Use of gardenia blue in liquid detergents, fabric softener and alkaline hard surface cleaners

Abstract

Consumer care formulation selected from the group consisting of alkaline liquid laundry detergents, alkaline liquid glass cleaner formulations, and liquid fabric softeners having a pH in the range of 5.0 to 7.0, containing Gardenia Blue in an amount from 0.00001 to 0.2 wt%, preferably from 0.0001 to 0.01 wt%, more preferably from 0.001 to 0.005 wt% of the formulation. Use of Gardenia Blue as a non¬ staining dye for the coloration of the formulation.

Description

Heubach Holding Switzerland AG COL24 / 75183PCUse of Gardenia Blue in Liquid Detergents, Fabric Softener and Alkaline Hard Surface CleanersThe invention concerns the use of Gardenia Blue in liquid detergent formulations, fabric softener formulations and alkaline hard surface cleaners.Color is a key ingredient in many household cleaning and fabric care products like detergents and fabric softeners. Brand owners use it to create distinctive brands and to visualize different product qualities. For example, blue might emphasize the hygienic properties of a household cleaner. Pink is frequently employed to visualize the softness for a wool detergent.In order to use dyes in fabric care and home care formulation, they need to be designed in a manner that they are not transferred from the formulations to the substrate, e.g. dyes in house hold cleaners shall not stick at the floor after cleaning and dyes in detergents shall be removed after the washing process with the washing liquor and not stick on the fabrics and make them colored. Such dyes are called nonstaining dyes.In the past decades strategies had been developed to prepare out of dyes with stable chromophores dyes with non-staining properties. A frequently used approach is the chemical modification of the dyes with several ethylene glycol units. This enhances the solubility of the dyes in water and reduces the adsorption of the dyes to the fabrics during the washing process. Such dyes are described e.g. in US 4,846,846 and EP 1 828 314 by Milliken.In addition to the non-staining properties it is more and more required that any ingredients for detergent formulations, fabric softener formulations and other cleaning formulations, including the dyes, are biodegradable. Typically most of the currently used non-staining dyes are not or only very poorly biodegradable. One approach tocome to non-staining biodegradable dyes for detergent formulations is the modification of synthetic dyes with natural building blocks.Alternatively, natural dyes or from natural base structures are supposed to be biodegradable and sustainable. However, most of these dyes are under aggressive conditions not long-term stable.It is an object of the present invention to provide a sustainable blue dye for liquid laundry detergent, fabric softeners and alkaline cleaning formulations like glass cleaners. This dye should be stable in the formulations especially under alkaline conditions. In addition, if used in such formulations, there should be no deposition of the dye on the fabric during the laundry process, if used in a detergent or fabric softener formulation (non-staining behavior). In case of the use of the dye in cleaning formulations like glass cleaners, the dye shall not be deposited on the surfaces to be cleaned. Finally dyes for such applications should be sufficiently stable in the formulation and during storage, without losing color strength caused by degradation processes.Gardenia Blue is a potential candidate for sustainable blue coloration of liquid detergent. It is formed by the reaction of Genipin with amino acids, peptides, proteins or protein hydrolysates.Gardenia blue is a natural blue dye and is typically used in Asia for food colorantion. Gardenia Blue is prepared by reaction of primary amine compounds with Genipin from the hydrosylate of Gardenia, which is colorful, safe, and has strong coloring power. Gardenia Blue is typically water-soluble, but it is unable to be dissolved in organic solvents and oil. See the following references:Jespersen, L.; Stromdahl, L.D.; Olsen, K.; Skibsted, L.H. Heat and light stability of three natural blue colorants for use in confectionery and beverages. Eur. Food Res. Technol. 2005, 220, 261-266.Wu, S.; Wu, Q.; Xu, L.; Xu, L.J. Progress in the development and application of natural edible pigment. Shandong Food Ferment. 2015, 179, 35-38.Li, Z.; Hu, C.; Jia, J.; Xia, Y.; Xie, H.; She, M.; Huang, R.; He, L.; Liu, C.; Wang, S.; et al. Establishment and evaluation of a simple size-selective method for exosome enrichment and purification. J. Biomed. Nanotechnol. 2019, 15, 1090-1096.Cho, Y.J.; Kim, S.Y.; Kim, J.; Choe, E.K.; Kim, S.I.; Shin, H.J. One-step enzymatic synthesis of blue pigments from geniposide for fabric dyeing. Biotechnol. Bioprocess Eng. 2006, 11 , 230-234.Kim, S.J.; Jang, H.G. Characterization and stability of Gardenia jasminoides biotransformed pigment produced in jar fermentor. J. Korean Soc. Food Sci. Nutr. 2005, 34, 880-884.Gardenia Blue is a polymer or oligomer and the topic of exact structure was investigated in the past in various publications. See e.g. Kaname Tsutsumiuchi et al, Molecular Structure of Gardenia Blue Pigments by Reaction of Genipin with Benzylamine and Amino Acids, J. Agric. Food Chem. 2021 , 69, 3904-3911. It is approved for food coloration in a couple of countries and described for the use in cosmetic formulations.According to Tsutsumiuchi et al. (J. Agric. Food Chem. 2021 , 69, 3904-3911) Gardenia Blue is the polymerization product of Genipin that is being formed in the presence of glycine. Genipocyanin is the blue dimer formed from genipin and glycine:In the literature about natural dyes frequently the expression “pigment” is used for water soluble dyes too. However, it has to be considered that the correct expression for a colored substance, which is dissolved in a solvent in form of single molecules, is dye. The expression pigment refers to a colored substance insoluble in the medium and present in the form of solid particles. Therefore, is the cited literature the expression pigment is in most cases used a synonym for dye.The stability of the natural dyes and pigments is challenged due to light, heat, pH, and the existence of metal ions or oxidants and reductants. Some researchers have studied the stability of Gardenia Blue, in aqueous solutions and they found that it was most unstable under light. Others tried to improve the dye’ stability by adding color fixative, embedding and chemical modifying, and other methods. See: Yakun Gao, Jinchuan Xu, Guorong Liu, Rong Nie, Jiaojiao Duan, Duoxia Xu and Chengtao Wang, Preparation and Characterization of Water-Insoluble Gardenia Blue Pigment, Materials 2021 , 14, 6594. https: / / doi.org / 10.3390 / ma14216594.Additionally, it is described in several supplier information that the dye is not suitable for any applications in which the formulation exhibits an alkaline pH value, like liquid detergents. See e.g. https: / / sensientcolors.cn / en / color-solutions / gardenia-blue / .If a stability study with commercially available Gardenia Blue is performed in aqueous buffers, using e.g. a storage test at 50 °C and a duration of 4 weeks, it is found, that the dye / color is stable under such conditions from pH 1 to pH 7. At pH values of 8 and above degradation of the dye take place, as seen by a lighter color after 4 weeks, or the complete disappearance of the blue shade after 4 weeks.Surprisingly it was found that a degradation of the Gardenia Blue dye under such storage conditions does not take place in liquid detergents or alkaline cleaning formulations like glass cleaners, exhibiting pH values of 8 and higher, although aqueous Gardenia Blue solutions in water are not storage stable. This makes itpossible to achieve a blue coloration with Gardenia Blue in such formulations. In addition, the liquid detergent formulations containing the Gardenia Blue do not exhibit a so-called spotting. This refers to a potential coloration of test fabrics with the dye contained in a detergent or softener formulation (see examples). Beside the stability of the dye in the formulation, this is the second important property of a dye for use in detergent formulations.The present invention therefore concerns the use of Gardenia Blue as non-staining dye for the coloration of a consumer care formulation selected from the group consisting of liquid laundry detergent, liquid fabric softener and liquid glass cleaner formulations.Liquid laundry detergent and glass cleaner formulations are in general alkaline formulations. Such formulations have in general a pH value of > 8.0, preferably from 8.0 to 10.0, in particular from 8.0 to 9.0.Liquid fabric softeners, also known also as “rinse added fabric conditioning compositions” (“RAFS”) exhibit typically a slightly acidic or neutral pH value, typically in the range of pH 5.0 to 7.0, preferably pH 5.5 to 6.5. Surprisingly the Gardenia Blue also exhibits for such formulations a non-staining behavior on the treated fabrics, although the Gardenia Blue is also typically used for coloration of fabrics; see e.g in Leo, Youngmi, Shin, Younsook: Inkjet Printing of Textiles Using Biodegradable Natural Dyes, Fibers and Polymers (2023), 24(5), 1695-1705; and Yeo, Youngmi, Shin, Younsook: Inkjet Printing of Textiles Using Biodegradable Natural Dyes, Fibers and Polymers (2023), 24(5), 1695-1705.The present invention furthermore concerns consumer care formulations selected from the group consisting of liquid detergent, fabric softener and glass cleaner formulations containing Gardenia Blue in an amount from 0.00001 to 0.2 wt%, preferably from 0.0001 to 0.01 wt%, more preferably from 0.001 to 0.005 wt% of the formulation.In one embodiment of the present invention, the consumer care formulation is a liquid laundry detergent formulation containing from 3 to 90 wt% of surfactants, from 0.5 to 50 wt% of builders, from 5 to 90 wt% of a non surface-active liquid carrier, preferably water, and optionally from 0 to 50 wt% of further additives selected from the group consisting of polymers, for example cationic polymers, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersing agents, clay soil removal / anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfume and perfume delivery systems, structure elasticizing agents, fabric softeners, hydrotropes, processing aids and / or other coloring agents.In one preferred embodiment of the present invention, the liquid laundry detergent formulation contains from 5 to 40 wt% of surfactants, from 0.5 to 50 wt% of builders, from 20 to 70 wt% of a non surface-active liquid carrier, preferably water, and from 0.1 to 10 wt% of one or more of the further additives.In another embodiment of the present invention, the consumer care formulation is a liquid fabric softener formulation containing from 5 to 50 wt% of fabric softening agents, from 0.001 to 0.2 wt% of preservatives, from 49.8 to 94.999 wt% of a non surface-active liquid carrier, preferably water, and optionally from 0.1 to 3 wt% of further additives such as perfumes, viscosity modifiers and dyes.In a further embodiment of the present invention, the consumer care formulation is a glass cleaner formulation containing from 0.5 to 10 wt% of surfactants, from 0.05 to 0.5 wt% of chelating agents, from 0.1 to 0.4 wt% of alkaline agents such as ammonium hydroxide, , optionally from 0.5 to 4 wt% of an additional solvent such as isopropanol, and optionally from 0.1 to 1 wt% of preservatives and fragrances. The rest of the formulation consists of the primary solvent water.In the following, typical liquid laundry detergent, liquid fabric softener and liquid alkaline glass cleaner compositions are described, in which Gardenia Blue can be used as a dye.Laundry detergent formulationsThe Gardenia Blue may be incorporated according to the present invention into a liquid alkaline laundry detergent formulation.The laundry detergent formulation may be in liquid form including a gel form. The laundry detergent formulation may also be in a unit dose pouch.The liquid laundry detergent formulation comprises a surfactant in an amount sufficient to provide desired cleaning properties. In one embodiment, the laundry detergent formulation comprises, by weight, from 3% to 90% of the surfactant, and more specifically from about 5% to 70% of the surfactant, and even more specifically from 5% to about 40%. The surfactant may comprise anionic, nonionic, cationic, zwitterionic and / or amphoteric surfactants. In a more specific embodiment, the detergent composition comprises anionic surfactant, nonionic surfactant, or mixtures thereof.Suitable anionic surfactants useful herein can comprise any of the conventional anionic surfactant types typically used in liquid detergent products. These include the alkyl benzene sulfonic acids and their salts as well as alkoxylated or non- alkoxylated alkyl sulfate materials. Exemplary anionic surfactants are the alkali metal salts of C10-16 alkyl benzene sulfonic acids, preferably C11-14 alkyl benzene sulfonic acids. Preferably, the alkyl group is linear and such linear alkyl benzene sulfonates are known as "LAS". Alkyl benzene sulfonates, and particularly LAS, are well known in the art. Such surfactants and their preparation are described for example in US 2,220,099 and US 2,477,383.Especially preferred are the sodium and potassium linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14. Sodium C11-C14, e.g. C12, LAS is a specific example of such surfactants.Another exemplary type of anionic surfactant comprises ethoxylated alkyl sulfate surfactants. Such materials, also known as alkyl ether sulfates or alkyl polyethoxylate sulfates, are those which correspond to the formula: R'-O-(C2H4O)n-SO3M wherein R' is a C8-C20 alkyl group, n is from about 1 to 20, and M is a salt-forming cation. In a specific embodiment, R' is C10-C18 alkyl, n is from about 1 to 15, and M is sodium, potassium, ammonium, alkylammonium, or alkanolammonium. In more specific embodiments, R' is a C12-C16, n is from about 1 to 6 or even from about 1 to 3 or from about 1 to 1 .5 and M is sodium.The alkyl ether sulfates will generally be used in the form of mixtures comprising varying R' chain lengths and varying degrees of ethoxylation. Frequently such mixtures will inevitably also contain some non-ethoxylated alkyl sulfate materials, i.e., surfactants of the above ethoxylated alkyl sulfate formula wherein n=0. Non-ethoxylated alkyl sulfates may also be added separately to the compositions of this invention and used as or in any anionic surfactant component which may be present. Specific examples of non- alkoxylated, e.g., non-ethoxylated, alkyl ether sulfate surfactants are those produced by the sulfation of higher C8-C20 fatty alcohols. Conventional primary alkyl sulfate surfactants have the general formula: ROSO3-M wherein R is typically a linear C8-C20 hydrocarbyl group, which may be straight chain or branched chain, and M is a water-solubilizing cation. In specific embodiments, R is a C10-C15 alkyl, and M is alkali metal, more specifically R is C12-C14 and M is sodium.Suitable nonionic surfactants useful herein can comprise any of the conventional nonionic surfactant types typically used in liquid detergent products. These include alkoxylated fatty alcohols and amine oxide surfactants. Preferred for use in the liquid detergent products herein are those nonionic surfactants, which are normally liquid.Suitable nonionic surfactants for use herein include the alcohol alkoxylate nonionic surfactants. Alcohol alkoxylates are materials which correspond to the general formula: R1(CmH2mO)nOH wherein R1is a Cs-C alkyl group, m is from 2 to 4, and n ranges from about 2 to 12. Preferably R1is an alkyl group, which may be primary or secondary, that comprises from about 9 to 15 carbon atoms, more preferably from about 10 to 14 carbon atoms. In one embodiment, the alkoxylated fatty alcohols will also be ethoxylated materials that contain from about 2 to 12 ethylene oxide moieties per molecule, more preferably from about 3 to 10 or even from about 7 to 9 ethylene oxide moieties per molecule.The alkoxylated fatty alcohol materials useful in the liquid detergent compositions herein will frequently have a hydrophilic-lipophilic balance (HLB) which ranges from about 3 to 17. More preferably, the HLB of this material will range from about 6 to 15, most preferably from about 8 to 15. Alkoxylated fatty alcohol nonionic surfactants have been marketed under the tradenames Neodol and Dobanol by the Shell Chemical Company.Another suitable type of nonionic surfactant useful herein comprises the amine oxide surfactants. Amine oxides are materials, which are often referred to in the art as "semi- polar" nonionics. Amine oxides have the formula: R(EO)x(PO)y(BO)zN(O)(CH2R')2 - qH2O. In this formula, R is a relatively long-chain hydrocarbyl moiety, which can be saturated or unsaturated, linear or branched, and can contain from 8 to 20, preferably from 10 to 16 carbon atoms, and is more preferably C12-C16 primary alkyl. R' is a short-chain moiety, preferably selected from hydrogen, methyl and -CH2OH. When x+y+z is different from 0, EO is ethyleneoxy, PO is propyleneneoxy and BO is butyleneoxy. Amine oxide surfactants are illustrated by C12-14 alkyldimethyl amine oxide.In the laundry detergent compositions herein, the detersive surfactant component may comprise combinations of anionic and nonionic surfactant materials. When this is thecase, the weight ratio of anionic to nonionic will typically range from 10:90 to 90:10, more typically from 30:70 to 70:30.Cationic surfactants are well known in the art and non-limiting examples of these include quaternary ammonium surfactants, which can have up to 26 carbon atoms.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.Non-limiting examples of ampholytic surfactants include aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines in which the aliphatic radical can be straight- or branched-chain. One of the aliphatic substituents comprises at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one comprises an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate.The liquid detergent compositions comprise an aqueous, non-surface active liquid carrier. Generally, the amount of the aqueous, non-surface active liquid carrier employed in the compositions herein will be effective to solubilize, suspend or disperse the composition components. For example, the compositions may comprise, by weight, from about 5% to about 90%, more specifically from about 10% to about 70%, and even more specifically from about 20% to about 70% of the aqueous, non surface-active liquid carrier.The most cost-effective type of aqueous, non-surface active liquid carrier is, of course, water itself. Accordingly, the aqueous, non-surface active liquid carrier component will generally be mostly, if not completely, comprised of water. However, other types of water- miscible liquids, such alkanols, diols, other polyols, ethers, amines, and the like, and mixtures thereof, may also be added to liquid detergent compositions as co solvents or stabilizers in addition to or in place of water. Accordingly, the aqueous non-surface activeliquid carrier component of the liquid detergent composition will generally be present in concentrations ranging from about 5% to about 90% by weight of the composition, more preferably from about 20% to about 70% by weight of the composition.Detergent compositions may also contain bleaching agents. Suitable bleaching agents include, for example, hydrogen peroxide sources, such as those described in detail in the herein incorporated Kirk Othmer's Encyclopedia of Chemical Technology, 4th Ed (1992, John Wiley & Sons), Vol. 4, pp. 271-300 "Bleaching Agents (Survey)." These hydrogen peroxide sources include the various forms of sodium perborate and sodium percarbonate, including various coated and modified forms of these compounds.The liquid detergent formulations are in the form of an aqueous solution or uniform dispersion or suspension of surfactant, Gardenia Blue, and certain optional other ingredients, some of which may normally be in solid form, that have been combined with the normally liquid components of the composition, such as the liquid alcohol ethoxylate nonionic, the aqueous liquid carrier, and any other normally liquid optional ingredients. Such a solution, dispersion or suspension will be acceptably phase stable and will typically have a viscosity, which ranges from about 100 to 600 cps, more preferably from about 150 to 400 cps.The liquid detergent formulations herein can be prepared by combining the components thereof in any convenient order and by mixing, e.g., agitating, the resulting component combination to form a phase stable liquid detergent composition. In a preferred process for preparing such compositions, a liquid matrix is formed containing at least a major proportion, and preferably substantially all, of the liquid components, e.g., nonionic surfactant, the non-surface active liquid carriers and other optional liquid components, with the liquid components being thoroughly admixed by imparting shear agitation to this liquid combination. For example, rapid stirring with a mechanical stirrer may usefully be employed. While shear agitation is maintained, substantially all of any anionic surfactants and the solid form ingredients can be added. Agitation of the mixture is continued, and ifnecessary, can be increased at this point to form a solution or a uniform dispersion of insoluble solid phase particulates within the liquid phase. After some or all of the solidform materials have been added to this agitated mixture, particles of any enzyme material to be included, e.g., enzyme prills, are incorporated. As a variation of the composition preparation procedure hereinbefore described, one or more of the solid components may be added to the agitated mixture as a solution or slurry of particles premixed with a minor portion of one or more of the liquid components. After addition of all of the composition components, agitation of the mixture is continued for a period of time sufficient to form compositions having the requisite viscosity and phase stability characteristics.In an alternate embodiment for forming the liquid detergent formulations, the Gardenia Blue is first combined with one or more liquid components to form a Gardenia Blue premix, and this premix is added to a composition formulation containing a substantial portion, for example more than 50% by weight, more specifically, more than 70% by weight, and yet more specifically, more than 90% by weight, of the balance of components of the laundry detergent composition. For example, in the methodology described above, both the Gardenia Blue premix and the enzyme component are added at a final stage of component additions. In a further embodiment, the Gardenia Blue is encapsulated prior to addition to the detergent composition, the encapsulated Gardenia Blue is suspended in a structured liquid, and the suspension is added to a composition formulation containing a substantial portion of the balance of components of the laundry detergent composition.While not essential for the purposes of the present invention, the non-limiting list of other ingredients illustrated hereinafter are suitable for use in the liquid detergent formulations and may be desirably incorporated in certain embodiments of the invention, for example to assist or enhance performance, for treatment of the substrate to be cleaned, or to modify the aesthetics of the composition as is the case with perfumes, colorants, dyes or the like. It is understood that such ingredients are in addition to the components that were previously listed for any particular embodiment. The total amount of such adjuncts mayrange from 0.1 to 50 wt%, or even from 1 to 30 wt% of the liquid laundry detergent formulation.The precise nature of these additional components, and levels of incorporation thereof, will depend on the physical form of the composition and the nature of the operation for which it is to be used. Suitable liquid detergent ingredients include, but are not limited to, polymers, for example cationic polymers, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersing agents, clay soil removal / anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfume and perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and / or other coloring agents. In addition to the disclosure below, suitable examples of such other adjuncts and levels of use are found in U.S. Patent Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1.As stated, the other ingredients are not essential to the liquid laundry detergent formulations of the invention. Thus, certain embodiments of the compositions do not contain one or more of the following adjuncts materials: bleach activators, surfactants, builders, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic metal complexes, polymeric dispersing agents, clay and soil removal / anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfumes and perfume delivery systems, structure elasticizing agents, fabric softeners, carriers, hydrotropes, processing aids and / or coloring agents. However, when one or more adjuncts are present, such one or more adjuncts may be present as detailed below:Builders - The compositions of the present invention can comprise one or more detergent builders or builder systems. When present, the compositions will typically comprise 0.5 wt% to 50 wt% of said builder. Builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates, alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicate builders polycarboxylate compoundsether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1 ,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid 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 contain one or more copper, iron and / or manganese chelating agents. If utilized, chelating agents will generally comprise from about 0.1 % by weight of the formulation to 15 wt%, or even from 3.0 wt% to 15 wt% of the formulation.Dye Transfer Inhibiting Agents - The formulations of the present invention may also 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 0.0001 wt%, from 0.01 wt%, from 0.05 wt% of the formulation to 10 wt%, 2 wt%, or even 1 wt% of the formulation.Dispersants - The compositions of the present invention can also contain dispersants. Suitable water-soluble organic materials are the homo- or co-polymeric acids or their salts.Enzymes - The compositions can comprise one or more detergent enzymes, which provide cleaning performance and / 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, tannases, pentosanases, malanases, b-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof. A typical combination is a cocktail of conventional applicable enzymes like protease, lipase, cutinase and / 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 sources of calcium and / or magnesium ions in the finished formulation that provide such ions to the enzymes.Catalytic Metal Complexes - Applicants’ compositions may include catalytic metal complexes. One type of metal-containing bleach catalyst is a catalyst system comprising a transition metal cation of defined bleach catalytic activity, such as copper, iron, titanium, ruthenium, tungsten, molybdenum, or manganese cations, an auxiliary metal cation having little or no bleach catalytic activity, such as zinc or aluminum cations, and a sequestrate having defined stability constants for the catalytic and auxiliary metal cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetra (methyl-enephos- phonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Patent No. 4,430,243.If desired, the formulations herein can be catalyzed by means of a manganese compound. Such compounds and levels of use are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Patent No. 5,576,282. Cobalt bleach catalysts useful herein are known, and are described, for example, in U.S. Patent Nos. 5,597,936 and 5,595,967. Such cobalt catalysts are readily prepared by known procedures, such as taught for example in U.S. Patent Nos. 5,597,936, and 5,595,967.The formulations herein may also suitably include a transition metal complex of a macropolycyclic rigid ligand - abbreviated as “MRL”. As a practical matter, and not by wayof limitation, the compositions and cleaning processes herein can be adjusted to provide on the order of at least one part per hundred million of the benefit agent MRL species in the aqueous washing medium, and may 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 instant transition-metal bleach catalyst include manganese, iron and chromium. Preferred MRL’s herein are a special type of ultra- rigid ligand that is cross-bridged such as 5, 12-diethyl-1 ,5,8, 12- tetraazabicyclo[6.6.2]hexadecane. Suitable transition metal MRLs are readily prepared by known procedures, such as taught for example in WO 00 / 32601 , and U.S. Patent No. 6,225,464.The inventive liquid detergent formulation containing Gardenia Blue can be present also in the form of so-called Laundry Detergent Pods (see e.g. https: / / en.wikipedia.org / wiki / Laundrv detergent pod). Laundry detergent pods (also called "packs" or "liquidtabs") are water-soluble pouches containing highly concentrated laundry detergent, softener and other laundry products. Notable brands of these packs include All, Arm & Hammer, Gain, Purex, Persil, Rinso and Tide. They first became popular in February 2012 when they were introduced by Procter & Gamble as Tide Pods (Ariel Pods in Europe). The chemistry of laundry detergent packs is the same as in liquid detergents (including alkylbenzenesulfonates). The dissolvable packets are typically made of polyvinylalcohol (PVA) or a derivative of PVA. Although the formulas are similar, the concentration varies; the liquid components of a detergent pod may contain 10% water compared to 50% in liquid detergents.Liquid fabric softening formulationsIn another specific embodiment of the present invention, the Gardenia Blue may be included in liquid fabric softening formulations. The fabric softening composition may becomprised of at least one Gardenia Blue and a rinse added fabric softening composition (“RAFS;” also known also as rinse added fabric conditioning compositions). Examples of typical rinse added softening compositions can be found in U.S. Provisional Patent Application Serial No. 60 / 687582 filed on October 8, 2004. The rinse added fabric softening compositions of the present invention may comprise (a) fabric softening active (“FSA”) The rinse added fabric softening composition may comprise from 1 to 90 wt% by weight of the FSA, more preferably from 5 to 50 wt% of the FSA. The Gardenia Blue may be present in the rinse added fabric softening composition in an amount from 0.00001 - 0.2 wt% of the composition, more preferably from about 0.0001 - 0.01 wt% of the composition, and even more preferably from about 0.001 - 0.005 wt% of the composition.In one embodiment of the invention, the fabric softening active is a quaternary ammonium compound suitable for softening fabric in a rinse step. In one embodiment, the FSA is formed from a reaction product of a fatty acid and an aminoalcohol obtaining mixtures of mono-, di-, and, in one embodiment, triester compounds. In another embodiment, the FSA comprises one or more softener quaternary ammonium compounds such, but not limited to, as a monoalkyquaternary ammonium compound, a diamido 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 (hereinafter “DQA”) compound composition. In certain embodiments of the present invention, the DQA compounds compositions also encompasses a description of diamido FSAs and FSAs with mixed amido and ester linkages as well as the aforementioned diester linkages, all herein referred to as DQA.A first type of DQA (“DQA (1)”) suitable as a FSA includes a compound comprising the formula:{R4-m-N(+)-[(CH2)n-Y-R1]m} X’ wherein each R substituent is either hydrogen, a short chain Ci-Ce, preferably C1-C3 alkyl or hydroxyalkyl group, e.g., methyl (most preferred), ethyl,Y1propyl, hydroxyethyl, and the like, poly (C2-3 alkoxy), preferably polyethoxy, group, benzyl, 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 R1, plus one when Y is -O-(O)C- or -NR- C(O) -, is C12-C22 preferably C14-C20 with each R1being a hydrocarbyl, or substituted hydrocarbyl group; it is acceptable for R1to be unsaturated or saturated and branched or linear and preferably it is linear; it is acceptable for each R1to be the same or different and preferably these are the same; and X can be any softener-compatible anion, preferably, chloride, bromide, methylsulfate, ethylsulfate, sulfate, phosphate, and nitrate, more preferably chloride or methyl sulfate. Preferred DQA compounds are typically made by reacting alkanolamines such as MDEA (methyldiethanolamine) and TEA (triethanolamine) with fatty acids. Some materials that typically result from such 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 fats, unsaturated, and polyunsaturated, fatty acids, e.g., tallow, hardened tallow, oleic acid, and / or partially hydrogenated fatty acids, derived from vegetable oils and / or partially hydrogenated vegetable oils, such as, canola oil, safflower oil, peanut oil, sunflower oil, corn oil, soybean oil, tall oil, rice bran oil, palm oil, etc.

[0112] Non-limiting examples of suitable fatty acids are listed in US Patent No. 5,759,990 at column 4, lines 45-66. In one embodiment, the FSA comprises other actives in addition to DQA (1 ) or DQA. In yet another embodiment, the FSA comprises only DQA (1 ) or DQA and is free or essentially free of any other quaternary ammonium compounds or other actives. In yet another embodiment, the FSA comprises the precursor amine that is used to produce the DQA.In another aspect of the invention, the FSA comprises a compound, identified as DTTMAC comprising the formula:[R4-m-N(+)-R1m] A’wherein each m is 2 or 3, each R1 is a C6-C22, preferably C14-C20 but no more than one being less than about C12 and then the other is at least about 16, hydrocarbyl, or substituted hydrocarbyl substituent, preferably C10-C20 alkyl or alkenyl(unsaturated alkyl, including polyunsaturated alkyl, also referred to sometimes as "alkylene"), most preferably C12-C18 alkyl or alkenyl, and branch or unbranched. In one embodiment, the Iodine Value (IV) of the FSA is from about 1 to 70; each R is H or a short chain Ci-Ce, preferably C1-C3 alkyl or hydroxyalkyl group, e.g., methyl (most preferred), ethyl, propyl, hydroxyethyl, and the like, benzyl, or (R2O)2-4H where each R2is a C1-6 alkylene group; and A- is a softener compatible anion, preferably, chloride, bromide, methyl sulfate, ethylsulfate, sulfate, phosphate, or nitrate; more preferably chloride or methyl sulfate.Examples of these FSAs include dialkydimethylammonium salts and dialkylenedimethylammonium salts such as ditallowdimethylammonium and ditallowdimethylammonium methylsulfate. Examples of commercially available dialkylenedimethylammonium salts usable in the present invention are di-hydrogenated tallow dimethyl ammonium chloride and ditallowdimethyl ammonium chloride available from Degussa under the trade names Adogen® 442 and Adogen® 470 respectively. In one embodiment, the FSA comprises other actives in addition to DTTMAC. In yet another embodiment, the FSA comprises only compounds of the DTTMAC and is free or essentially free of any other quaternary ammonium compounds or other actives.In one embodiment, the FSA is chosen from at least one of the following: ditallowoyloxyethyl dimethyl ammonium chloride, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, ditallow dimethyl ammonium chloride, ditallowoyloxyethyl dimethyl ammonium methyl sulfate, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, dihydrogenated-tallowoyloxyethyl dimethyl ammonium chloride, or combinations thereof.In one embodiment, the FSA may also include amide containing compound compositions. Examples of diamide comprising compounds may include but not limited to methyl- bis(tallowamidoethyl)-2-hydroxyethylammonium methyl sulfate (available from Degussa under the trade names Varisoft 110 and Varisoft 222). An example of an amide- estercontaining compound is N-[3-(stearoylamino)propyl]-N-[2-(stearoyloxy)ethoxy)ethyl)]-N- methylamine.Another specific embodiment of the invention provides for a rinse added fabric softening composition further comprising a cationic starch. Cationic starches are disclosed in US 2004 / 0204337 A1 .Glass cleaning formulationsSuch formulations typically contain a solvent, mostly water, surfactants, alkaline agents, complexing agents for water hardness and other additives like fragrances and dyes. In some cases to the aqueous solvent isopropanol, ethanol, and glycol ethers are added, e.g. to dissolve fats. As surfactants frequently amine oxide surfactants, alcohol ethoxylates or alkyl polyglycosides are used. Such inventive formulations contain Gardenia Blue in an amount from 0.00001 - 0.2 wt% of the composition, more preferably from 0.0001 - 0.01 wt% of the composition, and even more preferably from about 0.001 - 0.005 wt% of the composition. Typically the final glass cleaner exhibits a pH-value of 8-11.The invention is further detailed by the following examples.EXAMPLESFor the examples a Gardenia Blue powder (NIG Dyestuff 19 - BLUE-GARD; CAS No.: 92457-01-7; EG / EINECS No.: 296-280-9; INCI: Gardenia jasminoides fruit extract) was used, which was obtained from NIG Nahrungs-lngenieurtechnik GmbH, Wasserkunststr. 26, D-39124 Magdeburg, Germany.EXAMPLE 1 pH-stabilityThe pH stability of Gardenia Blue was studied using a homogeneous mixture of approx. 99.5 g pH buffer solutions (pH 1 to 13) and approx. 0.5 g Gardenia Blue 1 % aqueous solution. The mixtures have been stored for four weeks at room temperature and 50°C. The stability evaluation was done visually. Figure 1 shows the results of the pH-stability evaluation a) at start, b) after 4 weeks at room temperature, c) after 4 weeks at 50°C.EXAMPLE 2Stability in liquid laundry detergentThe liquid laundry detergent base (“Denkmit Nature”) used for this test has been bought from a local DM drug store. The liquid laundry detergent base has a pH = 8.5. For the test, approx. 99.5 g Denkmit Nature was homogeneously mixed with 0.5 g Gardenia Blue 1 % aqueous solution. The mixture has been stored for four weeks at room temperature and 50°C. The stability evaluation was done visually. Figure 2 shows the results of the stability evaluation in liquid detergent Denkmit Nature a) at start, b) after 4 weeks at room temperature, c) after 4 weeks at 50°C.EXAMPLE 3Stability in liquid laundry detergentThe liquid laundry detergent base (“Ecover Color”) used for this test has been bought from a local DM drug store. The liquid laundry detergent base has a pH = 8.0. For the test, approx. 99.5 g Ecover Color was homogeneously mixed with 0.5 g Gardenia Blue 1 % aqueous solution. The mixture has been stored for four weeks at room temperature and 50°C. The stability evaluation was done visually. Figure 3 shows the results for thestability evaluation in liquid detergent Ecover Color: a) start, b) after 4 weeks at room temperature, c) after 4 weeks at 50°C.EXAMPLE 4Stability in liquid glass cleanerThe colorless liquid glass cleaner used for this test has been bought from a local DM drug store. The liquid glass cleaner has a pH = 10.8. For the test, approx. 15 g liquid glass cleaner was homogeneously mixed with approx. 0.02 g Gardenia Blue 1 % aqueous solution. The mixture has been stored for four weeks at room temperature and 50°C. The stability evaluation was done visually. Figure 4 shows the results for the stability evaluation in liquid glass cleaner a) at start, b) after 4 weeks at room temperature, c) after 4 weeks at 50°C.EXAMPLE 5Non-staining test with liquid laundry detergentThe non-staining test has been done using a Lini apparatus and am EMPA multifibre test fabric (Art. No. 411). For this purpose, 4,65 ppm Gardenia Blue were dissolved in liquid laundry detergent (Ecover Color). 70 pL from this mixture was added dropwise on the test fabric and allowed to soak for 30 minutes. Afterwards, the fabric was washed within the Lini apparatus for 10 minutes, at 20°C using 200 ml water 15°dH. After washing, the test fabric was dried, and the evaluation was done visually. A scale 1 to 5 was used, where 1 = no staining and 5 = heavy staining. The results of the non-staining test in liquid laundry detergent are shown in Figure 5.EXAMPLE 6Non-staining test with liquid fabric softenerThe non-staining test has been done using a Lini apparatus and am EMPA multifibre test fabric (Art. No. 411). For this purpose, 4,65 ppm Gardenia Blue were dissolved in liquid fabric softener (Lenor Entspanung Orchidee & Vanille). 70 pL from this mixture was added dropwise on the test fabric and allowed to soak for 30 minutes. Afterwards, the fabric was washed within the Lini apparatus for 10 minutes, at 20°C using 200 ml water 15°dH. After washing, the test fabric was dried, and the evaluation was done visually. A scale 1 to 5 was used, where 1 = no staining and 5 = heavy staining. The results of the non-staining test with fabric softener are shown in Figure 6.

Claims

Claims1. Use of Gardenia Blue as a non-staining dye for the coloration of an alkaline liquid laundry detergent or alkaline liquid glass cleaner formulation.

2. Use as a non-staining dye for the coloration of a liquid fabric softener having a pH in the range of 5.0 to 7.0.

3. The use according to claim 1 or 2, wherein Gardenia Blue is obtained from the reaction of Genipin with amino acids, peptides, proteins or protein hydrolysates.

4. Consumer care formulation selected from the group consisting of alkaline liquid laundry detergents, alkaline liquid glass cleaner formulations, and liquid fabric softeners having a pH in the range of 5.0 to 7.0, containing Gardenia Blue in an amount from 0.00001 to 0.2 wt%, preferably from 0.0001 to 0.01 wt%, more preferably from 0.001 to 0.005 wt% of the formulation.

5. Liquid laundry detergent formulation according to claim 4 containing from 3 to 90 wt% of surfactants, from 0.5 to 50 wt% of builders, from 5 to 90 wt% of a non surface-active liquid carrier, preferably water, and optionally from 0 to 50 wt% of further additives selected from the group consisting of polymers, for example cationic polymers, chelating agents, dye transfer inhibiting agents, dispersants, enzymes, and enzyme stabilizers, catalytic materials, bleach activators, polymeric dispersing agents, clay soil removal / anti-redeposition agents, brighteners, suds suppressors, dyes, additional perfume and perfume delivery systems, structure elasticizing agents, fabric softeners, hydrotropes, processing aids and / or other coloring agents.

6. Liquid laundry detergent formulation according to claim 5 having a pH in the range of 8.0 to 10.0.

7. Liquid laundry detergent formulation according claim 5 or 6 comprising surfactants selected from the group consisting of nonionic surfactants, anionic surfactants, cationic surfactants, ampholytic surfactants, zwitterionic and semi- polar nonionic surfactants.

8. Liquid laundry detergent formulation according to any one of claims 4 to 7 comprising builders selected from the group of the alkali metal, ammonium and alkanolammonium salts of polyphosphates, alkali metal silicates, alkali metal and alkaline earth carbonates, aluminosilicate builders, ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1 ,3,5-trihydroxybenzene-2,4,6-trisulphonic acid, and carboxymethyl-oxysuccinic acid, alkali metal, ammonium and substituted ammonium salts of polyacetic acids, such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1 ,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

9. Liquid laundry detergent formulation according to any one of claims 4 to 8 comprising dispersants selected from homo- or co-polymeric acids or their salts.

10. Liquid laundry detergent formulation according to any one of claims 4 to 9 comprising enzymes selected from the group consisting of hemicellulases, peroxidases, proteases, cellulases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases,pentosanases, malanases, b-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase, and amylases, or mixtures thereof.11 . Liquid laundry detergent according to any one of claims 4 to 10 in the form of Laundry Detergent Pods.

12. Liquid fabric softener formulation according to claim 4 containing from 5 to 50 wt% of fabric softening agents, from 0.001 to 0.2 wt% of preservatives, from 49.8 to 94.999 wt% of a non surface-active liquid carrier, preferably water, and optionally from 0.1 to 3.0 wt% of further additives such as perfumes, viscosity modifiers and dyes.

13. Liquid fabric softener formulation according claim 12 comprising as fabric softening agent one or more softener quaternary ammonium compounds such, but not limited to, as a monoalkyquaternary ammonium compound, a diamido quaternary compound and a diester quaternary ammonium compound, or a combination thereof.

14. Liquid glass cleaner formulation according to claim 4 containing from 0.5 to 10 wt% of surfactants, from 0.05 to 0.5 wt% of chelating agents, from 0.1 to 0.4 wt% of alkaline agents such as ammonium hydroxide, optionally from 0.5 to 4 wt% of an additional solvent such as isopropanol, and optionally from 0.1 to 1 wt% of preservatives and fragrances, adding up with the primary solvent water to 100 wt%15. Liquid glass cleaner formulation according to claim 14 having a pH in the range of 8.0 to 11.0.

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