Fluorescent whitening agent

Abstract

Disclosed is a fluorescent whitening agent (OBA) comprising an anionic polysaccharide linked to a fluorophore (FG) having an absorption band in the UV light region and an emission band in the visible light region.

Description

Technical Field

[0001] The present invention relates to optical brightening agents (OBAs), more particularly to polysaccharide-based optical brightening agents and fabric treatment compositions comprising such OBAs. Background Art

[0002] Laundry detergent formulations include optical brighteners (OBAs) to improve the whiteness of washed fabrics. OBAs with improved biodegradability are highly desirable, however, while OBAs with some level of biodegradability are known, these OBAs exhibit instability and poor affinity for substrates.

[0003] Despite the prior art, there remains a need to provide improved optical brightening agents (OBAs).

[0004] The inventors have surprisingly found that linking fluorophores to certain anionic polysaccharides provides OBAs with improved affinity for textile substrates.

[0005] The inventors have found that these compounds, in combination with certain surfactants, provide improved properties with respect to fabrics. Summary of the Invention

[0006] Thus, in one aspect, the present invention provides a fabric treatment composition comprising:

[0007] a. an optical brightening agent (OBA) comprising an anionic polysaccharide attached to a fluorescent group (FG) having an absorption band in the UV light region and an emission band in the visible light region; and

[0008] b. Surfactant.

[0009] In a further aspect, the present invention provides an optical brightening agent (OBA) comprising an anionic polysaccharide linked to a fluorescent group (FG) having an absorption band in the UV light region and an emission band in the visible light region.

[0010] The OBAs of the present invention provide improved compatibility with anionic cleaning formulations, ie, those containing ionic (eg, anionic) detergents.

[0011] In a further aspect, the present invention provides a method of treating fabrics, the method comprising the step of treating the fabrics with a composition of the first aspect, for example by adding the substrate treatment composition to water to form a wash liquor and treating the fabrics with the wash liquor.

[0012] In a further aspect, the present invention provides a method of preparing a fabric treatment composition, the method comprising the step of including in the fabric treatment composition an OBA of the present invention and a surfactant.

[0013] Fluorophore (FG)

[0014] FG has an absorption band in the UV light region and an emission band in the visible light region (ie, preferably 420-470 nm and more preferably 435-450 nm).

[0015] The fluorescent group preferably comprises a monocyclic or polycyclic ring system, at least one heteroatom selected from N, O and S and a conjugated double bond.

[0016] Preferably, the heteroatom is present in the ring structure or as a ring substituent.

[0017] Preferably, the heteroatoms are selected from N and O.

[0018] Advantageously, the fluorescent group (FG) comprises at least one nitrogen or oxygen atom, and in addition, the fluorescent group (FG) may further comprise one or more other heteroatoms selected from O and S or N and S, respectively.

[0019] In particular, the OBAs of the present invention can be prepared by esterifying a polysaccharide with a reactive compound to form a compound of the formula:

[0020] PS-O-FG,

[0021] Where FG is the fluorescent group, and PS is the polysaccharide backbone, with only one substituent of each substituent type shown.

[0022] FG preferably contains a monocyclic or polycyclic ring system, at least one nitrogen atom or oxygen atom and conjugated double bonds.

[0023] The ring system may be optionally substituted by one or more groups selected from aryl (e.g. phenyl), heteroaryl (e.g. pyridyl) and halogen, hydroxy, amino, nitro, cyano, C1-3-alkyl, C1-3-haloalkyl, C1-3-alkoxy and SO2-substituted aromatic rings.

[0024] Keying

[0025] Preferably, the FG is linked to the anionic polysaccharide via a linkage. The linkage may comprise any chemical group resulting from the formation of a bond with a functional group of FG capable of forming a bond with a natural functional group of the polysaccharide repeating unit.

[0026] FG is preferably bonded to any natural hydroxyl group of the polysaccharide repeating unit via a linking group. The hydroxyl group may comprise any natural hydroxyl group of the sugar ring of the polysaccharide backbone or any hydroxyl group pendant to the backbone.

[0027] Preferably, the linkage comprises an ester bond or an amide bond.

[0028] The linkage may be selected from -C(O)(CH2) m -、-C(S)(CH2)m -、-O(CH2) m -、OCH2CH(OH)(CH2) m -、C(O)O(CH2) m -、C(S)O(CH2) m -、C(O)NH(CH2) m -、C(S)NH(CH2) m -, C(O)Ph-, C(S)Ph-, -Ph-, -C(O)OPh-, -C(S)OPh-, -C(O)NHPh- and -C(S)NHPh-, wherein m is an integer from 0 to 6, preferably 0-3, more preferably 0-1, and most preferably 0.

[0029] Highly preferred linkages include ester or amide groups, most preferably -C(O)-O-, ie via a direct ester bond between FG and the polysaccharide, and / or -C(O)-NH-, ie a direct amide bond (ie where m=0).

[0030] FG can be prepared by any suitable technique, for example, fluorescent groups can be grafted onto PS.

[0031] Preferably, FG comprises no more than four, more preferably no more than three, even more preferably no more than two, most preferably no more than one cyclic moiety.

[0032] Advantageously, the OBA of the present invention comprises only a single annular portion.

[0033] The single cyclic moiety may not include a thiazole structure.

[0034] The single cyclic moiety may not include a pyridine structure.

[0035] A single annular portion may not include one or more of the following structures:

[0036]

[0037] or

[0038]

[0039] Preferably, the FG used to prepare the OBA contains carboxyl and / or amide groups. Such functional groups can react with, for example, the hydroxyl groups of the polysaccharide to produce corresponding ester or amide bonds in the resulting OBA.

[0040] Preferably, the FG used to prepare the OBA comprises a carboxyl or amide functionalized cyclic moiety.

[0041] Preferably, the FG used to prepare the OBA comprises an amino-benzoate moiety. More preferably, the FG comprises 2-aminobenzoate.

[0042] Even more preferably, FG comprises an anthranilate moiety.

[0043] The anthranilate moiety can be attached to a carbon atom preferably in a ring of the polysaccharide residue. Thus, in a particularly preferred embodiment, FG comprises an ester of 2-aminobenzoic acid (anthranilic acid) and its N-alkyl derivatives, such as 2-(methylamino)benzoic acid (N-methylanthranilic acid or MANT), which has the following structure:

[0044]

[0045] Therefore, the OBA of the present invention may be a compound of the formula:

[0046]

[0047] in:

[0048] PS is the polysaccharide backbone with only one substituent of each substituent type shown.

[0049] The MANT-containing OBA is preferably prepared using an N-methylisatoic anhydride (MANT) precursor having the formula:

[0050]

[0051] The general reaction scheme is as follows (where PS is a polysaccharide, and OH is a natural functional group of PS):

[0052]

[0053] Alternatively, starting materials for FG include any amino-benzoate, such as methyl 2-aminobenzoate (methyl anthranilate) having the structure:

[0054]

[0055] Alternatively, FG may contain a section with the following structure:

[0056]

[0057] in:

[0058] PS is the polysaccharide backbone with only one substituent of each substituent type shown.

[0059] Coumarin substitutions that enable binding to polysaccharides may include carboxyl functional groups, such as carboxylic acids or acyl chlorides, to allow, for example, ester formation with native hydroxyl groups on anionic polysaccharides. Substitutions at positions 3, 4, 5, 6, 7, and 8 are possible, with 3- and 7-derivatives being preferred. The coumarin ring may also preferably be substituted with electron-donating substituents (e.g., at the 7-position) to increase fluorescence intensity—e.g., methyl, methoxy, NH2, NR2, where R is an alkyl group, such as methyl or ethyl.

[0060] Such structures may be referred to as coumarins or considered to belong to a class of lactones called benzopyrones.

[0061] Therefore, the OBA of the present invention may be a compound of the formula:

[0062]

[0063] In a further example, the natural functional group, FG and the linkage form a group O-FG of the formula:

[0064]

[0065] in

[0066] m is an integer from 0 to 6, preferably 0-3, more preferably 0-1, and most preferably 0; and Ra, Rb, Rc, Rd, Re and Rf are each independently selected from H, halogen, hydroxy, amino, nitro, cyano, C1-3 alkyl, C1-3 haloalkyl, C1-3 alkoxy and SO2, preferably each selected from H or methyl, more preferably each H.

[0067] Therefore, the OBA of the present invention may be a compound of the formula:

[0068]

[0069] in

[0070] m is an integer from 0 to 6, preferably 0-3, more preferably 0-1, and most preferably 0; and Ra, Rb, Rc, Rd, Re and Rf are each independently selected from H, halogen, hydroxy, amino, nitro, cyano, C1-3 alkyl, C1-3 haloalkyl, C1-3 alkoxy and SO2, preferably each selected from H or methyl, more preferably each H.

[0071] Thus, OBA may be a compound of the formula:

[0072]

[0073] in

[0074] PS is a polysaccharide, where only one substituent of each substituent type is shown;

[0075] m is an integer from 0 to 6, preferably from 0 to 3, more preferably from 0 to 1, and most preferably from 0; and Ra, Rb, Rc, Rd, Re, and Rf are each independently selected from H, halogen, hydroxy, amino, nitro, cyano, C 1-3 -alkyl, C 1-3 -haloalkyl, C 1-3 -alkoxy and SO2, preferably each is H.

[0076] OBAs may include compounds of the formula:

[0077]

[0078] in

[0079] PS is a polysaccharide showing only one substituent of each substituent type; m is an integer from 0 to 6, preferably 0-3, more preferably 0-1, most preferably 0.

[0080] In another advantageous embodiment, the natural functional group (F), FG and the linkage form a group O-FG of the formula:

[0081]

[0082] in:

[0083] m is an integer from 0 to 6, preferably from 0 to 3, more preferably from 0 to 1, and most preferably 0; and

[0084] R 10 H or C 1-3 alkyl; and

[0085] Ar is aryl or heteroaryl, preferably pyridyl, which is optionally substituted one or more times by groups selected from halogen, hydroxy, amino, nitro, cyano, C1-3-alkyl, C1-3-haloalkyl, C1-3-alkoxy and SO2.

[0086] Thus, OBA may be a compound of the formula:

[0087]

[0088] in

[0089] PS is a polysaccharide, where only one substituent of each substituent type is shown;

[0090] m is an integer from 0 to 6, preferably from 0 to 3, more preferably from 0 to 1, and most preferably 0; and

[0091] R 10 H or C 1-3 alkyl; and

[0092] Ar is aryl or heteroaryl, preferably pyridyl, which is optionally substituted one or more times by groups selected from halogen, hydroxy, amino, nitro, cyano, C1-3-alkyl, C1-3-haloalkyl, C1-3-alkoxy and SO2.

[0093] Preferably, OBA may be a compound of the formula:

[0094]

[0095] in

[0096] PS is a polysaccharide, where only one substituent of each substituent type is shown;

[0097] Advantageously, OBA is a compound of the formula:

[0098]

[0099] in

[0100] PS is a polysaccharide, where only one substituent of each substituent type is shown;

[0101] m is an integer from 0 to 6, preferably from 0 to 3, more preferably from 0 to 1, and most preferably 0; and

[0102] R 10 H or C 1-3 alkyl; and

[0103] Ar is aryl or heteroaryl, preferably pyridyl, which is optionally substituted one or more times by groups selected from halogen, hydroxy, amino, nitro, cyano, C1-3-alkyl, C1-3-haloalkyl, C1-3-alkoxy and SO2.

[0104] Anionic polysaccharides

[0105] Anionic polysaccharides may be linear or branched.Anionic polysaccharides may comprise branched or unbranched material.

[0106] Preferably, the anionicity of the polysaccharide results from the net negativity of the native functional groups of the polysaccharide. Thus, the ionicity of the polysaccharide is controlled by the native functional groups and not by, for example, any additional charged groups bonded to the native functional groups (other than FG). Preferably, no additional charged groups are bonded to the native functional groups (other than FG).

[0107] The anionic polysaccharide is preferably selected from carrageenan and xanthan gum.

[0108] Alternatively, the anionic polysaccharide may be a modified polysaccharide, preferably a chemically modified polysaccharide.

[0109] The modified polysaccharide can be a modified cellulose. Non-limiting examples include carboxymethyl cellulose (CMC), sulfoethyl cellulose (SEC).

[0110] The anionic polysaccharide is preferably a modified anionic polysaccharide, such as a modified polyglucose, for example a modified xyloglucan, such as sulfoethylxyloglucan (SEXG).

[0111] The polysaccharide is preferably modified with sulfur moieties to provide a sulfonated or sulfated polysaccharide.

[0112] Non-limiting examples of sulfonated polysaccharides include sulfoethylcellulose (SEC) and sulfoethylxyloglucan (SEXG), or mixtures thereof.

[0113] Carrageenan

[0114] A preferred anionic polysaccharide is carrageenan.

[0115] Carrageenan is the common name for a family of linear sulfated galactans obtained by extraction from certain species of marine red algae (Rhodophyta). Carrageenan consists of alternating 3-linked β-D-galactopyranose (G-units) and 4-linked α-D-galactopyranose (D-units) or 4-linked 3,6-anhydrogalactose (A-units), forming the disaccharide repeating unit of carrageenan (see Figure 1). Sulfated galactans are classified based on the presence of 3,6-anhydrogalactose on the 4-linked residues and the position and number of sulfate groups.

[0116]

[0117]

[0118] The carrageenan may be in any of the above-mentioned forms, i.e., alpha (α)-, beta (β)-, Iota (i)-, Kappa (k), Lambda (λ)-, Mu (μ)-, Nu (v)-, gamma (γ)-, Delta (δ)-, or Theta (θ)-carrageenan.

[0119] K-carrageenan is primarily obtained by extracting the tropical seaweed Kappaphycus alvarezii, commercially known as Eucheuma cottonii (or simply cottonii) (Rudolph, 2000). Eucheuma denticulatum (trade name Eucheuma spinosum, or spinosum) is the primary species used for i-carrageenan production. Seaweeds are typically extracted with alkali at high temperatures to convert the bioprecursors μ-carrageenan and v-carrageenan into commercial k-carrageenan and i-carrageenan.

[0120] Lambda-carrageenan is obtained from various species of the genera Gigartina and Chondrus.

[0121] The carrageenan preferably comprises lambda (λ) carrageenan and / or kappa (κ) carrageenan and / or iota (ι) carrageenan. Mixtures of any of the above materials may also be suitable. The mixture comprises at least two types, i.e., i- and κ-; i- and λ-; κ- and λ-.

[0122] In the case of a MANT fluorescer, the OBA may exclude iota carrageenan and contain lambda and / or kappa carrageenan.

[0123] Alternatively or additionally, carrageenan can be characterized by the degree of sulfation (D s ) selection. Preferably, D s It is at least 1, more preferably at least 2, even more preferably at least 3.

[0124] Alternatively or additionally, the carrageenan may be selected based on the amount of ester sulfate. Preferably, the ester sulfate content is at least 20 wt%, more preferably at least 30 wt%, most preferably at least 35 wt%, based on the total weight of the carrageenan.

[0125] Alternatively or additionally, the carrageenan may be selected based on its anhygalactose content. Preferably, less than 10% anhygalactose is present in the carrageenan by weight, more preferably less than 5% anhygalactose is present in the carrageenan by weight, more preferably less than 1% anhygalactose is present in the carrageenan by weight, more preferably less than 0.1% anhygalactose is present in the carrageenan by weight, and more preferably no anhygalactose is present in the carrageenan.

[0126] The carrageenan may comprise at least 50 wt%, preferably at least 60 wt%, more preferably at least 70 wt%, more preferably at least 80 wt%, most preferably at least 90 wt% carrageenan having the desired characteristics, i.e. the degree of sulfation and / or the amount of ester sulfate and / or the presence of anhydrous galactose.

[0127] Polysaccharides used in the present invention, such as carrageenan, generally have a weight average molecular weight (M) ranging from about 5 kDa to about 20,000 kDa, preferably from about 10 kDa to about 10,000 kDa, and more preferably from about 20 kDa to about 1,000 kDa. w ).

[0128] In the case of natural anionic polysaccharides, the natural functional groups are preferably hydroxyl groups and the degree of substitution may be in the range of 1 to 3.

[0129] Degree of substitution

[0130] Preferably, the anionic polysaccharide is substituted with a fluorescent group (FG) with a degree of substitution (DS1) of at least 0.001 to 1.5, preferably at least 0.002, more preferably 0.005 to 0.25.

[0131] Natural functional groups

[0132] The native functional group may comprise any functional group of the polysaccharide repeat unit.

[0133] The natural functional group includes hydroxyl, amino or carboxyl. Preferably, the natural functional group is hydroxyl.

[0134] "Native" means any group present in the polysaccharide prior to combination with FG. In the case of a modified polysaccharide (such as a sulfated polysaccharide, e.g., sulfoethylxyloglucan) linked to FG, the "native" group may be a group present in the base saccharide repeating unit of the polysaccharide prior to modification of the polysaccharide, e.g., hydroxyl, amino, carboxyl.

[0135] The native functional groups may be on the polysaccharide backbone or on any pendant or branched groups, if present.

[0136] Preferably, the linkage is achieved by reacting FG with any of the natural functional groups of the anionic polysaccharide repeating units, such as hydroxyl, amino, carboxyl and / or any other functional groups that may be present in the polysaccharide repeating units, for example via an esterification or etherification reaction.

[0137] The polysaccharide derivatives of the invention can be obtained in a manner known per se, in particular by functionalizing the polysaccharide with reactive compounds to form compounds of formula (I)

[0138] PS-N-FG (I)

[0139] in

[0140] Each N is the residue of any native functional group of a repeating unit (e.g., backbone or side chain) of the polysaccharide; and

[0141] PS is a polysaccharide, and for simplicity, only one substituent of each substituent type is shown;

[0142] definition

[0143] As used herein, the following terms are defined as follows:

[0144] "A" and "an" should be understood to mean one or more of what is claimed or described.

[0145] "Alkyl" refers to a straight or branched monovalent hydrocarbon radical having a specified number of carbon atoms. An alkyl group may be unsubstituted or substituted with substituents that do not interfere with the specified function of the composition, and may be substituted once or twice with the same or different groups. Substituents may include, for example, alkoxy, hydroxy, sulfhydryl, amino, alkyl-substituted amino, nitro, carboxyl, carbonyl, carbonyloxy, cyano, methylsulfonylamino, or halogen. Examples of "alkyl" include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, 3-methylpentyl, and the like.

[0146] In the context of the present invention, "detergent composition" refers to a cleaning composition, which typically contains a detersive surfactant, optionally other treatment ingredients, and is intended for and capable of treating a fabric substrate as defined herein. The phrases "detergent composition" and "cleaning composition" are used interchangeably and include compositions and formulations designed to clean soiled materials. Such compositions include, but are not limited to, laundry cleaning compositions and detergents, fabric softening compositions, fabric enhancing compositions, fabric refreshing compositions, laundry prewash agents, laundry pretreaters, laundry additives, spray products, dry cleaning agents or compositions, laundry rinse additives, washing additives, rinse-back fabric treatment agents, ironing aids, unit dose formulations, delayed delivery formulations, detergents included on or in porous substrates or nonwoven sheets, and other suitable forms that may be apparent to those skilled in the art in view of the teachings herein. Such compositions can be used as pre-wash treatment, post-wash treatment, or can be added during the rinsing or washing cycle of a washing operation.

[0147] In the context of the present invention, "detersive surfactant" means a surfactant that provides a detersive (ie cleaning) benefit to substrates (eg fabrics) that are treated as part of a household treatment (eg a washing process).

[0148] "Liquid" means that the continuous phase or major portion of the composition is liquid and that the composition is flowable at 15°C and above. Thus, the term "liquid" can encompass emulsions, suspensions, and compositions having a flowable but firmer consistency, referred to as gels or pastes, foams, and mousses. Non-limiting examples of liquids include light-duty and heavy-duty liquid detergent compositions, fabric enhancers, detergent gels typically used for laundry, bleaching agents, and laundry additives. Gases (e.g., suspended bubbles) or solids (e.g., particles) may be included in the liquid.

[0149] As used herein and hereinafter, "fluorescent whitening agent (OBA)" refers to a compound, also known as an optical brightener, that improves the visual appearance or optical properties, such as whiteness and / or brightness, of a material to which the fluorescent whitening agent is applied. The fluorophore of the OBA absorbs ultraviolet (UV) radiation from incident light and emits it as blue visible light. As a result, the material treated with the OBA is perceived as whiter. The fluorescent whitening agent improves the whiteness and / or optical brightness of the material to which it is applied, compared to the same material without the fluorescent whitening agent.

[0150] "Polymer" refers to a macromolecule comprising repeating units, wherein the macromolecule has a molecular weight of at least 1000 Daltons. A polymer can be a homopolymer, a copolymer, a terpolymer, etc.

[0151] "Substantially free" or "essentially free" means that the ingredient is completely absent or present only in minimal amounts as an impurity or unintended byproduct of another ingredient. A composition that is "substantially free" of a component means that the composition contains less than 0.5%, 0.25%, 0.1%, 0.05%, or 0.01%, or even 0%, of that component by weight of the composition.

[0152] As used in connection with the present invention, a "substrate" is a fabric. Fabric substrates include clothing, linens, and other household textiles, among others. In the context of fabrics, the term "linens" is used to describe certain types of laundry items, including sheets, pillowcases, towels, tablecloths, napkins, and uniforms, and the term "textile" may include woven, nonwoven, and knitted fabrics, and the fabric may include natural or synthetic fibers, such as silk, flax, cotton, polyester, polyamide fibers such as nylon, rayon, acrylic, acetate, and blends thereof, including cotton and polyester blends, as well as fabrics that are elastic and / or contain elastic fibers.

[0153] "Fabric treatment composition" refers to any type of treatment composition, and may include, but is not limited to, liquid cleaning and disinfectant laundry cleaning compositions, fabric softening compositions, fabric enhancing compositions, fabric refresher compositions, laundry pretreatment or prewash compositions, laundry pretreatment compositions, laundry additives (e.g., rinse additives, wash additives, etc.), post-rinse fabric treatment compositions, dryer compositions, dry cleaning compositions, ironing aids, etc. All such products, where applicable, may be in standard, concentrated, or even highly concentrated form, even to the extent that such products may be non-aqueous in some aspects.

[0154] In the context of treating substrates, especially fabrics, "treating" can include cleaning, washing, conditioning, lubricating, conditioning, softening, easy ironing, anti-wrinkle, perfumed, depilling, restoration (including color restoration), soaking, substrate pretreatment, bleaching, color treatment, soil removal, stain removal, and any combination thereof. The optical brighteners of the present invention can be used as part of any such treatment.

[0155] "Unit dose" means the amount of a composition suitable for treating one load of laundry, such as, for example, from about 0.05 g to about 100 g, or from 10 g to about 60 g, or from about 20 g to about 40 g. A unit dose product can be in the form of a tablet, pouch, sheet, fiber product, or polymer film package or capsule containing the composition. Such pouches typically include a water-soluble film, such as a polyvinyl alcohol water-soluble film, which at least partially encapsulates the composition. Suitable films can be obtained from MonoSol, LLC (Indiana, USA).

[0156] The multi-compartment pouch may have at least two, at least three, or at least four compartments.

[0157] The multi-compartment pouch may comprise compartments arranged side by side and / or stacked.The composition contained in the pouch or its compartments may be a liquid, a solid (such as a powder) or a combination thereof.

[0158] "Water-soluble" means that the product (film or package) dissolves in water at 20°C.

[0159] Unless otherwise indicated, all component or composition levels are in reference to the active moiety of that component or composition and are exclusive of impurities, for example, residual solvents or by-products, which may be present in commercially available sources of such components or compositions.

[0160] The dimensions and values disclosed herein should not be understood as being strictly limited to the exact numerical values recited. Instead, unless otherwise specified, each such dimension is intended to mean both the recited value and a functionally equivalent range surrounding that value. For example, a value disclosed as "50 microns" is intended to mean "about 50 microns."

[0161] Unless otherwise stated, all percentages and ratios are calculated by weight. Unless otherwise stated, all percentages and ratios are calculated based on the total composition. It should be understood that each maximum numerical value limit given throughout the specification includes each lower numerical value limit, as such lower numerical value limits are clearly written in this article. Each minimum numerical value limit given throughout this specification will include each higher numerical value limit, as such higher numerical value limits are clearly stated in this article. Each numerical range given throughout this specification will include each narrower numerical range that falls within such a wider numerical range, as such narrower numerical ranges are all clearly stated in this article.

[0162] All cited patents and other documents are, in relevant part, incorporated herein by reference as if fully set forth herein. The citation of any patent or other document is not an admission that the cited patent or other document is prior art with respect to the present invention.

[0163] OBA Level

[0164] Preferably, laundry compositions comprise from 0.01 to 10 wt% of an OBA of the present invention.

[0165] Product form

[0166] The composition can take any suitable form, including liquid or solid, and can include unit dose formulations, such as compositions encapsulated within a water-soluble polymer film, delayed delivery formulations, dilutable formulations, compositions contained on or within a porous matrix or nonwoven sheet, liquids stored in bulk for use in automatic dosing washing machines, and other suitable forms. Dilutable means that the consumer can purchase a concentrated product and take the concentrate home, where it can be diluted for use.

[0167] Liquid composition

[0168] A "liquid" composition has the continuous phase or major portion of the composition in liquid form and is flowable at and above 15° C. Thus, the term "liquid" can include emulsions, suspensions, and compositions having a flowable but firmer consistency, referred to as gels or pastes.

[0169] Liquid compositions may contain 10-80% by weight of water, depending on the level of surfactant.

[0170] Automatic quantitative feeding

[0171] Liquids can be provided in bulk storage containers, typically for use in automatic dosing washing machines. The bulk storage container holds multiple doses (i.e., for multiple wash cycles), preferably 80 ml to 3000 ml of liquid. A typical example of such a machine is found in EP-A-3 071 742 (Electrolux). The bulk storage container can be provided as a pre-filled cartridge, or the consumer can purchase the liquid, for example, in a sachet, and then empty the contents into the bulk storage container of the washing machine.

[0172] Solid composition

[0173] The solid composition can take a variety of physical solid forms, including forms such as powders, granules, strips, strips, pastes, tablets, flakes, lozenges and strips, and preferably, the composition is in the form of a powder, granules or tablets. The solid composition may preferably be in a form selected from a powder, unit dose or sachet form, tablet, strip or flake.

[0174] The solid composition preferably has a density greater than 350 g / l, more preferably greater than 450 g / l or even greater than 570 g / l. The solid laundry detergent composition according to the present invention is preferably free-flowing. Preferably, the composition is used to wash fabrics using a manual washing method. Preferably, the composition of the present invention is a solid laundry detergent composition. Preferably, the composition is in the form of a spray-dried powder or a granular, free-flowing form.

[0175] surfactants

[0176] The composition according to the present invention may comprise a surfactant or a surfactant system, wherein the surfactant may be selected from nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, zwitterionic surfactants, semi-polar nonionic surfactants and mixtures thereof.

[0177] Surfactant level

[0178] The compositions of the present invention preferably comprise from 0.1 wt% to 70 wt%, more preferably from 2 wt% to 60 wt%, from 1 wt% to 50 wt% or from 5 wt% to about 40 wt% or from 4 wt% to 30 wt% (total) surfactants, based on the weight of the composition.

[0179] Anionic surfactants

[0180] Preferably, the composition comprises anionic surfactants such as sulfonate and sulfate surfactants, preferably alkylbenzene sulfonates, alkyl sulfates and alkyl ether sulfates. The alkyl chain is preferably C10-C18. Alkyl ether sulfates are also known as alcohol ether sulfates.

[0181] Commonly used in laundry liquid compositions are C12-C14 alkyl ether sulfates having a linear or branched alkyl group containing 12 to 14 carbon atoms (C12-14) and containing an average of 1 to 3 EO units per molecule. A preferred example is sodium lauryl ether sulfate (SLES), in which predominantly C12 lauryl alkyl groups are ethoxylated with an average of 3 EO units per molecule.

[0182] Anionic surfactants are preferably added to the detergent composition in the form of salts. Preferred cations are alkali metal ions, such as sodium and potassium. However, the salt form of anionic surfactants can be formed in situ by neutralizing the acid form of the surfactant with a base (such as sodium hydroxide) or an amine (such as monoethanolamine, diethanolamine or triethanolamine). The weight ratios are calculated for the protonated form of the surfactant.

[0183] In anionic and nonionic surfactants, the ethoxy units can be partially replaced by propoxy units.

[0184] Further examples of suitable anionic surfactants are rhamnolipids, α-olefinsulfonates, olefinsulfonates, alkenesulfonates, alkane-2,3-diylbis(sulfates), hydroxyalkanesulfonates and disulfonates, fatty alcohol sulfates (FAS), alkanesulfonates, ester sulfonates, sulfonated fatty acid glycerides, methyl ester sulfonates alkyl- or alkenyl-succinic acid, dodecenyl / tetradecenylsuccinic acid (DTSA), fatty acid derivatives of amino acids, diacetyltartaric acid mono- and diglycerides (DATEM's), citric acid monostearate (CITREM's) and diesters and monoesters of sulfosuccinic acid.

[0185] C16 and / or C18 alcohol ether sulfates

[0186] Preferably, the composition comprises an alkyl ether sulfate anionic surfactant.Preferably, the alkyl ether sulfate comprises from 12 to 18 carbon atoms.

[0187] C12 alkyl ether sulfates are well documented and may be present in any amount from 1 to 30% by weight of the composition. However, a further preferred ether sulfate has the formula:

[0188] R2-O-(CH2CH2O) p SO3H

[0189] wherein R2 is selected from saturated, monounsaturated and polyunsaturated linear C16 and C18 alkyl chains, and wherein p is 3 to 20, preferably 4 to 12, more preferably 5 to 10. The monounsaturation is preferably at position 9 of the chain, with the carbons counted from the end of the chain to which the ethoxylate is attached. The double bond may be in cis or trans configuration (oleyl or elaido), but is preferably cis. cis or trans ether sulfates CH3(CH2)7-CH=CH-(CH2)8O-(OCH2CH2) n SO3H is described as C18:1(Δ9) ether sulfate. This follows the nomenclature CX:Y(ΔZ), where X is the number of carbons in the chain, Y is the number of double bonds, and ΔZ is the position of the double bond on the chain, with the carbons counted from the end of the chain where the OH is attached.

[0190] Preferably, R2 is selected from saturated C16, saturated C18, and monounsaturated C18. More preferably, the saturated C16 is a linear alkyl group with at least 90% by weight of the C16 content. With respect to the C18 content, it is preferred that the major C18 portion is C18:1, more preferably C18:1(Δ9). Preferably, the proportion of monounsaturated C18 is at least 50% by weight of the total C16 and C18 alkyl ether sulfate surfactants.

[0191] More preferably, the proportion of monounsaturated C18 is at least 60% by weight of the total C16 and C18 alkyl ether sulfate surfactants, most preferably at least 75% by weight.

[0192] Preferably, the C16 alcohol ethoxylate surfactant comprises at least 2 wt %, and more preferably 4 wt %, of the total C16 and C18 alkyl ether sulfate surfactants.

[0193] Preferably, the saturated C18 alkyl ether sulfate surfactant comprises at most 20 wt %, more preferably at most 11 wt % of the total C16 and C18 alkyl ether sulfate surfactant. Preferably, the saturated C18 content is at least 2 wt % of the total C16 and C18 alkyl ether sulfate content.

[0194] Where the composition comprises a mixture of C16 / 18 sources of alkyl ether sulphates as well as the more traditional C12 alkyl chain length materials, it is preferred that the total C16 / 18 alkyl ether sulphate content should comprise at least 10 wt %, more preferably at least 50 wt %, even more preferably at least 70 wt %, particularly preferably at least 90 wt % and most preferably at least 95 wt % of the total alkyl ether sulphates in the composition.

[0195] Ether sulfates are discussed in Anionic Surfactants: Organic Chemistry, edited by Helmut W. Stache (Marcel Dekker 1995), Surfactant Science Series, CRC Press.

[0196] Linear chain saturated or monounsaturated C20 and C22 ether sulfates may also be present.

[0197] Preferably, the weight fraction of the sum of "C18 ether sulfates" / "C20 and C22 ether sulfates" is greater than 10.

[0198] Preferably, the C16 and C18 ether sulfates contain less than 15%, more preferably less than 8%, most preferably less than 4% and most preferably less than 2% by weight of the ether sulfate of polyunsaturated ether sulfate. Polyunsaturated ether sulfates contain hydrocarbon chains with two or more double bonds.

[0199] Ether sulfates can be synthesized by sulfonation of the corresponding alcohol ethoxylates. Alcohol ethoxylates can be prepared by ethoxylation of alkyl alcohols. The alkyl alcohol used to produce the alcohol ethoxylates can be produced by transesterification of triglycerides to methyl esters, followed by distillation and hydrogenation to the alcohol. Kreutzer, UR, Journal of American Oil Chemists' Society. 61(2): 343-348 discusses this process. The preferred alkyl alcohol for the reaction is oleyl alcohol having an iodine value of 60 to 80, preferably 70 to 75, which is available from BASF, Cognis, and Ecogreen.

[0200] The degree of polyunsaturation in the surfactant can be controlled by hydrogenation of the triglycerides as described in A Practical Guide to Vegetable Oil Processing (Gupta MK Academic Press 2017). Distillation and other purification techniques can be used.

[0201] Ethoxylation reactions are described in Non-Ionic Surfactant Organic Chemistry (NM van ed.), Surfactant Science Series Vol. 72, CRC Press.

[0202] Preferably, the ethoxylation reaction is catalyzed using a base such as NaOH, KOH, or NaOCH3. Even more preferred are catalysts that provide a narrower ethoxyl distribution than NaOH, KOH, or NaOCH3. Preferably, these narrower distribution catalysts include Group II bases such as barium dodecanoate; Group II metal alkoxides; or Group II hydrotalcites as described in WO2007 / 147866. Lanthanides may also be used. Such narrower distribution alcohol ethoxylates are available from Azo Nobel and Sasol.

[0203] Preferably, the narrow ethoxyl distribution has more than 70 wt. %, more preferably more than 80 wt. % of the ethoxyl groups in R2-O-(CH2CH2O) z SO3H to R2-O-(CH2CH2O) w Ether sulfate R2-O-(CH2CH2O) in the range of SO3H q SO3H, where q is the molar average degree of ethoxylation, and x and y are absolute numbers, with z = p / 2 and w = p+p / 2. For example, when p = 6, then more than 70% by weight of the ether sulfates should consist of ether sulfates having 5, 6, 7, 8, or 9 ethoxy groups.

[0204] The weight of ether sulfate is calculated based on the protonated form: R2-O-(CH2CH2O) p SO3H. In the formulation, it will be in the ionic form R2-O-(CH2CH2O) p SO3- is present together with the corresponding counter ion, preferably a Group I and II metal, an amine, and most preferably sodium.

[0205] Methyl ester ethoxylate (MEE)

[0206] Preferred methyl ester ethoxylate surfactants are in the form of:

[0207] R3(-C=O)-O-(CH2CH2-O) n -CH3

[0208] Where R3COO is the fatty acid moiety, such as oleic acid, stearic acid, or palmitic acid. Fatty acid nomenclature describes the fatty acid by using two numbers, A:B, where A is the number of carbon atoms in the fatty acid and B is the number of double bonds it contains. For example, oleic acid is 18:1, stearic acid is 18:0, and palmitic acid is 16:0. The position of the double bond in the chain can be given in parentheses, such as 18:1 for oleic acid (9) and 18:2 for linoleic acid (9, 12), where 9 is the carbon number starting from the COOH end.

[0209] The integer n is the molar average ethoxylate number.

[0210] Methyl ester ethoxylate (MEE) is described in G.A. Smith's Biobased Surfactants (Second Edition), Chapter 8 Synthesis, Properties, and Applications, pp. 287-301 (AOCS press 2019); Cox ME and Weerasooriva U's J.Am.Oil.Chem.Soc.vol 74 (1997), pp. 847-859; Hreczuch et al. Tenside Surf.Det. Vol. 28 (2001), pp. 72-80; C.Kolano, Household and Personal Care Today (2012), pp. 52-55; A.Hama et al. J.Am.Oil.Chem.Soc. Vol. 72 (1995), pp. 781-784. MEE can be prepared by the reaction of methyl esters with ethylene oxide using a calcium or magnesium-based catalyst. The catalyst can be removed or left in the MEE.

[0211] Alternative preparation routes are transesterification of methyl esters or esterification of carboxylic acids with polyethylene glycols terminated at one end of the chain with a methyl group.

[0212] Methyl esters can be prepared by the transesterification of methanol and triglycerides or the esterification of methanol and fatty acids. The transesterification of triglycerides to fatty acid methyl esters and glycerol is discussed in Fattah et al. (Front. Energy Res., June 2020, Vol. 8, Chapter 101) and the references therein. Common catalysts for these reactions include sodium hydroxide, potassium hydroxide and sodium methoxide. Esterases and lipases can also be used. Triglycerides are naturally present in vegetable fats or oils, and preferred sources are rapeseed oil, castor oil, corn oil, cottonseed oil, olive oil, palm oil, safflower oil, sesame oil, soybean oil, high stearic acid / high oleic acid sunflower oil, high oleic acid sunflower oil, inedible vegetable oils, tall oil and any mixture thereof and any derivative thereof. The oil from trees is called tall oil. Used food cooking oil can be used. Triglycerides can also be obtained from algae, fungi, yeast or bacteria. Plant sources are preferred.

[0213] Distillation and fractionation processes can be used to produce methyl esters or carboxylic acids to produce the desired carbon chain distribution.Preferred sources of triglycerides are those containing less than 35% by weight polyunsaturated fatty acids in the oil prior to distillation, fractionation or hydrogenation.

[0214] Fatty acids and methyl esters can be obtained from oleochemical suppliers such as Wilmar, KLK Oleo, Unileveroleochemical Indonesia. Biodiesel is a methyl ester and these sources can be used.

[0215] When the ESB is MEE, it preferably has a molar average of 8 to 30, more preferably 10 to 20 ethoxylate groups (EO). Most preferred ethoxylates contain 12 to 18 EO.

[0216] Preferably, at least 10 wt. %, more preferably at least 30 wt. %, of the total C18:1 MEE in the composition has 9 to 11 EOs, and even more preferably at least 10 wt. % has exactly 10 EOs. For example, when the MEE has a molar average of 10 EOs, then at least 10 wt. % of the MEE should be composed of ethoxylates having 9, 10, and 11 ethoxylate groups.

[0217] The methyl ester ethoxylate preferably has a molar average of 8 to 13 ethoxylate groups (EO). The most preferred ethoxylate has a molar average of 9 to 11 EO, even more preferably 10 EO. When the MEE has a molar average of 10 EO, then at least 10% by weight of the MEE should be composed of ethoxylates having 9, 10, and 11 ethoxylate groups.

[0218] In the case of a broader MEE distribution, it is preferred that at least 40 wt% of the total MEE in the composition is C18:1.

[0219] Furthermore, it is preferred that the MEE component also comprises some C16 MEE.

[0220] Therefore it is preferred that the total MEE component comprises 5 to 50 wt% C16 MEE of the total MEE.Preferably, the C16 MEE is greater than 90 wt%, more preferably greater than 95 wt% C16:0.

[0221] In addition, it is preferred that the total MEE component comprises less than 15% by weight of the total MEE, more preferably less than 10% by weight, and most preferably less than 5% by weight of polyunsaturated C18, i.e., C18:2 and C18:3. Preferably, C18:3 is present in less than 1% by weight, more preferably less than 0.5% by weight, and most preferably substantially absent. The level of polyunsaturation can be controlled by distillation, fractionation, or partial hydrogenation of the feedstock (triglycerides or methyl esters) or MEE.

[0222] Furthermore, it is preferred that the C18:0 component is less than 10 wt% of the total MEE present.

[0223] Furthermore, it is preferred that components having carbon chains of 15 or less comprise less than 4 weight percent of the total MEE weight present.

[0224] Particularly preferred MEEs have 2 to 26% by weight of C16:0 chains, 1 to 10% by weight of C18:0 chains, 50 to 85% by weight of C18:1 chains and 1 to 12% by weight of C18:2 chains of the MEE.

[0225] Preferred sources of alkyl groups for MEE include methyl esters derived from distilled palm oil and distilled high oleic methyl esters derived from palm kernel oil, partially hydrogenated methyl esters of low oleic rapeseed oil, methyl esters of high oleic sunflower oil, methyl esters of high oleic safflower oil, and methyl esters of high oleic soybean oil.

[0226] High oleic oils are available from DuPont (Plenish high oleic soybean oil), Monsanto (Visitive Gold soybean oil), Dow (omega-9 canola oil, omega-9 sunflower oil), the National Sunflower Association, and Oilseeds International.

[0227] Preferably, more than 80% by weight of the double bonds in MEE are in cis configuration.

[0228] Preferably, the 18:1 component is oleic acid. Preferably, the 18:2 component is linoleic acid.

[0229] The methyl group of the methyl ester may be replaced by an ethyl group or a propyl group. The methyl group is most preferred.

[0230] Preferably, the methyl ester ethoxylate comprises from 0.1 to 95 wt% of the composition. More preferably the composition comprises from 2 to 40 wt% MEE and most preferably from 4 to 30 wt% MEE.

[0231] Preferably, the composition comprises at least 50% by weight water, but this will depend on the total surfactant content and will be adjusted accordingly.

[0232] Anionic surfactant weights are calculated in the protonated form.

[0233] Linear alkylbenzene sulfonate

[0234] Preferably, the composition comprises the anionic surfactant LAS (linear alkylbenzene sulfonate).

[0235] Suitable alkylbenzene sulfonates (LAS) can be obtained by sulfonating commercially available linear alkylbenzenes (LAB); suitable LABs include lower 2-phenyl LABs such as those supplied by Sasol under the trade name Isochem(R) or those supplied by Petresa under the trade name Petrelab(R), other suitable LABs include higher 2-phenyl LABs such as those supplied by Sasol under the trade name Suitable anionic detersive surfactants are alkylbenzene sulfonates obtained by a DETAL catalyzed process, although other synthetic routes (such as HF) are also suitable. In one aspect, magnesium salts of LAS are used. Suitable linear alkylbenzene sulfonates include those with an alkyl chain length of 10 to 18, preferably 11 to 15 carbon atoms, more preferably those with an average C12 chain length. Each alkyl chain homologue consists of a mixture of all possible sulfophenyl isomers except the 1-phenyl isomer. LAS is typically formulated into the composition in the form of an acid (i.e., HLAS) and then at least partially neutralized in situ.

[0236] Preferably, the linear alkylbenzene sulfonate surfactant is present in an amount of from 1 to 20%, more preferably from 2 to 15%, most preferably from 8 to 12% by weight of the composition.

[0237] nonionic surfactants

[0238] Preferably, the composition comprises a nonionic surfactant including any one of alcohol ethoxylates, alkoxylated fatty acid alkyl esters, alkyl polyglycosides (APGs), alkoxylated amines, ethoxylated glycerides, fatty acid monoethanolamides, fatty acid diethanolamides, ethoxylated fatty acid monoethanolamides, propoxylated fatty acid monoethanolamides, polyhydroxyalkyl fatty acid amides or N-acyl N-alkyl derivatives of glucosamine, polysorbates (Tweens), or mixtures thereof.

[0239] The composition may comprise soap.

[0240] The compositions of the present invention may contain amphoteric (zwitterionic) and / or cationic surfactants alone or in addition to the non-soap anionic and / or nonionic surfactants described above.

[0241] Specific cationic surfactants include C8 to C18 alkyl dimethyl ammonium halides and derivatives thereof in which one or two hydroxyethyl groups replace one or two methyl groups, and mixtures thereof.

[0242] Cationic surfactants include quaternary ammonium compounds.

[0243] Specific amphoteric (zwitterionic) surfactants include amine oxides and / or betaines, such as alkylamine oxides, alkyl betaines, alkylamidopropyl betaines, alkyl sulfobetaines (sulfobetaines), alkyl glycinates, alkyl carboxyglycinates, alkyl amphoacetates, alkyl amphopropionates, alkyl amphoglycinates, alkylamidopropyl hydroxysulfobetaines, acyltaurates and acylglutamates, having an alkyl group containing from about 8 to about 22 carbon atoms, preferably selected from C12, C14, C16, C18 and C18:1, the term "alkyl" being used to include the alkyl portion of higher acyl groups.

[0244] Preferred amine oxides are alkyl dimethylamine oxide and alkyl amidopropyl dimethylamine oxide, more preferably alkyl dimethylamine oxide. Particularly preferred are lauryl dimethylamine oxide, coco dimethylamine oxide and cocoamidopropyl dimethylamine oxide.

[0245] Suitable betaines include alkyl betaines, alkyl amido betaines, alkyl amidopropyl betaines, alkyl sulfobetaines and alkyl phosphobetaines, wherein the alkyl group preferably has 8 to 19 carbon atoms.

[0246] Examples include cocodimethyl sulphopropyl betaine, cetyl betaine, laurylamidopropyl betaine, caprylic / capric betaine, caprylic / capramidopropyl betaine, cocamidopropyl hydroxysultaine, cocobutyramidohydroxysultaine, and preferably lauryl betaine, cocamidopropyl betaine and sodium coamphopropionate. Preferably, the betaine is cocamidopropyl betaine (CAPB).

[0247] Some compositions may be free of anionic surfactants, for example cationic active materials such as quaternary ammonium compounds.

[0248] Some compositions, such as fabric softening compositions, may contain low levels (less than 4% by weight) of anionic or cationic surfactants or may be free of anionic or cationic surfactants.

[0249] The composition may contain a fabric softening active. These may be any material known to soften fabrics. These may be polymeric materials or compounds known to soften materials. Examples of suitable fabric softening actives include quaternary ammonium compounds, silicone polymers, polysaccharides, clays, amines, fatty esters, fatty N-oxides, dispersible polyolefins, polymer latexes, and mixtures thereof.

[0250] The fabric softening active may preferably be a cationic or nonionic material. Preferably, the fabric softening active of the present invention is a cationic material. Preferred softening actives for use in the fabric conditioning compositions of the present invention are quaternary ammonium compounds (QACs). Most preferably, the quaternary ammonium compound is a triethanolamine quaternary ammonium (TEA) compound. The quaternary ammonium compound may comprise a fatty acid chain from any suitable source, preferably palm oil or tallow. It may be preferred that the fatty acid chain is derived from a plant source.

[0251] Optional ingredients

[0252] The compositions of the present invention may contain additional optional home care ingredients including additional surfactants, builders, chelants, organic acids, preformed peracids, polymeric dispersants, clay soil removal / anti-redeposition agents, dye transfer inhibitors, alkoxylated cationic or zwitterionic diamine or polyamine polymers, anti-redeposition polymers (e.g., alkoxylated polyamines), soil release polymers, dispersants, enzymes and enzyme stabilizers, catalytic materials, bleach activators, thickening polymers, foam boosters, defoamers, insect repellents, dyes (e.g., hueing or shade dyes), preservatives (e.g., bactericides), pH Buffering agents, perfumes, perfume delivery systems (including perfume microcapsules, preferably with cationic deposition aids), hydrotropes, carriers, structural elastic agents, polyelectrolytes, processing aids, solvents and / or pigments and mixtures thereof, anti-wrinkle agents, anti-shrinkage agents, antioxidants, anti-corrosion agents, drape-imparting agents, antistatic agents, ironing aids, anti-foaming agents, colorants, pearlescent and / or opacifying agents, processing aids (e.g., electrolytes), sanitation agents (e.g., antibacterial and antifungal agents, for example, quaternary ammonium compounds, organic acids, hydrogen peroxide or chloroxylenol), skin benefit agents, anti-redeposition agents, sunscreens or any combination thereof. DETAILED DESCRIPTION

[0253] Example

[0254] Example 1: Synthesis of N-methyl-anthranilate-substituted anionic polysaccharides

[0255] Anionic polysaccharide (1g) is dissolved in a 50:50 mixture (90ml) of dimethyl sulfoxide (DMSO) and 0.1M sodium borate aqueous solution. The mixture is stirred at room temperature for 20 minutes to obtain a clear viscous solution. A solution of N-methyl isatoic anhydride (0.1g) in DMSO (3ml) is added, and the solution is stirred at room temperature for another 18 hours. The solution is then added dropwise to vigorously stirred isopropanol (400ml) to obtain a white precipitate. The precipitate is filtered out, washed with more isopropanol and dried in vacuo at 40°C. The polymer is dissolved in water (20ml) and dialyzed for 72 hours against deionized water (3,000 molecular weight cut-off membrane) to remove any residual N-methyl isatoic anhydride and its N-methyl anthranilic acid reaction product. Finally, the purified polymer solution is freeze-dried. The resulting powder is optically white. The molecular weight of the modified polymer is measured using gel permeation chromatography. The degree of substitution (DS) for MANT grafting was determined by hydrolyzing the polymer (dissolved in water and adjusted to pH 13 for 12 h) and then measuring the fluorescence spectrum and comparing it with N-methylanthranilic acid solutions containing 0.1 mg / mL polymer at different concentrations.

[0256] λ-carrageenan having a molecular weight of about 733 kDa was reacted with N-methylisatoic anhydride by the above method. The measured molecular weight of the obtained product was 491 kDa, and the degree of substitution with respect to 2-(methylamino)benzoate was 0.017.

[0257] Sulfoethyl-xyloglucan with a molecular weight of 132 kDa (SE substitution degree of 0.23) was reacted with N-methylisatoic anhydride by the above method. The resulting product had a measured molecular weight of 110 kDa and a degree of substitution with 2-(methylamino)benzoate of 0.007.

[0258] Example 2: Fluorescent whitening of non-fluorescent textiles

[0259] Non-fluorescent cotton fabric was treated with the OBA of the present invention as follows.

[0260] Use a laundry liquid detergent with the following recipe.

[0261] Components Contains % (w / w) glycerin 2.0 Alcohol ethoxylate (25-7) 4.3 LAS acid 5.8 TEA 8.8 Lauric acid 0.9 SLES1EO 4.3 water to 100%

[0262] A wash liquor containing 3 g / L of liquid detergent formulation was prepared in 24°F (calcium) hard water. Fluorescent brightener was post-dosed into the wash liquor at the following dosages: 0.05 g / L 2-(methylamino)benzoic acid-xyloglucan; 0.005 g / L 2-(methylamino)benzoic acid. A negative control was provided by a wash liquor without added fluorescent brightener.

[0263] A single textile cotton fabric disc (0.5mm diameter) is placed at the bottom of each well of a 96-well microtiter plate. 200 μl of washing solutions are pipetted into each well using the CyBio SELMA automatic liquid handler. 8 replicates are used for each washing solution. The microtiter plate is sealed with a plate sealing film and stirred in a Varioscan plate reader (500rpm, 30°C). After 30 minutes, the microtiter plate is taken out from the plate reader and washing solutions are aspirated from each well using an automatic liquid handler. 200 μl of water is then pipetted into each well, and the plate is returned to the plate reader and stirred for 5 minutes under the same conditions. Rinse water is then aspirated. The microtiter plate containing the textile disc is placed in an oven set at 37°C and dried for 24 hours. This constitutes a single model wash cycle. Tweezers are then used to remove the textile disc from the wash plate and transferred to a black flat-bottom fluorescent 96-well plate. The fluorescence intensity of the textile disc was measured using a Varioscan plate reader with an excitation wavelength of 350 nm and an emission wavelength of 424 nm. The textile disc was then inverted so that the opposite side of the disc was on top, and the fluorescence measurement was repeated. The average of the two results from each side of the textile disc was recorded.

[0264] The results are listed in the table below.

[0265] No fluorescent agent MANT acid MANT-SE-XG MANT-CARR Fluorescence intensity (AU) 150 201 693 759

[0266] The results showed that 2-(methylamino)benzoic acid (MANT acid) had low substantivity to textiles. In contrast, 2-(methylamino)benzoate showed higher substantivity to sulfoethylxyloglucan and λ-carrageenan.

[0267] Example

[0268] Typical preparations include:

[0269]

[0270]

[0271] 1,2 Also prepared using the C12-18 form.

Claims

1. A fabric treatment composition comprising: a. an optical brightening agent (OBA) comprising an anionic polysaccharide attached to a fluorescent group (FG) having an absorption band in the UV light region and an emission band in the visible light region; and b. Surfactant.

2. The fabric treatment composition according to claim 1, wherein the surfactant comprises an anionic surfactant and / or a nonionic surfactant and / or a zwitterionic surfactant.

3. A fabric treatment composition according to claim 1 or claim 2, wherein the anionic surfactant comprises a sulphonate and / or sulphate surfactant.

4. A method of treating fabrics, said method comprising the step of treating the fabrics with a fabric treatment composition according to any one of the preceding claims.

5. A method according to claim 6 comprising the steps of adding the fabric treatment composition to water to form a wash liquor and treating the substrate with the wash liquor.

6. A method for preparing a fabric treatment composition according to claim 7, comprising the steps of including an optical brightener (OBA) and a surfactant in the fabric treatment composition, wherein the optical brightener (OBA) comprises an anionic polysaccharide to which a fluorescent group (FG) having an absorption band in the UV light region and an emission band in the visible light region is linked.

7. An optical brightening agent (OBA) comprising an anionic polysaccharide linked to a fluorescent group (FG) having an absorption band in the UV light region and an emission band in the visible light region.

8. The OBA of claim 7, wherein the anionic polysaccharide comprises sulfur moieties such that the anionic polysaccharide is a sulfonated or sulfated polysaccharide.

9. The OBA of claim 7 or 8, wherein the anionic polysaccharide comprises carrageenan.

10. The OBA according to any one of claims 7 to 9, wherein the FG comprises a monocyclic or polycyclic ring system, at least one heteroatom selected from N, O and S, and a conjugated double bond.

11. The OBA according to any one of the preceding claims, wherein the FG comprises no more than four, more preferably no more than three, even more preferably no more than two, most preferably no more than one cyclic moiety.

12. The OBA of any preceding claim, wherein the FG comprises an aminobenzoate moiety.

13. The OBA of any preceding claim, wherein the FG comprises methyl 2-aminobenzoate (MANT).

14. The OBA of any one of claims 1-6, wherein the FG comprises coumarin.

15. A method for preparing an OBA, comprising the step of linking a fluorescent group (FG) having an absorption band in a UV light region and an emission band in a visible light region to an anionic polysaccharide.

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