and mechanical stirrer. The reaction mixture is heated at 70 ° C for two hours. The reaction is cooled and the pH adjusted to 7 with 10 grams of 20% ammonium hydroxide and used without further pication.

EXAMPLE 5 The procedure of Example 4 is used to make N-ethyl-mtol-5EO, the difference being the use of the following m-toluidine intermediates: EXAMPLE 6 The procedure of Example 5 is used, with the indicated changes, to elaborate: Twenty grams of the orange liquid are placed according to Example 5, as obtained by way of Example 4, and nine grams of benzyl bromide in a 250 milliliter bottle equipped with a reflux condenser, thermometer, heating mantle and mechanical stirrer. The reaction mixture is heated at 70 ° C for two hours. The reaction is cooled and the pH adjusted to 7 with 4 grams of 50% sodium hydroxide and used without further pication. While particular embodiments of the present invention have been illustrated and described, it will be apparent to those skilled in the industry that various changes and modifications can be made without departing from the spirit and scope of the invention. It has been intended, therefore, to cover all the changes and modifications within the scope of the invention in the appended claims.

Claims (10)

NOVELTY OF THE INVENTION CLAIMS

1 . - A composition for the care of clothes comprising a thiazolium dye and an ingredient for the care of clothes. 2. The composition for the care of clothes according to claim 1, further characterized in that the thiazolium dye is selected from an azo dye of the general Formula (V);

Formula V wherein: a.) Ri is selected from a branched or unbranched (C 1 -C 22) alkyl portion, an aromatic alkyl portion, a polyalkylene oxide moiety, a moiety having the following Formula (VI);

Formula VI wherein (i) R2 is selected from hydrogen, methyl, ethyl, propyl, acetate or a hydroxyl portion; myp are, independently, integers from 0 to (n-1), with the proviso that n is an integer from 1 to 6 and m + p = (n-1) (ii) Y is selected from a hydroxyl, sulfonate moiety , sulfate, carboxylate or acetate; b.) R3 and R: i.) are independently selected from hydrogen; a saturated or unsaturated alkyl portion (C 1 -C 22); a hydroxyalkyl (C2-C22) moiety; a hydroxyalkyl (C2-C22) moiety comprising, in addition to the hydroxyl oxygen, an oxygen atom; a polyether portion; an alkylamino (C1-C22) moiety; a substituted or unsubstituted phenyl portion; a substituted or unsubstituted benzyl moiety; a (C 1 -C 22) alkyl portion terminated by sulfonate, sulfate, acetate, or carboxylate; or ii.) when taken together they form a saturated or unsaturated carbocyclic or heterocyclic moiety; or iii.) when taken together they form a saturated or unsaturated carbocyclic or heterocyclic portion substituted by sulfate, sulfonate, phosphate, nitrate, and carboxylate; c.) X is a portion having the following Formula VII; wherein: i.) R5 and R6: (a) are independently selected from hydrogen; a saturated or unsaturated alkyl portion (C-1-C22); a hydroxyalkyl (C2-C22) moiety; a hydroxyalkyl (C2-C22) moiety comprising, in addition to the hydroxyl oxygen, an oxygen atom; a finished or non-finished polyether portion; an alkylamino (C1-C22) moiety; a substituted or unsubstituted phenyl portion; a substituted or unsubstituted benzyl moiety; an alkyl portion (CrC22) comprising a terminal portion of C1-C4 alkyl ether, sulfonate, sulfate, acetate or carboxylate moiety; a thiazole moiety or (b) when taken together form a saturated or unsaturated heterocyclic moiety; (c) when taken together they form a saturated or unsaturated heterocyclic portion substituted by one or more alkoxylate, sulfate, sulfonate, phosphate, nitrate, and / or carboxylate moieties; (d) when taken in conjunction with R7, R8l or R7 and R8 form one or more saturated or unsaturated heterocyclic portions, optionally substituted by one or more alkoxylate, sulfate, sulfonate, phosphate, nitrate, and / or carboxylate moieties; (e) when taken together they form a thiazole moiety; ii.) R7 and R8 can be independently selected from hydrogen or a saturated or unsaturated alkyl portion; d.) Q 'is an anion that provides full charge equilibrium of the compound of Formula I, and the index q is 0 or 1. 3. The composition for the care of clothes according to claim 2, further characterized in that for the thiazolium dye: a.) R1 is a methyl portion; b.) R3 and R4 are hydrogen; and c.) X has the following Formula VIII: wherein (i) R5 and R6 are as defined in claim 2; (ii) R7 is hydrogen or a methyl portion; and (ii) R8 is hydrogen.

4. The garment care composition according to claim 2, further characterized in that R5 and R6 are each, independently, from 1 to 20 alkylene oxide units and, independently, a portion selected from the group comprising oxide of styrene, glycidyl methyl ether, isobutyl glycidyl ether, isopropyl glycidyl ether, tert-butyl glycidyl ether, 2-ethylhexylglycidyl ether, or glycidylhexadecyl ether.

5. The composition for the care of clothes in accordance with claim 1, further characterized in that the thiazolium dye is selected from thiazolium dyes 1 to 80, and mixtures of these from the Table.

6. The composition for the care of clothes according to claim 5, further characterized in that the thiazolium dye is selected from thiazolium dyes 1, 4, 5, 7, 8, 12, 13, 15, 16, 17, 21, 24, 25, 26, 30, 31, 33, 36, 38, 40, 45, 48 and mixtures of these from Table 1.

7. The composition for the care of clothes according to claim 6, further characterized in that the thiazolium dye is selected from the thiazolium dyes 12, 13, 5, 16, 24, 25, 26, 30, 31, 33, 36 , 38, 40, 45, 48 and mixtures of these from Table 1.

8. The composition for the care of clothes according to any of the preceding claims, further characterized in that it comprises a surfactant, preferably an anionic surfactant and a nonionic surfactant.

9. - The composition for the care of clothes according to any of the preceding claims, further characterized in that it comprises, by weight, (a) from 5% to 90% of the surfactant, and (b) from 0.0001% to 0.05% of the thiazolium dye.

10. - The composition for the care of clothes according to any of claims 1 to 7, further characterized in that it comprises, by weight, (a) from 1% to 90% of a fabric softening active, and (b) of 0.1 ppm to 10,000 ppm of the thiazolium dye. eleven . - The composition for the care of clothes according to any of the preceding claims, further characterized in that it additionally comprises a non-tonalizing dye. 12. The composition for the care of clothes according to any of the preceding claims, further characterized in that it additionally comprises one or more additional components selected from the group comprising detergent additives, enzymes, stabilizers of enzymes, suds suppressors, soil suspending agents, soil release agents, pH adjusting agents, chelating agents, smectite clays, hydrotrope solvents, phase stabilizers, structuring agents, dye transfer inhibiting agents, optical brighteners, and perfumes. 13. - The composition for the care of clothes according to any of the preceding claims, further characterized in that the composition is a liquid. 14. - The composition for the care of clothes according to any of the preceding claims, further characterized in that the composition is a solid. 15. - The composition for the care of clothes according to any of the preceding claims, further characterized in that said composition has a tonality efficiency greater than 10 but less than 40, preferably 15 to 30, and a removal capacity in the wash from 30% to 85%, preferably from 50% to 85%. 16. - A method for preparing a laundry care composition comprising combining a thiazolium dye with a liquid to form a premix of thiazolium dye and adding the thiazolium dye premix to a composition comprising one or more components for the care of clothes. 17. - The method for preparing a composition for the care of clothes according to claim 16, further characterized because it comprises encapsulating the thiazolium dye, suspending the encapsulated dye in a structuring liquid, and adding the suspension to a composition comprising one or more components for the care of clothes. 18. - The method for preparing a laundry care composition according to claim 17, further characterized in that it comprises combining a thiazolium dye in particulate form, optionally including additional components of the laundry care composition, with a second particulate that contains a balance of components of the composition for the care of clothes. 19. - A method for treating a laundry item; the method optionally comprises washing, rinsing and / or drying a laundry article with a laundry care composition of any of claims 1 to 15, and then washing, rinsing and / or drying the laundry article.