Cationic poly alpha-1,6-glucan ether and compositions comprising the same

Abstract

The present disclosure relates to poly alpha-1,6-glucan ether compounds comprising poly alpha-1,6-glucan substituted with at least one positively charged organic group and having a degree of substitution of about 0.001 to about 3.0. The poly alpha-1,6-glucan comprises a backbone of glucose monomer units, wherein greater than or equal to 40% of the glucose monomer units are linked via alpha-1,6 glycosidic bonds, and optionally about 3% of the backbone glucose monomer units have branches via alpha-1,2 and / or alpha-1,3 glycosidic bonds. Compositions comprising poly alpha-1,6-glucan ether compounds can be used in various applications.

Description

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 040,569 (filed June 18, 2020), which is incorporated herein by reference in its entirety. Technical Field

[0002] This disclosure relates to cationic poly-1,6-glucan ether compounds comprising poly-1,6-glucan substituted with at least one positively charged organic group. The poly-1,6-glucan comprises a backbone of glucose monomer units, wherein greater than or equal to 40% of these glucose monomer units are linked via α-1,6 glycosidic bonds and optionally at least 3% of the backbone units are branched via α-1,2 and / or α-1,3 glycosidic bonds. Background Technology

[0003] Driven by the hope of finding new structural polysaccharides through enzymatic synthesis or microbial genetic engineering, researchers have discovered biodegradable oligosaccharides and polysaccharides that can be economically produced from renewable sources. Cationic polysaccharides have practical applications in personal care, household, industrial, and institutional products. Cationic polysaccharides derived from enzymatic synthesis or microbial genetic engineering can be used as viscosity modifiers, emulsifiers, adhesives, film-forming agents, spreading and deposition aids, and as carriers to enhance the rheology, efficacy, deposition, aesthetics, and delivery of active ingredients in personal care, household, or pet care products, and to provide these functions in formulations such as clothing, fabric care, cleaning, and personal care compositions.

[0004] Modern detergent compositions (including those for clothing, fabrics, dishes, or other cleaning) contain common detergent ingredients such as anionic, nonionic, cationic, amphoteric, zwitterionic, and / or semipolar surfactants; and enzymes such as proteases, cellulases, lipases, amylases, and / or peroxidases. Laundry detergent and / or fabric care compositions may further contain a variety of detergent ingredients that have one or more uses in obtaining fabrics that are not only clean, fresh, and sterilized, but also retain their appearance and integrity. Therefore, beneficial agents such as fragrances, hygiene agents, insect control agents, bleaches, fabric softeners, dye fixatives, stain removers, and fabric brighteners have been incorporated into laundry detergent and / or fabric care compositions. When using such detergent components, it is important that some of these compounds deposit on the fabric to be effective during or after washing and / or fabric care.

[0005] There remains a need for new materials that can be used in water-based applications (such as fabric care, for example as an anti-settling agent and / or anti-greying agent in laundry detergents), as well as in household, personal care, and industrial applications. Such materials that can be made from renewable resources are also in demand. Summary of the Invention

[0006] This article discloses polyα-1,6-glucan ether compounds, which contain:

[0007] (i) a poly-α-1,6-glucan substituted with at least one positively charged organic group;

[0008] (ii) a weight-average degree of polymerization of at least 5; and

[0009] (iii) A degree of substitution of about 0.001 to about 3.0;

[0010] The poly-α-1,6-glucan comprises a backbone of glucose monomer units, and at least 40% of these glucose monomer units are linked by α-1,6 glycosidic bonds.

[0011] In one embodiment, at least 3% of the main-chain glucose monomer units are branched via α-1,2 and / or α-1,3-glycosidic bonds. In one embodiment, from about 3% to about 50% of the main-chain glucose monomer units are branched via α-1,2- and / or α-1,3-glycosidic bonds. In one embodiment, from about 3% to about 35% of the main-chain glucose monomer units are branched via α-1,2- and / or α-1,3-glycosidic bonds. In one embodiment, the branching is via α-1,2-glycosidic bonds. In one embodiment, the branching is via α-1,3-glycosidic bonds.

[0012] In one embodiment, the polyα-1,6-glucan ether compound has a weight-average degree of polymerization in the range of about 5 to about 6000.

[0013] In one embodiment, the degree of substitution is from about 0.01 to about 1.5.

[0014] In one embodiment, the positively charged organic group comprises a substituted ammonium group. In one embodiment, the substituted ammonium group comprises a quaternary ammonium group. In one embodiment, the quaternary ammonium group comprises a trimethylammonium group.

[0015] In one embodiment, the quaternary ammonium group comprises at least one C1 to C2 group. 18 Alkyl group. In one embodiment, the quaternary ammonium group comprises at least one C1 to C4 alkyl group. In one embodiment, the quaternary ammonium group comprises at least one C1 to C4 alkyl group. 10 To C 16 Alkyl group. In one embodiment, the quaternary ammonium group comprises at least one C 10 To C 16 It contains alkyl groups and further comprises two methyl groups.

[0016] In one embodiment, the positively charged organic group comprises a quaternary ammonium hydroxyalkyl group. In one embodiment, the quaternary ammonium hydroxyalkyl group comprises a quaternary ammonium hydroxymethyl group, a quaternary ammonium hydroxyethyl group, or a quaternary ammonium hydroxypropyl group. In one embodiment, the quaternary ammonium hydroxyalkyl group comprises a trimethylammonium hydroxyalkyl group. In one embodiment, the trimethylammonium hydroxyalkyl group is a trimethylammonium hydroxypropyl group.

[0017] This document also discloses compositions comprising poly(α-1,6-glucan ether) compounds as disclosed herein. Furthermore, this document discloses personal care products, home care products, and industrial products comprising poly(α-1,6-glucan ether) compounds as disclosed herein, or compositions comprising poly(α-1,6-glucan ether) compounds as disclosed herein.

[0018] In another embodiment, the composition is in the form of a liquid, gel, powder, hydrocolloid, aqueous solution, granules, tablet, capsule, bead or lozenge, single-compartment sachet, pad, multi-compartment sachet, single-compartment pouch, or multi-compartment pouch.

[0019] In yet another embodiment, the composition further comprises at least one of the following: surfactants, enzymes, detergent builders, complexing agents, polymers, detergency polymers, surfactant-enhancing polymers, bleaching agents, bleaching activators, bleaching catalysts, fabric conditioning agents, clays, foam promoters, foam inhibitors, corrosion inhibitors, dirt suspending agents, anti-dirt redeposition agents, dyes, bactericides, dulling inhibitors, optical brighteners, fragrances, saturated or unsaturated fatty acids, dye transfer inhibitors, chelating agents, tinting dyes, calcium cations, magnesium cations, visual signaling components, defoamers, structuring agents, thickeners, anti-caking agents, starch, sand, gelling agents, or combinations thereof.

[0020] In one embodiment, the enzyme is a cellulase, protease, lipase, amylase, or a combination thereof. In one embodiment, the enzyme is a cellulase. In another embodiment, the enzyme is a protease. In yet another embodiment, the enzyme is an amylase.

[0021] This article also discloses a personal care product, home care product, industrial product, or fabric care product comprising a composition.

[0022] This article also discloses a method for treating a substrate, the method comprising the following steps:

[0023] (a) Providing compositions comprising polyα-1,6-glucan ether compounds as disclosed herein;

[0024] (b) bringing the substrate into contact with the composition; and

[0025] (c) Optionally rinse the substrate;

[0026] The substrate can be textiles, fabrics, carpets, interior decorations, clothing, or surfaces. Detailed Implementation

[0027] All cited patent and non-patent literature disclosures are incorporated herein by reference in their entirety.

[0028] As used herein, the terms “embodiment” or “disclosure” are not intended to be limiting, but are generally applicable to any embodiment defined in the claims or described herein. These terms are used interchangeably herein.

[0029] Many terms and abbreviations are used in this disclosure. Unless otherwise specified, the following definitions apply.

[0030] The articles “a / an” and “the” preceding an element or component are intended to be non-restrictive in terms of the number of instances (i.e., occurrences) of that element or component. These articles “a / an” and “the” should be understood to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.

[0031] The term "comprising" means the presence of the stated features, integers, steps, or components as claimed in the claims, but does not exclude the presence or addition of one or more other features, integers, steps, components, or groups thereof. The term "comprising" is intended to include embodiments covered by the terms "substantially consisting of" and "consisting of". Similarly, the term "substantially consisting of" is intended to include embodiments covered by the term "consisting of".

[0032] Where applicable, all ranges are composable and include end values. For example, when listing the range “1 to 5”, the listed ranges should be interpreted as including the ranges “1 to 4”, “1 to 3”, “1-2”, “1-2 and 4-5”, “1-3 and 5”, etc.

[0033] Each maximum numerical limit given throughout this specification is intended to include each lower numerical limit, as such lower numerical limit is explicitly stated herein. Each minimum numerical limit given throughout this specification will include each higher numerical limit, as such higher numerical limit is explicitly stated herein. Each numerical range given throughout this specification will include each narrower numerical range falling within such a wider numerical range, as such narrower numerical range is explicitly stated herein.

[0034] Unless otherwise expressly indicated, the use of numerical values ​​within the various ranges specified in this application is stated as approximations, as the minimum and maximum values ​​within the stated ranges are preceded by the word "approximately". In this way, slightly higher and lower than the stated ranges can achieve substantially the same results as values ​​within these ranges. Moreover, these ranges are intended to be disclosed as continuous ranges encompassing every value between the minimum and maximum values.

[0035] By reading the following detailed description, those skilled in the art will more readily understand the features and advantages of this disclosure. It should be understood that, for clarity, certain features of this disclosure described above and below in the context of individual embodiments may also be provided in combination of single elements. Conversely, for brevity, various features of this disclosure described in the context of individual embodiments may also be provided individually or in any sub-combination. Furthermore, unless the context specifically indicates otherwise, references to the singular may also include the plural (e.g., "an" may refer to one or more).

[0036] As used in this article:

[0037] The term "polysaccharide" refers to a polymeric carbohydrate molecule consisting of long chains of monosaccharide units linked together by glycosidic bonds, which, upon hydrolysis, produce the constituent monosaccharides or oligosaccharides.

[0038] In this article, the terms "poly-α-1,6-glucan", "α-1,6-glucan", "dextran", and "dextran polymer" refer to α-glucan containing at least 40% α-1,6 glycosidic bonds.

[0039] The terms “percentage by weight,” “weight percentage (wt%),” and “weight-to-weight percentage (%w / w)” are used interchangeably herein. Weight percentage refers to the percentage of a material on a mass basis when the material is contained in a composition, mixture, or solution.

[0040] As used herein, the term "polysaccharide derivative" refers to a chemically modified polysaccharide in which at least some of the hydroxyl groups of the glucose monomer units have been replaced by one or more ether groups. As used herein, the term "polysaccharide derivative" is used interchangeably with "poly-α-1,6-glucan ether" and "poly-α-1,6-glucan ether compound".

[0041] The term "hydrophobic" refers to nonpolar molecules or substituents that have little or no affinity for water and tend to repel water.

[0042] The term "hydrophilic" refers to a polar molecule or substituent that has an affinity for polar solvents, particularly water, or other polar groups. Hydrophilic molecules or substituents tend to attract water.

[0043] The molecular weight of polyα-1,6-glucan or polyα-1,6-glucan ether can be expressed as the statistically average molecular weight distribution, i.e., the number-average molecular weight (M). n ) or expressed as weight-average molecular weight (M w Both are typically given in Daltons (Da), i.e., in grams per mole. Alternatively, molecular weight can be expressed as DPw (weight-average degree of polymerization) or DPn (number-average degree of polymerization). Various methods for calculating these molecular weights using techniques such as high-performance liquid chromatography (HPLC), size exclusion chromatography (SEC), gel permeation chromatography (GPC), and gel filtration chromatography (GFC) are known in the art.

[0044] As used in this article, "weight-average molecular weight" or "M" w "Calculated as M" w =ΣN i M i 2 / ΣN i M i ; where M i It is the molecular weight of a single chain i and N i It is the number of chains with that molecular weight. In addition to using SEC, weight-average molecular weight can be determined by other techniques such as static light scattering, mass spectrometry, especially MALDI-TOF (matrix-assisted laser desorption / ionization time-of-flight), small-angle X-ray or neutron scattering, and ultracentrifugation.

[0045] As used in this article, "number-average molecular weight" or "M" n "Number average molecular weight" refers to the statistical average molecular weight of all polymer chains in the sample. The number average molecular weight is calculated as M. n =ΣN i M i / ΣN i M i It is the molecular weight of chain i and N i It is the number of chains with that molecular weight. In addition to using SEC, the number-average molecular weight of a polymer can be determined by various colligative methods such as vapor pressure osmotic pressure measurement or by spectroscopic methods such as proton NMR, FTIR or UV-vis end-group determination.

[0046] As used herein, the number-average degree of polymerization (DPn) and weight-average degree of polymerization (DPw) are calculated by dividing the corresponding average molecular weight Mw or Mn by the molar mass of a monomer unit M1. In the case of unsubstituted dextran polymers, M1 = 162. In the case of substituted dextran polymers, M1 = 162 + M f ×DoS, where M fIt is the molar mass of the substituent group, and DoS is the degree of substitution of that substituent group (average number of substituent groups / one glucose unit).

[0047] As mentioned herein, the glucose carbon positions 1, 2, 3, 4, 5, and 6 are known in the art and are depicted in Structure I:

[0048]

[0049] The terms “glycosidic bond” and “glycan bond” are used interchangeably herein and refer to the type of covalent bond that links a carbohydrate (sugar) molecule to another group, such as another carbohydrate. As used herein, the term “α-1,6-glycosidic bond” refers to a covalent bond that links α-D-glucose molecules together via carbons 1 and 6 of adjacent α-D-glucose rings. As used herein, the term “α-1,3-glycosidic bond” refers to a covalent bond that links α-D-glucose molecules together via carbons 1 and 3 of adjacent α-D-glucose rings. As used herein, the term “α-1,2-glycosidic bond” refers to a covalent bond that links α-D-glucose molecules together via carbons 1 and 2 of adjacent α-D-glucose rings. As used herein, the term “α-1,4-glycosidic bond” refers to a covalent bond that links α-D-glucose molecules together via carbons 1 and 4 of adjacent α-D-glucose rings. In this document, “α-D-glucose” will be referred to as “glucose”.

[0050] The glycosidic bond profile of dextran, dextran, substituted dextran, or substituted dextran can be determined using any method known in the art. For example, nuclear magnetic resonance (NMR) spectroscopy can be used (e.g., 13 CNMR or 1 Bond spectra can be determined using ¹H NMR. These and other methods that can be used are disclosed in [the relevant documentation]. Food Carbohydrates:Chemistry,Physical Properties,and Applications [ Food carbohydrates: Chemical and physical properties and applications [(SWCui, ed., Chapter 3, SWCui, Structural Analysis of Polysaccharides, Taylor & Francis Group LLC, Pocaraton, Florida, 2005), which is incorporated herein by reference.]

[0051] The structure, molecular weight, and degree of substitution of polysaccharides or polysaccharide derivatives can be confirmed using a variety of physicochemical analyses known in the art, such as NMR spectroscopy and size exclusion chromatography (SEC).

[0052] As used herein, the term "alkyl group" refers to a straight-chain, branched, aralkyl (such as benzyl), or cyclic ("cycloalkyl") hydrocarbon group that is free from unsaturation. As used herein, the term "alkyl group" includes substituted alkyl groups, such as alkyl groups substituted with at least one hydroxyalkyl group or dihydroxyalkyl group, and alkyl groups containing one or more heteroatoms (such as oxygen, sulfur, and / or nitrogen) within the hydrocarbon chain.

[0053] As used herein, the term "aryl" means an aromatic / carbocyclic group having a monocyclic (e.g., phenyl), polycyclic (e.g., biphenyl), or multiple fused rings, at least one of which is aromatic (e.g., 1,2,3,4-tetrahydronaphthyl, naphthyl, anthraceneyl, or phenanthryl) and optionally mono, di, or trisubstituted with an alkyl group. Aryl also means a heteroaryl group, wherein a heteroaryl is defined as a 5-, 6-, or 7-membered aromatic ring system having at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur. Examples of heteroaryl groups include pyridinyl, pyrimidinyl, pyrroloyl, pyrazolyl, pyrazinyl, pyridazinyl, oxazolyl, furanyl, imidazole, quinolinyl, isoquinolinyl, thiazolyl, and thiopheneyl, which may optionally be substituted with an alkyl group.

[0054] The terms "home care products," "family care products," and similar terms typically refer to products, goods, and services relating to the handling, cleaning, care, and / or conditioning of the home and its interior. This includes, for example, chemicals, compositions, products, or combinations thereof intended for use in such care.

[0055] The term "personal care products" and similar terms typically refer to products, goods, and services relating to the treatment, cleaning, washing, care, or conditioning of a person. This includes, for example, chemicals, compositions, products, or combinations thereof used in such care.

[0056] The term "industrial product" and similar terms typically refer to products, goods and services used in an industrial setting, but not typically used by individual consumers.

[0057] This disclosure relates to a polyα-1,6-glucan ether compound comprising:

[0058] (i) a poly-α-1,6-glucan substituted with at least one positively charged organic group;

[0059] (ii) a weight-average degree of polymerization of at least 5; and

[0060] (iii) A degree of substitution of about 0.001 to about 3.0;

[0061] The poly-α-1,6-glucan comprises a backbone of glucose monomer units, wherein at least 40% of these glucose monomer units are linked via α-1,6-glycosidic bonds, and optionally at least 3% of the backbone glucose monomer units are branched via α-1,2 and / or α-1,3 glycosidic bonds. Optionally, the poly-α-1,6-glucan (a) is substituted with only at least one positively charged organic group, or (b) is not substituted with a hydrophobic group or a negatively charged organic group.

[0062] The poly-α-1,6-glucan ether compounds disclosed herein comprise poly-α-1,6-glucan substituted with at least one positively charged organic group, wherein one or more organic groups are independently linked via ether (-O-) bonds to the poly-α-1,6-glucan backbone and / or any branch (if present). The at least one positively charged organic group may derive poly-α-1,6-glucan at the 2, 3, and / or 4 glucose carbon positions of glucose monomers on the glucan backbone, and / or at the 2, 3, 4, or 6 glucose carbon positions of glucose monomers on branches (if present). At unsubstituted positions, hydroxyl groups are present in the glucose monomers.

[0063] The polyα-1,6-glucan ether compounds disclosed herein are referred to as "cationic" ether compounds due to the presence of one or more positively charged organic groups. The terms "positively charged organic group," "positively charged ionic group," and "cationic group" are used interchangeably herein. Positively charged groups include cations (positively charged ions). Examples of positively charged groups include substituted ammonium groups, carbocation groups, and acylcation groups.

[0064] The cationic poly-1,6-glucan ether compounds disclosed herein comprise water-soluble poly-1,6-glucan comprising a backbone of glucose monomer units, wherein at least 40% of the glucose monomer units are linked via α-1,6-glycosidic bonds, and optionally at least 3% of the backbone glucose monomer units are branched via α-1,2 and / or α-1,3-glycosidic bonds. The poly-1,6-glucan is substituted (preferably randomly substituted) with positively charged organic groups on the polysaccharide backbone and / or on any branches that may be present, such that the poly-1,6-glucan ether compounds comprise unsubstituted and substituted α-D-glucose rings. As used herein, the term "randomly substituted" means that the substituents on the glucose ring in a randomly substituted polysaccharide appear in a non-repeating or random manner. In other words, the substitutions on the substituted glucose rings can be the same as or different from the substitutions on the second substituted glucose rings in the polysaccharide [i.e., substituents on different atoms in the glucose rings of the polysaccharide (which can be the same or different)], resulting in no pattern of overall substitution on the polymer. Furthermore, the substituted glucose rings exist randomly within the polysaccharide (i.e., there is no pattern between substituted and unsubstituted glucose rings within the polysaccharide).

[0065] In some embodiments, depending on the reaction conditions and the specific substituents used to derive the poly-α-1,6-glucan, the glucose monomers of the polymer backbone may be disproportionately substituted relative to the glucose monomers of any branch (including branches via α-1,2 and / or α-1,3 bonds, if present). In another embodiment, the glucose monomers of branches (including branches via α-1,2 and / or α-1,3 bonds, if present) may be disproportionately substituted relative to the glucose monomers of the polymer backbone. In some embodiments, depending on the reaction conditions and the specific substituents used, the substitution of the poly-α-1,6-glucan may occur in a block manner.

[0066] In some embodiments, depending on the reaction conditions and the specific substituents used to derive the poly-α-1,6-glucan, the glucose monomers of the polymer backbone may be disproportionately substituted relative to the glucose monomers of any branch (including branches via α-1,2 and / or α-1,3 bonds, if present). In another embodiment, the glucose monomers of branches (including branches via α-1,2 and / or α-1,3 bonds, if present) may be disproportionately substituted relative to the glucose monomers of the polymer backbone. In some embodiments, depending on the reaction conditions and the specific substituents used, the substitution of the poly-α-1,6-glucan may occur in a block manner.

[0067] The poly(α-1,6-glucan ether) compounds disclosed herein contain positively charged organic groups and have attracted attention due to their solubility properties in water, which can be modified by appropriately selecting substituents and the degree of substitution. Compositions containing poly(α-1,6-glucan ether) compounds can be used in a wide range of applications, including laundry, cleaning, food, cosmetics, industrial, membrane, and paper production. Poly(α-1,6-glucan ether) compounds having a solubility in water greater than 0.1 wt% can be used as rheology modifiers, emulsion stabilizers, and dispersants in cleaning, detergent, cosmetic, food, cement, membrane, and paper production, where these products are primarily water-based formulations and optical transparency is desirable. Poly(α-1,6-glucan) ether compounds having a solubility of less than 0.1 wt% in water can be used as rheology modifiers, emulsion stabilizers, and dispersants in cleaning, detergent, cosmetic, food, cement, film, and paper production, wherein these products are formulations containing organic solvents to dissolve or disperse poly(α-1,6-glucan) derivatives. In one embodiment, the poly(α-1,6-glucan) ether compound has a DoS of about 0.001 to about 1.5 and a solubility of 0.1 wt% or higher in deionized water at 25°C. In another embodiment, the poly(α-1,6-glucan) ether compound has a DoS of about 0.05 to about 1.5 and a solubility of less than 0.1 wt% in water at pH 7 at 25°C.

[0068] The cationic poly(α-1,6-glucan ether) compounds disclosed herein may be included in personal care products, pharmaceutical products, household products, or industrial products in amounts of one or more of the following physical properties to provide the desired degree of the product: for example, thickening, freeze / thaw stability, lubricity, moisture retention and release, texture, consistency, shape retention, emulsification, adhesion, suspension, dispersion, and gelation. Examples of concentrations or amounts of the poly(α-1,6-glucan ether) compounds disclosed herein in a product, based on weight, may be about 0.01-10 wt%, 0.1-0.8 wt%, 0.1-1 wt%, 0.1-2 wt%, 0.1-3 wt%, 0.1-5 wt%, 1-2 wt%, 1.5-2.5 wt%, 2.0 wt%, 0.1-4 wt%, 0.1-5 wt%, or 0.1-10 wt%.

[0069] For example, aqueous compositions containing the cationic poly-1,6-glucan ether compound described herein may have a viscosity of about, or at least about, 5, 10, 100, 200, 300, 400, 500, 600, 700, 1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, 10000, 15000, 1-1500, 100-1000, 100-500, 100-300, or 100-200 centipoise (cps). For example, viscosity may be measured at any temperature between about 3°C ​​and about 80°C (e.g., 4°C-30°C, 15°C-30°C, 15°C-25°C), as with aqueous compositions. Viscosity is typically measured at atmospheric pressure (about 760 Torr) or at ±10% of that pressure. Viscosity can be measured using, for example, a viscometer or rheometer, and can optionally be measured in, for example, at values ​​of about 0.1, 0.5, 1.0, 5, 10, 50, 100, 500, 1000, 0.1-500, 0.1-100, 1.0-500, 1.0-1000, or 1.0-100s. -1 The shear rate (rotational shear rate) was measured at (1 / s).

[0070] For example, compositions comprising cationic poly(α-1,6-glucan ether) compounds as disclosed herein may have a turbidity of about, or less than, about 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 0.5-20, 0.5-15, 0.5-10, 0.5-5, 0.5-3, 1-20, 1-15, 1-10, 1-5, or 1-3 NTU (turbidimetric turbidity units). For example, the turbidity may be measured at any temperature between about 3°C ​​and about 80°C (e.g., 4°C-30°C, 15°C-30°C, 15°C-25°C) using an aqueous composition. Any suitable method may be used to measure the turbidity, such as... Progress in Filtration and Separation [Advances in Filtering and Separation] The methods disclosed in (Version: 1, Chapter 16. Turbidity: Measurement of Filtrate and Supernatant Quality?, Publisher: Academic Press, Editor: E.T. Sarleton, July 2015) are incorporated herein by reference.

[0071] Household and / or industrial products described herein may take the form of, for example, the following: drywall tape bonding compounds; mortars; slurries; cement plaster; spray plaster; cement mortar; adhesives; pastes; wall / ceiling conditioners; adhesives and processing aids for tape casting, extrusion molding, injection molding, and ceramics; spray adhesives and suspending / dispersing aids for pesticides, herbicides, and fertilizers; fabric care products, such as fabric softeners and laundry detergents; hard surface cleaners; air fresheners; polymer emulsions; gels, such as water-based gels; surfactant solutions; coatings, such as water-based coatings; protective coatings; adhesives; sealants and caulking agents; inks, such as water-based inks; metalworking fluids; emulsion-based metal cleaners for electroplating, phosphating, galvanizing, and / or general metal cleaning operations; hydraulic fluids (e.g., those used for fracturing in downhole operations); and aqueous mineral slurries.

[0072] The terms “poly-α-1,6-glucan” and “dextran” are used interchangeably herein. Dextran represents a series of complex branched α-glucans that typically comprise chains of α-1,6-linked glucose monomers with periodic side chains (branches) linked to the straight chain via α-1,3-bonds (Ioan et al., Macromolecules 33:5730-5739) and / or α-1,2-bonds. The production of dextran for the production of the poly-α-1,6-glucan derivatives described herein can be carried out, for example, by fermenting sucrose with bacteria (e.g., species of Leuconostoc or Streptococcus), where sucrose serves as a source of glucose for dextran polymerization (Naessens et al., J. Chem. Technol. Biotechnol. 80:845-860; Sarwat et al., Int. J. Biol. Sci. 4:379-386; Onilude et al., Int. Food Res. J. 20:1645-1651). Alternatively, poly-α-1,6-glucan can be prepared using glucosyltransferases (dextrose sucrase), such as (but not limited to) GTF1729, GTF1428, GTF5604, GTF6831, GTF8845, GTF0088 and GTF8117 as described in International Patent Application Publication Nos. WO 2015 / 183714 or WO 2017 / 091533, or U.S. Patent Application Publication Nos. 2017 / 0218093 or 2018 / 0282385 (all of which are incorporated herein by reference).

[0073] In some embodiments, the cationic poly-α-1,6-glucan ether compound comprises a backbone of glucose monomer units, wherein 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, 99%, 99.5%, or 100% of the glucose monomer units are linked via α-1,6-glycosidic bonds. The backbone of the cationic poly-α-1,6-glucan ether compound may comprise 0.5%, 1%, 2%, 3%, 4%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, or 60% of glucose monomer units linked via α-1,2, α-1,3, and / or α-1,4 glycosidic bonds. In some respects, poly-α-1,6-glucan derivatives contain a linear (unbranched) backbone.

[0074] The dextran “long chain” may contain “substantially (or predominantly) α-1,6-glycosidic bonds,” meaning that in some respects they may have at least about 98.0% α-1,6-glycosidic bonds. In some respects, the dextran of this paper may contain a “branched structure” (branched structure, dendritic). It is envisioned that in this structure, the long chain may branch from other long chains in an iterative manner (e.g., a long chain may be a branch from another long chain, which in turn may itself be a branch from another long chain, etc.). It is envisioned that the long chains in this structure may be “similar in length,” meaning that at least 70% of the length (DP [degree of polymerization]) of all long chains in the branched structure is within ±30% of the average length of all long chains in the branched structure.

[0075] In some embodiments, dextran may also comprise “short chains” branching from the long chain, typically one to three glucose monomers in length, and typically comprising less than about 10% of all glucose monomers of the dextran polymer. Typically, such short chains contain α-1,2-, α-1,3-, and / or α-1,4-glycosidic bonds (it should be understood that, in some aspects, a small percentage of such non-α-1,6-bonds may also be present in the long chain). In some embodiments, the branched poly-1,6-glucan is enzymatically produced according to procedures in WO2015 / 183714 and WO 2017 / 091533 (both incorporated herein by reference), wherein, for example, α-1,2-branching enzymes such as GTFJ18T1 or GTF9905 may be added during or after the production of the dextran polymer (polysaccharide). In some embodiments, any other enzymes known to produce α-1,2-branching may be added. Poly-α-1,6-glucan having α-1,3-branching can be prepared as disclosed in Vuillemin et al. (2016, J. Biol Chem. 291:7687-7702), International Patent Application Publication No. WO 2021 / 007264, or U.S. Application No. 62 / 871,796 (as originally filed) (which is incorporated herein by reference). In such embodiments, the poly-α-1,6-glucan or poly-α-1,6-glucan derivative has a degree of branching of less than or equal to 50%, 40%, 30%, 20%, 10%, or 5% (or any integer value between 5% and 50%) of short branches, such as α-1,2-branching or 1,3-branching. In one embodiment, the poly-α-1,6-glucan or poly-α-1,6-glucan derivative has a degree of α-1,2-branching of less than 50%. In another embodiment, the poly-α-1,6-glucan or poly-α-1,6-glucan derivative has at least 3% α-1,2-branching. In one embodiment, at least 3% of the main chain glucose monomer units of the poly-α-1,6-glucan derivative are branched via α-1,2- or α-1,3-glycosidic bonds. In one embodiment, the poly-α-1,6-glucan or poly-α-1,6-glucan derivative comprises a main chain of glucose monomer units, wherein greater than or equal to 40% of these glucose monomer units are linked via α-1,6-glycosidic bonds. In one embodiment, the poly-α-1,6-glucan derivative comprises a main chain of glucose monomer units, wherein greater than or equal to 40% of these glucose monomer units are linked via α-1,6-glycosidic bonds, and at least 3% of these glucose monomer units are branched via α-1,2- or α-1,3-glycosidic bonds.In one embodiment, the poly-α-1,6-glucan derivative comprises a backbone of glucose monomer units, wherein greater than or equal to 40% of these glucose monomer units are linked via α-1,6-glycosidic bonds, and at least 3% of these glucose monomer units are branched via α-1,2 bonds. In one embodiment, the poly-α-1,6-glucan derivative comprises a backbone of glucose monomer units, wherein greater than or equal to 40% of these glucose monomer units are linked via α-1,6-glycosidic bonds, and at least 3% of these glucose monomer units are branched via α-1,3 bonds. In one embodiment, the poly-α-1,6-glucan or the poly-α-1,6-glucan derivative is linear or predominantly linear. In some respects, about, at least about, or less than about 1%, 2%, 3%, 4%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 20%-50%, 20%-60%, 30%-50%, 30%-60%, or 35%-45% of the main chain glucose monomer units of the poly-α-1,6-glucan or its derivatives disclosed herein may be branched via α-1,2 and / or α-1,3 glycosidic bonds. In some respects, as disclosed herein, about, at least about, or less than about 1%, 2%, 2.5%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 10%-25%, 10%-30%, 15%-25%, 15%-30%, or 17%-23% of all glycosidic bonds in α-1,2- and / or α-1,3-branched poly-α-1,6-glucan or its derivatives are α-1,2- and / or α-1,3-glycosidic bonds. The amount of α-1,2- or α-1,3-branched poly-α-1,6-glucan or its derivatives can be determined by NMR methods, as disclosed in the examples.

[0076] In one embodiment, the poly-α-1,6-glucan ether compound has less than 50% α-1,2-branching. In another embodiment, the poly-α-1,6-glucan ether compound has at least 3% α-1,2-branching. In one embodiment, about 3% to about 50% of the main-chain glucose monomer units of the poly-α-1,6-glucan ether compound are branched via α-1,2 or α-1,3 glycosidic bonds. In yet another embodiment, about 3% to about 35% of the main-chain glucose monomer units of the poly-α-1,6-glucan ether compound are branched via α-1,2 or α-1,3 glycosidic bonds.

[0077] In one embodiment, at least 3% of the main chain glucose monomer units of the poly-α-1,6-glucan ether compound are branched via α-1,2- or α-1,3-glycosidic bonds. In one embodiment, the poly-α-1,6-glucan ether compound comprises a main chain of glucose monomer units, wherein greater than or equal to 40% of these glucose monomer units are linked via α-1,6-glycosidic bonds. In one embodiment, the poly-α-1,6-glucan ether compound comprises a main chain of glucose monomer units, wherein greater than or equal to 40% of these glucose monomer units are linked via α-1,6-glycosidic bonds, and at least 3% of these glucose monomer units are branched via α-1,2- or α-1,3-glycosidic bonds. In one embodiment, the poly-α-1,6-glucan ether compound comprises a main chain of glucose monomer units, wherein greater than or equal to 40% of these glucose monomer units are linked via α-1,6-glycosidic bonds, and at least 3% of these glucose monomer units are branched via α-1,2- bonds. In one embodiment, the polyα-1,6-glucan ether compound comprises a backbone of glucose monomer units, wherein greater than or equal to 40% of these glucose monomer units are linked via α-1,6-glycosidic bonds, and at least 3% of these glucose monomer units are branched via α-1,3-bonds. In another embodiment, the polyα-1,6-glucan ether compound comprises a backbone of glucose monomer units, wherein greater than or equal to 40% of these glucose monomer units are linked via α-1,6-glycosidic bonds, and from about 3% to about 50% of these glucose monomer units are branched via α-1,2- or α-1,3-glycosidic bonds. In yet another embodiment, the polyα-1,6-glucan ether compound comprises a backbone of glucose monomer units, wherein greater than or equal to 70% of these glucose monomer units are linked via α-1,6-glycosidic bonds, and from about 3% to about 35% of these glucose monomer units are branched via α-1,2- or α-1,3-glycosidic bonds.

[0078] In one embodiment, the polyα-1,6-glucan ether compound comprises a backbone of glucose monomer units, wherein greater than or equal to 90% of these glucose monomer units are linked via α-1,6-glycosidic bonds. In another embodiment, the polyα-1,6-glucan ether compound comprises a backbone of glucose monomer units, wherein greater than or equal to 90% of these glucose monomer units are linked via α-1,6-glycosidic bonds, and at least 3% of these glucose monomer units are branched via α-1,2- or α-1,3-glycosidic bonds. In yet another embodiment, the polyα-1,6-glucan ether compound comprises a backbone of glucose monomer units, wherein greater than or equal to 90% of these glucose monomer units are linked via α-1,6-glycosidic bonds, and at least 3% of these glucose monomer units are branched via α-1,2-bonds. In one embodiment, the polyα-1,6-glucan ether compound comprises a backbone of glucose monomer units, wherein greater than or equal to 90% of these glucose monomer units are linked via α-1,6-glycosidic bonds, and at least 3% of these glucose monomer units are branched via α-1,3-bonds. In another embodiment, the polyα-1,6-glucan ether compound comprises a backbone of glucose monomer units, wherein greater than or equal to 90% of these glucose monomer units are linked via α-1,6-glycosidic bonds, and from about 3% to about 50% of these glucose monomer units are branched via α-1,2- or α-1,3-glycosidic bonds. In yet another embodiment, the polyα-1,6-glucan ether compound comprises a backbone of glucose monomer units, wherein greater than or equal to 90% of these glucose monomer units are linked via α-1,6-glycosidic bonds, and from about 3% to about 35% of these glucose monomer units are branched via α-1,2- or α-1,3-glycosidic bonds.

[0079] The poly-α-1,6-glucan and poly-α-1,6-glucan derivatives disclosed herein may have a number-average degree of polymerization (DPn) or weight-average degree of polymerization (DPw) in the range of 5 to 6000. In some embodiments, DPn or DPw may be in the range of 5 to 100, 5 to 500, 5 to 1000, 5 to 1500, 5 to 2000, 5 to 2500, 5 to 3000, 5 to 4000, 5 to 5000, or 5 to 6000. In some embodiments, DPn or DPw may be in the range of 50 to 500, 50 to 1000, 50 to 1500, 50 to 2000, 50 to 3000, 50 to 4000, 50 to 5000, or 50 to 6000. In some embodiments, DPn or DPw may be in the range of 400 to 6000, 400 to 5000, 400 to 4000, 400 to 3000, 400 to 2000, or 400 to 1000.In some embodiments, DPn or DPw can be about, at least about, or less than about 5, 10, 25, 50, 100, 250, 500, 1000, 1500, 2000, 2500, 3000, 4000, 5000, 6000, 5-100, 5-250, 5-500, 5-1000, 5-1500, 5-2000, 5-2500, 5-3000, 5-4000, 5-5000, 5-6000, 10-100, 10-250, 10-500, 10-1000, 10-1500, 10-2000, 10-2500, 10-3000, 10-4000, 10-5000, 1 0-6000, 25-100, 25-250, 25-500, 25-1000, 25-1500, 25-2000, 25-2500, 25-3000, 25-4000, 25-5000, 25-6000, 50-100, 50-250, 50-500, 50-1000, 50-1500, 50-2000, 50-2500, 50-3000, 50-4000, 50-5000, 50-6000, 100-100, 100-250, 100-400, 100-500, 100-1000, 100-1500, 100-2000, 100-2500 100-3000, 100-4000, 100-5000, 100-6000, 250-500, 250-1000, 250-1500, 250-2000, 250-2500, 250-3000, 250-4000, 250-5000, 250-6000, 300-2800, 300-3000, 350-2800, 350-3000, 500-1000, 500-1500, 500-2000, 500-2500, 500-2800, 500-3000, 500-4000, 500-5000, 500-6000, 600-1550, 6 00-1850, 600-2000, 600-2500, 600-3000, 750-1000, 750-1250, 750-1500, 750-2000, 750-2500, 750-3000, 750-4000, 750-5000, 750-6000, 900-1250, 900-1500, 900-2000, 1000-1250, 1000-1400, 1000-1500, 1000-2000, 1000-2500, 1000-3000, 1000-4000, 1000-5000, 1000-6000, or 1100-1300.

[0080] As used herein, the term "degree of substitution" (DoS) refers to the average number of substituted hydroxyl groups in each monomer unit (glucose) of a cationic poly-α-1,6-glucan ether compound, which includes monomer units within the main chain and any α-1,2 or α-1,3 branches that may be present. Since there are at most three hydroxyl groups in the glucose monomer unit of the poly-α-1,6-glucan polymer, the total degree of substitution can be no higher than 3.0. Those skilled in the art will understand that since cationic poly-α-1,6-glucan ether compounds as disclosed herein can have a degree of substitution between about 0.001 and about 3.0, the substituents on the polysaccharide are not limited to hydroxyl groups. The degree of substitution of a poly-α-1,6-glucan ether compound can be expressed based on specific substituents or based on the total degree of substitution (i.e., the sum of the DoS of each different substituent in the ether compound as defined herein). As used herein, when the degree of substitution is not expressed according to a specific substituent or substituent type, it refers to the total degree of substitution of the cationic poly-α-1,6-glucan ether compound. A target DoS can be selected to provide the desired solubility and properties of compositions containing the cationic poly-α-1,6-glucan ether compound in the specific application of interest.

[0081] The cationic polyα-1,6-glucan ether compounds disclosed herein have a DoS of about 0.001 to about 3.0 with respect to the positively charged organic groups. In another embodiment, the cationic polyα-1,6-glucan ether has a DoS of about 0.01 to about 1.5. In another embodiment, the polyα-1,6-glucan ether has a DoS of about 0.01 to about 0.7. In yet another embodiment, the polyα-1,6-glucan ether has a DoS of about 0.01 to about 0.4. In yet another embodiment, the polyα-1,6-glucan ether has a DoS of about 0.01 to about 0.2.In yet another embodiment, the DoS of the polyα-1,6-glucan ether compound may be about, at least about, or less than about 0.001, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8. 2.9, 3.0, 0.01-1.5, 0.01-1.0, 0.01-0.8, 0.01-0.6, 0.01-0.5, 0.01-0.25, 0.01-0.2, 0.01-0.15, 0.01-0.12, 0.01-0.1, 0.01-0.08, 0.02-1.5, 0.02-1.0, 0.02-0.8, 0.02-0.6, 0.02-0.5, 0.02-0.25, 0.02-0.2, 0.02-0.15, 0.02-0.12, 0.02-0.1, 0.02-0.08, 0 .03-1.5, .03-1.0, 0.03-0.8, 0.03-0.7, 0.03-0.6, 0.03-0.5, 0.03-0.25, 0.03-0.2, 0.03-0.15, 0.03-0.12, 0.03-0.1, 0.03-0.08, 0.04-1.5, 0.04-1.0, 0.04-0.8, 0.04-0.7, 0.04-0.6, 0.04-0.5, 0.04-0.25, 0.04-0.2, 0.04-0.15, 0.04-0.12, 0.04-0.1, 0 0.04-0.08, 0.05-0.6, 0.05-0.5, 0.06-1.5, 0.06-1.0, 0.06-0.8, 0.06-0.7, 0.06-0.6, 0.06-0.5, 0.06-0.25, 0.06-0.2, 0.06-0.15, 0.06-0.12, 0.06-0.1, 0.06-0.08, 0.2-0.8, 0.2-0.6, 0.2-0.5, 0.3-0.8, 0.3-0.6, 0.3-0.5, or 0.4-0.6, or any value between 0.001 and 3.0.

[0082] The polyα-1,6-glucan ether compounds disclosed herein include:

[0083] (i) a poly-α-1,6-glucan substituted with at least one positively charged organic group;

[0084] (ii) a weight-average degree of polymerization of at least 5; and

[0085] (iii) A degree of substitution of about 0.001 to about 3.0;

[0086] The poly-α-1,6-glucan comprises a backbone of glucose monomer units, wherein at least 40% of these glucose monomer units are linked by α-1,6-glycosidic bonds, and optionally at least 3% of the backbone glucose monomer units are branched by α-1,2 and / or α-1,3-glycosidic bonds.

[0087] A positively charged organic group comprises a chain of one or more carbon atoms having one or more hydrogen atoms substituted with another atom or functional group, wherein one or more of the substitutions are with a positively charged group. As used herein, the term "chain" includes straight chains, branched chains, and cyclic arrangements of carbon atoms, as well as combinations thereof.

[0088] Poly-α-1,6-glucan derivatives comprise poly-α-1,6-glucan in which at least one positively charged organic group is substituted on the polysaccharide backbone and / or on one or more optional branches. When substitution occurs on glucose monomers contained in the backbone, the polysaccharide is derived at the 2, 3, and / or 4 glucose carbon positions by an organic group as defined herein, which is linked to the polysaccharide via an ether (-O-) bond to replace the hydroxyl groups originally present in the underived (unsubstituted) poly-α-1,6-glucan. When substitution occurs on glucose monomers contained in branches, the polysaccharide is derived at the 2, 3, 4, or 6 glucose carbon positions by a positively charged organic group as defined herein, which is linked to the polysaccharide via an ether (-O-) bond.

[0089] As disclosed in this paper, the polyα-1,6-glucan ether compounds contain the substructure -C G -OC R -and is called a dextran "ether", in which "-C" G -” represents the carbon atom of the glucose monomer unit in the polyα-1,6-glucan ether compound, and where “-C R -"Contains positively charged organic groups. Cationic poly-α-1,6-glucan monoethers contain one type of positively charged organic group. Cationic poly-α-1,6-glucan mixed ethers contain two or more types of positively charged organic groups. Mixtures of cationic poly-α-1,6-glucan ether compounds may also be used.

[0090] The compositions disclosed herein may comprise, or consist substantially of, one or more cationic poly(α-1,6-glucan ether) compounds as disclosed herein. In one embodiment, the composition may comprise one poly(α-1,6-glucan ether) compound. In another embodiment, the composition may comprise two or more poly(α-1,6-glucan ether) compounds, for example, wherein the positively charged organic groups are different.

[0091] As used herein, a “positively charged organic group” refers to a chain of one or more carbon atoms having one or more hydrogen atoms substituted with another atom or functional group, wherein one or more of the substitutions are positively charged groups. Positively charged groups are typically bonded to the terminal carbon atom of the carbon chain. Positively charged organic groups are considered to have a net positive charge because they contain one or more positively charged groups and contain cations (positively charged ions). Positively charged organic groups or compounds typically have more protons than electrons and are repelled by other positively charged substances but attracted by negatively charged substances. Examples of positively charged groups include substituted ammonium groups. In some embodiments, a positively charged organic group may have additional substitutions, such as being substituted with one or more hydroxyl groups, oxygen atoms (forming ketone groups), alkyl groups, and / or at least one other positively charged group.

[0092] In one embodiment, the positively charged organic group comprises a substituted ammonium group that can be represented by structure II:

[0093]

[0094] In structure II, R2, R3, and R4 each independently represent a hydrogen atom, an alkyl group, or a C6-C group. 24 Aryl group. The carbon atom (C) shown in Structure II is part of the carbon chain of a positively charged organic group. The carbon atom is either directly etherified to the glucose monomer of poly-α-1,6-glucan, or etherified to part of a chain of two or more carbon atoms of the glucose monomer of poly-α-1,6-glucan. The carbon atom shown in Structure II can be -CH2-, -CH- (where one H is replaced by another group such as a hydroxyl group), or -C- (where both H are replaced). Although the positively charged organic groups herein typically contain one type of substituted ammonium group, positively charged organic groups can contain, for example, two or more different substituted ammonium groups.

[0095] In some embodiments, the alkyl group may be C1-C2. 30Alkyl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, nonadecanyl, icosyl, heptadecyl, dodecyl, tridecyl, tetradecyl, C 25 C 26 C 27 C 28 C 29 or C 30 Alkyl groups. In some embodiments, the alkyl group may be C1-C60. 24 alkyl groups, or C1-C 18 Or C6-C 20 alkyl groups, or C 10 -C 16 Alkyl groups, or C1-C4 alkyl groups. When a positively charged organic group contains a substituted ammonium group having two or more alkyl groups, each alkyl group may be the same as or different from the others.

[0096] In some embodiments, the aryl group may be a C6-C group optionally substituted with an alkyl substituent. 24 Aryl group. In some embodiments, the aryl group may be a C group optionally substituted with an alkyl substituent. 12 -C 24 aryl group, or C6-C group optionally substituted with alkyl substituents. 18 Aryl groups. In some respects, positively charged organic groups can contain heteroaryl groups, such as imidazole groups.

[0097] The substituted ammonium group can be a "primary ammonium group," a "secondary ammonium group," a "tertiary ammonium group," or a "quaternary ammonium group," depending on the composition of R2, R3, and R4 in structure II. A primary ammonium group is an ammonium group represented by structure II, where each of R2, R3, and R4 is a hydrogen atom (i.e., -C-NH3). + ).

[0098] The secondary ammonium group is an ammonium group represented by structure II, wherein each of R2 and R3 is a hydrogen atom, and R4 is C1-C. 30 alkyl groups or C6-C 24Aryl group. "Secondary ammonium poly-α-1,6-glucan ether compounds" contain a positively charged organic group having a monoalkylammonium group. Secondary ammonium poly-α-1,6-glucan ether compounds can be abbreviated as monoalkylammonium poly-α-1,6-glucan ethers, such as monomethyl-, monoethyl-, monopropyl-, monobutyl-, monopentyl-, monohexyl-, monoheptyl-, monooctyl-, monononyl-, monodecyl-, monoundecyl-, monododecyl-, monotridecyl-, monotetradecyl-, monopentadecanyl-, monohexadecyl-, monoheptadecyl-, or monooctadecyl-ammonium poly-α-1,6-glucan ethers. These polyα-1,6-glucan ether compounds can also be referred to as methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, heptyl-, octyl-, nonyl-, decyl-, undecyl-, dodecyl-, tridecyl-, tetradecyl-, pentadecyl-, hexadecyl-, heptadecanyl-, or octadecyl-ammonium polyα-1,6-glucan ether compounds, respectively. The octadecylammonium group is an example of a monoalkylammonium group, wherein each of R2 and R3 is a hydrogen atom, and R4 is an octadecyl group. It should be understood that the second member implied by "secondary" in the above nomenclature (i.e., R1) is a chain of one or more carbons of a positively charged organic group attached to the glucose monomer of polyα-1,6-glucan.

[0099] The tertiary ammonium group is an ammonium group represented by structure II, where R2 is a hydrogen atom and each of R3 and R4 is independently C1-C. 24 alkyl groups or C6-C 24 Aryl group. Alkyl groups may be the same or different. "Tertiary ammonium poly-α-1,6-glucan ether compound" contains a positively charged organic group having a dialkylammonium group. Tertiary ammonium poly-α-1,6-glucan ether compound can be abbreviated as dialkylammonium poly-α-1,6-glucan ether, such as dimethyl-, diethyl-, dipropyl-, dibutyl-, dipentyl-, dihexyl-, diheptyl-, dioctyl-, dinonyl-, didecyl-, diundecyl-, didodecyl-, ditridecyl-, ditetradecyl-, dipentadecanyl-, dipentadecanyl-, dihexadecyl-, diheptadecyl-, or dioctadecyl-ammonium poly-α-1,6-glucan ether. The didodecylammonium group is an example of a dialkylammonium group, wherein R2 is a hydrogen atom and each of R3 and R4 is a dodecyl group. It should be understood that the third member implied by "tertiary" in the above nomenclature (i.e., R1) is a chain of one or more carbons of a positively charged organic group of a glucose monomer of poly-α-1,6-glucan.

[0100] The quaternary ammonium group is an ammonium group represented by structure II, wherein each of R2, R3, and R4 is independently C1-C. 30 alkyl groups or C6-C 24Aryl groups (i.e., none of R2, R3, and R4 are hydrogen atoms).

[0101] In one embodiment, the quaternary ammonium polyα-1,6-glucan ether compound may contain trialkylammonium groups, wherein each of R2, R3, and R4 is independently C1-C2. 30 Alkyl groups. Alkyl groups can be all the same, or two of the alkyl groups can be the same and one different from the others, or all three alkyl groups can be different from each other. Quaternary ammonium polyα-1,6-glucan ether compounds can be abbreviated as trialkylammonium polyα-1,6-glucan ethers, such as trimethyl-, triethyl-, tripropyl-, tributyl-, tripentyl-, trihexyl-, triheptyl-, trioctyl-, trinonyl-, tridecyl-, triundecyl-, tridodecyl-, tritetradecyl-, tripentadecanyl-, tripentadecanyl-, trihexadecyl-, trihexadecyl-, triheptadecyl-, or trioctadecyl-ammonium polyα-1,6-glucan ethers. It should be understood that the fourth member implied by "quaternary" in this nomenclature (i.e., R1) is a chain of one or more carbons of a positively charged organic group attached to the glucose monomer of polyα-1,6-glucan. The trimethylammonium group is an example of a trialkylammonium group, wherein each of R2, R3 and R4 is a methyl group.

[0102] In another embodiment, the positively charged organic group comprising the substituted ammonium group represented by structure II may allow each of R2, R3, and R4 to independently represent a hydrogen atom or an aryl group (such as a phenyl or naphthyl group), or an aralkyl group (such as a benzyl group), or a cycloalkyl group (such as a cyclohexyl or cyclopentyl group). Each of R2, R3, and R4 may further comprise an amino group or a hydroxyl group.

[0103] The positively charged organic group with substituted ammonium groups is a substituent on one or more carbon atoms of the chain of the glucose monomer of α-1,6-glucan, which is attached to the ether. The carbon chain can contain from one to 30 carbon atoms. In one embodiment, the carbon chain can be a straight chain. Examples of straight-chain carbon chains include, for example, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH 2( CH2)2CH2-、-CH2 ( CH2)3CH2-、-CH 2( CH2)4CH2-、-CH 2( CH2)5CH2-、-CH 2( CH2)6CH2-、-CH 2( CH2)7CH2-、-CH 2( CH2)8CH2-、-CH 2( CH2)9CH2-, and -CH 2( CH2)10 CH2-; longer carbon chains may also be used if desired. In another embodiment, the carbon chain may be branched, meaning that the carbon chain is substituted with one or more alkyl groups such as methyl, ethyl, propyl, or butyl groups. The substitution point may be anywhere along the carbon chain. Examples of branched carbon chains include -CH(CH3)CH2-, -CH(CH3)CH2CH2-, -CH2CH(CH3)CH2-, -CH(CH2CH3)CH2-, -CH(CH2CH3)CH2CH2-, -CH2CH(CH2CH3)CH2-, -CH(CH2CH2CH3)CH2-, -CH(CH2CH2CH3)CH2-, and -CH2CH(CH2CH2CH3)CH2-; longer branched carbon chains may also be used if desired. When the positively charged group is a substituted ammonium group, the first carbon atom in the chain is etherified to the glucose monomer of poly-α-1,6-glucan, and the last carbon atom of the chain in each of these examples is represented by C in structure II.

[0104] In another embodiment, one or more carbon chains are further substituted with one or more hydroxyl groups. Examples of carbon chains having one or more substituted hydroxyl groups include hydroxyalkyl (e.g., hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, hydroxyoctyl) groups and dihydroxyalkyl (e.g., dihydroxyethyl, dihydroxypropyl, dihydroxybutyl, dihydroxypentyl, dihydroxyhexyl, dihydroxyheptyl, dihydroxyoctyl) groups. Examples of hydroxyalkyl and dihydroxyalkyl (diol) carbon chains include -CH(OH)-, -CH(OH)CH2-, -C(OH)2CH2-, -CH2CH(OH)CH2-, -CH(OH)CH2CH2-, -CH(OH)CH(OH)CH2-, -CH2CH2CH(OH)CH2-, -CH2CH(OH)CH2CH2-, -CH(OH)CH2CH2CH2-, -CH2CH(OH)CH(OH)CH2-, -CH(OH)CH(OH)CH2CH2-, and -CH(OH)CH2CH(OH)CH2-. In each of these examples, the first carbon atom of the chain is ether-linked to the glucose monomer of the poly-α-1,6-glucan, and the last carbon atom of the chain is linked to a positively charged group. In the case where the positively charged group is a substituted ammonium group, the last carbon atom of the chain in each of these examples is represented by C in structure II.

[0105] In some respects, the substituted ammonium group of the positively charged organic group is a substituent on the polyether chain of the glucose monomer of α-1,6-glucan. The polyether chain may contain, for example, repeating units such as (-CH2CH2O-), (-CH2CH(CH3)O-), or mixtures thereof. The total number of repeating units in the polyether chain herein may range from, for example, 2 to 100 (e.g., 4-100).

[0106] An example of a quaternary ammonium poly-α-1,6-glucan ether compound is trimethylammonium hydroxypropyl poly-α-1,6-glucan. The positively charged organic groups of this ether compound can be represented by the following structure:

[0107]

[0108] Each of R2, R3, and R4 is a methyl group. The above structure is an example of a quaternary ammonium hydroxypropyl group.

[0109] In cases where the carbon chain of a positively charged organic group has substitutions other than those made with a positively charged group, such additional substitutions can be made with one or more hydroxyl groups, oxygen atoms (thus forming aldehyde or ketone groups), alkyl groups (e.g., methyl, ethyl, propyl, butyl), and / or other positively charged groups. The positively charged groups are typically bonded to the terminal carbon atom of the carbon chain. The positively charged groups may also contain one or more imidazoline rings.

[0110] The cationic poly(α-1,6-glucan ether) compounds disclosed herein are salts. The counter ion of the positively charged organic group can be any anion, including acetate, borate, bromate, bromide, carbonate, chlorate, chloride, chlorite, dihydrogen phosphate, fluoride, bicarbonate, hydrogen phosphate, bisulfate, hydrogen sulfide, bisulfite, hydroxide, hypochlorite, iodate, iodide, nitrate, nitride, oxalate, oxide, perchlorate, permanganate, phosphate, phosphide, phosphite, silicate, stannate, stansite, sulfate, sulfide, sulfite, tartrate, or thiocyanate anions. In aqueous solution, the poly(α-1,6-glucan ether) compounds are in cationic form. The positively charged organic groups of cationic poly-α-1,6-glucan ether compounds can interact with salt anions (such as those listed above in this article) that can be present in aqueous solutions.

[0111] The poly-α-1,6-glucan ether compounds described herein may contain, for example, one type of etherified cationic organic group. In some aspects, the poly-α-1,6-glucan ether compounds may contain two or more different types of etherified and / or otherwise linked organic groups, wherein at least one of the organic groups is an ether-linked cationic group. Examples of other types of groups include nonionic ether-linked organic groups and anionic ether-linked organic groups. The poly-α-1,6-glucan ether compounds disclosed herein may optionally be characterized by a cationic charge density (CCD). CCD may be expressed as milliequivalents of charge per gram of compound (meq / g) and may be determined according to examples (hereinafter). The poly-α-1,6-glucan ether compounds may be characterized by, for example, having a CCD of about 0.05-12, 0.1-8, 0.1-4, 0.1-3, or 0.1-2.6 meq / g. In some aspects, the polyα-1,6-glucan ether compound may have a DoS of less than about 1.0, 0.5, 0.2, or 0.1 with respect to a non-cationic substitution, or may not have a non-cationic substitution. In some aspects, the polyα-1,6-glucan ether compound may have a DoS of less than about 1.0, 0.5, 0.2, or 0.1 with respect to a hydrophobic substitution (e.g., benzyl substitution), or may not have a hydrophobic substitution (e.g., no benzyl substitution).

[0112] In one embodiment, the poly-α-1,6-glucan ether compound comprises a positively charged organic group, wherein the positively charged organic group comprises a substituted ammonium group. In one embodiment, from about 0.5% to about 50% of the main chain glucose monomer units of the ether compound are branched via α-1,2 glycosidic bonds, and the positively charged organic group comprises a substituted ammonium group. In one embodiment, from about 3% to about 35% of the main chain glucose monomer units of the ether compound are branched via α-1,2 glycosidic bonds, and the substituted ammonium group comprises a substituted ammonium group. In one embodiment, from about 0.5% to about 50% of the main chain glucose monomer units of the ether compound are branched via α-1,2 glycosidic bonds, and the substituted ammonium group comprises a trimethylammonium group. In one embodiment, from about 3% to about 35% of the main chain glucose monomer units of the ether compound are branched via α-1,2 glycosidic bonds, and the substituted ammonium group comprises a trimethylammonium group.

[0113] In one embodiment, the poly-α-1,6-glucan ether compound comprises a positively charged organic group, wherein the positively charged organic group comprises a trimethylammonium hydroxyalkyl group. In one embodiment, from about 0.5% to about 50% of the main chain glucose monomer units of the ether compound are branched via α-1,2 glycosidic bonds, and the positively charged organic group comprises a trimethylammonium hydroxyalkyl group. In one embodiment, from about 3% to about 35% of the main chain glucose monomer units of the ether compound are branched via α-1,2 glycosidic bonds, and the positively charged organic group comprises a trimethylammonium hydroxyalkyl group. In one embodiment, from about 0.5% to about 50% of the main chain glucose monomer units of the ether compound are branched via α-1,2 glycosidic bonds, and the trimethylammonium hydroxyalkyl group comprises a trimethylammonium hydroxypropyl group. In one embodiment, from about 3% to about 35% of the main chain glucose monomer units of the ether compound are branched via α-1,2 glycosidic bonds, and the trimethylammonium hydroxyalkyl group comprises a trimethylammonium hydroxypropyl group.

[0114] In one embodiment, the polyα-1,6-glucan ether compound comprises a positively charged organic group, wherein the positively charged organic group comprises a substituted ammonium group, the substituted ammonium group comprising a quaternary ammonium group. In one embodiment, the main chain glucose monomer units of the ether compound are branched from about 0.5% to about 50% via α-1,2 glycosidic bonds, and the quaternary ammonium group comprises at least one C1 to C2 glycosidic group. 18 Alkyl groups. In one embodiment, the main chain glucose monomer units of the ether compound are branched from about 3% to about 35% via α-1,2 glycosidic bonds, and the quaternary ammonium groups comprise at least one C1 to C2 group. 18 Alkyl groups. In one embodiment, from about 0.5% to about 50% of the main chain glucose monomer units of the ether compound are branched via α-1,2 glycosidic bonds, and the quaternary ammonium group comprises at least one C1 to C4 alkyl group. In one embodiment, from about 3% to about 35% of the main chain glucose monomer units of the ether compound are branched via α-1,2 glycosidic bonds, and the quaternary ammonium group comprises at least one C1 to C4 alkyl group. In another embodiment, from about 0.5% to about 50% of the main chain glucose monomer units of the ether compound are branched via α-1,2 glycosidic bonds, and the quaternary ammonium group comprises at least one C1 to C4 alkyl group. 10 To C 16 Alkyl groups. In one embodiment, the main chain glucose monomer units of the ether compound are branched from about 3% to about 35% via α-1,2 glycosidic bonds, and the quaternary ammonium group contains at least one C 10 To C 16 Alkyl groups.

[0115] In one embodiment, the polyα-1,6-glucan ether compound comprises a C 10To C 16 The alkyl group contains a quaternary ammonium group, and the quaternary ammonium group further comprises two methyl groups. In one embodiment, the main chain glucose monomer unit of the ether compound is branched from about 0.5% to about 50% via an α-1,2 glycosidic bond and contains a C 10 To C 16 The quaternary ammonium group of the alkyl group further comprises two methyl groups. In one embodiment, the main chain glucose monomer unit of the ether compound is branched from about 3% to about 35% via an α-1,2 glycosidic bond and contains a C 10 To C 16 The quaternary ammonium group of the alkyl group further includes two methyl groups.

[0116] In one embodiment, the main chain glucose monomer units of the ether compound are branched from about 0.5% to about 50% via α-1,2 glycosidic bonds, and the quaternary ammonium group contains a C 10 An alkyl group and two methyl groups. In one embodiment, the main chain glucose monomer units of the ether compound are branched from about 3% to about 35% via α-1,2 glycosidic bonds, and the quaternary ammonium group contains a C1000 methyl group. 10 Alkyl group and two methyl groups.

[0117] In one embodiment, the polyα-1,6-glucan ether compound comprises a positively charged organic group, wherein the positively charged organic group comprises a quaternary ammonium hydroxyalkyl group. In one embodiment, from about 0.5% to about 50% of the main chain glucose monomer units of the ether compound are branched via α-1,2 glycosidic bonds, and the positively charged organic group comprises a quaternary ammonium hydroxyalkyl group. In one embodiment, from about 3% to about 35% of the main chain glucose monomer units of the ether compound are branched via α-1,2 glycosidic bonds, and the positively charged organic group comprises a quaternary ammonium hydroxyalkyl group. In one embodiment, from about 0.5% to about 50% of the main chain glucose monomer units of the ether compound are branched via α-1,2 glycosidic bonds, and the quaternary ammonium hydroxyalkyl group comprises a quaternary ammonium hydroxymethyl group, a quaternary ammonium hydroxyethyl group, or a quaternary ammonium hydroxypropyl group. In one embodiment, from about 3% to about 35% of the main chain glucose monomer units of the ether compound are branched via α-1,2 glycosidic bonds, and the quaternary ammonium hydroxyalkyl group comprises a quaternary ammonium hydroxymethyl group, a quaternary ammonium hydroxyethyl group, or a quaternary ammonium hydroxypropyl group. In one embodiment, from about 0.5% to about 50% of the main chain glucose monomer units of the ether compound are branched via α-1,2 glycosidic bonds, and the quaternary ammonium hydroxyalkyl group comprises a quaternary ammonium hydroxymethyl group. In one embodiment, from about 3% to about 35% of the main chain glucose monomer units of the ether compound are branched via α-1,2 glycosidic bonds, and the quaternary ammonium hydroxyalkyl group comprises a quaternary ammonium hydroxymethyl group. In one embodiment, from about 0.5% to about 50% of the main chain glucose monomer units of the ether compound are branched via α-1,2 glycosidic bonds, and the quaternary ammonium hydroxyalkyl group comprises a quaternary ammonium hydroxyethyl group. In one embodiment, from about 3% to about 35% of the main chain glucose monomer units of the ether compound are branched via α-1,2 glycosidic bonds, and the quaternary ammonium hydroxyalkyl group comprises a quaternary ammonium hydroxypropyl group. In one embodiment, the main chain glucose monomer units of the ether compound are branched from about 3% to about 35% via α-1,2 glycosidic bonds, and the quaternary ammonium hydroxyalkyl group comprises a quaternary ammonium hydroxypropyl group.

[0118] For example, the polyα-1,6-glucan ether compounds described herein may have a biodegradability of at least 10% after a 90-day test, as determined by a carbon dioxide emission test method (OECD Guideline 301B, incorporated herein by reference, e.g., the test method of the examples below). In some aspects, after a 30, 60, or 90-day test, the biodegradability is about, or at least about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 5%-60%, 5%-80%, 5%-90%, 40%-70%, 50%-70%, 60%- 70%, 40%-75%, 50%-75%, 60%-75%, 70%-75%, 40%-80%, 50%-80%, 60%-80%, 70%-80%, 40%-85%, 50%-85%, 60%-85%, 70%-85%, 40%-90%, 50%-90%, 60%-90%, or 70%-90%, or any value between 5% and 90%.

[0119] Poly(α-1,6-glucan) ether compounds containing positively charged organic groups (such as trimethylammonium groups, substituted ammonium groups, or quaternary ammonium groups) can be prepared using methods similar to those disclosed in published patent application US2016 / 0311935, which is incorporated herein by reference in its entirety. US2016 / 0311935 discloses poly(α-1,3-glucan) ether compounds containing positively charged organic groups and having a degree of substitution of up to about 3.0, and methods for producing such ether compounds. Cationic poly(α-1,6-glucan) ethers can be prepared by contacting poly(α-1,6-glucan) with at least one etherifying agent containing a positively charged organic group under alkaline conditions. In one embodiment, alkaline conditions are prepared by contacting poly(α-1,6-glucan) with a solvent and one or more alkali metal hydroxides to provide a solution or mixture, and then adding at least one etherifying agent. In another embodiment, at least one etherifying agent may be contacted with polyα-1,6-glucan and a solvent, and then an alkali metal hydroxide may be added. Depending on the etherifying agent and / or solvent used, the mixture of polyα-1,6-glucan, etherifying agent, and alkali metal hydroxide may be maintained at ambient temperature or optionally heated to, for example, a temperature between about 25°C and about 200°C. The reaction time for producing polyα-1,6-glucan ethers will vary corresponding to the reaction temperature, with longer reaction times required at lower temperatures and shorter reaction times required at higher temperatures.

[0120] Typically, the solvent contains water. Optionally, additional solvents, such as alcohols like isopropanol, acetone, dioxane, and toluene, can be added to the alkaline solution. Alternatively, solvents such as lithium chloride (LiCl) / N,N-dimethylacetamide (DMAc), SO2 / diethylamine (DEA) / dimethyl sulfoxide (DMSO), LiCl / 1,3-dimethyl-2-imidazolium ketone (DMI), N,N-dimethylformamide (DMF) / N2O4, DMSO / tetrabutylammonium fluoride trihydrate (TBAF), N-methylmorpholine-N-oxide (NMMO), aqueous solutions of Ni(tren)(OH)2 [tren = tris(2-aminoethyl)amine] and LiClO4·3H2O, aqueous solutions of NaOH / urea, aqueous solutions of sodium hydroxide, aqueous solutions of potassium hydroxide, formic acid, and ionic liquids can be used.

[0121] In one embodiment, the etherifying agent can be an etherifying agent that can etherify polyα-1,6-glucan with a positively charged organic group, wherein the carbon chain of the positively charged organic group has only been substituted with a positively charged group (e.g., a substituted ammonium group, such as trimethylammonium). Examples of such etherifying agents include dialkyl sulfates, dialkyl carbonates, alkyl halides (e.g., alkyl chlorides), iodoalkyl, alkyl trifluoromethanesulfonates (alkyl trifluoromethanesulfonates), and alkyl fluorosulfonates, wherein one or more alkyl groups of each of these reagents have one or more substitutions with a positively charged group (e.g., a substituted ammonium group, such as trimethylammonium). Other examples of such etherifying agents include dimethyl sulfate, dimethyl carbonate, chloromethane, iodomethane, methyl trifluoromethanesulfonate, and methyl fluorosulfonate, wherein one or more methyl groups of each of these reagents have been substituted with a positively charged group (e.g., a substituted ammonium group, such as trimethylammonium). Other examples of such etherifying agents include diethyl sulfate, diethyl carbonate, chloroethane, iodoethane, ethyl trifluoromethanesulfonate, and ethyl fluorosulfonate, wherein one or more ethyl groups in each of these reagents are substituted with a positively charged group (e.g., a substituted ammonium group, such as trimethylammonium). Other examples of such etherifying agents include dipropyl sulfate, dipropyl carbonate, chloropropane, iodopropane, propyl trifluoromethanesulfonate, and propyl fluorosulfonate, wherein one or more propyl groups in each of these reagents are substituted with one or more positively charged groups (e.g., a substituted ammonium group, such as trimethylammonium). Other examples of such etherifying agents include dibutyl sulfate, dibutyl carbonate, chlorobutane, iodobutane, and butyl trifluoromethanesulfonate, wherein one or more butyl groups in each of these reagents are substituted with one or more positively charged groups (e.g., a substituted ammonium group, such as trimethylammonium). Other examples of etherifying agents include halides of compounds containing an imidazoline ring.

[0122] In another embodiment, the etherifying agent can be an etherifying agent that can etherify polyα-1,6-glucan with a positively charged organic group, wherein, in addition to substitution with a positively charged group (e.g., a substituted ammonium group, such as trimethylammonium), the carbon chain of the positively charged organic group also has a substitution, such as a hydroxyl group. Examples of such etherifying agents include hydroxyalkyl halides (e.g., hydroxyalkyl chlorides), such as hydroxypropyl halides and hydroxybutyl halides, wherein the terminal carbon of each of these agents has a substitution with a positively charged group (e.g., a substituted ammonium group, such as trimethylammonium); an example is 3-chloro-2-hydroxypropyl-trimethylammonium. Further examples of etherifying agents containing positively charged organic groups include 2,3-epoxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyldodecyldimethylammonium chloride, 3-chloro-2-hydroxypropylcocoyldimethylammonium chloride, 3-chloro-2-hydroxypropylstearyldimethylammonium chloride, and halides of quaternary ammonium compounds such as compounds containing an imidazoline ring. Other examples of such etherifying agents include epoxides such as propylene oxide (e.g., 1,2-epoxypropylene) and epoxides such as 1,2-epoxides; 2,3-epoxides, wherein the terminal carbon of each of these agents is substituted with a positively charged group (e.g., a substituted ammonium group, such as trimethylammonium).

[0123] When producing polyα-1,6-glucan ether compounds containing two or more distinct positively charged organic groups, two or more different etherifying agents are used accordingly. Any of the etherifying agents disclosed herein can be combined to produce polyα-1,6-glucan ether compounds having two or more distinct positively charged organic groups. Such two or more etherifying agents can be used simultaneously in the reaction or sequentially in the reaction. When used sequentially, any temperature treatment (e.g., heating) step can optionally be used between each addition. The desired DoS of each positively charged organic group can be controlled by the sequential introduction of the etherifying agents. Generally, if it is desired that the organic group formed by a particular etherifying agent in the ether product has a higher DoS than the DoS of another organic group to be added, that particular etherifying agent will be used first.

[0124] The amount of etherifying agent to be contacted with poly-1,6-glucan in the reaction under alkaline conditions can be selected based on the desired degree of substitution in the ether compound. The amount of ether substituent groups on each monomer unit in the poly-1,6-glucan ether compound can be determined using nuclear magnetic resonance (NMR) spectroscopy. Generally, the etherifying agent can be used at a rate of at least about 0.01, 0.02, 0.03, 0.04, or 0.05 mol / mol of polyglucan. There is no upper limit to the amount of etherifying agent that can be used.

[0125] The reaction for producing poly(α-1,6-glucan ether) compounds can optionally be carried out in a pressure vessel (such as a Parr reactor, autoclave, vibrating tube, or any other pressure vessel known in the art). Optionally, the poly(α-1,6-glucan ether) compounds can be prepared under an inert atmosphere, with or without heating. As used herein, the term "inert atmosphere" refers to a non-reactive gas atmosphere, such as nitrogen, argon, or helium.

[0126] After contacting the poly-α-1,6-glucan, solvent, alkali metal hydroxide, and etherifying agent for a sufficient reaction time to produce the poly-α-1,6-glucan ether compound, the reaction mixture may optionally be filtered by any means known in the art that allows for the removal of liquid from a solid.

[0127] Following etherification, one or more acids may optionally be added to the reaction mixture to lower the pH to a neutral pH range that is neither significantly acidic nor significantly acidic, for example, if desired, about 6-8, or about 6.0, 6.2, 6.4, 6.6, 6.8, 7.0, 7.2, 7.4, 7.6, 7.8, or 8.0. Various acids suitable for this purpose include sulfuric acid, acetic acid, hydrochloric acid, nitric acid, any mineral (inorganic) acid, any organic acid, or any combination of these acids.

[0128] Poly(α-1,6-glucan ether) compounds can optionally be washed once or multiple times with a liquid that does not readily dissolve the compound. For example, poly(α-1,6-glucan ether) can be washed with water, alcohol, isopropanol, acetone, aromatic compounds, or any combination thereof, depending on the solubility of the ether compound therein (where the washing is desired to be soluble). Generally, solvents containing organic solvents (such as alcohols) are preferred for washing. Poly(α-1,6-glucan ether) products can be washed once or multiple times with an aqueous solution containing, for example, methanol or ethanol. For example, 70-95 wt% ethanol can be used to wash the product. In another embodiment, the poly(α-1,6-glucan ether) product can be washed with a methanol:acetone (e.g., 60:40) solution.

[0129] Poly-α-1,6-glucan ether compounds can optionally be purified by membrane filtration.

[0130] The poly-α-1,6-glucan ether produced using the methods disclosed above can be separated. This step can be performed before or after the neutralization and / or washing steps using a funnel, centrifuge, filter press, or any other method or apparatus known in the art that allows the removal of liquid from a solid. The separated poly-α-1,6-glucan ether product can be dried using any method known in the art, such as vacuum drying, air drying, or freeze drying.

[0131] The poly(α-1,6-glucan) ether product can be used as a starting material for further modification to repeat any of the above etherification reactions. This method is applicable to adding positively charged organic groups to the DoS, and / or adding one or more different positively charged organic groups to the ether product. Furthermore, this method is applicable to the addition of one or more non-positively charged organic groups, such as alkyl groups (e.g., methyl, ethyl, propyl, butyl) and / or hydroxyalkyl groups (e.g., hydroxyethyl, hydroxypropyl, hydroxybutyl). Any of the above etherifying agents, but not substituted with a positively charged group, can be used for this purpose.

[0132] Depending on the desired application, compositions comprising cationic poly(α-1,6-glucan ether) compounds as disclosed herein may be formulated with one or more other materials and / or active ingredients suitable for use in various compositions (e.g., for use in garment care, textile / fabric care, other home care applications, and / or personal care products), for example, by blending, mixing, or incorporating. In this context, the term "composition comprising cationic poly(α-1,6-glucan ether) compounds" may include, for example, aqueous formulations, rheology-modified compositions, fabric treatment / care compositions, garment care formulations / compositions, fabric softeners, or personal care compositions (hair, skin, and oral care) each comprising a cationic poly(α-1,6-glucan ether) compound as disclosed herein.

[0133] As used herein, the term "effective amount" refers to the amount of substance used or applied that is suitable for achieving the desired effect. The effective amount of a material can vary depending on the application. Typically, those skilled in the art will be able to determine the effective amount for a particular application or subject without conducting experiments.

[0134] The term "resistance to enzymatic hydrolysis" refers to the relative stability of poly(α-1,6-glucan ether) against enzymatic hydrolysis. Resistance to hydrolysis is important for applications where enzymes are present, such as in detergents, fabric care, and / or garment care applications. In some embodiments, the poly(α-1,6-glucan ether compound is resistant to cellulase. In other embodiments, the poly(α-1,6-glucan ether compound is resistant to protease. In still other embodiments, the poly(α-1,6-glucan ether compound is resistant to amylase. In yet another embodiment, the poly(α-1,6-glucan ether) is resistant to mannanase. In still other embodiments, the poly(α-1,6-glucan ether) is resistant to multiple classes of enzymes, such as two or more cellulases, proteases, amylases, mannanases, or combinations thereof. Resistance to any specific enzyme is defined as having at least 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, or 100% of the material remaining after treatment with the corresponding enzyme. The percentage of remaining material can be determined by measuring the supernatant after enzyme treatment using SEC-HPLC. Enzyme resistance can be determined using the following procedure: A sample of the poly(α-1,6-glucan ether) compound is added to water in a vial and mixed using a PTFE magnetic stir bar to produce a 1% by weight aqueous solution. An aqueous mixture is produced at pH 7.0 and 20°C. After the poly(α-1,6-glucan ether) compound has completely dissolved, 1.0 mL (1% by weight) of cellulase ( ) is added. EGL), amylase ( ST L), protease ( 16.0L), or lipase ( 100 L) was stirred at 20 °C for 72 hours (hr). After stirring for 72 hours, the reaction mixture was heated to 70 °C for 10 minutes to inactivate the added enzyme, and the resulting mixture was cooled to room temperature and centrifuged to remove any precipitate. The recovered polyα-1,6-glucan ether compounds in the supernatant were analyzed by SEC-HPLC and compared with a control in which no enzyme was added to the reaction mixture. The percentage change in the area count of the corresponding polyα-1,6-glucan ether compounds can be used to test the relative resistance of the material to the corresponding enzyme treatment. The percentage change in area relative to the total amount will be used to assess the relative amount of material remaining after treatment with the specific enzyme. Material with a percentage recovery of at least 10%, preferably at least 50%, 60%, 70%, 80%, 90%, 95%, or 100%, will be considered "resistant" to the corresponding enzyme treatment.

[0135] The phrase “aqueous composition” as used herein refers to a solution or mixture in which the solvent is at least about 1% by weight of water and contains polyα-1,6-glucan ether.

[0136] The terms “hydrocolloid” and “hydrogel” are used interchangeably herein. A hydrocolloid refers to a colloidal system in which water is the dispersion medium. A “colloid” herein refers to a substance that is microscopically dispersed throughout another substance. Therefore, a hydrocolloid may also refer herein to a dispersion, emulsion, mixture, or solution of a cationic poly(α-1,6-glucan ether) compound in water or an aqueous solution.

[0137] The term "aqueous solution" as used herein refers to a solution in which the solvent is water. Poly(α-1,6-glucan ether) compounds can be dispersed, mixed, and / or dissolved in aqueous solutions. Aqueous solutions may serve as the dispersion medium for hydrocolloids herein.

[0138] The terms "dispersant" and "dispersion agent" are used interchangeably herein to refer to materials that promote the formation and stabilization of a dispersion of one substance in another. "Dispersion" herein refers to an aqueous composition comprising one or more particles dispersed or uniformly distributed throughout the aqueous composition (e.g., any ingredient in personal care products, pharmaceutical products, food products, household products, or industrial products). It is believed that cationic poly(α-1,6-glucan ether compounds can act as dispersants in the aqueous compositions disclosed herein.

[0139] As used herein, the term “viscosity” is a measure of the degree to which a fluid or aqueous composition, such as a hydrocolloid, resists forces that tend to cause it to flow. Various units of viscosity that may be used herein include centipoise (cps) and pascal-second (Pa·s). One centipoise is one-hundredth of a poise; one poise is equal to 0.100 kg·m³. -1 ·s -1 Therefore, as used herein, the term "viscosity modifier / viscosity-modifying agent" refers to any substance that can change / alter the viscosity of a fluid or aqueous composition.

[0140] The terms “fabric,” “textile,” and “cloth” are used interchangeably herein to refer to woven or nonwoven materials having a network of natural and / or man-made fibers. Such fibers may be, for example, threads or yarns.

[0141] "Fabric care composition" as used herein is any composition suitable for treating fabrics in a certain way. Suitable examples of such compositions include non-laundry fiber treatment agents (for desizing, scrubbing, mercerizing, bleaching, coloring, dyeing, printing, biopolishing, antimicrobial treatment, anti-wrinkle treatment, stain resistance treatment, etc.), garment care compositions (e.g., garment care detergents), and fabric softeners.

[0142] The terms “detergent composition,” “heavy-duty detergent,” and “general-purpose detergent” are used interchangeably herein to refer to compositions suitable for routine washing of substrates such as tableware, cutlery, vehicles, fabrics, carpets, clothing, and white and colored textiles at any temperature. Detergent compositions for treating fabrics, hard surfaces, and any other surfaces in the fabric and home care fields include: laundry detergents, fabric conditioners (including softeners), laundry and rinsing additives and care compositions, fabric freshening compositions, laundry pre-washes, laundry pretreatments, hard surface treatment compositions, automotive care compositions, dishwashing compositions (including handwashing and automatic dishwashing products), air care products, detergents contained on or in porous substrates or nonwoven sheets, and other cleaning products for consumer or institutional use.

[0143] The term "cellulase" is used interchangeably herein to refer to an enzyme that hydrolyzes the β-1,4-D-glycosidic bonds in cellulose, thereby partially or completely degrading cellulose. Alternatively, cellulase may be referred to as, for example, "β-1,4-glucanase" and may have endocellulase activity (EC 3.2.1.4), exocellulase activity (EC 3.2.1.91), or cellobiase activity (EC 3.2.1.21). In some embodiments herein, the cellulase may also hydrolyze the β-1,4-D-glycosidic bonds in cellulose ether derivatives such as carboxymethyl cellulose. "Cellulose" refers to a linear, insoluble polysaccharide having β-1,4-linked D-glucose monomer units.

[0144] As used herein, the terms "fabric hand" or "handle" refer to an individual's tactile sensory response to a fabric, which may be physical, physiological, psychological, social, or any combination thereof. In some embodiments, fabric hand can be measured using relative hand values. The system (available from Nu Cybertek, Inc., Davis, California) was used to measure the values ​​as provided by the American Association of Textile Chemists and Colorists (AATCC Test Method “202-2012, Relative Hand Value of Textiles: Instrumental Method”).

[0145] The composition may be in the form of a liquid, gel, powder, hydrocolloid, aqueous solution, granules, tablet, capsule, bead or lozenge, single-compartment packet, multi-compartment packet, single-compartment sachet, or multi-compartment sachet. In some embodiments, the composition is in the form of a liquid, gel, powder, single-compartment packet, or multi-compartment sachet.

[0146] In some embodiments, compositions comprising cationic poly(α-1,6-glucan ether) compounds as disclosed herein may be in the form of fabric care compositions. For example, fabric care compositions may be used for hand washing, machine washing, and / or other purposes, such as soaking and / or pretreatment of fabrics. Fabric care compositions may take the form of: for example, laundry detergents; fabric conditioners; any product added during washing, rinsing, or drying; unit dosage forms or sprays. Fabric care compositions in liquid form may be in the form of aqueous compositions. In other embodiments, fabric care compositions may be in dry forms, such as granular detergents or fabric softener sheets added to a dryer. Other non-limiting examples of fabric care compositions may include: general-purpose or heavy-duty detergents in granular or powder form; general-purpose or heavy-duty detergents in liquid, gel, or paste form; liquid or dry detergents for delicate fabrics (e.g., fine clothing); cleaning aids such as bleach additives, “stain remover sticks,” or pretreatments; products containing a base material, such as dry and wet wipes, pads, or sponges; sprays and fine mists; and water-soluble unit dosage products.

[0147] In some embodiments, compositions comprising cationic poly-1,6-glucan ether compounds may be in the form of personal care products. Personal care products include, but are not limited to, hair care compositions, skin care compositions, sun protection compositions, body cleansing compositions, oral care compositions, wipes, beauty care compositions, cosmetic compositions, antifungal compositions, and antimicrobial compositions. Personal care products may include cleansing, cleansing, protecting, depositing, moisturizing, conditioning, barrier-closing, and emollient compositions.

[0148] As used herein, "personal care products" also includes products for cleaning, bleaching, and / or disinfecting hair, skin, scalp, and teeth, including but not limited to shampoos, body lotions, shower gels, topical moisturizers, toothpaste, teething gels, mouthwashes, mouthwashes, anti-spot bleaching agents, and / or other topical cleansers. In some embodiments, these products are for human use, while in other embodiments, these products are for use in non-human animals (e.g., in veterinary applications). In one aspect, "personal care products" includes hair care products. Hair care products may be in the form of powders, pastes, gels, liquids, oils, ointments, sprays, foams, tablets, shampoos, hair conditioning bleaching agents, or any combination thereof.

[0149] Product formulations containing the cationic poly(α-1,6-glucan ether) compounds described herein can optionally be diluted with water or a solution consisting primarily of water to produce formulations having a desired concentration of the poly(α-1,6-glucan ether) compound for the target application. It will be apparent to those skilled in the art that the reactants and / or dilution amounts can be adjusted to achieve a desired concentration of the poly(α-1,6-glucan ether) for the selected personal care product.

[0150] The personal care compositions described herein may further comprise one or more dermatologically or cosmetically acceptable components that are known or otherwise effective in hair care or other personal care products, provided that the optional components are physically and chemically compatible with the basic components described herein, or do not otherwise unduly impair the product's stability, aesthetics, or performance. Non-limiting examples of such optional components are disclosed herein. International Cosmetic Ingredient Dictionary [International Dictionary of Cosmetic Ingredients], 9th Edition, 2002 and CTFA Cosmetic Ingredient Handbook, 10th Edition, 2004.

[0151] In one embodiment, a dermatologically acceptable carrier may comprise about 10 wt% to about 99.9 wt%, alternatively about 50 wt% to about 95 wt%, and alternatively about 75 wt% to about 95 wt% of a dermatologically acceptable carrier. Carriers suitable for use with one or more compositions may include, for example, those used in the formulation of hair sprays, mousses, tonics, gels, skin moisturizers, lotions, and leave-on conditioners. The carrier may comprise water; organic oils; silicones, such as volatile silicones, amino or non-amino silicone gums or oils, and mixtures thereof; mineral oils; vegetable oils, such as olive oil, castor oil, rapeseed oil, coconut oil, wheat germ oil, sweet almond oil, avocado oil, macadamia nut oil, apricot oil, safflower oil, candelilla oil, linseed oil, tamanu oil, lemon oil, and mixtures thereof; waxes; and organic compounds, such as C2-C 10Alkanes, acetone, methyl ethyl ketone, volatile organic compounds (C1-C) 12 alcohols, C1-C 20 Esters of acids and C1-C8 alcohols (where the choice of one or more esters can be understood depending on whether they can serve as substrates for carboxylic acid esters of hydrolases), such as methyl acetate, butyl acetate, ethyl acetate, and isopropyl myristate, dimethoxyethane, diethoxyethane, C1-C8 alcohols, etc. 10 -C 30 Fatty alcohols, such as lauryl alcohol, cetyl alcohol, stearyl alcohol, and behenyl alcohol; C 10 -C 30 Fatty acids, such as lauric acid and stearic acid; C 10 -C 30 Fatty amides, such as lauric acid diethanolamide; C 10 -C 30 Fatty alkyl esters, such as C 10 -C 30 Fatty alkyl benzoates; hydroxypropyl cellulose and mixtures thereof. In one embodiment, the carrier comprises water, fatty alcohol, volatile organic alcohol, and mixtures thereof.

[0152] One or more compositions disclosed herein may further comprise about 0.1% to about 10%, and alternatively about 0.2% to about 5.0%, of a gelling agent to help provide the desired viscosity to one or more compositions. Non-limiting examples of suitable optional gelling agents include crosslinked carboxylic acid polymers; unneutralized crosslinked carboxylic acid polymers; unneutralized modified crosslinked carboxylic acid polymers; crosslinked ethylene / maleic anhydride copolymers; unneutralized crosslinked ethylene / maleic anhydride copolymers (e.g., EMA 81, commercially available from Monsanto); and unneutralized crosslinked alkyl ether / acrylate copolymers (e.g., SALCARE, commercially available from Allied Colloids). TM SC90); an unneutralized crosslinked copolymer of sodium polyacrylate, mineral oil, and PEG-1 tridecyl ether-6 (e.g., SALCARE, commercially available from United Colloids). TM SC91); unneutralized cross-linked copolymers of methyl vinyl ether and maleic anhydride (e.g., STABILEZE, commercially available from International Specialty Products). TM QM-PVM / MA copolymer); hydrophobically modified nonionic cellulose polymers; hydrophobically modified ethoxylated urethane polymers (e.g., UCARE, commercially available from Union Carbide). TMPolyphobe series alkali-swellable polymers; and combinations thereof. In this document, the term "unneutralized" means that the optional polymer and copolymer gelling material contains unneutralized acid monomers. Preferred gelling agents include water-soluble unneutralized crosslinked ethylene / maleic anhydride copolymers, water-soluble unneutralized crosslinked carboxylic acid polymers, water-soluble hydrophobically modified nonionic cellulose polymers, and surfactant / fatty alcohol gel networks, such as those used in hair conditioning products.

[0153] The cationic poly(α-1,6-glucan ether) compounds described herein can be incorporated into hair care compositions and products (such as, but not limited to, hair conditioners). Hair conditioners are well known in the art, see, for example, Green et al. (WO 0107009), and are commercially available from various sources. Examples of suitable hair conditioners include, but are not limited to, cationic polymers such as cationic guar gum, diallyl quaternary ammonium salt / acrylamide copolymers, quaternized polyvinylpyrrolidone and its derivatives, and various polyquaternary ammonium compounds; cationic surfactants such as silachlor, cetrimonium chloride, and sapamin hydrochloride; fatty alcohols such as behenol; fatty amines such as stearylamine; waxes; esters; nonionic polymers such as polyvinylpyrrolidone, polyvinyl alcohol, and polyethylene glycol; silicones; siloxanes such as decamethylcyclopentasiloxane; polymer emulsions such as amino-terminated polydimethylsiloxane; and nanoparticles such as silica nanoparticles and polymer nanoparticles.

[0154] Hair care products may also include additional components typically found in cosmetically acceptable media. Non-limiting examples of such components are disclosed in the International Cosmetic Ingredient Dictionary, 9th edition, 2002 and the CTFA Cosmetic Ingredient Handbook, 10th edition, 2004. A non-limiting list of components frequently included in cosmetically acceptable media for use in hair care is also disclosed by Philippe et al. in U.S. Patent No. 6,280,747, by Omura et al. in U.S. Patent No. 6,139,851, and by Cannell et al. in U.S. Patent No. 6,013,250, all of which are incorporated herein by reference. For example, hair care compositions may be aqueous solutions, alcoholic solutions, or water-alcohol solutions, wherein the alcohol is preferably ethanol or isopropanol, and for water-alcohol solutions, the proportion is from about 1% by weight to about 75% by weight relative to the total weight. Additionally, hair care compositions may contain one or more conventional cosmetic or skin care additives or adjuvants, including but not limited to antioxidants, preservatives, fillers, surfactants, UVA and / or UVB sunscreens, fragrances, thickeners, gelling agents, wetting agents and anionic, nonionic or amphoteric polymers, as well as dyes or pigments.

[0155] Hair care compositions and methods may also include at least one coloring agent, such as any dye, lake, pigment, etc., which can be used to change the color of hair, skin, or nails. Hair colorants are well known in the field (see, for example, Green et al., ibid., CFTA International Color Handbook, 2nd edition, Micelle Publishing, England (1992) and Cosmetic Handbook, FDA / IAS pamphlet (1992)), and are commercially available from a variety of sources (e.g., Bayer, Pittsburgh, PA; Ciba-Geigy, Tarrytown, NY; ICI, Bridgewater, NJ; Sandoz, Vienna, Austria; BASF, Mount Olive, NJ; and Hoechst, Frankfurt, Germany). Suitable hair coloring agents include, but are not limited to, dyes such as 4-hydroxypropylamino-3-nitrophenol, 4-amino-3-nitrophenol, 2-amino-6-chloro-4-nitrophenol, 2-nitro-p-phenylenediamine, N,N-hydroxyethyl-2-nitro-phenylenediamine, 4-nitro-indole, henna, HC Blue 1, HC Blue 2, HC Yellow 4, HC Red 3, HC Red 5, Disperse Violet 4, Disperse Black 9, HC Blue 7, HC Blue 12, HC Yellow 2, HC Yellow 6, HC Yellow 8, HC Yellow 12, HC Brown 2, D&C Yellow 1, D&C Yellow 3, D&C Blue 1, Disperse Blue 3, Disperse Violet 1, eosin derivatives such as D&C Red 21, and halogenated... Fluorescein derivatives such as D&C Red 27, D&C Red Orange 5 (combined with D&C Red 21 and D&C Orange 10); and pigments such as D&C Red 36 and D&C Orange 17, calcium lakes of D&C Red 7, 11, 31 and 34, barium lake of D&C Red 12, strontium lake of D&C Red 13, aluminum lakes of FD&C Yellow 5, FD&C Yellow 6, D&C Red 27, D&C Red 21 and FD&C Blue 1, iron oxide, manganese violet, chromium oxide, titanium dioxide, titanium dioxide nanoparticles, zinc oxide, barium oxide, ultramarine blue, bismuth citrate, and carbon black particles. In one embodiment, the hair coloring agent is D&C Yellow 1 and 3, HC Yellow 6 and 8, D&C Blue 1, HC Blue 1, HC Brown 2, HC Red 5, 2-nitro-p-phenylenediamine, N,N-hydroxyethyl-2-nitro-phenylenediamine, 4-nitro-indole, and carbon black.Metal and semiconductor nanoparticles can also be used as hair coloring agents due to their strong light emission (U.S. Patent Application Publication No. 2004-0010864, ​​Vic et al.).

[0156] Hair care compositions may include, but are not limited to, shampoos, conditioners, lotions, aerosols, gels, mousses, and hair dyes.

[0157] Personal care products may be in the form of lotions, creams, pastes, balms, ointments, hair oils, gels, liquids, or combinations thereof. Personal care products can also take the form of, for example, the following: cosmetics, lipsticks, mascaras, blushes, foundations, blushes, eyeliners, lip liners, lip glosses, other cosmetics, sunscreens, sunblocks, nail polishes, mousses (e.g., hair styling mousses), hairsprays (e.g., hair styling gels), styling gels (e.g., hair styling gels), nail conditioners, bath gels, shower gels, body washes, facial cleansers, shampoos, hair conditioners (leave-in or rinse-out), nourishing hair products, hair dyes, hair coloring products, hair shine products, hair serums, anti-frizz hair products, split end repair products, lip balms, skin conditioners, cold creams, moisturizing creams, body sprays, soaps, body scrubs, exfoliants, astringents, scrubbing lotions, hair removal products, and permanent waving solutions. (solution), anti-dandruff formulations, antiperspirant compositions, deodorants, shaving products, pre-shaving products, after-shaving products, cleansers, skin gels, hair dyes, dental compositions, toothpaste, or mouthwash.

[0158] In some respects, the composition can be a hair care composition, such as a hair styling or setting composition (e.g., hair gel, hair gel or shampoo, hair mousse / foam) (e.g., aerosol hair gel, non-aerosol pump hair gel, spray, foam, cream, paste, non-runny gel, mousse, hair oil, lacquer, hair wax). Hair styling / compositions / formulations that can be adapted to contain the poly-α-1,6-glucan ether compound described herein can be, for example, US20090074697, WO 1999048462, US20130068849, JPH 0454116A, US 5304368, AU 667246B2, US 5413775, US 5441728, US5939058, JP 2001302458 A, US 6346234, US20020085988, US 7169380, US20090060858, US20090326151, US20160008257, WO The information disclosed in 2020164769 or US20110217256 is incorporated herein by reference in its entirety.Hair care compositions, such as hair styling / setting compositions, may contain one or more ingredients / additives as disclosed in any of the foregoing references, and / or one or more of the following: fragrances / fragrances, aromatherapy essences, vanilla, infusions, antimicrobial agents, stimulants (e.g., caffeine), essential oils, hair dyes, colorants or pigments, anti-greying agents, defoamers, sunscreens / UV blockers (e.g., benzophenone-4), vitamins, antioxidants, surfactants or other wetting agents, mica, silica, metallic flakes or other shimmering materials, conditioning agents (e.g., volatile or non-volatile silicone fluids), antistatic agents, sunscreens, detackifying agents, penetrants, preservatives (e.g., phenoxyethanol, ethylhexylglycerin, benzoates, diazolidinyl urea). urea), butylcarbamate iodopropynyl ester), emollients (e.g., panthenol, isopropyl myristate), rheology-modified or thickening polymers (e.g., acrylate / methacrylamide copolymer, polyacrylic acid [e.g., CARBOMER]), emulsified oil phase, petrolatum, fatty alcohols, glycols and polyols, emulsifiers (e.g., PEG-40 hydrogenated castor oil, oleyl alcohol polyether-20), humectants (e.g., glycerin, octyl glycol), silicone derivatives, proteins, amino acids (e.g., isoleucine), conditioning agents, chelating agents (e.g., EDTA), solvents (e.g., see below), monosaccharides (e.g., dextrose), disaccharides, oligosaccharides, pH-stabilizing compounds (e.g., aminomethylpropanol), film-forming agents (e.g., acrylate / hydroxy acrylate copolymers, polyvinylpyrrolidone / vinyl acetate copolymers, triethyl acetate), aerosol propellants (e.g., C3-C5 alkanes, such as propane, isobutane, or n-butane, monoalkyl ethers, dialkyl ethers, such as di(C1-C4 alkyl) ethers [e.g., dimethyl ether]), and / or any other suitable materials herein. Poly(α-1,6-glucan ether compounds used in hair styling / fixing compositions herein may act as, for example, hair fixatives / styling agents (typically non-permanent hair fixation, but long-lasting), and optionally be the sole hair fixative in the composition. Other optional hair fixation / styling agents mentioned above include PVP (polyvinylpyrrolidone), octylacrylamide / acrylate / butylaminoethyl methacrylate copolymer, vinylcaprolactam / PVP / dimethylaminoethyl methacrylate copolymer, AMPHOMER, or any film-forming agent listed above.

[0159] The total content of one or more polyα-1,6-glucan ether compounds in hair care compositions such as the hair styling / styling compositions described herein may be, for example, about, at least about, or less than about 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 0.5-15 wt%, 0.5-10 wt%, 0.5-5 wt%, 0.5-2 wt%, 1-15 wt%, 1-10 wt%, 1-5 wt%, 1-2 wt%, 2.5-7.5 wt%, 3-7 wt%, or 4-6 wt%. For example, hair styling / styling compositions may contain a solvent comprising water and optionally a water-miscible (typically polar) organic compound (e.g., liquid or gas), such as alcohols (e.g., ethanol, propanol, isopropanol, n-butanol, isobutanol, tert-butanol), alkylene glycol alkyl ethers, and / or monoalkyl or dialkyl ethers (e.g., dimethyl ether). If an organic compound is contained, it may constitute, for example, about 10%, 20%, 30%, 40%, 50%, or 60% by weight or volume of the solvent (the balance being water). For example, the amount of solvent in the hair styling / styling compositions herein may be about 50-90 wt%, 60-90 wt%, 70-90 wt%, 80-90 wt%, 50-95 wt%, 60-95 wt%, 70-95 wt%, 80-95 wt%, or 90-95 wt%.

[0160] Examples of hair styling gel formulations described herein may contain about 90-95 wt% (e.g., about 92 wt%) of solvent (e.g., water), 0.3-1.0 wt% (e.g., about 0.5 wt%) of thickener (e.g., polyacrylic acid), 0.1-0.3 wt% (e.g., about 0.2 wt%) of chelating agent (e.g., EDTA) (optional), 0.2-1.0 wt% (e.g., about 0.5 wt%) of humectant (e.g., glycerin), 0.01-0.05 wt% (e.g., about 0.02 wt%) of UV blocker (e.g., benzophenone-4) (optional), and 0. 0.5-0.3 wt% (e.g., about 0.1 wt%) of preservatives (e.g., diazoalkyl urea) (optional), 0.5-1.2 wt% (e.g., about 0.8 wt%) of emulsifiers (e.g., oleyl alcohol polyether-20), 0.1-0.3 wt% (e.g., about 0.2 wt%) of fragrances / perfumes (optional), 0.2-1.0 wt% (e.g., about 0.5 wt%) of pH stabilizing compounds (e.g., aminomethylpropanol), and 3-7 wt% (e.g., about 5 wt%) of the polyα-1,6-glucan ether compounds herein (e.g., as hair fixation / styling agents).

[0161] Examples of hair styling gel formulations described herein may contain about 0.2-1.0 wt% (e.g., about 0.5 wt%) of a pH-stabilizing compound (e.g., aminomethylpropanol), 0.1-0.3 wt% (e.g., about 0.2 wt%) of a fragrance / perfume (optional), 0.05-0.12 wt% (e.g., about 0.08 wt%) of a surfactant (e.g., ethoxylated polydimethylsiloxane polyol), 0.05-0.12 wt% (e.g., about 0.08 wt%) of a conditioning agent (e.g., cyclic polydimethylsiloxane) (optional), and 0.05-0.3 wt% of a pH-stabilizing compound (e.g., aminomethylpropanol), 0.1-0.3 wt% (e.g., about 0.2 wt%) of a conditioning agent (e.g., cyclodimethylsiloxane) (optional), and 0.05-0.3 wt% of a pH-stabilizing compound (e.g., aminomethylpropanol), 0.1-0.3 wt% (e.g., about 0.2 wt%) of a pH-stabilizing compound (e.g., aminomethylpropanol), 0.1-0.3 wt% (e.g., about 0.2 wt%) of a pH-stabilizing compound (e.g., aminomethylpropanol), 0.05-0.12 ... t% (e.g., about 0.2 wt%) of preservative (e.g., sodium benzoate) (optional), 15-20 wt% (e.g., about 17 wt%) of water, 30-40 wt% (e.g., about 65 wt%) of alcohol (e.g., ethanol), 40-60 wt% (e.g., about 45 wt%) of propellant (e.g., dimethyl ether, or a mixture of dimethyl ether and C3-C5 alkanes in a ratio of about 2:1 [e.g., a mixture of propane and isobutane]), and 2-4 wt% (e.g., about 2.75 wt%) of the polyα-1,6-glucan ether compound herein (e.g., as a hair fixation / styling agent).

[0162] Some aspects of this disclosure relate to hair that has been treated with the hair care compositions described herein (e.g., hair styling / composition compositions, shampoos, or conditioners). For example, the hair may contain poly-α-1,6-glucan ether compounds on its surface, such as in the form of a film / coating of the hair; optionally, one or more other ingredients of the hair care compositions described herein may also be present.

[0163] Personal care products may include poly(α-1,6-glucan ether) compounds as disclosed herein, and may further include personal care active ingredient materials, including sunscreens, moisturizers, humectants, beneficial agents for hair, skin, nails, and oral cavity, depositing agents such as surfactants, occlusive agents, moisture barriers, lubricants, emollients, anti-aging agents, antistatic agents, abrasives, antibacterial agents, conditioning agents, exfoliating agents, fragrances, thickeners, salts, lipids, phospholipids, vitamins, foam stabilizers, pH adjusters, preservatives, suspending agents, silicone oils, silicone derivatives, essential oils, oils, fats, fatty acids, fatty acid esters, fatty alcohols, waxes, polyols, hydrocarbons, and mixtures thereof. Active ingredients are generally considered to be the components that cause the intended pharmacological action.

[0164] In some embodiments, the skin care product includes at least one active ingredient for treating or preventing skin conditions, providing cosmetic effects, or providing moisturizing benefits to the skin, such as zinc oxide, petrolatum, white petrolatum, mineral oil, cod liver oil, lanolin, dimethicone, stearin, vitamin A, allantoin, calamine, kaolin, glycerin, or colloidal oatmeal, and combinations thereof. The skin care product may include one or more natural moisturizing factors, such as ceramides, hyaluronic acid, glycerin, squalane, amino acids, cholesterol, fatty acids, triglycerides, phospholipids, glycosphingolipids, urea, linoleic acid, glucosamine, mucopolysaccharides, sodium lactate, or sodium pyrrolidone carboxylate. Other ingredients that may be included in skin care products include, but are not limited to, glycerides, almond oil, low-erucic acid rapeseed oil, squalane, squalene, coconut oil, corn oil, jojoba oil, jojoba wax, lecithin, olive oil, safflower oil, sesame oil, shea butter, soybean oil, sweet almond oil, sunflower oil, tea tree oil, shea butter, palm oil, cholesterol, cholesterol esters, wax esters, fatty acids, and orange peel oil.

[0165] Various examples of personal care formulations comprising at least one polyα-1,6-glucan ether as disclosed herein are disclosed below (1-3).

[0166] (1) A hair conditioning composition comprising: cetyl alcohol (1%-3%), isopropyl myristate (1%-3%), hydroxyethyl cellulose ( 250HHR)(0.1%-1%), poly-α-1,6-glucan ether(0.1%-2%), potassium salt(0.1%-0.5%) II. Preservative (0.5%, available from International Specialty Products), with the remainder being water.

[0167] (2) A hair shampoo composition comprising: 5%-20% sodium lauryl ether sulfate (SLES), 1-2 wt% cocamidopropyl betaine, 1-2 wt% sodium chloride, 0.1%-2% poly(α-1,6-glucan ether), preservative (0.1%-0.5%), and the balance being water.

[0168] (3) A skin lotion composition comprising: 1%-5% glycerin, 1%-5% ethylene glycol stearate, 1%-5% stearic acid, 1%-5% mineral oil, and 0.5%-1% acetylated lanolin ( 98), 0.1-0.5% cetyl alcohol, 0.2%-1% triethanolamine, 0.1-1 wt% II. Preservative, 0.5-2 wt% poly(α-1,6-glucan ether), and the balance being water.

[0169] The personal care compositions disclosed herein may be in the form of oral care compositions. The term "oral care composition" as used herein refers to any composition suitable for treating any soft or hard surface of the oral cavity, including dental (teeth) and / or gingival surfaces. Examples of oral care compositions include dental cleaning agents, toothpastes, mouthwashes, oral rinses, chewing gum, and edible strips that provide some form of oral care (e.g., treatment or prevention of cavities [dental caries], gingivitis, plaque, tartar, and / or periodontal disease). Oral care compositions may also be used to treat "oral surfaces," which encompass any soft or hard surface within the oral cavity, including the surfaces of the tongue, hard and soft palate, buccal mucosa, gingiva, and teeth. The term "teeth surface" as used herein refers to the surface of natural teeth or the hard surface of artificial dentition (including, for example, crowns, caps, fillings, bridges, dentures, or dental implants).

[0170] One or more polyα-1,6-glucan ethers included in oral care compositions are typically provided therein as thickeners and / or dispersants that can be used to impart a desired consistency and / or mouthfeel to the composition. The oral care compositions described herein may contain about 0.01-15.0 wt% (e.g., about 0.1-10 wt% or about 0.1-5.0 wt%, about 0.1-2.0 wt%) of one or more of the polyα-1,6-glucan ethers disclosed herein. One or more other thickeners or dispersants, such as, for example, carboxyethylene polymers, carrageenan (e.g., L-carrageenan), natural gums (e.g., karaya gum, xanthan gum, gum arabic, astragalus gum), colloidal magnesium aluminum silicate, or colloidal silica, may also be provided in the oral care compositions described herein.

[0171] The oral care compositions described herein may be, for example, toothpaste or other dental cleaning agents. Such compositions, as well as any other oral care compositions described herein, may additionally contain, but are not limited to, one or more anti-caries agents, antimicrobial or antibacterial agents, anti-tartar or plaque control agents, surfactants, abrasives, pH adjusters, foam adjusters, humectants, flavorings, sweeteners, pigments / colorings, whitening agents, and / or other suitable components.

[0172] The caries prevention agents described herein can be orally acceptable sources of fluoride ions. Suitable sources of fluoride ions include, for example, fluorides, monofluorophosphates and fluorosilicates, and amine fluorides, including olafluridine (N'-octadecyltrimethylenediamine-N,N,N'-tris(2-ethanol)-dihydrofluoride). For example, the caries prevention agent can be present in an amount providing a total of about 100-20000 ppm, about 200-5000 ppm, or about 500-2500 ppm of fluoride ions to the composition. In oral care compositions where sodium fluoride is the sole source of fluoride ions, for example, an amount of about 0.01-5.0 wt%, about 0.05-1.0 wt%, or about 0.1-0.5 wt% sodium fluoride can be present in the composition.

[0173] Antimicrobial or antibacterial agents in the oral care compositions applicable to this document include, for example, phenolic compounds (e.g., 4-allyl catechol; parabens such as benzyl paraben, butyl paraben, ethyl paraben, methyl paraben, and propyl paraben; 2-benzylphenol; butylated hydroxyanisole; butylated hydroxytoluene; capsaicin; carvacrol; lignochlorophenol; eugenol; guaiacol; halogenated bisphenols such as hexachlorobenzene). Phenols (hexachlorophene and bromochlorophene); 4-hexylresorcinol; 8-hydroxyquinoline and its salts; salicylates, such as menthyl salicylate, methyl salicylate and phenyl salicylate; phenol; pyrocatechol; N-salicylic acid aniline; thymol; halodiphenyl ether compounds, such as triclosan and triclosan monophosphate); copper(II) compounds (e.g., copper(II) chlorides, fluorides, sulfates). (and hydroxides); zinc ion sources (e.g., zinc acetate, citrate, gluconate, glycine, oxides, and sulfates); phthalic acid and its salts (e.g., magnesium monopotassium phthalate); dioctylhydrochloride; otetinib; sanguisorbide; benzalkonium chloride; duloxetine bromide; alkylpyridine chlorides (e.g., hexadecylpyridine chloride, tetradecylpyridine chloride, N-tetradecyl-4-ethylpyridine chloride); iodine; sulfonamides; biguanides (e.g., arazide, chlorhexidine, etc.). Hexidine, chlorhexidine digluconate; azacyclohexane derivatives (e.g., dimopistol, octopiol); magnolia extract, grape seed extract, rosemary extract, menthol, geraniol, citral, eucalyptol; antibiotics (e.g., vogmundin, amoxicillin, tetracycline, doxycycline, minocycline, metronidazole, neomycin, kanamycin, clindamycin), and / or any antibacterial agent disclosed in U.S. Patent 5,776,435 (which is incorporated herein by reference). One or more antimicrobial agents may optionally be present in about 0.01-10 wt% (e.g., 0.1-3 wt%), for example, in the disclosed oral care compositions.

[0174] Anti-tartar or plaque control agents suitable for use in the oral care compositions described herein include, for example, phosphates and polyphosphates (e.g., pyrophosphates), polyaminopropanesulfonic acid (AMPS), zinc citrate trihydrate, peptides (e.g., polyaspartic acid and polyglutamic acid), polyolefin sulfonates, polyolefin phosphates, bisphosphonates (e.g., aziridine-2,2-bisphosphonates, such as aziridine-2,2-bisphosphonic acid), N-methylaziridine-2,3-bisphosphonic acid, ethane-1-hydroxy-1,1-bisphosphonic acid (EHDP), ethane-1-amino-1,1-bisphosphonate, and / or phosphonoalkylcarboxylic acids and their salts (e.g., their alkali metal salts and ammonium salts). Useful inorganic phosphates and polyphosphates include, for example, monobasic, dibasic, and ternary sodium phosphates; sodium tripolyphosphate; tetrapolyphosphate; monosodium, disodium, trisodium, and tetrasodium pyrophosphate; disodium dihydrogen pyrophosphate; sodium trimetaphosphate; sodium hexametaphosphate; or any of these in which sodium is replaced by potassium or ammonium. In some embodiments, other useful anti-tartar agents include anionic polycarboxylic acid polymers (e.g., polymers or copolymers of acrylic acid, methacrylic acid, and maleic anhydride, such as polyvinyl methyl ether / maleic anhydride copolymer). Other useful anti-tartar agents include chelating agents such as hydroxycarboxylic acids (e.g., citric acid, fumaric acid, malic acid, glutaric acid, and oxalic acid and their salts) and aminopolycarboxylic acids (e.g., EDTA). One or more anti-tartar or plaque control agents may optionally be present in about 0.01-50 wt% (e.g., about 0.05-25 wt% or about 0.1-15 wt%), for example, in the disclosed oral care compositions.

[0175] Surfactants suitable for use in the oral care compositions described herein can be, for example, anionic, nonionic, or amphoteric. Suitable anionic surfactants include, but are not limited to, C64. 8-20 Water-soluble salts of alkyl sulfates, C 8-20 Fatty acid sulfonated monoglycerides, sarcosinates, and taurine salts are suitable surfactants. Examples of anionic surfactants include sodium lauryl sulfate, sodium coconut monoglyceride sulfonate, sodium lauryl sarcosinate, sodium lauryl hydroxyethyl sulfonate, sodium polyethylene glycol monododecyl ether carboxylate, and sodium dodecylbenzene sulfonate. Suitable nonionic surfactants include, but are not limited to, poloxamer, polyoxyethylene dehydrated sorbitol esters, fatty alcohol ethoxylates, alkylphenol ethoxylates, tertiary amine oxides, tertiary phosphine oxides, and dialkyl sulfoxides. Suitable amphoteric surfactants include, but are not limited to, C-type surfactants having anionic groups such as carboxyl, sulfate, sulfonate, phosphate, or phosphonate groups. 8-20 Derivatives of aliphatic secondary and tertiary amines. An example of a suitable amphoteric surfactant is cocamidopropyl betaine. One or more surfactants are optionally present in a total amount of about 0.01-10 wt% (e.g., about 0.05-5.0 wt% or about 0.1-2.0 wt%) in, for example, the disclosed oral care compositions.

[0176] Abrasives suitable for use in the oral care compositions herein may include, for example, silica (e.g., silica gel, hydrated silica, precipitated silica), alumina, insoluble phosphates, calcium carbonate, and resin abrasives (e.g., urea-formaldehyde condensate products). Examples of insoluble phosphates that may be used as abrasives herein are orthophosphates, polymetaphosphates, and pyrophosphates, and include dicalcium orthophosphate dihydrate, calcium pyrophosphate, β-calcium pyrophosphate, tricalcium phosphate, polymetaphosphate, and insoluble sodium polymetaphosphate. One or more abrasives are optionally present in a total amount of about 5-70 wt% (e.g., about 10-56 wt% or about 15-30 wt%) in, for example, the disclosed oral care compositions. In some embodiments, the average particle size of the abrasive is about 0.1-30 micrometers (e.g., about 1-20 micrometers or about 5-15 micrometers).

[0177] In some embodiments, the oral care composition may contain at least one pH adjuster. Such agents may be selected to acidify the composition, make it more alkaline, or buffer a pH range of about 2-10 (e.g., pH ranges from about 2-8, 3-9, 4-8, 5-7, 6-10, or 7-9). Examples of pH adjusters that may be used herein include, but are not limited to, carboxylic acids, phosphoric acids, and sulfonic acids; acidic salts (e.g., monosodium citrate, disodium citrate, monosodium malate); alkali metal hydroxides (e.g., sodium hydroxide, carbonates such as sodium carbonate, bicarbonate, sesquicarbonate); borates; silicates; phosphates (e.g., monosodium phosphate, trisodium phosphate, pyrophosphate); and imidazoles.

[0178] Foam modifiers suitable for use in the oral care compositions herein may be, for example, polyethylene glycol (PEG). High molecular weight PEGs are suitable, including those having, for example, an average molecular weight of about 200,000 to 7,000,000 (e.g., about 500,000 to 5,000,000 or about 1,000,000 to 2,500,000). One or more PEGs are optionally present in a total amount of about 0.1 to 10 wt% (e.g., about 0.2 to 5.0 wt% or about 0.25 to 2.0 wt%) in, for example, the oral care compositions disclosed herein.

[0179] In some embodiments, the oral care composition may contain at least one humectant. In some embodiments, the humectant may be a polyol, such as glycerin, sorbitol, xylitol, or low molecular weight PEG. The most suitable humectant may also be used as a sweetener herein. One or more humectants are optionally present in a total amount of about 1.0-70 wt% (e.g., about 1.0-50 wt%, about 2-25 wt%, or about 5-15 wt%) in, for example, the disclosed oral care composition.

[0180] Natural or artificial sweeteners may optionally be included in the oral care compositions herein. Examples of suitable sweeteners include dextrose, sucrose, maltose, dextrin, invert sugar, mannose, xylose, ribose, fructose, levulose, galactose, corn syrup (e.g., high fructose corn syrup or corn syrup solids), partially hydrolyzed starch, hydrogenated starch hydrolysates, sorbitol, mannitol, xylitol, maltitol, isomaltitol, aspartame, neotame, saccharin and its salts, dipeptide-based strong sweeteners, and cyclosulfonates. One or more sweeteners may optionally be present in a total amount of about 0.005-5.0 wt% in, for example, the oral care compositions disclosed herein.

[0181] Natural or artificial edible flavorings may optionally be included in the oral care compositions described herein. Examples of suitable edible flavorings include vanillin; sage; marjoram; celery oil; spearmint oil; cinnamon oil; wintergreen oil (methyl salicylate); peppermint oil; clove oil; laurel oil; anise oil; eucalyptus oil; citrus oil; fruit oils; flavorings such as those derived from lemon, orange, lime, grapefruit, apricot, banana, grape, apple, strawberry, cherry, or pineapple; flavorings derived from legumes and nuts, such as coffee, cocoa beans, cola, peanuts, or almonds; and adsorbent and encapsulated edible flavorings. Also covered in the edible flavorings described herein are ingredients that provide flavor and / or other sensory effects in the mouth, including cooling or warming effects. Such ingredients include, but are not limited to, menthol, menthyl acetate, menthyl lactate, camphor, eucalyptus oil, eucalyptol, anethole, eugenol, cinnamon, and oxanone. Hydroxymethyl anethole, thymol, linalool, benzaldehyde, cinnamaldehyde, N-ethyl-p-menthane-3-carboxamide, N,2,3-trimethyl-2-isopropylbutyramide, 3-(1-menthoxy)-propane-1,2-diol, cinnamaldehyde glycerol acetal (CGA), and menthone glycerol acetal (MGA). One or more edible flavorings are optionally present in a total amount of about 0.01-5.0 wt% (e.g., about 0.1-2.5 wt%) in, for example, the disclosed oral care compositions.

[0182] In some embodiments, the oral care composition may contain at least one bicarbonate. Any orally acceptable bicarbonate may be used, including, for example, alkali metal bicarbonates such as sodium or potassium bicarbonate, and ammonium bicarbonate. For example, one or more bicarbonates may optionally be present in the disclosed oral care composition in a total amount of about 0.1-50 wt% (e.g., about 1-20 wt%).

[0183] In some embodiments, the oral care composition may comprise at least one whitening agent and / or coloring agent. Suitable whitening agents are peroxide compounds, such as any of those disclosed in U.S. Patent No. 8,540,971, which is incorporated herein by reference. Suitable coloring agents herein include, for example, pigments, dyes, lakes, and agents, such as pearlescent agents, that impart a particular gloss or reflectivity. Specific examples of coloring agents that may be used herein include talc; mica; magnesium carbonate; calcium carbonate; magnesium silicate; magnesium aluminum silicate; silica; titanium dioxide; zinc oxide; red, yellow, brown, and black iron oxides; ferric ammonium ferrocyanide; manganese violet; deep blue; titanic mica; and bismuth oxychloride. For example, one or more coloring agents may optionally be present in the disclosed oral care composition in a total amount of about 0.001-20 wt% (e.g., about 0.01-10 wt% or about 0.1-5.0 wt%).

[0184] Additional components that may optionally be included in the oral compositions herein include, for example, one or more enzymes (above), vitamins, and anti-adhesion agents. Examples of vitamins that may be used herein include vitamin C, vitamin E, vitamin B5, and folic acid. Examples of suitable anti-adhesion agents include methylparaben (solbrol), figokinase, and quorum sensing inhibitors.

[0185] The composition can be in any useful form, such as as powder, granules, paste, rod, unit dose, or liquid.

[0186] The unit dosage form can be water-soluble, for example, a water-soluble unit dosage article comprising a water-soluble film and a liquid or solid laundry detergent composition, also known as a sachet. A water-soluble unit dosage sachet comprises a water-soluble film that completely encapsulates the liquid or solid detergent composition in at least one compartment. A water-soluble unit dosage article can comprise a single compartment or multiple compartments. A water-soluble unit dosage article can comprise at least two compartments or at least three compartments. These compartments can be arranged in a stacked orientation or a side-by-side orientation.

[0187] Unit-dose products are typically closed structures made of a water-soluble film encapsulating an internal volume containing a liquid or solid laundry detergent composition. The sachet can have any form and shape suitable for retaining and protecting the composition, for example, preventing the composition from being released from the sachet before it comes into contact with water.

[0188] Liquid detergent compositions can be aqueous, typically containing up to about 70% by weight of water and 0% to about 30% by weight of organic solvents. They can also be in the form of a dense gel containing less than or equal to 30% by weight of water.

[0189] The cationic poly(α-1,6-glucan ether) compounds disclosed herein can be used as an ingredient in desired products or can be blended with one or more other suitable ingredients and used, for example, in fabric care, garment care, and / or personal care applications. Any of the disclosed compositions, such as fabric care, garment care, or personal care compositions, may comprise a poly(α-1,6-glucan ether) compound in the range of 0.01 to 99 percent by weight based on the total dry weight (dry solids basis) of the composition. The term "total dry weight" means the weight of the composition excluding any solvents (e.g., any water that may be present). In other embodiments, the composition comprises 0.1 wt% to 10 wt%, or 0.1 wt% to 9 wt%, or 0.5 wt% to 8 wt%, or 1 wt% to 7 wt%, or 1 wt% to 6 wt%, or 1 wt% to 5 wt%, or 1 wt% to 4 wt%, or 1 wt% to 3 wt%, or 5 wt% to 10 wt%, or 10 wt% to 15 wt%, or 15 wt% to 20 wt%, or 20 wt% to 25 wt%, or 25 wt% to 30 wt%, or 30 wt% to 35 wt%, or 35 wt% to 40 wt%. Cationic poly(α-1,6-glucan ether) compounds, wherein the weight percentages are based on the total dry weight of the composition.

[0190] In some aspects, the composition may comprise one or more cationic polyalpha-1,6-glucan ether compounds as disclosed herein and one or more unsubstituted and / or non-cationic polyalpha-1,6-glucan compounds, which may be unreacted / unsubstituted residual reactants or may have been hydrolyzed. Typically, low levels of unsubstituted / non-cationic polyalpha-1,6-glucan compounds indicate the completeness of the reaction with respect to substitution and / or the chemical stability of the compounds in the composition. The weight ratio of the cationic polyalpha-1,6-glucan ether compound to the unsubstituted / non-cationic polyalpha-1,6-glucan compound may be 95:5, 96:4, 97:3, 98:2, 99:1, or greater.

[0191] The composition may further comprise at least one of the following: surfactants, enzymes, detergent builders, complexing agents, polymers, detergency polymers, surfactant-enhancing polymers, bleaching agents, bleaching activators, bleaching catalysts, fabric conditioners, clays, foam promoters, foam inhibitors, corrosion inhibitors, dirt suspending agents, anti-redeposition agents, dyes, bactericides, dulling inhibitors, optical brighteners, fragrances, saturated or unsaturated fatty acids, dye transfer inhibitors, chelating agents, tinting dyes, calcium cations, magnesium cations, visual signaling components, defoamers, structuring agents, thickeners, anti-caking agents, starch, sand, gelling agents, or combinations thereof. In one embodiment, the enzyme is a cellulase. In another embodiment, the enzyme is a protease. In yet another embodiment, the enzyme is an amylase.

[0192] The composition may be a detergent composition applicable to, for example, fabric care, garment care, and / or personal care, and may further contain one or more active enzymes. Non-limiting examples of suitable enzymes include proteases, cellulases, hemicellulases, peroxidases, lipolytic enzymes (e.g., metallolipolytic enzymes), xylanases, phospholipases, peroxyhydrolases, keratinases, pectinases, pectin lyases, mannanases, keratinases, reductases, oxidases (e.g., choline oxidases), phenol oxidases, lipoxygenases, ligninases, amylopectinases, tanninases, pentosanases, malicases, β-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, metalloproteinases, amadoriases, glucosylamylases, arabinofuranases, inositol hexaphosphatases, isomerases, transferases, nucleases, amylases, or combinations thereof. In some embodiments, a combination of two or more enzymes may be used in the composition. In some embodiments, the two or more enzymes are cellulases and one or more of the following: proteases, hemicellulases, peroxidases, lipases, xylanases, phospholipases, hydrolases, keratins, pectins, pectinases, mannanases, keratinases, reductases, oxidases, phenol oxidases, lipoxygenases, ligninases, amylopectinases, tanninases, pentosanases, malicases, β-glucanases, arabinosidases, hyaluronidases, chondroitinases, laccases, metalloproteinases, amylases, glucosylamylases, arabinofuranases, phytases, isomerases, transferases, nucleases, amylases, or combinations thereof.

[0193] Cellulases can have endocellulase activity (EC 3.2.1.4), exocellulase activity (EC 3.2.1.91), or cellobiase activity (EC 3.2.1.21). A cellulase is an "active cellulase" that is active under suitable conditions for maintaining its activity; determining such suitable conditions is within the scope of the art. In addition to being able to degrade cellulose, in some embodiments, the cellulase can also degrade cellulose ether derivatives such as carboxymethyl cellulose.

[0194] Cellulases can be derived from any microbial source, such as bacteria or fungi. This includes chemically modified cellulases or protein-engineered mutant cellulases. Suitable cellulases include, for example, cellulases from the genera *Bacillus*, *Pseudomonas*, *Streptomyces*, *Trichoderma*, *Pyrophyllus*, *Fusarium*, *Thielavia*, and *Cladosporium*. As other examples, cellulases can be derived from *Humicola insolens*, *Myceliophthora thermophile*, *Fusarium oxysporum*, *Trichoderma reesei*, or combinations thereof. Cellulases, such as any of the foregoing, can be in a mature form lacking an N-terminal signal peptide. Commercially available cellulases that can be used in this document include... and (Novozymes A / S); and HA and REVITALENZ TM (DuPont Industrial Biosciences) (AB Enzymes); and (Kao Corporation).

[0195] Alternatively, the cellulase described herein can be produced by any means known in the art, for example, by recombinant production in a heterologous expression system, such as a microbial or fungal heterologous expression system. Examples of heterologous expression systems include bacterial (e.g., *Escherichia coli*, *Bacillus* sp.)) and eukaryotic systems. Eukaryotic systems can employ expression systems such as yeast (e.g., *Pichia* sp., *Saccharomycess* sp.) or fungal (e.g., *Trichoderma* sp., such as *Trichoderma reesei*, *Aspergillus* sp., such as *A. niger*) expression systems.

[0196] In some embodiments, cellulases may be thermostable. Thermostable cellulase refers to the ability of an enzyme to retain its activity after exposure to high temperatures (e.g., about 60°C–70°C) for a sustained period of time (e.g., about 30–60 minutes). Thermostable cellulase can be measured by its half-life (t1 / 2), given in minutes, hours, or days, during which half of the cellulase activity is lost under defined conditions.

[0197] In some embodiments, cellulases can be stable over a wide range of pH values ​​(e.g., neutral or alkaline pH, such as about 7.0 to about 11.0). Such enzymes can remain stable under these pH conditions for a predetermined period of time (e.g., at least about 15 min, 30 min, or 1 hour).

[0198] At least one, two, or more cellulases may be included in the composition. Typically, the total amount of cellulase in the compositions herein is an amount suitable for the purpose of using the cellulase in the composition (“effective amount”). For example, the effective amount of cellulase in a composition intended to improve the hand feel and / or appearance of a cellulose-containing fabric is an amount that produces a measurable improvement in the fabric hand feel (e.g., improved fabric smoothness and / or appearance, removal of granules and fibrils that tend to reduce the appearance clarity of the fabric). As another example, the effective amount of cellulase in the fabric stonewashing compositions herein is an amount that will provide the desired effect (e.g., producing an worn and faded appearance at seams and on fabric pieces). For example, the amount of cellulase in the compositions herein may also depend on the process parameters (e.g., equipment, temperature, time, etc.) and cellulase activity used in using the composition. The effective concentration of cellulase in an aqueous composition treating a fabric can be readily determined by those skilled in the art.

[0199] Suitable enzymes are known in the art and may include, for example, MAXACAL TMMAXAPEM TM , OXP, PURAMAX TM EXCELLASE TM PREFERENZ TM Proteases (e.g., P100, P110, P280), EFFECTENZ TM Proteases (e.g., P1000, P1050, P2000), EXCELLENZ TM Proteases (e.g., P1000), and PURAFAST TM Genencor Corporation; DURAZYM TM , and (Novozymes); BLAP TM and BLAP TM Variant (Henkel Kommanditgesellschaft auf Aktien, Duesseldorf, Germany) and KAP (Bacillus alkalophilus subtilisin; Kao Corp., Tokyo, Japan) protease; PURABRITE TM and Mannanase; M1 LIPASE TM LUMA FAST TM and LIPOMAX TM (Genetronics Corporation); and ULTRA (Novozymes); and LIPASE P TM Amano (Amano Pharmaceutical Co., Ltd., Japan) lipase; STAINZYME TERMAMYL and BAN TM (Novo Nordisk A / S and Novozymes); and PREFERENZ TM (DuPont Industrial Biosciences) Amylase; GUARDZYME TM(Novo Nordisk and Novozymes) Peroxidase or combinations thereof.

[0200] In some embodiments, the enzymes in the composition may be stabilized using conventional stabilizers such as: polyols such as propylene glycol or glycerol; sugars or sugar alcohols; lactic acid; boric acid or boric acid derivatives (e.g., aromatic borate esters).

[0201] Typically, the detergent compositions described herein comprise one or more surfactants selected from nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, amphoteric surfactants, semi-polar nonionic surfactants, and mixtures thereof. Surfactants can be petroleum-derived (also known as synthetic) or non-petroleum-derived (also known as natural). Detergents will generally contain anionic surfactants such as linear alkylbenzene sulfonates (LAS), α-olefin sulfonates (AOS), alkyl sulfates (fatty alcohol sulfates) (AS), alcohol ethoxysulfates (AEOS or AES), secondary alkyl sulfonates (SAS), α-sulfonyl fatty acid methyl esters, alkyl- or alkenyl succinic acids, or soaps.

[0202] Detergent compositions may contain ingredients having formula R 1 -(OCH2CH2) x -O-SO3M alcohol ethoxy sulfate, where R 1 These are non-petroleum-derived straight-chain or branched fatty alcohols, ranging from approximately C8 to approximately C6. 20 It consists of an even number of carbon chain lengths, where x is from about 0.5 to about 8, and where M is an alkali metal or ammonium cation. The fatty alcohol moiety of alcohol ethoxysulfate (R 1 Fatty alcohols are derived from renewable sources (e.g., animal or plant-derived) rather than geologically derived (e.g., petroleum-derived). Fatty alcohols derived from renewable sources can be called natural fatty alcohols. Natural fatty alcohols have an even number of carbon atoms, with a single alcohol (-OH) attached to the terminal carbon. The fatty alcohol moiety (R) of a surfactant... 1 It can include the distribution of even-numbered carbon chains, such as C12, C14, C16, C18, etc.

[0203] Additionally, the detergent composition may optionally contain nonionic surfactants, such as alcohol ethoxylates (AEO or AE), carboxylated alcohol ethoxylates, nonylphenol ethoxylates, alkyl polyglycosides, alkyl dimethylamine oxides, ethoxylated fatty acid monoethanolamides, fatty acid monoethanolamides, or polyhydroxyalkyl fatty acid amides. The detergent composition may contain a surfactant having the formula R. 2 -(OCH2CH2) y -OH alcohol ethoxylates, where R 2 These are non-petroleum-derived straight-chain or branched fatty alcohols, composed of approximately C...10 About C 18 It consists of an even number of carbon chain lengths, where y is from about 0.5 to about 15. The fatty alcohol moiety of the alcohol ethoxylate (R... 2 It is derived from renewable sources (e.g., animal or plant-derived) rather than geologically derived (e.g., petroleum-derived). The fatty alcohol portion (R...) of the surfactant... 2 It can contain a distribution of even-numbered carbon chains, for example, C 12 C 14 C 16 C 18 wait.

[0204] The composition may further comprise one or more detergent builders or builder systems. Builders include, for example, alkali metal, ammonium, and / or alkanol ammonium salts of polyphosphates; alkali metal silicates, alkaline earth metals, and alkali metal carbonates; aluminosilicates; polycarboxylic acid compounds; ether hydroxy polycarboxylic acid esters; copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyloxysuccinic acid; various alkali metal, ammonium, and substituted ammonium salts of polyacetic acid, such as ethylenediaminetetraacetic acid and hypozoxytriacetic acid; together with polycarboxylic acids, such as hexacarboxylic acid, succinic acid, citric acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and their soluble salts. Examples of detergent builders or complexing agents include zeolites, diphosphates, triphosphates, phosphonates, citrates, nitrosotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTMPA), alkyl or alkenyl succinic acids, soluble silicates, or layered laurates (e.g., SKS-6 from Hoechst). Detergents may also be additive-free, i.e., substantially free of detergent builders.

[0205] The composition may further comprise at least one chelating agent. Suitable chelating agents include, for example, copper, iron, and / or manganese chelating agents and mixtures thereof.

[0206] The composition may further comprise at least one deposition aid. Suitable deposition aids include, for example, polyethylene glycol, polypropylene glycol, polycarboxylates, detergency polymers such as polyterephthalic acid, clays such as kaolin, montmorillonite, palygorskite, illite, bentonite, hydrous kaolin, or combinations thereof.

[0207] The composition may further comprise one or more dye transfer inhibitors. Suitable dye transfer inhibitors include, for example, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinyloxazolidinone, polyvinylimidazole, manganese phthalocyanine, peroxidase, polyvinylpyrrolidone polymers, ethylenediaminetetraacetic acid (EDTA); diethylenetriaminepentamethylenephosphonic acid (DTPMP); hydroxyethanediphosphonic acid (HEDP); ethylenediamine N,N'-disuccinic acid (EDDS); methylglycine diacetic acid (MGDA); diethylenetriaminepentaacetic acid (DTPA); propylenediaminetetraacetic acid (PDT). A); 2-hydroxypyridine-N-oxide (HPNO); or methylglycine diacetic acid (MGDA); N,N-diacetic acid (N,N-dicarboxymethylglutamate tetrasodium salt (GLDA); nitrotriacetic acid (NTA); 4,5-dihydroxyisophenylsulfonic acid; citric acid and any salt thereof; N-hydroxyethylethylenediaminetriacetic acid (HEDTA), triethylenetetraminehexaacetic acid (TTHA), N-hydroxyethyliminodiacetic acid (HEIDA), dihydroxyethylglycine (DHEG), ethylenediaminetetrapropionic acid (EDTP) and their derivatives or combinations thereof.

[0208] The composition may further comprise silicates. Suitable silicates may include, for example, sodium silicate, sodium disilicate, sodium metasilicate, crystalline silicates, or combinations thereof.

[0209] The composition may further comprise a dispersant. Suitable water-soluble organic materials may include, for example, homopolymerized or copolymerized acids or salts thereof, wherein the polycarboxylic acid comprises at least two carboxyl groups separated from each other by no more than two carbon atoms.

[0210] In addition to the polyα-1,6-glucan ether compound of the present invention, the composition may further comprise one or more other types of polymers. Examples of other types of polymers that may be used herein include carboxymethyl cellulose (CMC), poly(vinylpyrrolidone) (PVP), polyethylene glycol (PEG), poly(vinyl alcohol) (PVA), polycarboxylate esters such as polyacrylates, maleic acid / acrylic acid copolymers, and lauryl methacrylate / acrylic acid copolymers.

[0211] The composition may further comprise a bleaching system. For example, the bleaching system may comprise an H₂O₂ source, such as perborate, percarbonate, hydrogen peroxide salt, sodium monohydrate or tetrahydrate of perborate, persulfate, superphosphate, persilicate, percarboxylic acid and salt, percarbonate and salt, perimidic acid and salt, peroxymonosulfate and salt, zinc phthalocyanine sulfonate, aluminum phthalocyanine sulfonate, or sulfone dye, which may be combined with a bleaching activator that forms a peracid, such as, for example, dodecyloxybenzenesulfonate, decyloxybenzenesulfonate, decyloxybenzoic acid or its salts, tetraacetylethylenediamine (TAED), or nonanoyloxybenzenesulfonate (NOBS). Alternatively, the bleaching system may comprise a peroxyacid (e.g., an amide, imide, or sulfone-type peroxyacid). In other embodiments, the bleaching system may be an enzymatic bleaching system comprising a perhydrolase. Any combination of the above may also be used.

[0212] The composition may further comprise conventional detergent ingredients such as fabric conditioners, clays, foam promoters, foam inhibitors, corrosion inhibitors, soil suspenders, anti-redeposition agents, dyes, bactericides, dulling inhibitors, optical brighteners, or fragrances. The pH of the detergent compositions described herein (measured in an aqueous solution at the concentration used) may be neutral or alkaline (e.g., pH from about 7.0 to about 11.0).

[0213] The composition may be a detergent composition and optionally a heavy-duty (general purpose) laundry detergent composition.

[0214] The composition may be a detergent composition, optionally comprising, for example, a surface-enhancing polymer composed of an amphiphilic alkoxylated oleoyl cleaning polymer. Suitable amphiphilic alkoxylated oleoyl cleaning polymers may include, for example, alkoxylated polymers (such as alkoxylated polyalkylene imines) having branched hydrophilic and hydrophobic properties; random graft polymers comprising: a hydrophilic backbone containing monomers, such as unsaturated C1-C6 carboxylic acids, ethers, alcohols, aldehydes, ketones, esters, sugar units, alkoxy units, maleic anhydrides, saturated polyols (such as glycerol), and mixtures thereof; and one or more hydrophobic side chains, such as one or more C4-C6... 25 Alkyl groups, polypropylene, polybutene, vinyl esters of saturated C1-C6 monocarboxylic acids, C1-C6 alkyl esters of acrylic acid or methacrylic acid, and mixtures thereof.

[0215] Suitable heavy-duty laundry detergent compositions may optionally contain additional polymers, such as stain-removing polymers (including anionic-terminated polyesters (e.g., SRP1); polymers in a random or block configuration comprising at least one monomer unit selected from sugars, dicarboxylic acids, polyols, and combinations thereof; ethylene glycol terephthalate-based polymers and their copolymers in a random or block configuration, such as REPEL-O-TEX SF, SF-2 AND SRP6, TEXCARE SRA100, SRA300, SRN100, SRN170, SRN240, SRN300 AND SRN325, MARLOQUEST. SL); anti-redeposition polymers, including carboxylic acid ester polymers, such as polymers containing at least one monomer selected from acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesoconic acid, citraconic acid, methylene malonic acid, and any mixture thereof; vinylpyrrolidone homopolymers; and / or polyethylene glycol with a molecular weight in the range of 500 to 100,000 Daltons (Da); and polymeric carboxylic acid esters (such as maleate / acrylate random copolymers or polyacrylate homopolymers).

[0216] Heavy-duty laundry detergent compositions may optionally further comprise saturated or unsaturated fatty acids, preferably saturated or unsaturated C. 12 -C 24 Fatty acids; deposition aids, such as polysaccharides, cellulose polymers, polydiallyl dimethyl ammonium halide (DADMAC), and copolymers of DADMAC in random or block configurations with vinylpyrrolidone, acrylamide, imidazole, halogenated imidazolines and mixtures thereof, cationic guar gum, cationic starch, cationic polyacrylamide or combinations thereof.

[0217] The compositions disclosed herein may be in the form of dishwashing detergent compositions. Examples of dishwashing detergents include automatic dishwashing detergents (typically used in dishwashing machines) and hand-washing dishwashing detergents. Dishwashing detergent compositions may be, for example, in any dry or liquid / aqueous form as disclosed herein. Components that may be included in certain embodiments of dishwashing detergent compositions include, for example, one or more of the following: phosphates; oxygen- or chlorine-based bleach; nonionic surfactants; alkaline salts (e.g., metasilicates, alkali metal hydroxides, sodium carbonate); any active enzymes disclosed herein; corrosion inhibitors (e.g., sodium silicate); defoamers; additives that slow the removal of glaze and patterns from ceramics; fragrances; anti-caking agents (in granular detergents); starch (in tablet-based detergents); gelling agents (in liquid / gel-based detergents); and / or sand (in powdered detergents).

[0218] Further examples of personal care, home care, and other products and ingredients described herein may be any of those disclosed in U.S. Patent No. 8,796,196, which is incorporated herein by reference. Examples of personal care, home care, and other products and ingredients described herein include fragrances, aromatherapy agents, air odor-reducing agents, insect repellents and insecticides, foaming agents such as surfactants, pet deodorants, pet insecticides, pet shampoos, disinfectants, hard surface treatment products (e.g., floors, bathtubs / showers, sinks, toilets, door / cabinet handles / panels, glass / windows, tables, countertops, desks) (e.g., cleaning products, disinfectant products, coating products, wipes), wipes and other nonwoven materials, colorants, preservatives, antioxidants, emulsifiers, emollients, oils, pharmaceuticals, fragrances, and suspending agents.

[0219] In other embodiments, this disclosure relates to a method for treating a substrate, the method comprising the following steps:

[0220] (a) A composition comprising a polyα-1,6-glucan ether compound, the ether compound comprising:

[0221] (i) a poly-α-1,6-glucan substituted with at least one positively charged organic group;

[0222] (ii) a weight-average degree of polymerization of at least 5; and

[0223] (iii) A degree of substitution of about 0.001 to about 3.0;

[0224] The poly-α-1,6-glucan comprises a backbone of glucose monomer units, wherein at least 40% of these glucose monomer units are linked by α-1,6-glycosidic bonds, and optionally at least 3% of the backbone glucose monomer units are branched by α-1,2 and / or α-1,3-glycosidic bonds.

[0225] (b) bringing the substrate into contact with the composition; and

[0226] (c) Optionally rinse the substrate.

[0227] In one embodiment, the substrate may be a textile, fabric, carpet, or garment. In another embodiment, the substrate may be a carpet, upholstery, or surface. "Upholstery" means a soft, padded textile covering attached to furniture, such as armchairs and sofas. The treatment provides benefits to the substrate, such as one or more of the following: improved fabric feel, improved resistance to staining, improved colorfastness, improved abrasion resistance, improved wrinkle resistance, improved antifungal activity, improved antimicrobial activity, improved freshness, improved stain resistance, improved cleaning performance during washing, improved drying rate, improved dye, pigment, or lake renewal, improved whiteness retention, or a combination thereof. In another embodiment, the substrate may be a surface, such as a wall, floor, door, or panel, or paper, or the substrate may be the surface of an object, such as a table. The treatment provides benefits to the substrate, such as improved resistance to staining, improved stain resistance, improved cleaning performance, improved antifungal activity, improved antimicrobial activity, or a combination thereof.

[0228] In one embodiment, the method of treating the substrate can impart anti-ashing properties to the substrate, meaning that dirt detached from the fabric during washing is suspended in the washing liquid and thus prevents its redeposition onto the fabric. In another embodiment, the method of treating the substrate can impart anti-redeposition properties to the substrate. The effectiveness of anti-ashing agents and anti-redeposition agents can be determined, for example, by using a detergent and performing multiple washes on a pre-soiled fabric in the presence of an initial clean fabric, which acts as a redeposition monitor, using methods known in the art.

[0229] The fabrics described herein may comprise natural fibers, synthetic fibers, semi-synthetic fibers, or any combination thereof. Semi-synthetic fibers are produced using naturally occurring materials that have been chemically derived; an example of such material is rayon. Non-limiting examples of fabric types described herein include fabrics made from: (i) fibrous fibers such as cotton (e.g., velvet, canvas, striped or checkered fabrics, chenille, printed cotton, corduroy, brocade, denim, flannel, striped cotton, jacquard fabrics, knitted fabrics, matras, oxford cloth, high-denier cotton, poplin, pleats, cotton satin, seersucker, sheer fabrics, terry cloth, twill, velvet), rayon (e.g., viscose, modal, lyocell), linen, and (ii) Protein fibers, such as silk, wool, and related mammalian fibers; (iii) Synthetic fibers, such as polyester, acrylic, nylon, etc.; (iv) Long plant fibers from jute, flax, ramie, coconut fiber, kapok, sisal, henaquin fiber, Manila hemp, and tamarisk; and (v) Any combination of fabrics from (i)-(iv). Fabrics containing a combination of fiber types (e.g., natural and synthetic) include, for example, those containing both cotton and polyester. Materials / articles containing one or more fabrics include, for example, clothing, curtains, drapes, furniture upholstery, carpets, sheets, bath towels, tablecloths, sleeping bags, tents, automotive interiors, etc. Other materials containing natural and / or synthetic fibers include, for example, nonwoven fabrics, padding, paper, and foam. Fabrics are typically woven or knitted structures.

[0230] The contact step can be performed under various conditions, such as time, temperature, and washing / rinsing volume. Methods for contacting fabrics or textile substrates, such as fabric care methods or washing methods, are generally well known. For example, materials containing fabrics can be contacted with the disclosed composition for: (i) at least about 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, or 120 minutes; (ii) at a temperature of at least about 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, or 95°C (e.g., for washing or rinsing clothes: about 15°C-). (i) at a “cold” temperature of 30°C, a “warm” temperature of about 30°C–50°C, or a “hot” temperature of about 50°C–95°C; (iii) at a pH of about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 (e.g., a pH range of about 2–12 or about 3–11); (iv) at a salt (e.g., NaCl) concentration of at least about 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, or 4.0% by weight; or any combination of (i)–(iv). For example, the contact step in a fabric care method or laundry method may include any one of a washing, soaking, and / or rinsing step. In some embodiments, the rinsing step is a rinsing step with water.

[0231] Other substrates that may come into contact with include, for example, surfaces that can be treated with dishwashing detergents (e.g., automatic or hand-washing detergents). Examples of such materials include surfaces of tableware, glassware, bowls, plates, baking trays, cookware, and flat tableware (collectively referred to herein as “tableware”) made of ceramic, porcelain, metal, glass, plastics (e.g., polyethylene, polypropylene, and polystyrene), and wood. Examples of conditions (e.g., time, temperature, washing volume) used for methods of washing tableware or tableware are known in the art. In other instances, tableware articles may come into contact with the compositions herein under a suitable set of conditions, such as any of those disclosed above regarding contact with fabric-containing materials.

[0232] Some embodiments of the method for treating the substrate further include a drying step, wherein the material is dried after contact with the composition. The drying step may be performed directly after the contact step, or after one or more additional steps that may immediately follow the contact step, such as drying the fabric after washing in an aqueous composition, for example, after rinsing in water. Drying can be carried out by any of several means known in the art, such as air drying, for example, at temperatures of at least about 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 120°C, 140°C, 160°C, 170°C, 175°C, 180°C, or 200°C. The materials dried herein typically contain less than 3 wt%, 2 wt%, 1 wt%, 0.5 wt%, or 0.1 wt% water.

[0233] In another embodiment, the substrate may be a surface, such as a wall, floor, door, or panel, or the substrate may be the surface of an object, such as a table or tableware. The treatment provides benefits to the substrate, such as improved resistance to dirt deposition, improved stain resistance, improved cleaning performance, or a combination thereof. The contact step may include wiping or spraying the substrate with the composition.

[0234] Non-limiting examples of the embodiments disclosed herein include:

[0235] 1. A polyα-1,6-glucan ether compound comprising: (i) a polyα-1,6-glucan substituted with at least one positively charged organic group; (ii) a weight-average degree of polymerization of at least 5; and (iii) a degree of substitution of about 0.001 to about 3.0; wherein the polyα-1,6-glucan comprises a backbone of glucose monomer units, and wherein at least 40% of these glucose monomer units are linked via α-1,6-glycosidic bonds; optionally wherein the polyα-1,6-glucan (a) is substituted with only at least one positively charged organic group, or (b) is not substituted with a hydrophobic group or a negatively charged organic group.

[0236] 2. The polyα-1,6-glucan ether compound as described in Example 1, wherein at least 3% of these main-chain glucose monomer units are branched via α-1,2- and / or α-1,3-glycosidic bonds.

[0237] 3. The polyα-1,6-glucan ether compound as described in Example 1 or 2, wherein about 3% to about 35% of these main-chain glucose monomer units are branched via α-1,2 and / or α-1,3 glycosidic bonds.

[0238] 4. The polyα-1,6-glucan ether compound as described in Examples 1, 2, or 3, wherein the degree of substitution is from about 0.01 to about 1.5.

[0239] 5. The polyα-1,6-glucan ether compound as described in Examples 1, 2, 3, or 4, wherein the degree of substitution is from about 0.01 to about 0.7.

[0240] 6. The polyα-1,6-glucan ether compound as described in Examples 1, 2, 3, 4, or 5, wherein the degree of substitution is from about 0.01 to about 0.4.

[0241] 7. The polyα-1,6-glucan ether compound as described in Examples 1, 2, 3, 4, 5, or 6, wherein the degree of substitution is from about 0.01 to about 0.2.

[0242] 8. The polyα-1,6-glucan ether compound as described in Examples 1, 2, 3, 4, 5, 6, or 7, wherein the polyα-1,6-glucan ether has a weight-average degree of polymerization in the range of about 5 to about 6000.

[0243] 9. The polyα-1,6-glucan ether compound as described in Examples 1, 2, 3, 4, 5, 6, 7, or 8, wherein at least 90% of the glucose monomer units in the main chain of the ether compound are linked via α-1,6-glycosidic bonds.

[0244] 10. The polyα-1,6-glucan ether compound as described in Examples 1, 2, 3, 4, 5, 6, 7, 8, or 9, wherein the positively charged organic group comprises a substituted ammonium group.

[0245] 11. The polyα-1,6-glucan ether compound as described in Example 10, wherein the substituted ammonium group comprises a quaternary ammonium group.

[0246] 12. The polyα-1,6-glucan ether compound as described in Example 11, wherein the quaternary ammonium group comprises at least one C1 to C2 group. 18 Alkyl groups.

[0247] 13. The polyα-1,6-glucan ether compound as described in Example 11 or 12, wherein the quaternary ammonium group comprises at least one C1 to C4 alkyl group.

[0248] 14. The polyα-1,6-glucan ether compound as described in Examples 11, 12, or 13, wherein the quaternary ammonium group comprises at least one C 10 To C 16 Alkyl groups.

[0249] 15. The polyα-1,6-glucan ether compound as described in Examples 11, 12, 13, or 14, wherein the quaternary ammonium group further comprises two C1 to C4 alkyl groups.

[0250] 16. The polyα-1,6-glucan ether compound as described in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15, wherein the quaternary ammonium group comprises a trimethylammonium group.

[0251] 17. The polyα-1,6-glucan ether compound as described in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16, wherein the positively charged organic group comprises a quaternary ammonium hydroxyalkyl group.

[0252] 18. The polyα-1,6-glucan ether compound as described in Example 17, wherein the quaternary ammonium hydroxyalkyl group comprises a quaternary ammonium hydroxymethyl group, a quaternary ammonium hydroxyethyl group, or a quaternary ammonium hydroxypropyl group.

[0253] 19. The polyα-1,6-glucan ether compound as described in Example 17 or 18, wherein the quaternary ammonium hydroxyalkyl group comprises a trimethylammonium hydroxyalkyl group.

[0254] 20. The polyα-1,6-glucan ether compound as described in Example 19, wherein the trimethylammonium hydroxyalkyl group is a trimethylammonium hydroxypropyl group.

[0255] 21. A composition comprising the polyα-1,6-glucan ether compound as described in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

[0256] 22. The composition as described in Example 21, which is in the form of liquid, gel, powder, hydrocolloid, aqueous solution, granules, tablet, capsule, bead or lozenge, single-compartment packet, pad, multi-compartment packet, single-compartment sachet or multi-compartment sachet.

[0257] 23. The composition as described in Example 22, further comprising at least one of the following: enzymes, detergent builders, complexing agents, polymers, detergency polymers, surfactant-enhancing polymers, bleaching agents, bleaching activators, bleaching catalysts, fabric conditioning agents, clays, foam promoters, foam inhibitors, corrosion inhibitors, dirt suspending agents, anti-dirt redeposition agents, dyes, bactericides, dulling inhibitors, optical brighteners, fragrances, saturated or unsaturated fatty acids, dye transfer inhibitors, chelating agents, tinting dyes, calcium cations, magnesium cations, visual signaling components, defoamers, structuring agents, thickeners, anti-caking agents, starch, sand, gelling agents, or combinations thereof.

[0258] 24. The composition as described in Example 23, wherein the enzyme is cellulase, protease, amylase, or a combination thereof.

[0259] 25. A personal care product, home care product, industrial product, or fabric care product comprising the composition described in Examples 21, 22, 23, or 24.

[0260] 26. A personal care product comprising a polyα-1,6-glucan ether compound as described in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

[0261] 27. A home care product comprising a polyα-1,6-glucan ether compound as described in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

[0262] 28. An industrial product comprising the polyα-1,6-glucan ether compound as described in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20.

[0263] 29. A product comprising a polyα-1,6-glucan ether compound as described in Examples 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20, wherein (i) the product further comprises one or more of the following: fragrance, aromatherapy, flavoring, air freshener, insect repellent, pesticide, foaming agent, nonwoven material, colorant, preservative, antioxidant, emulsifier, emollient, oil, pharmaceutical, or suspending agent; and / or (ii) the product is a disinfectant, cleaning product, coating product, wipe, or hard surface cleaner, such as for floors, countertops, tables, desks, bathtubs / showers, sinks, toilets, door / cabinet handles / panels, or glass / windows; wherein the product is not a fabric care product or a tableware care product.

[0264] 30. A method for treating a substrate, the method comprising the steps of: (a) providing a composition as described in Examples 21, 22, 23, 24, 25, 26, 27, or 28; (b) contacting the substrate with the composition; and (c) optionally rinsing the substrate; wherein the substrate is not a fabric substrate or a tableware substrate.

[0265] 30. The method as described in Example 29, wherein the substrate is a surface.

[0266] Further non-limiting examples of the embodiments disclosed herein include:

[0267] A. A composition, such as any of those disclosed herein, comprising: a polyα-1,6-glucan ether compound comprising a polyα-1,6-glucan substituted with at least one positively charged organic group, wherein the polyα-1,6-glucan comprises a backbone of glucose monomer units, wherein at least 65% of these glucose monomer units are linked via α-1,6 glycosidic bonds, and wherein the polyα-1,6-glucan ether compound is characterized by: i) a weight-average degree of polymerization of at least 5 (e.g., about 500-2000), and ii) a degree of substitution of about 0.001 to about 3.0.

[0268] B1. A composition, such as any of those disclosed herein, comprising: a polyα-1,6-glucan ether compound comprising a polyα-1,6-glucan substituted with at least one positively charged organic group, wherein the polyα-1,6-glucan comprises a backbone of glucose monomer units, wherein at least 65% of these glucose monomer units are linked via α-1,6 glycosidic bonds, and wherein the polyα-1,6-glucan ether compound is characterized in that: a) about 1000 to about 500,0 The weight-average molecular weight is 0.00 Daltons (e.g., about 80,000 to 500,000 Daltons), and / or b) derived from polyα-1,6-glucan having a weight-average molecular weight of about 900 to about 450,000 Daltons (e.g., about 50,000 to 450,000 Daltons), as determined before being substituted with at least one positively charged organic group; wherein the polyα-1,6-glucan ether compound is further characterized by a degree of substitution of about 0.001 to about 3.0.

[0269] B2. A composition, such as any of those disclosed herein, comprising: a polyα-1,6-glucan ether compound comprising a polyα-1,6-glucan substituted with at least one positively charged organic group, wherein the polyα-1,6-glucan ether compound is characterized by: (a) a weight-average molecular weight of about 1,000-150,000, 5,000-100,000, 10,000-80,000, or 20,000-60,000 Daltons; (b) a backbone of glucose monomer units, wherein greater than or equal to 65% of the glucose monomer units are linked via α-1,6-glycosidic bonds; (c) about 20%-60%, 30%-60%, 30%-50%, 35%-45%, or 40% of the glucose monomer units are branched via α-1,2- and / or α-1,3-glycosidic bonds; and (d) a degree of cationic substitution of about 0.001 to about 3.0.

[0270] C. The composition as described in any one of paragraphs A, B1, or B2, wherein at least 3%, or at least about 5%, preferably about 5% to about 35%, more preferably about 5% to about 30%, more preferably about 5% to about 30%, more preferably about 5% to about 25%, and even more preferably about 5% to about 20% of the main-chain glucose monomer units are branched via α-1,2 and / or α-1,3 glycosidic bonds.

[0271] D. The composition as described in any one of paragraphs A, C, and D, wherein the positively charged organic group comprises a substituted ammonium group, preferably a quaternary ammonium group.

[0272] E. The composition as described in paragraph D, wherein the quaternary ammonium group comprises at least one C1 to C2 group. 18 Alkyl groups.

[0273] F. The composition as described in any one of paragraphs D or E, wherein the quaternary ammonium group comprises at least one C1 to C4 alkyl group.

[0274] G. The composition as described in any one of paragraphs DF, wherein the quaternary ammonium group comprises at least one C 10 To C 16 Alkyl groups, preferably wherein the quaternary ammonium group further comprises two C1 to C4 alkyl groups.

[0275] H. The composition as described in any one of paragraphs DG, wherein the quaternary ammonium group comprises a trimethylammonium group.

[0276] I. The composition as described in any one of paragraphs A and H, wherein the positively charged organic group comprises a quaternary ammonium hydroxyalkyl group, preferably wherein the quaternary ammonium hydroxyalkyl group comprises a quaternary ammonium hydroxymethyl group, a quaternary ammonium hydroxyethyl group, or a quaternary ammonium hydroxypropyl group.

[0277] J. The composition as described in paragraph I, wherein the quaternary ammonium hydroxyalkyl group comprises a trimethylammonium hydroxyalkyl group, preferably a trimethylammonium hydroxypropyl group.

[0278] K. The composition as described in any one of paragraphs A and J, wherein the degree of substitution is from about 0.01 to about 1.5, preferably from about 0.01 to about 1.0, more preferably from about 0.01 to about 0.8, more preferably from about 0.03 to about 0.7, or from about 0.04 to about 0.6, or from about 0.05 to about 0.5.

[0279] L. The composition as described in any one of paragraphs AK, wherein the polyα-1,6-glucan ether compound has a weight-average degree of polymerization in the range of about 5 to about 6000, preferably about 50 to 5000, or 100 to 4000, or 250 to 3000, or 500 to 2000, or 750 to 1500, or 1000 to 1400, or 1100 to 1300.

[0280] M. The composition as described in any one of paragraphs A and B, wherein the poly-α-1,6-glucan ether compound is characterized by a weight-average molecular weight of about 10,000 to about 400,000 Daltons, or about 40,000 to about 300,000 Daltons, or about 80,000 to about 300,000 Daltons, or about 100,000 to about 250,000 Daltons, or about 150,000 to about 250,000 Daltons, or about 180,000 to about 225,000 Daltons, or about 180,000 to about 200,000 Daltons.

[0281] N. The composition as described in any one of paragraphs A and B, wherein the poly-α-1,6-glucan ether compound is characterized by being derived from a poly-α-1,6-glucan having a weight-average molecular weight of about 10,000 to about 350,000 Daltons, or about 50,000 to about 350,000 Daltons, or about 90,000 to about 300,000 Daltons, or about 125,000 to about 250,000 Daltons, or about 150,000 to about 200,000 Daltons, as determined before substitution with at least one positively charged organic group.

[0282] O. The composition as described in any one of paragraphs AN, wherein the poly-α-1,6-glucan comprises a backbone of glucose monomer units, wherein at least 70%, or at least 75%, or at least 80%, or at least 90%, or at least 95% of the glucose monomer units are linked via α-1,6-glycosidic bonds.

[0283] P. The composition as described in any one of paragraphs A and B, wherein the poly-α-1,6-glucan ether compound is characterized by a weight-average molecular weight of about 150,000 to about 225,000, a degree of substitution of about 0.05 to about 0.5, and wherein about 5% to about 20% of the main-chain glucose monomer units are branched via α-1,2 and / or α-1,3 glycosidic bonds, preferably α-1,2 glycosidic bonds.

[0284] Q. The composition as described in any one of paragraphs AP, wherein the poly-α-1,6-glucan ether compound is characterized by at least 5% biodegradability on the 90th day of the test duration, more preferably on the 60th day of the test duration, as determined by the biodegradability test method described herein (i.e., the CO2 emission test method of OECD Guideline 301B), and even more preferably at least 10%, or at least 15%, or at least 20%, or at least 25%, or at least 30%, or at least 35%, or at least 40%, or at least 45%, or at least 50%, or at least 55%, or at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80% biodegradability on the 90th or 60th day of the test duration.

[0285] R. The composition as described in any one of paragraphs AQ, wherein the composition comprises about 0.01% to about 10%, or about 0.1% to about 5%, or about 0.1% to about 3%, or about 0.1% to about 2%, or about 0.1% to about 1%, or about 0.1% to about 0.8% of a poly-α-1,6-glucan ether compound by weight of the composition.

[0286] S. The composition as described in any one of paragraphs A, R, and C, further comprises an ingredient selected from the group consisting of: surfactants, conditioning agents, deposition aids, rheology modifiers or structural agents, bleaching systems, stabilizers, detergent builders, chelating agents, dye transfer inhibitors, dispersants, enzymes and enzyme stabilizers, catalytic metal complexes, polymer dispersants, clay and dirt removers / anti-redeposition agents, brighteners, foam inhibitors, silicones, hueing agents, aesthetic dyes, additional fragrances and fragrance delivery systems, structure-elasticizing agents, carriers, water-soluble additives, processing aids, anti-aggregating agents, coatings, formaldehyde removers, pigments, and mixtures thereof.

[0287] T. The composition as described in any one of paragraphs A, wherein the composition is in the form of: liquid composition, granular composition, hydrocolloid, single-compartment pouch, multi-compartment pouch, soluble sheet, tablet or bead, fibrous article, tablet, rod, strip, sheet, foam / mousse, nonwoven sheet, or mixture thereof.

[0288] U. The composition as described in any one of paragraphs AT, wherein the composition is a liquid, characterized in that it reacts in 20 seconds. -1 Viscosities of approximately 1 to 1500 centipoise (1-1500 mPa*s) at 21°C, or 100 to 1000 centipoise (100-1000 mPa*s), or 100 to 500 centipoise (100-500 mPa*s), or 100 to 300 centipoise (100-300 mPa*s), or 100 to 200 centipoise (100-200 mPa*s).

[0289] V. The composition as described in any one of paragraphs AU, wherein at least one of (a)-(d) is true: (a) the composition is in the form of a single-compartment or multi-compartment pouch, and wherein the additional component comprises less than 20% water by weight of the composition, and optionally wherein the poly-α-1,6-glucan ether compound is characterized by a weight-average molecular weight of about 150,000 to about 225,000, a degree of substitution of about 0.05 to about 0.4, and wherein about 5% to about 20% of the main-chain glucose monomer units are via α-1,2 and / or α-1,3 glycosidic bonds, preferably α-1,2 having branches; or (b) the composition is in the form of granules The product is in granular form, wherein each granule has a mass of about 1 mg to about 1 gram, and wherein the granules comprise a polyα-1,6-glucan ether compound dispersed in a water-soluble carrier, preferably selected from the group consisting of: polyethylene glycol, sodium acetate, sodium bicarbonate, sodium chloride, sodium silicate, polypropylene glycol polyoxyethylene, polyethylene glycol fatty acid esters, polyethylene glycol ethers, sodium sulfate, starch, and mixtures thereof; and optionally wherein the polyα-1,6-glucan ether compound is characterized by a weight-average molecular weight of about 150,000 to about 225,000, a degree of substitution of about 0.1% to about 0.4%, and wherein about 5% to about 10% of the product has a specific molecular weight. The main-chain glucose monomer units are branched via α-1,2 and / or α-1,3 glycosidic bonds, preferably with α-1,2 branched bonds; or (c) the composition is in liquid form, comprising about 40% to about 95% water by weight of the composition, further comprising about 5% to about 50% surfactant by weight of the composition, and optionally wherein the polyα-1,6-glucan ether compound is characterized by a weight-average molecular weight of about 150,000 to about 225,000, a degree of substitution of about 0.05 to about 0.4, and wherein from about 5% to about 20% of the main-chain glucose monomer units are branched via α-1,2 and / or α-1,3 branched bonds; The glycosidic bond, preferably α-1,2-branched; or (d) the composition is in liquid form, comprising about 40% to about 98% water by weight of the composition, and about 1% to about 35% fabric softener, preferably a quaternary ammonium compound and / or silicone by weight of the composition, and optionally wherein the polyα-1,6-glucan ether compound is characterized by a weight average molecular weight of about 150,000 to about 225,000, a degree of substitution of about 0.4 to about 0.5, and wherein about 5% to about 10% of the main-chain glucose monomer units are branched via α-1,2 and / or α-1,3 glycosidic bonds, preferably α-1,2-branched.

[0290] W. A method of treating a surface with a composition according to any one of paragraphs AV, the method comprising the step of contacting the surface with the composition optionally in the presence of water.

[0291] Example

[0292] Unless otherwise stated, all ingredients were purchased from Sigma-Aldrich, St. Louis, Missouri and used as is. 3-Chloro-2-hydroxypropyltrimethylammonium chloride (QUAB 188), glycidyltrimethylammonium chloride (also known as 2,3-epoxypropyltrimethylammonium chloride) (QUAB 151), and 3-chloro-2-hydroxypropyldodecyldimethylammonium chloride (QUAB 342) were obtained from SKW QUAB Chemicals.

[0293] As used in this article, “Comp.Ex.” means comparative example; “Ex.” means example; “std dev” means standard deviation; “g” means gram; “kg” means kilogram; “mL” means milliliter; “uL” means microliter; “wt” means weight; “L” means liter; “min” means minute; “kDa” means kilodalton; and “PES” means polyethersulfone.

[0294] Methods for determining end-group isomer bonds using NMR spectroscopy

[0295] pass 1 ¹H NMR (nuclear magnetic resonance spectroscopy) was used to determine glycosidic bonds in water-soluble oligosaccharide and polysaccharide products synthesized by glucosyltransferase GTF8117 and α-1,2-branched enzymes. The dried oligosaccharide / polysaccharide polymer (6 mg to 8 mg) was dissolved in 0.7 mL of 1 mM DSS (4,4-dimethyl-4-silylpentane-1-sulfonic acid; NMR reference standard) in D₂O. The sample was stirred overnight at ambient temperature. 525 μL of the clear, homogeneous solution was transferred to a 5 mm NMR tube. 2D NMR experiments were performed. 1 H, 13 C iso / heteronuclear kits were used to identify AGU (agglutinin unit) bonds. Data were collected at 20 °C and processed on a Bruker Avance III NMR spectrometer operating at 500 MHz or 600 MHz. The system was equipped with a proton-optimized helium-cooled cryoprobe. 1D was used. 1 ¹H NMR spectra were used to quantify the distribution of glycosidic bonds and it was found that the polysaccharide backbone was mainly α-1,6. The results reflect the ratio of the overall intensity of the NMR resonances representing individual bond types to the sum of the overall intensities of all peaks representing glucose bonds multiplied by 100.

[0296] Used to determine the molar degree of substitution of polyα-1,6-glucan ether derivatives 1 1H nuclear magnetic resonance (NMR) method

[0297] Approximately 30 mg of the poly(α-1,6-glucan ether) derivative was weighed into a vial using an analytical balance. The vial was removed from the balance, and 1.0 mL of deuterium oxide was added. A magnetic stir bar was added to the vial, and the mixture was stirred to suspend the solid. Then, 1.0 mL of deuterated sulfuric acid (50% v / v, in D₂O) was added to the vial, and the mixture was heated at 90 °C for 1 hour to depolymerize and dissolve the polymer. The solution was cooled to room temperature, and then 0.8 mL aliquots of the solution were transferred to 5 mm NMR tubes using glass pipettes. Quantitative analysis was performed using an Agilent VNMRS 400 MHz NMR spectrometer equipped with a 5 mm auto-switching four-probe system. 1 1H NMR spectra. Spectra were acquired at a frequency of 399.945 MHz using a spectral window of 6410.3 Hz, an acquisition time of 3.744 seconds, an inter-pulse delay of 10 seconds, and 64 pulses. Time-domain data were transformed using an exponential multiplication method at 0.50 Hz.

[0298] Determination of weight-average molecular weight and / or degree of polymerization

[0299] The degree of polymerization (DP) was determined by size exclusion chromatography (SEC). For SEC analysis, the dried poly-α-1,6-glucan ether derivative was dissolved in phosphate-buffered saline (PBS) (0.02–0.2 mg / mL). The chromatographic system used was an Alliance system from Waters Corporation (Milford, MA). TM The 2695 liquid chromatograph is coupled with three online detectors: a differential refractometer 410 from Waters, a multi-angle light scattering spectrophotometer Heleos from Wyatt Technologies (Santa Barbara, California). TM 8+, and the ViscoStar differential capillary viscometer from Wyatt Technologies. TM The columns used for SEC are two Tosoh Haas Bioscience TSK GMPW columns used for aqueous polymers. XL G3K and G4K G3000PW and G4000PW polymer columns. The mobile phase was PBS. The chromatographic conditions used were: 30°C in the column and detector compartment, 30°C in the sample and syringe compartment, a flow rate of 0.5 mL / min, and an injection volume of 100 μL. The software package used for data simplification was Astra version 6 (triple detection method with column calibration) from Wyatt.

[0300] milliequivalence calculation

[0301] As used herein, the term “cationic charge density (CCD) / dose” refers to the amount of positive charge present in the volume of a single dose of the fabric conditioner composition to be dispensed. As an example, assuming a 48.5 g dose of fabric conditioner contains 0.48% of a cationic polymer having a monomer average molecular weight of 220 g / mol and a cationic degree of substitution of 0.38, the CCD is calculated as follows: the polymer charge density is 0.38 / 220 × 1000 or 1.7 meq / g, and the CCD is 48.5 g × 0.0048 × 1.7 meq / g or 0.40 meq / dose.

[0302] ζ potential measurement

[0303] The zeta potential was measured using a Malvern Zeta Sizer ZEN3600 and a disposable capillary sample cell (green cell). The instrument was calibrated using the zeta potential transfer standard DTS1235, lot number #311808, -42mV + / -4.2m to ensure proper instrument function. Before starting the experiment, the capillary cell was rinsed with 1–2 mL of ethanol, followed by DI water. The sample was prepared by mixing 99.75 g of Tide HDL solution at the target concentration with 0.25 g of the fabric conditioning composition. The Tide HDL solution was prepared by diluting the target amount of Tide HDL detergent with 7 g pg water hardness. The sample was transferred into the capillary sample cell using a syringe, ensuring no air bubbles were present. The cell was filled to the top, and the cap was placed over the cell outlet and inlet, again ensuring no air bubbles were present in the sample. Finally, the cell was placed in the sample chamber with the electrodes facing the side of the system. The experiment was conducted using a refractive index of 1.46 (this value can vary for suspensions, and the refractive index of any particulate suspension can be measured using a refractometer), a temperature of 25°C, and an equilibration time of 120 seconds. The instrument used the Smoluchowski model to calculate the zeta potential of the sample.

[0304] Biodegradation test methods

[0305] The biodegradability of polysaccharide derivatives was determined according to the OECD 301B Guideline for Rapid Biodegradability and CO2 Emission Testing (see OECD, 1992, OECD 301 Rapid Biodegradability, OECD Guideline for Testing Chemicals, Part 3 – incorporated herein by reference). In this study, the test substance was the sole source of carbon and energy, and under aerobic conditions, microorganisms metabolized the test substance to produce CO2 or incorporated carbon into the biomass. The amount of CO2 produced by the test substance (corrected for CO2 released from a blank inoculum) is expressed as a percentage of the theoretical amount of CO2 (ThCO2) that could be produced if all the organic carbon in the test substance were converted to CO2.

[0306] Homogenize

[0307] Equalization was performed using an IKA ULTRA TURRAX T25 digital equalizer (IKA, Wilmington, North Carolina).

[0308] Fabric preparation

[0309] To evaluate the properties of the conditioning composition and / or the polymers contained therein, fabrics were prepared / treated according to the following methods.

[0310] A. Equipment and Materials

[0311] Fabrics were evaluated using Kenmore FS 600 and / or 80 series washing machines. The washing machine was set to: 32°C / 15°C wash / rinse temperature, 6 gpg stiffness, normal cycle, and medium load (64 liters). The fabric bundle consisted of 2.5 kg of clean fabric made of 100% cotton. Test samples were included in this bundle and also included 100% cotton Euro Touch terry cloth towels (purchased from Standard Textile, Inc., Cincinnati, Ohio).

[0312] B. Stripping and Desizing

[0313] Before treating with any test product, peel the fabric bundles according to the fabric preparation-peeling and desizing procedure, and then test.

[0314] Fabric preparation – peeling and desizing procedure consisted of washing a clean fabric bundle (2.5 kg of fabric containing 100% cotton) (this fabric bundle included a test sample of 100% cotton EuroTouch terry cloth towels) for 5 consecutive wash cycles, followed by a drying cycle. Peeling / desizing was performed on the test sample fabric and the clean fabric bundle (1x recommended dose / wash cycle) using AATCC (American Association of Textile Chemists and Colorists) High Efficiency (HE) liquid detergent. Washing conditions were as follows: Kenmore FS 600 and / or 80 series washer (or equivalent), set to: 48°C / 48°C wash / rinse temperature, water hardness equal to 0 gpg, normal wash cycle, and medium load (64 liters). The dryer timer was set to 55 minutes on the cotton / high / timed dry setting.

[0315] C. Test Processing

[0316] After the machine was at least half full, add Tide Free liquid detergent (1x recommended dose) below the surface of the water. Once the water stopped flowing and the washing machine began agitation, add the clean fabric bundles. When the machine was almost full of rinse water and before agitation began, slowly add the fabric care test composition (e.g., liquid conditioning composition) (1x dose), ensuring that no fabric care test composition came into direct contact with the test sample or fabric bundle. When the wash / rinse cycle was complete, each wet fabric bundle was transferred to the appropriate dryer. The dryers used were Maytag commercial series (or equivalent) electric dryers with the timer set to 55 minutes on the cotton / high heat / timed drying setting. The process was repeated for a total of three (3) complete wash-dry cycles. After the third drying cycle and once the dryer stopped, 12 terry cloth towels were removed from each fabric bundle for active substance deposition analysis. The fabrics were then placed in a grading chamber controlled by constant temperature / relative humidity (21°C, 50% RH) for 12–24 hours and then graded for softness and / or active substance deposition.

[0317] Secant Modulus Instron Method

[0318] The secant modulus was measured using a tensile and compression testing instrument such as the Instron Model 5565 (Instron Corp., Norwood, Massachusetts, USA). The instrument was configured according to the fabric type by selecting the following settings: mode is tensile stretch; waveform shape is triangular; maximum strain of 479 pre-shrinkage is 10% and maximum strain of 7422 knit is 35%; 479 pre-shrinkage rate is 0.83 mm / sec and 7422 knitting rate is 2.5 mm / sec; number of cycles is 4; and the holding time between cycles is 15 seconds.

[0319] 1. Using scissors, cut the rough seam edge of the entire side of each sample warp-up, and carefully peel the thread without stressing the fabric until a uniform edge is obtained.

[0320] 2. Place a fabric pressing die that cuts strips 1” wide and at least 4” long parallel to the uniform edge and longitudinally cuts the strips in the warp direction.

[0321] 3. Cut three strips from three separate fabric samples / treatments: test fabric 479 pre-shrinked 100% cotton fabric or test fabric 742250:50 knitted polyester-cotton fabric. Condition the fabrics in a room with constant temperature (70°F) and humidity (50% RH) for at least 6 hours prior to analysis.

[0322] 4. Clamp the top and then the bottom of the fabric strip in the 2.54cm clamp on the tensile testing machine, set the gap to 2.54cm, and apply a small force (0.05N-0.2N) to the sample.

[0323] 5. During the holding cycle, loosen the bottom clamp and re-clamp the sample, apply a force of 0.05N-0.2N to the sample, and eliminate the slack by applying the same force again.

[0324] 6. Report the secant modulus in megapascals (MPa) when the sample has completed 4 hysteresis cycles. The final result is the average of the 4 modulus results from a single cycle for a given treatment on a given fabric type. Calculate the reported secant modulus at maximum strain for each fabric type.

[0325] Methods for determining viscosity

[0326] The viscosity of the fabric conditioning composition was measured using a TA AR G2 controlled stress rheometer with concentric cylindrical geometry. The temperature was maintained constant at 20°C for 2 minutes before testing. Viscosity was then measured at different shear rates from 0.01 to 100 sec⁻¹ using a logarithmic steady-state flow rate ramp of 5 points upwards per decimal.

[0327] Professional olfactory expert group

[0328] After the dry fabrics were equilibrated overnight in a constant temperature of 70°F and humidity of 50%, the dry olfactory properties of cotton terry cloth towels from Calderon Textiles were evaluated by a panel of 20 experts. Comparisons were made using an intensity scale from 0 to 10, where 0 indicates undetectable, 1-3: slightly fragrant, 4-7: moderately fragrant, and 8-10: strongly fragrant. The expert panel members' ratings were converted to a scale of 10-100, and the average was taken across all 20 expert panel members.

[0329] Determine the coefficient of friction (CoF)

[0330] To determine the coefficient of friction (CoF or kCoF (coefficient of kinetic friction)), the following method is used.

[0331] Five fabrics (32cm x 32cm 100% cotton terrywash cloth, such as RN37002LL from Calderon Textiles, Indianapolis, Indiana, USA) were treated three times with a standard wash / dry cycle.

[0332] Upon completion of the third drying cycle, the treated fabric was equilibrated at 23°C and 50% relative humidity for at least 8 hours. The treated fabric was laid flat and stacked no more than 10 pieces high during equilibration. Friction measurements of the test product and the zero-polymer control product were performed on the same day under the same environmental conditions used during the equilibration step.

[0333] Fabric-to-fabric friction was measured using a friction / peel tester with a 2 kgf force sensor (e.g., model FP2250, Thwing-Albert Instruments, West Berlin, NJ, USA). A clamping skid with a 6.4 × 6.4 cm footprint and a weight of 200 g was used (e.g., product number 00225-218, Thwing Albert Instruments, West Berlin, NJ, USA). The distance between the force sensor and the skid was set to 10.2 cm. The distance between the crosshead and the sample stage was adjusted to 25 mm, as measured from the bottom of the crosshead to the top of the sample stage. The instrument was configured with the following settings: a T2 measurement time of 10.0 sec, a total measurement time of 20.0 sec, and a test rate of 20 cm / min.

[0334] Place the terry cloth / washing cloth label side down, and then define the right side of the fabric as the side facing up. If there is no label and the front and back of the fabric are different, it is important to designate one side of the terry cloth fabric as the "right side" and maintain consistency in this designation across all terry cloth / washing cloths. Then orient the terry cloth / washing cloth so that the loops are pointing to the left. Using fabric scissors, cut an 11.4cm x 6.4cm fabric sample from the terry cloth / washing cloth, 2.54cm from the bottom and sides. The fabric sample should be aligned so that the 11.4cm length is parallel to the bottom of the cloth and the 6.4cm edge is parallel to the left and right sides of the cloth. Then attach the wash cloth from which the sample was cut to the instrument's sample stage, maintaining this same orientation.

[0335] Attach an 11.4cm × 6.4cm fabric sample to the clamping sled with the right side facing out, so that the right side of the fabric sample on the sled can be pulled over the right side of the washcloth on the sample plate. Then place the sled on the washcloth so that the loops of the sample on the sled are aligned against the pile of the washcloth loops. Attach the sled to the force sensor. Move the crosshead until the force sensor shows 1.0–2.0 gf (gram force), and then move it backward until the load reading is 0.0 gf. Next, begin the measurement, and record the coefficient of kinetic friction (kCOF) per second using the instrument during sled dragging.

[0336] For each type of washing cloth, calculate the average kCOF over a measurement time range of 10 to 20 seconds:

[0337] f=(kCOF10s +kCOF 11s +kCOF 12s +…+kCOF 20s ) / 12

[0338] Then calculate the average kCOF of the five washcloths for each product:

[0339] F = (f1 + f2 + f3 + f4 + f5) / 5

[0340] The change in friction of the test product relative to the control detergent was calculated as follows:

[0341] F (对照) -F (测试产品) =Change in frictional force

[0342] Ingredients

[0343] For the following examples of formulations, unless otherwise specified, the ingredients are indicated by the following symbols:

[0344]

[0345]

[0346] Preparation of poly-α-1,6-glucan samples

[0347] A method for preparing poly-α-1,6-glucan containing varying amounts of α-1,2-branched polysaccharides is disclosed in published patent application WO2017 / 091533 (which is incorporated herein by reference). Reaction parameters such as sucrose concentration, temperature, and pH can be adjusted to provide poly-α-1,6-glucan with various levels of α-1,2-branching and molecular weight. A representative procedure for preparing α-1,2-branched poly-α-1,6-glucan (containing 24% α-1,2-branching and 76% α-1,6-bonds) is provided below. Using 1D 1 ¹H NMR spectra were used to quantify the distribution of glycosidic bonds. Similarly, other samples of poly-α-1,6-glucan with α-1,2-branching were prepared. For example, one sample contained 32% α-1,2-branching and 68% α-1,6 bonds, another contained 10% α-1,2-branching and 90% α-1,6 bonds, and yet another contained 5% α-1,2-branching and 90% α-1,6 bonds.

[0348] Preparation of poly-α-1,6-glucan with 24% α-1,2-branchs

[0349] Soluble α-1,2-branched poly-α-1,6-glucan was prepared by stepwise combination of glucosyltransferase GTF8117 and α-1,2-branched enzyme GTFJ18T1 according to the following procedure.

[0350] A reaction mixture (2 L) consisting of sucrose (450 g / L), GTF8117 (9.4 U / mL), and 50 mM sodium acetate was adjusted to pH 5.5 and stirred at 47 °C. Aliquots (0.2–1 mL) were taken out at a predetermined time and quenched by heating at 90 °C for 15 min. The resulting heat-treated aliquots were passed through a 0.45 μm filter. The concentrations of sucrose, glucose, fructose, Leuconostoc disaccharide, oligosaccharides, and polysaccharides were determined by HPLC analysis. After 23.5 h, the reaction mixture was heated to 90 °C for 30 min. The heat-treated reaction mixture of aliquots was passed through a 0.45 μm filter, and the soluble monosaccharides / disaccharides, oligosaccharides, and polysaccharides in the flow mixture were analyzed. The major product was linear dextran with a DPw of 93.

[0351] A second reaction mixture was prepared by adding 238.2 g of sucrose and 210 mL of α-1,2-branching enzyme GTFJ18T1 (5.0 U / mL) to the remaining heat-treated reaction mixture obtained from the GTF8117 reaction described above. The mixture was stirred at 30 °C in a volume of approximately 2.2 L. Aliquots (0.2–1 mL) were taken out at a predetermined time and quenched by heating at 90 °C for 15 min. The resulting heat-treated aliquots were passed through a 0.45 μm filter. The flow-through was analyzed by HPLC to determine the concentrations of sucrose, glucose, fructose, Leuconostoc disaccharide, oligosaccharides, and polysaccharides. After 95 h, the reaction mixture was heated to 90 °C for 30 min. The heat-treated reaction mixture of aliquots was passed through a 0.45 μm filter, and the soluble monosaccharides / disaccharides, oligosaccharides, and polysaccharides in the flow-through were analyzed. The remaining heat-treated mixture was centrifuged using a 1 L centrifuge flask. Collect the supernatant and clean it more than 200 times using an ultrafiltration system with a 1 or 5 kDa MWCO cartridge and deionized water. Dry the cleaned oligosaccharide / polysaccharide product solution. Then pass through... 1 1H NMR spectroscopy was used to analyze the dried samples to determine the end-group isomer bonds of oligosaccharides and polysaccharides.

[0352] Example 1

[0353] This example describes the preparation of quaternary ammonium poly-α-1,6-glucan ether compounds, specifically trimethylammonium hydroxypropyl poly-α-1,6-glucan.

[0354] A polysaccharide solution (43% solids, 7.3 kg; α-1,6-glucan with 32% α-1,2-branchs and 68% α-1,6 bonds, Mw 53 kDa) was loaded into a 22 L reactor equipped with a top stirrer. 2.72 kg of 50% NaOH solution was added to the stirred solution. The mixture was heated to 50 °C. 7.6 kg of a 65% solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride (QUAB 188) was added via a feeding funnel over 2 hours and 45 minutes. The reaction was then maintained at 58 °C for 3 hours. The reaction mixture was diluted with water (500 mL) and neutralized with 18 wt% HCl. The product was purified by ultrafiltration (10-kDa membrane) and lyophilized. The degree of substitution of the product was determined by... 1 The H NMR value was determined to be 0.4.

[0355] Example 2

[0356] This example describes the preparation of quaternary ammonium poly-α-1,6-glucan ether compounds, specifically trimethylammonium hydroxypropyl poly-α-1,6-glucan.

[0357] Add 100 mL of water to a 1-L round-bottom flask equipped with a top stirrer, followed by 100 g of a polysaccharide (α-1,6-glucan with 10% α-1,2-branchs and 90% α-1,6 bonds, Mw 60 kDa). After dissolution, add 87 g of 50% sodium hydroxide solution over 5–10 min. Stir the mixture at room temperature for 1 hour. After another 10 min, add 265 g of a 60% solution of 3-chloro-2-hydroxypropyltrimethylammonium chloride (QUAB 188). Heat the mixture at 60 °C for 3 hours under nitrogen. Cool the mixture to approximately 50 °C and neutralize with 18% HCl. Dilute the resulting solution with water (4 L), purify the product by ultrafiltration (30-kDa membrane), and freeze-dry. The degree of substitution of the product is determined by… 1 The H NMR value was determined to be 0.6.

[0358] Example 3

[0359] This example describes the preparation of quaternary ammonium poly-α-1,6-glucan ether compounds, specifically trimethylammonium propyl poly-α-1,6-glucan.

[0360] Add 690 g of a polysaccharide solution (29% solids; α-1,6-glucan with 5% α-1,2-branchs and 95% α-1,6 bonds, Mw 185 kDa) to a 2-L reactor equipped with a top stirrer. Stir the solution. Add 12 g of 50% sodium hydroxide dropwise to the stirred solution. Stir the mixture at room temperature for 45 min. Add 100 g of a 71%-75% solution of glycidyltrimethylammonium chloride (QUAB 151) to the stirred mixture. Heat the mixture at 60 °C for 4 h. Dilute the mixture with 200 mL of water and neutralize with 18 wt% HCl. Purify the product by ultrafiltration (30-kDa membrane) and freeze-dry. The degree of substitution of the product is determined by... 1 The H NMR value was determined to be 0.4.

[0361] Example 4

[0362] This example describes the preparation of quaternary ammonium poly-α-1,6-glucan ether compounds, specifically trimethylammonium propyl poly-α-1,6-glucan.

[0363] Add 690 g of a polymer solution (29% solids; α-1,6-glucan with 5% α-1,2-branchs and 95% α-1,6 bonds, Mw 185 kDa) to a 2-L reactor equipped with a top stirrer. Stir the solution. Add 12 g of 50% sodium hydroxide dropwise to the stirred solution. Stir the mixture at room temperature for 45 min. Add 33 g of a 71%-75% solution of glycidyltrimethylammonium chloride (QUAB 151) to the stirred mixture. Heat the mixture at 60 °C for 4 h. Dilute the mixture with 200 mL of water and neutralize with 18 wt% HCl. Purify the product by ultrafiltration (30-kDa membrane) and freeze-dry. The degree of substitution of the product is determined by... 1 The H NMR value was determined to be 0.03.

[0364] Example 5

[0365] This example describes the preparation of quaternary ammonium poly-α-1,6-glucan ether compounds, specifically dodecyl dimethylammonium hydroxypropyl poly-α-1,6-glucan.

[0366] 19 g of water was added to a 4-necked, 500-mL reactor equipped with a mechanical stir bar, thermocouple, and feeding funnel. Then, 21 g of polysaccharide (α-1,6-glucan with 32% α-1,2-branchs and 68% α-1,6 bonds, Mw 68 kDa) was added to provide a solution. The solution was stirred while 137 g of 40 wt% 3-chloro-2-hydroxypropyldodecyl dimethylammonium chloride (QUAB 342) was added. The resulting mixture was stirred at room temperature for 2 hours. Sodium hydroxide (15.8 g, 50 wt%) was added over 10-minute intervals. The reaction mixture was heated to 60 °C (10 min) and stirred at 57 °C–60 °C for 3 hours. After cooling to 35 °C, the reaction mixture was poured into water to a total volume of approximately 3 L. The pH of the mixture was adjusted to approximately 7 by adding 18.5 wt% hydrochloric acid. The product was purified by ultrafiltration (5-kDa membrane) and lyophilized. The degree of substitution of the product was determined by... 1 The HNMR value was determined to be 0.4.

[0367] Example 6

[0368] This example describes the preparation of quaternary ammonium poly-α-1,6-glucan ether compounds, specifically dodecyl dimethylammonium hydroxypropyl poly-α-1,6-glucan.

[0369] 80 g of a 3-chloro-2-hydroxypropyldodecyl dimethylammonium chloride (QUAB 342) formulation containing 32 g of chloride and 48 g of water was charged into a 4-necked, 500-mL reactor equipped with a mechanical stir bar, thermocouple, and feeding funnel. Then, 21 g of dextran powder (containing 32% α-1,2-branched and 68% α-1,6-bonded α-1,6-glucan, Mw 68 kDa) was added. The mixture was stirred at room temperature for 2 hours. Sodium hydroxide (10 g, 50 wt%) was added over a 10-minute interval. Then, water (10 mL) was added. The reaction mixture was heated to 60 °C (10 min) and stirred at 58 °C–60 °C for 3 hours. After cooling to 35 °C, the reaction mixture was poured into water to approximately 3 L of total volume. The pH of the mixture was adjusted to approximately 7 by adding 18.5 wt% HCl. The mixture was filtered, and no solids were observed in the filter. The filtrate was purified by ultrafiltration (10K membrane) and then freeze-dried to provide the product. The degree of substitution of the product was determined by... 1 The H NMR value was determined to be 0.4.

[0370] Example 7

[0371] This example describes various quaternary ammonium poly-α-1,6-glucan ether compounds produced according to the procedures of this disclosure. In the compounds listed in Table 1 below, the cationic group is a quaternary ammonium group substituted with three methyl groups (i.e., trimethylammonium), unless otherwise indicated by an asterisk (*). In each compound, the quaternary ammonium group is linked to the ether group (and thus to the dextran backbone) via a hydroxypropyl group, but any suitable alkyl group or other hydroxyalkyl group may be used accordingly for the linkage.

[0372] Table 1

[0373]

[0374]

[0375] *Cat group: surrounded by two methyl groups and one C 12 Alkyl-substituted quaternary ammonium groups (dimethyl, C12 ammonium groups).

[0376] **The numbers in parentheses are the molecular weights of the ether compounds (i.e., the main chain plus derived cationic ether groups).

[0377] Example 8. Benefits of Softness

[0378] The following tests were conducted to demonstrate that the presence of a cationicly charged poly-α-1,6-glucan ether compound can improve the performance of liquid conditioning compositions.

[0379] Fabrics were treated according to the fabric preparation method provided above. The liquid conditioning composition was a liquid fabric reinforcing agent formulated according to the formulations shown in Table 2 below. Formulations V and VI comprise cationic poly-α-1,6-glucan ether compounds as disclosed herein; formulation IV does not include and is therefore a comparative example. For each test, 49.5 g / dose of the liquid conditioning composition was provided. After fabric treatment, the mitral modulus and freshness properties of the fabric were determined using an Instron instrument according to the method described above.

[0380] Table 2: Improving Fabric Cutting Modulus

[0381]

[0382]

[0383] As shown in Table 2, even when the composition contains relatively low amounts of fabric softening active material, the addition of the cationic-substituted poly-α-1,6-glucan ether compound according to this disclosure can result in lower secant modulus measurements, which are associated with improved softness.

[0384] Example 9. Benefits of Softness and Freshness (1)

[0385] The following tests were conducted to demonstrate the effect of the molecular weight of the poly-α-1,6-glucan ether compound on the secant modulus value and its benefit to freshness, as determined by a panel of expert olfactory specialists.

[0386] The fabric was treated according to the fabric preparation method provided above. The liquid conditioning composition was a liquid fabric reinforcing agent formulated according to the formulations shown in Table 3 below, and the cationic poly-α-1,6-glucan ether compounds used were shown in Table 4 below. Formulation VIII (Table 3) included the cationic poly-α-1,6-glucan ether compounds listed in Table 4; Formulation VII did not include and was therefore a comparative example. For each test, 49.5 g / dose of the liquid conditioning composition was provided. After treatment, the mitral modulus and freshness properties of the fabric were determined using Instron instruments and a panel of professional olfactory experts according to the methods described above. The results are shown in Table 4.

[0387] Table 3: Liquid Fabric Conditioning Compositions

[0388]

[0389]

[0390] Table 4: Cutting modulus and freshness properties of liquid fabric conditioning compositions

[0391]

[0392] **The numbers in parentheses are the molecular weights of the ether compounds (i.e., the main chain plus derived cationic ether groups).

[0393] A relatively lower secant modulus value and / or a relatively higher olfactory expert panel score are associated with enhanced performance. Therefore, the data in Table 4 suggest that poly-α-1,6-glucan ether compounds according to this disclosure, having a weight-average molecular weight, for example, greater than 100,000 Daltons, can provide improved benefits.

[0394] Example 10. Benefits of Softness and Freshness (2)

[0395] The following tests were performed to demonstrate the effect of the DoS of the poly-α-1,6-glucan ether compound on the secant modulus value.

[0396] The fabric is treated according to the fabric preparation method provided above. The liquid conditioning composition is a liquid fabric reinforcing agent formulated according to the formulations shown in Table 5 below, and the cationic poly-α-1,6-glucan ether compound used is shown in Table 6 below. Formulations IX to XII comprise cationic poly-α-1,6-glucan ether compounds.

[0397] Table 5: Liquid Fabric Conditioning Compositions

[0398]

[0399] For each test, 49.5 g / dose of the liquid conditioning composition was provided. Following treatment, the cut modulus and freshness properties of the fabric were determined using Instron instruments and a panel of expert olfactory specialists according to the methods described above. The results are shown in Table 6, including the cationic charge density (CCD) per dose delivered, as attributable to the included poly(α-1,6-glucan ether) compound (as measured above).

[0400] Table 6: Cutting modulus and freshness properties of liquid fabric conditioning compositions

[0401]

[0402]

[0403] 1 Information on the cationic poly-1,6-glucan ethers of polymers J, M, and K is provided in Table 1.

[0404] The examples in Table 6 illustrate that when the equivalent of the cationic charge density per dose of the fabric conditioning composition is greater than 0.1 milliequivalents, the polyα-1,6-glucan ether compounds according to this disclosure, having a weight-average molecular weight between about 185,000 and about 200,000 Da and a relatively low degree of branching, for example, about 5% to about 20% (see Table 1 for MW and branches), provide improved benefits.

[0405] Example 11. Viscosity Effect

[0406] The following tests were performed to demonstrate the relative effect on the viscosity of the α-1,2-branch of the cationic poly-α-1,6-glucan ether compound, including a comparison with the cationic poly-α-1,3-glucan ether compound.

[0407] Liquid conditioning compositions having formulations according to Table 7 were prepared using different cationic dextran ethers as indicated below. The viscosity of each liquid conditioning composition was determined according to the methods described above. The results are shown in Table 8.

[0408] Table 7: Liquid Fabric Conditioning Compositions

[0409]

[0410] Table 8: Viscosity of fabric conditioning agent at 60 rpm

[0411]

[0412] 1 Information on the cationic poly-1,6-glucan ethers of polymers L, J, K, S and N is provided in Table 1.

[0413] 2 A cationic poly-1,3-glucan ether compound with a total MW of 145 kDa and derived from a trimethylammonium hydroxypropyl group.

[0414] As shown in Table 8, the product viscosity associated with the polyα-1,6-glucan ether compound in Formulation XIII is relatively lower than that associated with polyα-1,3-glucan ether. It is believed that addition branching into the polyα-1,6-glucan ether disrupts the internal interactions between the polyα-1,6-glucan chains, resulting in a more disordered crystal structure that is easier to formulate into compositions without adversely affecting product viscosity. Lower viscosity can lead to an improved dispensing experience and less machine residue.

[0415] Example 12. Examples of different cationic functional groups

[0416] The following tests were conducted to demonstrate the effect of the type of cationic functional group on the cleavage modulus of the fabric.

[0417] The fabric was treated according to the fabric preparation method provided above. The liquid conditioning composition was a liquid fabric reinforcing agent according to formulation XIV shown in Table 9A below. For each test, 80 g / dose of the fabric reinforcing agent composition was provided. After treatment, the secant modulus of the fabric was determined using an Instron instrument according to the method described above; the results are provided in Table 9B.

[0418] Table 9A

[0419]

[0420] Table 9B: Cutting modulus of liquid fabric conditioning compositions

[0421]

[0422] 1 Information on the cationic poly-1,6-glucan ethers of polymers B, D, and E is provided in Table 1.

[0423] **The numbers in parentheses are the molecular weights of the ether compounds (i.e., the main chain plus derived cationic ether groups).

[0424] Example 13. Ratio of cationic dextran polymer to softening active substance

[0425] It is known in the art that cationic polymers interact with anionic surfactants to produce insoluble polymer-enriched phases of composite polymers held together by electrostatic and hydrophobic interactions. Typically, electropositive insoluble composite systems have a relatively higher affinity for cellulose-based fabrics due to their anionic properties. It is possible to modify the electrostatic potential of the insoluble composite system under a fixed set of conditions, for example, by adjusting the ratio of total cationic active substances in the composition.

[0426] The zeta potential was determined according to the test methods provided above. The detergent was equivalent to 3 wt% liquid TIDE detergent in water with a water hardness of 7 g pg. The liquid fabric reinforcing / softening composition contained 4 wt% cationic alkyl ester quaternary ammonium salt (quat) fabric softening active material (“FSA”), wherein the level of the cationic poly-α-1,6-glucan ether compound is provided in Table 10. The results are shown in Table 10.

[0427] Table 10

[0428]

[0429] 1 Polymer K-Reference Table 1.

[0430] The zeta potential measurements in Table 10 show that when the weight ratio of cationic poly-α-1,6-glucan ether to FSA is greater than 1:40, the liquid fabric reinforcing agent compositions according to this disclosure containing cationic poly-α-1,6-glucan ether polymers are relatively more effective in producing more electropositive insoluble composite systems. Larger ratios, such as equal to or less than 8 wt%, may be particularly relevant when the level of FSA in the treated composition is relatively low.

[0431] Example 14. Softening properties in heavy-duty liquid detergents

[0432] In the following examples, fabrics are treated with heavy-duty liquid detergent formulations. Detergent formulations are provided in Table 11.

[0433] Table 11

[0434]

[0435]

[0436] Various polymers were tested in combination with detergent formulations as listed in Table 12 below, and Instron secant modulus (7422) data were collected. The results are presented in Table 12.

[0437] Table 12

[0438]

[0439] 1 Information on the cationic poly-1,6-glucan ethers of polymers T, K, and L is provided in Table 1.

[0440] Example 15. Softness performance in laundry additive granules (1)

[0441] In the following examples, fabrics were treated with laundry additive formulations in granular (tablet or bead) form. The treatment occurred during a wash cycle in an automatic washing machine combined with a heavy-duty laundry detergent. The additive formulations are provided in Table 13. Following treatment, the secant modulus of the fabric was tested using Instron instruments, and the values ​​are provided in Table 14.

[0442] Table 13

[0443]

[0444] Table 14

[0445]

[0446] 1 Information on the cationic poly-1,6-glucan ethers of polymers J, K, and L is provided in Table 1.

[0447] Example 16. Softness performance in laundry additive granules (2)

[0448] In the following examples, fabrics were treated with laundry additive formulations in granular (tablet or bead) form. The treatment occurred during a wash cycle in an automatic washing machine combined with a heavy-duty laundry detergent. The additive formulations are provided in Table 15. Following treatment, the secant modulus of the fabric was tested using Instron instruments, and the values ​​are provided in Table 16.

[0449] Table 15.

[0450]

[0451] Table 16

[0452]

[0453] 1 Information on the cationic poly-1,6-glucan ethers of polymers A, B, and C is provided in Table 1.

[0454] Example 17. Exemplary Heavy-Duty Liquid Laundry Detergent Formulation

[0455] Table 17 shows exemplary formulations (1-7) for heavy-duty liquid (HDL) laundry detergent compositions.

[0456] Table 17

[0457]

[0458]

[0459]

[0460] Based on the total weight of the cleaning and / or treatment composition. Report enzyme levels as raw materials.

[0461] Table 17 Symbol Explanation:

[0462] AE7 is C 12-13 Alcohol ethoxylates have an average degree of ethoxylation of 7.

[0463] AE8 is C 12-13 Alcohol ethoxylates have an average degree of ethoxylation of 8.

[0464] AE9 is C 12-13 Alcohol ethoxylates have an average degree of ethoxylation of 9.

[0465] Amylase 1 is 15 mg of active substance / g, supplied by Novozymes.

[0466] Amylase 2 is 29 mg of active substance / g, supplied by Novozymes.

[0467] Xyloglucanase is 20 mg of active substance / g, supplied by Novozymes.

[0468] The chelating agent is diethylenetriaminepentaacetic acid.

[0469] Dispersin B is a glycoside hydrolase, reported as 1000 mg of active substance / g.

[0470] DTI is poly(4-vinylpyridine-1-oxide) (such as Chromabond) ), or poly(1-vinylpyrrolidone-co-1-vinylimidazolium) (such as Sokalan) ).

[0471] Dye control agents are suitable dye control agents, such as O.IN(M1), P(M2), PM (M3), or HF(M4).

[0472] HSAS are the centrally branched alkyl sulfates disclosed in US 6020303 and US 6060443.

[0473] LAS is a carbon chain with an average aliphatic carbon chain length of C9-C. 15 Straight-chain alkylbenzene sulfonates (HLAS are in acid form).

[0474] Leuco colorant is any suitable leuco colorant or a mixture thereof.

[0475] Lipase is 18 mg active substance / g, supplied by Novozymes.

[0476] V200 is a thiophene azo dye supplied by Milliken.

[0477] Mannanase is 25 mg active substance / g, supplied by Novozymes.

[0478] The nuclease is a phosphodiesterase, reported as 1000 mg of active substance / g.

[0479] Optical brightener 1 is 4,4'-bis{[4-anilino-6-morpholino- s Disodium triazine-2-yl]-amino}-2,2'-bis(phenylene disulfonate).

[0480] Optical brightener 2 is Optiblanc from 3V Sigma.

[0481] The fragrance encapsulation is a core-shell melamine-formaldehyde fragrance microcapsule (ex Encapsys).

[0482] The polishing enzyme is p-nitrobenzyl esterase, reported as 1000 mg active substance / g.

[0483] Polymer 1 is bis((C2H5O)(C2H4O)n)(CH3)-N + -C x H 2x -N + -(CH3)-bis((C2H5O)(C2H4O)n), where n = 20-30, x = 3 to 8, or its sulfided or sulfonated variants.

[0484] Polymer 2 is ethoxylated (EO) 15 Tetraethylenepentamine.

[0485] Polymer 3 is ethoxylated polyethyleneimine.

[0486] Polymer 4 is ethoxylated hexamethylenediamine.

[0487] Polymer 5 is a cationic poly-α-1,6-glucan ether according to this disclosure - for example, see Table 1 above (Polymer AT).

[0488] The protease is Purafect 40.6 mg of active substance / g, supplied by DuPont.

[0489] Example 18. Exemplary soluble unit dose formulation

[0490] Table 18 shows exemplary formulations for use in water-soluble unit-dose articles. The composition may be part of a single-compartment water-soluble unit-dose article, or it may be separated into multiple compartments to obtain a complete article composition that is “averaged across compartments.” The composition is encapsulated by a water-soluble film forming the compartments. Multi-compartment pouches may include side-by-side compartments or overlapping compartments.

[0491] Table 18

[0492]

[0493]

[0494] Example 19. Exemplary powdered detergent formulation

[0495] Table 19 shows exemplary formulations of solid free-flowing particulate laundry detergent compositions.

[0496] Table 19

[0497]

[0498]

[0499] Example 20. Exemplary shampoo formulation and its use in conditioning hair.

[0500] Table 20

[0501] Element quantity Cocamidopropyl betaine 3wt% Sodium lauryl ether sulfate (SLES) 14wt% Example 1: Cationic polyα-1,6-glucan ether 1wt% Sodium chloride 2.2wt%

[0502] Lubrication can be measured, for example, by methods described by Garcia and Diaz (1976, J. Soc. Cosmet. Chem. [Journal of the Society for Cosmetic Chemistry] 27:379-398) (which are incorporated herein by reference). The formulations in Table 20 exhibit hair lubricating properties compared to control formulations that differ only in the absence of cationic poly-α-1,6-glucan ether. For example, washing hair with the formulations in Table 20 results in a 35% reduction in the maximum force required to comb the washed hair compared to the force required to comb the control formulation.

[0503] Example 21. Confirmation of the benefits of beauty care: Hair styling application

[0504] Polymer Q from Example 7 (Table 1, 185 kDa poly-α-1,6-glucan backbone with 5% α-1,2-branching, with 0.07 DoS of hydroxypropyltrimethylammonium) was completely dissolved at 1 wt% in an ethanol / water (1 / 1) mixture. The turbidity of the solution was measured to 1 NTU (turbidimetric turbidity unit) using a calibrated turbidimeter (HACH 2100P). The solution was then poured into Petri dishes and allowed to evaporate overnight at room temperature. The resulting film was examined and found to be clear and coherent. These characteristics (low turbidity, ability to form a clear film) are considered suitable for use in hair styling products—for example, providing a clear and transparent application to the hair to provide hold while avoiding an unsightly appearance. In the curl retention test, approximately 0.5% of the polymer solution was applied to hair strands (8” RINBOOOL hair samples). In the control test, the above solvent (without Polymer Q) was applied alone. Each strand was then dried overnight at room temperature, with half of the strand curled back at an angle >90 degrees. The treated strands were then suspended in a 45°C oven and heated for 3 hours. The height of the curled half of each strand was then measured. In the control experiment, the height of the curled half of the strand changed by 4.1 cm. However, the height of the curled half of the strand treated with Polymer Q changed by only 1.2 cm, indicating a significant improvement in hair style retention.

Claims

1. A composition comprising a fabric conditioner ingredient and a poly alpha-1,6-glucan ether compound, the poly alpha-1,6-glucan ether compound comprising: (i) a poly alpha-1,6-glucan substituted with at least one positively charged organic group; (ii) a weight average degree of polymerization of from 1000 to 1500; and (iii) a degree of substitution of from 0.1 to 0.4; wherein the poly alpha-1,6-glucan comprises a backbone of glucose monomer units, and wherein at least 90% of the backbone glucose monomer units are linked via alpha-1,6-glycosidic bonds, from 4% to 20% of the backbone glucose monomer units have branching via alpha-1,2 glycosidic bonds, and less than 1 % of the glycosidic bonds of the poly alpha-1,6-glucan are alpha-1,3 glycosidic bonds; and wherein the positively charged organic group comprises a substituted quaternary ammonium group, wherein the substituted quaternary ammonium group comprises at least one C1to C 16 alkyl group.

2. The composition of claim 1, wherein, the quaternary ammonium group comprises at least one Ci to C4 alkyl group.

3. The composition of claim 1, wherein, The quaternary ammonium group comprises at least one C 10 to C 16 alkyl group.

4. The composition of claim 3, wherein, the quaternary ammonium group further comprises two Ci to C4 alkyl groups.

5. The composition of claim 1, wherein, the quaternary ammonium group comprises a trimethylammonium group.

6. The composition of claim 1, wherein, the positively charged organic group comprises a quaternary ammonium hydroxyalkyl group.

7. The composition of claim 6, wherein, the quaternary ammonium hydroxyalkyl group comprises a quaternary ammonium hydroxymethyl group, a quaternary ammonium hydroxyethyl group, or a quaternary ammonium hydroxypropyl group.

8. The composition of claim 6, wherein, the quaternary ammonium hydroxyalkyl group comprises a trimethylammonium hydroxyalkyl group.

9. The composition of claim 8, wherein, the trimethylammonium hydroxyalkyl group is a trimethylammonium hydroxypropyl group.

10. The composition of any one of claims 1-9 in the form of a liquid, a gel, a powder, a hydrocolloid, a granule, a tablet, a capsule, a bead or pastille, a single-compartment pouch, a pad, a multi- compartment pouch, a single-compartment sachet, or a multi-compartment sachet.

11. The composition of any one of claims 1-9 in the form of an aqueous solution.

12. The composition of claim 10 further comprising at least one of an enzyme, a detergent builder, a complexing agent, a polymer, a bleach, a bleach activator, a bleach catalyst, a clay, a suds booster, a suds suppressor, an anti-corrosion agent, a soil-suspending agent, an anti-soil redeposition agent, a dye, a bactericide, a tarnish inhibitor, an optical brightener, a perfume, a saturated or unsaturated fatty acid, a dye transfer inhibitor, a calcium cation, a magnesium cation, a visual signal ingredient, an antifoam, a structurant, a thickener, an anti-caking agent, a starch, a sand, a gelling agent, or a combination thereof.

13. The composition of claim 10 further comprising at least one of a soil release polymer, a hueing dye, or a combination thereof.

14. The composition of claim 12, wherein, the enzyme is a cellulase, a protease, an amylase, or a combination thereof.

15. A personal care product or an industrial product comprising the composition of any one of claims 1-14.

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