Polymeric dyes with enhanced biodegradability containing polycarboxylic acids, amino acids, polyamino acids and / or peptide building blocks

Abstract

A polymeric colorant of formula (III) wherein: (III) wherein A1 and A2 are, independently of each other, a polyethyleneoxy-, polypropyleneoxy-, or a polyethyleneoxy-Zpolypropyleneoxy-linker; the number of repeating ethyleneoxy- and / or propyleneoxy-units in each of A1 and A2 is less than or equal to 25; or A1 and A2 are, independently of each other, -CH2CH2CH2- M[(CH2CH2O)x-CH2CH2NH-]y; M can be either 0 or N and x = 1 - 5, and if M is O then y = 1, and if M is N then y = 2; and R4 and R5 represent the terminal group of the polyalkyleneoxy chain and are, independently of each other, selected from the group consisting of an amino acid residue, a polyamino acid residue, a peptide residue, a hydroxycarboxylic acid residue, a hydroxypolycarboxylic acid residue or a polycarboxylic acid residue linked with an amino group, an ether group or an ester group to the polyalkyleneoxy chain. Those compounds are non-staining dyes with enhanced biodegradability.

Description

Polymeric Dyes with enhanced Biodegradability containing Polycarboxylic Acids, Amino Acids, Polyamino Acids and / or Peptide building blocksThe invention concerns non-staining dyes with enhanced biodegradability. 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 non staining 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 4846846 and EP 1828314 by Milliken.In the following, the prior art is summarizes with respect to a modification of dyes with natural, biodegradable building blocks. US 6281269 to Hewlett Packard with the title “Fluid set for ink-jet printers” describes dyes, and more particularly, water fast ink-jet ink compositions containing the same. The dyes of this invention, when interacted with a second reactive fluid or 5th pen fluid, provides permanence benefits, such as smear fastness, smudge fastness, and water fastness. The invention describedtherein includes sugar modified triazine dyes. The focus of this patent is on the application properties of the dyes. Biodegradability of the protected dyes is not mentioned. EP 1462484 relates to new coloring agents comprising a chromophore bound, via an ether or ester bond, to one or more molecules of a mono- or disaccharide, the process for preparing them, and their use in the dyeing of textile fibers. These dyes however turned to be soluble in water only when the chromophore molecular weight is below 250.EP 2085434 describes disperse dyes soluble in water of general formula D-L-Sn wherein D is a disperse dye insoluble in water, L is a linker, S is a sugar, and n is from 2 to 4. In particular are described dyes wherein the sugar S is 6'-deoxy-6'- amino-lactose. Said dyes, in comparison with the corresponding non- glycoconiugated dyes, are able to dye in a homogeneous way natural fibers and textiles and also textile materials including different fibers, and have high biodegradability through digestion by microorganisms, that found in the molecule itself a useful nourishment for their survival and proliferation. Processes for the preparation of the above said dyes and their use are also described. In the former two references, the modification of the original dyes aims at an enhancement of the water solubility of the original dye. Although a potential improvement in the environmental impact is mentioned in these documents, no biodegradability data or calculations are provided. EP 2992053 with the title “Coloring agents naturalized with the 6’-deoxy-6’-(piperazinyl)lactose moiety” refers to coloring products soluble in water at room temperature. Here a piperazine unity is inserted, bonded directly to the saccharidic unity. This moiety afford to the final glycoconjugated colorants some very advantageous characteristics for dyeing leather, textiles, wood and hairs. The main focus of the modifications of the original dye is enhancement of solubility. WO 2022 / 197295 with the title “Polymeric colorants with reduced staining” relates to polymeric colorants that do not stain clothing, plastic or metal when used in consumer products, such as laundry detergents, fabric softeners and dish detergents. The polymeric colorants contain at least one carboxymethyl capped alkyleneoxy chain to improve the fugitivity and staining properties. It is believed that the incorporation of a carboxymethyl cap on the end of the alkyleneoxy chain of polymeric colorants further increases the water solubility, while not decreasing the color strength of the colorant.It is an object of the present invention to provide further non-staining colorants for the use in household cleaning and fabric care products with improved biodegradability. The object is achieved by a polymeric colorant of formula (I) wherein:A is a chromophore selected from the group consisting of nitro, nitroso, monazo, bisazo, diarylmethane, triarylmethane, acridine, ethine, thiazole, indamine, oxazine, pthalocyanine, and anthraquinone dye residues;L is a polyalkylene oxide linker composed of one or more alkylene oxides selected from ethylene oxide, propylene oxide and butylene oxide;Ri is nitrogen, oxygen, or sulfur;R2 is hydrogen, a methyl group, or an ethyl group;X is -NH-, -0- or -O-C(O)-; b is 1 , 2 or 3, preferably 2; c is 1 if R1 is oxygen or sulfur, and 2 if R1 is nitrogen;B is an amino acid residue, a polyamino acid residue, a peptide residue, a hydroxycarboxylic acid residue, a hydroxypolycarboxylic acid residue or a polycarboxylic acid residue.Preferred hydroxycarboxylic acids, hydroxypolycarboxylic acids and polycarboxylic acid have form 2 to 6 carbon atoms, 1 or 2 carboxylic acid groups and up to 4 OH- groups.The non-staining dyes available on the market are typically not biodegradable, as they mainly consist of non-natural components. The invention describes an approach to non-staining dyes with increased biodegradability by modification of the non-staining dyes with amino acids, oligo peptides or peptides. Surprisingly, itwas found that the biodegradability is strongly enhanced by such modifications. Preferred amino acids for the modification are aspartic acid and glutaminic acid. Preferred polyamino acids are polyaspartic acid and polyglutaminic acid. The linker L can be a polyalkylene oxide-homopolymer, such as a polyethylene oxide-, a polypropylene oxide or a polybutylene oxide-homopolymer. The linker L can be a polyalkylenoxide-copolymer, such as a polyethyleneoxy-Zpolypropyleneoxy- copolymer. The copolymer can be a random-copolymer (statistical copolymer) or a blockcopolmer, such as a polyethyleneoxy-Zpolypropyleneoxy-blockcopolymer.The polyalkylene oxide linker L has in general e molecular weight ranging from 132 to 10 000 gZmol, preferably from 104 to 5 000 gZmol.Preferably, L has the formula (II)-(CH2CH2O)a— (CH2CHO)b— (II)R3wherein R3 is a methyl group or an ethyl group, preferably a methyl group; a is an integer of from 0 to 20, preferably from 0 to 10, more preferably from 0 to 5; b is an integer of from 0 to 20, preferably from 0 to 10, more preferably from 0 to 5. a + b is in general 2 to 20, preferably 2 to 10, more preferably 2 to 8.Through the modification with the amino acids, poly amino acids or peptides, the biodegradability of the original dye is improved. The amino acid can be any natural amino acid, or a chemically modified amino acid. Examples of suitable amino acids are aspartic acid, glutamic acid, beta-alanine, lysine, glycine and tyrosine.Examples of suitable polyamino acids are polyaspartic acid, polyglutamic acid, and polylysine. Polyaspartic acid (PASA) is a biodegradable, water-soluble condensation polymer based on the amino acid aspartic acid. It is a biodegradable replacement for water softeners and related applications. PASA can be chemically crosslinked with a wide variety of methods to yield PASA hydrogels. The resulting hydrogels are pH-sensitive such that under acidic conditions, they shrink, while the swelling capacity increases under alkaline conditions. Polyglutamic acid (PGA) is a polymer of the amino acid glutamic acid (GA). Depending on where the individual monomers connect, PGA can be gamma PGA (poly-y-glutamic acid, y-PGA), the form where the peptide bonds are between the amino group of GA and the carboxyl group at the end of the GA side chain, or alpha PGA, the form where the alpha-carboxyl is used to form the peptide bond. Gamma PGA is formed by bacterial fermentation. It is a major constituent of the Japanese food natto and has a wide range of uses. Gamma PGA is non-immunogenic and biodegradable. It hydrolyzes in hot water. Both forms are amphiphilic, water-soluble, and have a negative charge. Peptides are short chains of amino acids linked by peptide bonds. A polypeptide is a longer, continuous, unbranched peptide chain. Polypeptides, which have a molecular mass of 10,000 Da or more, are called proteins. Chains of fewer than twenty amino acids are called oligopeptides, and include dipeptides, tripeptides, and tetrapeptides.Peptides fall under the broad chemical classes of biological polymers and oligomers, alongside nucleic acids, oligosaccharides, polysaccharides, and others. Suitable peptides are oligopeptides contain from 2 to 10 amino acid units.Amino acids that have been incorporated into peptides are termed residues. A water molecule is released during formation of each amide bond. All peptides except cyclic peptides have an N-terminal (amine group) and C-terminal (carboxyl group) residue at the end of the peptide.Suitable hydroxypolycarboxylic acids and polycarboxylic acids are citric acid, isocitric acid tartronic acid, malic acid, 3-hydroxyglutaric acid, 2-hydroxyglutaric acid, 2- hydroxyadipic acid, 3-hydroxyadipic acid, tartaric acid, keto-oxalacetic acid and enoloxalacetic acid.Further suitable hydroxypolycarboxylic acids are sugar acids, preferably those having from 3 to 6 carbon atoms. Main classes of sugar acids include:Aldonic acids, in which the aldehyde group (-CHO) located at the initial end (of an aldose is oxidized.• Ulosonic acids, in which the -CH2(OH) group at the initial end of a 2-ketose is oxidized creating an a-ketoacid.• llronic acids, in which the -CH2(OH) group at the terminal end of an aldose or ketose is oxidized.• Aldaric acids, in which both ends (-CHO and -CH2(OH)) of an aldose are oxidized.Examples of sugar acids include:• Aldonic acids o Glyceric acid (3C) o Xylonic acid (5C) o Gluconic acid (6C) o Ascorbic acid (6C, unsaturated lactone)• Ulosonic acids o Neuraminic acid (5-amino-3,5-dideoxy-D-g / ycero-D-ga / acto-non-2- ulosonic acid) o Ketodeoxyoctulosonic acid (KDO or 3-deoxy-D-manno-oct-2-ulosonic acid)• Uronic acids o Glucuronic acid (6C) o Galacturonic acid (6C) o Iduronic acid (6C)• Aldaric acids o Tartaric acid (4C) o meso-Galactaric acid (Mucic acid) (6C) o D-Glucaric acid (Saccharic acid) (6C)Polycarboxylic acids within this embodiment are molecules carrying 2 or more carboxylic groups in a molecule, oligomers or polymers of these molecules.Suitable polycarboxylic acids are oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, adipic acid and analogues.In a particular preferred embodiment, the polymeric colorant is a modified polymeric anthraquinone dye. Aminoanthraquinones are well known for use as dyes and coloring agents for oils, drugs, cosmetic products, waxes, and detergents. N,N'-dialkyleneoxy- substituted 1 ,4-diaminoanthraquinones are usually blue in shade, generally more brilliant than many other blue chromophores, and have good desirable stability properties, especially toward high alkaline environments, heat, and light. One preferred example is a polymeric colorant having the general formula (III):wherein:Ai and A2 are, independently of each other, a polyethyleneoxy-, polypropyleneoxy-, or polyethyleneoxy-Zpolypropyleneoxy-linker; the number of repeating ethyleneoxy- and / or propyleneoxy-units in each of A1 and A2 is less than or equal to 25; orA1 and A2 are, independently of each other, -CH2CH2CH2-M[(CH2CH2O)x-CH2CH2NH- ]y;M can be either 0 or N and x = 1 - 5, and if M is 0 then y = 1 , and if M is N then y = 2; andR1 and R2 represent the terminal group of the polyalkyleneoxy chain and are independently of each other selected from the group consisting of an amino acid residue, a polyamino acid residue, a peptide residue, a hydroxycarboxylic acid residue, a hydroxypolycarboxylic acid residue or a polycarboxylic acid residue.The final dyes are typically produced starting from the N,N'-dialkyleneoxy-substituted 1 ,4-diaminoanthraquinone dyes e.g. described in EP1828314B1. Typically N,N'- dialkyleneoxy-substituted 1 ,4-diaminoanthraquinone dyes with OH end groups are first chemically activated by transfer in their tosylates, mesylates, chlorides or a morepreferred more reactive iodide and then reacted with the amino acids, polyamino acids or peptides to form the final products. Intermediate A (dye dichloride) is prepared according to Scheme 1 via condensation of commercially available Sanoli lave blue A with thionyl chloride or oxalyl chloride to yield dye chloride. A Finkelstein reaction of dye chloride A with sodium iodide in acetone, can be catalyzed by camphorsulfonic acid (CSA) or tertbutyl ammonium iodide if the reaction is carried out in toluene instead of acetone ( ref. JP2022034093A) results in dye diiodide - Intermediate B (Scheme 2).Scheme 1Scheme 2The invention also concerns the use of the polymeric colorants according to the invention as non-staining dyes in laundry detergent formulations, fabric treatment compositions, automatic dishwasher detergent compositions, dishwashing liquids, handsoap formulations, hair shampoo compositions, household cleaner or toilet cleaner compositions.Such compositions are described in detail in Eduard Smulders, Laundry Detergents, 1stEdition 2001 , Wiley-VCH, Weinheim; Liquid Detergents, Edited by Kuo-Yann Lai, 2ndEdition, CRC Press; Handbook of Detergents, Edited by Uh Zoller, 1stEdition, CRC Press.Laundry detergent formulationsThe polymeric colorant of the present invention may be incorporated into a laundry care composition including but not limited to laundry detergents and fabric treatment compositions. As used herein, the term “laundry care composition” includes, unless otherwise indicated, granular, powder, liquid, gel, paste, unit dose bar form and / or flake type washing agents and / or fabric treatment compositions. As used herein, the term “fabric treatment composition” includes, unless otherwise indicated, fabricsoftening compositions, fabric enhancing compositions, fabric freshening compositions, and combinations thereof. Such compositions may be, but need not be, rinse added compositions.Laundry care compositions of the present invention comprise one or more of said polymeric colorants containing at least one carboxymethyl capped alkyleneoxy chain and a laundry care ingredient. The polymeric colorant may be added to substrates using a variety of application techniques. For application to textile substrates, the polymeric colorant is preferably included as an additive in laundry detergent. Thus, application to the textile substrate actually occurs when a consumer adds laundry detergent to a washing machine. Similarly, rinse added fabric softening (“RAFS”) compositions are typically added in the rinse cycle, which is after the detergent solution has been used and replaced with the rinsing solution in typical laundering processes. The laundry care compositions including laundry detergents may be in solid or liquid form, including a gel form. The laundry care compositions including laundry detergents may also be in a unit dose pouch. The laundry detergent composition comprises a surfactant in an amount sufficient to provide desired cleaning properties.The polymeric colorant may be present in the laundry care composition (such as the laundry detergent composition) in an amount from about 0.0001 % to about 10% by weight of the composition, more preferably from about 0.0001 % to about 5% by weight of the composition, and even more preferably from about 0.0001 % to about 1 % by weight of the composition.The laundry detergent composition comprises a surfactant in an amount sufficient to provide desired cleaning properties. In one embodiment, the laundry detergent composition comprises, by weight, from about 5% to about 90% of the surfactant, and more specifically from about 5% to about 70% of the surfactant, and even more specifically from about 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.

[0050] Exemplary anionic surfactants are the alkali metal salts of C 10-16 alkyl benzene sulfonic acids, preferably CU.M 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 U.S. Pat. Nos. 2,220,099 and 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'--0--(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. Nonethoxylated 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 chainor 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(CmH mOJnOH 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 the case, 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 watersolubilizing group, e.g. carboxy, sulfonate, sulfate.As noted, the compositions may be in the form of a solid, either in tablet or particulate form, including, but not limited to particles, flakes, or the like, or the compositions may be in the form of a liquid. 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 cosolvents or stabilizers in addition to or in place of water. Accordingly, the aqueous non surface active liquid 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 compositions are in the form of an aqueous solution or uniform dispersion or suspension of surfactant, polymeric colorant, 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. For purposes of this invention, viscosity is measured with a Brookfield LVDV-II+ viscometer apparatus using a #21 spindle.The liquid detergent compositions 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 if necessary, can be increased at this pointto form a solution or a uniform dispersion of insoluble solid phase particulates within the liquid phase. After some or all of the solid-form 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. Frequently this will involve agitation for a period of from about 30 to 60 minutes.In an alternate embodiment for forming the liquid detergent compositions, the polymeric colorant is first combined with one or more liquid components to form a polymeric colorant 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 polymeric colorant premix and the enzyme component are added at a final stage of component additions. In a further embodiment, the polymeric colorant is encapsulated prior to addition to the detergent composition, the encapsulated polymeric colorant 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.As noted previously, the detergent compositions may be in a solid form. Suitable solid forms include tablets and particulate forms, for example, granular particles or flakes. Various techniques for forming detergent compositions in such solid forms are well known in the art and may be used herein. In one embodiment, for example when the composition is in the form of a granular particle, the polymeric colorant is provided in particulate form, optionally including additional but not all components of the laundry detergent composition. The polymeric colorant particulate is combined with one or more additional particulates containing a balance of components of the laundry detergent composition. Further, the polymeric colorant, optionally including additional but not all components of the laundry detergent composition, may be provided in anencapsulated form, and the polymeric colorant encapsulate is combined with particulates containing a substantial balance of components of the laundry detergent composition.The compositions of this invention, prepared as hereinbefore described, can be used to form aqueous washing solutions for use in the laundering of textile substrates such as fabrics. Generally, an effective amount of such compositions is added to water, preferably in a conventional fabric laundering automatic washing machine, to form such aqueous laundering solutions. The aqueous washing solution so formed is then contacted, preferably under agitation, with the fabrics to be laundered therewith. An effective amount of the liquid detergent compositions herein added to water to form aqueous laundering solutions can comprise amounts sufficient to form from about 500 to 7,000 ppm of composition in aqueous washing solution. More preferably, from about 1 ,000 to 3,000 ppm of the detergent compositions herein will be provided in aqueous washing solution.Fabric Treatment Compositions / Rinse Added Fabric Softening CompositionsIn another specific embodiment, the polymeric colorant of the present invention may be included in a fabric treatment composition. The fabric treatment composition may be comprised of at least one polymeric colorant and a rinse added fabric softening composition (“RAFS;” also known 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”) and (b) a polymeric colorant containing at least one carboxymethyl capped alkyleneoxy chain. The rinse added fabric softening composition may comprise from about 1 % to about 90% by weight of the FSA, more preferably from about 5% to about 50% by weight of the FSA. The polymeric colorant may be present in the rinse added fabric softening composition in an amount from about 0.5 ppb to about 50 ppm, more preferably from about 0.5 ppm to about 30 ppm. 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 obtainingmixtures 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-NW-[(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, propyl, 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-NW-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, methylsulfate, 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 dihydrogenated 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- ester containing 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 .Suitable Laundry Care IngredientsWhile not essential for the purposes of the present invention, the non-limiting list of laundry care ingredients illustrated hereinafter are suitable for use in the laundry care compositions 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 may range 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 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 laundry care ingredients include, but are not limited to, polymers, for example cationic polymers, surfactants, builders, chelating agents, dyetransfer 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 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 that are incorporated by reference.As stated, the laundry care ingredients are not essential to Applicants’ laundry care compositions. Thus, certain embodiments of Applicants’ 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:Surfactants - The compositions according to the present invention can comprise a surfactant or surfactant system wherein the surfactant can be selected from nonionic and / or anionic and / or cationic surfactants and / or ampholytic and / or zwitterionic and / or semi-polar nonionic surfactants. The surfactant is typically present at a level of from about 0.1 %, from about 1 %, or even from about 5% by weight of the cleaning compositions to about 99.9%, to about 80%, to about 35%, or even to about 30% by weight of the cleaning compositions.Builders - The compositions of the present invention can comprise one or more detergent builders or builder systems. When present, the compositions will typically comprise at least about 1 % builder, or from about 5% or 10% to about 80%, 50%, or even 30% by weight, 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 builderspolycarboxylate compounds 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, 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 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 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 about 0.0001 %, from about 0.01 %, from about 0.05% by weight of the cleaning compositions to about 10%, about 2%, or even about 1 % by weight of the cleaning compositions.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, in which the polycarboxylic acid may comprise at least two carboxyl radicals separated from each other by not more than two carbon atoms.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 typicalcombination 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 compositions 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-enephosphonic acid) and water-soluble salts thereof. Such catalysts are disclosed in U.S. Patent No. 4,430,243.If desired, the compositions 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.Compositions herein may also suitably include a transition metal complex of a macropolycyclic rigid ligand - abbreviated as “MRL”. As a practical matter, and not by way of 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.Automatic Dishwasher DetergentDifferent kinds of dishwashing detergents contain different combinations of ingredients. Common ingredients include:Sequestrants / Blulders: Bind calcium and magnesium ions to prevent 'hard-water' type limescale deposits. They can cause ecological damage, and have been partially banned or phased out. Typicals sequestrants are phosphates. Due to their environmental impacts they have been substitutes by other compounds: Phosphate- free automatic dishwashing compositions typically rely on non-phosphate builders, such as salts of citrate, carbonate, silicate, disilicate, bicarbonate, aminocarboxylates and others to sequester calcium and magnesium from hard water, and upon drying, leave an insoluble visible deposit. Content typically: 20 to < 98.6 wt% (preferably, 30 to 90 wt%; more preferably, 40 to 85 wt%; most preferably, 50 to 75 wt%), based on weight of the automatic dishwashing composition.Oxygen-based bleaching agents (older-style powders and liquids contain chlorinebased bleaching agents): Break up and bleach organic deposits. An example is an percarbonate / TAED (tetra acetyl ethylene diamine)mixture.Non-ionic surfactants: Lower the surface tension of the water, emulsifies oil, lipid and fat food deposits, prevents droplet spotting on drying. Content of nonionic surfactant is 0.2 to 20 wt% (preferably, 1 to 15 wt%; more preferably, 2 to 12 wt%; most preferably, 3 to 10 wt% wherein the non-ionic surfactant is selected from the group consisting of polyoxyalkylene surfactants, polyalkylene glycol esters, polyoxyethylene derivatives of fatty acid esters of polyhydric alcohols, fatty acid esters ofpolyalkoxylated polyhydric alcohols, polyalkoxylated natural fats and oils, polyalkylene oxide block copolymers, alkyl poly glucosides, sucrose esters and mixtures thereof. Still more preferably, the automatic dishwashing composition of the present invention, comprises: 0.2 to 20 wt% (preferably, 1 to 15 wt%; more preferably, 2 to 12 wt%; most preferably, 3 to 10 wt%), based on weight of the automatic dishwashing composition, of a nonionic surfactant: wherein the non-ionic surfactant includes a fatty alcohol alkoxylate.Alkaline salts: These are a primary component in older and original-style dishwasher detergent powders. Highly alkaline salts attack and dissolve grease, but are extremely corrosive (fatal) if swallowed. Salts used may include metasilicates, alkali metal hydroxides, sodium carbonate etc.Enzymes: Break up protein-based food deposits, and possibly oil, lipid and fat deposits. The enzymes used are similar to the ones used in laundry. Typical enzymes in ADW formulations are Proteases and Amylases.Anti-corrosion agent(s): Often sodium silicate, this prevents corrosion of dishwasher components.Dishwashing detergent may also containAnti-foaming agents: Foam interferes with the washing action. Foam may affect operation of the machine's water-level sensors and will leak past the door seals. Additives to slow down the removal of glaze & patterns from glazed ceramics PerfumesAnti-caking agents (in granular detergent)Starches (in tablet based detergents)Gelling agents (in liquid / gel based detergents)Dishwasher detergents are generally strongly alkaline (basic).In cased of ADW tabs additional components are needed to get stable tabs on the one hand and fast dissolution of the tabs on the other hand.Tabletting and filling agents: These agents are vital for the success of the tabletting process, which is a critical stage, especially at high speeds. Poor compression can lead to a lot of powder waste, problems with tablet ejection, clogging of tools, repeated defects, and even line stoppage.Effervescent agents: The role of effervescent agents is to help dissolve the tablet in contact with water. Effervescent agents ensure excellent dissolution of the tablet, as its breakdown time is a major factor in washing efficiency, and therefore the presence of residues is not acceptable.Dishwashing LiquidsDishwashing liquids are formulated with a combination of ingredients that work together to remove food residues, grease, and dirt from your dishes. The main components include surfactants, enzymes, fragrances, dyes, and preservatives. Each ingredient plays a crucial role in the overall cleaning process and contributes to the effectiveness of the product. In addition to these primary ingredients, dishwashing liquids may also contain other additives, such as foam boosters, stabilizers, and pH adjusters, which help improve the product’s performance and stability. In the following sections, we will delve deeper into the functions and properties of each of these key dishwashing liquid active ingredients.Surfactants, or surface-active agents, are the primary cleaning agents in dishwashing liquids. They reduce the surface tension of water, allowing it to penetrate and lift away grease, oil, and dirt from the surfaces of dishes. The three main types of surfactants used in dishwashing liquids are anionic, nonionic, and amphoteric surfactants.Anionic SurfactantsAnionic surfactants are the most commonly used surfactants in dishwashing liquids due to their excellent cleaning power and foaming properties. They carry a negative charge, which helps them effectively bind to and remove positively charged dirt and grease particles. Here are three widely used anionic surfactants in dishwashing liquids:Sodium Lauryl Sulfate (SLS): SLS is a strong surfactant known for its excellent foaming and emulsifying abilities. It effectively breaks down grease and oil and is commonly used in many household cleaning products, including dishwashing liquids. Sodium Laureth Sulfate (SLES): SLES is a milder surfactant compared to SLS and is often used as an alternative for those with sensitive skin. It also provides excellent cleaning and foaming properties, making it a popular choice for dishwashing liquids. Currently, SLES is the most used surfactant in dishwashing liquid worldwide. It’s highly cost-effective and accessible.Linear Alkyl Benzene Sulphonic Acid (LABSA): LABSA is a biodegradable anionic surfactant with powerful cleaning and foaming capabilities. It is widely used in dishwashing liquids, laundry detergents, and other cleaning products.Nonionic SurfactantsNonionic surfactants do not carry a charge and are known for their mildness and compatibility with other surfactants. They are often used in dishwashing liquids formulated for sensitive skin or in combination with anionic surfactants to enhance cleaning performance. Here are two examples of nonionic surfactants commonly used in dishwashing liquids:Fatty Alcohol Polyoxyethylene Ether (AEO-9): AEO-9 is a mild, nonionic surfactant derived from fatty alcohols. It provides effective cleaning and emulsification properties while being gentle on the skin.Cocam ide DEA: Cocam ide DEA is a nonionic surfactant derived from coconut oil. It acts as a foam booster and stabilizer, enhancing the cleaning performance and foam quality of dishwashing liquids. It also contributes to the thickness and texture of the formula.Amphoteric SurfactantsAmphoteric surfactants can carry either a positive or negative charge depending on the pH of the solution. They are typically used in dishwashing liquids to enhance the cleaning and foaming properties of anionic and nonionic surfactants. Here are two examples of amphoteric surfactants commonly used in dishwashing liquids:Cocam idopropyl Betaine: This amphoteric surfactant is derived from coconut oil and has excellent foaming and thickening properties. It is often used in combination withother surfactants to boost cleaning performance and enhance the mildness of the product.Cocam idopropylamine Oxide: This amphoteric surfactant is also derived from coconut oil and is known for its excellent foam stability and cleaning capabilities. It can enhance the performance of other surfactants and is often used in formulations for sensitive skin.In conclusion, the choice of surfactants in dishwashing liquids plays a crucial role in their cleaning performance, foam quality, and mildness. With the growing trend towards gentle, skin-friendly products, ultra-mild surfactants such as amino acidbased surfactants and Alkyl Polyglycosides are gaining popularity in the formulation of dishwashing liquids. Amino acid-based surfactants, derived from natural amino acids, offer good cleaning performance and outstanding compatibility with the skin, making them ideal for sensitive skin or allergy-prone users. Alkyl Polyglycosides, which are plant-derived and readily biodegradable, also provide effective cleaning and foaming properties while being gentle on the skin and the environment.The Role of Enzymes in Dishwashing LiquidsEnzymes are protein molecules that act as biological catalysts, speeding up chemical reactions without being consumed in the process. In dishwashing liquids, enzymes are added to enhance the cleaning performance by breaking down stubborn food residues, such as proteins, starches, and fats.Common enzymes found in dishwashing liquids include proteases, which break down proteins; amylases, which break down starches; and lipases, which break down fats and oils. By targeting specific types of food residues, enzymes help to remove tough stains and build-up that may be resistant to surfactants alone.Fragrances, Dyes, and Preservatives in Diswashing LiquidsFragrances and dyes are added to dishwashing liquids to provide a pleasant scent and appealing color. These ingredients do not contribute to the cleaning power of the product but can enhance the user experience. Fragrances are typically synthetic, butsome natural and essential oil-based fragrances can also be found in eco-friendly and organic dishwashing liquids.Dyes are used to give the dishwashing liquid its color and can be either synthetic or natural, depending on the product’s formulation. While dyes have no impact on cleaning performance, they can make the product more visually appealing to consumers.Preservatives are added to dishwashing liquids to prevent microbial growth and prolong the shelf life of the product. Common preservatives used in dish soaps include benzisothiazolinone, methylisothiazolinone, and phenoxyethanol. These ingredients help to maintain the product’s quality and effectiveness over time by inhibiting the growth of bacteria, mold, and yeast that could otherwise spoil the liquid.Handsoap formulationsThe primary components include water, surfactants, co-surfactants, emollients, thickeners, preservatives, fragrances. Additional components can be Foaming agent, humectants like Glycerol for moisture retention and chelating agent like EDTA salts for formulation stabilization.Surfactants are the backbone of hand soap formulations, with Sodium Lauryl Sulfate (SLS) and Sodium Laureth Sulfate (SLES) being the most common. They help in breaking down oils and dirt on the skin, making it easier to rinse them away.Co- surfactants, or known as secondary surfactants such as Cocam idopropyl Betaine and Dodecyl Dimethyl Betaine, enhance the foaming and cleaning abilities of the surfactants, while also adding a layer of mildness to the formulation.ShampooThe composition of a typical Hair shampoo is given in the following Table.The invention is further detailed by the following examples.EXAMPLESEXAMPLE 1Intermediate A - dichloride of dye 140.9 g of Blue dye Structure 1 (530.6 g / mol; 77.1 mmol; 1 equivalent) is added to a flat-bottomed flask containing CHCI3 in an amount of 9.8 g / g dye. The mixture is stirred for 15 minutes at 20-30°C. The mixture of 20,2 g of thionyl chloride (SOCI2; 119 g / mol; 170 mmol; 2.2 equivalents) and 100 g CHCI3 are added dropwise over 4 hours at 10- 15°C, followed by 0.2 g DMF (73.1 g / mol; 0.7 mmol; 0.036 equivalents). The mixture is then kept at 36°C for 12 hrs until the original dye has completely reacted. The mixture changes color from blue to red violet after adding SOCI2. The reaction mixture is then poured into a beaker with 1 L of water (10-15°C). The mixture is stirred for 5 minutes, then the aqueous top layer is decanted. Then 1 L of cold water is added again and the decantation process is repeated until the pH of the aqueous phase is > 4. Then the CHCI3 layer with a small amount of water is put into a separator and the water is separated more completely.The organic layer with very small amounts of water is placed in a beaker with a stirrer, about 5 g of anhydrous CaCI2 are added, and the organic layer is stirred for about 1 h. Solid parts are then separated from the organic phase by filtration, CHCI3 is then distilled off from the organic layer at 90-95 °C / 50 mbar. 42 g of the product dichloride of the dye (structure 2; 567 g / mol; 96% theoretical yield) are obtained in in the form of a blue thick liquid. The Intermediate A is the dichloride of dye, Rf = 0.54 (TLC, Silufol UV 254, acetone - hexane 1 : 2).EXAMPLE 2Intermediate B - diiodide of dye 1 I Scheme 2To a 250 ml Erlenmeyer flask was added intermediate A (dye dichloride; 3 g; 1 eq; 5.3 mmol, 567 g / mol), 40 g of acetone, Nal (4.8 g; 6 eq; 32 mmol). The resulting solution was stirred for 48 h at 70°C. After evaporation of the acetone, 40 g CHCh was added,then 100 ml of H2O was added. The organic layer was separated after shaking, washed again with 50 mL of H2O, and then dried over anhydrous sodium sulfate. After evaporation of CHCI3, 3.7 g (750.4 g / mol) of a blue viscous substance is obtained, diiodide of dye - Intermediate B, structure 3 . Yield 93% th. Rf = 0.61 (TLC, Silufol UV 254, acetone - hexane 1 :2).EXAMPLE 320 g dichloride of dye - Intermediate (structure 2; 567 g / mol; 35.2 mmol; 1 equivalent) is added to a flat-bottomed flask containing DMF in an amount of 7.5 g / g of dye chloride. The mixture is stirred for 15 minutes at 80°C. At the same temperature, 10.4 g of aspartic acid (ASP; 133 g / mol; 77.4 mmol; 2.2 equivalent), 7.8 g of triethyl amine (TEA; 73.1 g / mol; 77.4 mmol; 2.2 equivalent) and 0.1 g of 4-dimethylaminopyridine are added. (DMAP; 122 g / mol; 0.8 mmol; 0.02 equivalent). The mixture is then kept at 35°C for 5 days until the dye chloride is completely reacted. After the reaction of the dye chloride, DMF is completely distilled from the reaction mixture at 100°C under vacuum. 19 g of product structure 4 (760.8 g / mol; 70% yield) were obtained in the form of a dark blue thick liquid.Rf = 0.05 (TLC, Silufol UV 254, acetone - hexane 1 :2).EXAMPLE 4The intermediate B, diiodide of dye from example 2 in the amount of 3.7 g (4,9 mmol, 1 eq; 750,4 g / mol), 40 g of acetone, 1.4 g of aspartic acid (10.5 mmol, 2.15 eq, 133 g / mol), 1.4 g of triethylamine (TEA; 13.8 mmol, 2.8 eq, 101.2 g / mol) and 0.1 g of DMAP (0,8 mmol; 0.16 eq, 122 g / mol) were added into a 250 ml flask with a flat bottom, the reaction mixture is heated at 70°C for 24 h. The acetone and TEA are distilled off. The product, structure 4 (3,5 g; 95% th.) is obtained as thick blue liquid, completely soluble in water. Rf = 0.05 (TLC, Silufol UV 254, acetone - hexane 1 :2).Structure 1 :1 ,4-bis({3-[2-(2-hydroxyethoxy)ethoxy]propyl}amino)-9,10-dihydroanthracene-9, 10- dioneStructure 2:1 ,4-bis({3-[2-(2-chloroethoxy)ethoxy]propyl}am ino)-9 O-dihydroanthracene-9, 10- dioneStructure 3:1 ,4-bis({3-[2-(2-iodoethoxy)ethoxy]propyl}amino)-9,10-dihydroanthracene-9, 10-dioneStructure 4:EXAMPLE 5 (comparison)This Test Guideline describes the Zahn-Wellens / EMPA Test. It is used to determine the inherent biodegradability of Sanolin Lave Blue A (Structure 1 ).A mixture containing the non-volatile and water soluble test substance, mineral nutrients and a relatively large amount of activated sludge in aqueous medium is agitated and aerated at 20-25°C in the dark or in diffuse light, for up to 28 days. Blank controls, containing activated sludge and mineral nutrients but no test substance, are run in parallel. The functional capability of the activated sludge is tested using a reference compound (ethylene glycol, diethylene glycol, lauryl sulfonate or aniline). In a typical run 1 or 2 vessels for the test suspension and for the inoculum blank, 1 for procedure control are used. The biodegradation process is monitored by determination of DOC, Dissolved Organic Carbon, (or COD, Chemical Oxygen Demand) in filtered samples, taken at daily or other time intervals. It is mandatory to follow DOC in the test suspension and inoculum blanks in parallel. The ratio of eliminated DOC (or COD), corrected for the blank, after each time interval, to the initial DOC value is expressed as the percentage biodegradation at the sampling time. The percentage biodegradation is plotted against time to give the biodegradation curve. The test is considered valid if the procedural control shows the removal of the referencecompound by at least 70% within 14d and if DOC (or COD) in the test suspension is removed relatively gradually over days or weeks, since this indicates biodegradationThe test resulted 4% degradation after 28 days, which means that the dye is considered to be poorly biodegradable.EXAMPLES 6 to 13QSAR Predictions of New StructuresIn the past, so-called Quantitative-Structure-Activity-Relationships QSAR have been developed and successfully applied to predict the biodegradability of chemical structures. The details of such approaches are described e.g. in:OECD QSAR Toolbox Application Manual: https: / / www.oecd.org / chemicalsafetv / risk- assessment / TB4 Application manual F1.compressed.pdfECHA Guidance on information requirements and chemical safety assessment - Chapter R.6: QSARs and grouping of chemicals: https: / / echa.europa.eu / documents / 10162 / 17224 / information_requirements_r6_en.pd f / 77f49f81 -b76d-40ab-8513-4f3a533b6ac9In-silico analyses were conducted using various models integrated into Estimation Program Interface (EPI) Suite (v4.11 , June 2017) and Danish (Q)SAR Models1. EPI SuiteTM-Estimation Program https: / / www.epa.gov / tsca-screening-tools / epi-suitetm-estimation-program-interfaceThis Windows-based physical-chemical properties and environmental fate estimation software package was developed by the U.S. Environmental Protection Agency (US EPA) and Syracuse Research Corporation (SRC). The EPI Suite calculations are based primarily on fragment constants (group contributions) method utilizing a training set of chemicals and validated using another independent set of chemicals. EPI Suiteruns all estimation programs using input such as the canonical Simplified Molecular Line Input System (SMILES) (US EPA and OCSPP, 2017).In order to estimate potential biodegradability of a substance, BIOWIN v4.11 , one of the models within EPISUITE, was used.BIOWIN estimates the probability of rapid aerobic and anaerobic biodegradation of an organic compound in the presence of mixed populations of environmental microorganisms. BIOWIN contains seven separate models. This version (v4.11 ) designates the models as follows:Biowinl = linear probability modelBiowin2= nonlinear probability modelBiowin3 = expert survey ultimate biodegradation modelBiowin4 = expert survey primary biodegradation modelBiowin5 = MITI linear modelBiowin6 = MITI nonlinear modelBiowin7 = anaerobic biodegradation modelReady biodegradability is predicted using Biowin3 and Biowin5 results. The exact method is described in the BIOWIN manual and is based on the application of Bayesian analysis to ready biodegradation data for US Premanufacture Notification (PMN) chemicals, derived collectively from all six OECD301 test methods plus OECD310.2. Danish (Q)SAR Models https: / / qsarmodels.food.dtu.dkThe Danish (Q)SAR Models interface is a publicly accessible, browser-based tool, using several models developed by the Technical University of Denmark (DTU) in the Leadscope Software (Leadscope Predictive Data Miner I LSE v. 3.5.3-5 ) in order to predict (eco)toxicological and biodegradability properties of chemical structures.Model input parameters include drawing of chemical structure, SMILES / MOL / SDF input, or chemical name search.Ready biodegradability is assessed based on a training set of 735 structures, with cross validation results of sensitivity = 87.3%, specificity = 85.2 %, and concordance = 86.4 %.Used Model in the Examples and ResultsThe Biowin 5 model (Linear MITI Model) is applied to the structures claimed in this patent. In the following the results are presented with the results of the starting compound [base dye: (1 ,4-bis({3-[2-(2-hydroxyethoxy)ethoxy]propyl}amino)-9,10- dihydroanthracene-9, 10-dione] as comparison.The calculations reflect the significant increase in biodegradability of the claimed chemical structures in compared to the starting structure. Surprisingly this increase in biodegradability was achieved by these only small modification of the entire structure. The data show, that the highest increase of predicted biodegradability was achieved with Amino acids carrying additional acid groups like aspartic acid and glutamic acid. In addition, modification of the starting structure with two citric acids or with two units of 2-hydroxy-1 ,5-pentane diacid leads to a strong increase in biodegradability.EXAMPLE 7 (comparison)Sanolin Lave Blue AResult from MITI model calculation: 0.1229EXAMPLE 8 aspartic acid (di-ASP) Sanolin Lave Blue AResult from MITI model calculation: 0.6712EXAMPLE 9 glutamic acid (di-GLU) modified Sanolin Lave Blue AThe intermediate B, the diiodide of the dye from example 2, in an amount of 5 g (6.7 mmol, 1 eq; 750.4 g / mol), 100 g of acetone, 2.96 g of glutamic acid (20.1 mmol, 3 eq; 147.1 g / mol), 1.13 g of KOH (20.1 mmol, 3 eq, 56.1 g / mol) are added into a 250 ml flask with a flat bottom and, the reaction mixture is heated at 60°C for 72 h. The product is formed as a solid on bottom of the flask. After the reaction is complete, the aceton with unreacted intermediate B is decanted and the remaining solid is mixed with 100 ml of acetone and the solid product is filtered off and dried at 60°C. The product (3,5 g; 941 ,2 g / mol; 55 % theoretical yield) is completely soluble in water as dark blue solution. Rf = 0.05 (TLC, Silufol UV 254, acetone : H2O = 1 : 2).Result from MITI model calculation: 0.678EXAMPLE 10 a-hydroxyglutaric acid (2-hydroxyglutaric acid) modified Sanolin Lave Blue AResult from MITI model calculation: 0.6871EXAMPLE 11 glycine (di-DGA) modified Sanolin Lave Blue AThe intermediate B, the diiodide of the dye from example 2, in an amount of 5 g (6.7 mmol, 1 eq; 750.4 g / mol), 100 g of acetone, 1.51 g of Glycine (20.1 mmol, 3 eq; 75.1 g / mol), 1 .13 g of KOH (20.1 mmol, 3 eq, 56.1 g / mol) are added into a 250 ml flask with a flat bottom and, the reaction mixture is heated at 60°C for 72 h. The product is formed as a solid on bottom of the flask. After the reaction is complete, the aceton with unreacted intermediate B is decanted and the remaining solid is mixed with 100 ml of acetone and the solid product is filtered off and dried at 60°C. The product (2,9 g; 720.9 g / mol; 60% theoretical yield) is completely soluble in water as dark blue solution. Rf = 0.05 (TLC, Silufol UV 254, acetone : H2O = 1 : 2).Result from MITI model calculation: 0.3518EXAMPLE 12 propionic acid (di-DPA) modified Sanolin Lave Blue AResult from MITI model calculation: 0.3677EXAMPLE 13 citric acid (di-DCITA) modified Sanolin Lave Blue AResult from MITI model calculation: 0.9228EXAMPLE 14Lysine (di-LYS) modified Sanolin Lave Blue AThe intermediate B, the diiodide of the dye from example 2, in an amount of 5 g (6.7 mmol, 1 eq; 750.4 g / mol), 100 g of acetone, 2.95 g of Lysine (20.1 mmol, 3 eq; 146.2 g / mol), 0.79 g of KOH (16.8 mmol, 2.1 eq, 56.1 g / mol) are added into a 250 ml flask with a flat bottom and, the reaction mixture is heated at 60°C for 72 h. The product is formed as a solid on bottom of the flask. After the reaction is complete, the aceton with unreacted intermediate B is decanted and the remaining solid is mixed with 100 ml of acetone and the solid product is filtered off and dried at 60°C. The product (4,2 g; 863 g / mol; 73% theoretical yield) is completely soluble in water as dark blue solution. Rf = 0.05 (TLC, Silufol UV 254, acetone : H2O = 1 : 2).Results from Miti-Calculation: 0.1176Further possible structures:EXAMPLE 153-hydroxy glutaric acid modified Sanolin Lave Blue A (O-bonding)EXAMPLE 16 citric acid modifiedf Sanolin Lave Blue A (ester-bonding)EXAMPLE 17 malic acid modified Sanolin Lave Blue A (O-bonding)

Claims

Claims1 . A polymeric colorant of formula (I)R2wherein:A is a chromophore selected from the group consisting of nitro, nitroso, monazo, bisazo, diarylmethane, triarylmethane, acridine, ethine, thiazole, indamine, oxazine, pthalocyanine, and anthraquinone dye residues;L is a polyalkylene oxide linker composed of one or more alkylene oxides selected from the group consisting of ethylene oxide, propylene oxide and butylene oxide;Ri is nitrogen, oxygen, or sulfur;R2 is hydrogen, a methyl group, or an ethyl group;X is -NH-, -0- or -O-C(O)-; b is 1 , 2 or 3; c is 1 if R1 is oxygen or sulfur, and 2 if R1 is nitrogen;B is an amino acid residue, a polyamino acid residue, a peptide residue, a hydroxycarboxylic acid residue, a hydroxypolycarboxylic acid residue or a polycarboxylic acid residue.

2. The polymeric colorant of claim 1 , wherein L in formula (I) has the formula (II)-(CH2CH2O)— (CH2CHO)b—R3whereinR3 is a methyl group or an ethyl group, preferably a methyl group; a is an integer of from 0 to 20, preferably from 0 to 10, more preferably from 0 to 5; b is an integer of from 0 to 20, preferably from 0 to 10, more preferably from 0 to5.

3. The polymeric colorant of claim 1 or 2, wherein the polyalkylene oxide linker L is a homopolymer.

4. The polymeric colorant of claim 1 or 2, wherein the polyalkylene oxide linker L is a copolymer.

5. The polymeric colorant of claim 4, wherein the polyalkylene oxide linker L is a block copolymer.

6. The polymeric colorant according to any one of claims 1 to 5, wherein B in formula (I) is a polyaspartic acid residue, polyglutaminic acid residue, or a polylysine residue.

7. The polymeric colorant according to any one of claims 1 to 5, wherein B in formula (I) is a aspartic acid residue or a glutamic acid residue.

8. The polymeric colorant according to any one of claims 1 to 5, wherein B in formula (I) is a citric acid residue, a 2- or 3-hydroxyglutaric acid residue, a malic acid residue, or a sugar acid residue.

9. The polymeric colorant according to any one of claims 1 to 8, wherein the chromophore A is an anthraquinone dye residue.

10. The polymeric colorant according to claim 9 having the general formula (III):whereinAi and A2 are, independently of each other, a polyethyleneoxy-, polypropyleneoxy- , or a polyethyleneoxy-Zpolypropyleneoxy-linker; the number of repeating ethyleneoxy- and / or propyleneoxy-units in each of A1 and A2 is less than or equal to 25; orA1 and A2 are, independently of each other, -CH2CH2CH2-M[(CH2CH2O)x- CH2CH2NH- ;M can be either 0 or N and x = 1 - 5, and if M is 0 then y = 1 , and if M is N then y = 2; andR4 and Rs represent the terminal group of the polyalkyleneoxy chain and are, independently of each other, selected from the group consisting of an amino acid residue, a polyamino acid residue, a peptide residue, a hydroxycarboxylic acid residue, a hydroxypolycarboxylic acid residue or a polycarboxylic acid residue linked with an amino group, an ether group or an ester group to the polyalkyleneoxy chain.11 . The use of the polymeric colorants according to any one of claims 1 to 10 as nonstaining dyes in laundry detergent formulations, fabric treatment compositions, automatic dishwasher detergent compositions, dishwashing liquids, handsoap formulations, hair shampoo compositions, household and toilet cleaner compositions.

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