A water-soluble unit-dose article containing a polyvinyl alcohol film and a cationic poly-α-1,6-glucan ether compound.

Abstract

A water-soluble unit dose article containing a polyvinyl alcohol film and a cationic poly alpha-1,6-glucan ether compound, a method of making the water-soluble unit dose article, and a method of using the water-soluble unit dose article.

Description

Technical Field

[0001] A water-soluble unit-dose article containing a polyvinyl alcohol film and a cationic poly-α-1,6-glucan ether compound, a method for producing the water-soluble unit-dose article, and a method for using the water-soluble unit-dose article.

Background Art

[0002] Water-soluble unit-dose articles are preferred by consumers because they provide convenience and ease in the washing process. Without being bound by theory, water-soluble unit-dose articles include a water-soluble film and a washing treatment composition subdivided into dose units that may involve one or more compartments within the unit-dose article.

[0003] Such water-soluble unit-dose articles are desired to provide the advantages of both fabric washing and fabric improvement in the washing process. Fabric improvement includes advantages such as fabric shape retention, fabric softening, and fabric freshness. Fabric freshness is provided by the use of fragrances and fragrance delivery technologies.

[0004] European Patent No. 2399979 (A) discloses a water-soluble unit-dose article containing a polyvinyl alcohol-based water-soluble film and a cationic polysaccharide polymer. In the examples, cationic modified hydroxyethyl cellulose, which is known from International Publication No. 2004069979 to provide both fabric shape retention and fabric softening effects, is exemplified.

[0005] However, a problem observed with such water-soluble unit-dose articles is that both the polyvinyl alcohol film and the cationic modified hydroxyethyl cellulose have an adverse effect on the freshness effect on the fabric.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

[0007] Therefore, in this technical field, there is a need for a water-soluble unit-dose article containing a polyvinyl alcohol film that provides the advantages of maintaining fabric shape and making fabric flexible, and that at least partially reduces the adverse effects on fabric freshness compared to a water-soluble unit-dose article containing a polyvinyl alcohol water-soluble film and cationic modified hydroxyethyl cellulose.

[0008] Surprisingly, it has been discovered that the present invention overcomes this problem. Although we do not wish to be bound by theory, it has been surprisingly discovered that a water-soluble unit-dose article comprising a polyvinyl alcohol water-soluble film and a cation-modified poly-α-1,6-glucan ether compound provides superior fabric shape retention and fabric softening, while improving the advantages of fabric freshness, compared to a water-soluble unit-dose article comprising a polyvinyl alcohol water-soluble film and a cation-modified hydroxyethylcellulose. [Means for solving the problem]

[0009] A first aspect of the present invention relates to a water-soluble unit-dose article comprising a water-soluble film and a liquid laundry treatment composition, wherein the water-soluble film comprises polyvinyl alcohol and is molded to create an internal compartment, the liquid laundry treatment composition is contained within the internal compartment, and the liquid laundry treatment composition comprises a cation-modified poly-α-1,6-glucan ether compound.

[0010] A second aspect of the present invention is a method for washing fabric, comprising the steps of: preparing a washing solution by diluting a water-soluble unit-dose article according to the present invention 200 to 3000 times in water; and bringing the fabric to be washed into contact with the washing solution. [Brief explanation of the drawing]

[0011] [Figure 1] This is a water-soluble unit-dose article according to the present invention. [Modes for carrying out the invention]

[0012] Water-soluble unit dose articles A first aspect of the present invention is a water-soluble unit-dose article comprising a water-soluble film and a liquid laundry treatment composition. The water-soluble film and the liquid laundry treatment composition will be described in more detail below.

[0013] A water-soluble unit-dose article includes a water-soluble film molded to contain at least one internal compartment surrounded by a water-soluble film. The unit-dose article may include a first water-soluble film and a second water-soluble film sealed together to define the internal compartment. The water-soluble unit-dose article is configured to prevent the laundry treatment composition from leaking out of the compartment during storage. However, when the water-soluble unit-dose article is added to water, the water-soluble film dissolves, releasing the contents of the internal compartment into the washing solution.

[0014] A compartment should be understood as a closed internal space within a unit-dose article that holds a liquid laundry treatment composition. During manufacturing, a first water-soluble film may be molded to include an opening compartment into which the liquid laundry treatment composition is added. Next, the first film is covered with a second water-soluble film in a direction that closes the opening of the compartment. The first and second films are then sealed together along the sealing region.

[0015] A unit dose article may contain more than one compartment, more than two compartments, more than three compartments, or more than four compartments. The compartments may be arranged in an overlapping orientation, that is, one positioned on top of the other. In such an orientation, the unit dose article contains at least three films, one at the top, one in the middle, and one at the bottom. Alternatively, the compartments may be arranged in an adjacent orientation, that is, one adjacent to the other. The compartments may be oriented in a "tire and rim" arrangement, that is, the first compartment is positioned adjacent to the second compartment, but the first compartment at least partially surrounds the second compartment but does not completely enclose it. Alternatively, one compartment may be completely enclosed within another compartment.

[0016] If a unit dose article contains at least two compartments, one of the compartments may be smaller than the other. If a unit dose article contains at least three compartments, two of the compartments may be smaller than the third compartment, preferably with the smaller compartments overlapping the larger one. The overlapping compartments are preferably oriented adjacent to each other.

[0017] If the unit dose article contains at least four compartments, three of the compartments may be smaller than the fourth compartment, preferably the smaller compartments are superimposed on the larger compartments. The superimposed compartments are preferably oriented adjacent to each other.

[0018] In a multi-compartment orientation, the detergent composition according to the present invention may be contained in at least one of the compartments. For example, the detergent composition may be contained in only one compartment, or in two compartments, or even three compartments, or even all of the compartments.

[0019] Each section may contain the same composition or different compositions. The different compositions may all be in the same form or in different forms.

[0020] The water-soluble unit dose article may include at least two internal compartments, with the liquid laundry detergent composition contained in at least one of these compartments, and preferably the unit dose article includes at least three or even four compartments, with the liquid laundry treatment composition contained in at least one of these compartments.

[0021] Preferably, the water-soluble unit dose article contains 0 ppm to 20 ppm, preferably 0 ppm to 15 ppm, more preferably 0 ppm to 10 ppm, even more preferably 0 ppm to 5 ppm, even more preferably 0 ppm to 1 ppm, even more preferably 0 ppb to 100 ppb, and most preferably 0 ppb of dioxane. Those skilled in the art will recognize known techniques for determining dioxane.

[0022] Figure 1 discloses a water-soluble unit-dose article (1) according to the present invention. The water-soluble unit-dose article (1) comprises a first water-soluble film (2) and a second water-soluble film (3), which are sealed together in a sealing region (4). The laundry treatment composition (5) is contained within the water-soluble unit-dose article (1).

[0023] Surprisingly, a water-soluble unit-dose article containing a polyvinyl alcohol water-soluble film and a cationic modified poly-α-1,6-glucan ether compound was found to provide superior fabric shape retention and fabric softening, while improving the fabric freshness advantage, compared to a water-soluble unit-dose article containing a polyvinyl alcohol water-soluble film and a cationic modified hydroxyethylcellulose. While we do not wish to be bound by theory, it is thought that the fabric care advantage is promoted via the cationic modified polyglucan, which forms a coacervate phase when diluted with an anionic surfactant. The degree of coacervation depends on the applied molecular modification, including but not limited to molecular weight, degree of cationic substitution, and degree of hydrophobic modification.

[0024] In addition to providing excellent fabric shape retention and flexibility while exhibiting the benefits of improved fabric freshness, it was surprisingly discovered that cationically modified polyglucans enable higher water levels in water-soluble unit-dose articles without adversely affecting film fit. While we do not wish to be bound by theory, cationically modified polyglucan polymers are thought to be useful in controlling the amount of free water in sealed liquid detergent compositions.

[0025] Water-soluble film The water-soluble film of the present invention is water-soluble or water-dispersible. The water-soluble film preferably has a thickness of 20 to 150 micrometers, preferably 35 to 125 micrometers, more preferably 50 to 110 micrometers, and most preferably about 76 micrometers.

[0026] Preferably, the water solubility of the film is at least 50%, preferably at least 75%, or even more than 95%, when measured by the method described herein after using a glass filter with a maximum pore size of 20 micrometers.

[0027] Add 5 grams ± 0.1 grams of film material to a pre-weighed 3 L beaker, and add 2 L ± 5 mL of distilled water. Vigorously stir this mixture for 30 minutes at 30°C using a magnetic stirrer (Labline model number 1250) or equivalent set to 600 rpm, and a 5 cm magnetic stirrer. The mixture is then filtered through a folded qualitative sintered glass filter with the pore size defined above (maximum 20 micrometers). The water is dried from the recovered filtrate by any conventional method, and the weight of the remaining material is determined (this is the dissolved fraction or dispersed fraction). The solubility or dispersion rate can then be calculated.

[0028] Water-soluble film materials can be obtained by methods known in the art, such as casting, blow molding, extrusion, or blow extrusion of polymer materials.

[0029] The water-soluble film contains polyvinyl alcohol. Polyvinyl alcohol may be present in the water-soluble film at an amount of 50% to 95% by weight, preferably 55% to 90% by weight, and more preferably 60% to 80% by weight. Preferably, the water-soluble film contains a polyvinyl alcohol homopolymer or polyvinyl alcohol copolymer, preferably a blend of polyvinyl alcohol homopolymer and / or anionic polyvinyl alcohol copolymer, preferably selected from sulfonated and carboxylated anionic polyvinyl alcohol copolymers, particularly carboxylated anionic polyvinyl alcohol copolymers, and most preferably a blend of polyvinyl alcohol homopolymer and carboxylated anionic polyvinyl alcohol copolymer. Although not bound by theory, the term “homopolymer” generally includes polymers having one type of monomer repeating unit (e.g., polymer chains consisting of or essentially consisting of a single monomer repeating unit). In the case of polyvinyl alcohol in particular, the term "homopolymer" further encompasses copolymers having a certain distribution of vinyl alcohol monomer units and optionally vinyl acetate monomer units, depending on the degree of hydrolysis (e.g., polymer chains consisting of, or essentially consisting of, vinyl alcohol monomer units and vinyl acetate monomer units). In the limited case where hydrolysis is 100%, polyvinyl alcohol homopolymers may also include pure homopolymers having only vinyl alcohol units. While not theoretically bound, the term "copolymer" generally includes polymers having two or more types of monomer repeating units (e.g., polymer chains consisting of, or essentially consisting of, two or more different monomer repeating units, whether random copolymers, block copolymers, etc.).In particular, in the case of polyvinyl alcohol, the term “copolymer” (or “polyvinyl alcohol copolymer”) further includes, depending on the degree of hydrolysis, a copolymer having a distribution of vinyl alcohol monomer units and vinyl acetate monomer units, and at least one other type of monomer repeating unit (e.g., a ter (or more) polymer chain consisting of, or essentially comprising, vinyl alcohol monomer units, vinyl acetate monomer units, and one or more other monomer units, e.g., anionic monomer units). In the limited case where hydrolysis is 100%, a polyvinyl alcohol copolymer may include a copolymer having vinyl alcohol units and one or more other monomer units, but not vinyl acetate units. While not wishing to be bound by theory, the term “anionic copolymer” includes copolymers having anionic monomer units containing anionic moieties. A general classification of anionic monomer units that can be used in anionic polyvinyl alcohol polymers includes vinyl polymerization units corresponding to monocarboxylate vinyl monomers, their esters and anhydrides, dicarboxylate monomers having polymerizable double bonds, their esters and anhydrides, vinyl sulfonic acid monomers, and alkali metal salts of any of the above.Examples of suitable anionic monomer units include vinyl polymerization units corresponding to vinyl anionic monomers, such as vinyl acetic acid, maleic acid, monoalkyl maleic acid, dialkyl maleic acid, monomethyl maleic acid, dimethyl maleic acid, maleic anhydride, fumaric acid, monoalkyl fumaric acid, dialkyl fumaric acid, monomethyl fumaric acid, dimethyl fumarate, fumaric anhydride, itaconic acid, monomethyl itaconic acid, dimethyl itaconic acid, itaconic anhydride, vinyl sulfonic acid, allyl sulfonic acid, ethylene sulfonic acid, 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid, and 2-sulfoethyl acrylate (2-sufoethyl Examples include acrylate, alkali metal salts (e.g., sodium salt, potassium salt, or other alkali metal salt), esters (e.g., methyl, ethyl, or other C1-C4 or C6 alkyl esters), and combinations thereof (e.g., multiple types of anionic monomers, or equivalent forms of the same anionic monomer). The anionic monomer may be one or more of acrylamide-methylpropanesulfonic acid (e.g., 2-acrylamido-1-methylpropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methylacrylamido-2-methylpropanesulfonic acid), its alkali metal salt (e.g., sodium salt), and combinations thereof. Preferably, the anionic portion of the first anionic monomer unit is selected from sulfonates, carboxylates, or mixtures thereof, more preferably carboxylates, most preferably acrylates, methacrylates, maleates, or mixtures thereof. Preferably, the anionic monomer units are present in the anionic polyvinyl alcohol copolymer in an average amount ranging from 1 mol% to 10 mol%, preferably 2 mol% to 5 mol%.Preferably, polyvinyl alcohol and / or, in the case of polyvinyl alcohol, individual polyvinyl alcohol polymers have an average viscosity (μ1) in the range of 4 mPa.s to 30 mPa.s, preferably 10 mPa.s to 25 mPa.s, and are measured as a 4% polyvinyl alcohol polymer solution in desalted water at 20°C. The viscosity of the polymer is determined by measuring a freshly prepared solution using a Brookfield LV viscometer with a UL adapter, as described in British Standard EN ISO15023-2:2006 Annex E Brookfield Test method. It is international practice to specify the viscosity of a 4% polyvinyl alcohol aqueous solution at 20°C. It is well known in the art that the viscosity of an aqueous solution of a water-soluble polymer (polyvinyl alcohol or others) correlates with the weight-average molecular weight of the same polymer, and that viscosity is often used as a substitute for weight-average molecular weight. Therefore, the weight-average molecular weight of polyvinyl alcohol may be in the range of 30,000 to 175,000, or 30,000 to 100,000, or 55,000 to 80,000. Preferably, in the case of polyvinyl alcohol and / or polyvinyl alcohol blends, each polyvinyl alcohol polymer has an average degree of hydrolysis in the range of 75% to 99%, preferably 80% to 95%, and most preferably 85% to 95%. A suitable test method for measuring the degree of hydrolysis is in accordance with the standard method JIS K6726.

[0030] Most preferably, the polyvinyl alcohol is a blend of a polyvinyl alcohol homopolymer and a carboxylated anionic polyvinyl alcohol copolymer, wherein the homopolymer and the anionic copolymer are present in a relative weight ratio of 90 / 10 to 10 / 90, preferably 80 / 20 to 20 / 80, and more preferably 70 / 30 to 50 / 50.

[0031] Preferably, the water-soluble film contains a non-aqueous plasticizer. Preferably, the non-aqueous plasticizer is selected from polyols, sugar alcohols, and mixtures thereof. Suitable polyols include polyols selected from the group consisting of glycerol, diglycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol of 400 MW or less, neopentyl glycol, 1,2-propylene glycol, 1,3-propanediol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3-propanediol, trimethylolpropane, and polyether polyols, or mixtures thereof. Suitable sugar alcohols include sugar alcohols selected from the group consisting of isomalt, maltitol, sorbitol, xylitol, erythritol, adonitol, dulcitol, pentaerythritol, and mannitol, or mixtures thereof. More preferably, the non-aqueous plasticizer is selected from glycerol, 1,2-propanediol, dipropylene glycol, 2-methyl-1,3-propanediol, trimethylolpropane, triethylene glycol, polyethylene glycol, sorbitol, or mixtures thereof, and most preferably selected from glycerol, sorbitol, trimethylolpropane, dipropylene glycol, and mixtures thereof. One particularly preferred plasticizer system comprises a blend of glycerol, sorbitol, and trimethylolpropane. Another particularly preferred plasticizer system comprises a blend of glycerin, dipropylene glycol, and sorbitol. Preferably, the film contains 5% to 50% by weight, preferably 10% to 40% by weight, more preferably 20% to 30% by weight of the non-aqueous plasticizer.

[0032] Preferably, the water-soluble film contains a surfactant. Preferably, the water-soluble film contains 0.1% to 2.5% by weight, preferably 1% to 2% by weight, of the surfactant. Suitable surfactants include nonionic, cationic, anionic, and bipolar types. Suitable surfactants include, but are not limited to, polyoxyethylene-modified polyoxypropylene glycol, alcohol ethoxylates, alkylphenol ethoxylates, tertiary acetylene glycols and alkanolamides (nonionic substances), polyoxyethylene-modified amines, quaternary ammonium salts and quaternized polyoxyethylene-modified amines (cationic substances), and amine oxides, N-alkyl betaines and sulfobetaines (bipolar substances). Other suitable surfactants include sodium dioctyl sulfosuccinate, lactyl fatty acid esters of glycerol and propylene glycol, lactyl esters of fatty acids, sodium alkyl sulfate, polysorbate 20, polysorbate 60, polysorbate 65, polysorbate 80, lecithin, acetylated fatty acid esters of glycerol and propylene glycol, and acetylated esters of fatty acids, as well as combinations thereof.

[0033] Preferably, the water-soluble film according to the present invention contains a lubricant / release agent. Suitable lubricants / release agents include, but are not limited to, fatty acids and their salts, aliphatic alcohols, fatty acid esters, aliphatic amines, aliphatic amine acetates, and fatty acid amides. Preferred lubricants / release agents are fatty acids, fatty acid salts, and aliphatic amine acetates, and the amount of lubricant / release agent in the water-soluble film is in the range of 0.02% to 1.5% by weight of the water-soluble film, preferably 0.1% to 1% by weight.

[0034] Preferably, the water-soluble film contains a filler, a spreader, an anti-tack agent, a detack agent, or a mixture thereof. Suitable fillers, fillers, anti-blocking agents, detack agents, or mixtures thereof include, but are not limited to, starch, modified starch, cross-linked polyvinylpyrrolidone, cross-linked cellulose, microcrystalline cellulose, silica, metal oxides, calcium carbonate, talc, and mica. Preferred materials are starch, modified starch, and silica. Preferably, the amount of filler, spreader, anti-tack agent, detack agent, or mixture thereof in the water-soluble film is in the range of 0.1% to 25% by weight of the water-soluble film, preferably 1% to 10% by weight, more preferably 2% to 8% by weight, and most preferably 3% to 5% by weight. In the absence of starch, one preferred range of suitable fillers, spreaders, anti-tacks, detacks, or mixtures thereof is 0.1% to 1% by weight, preferably 4% by weight, more preferably 6% by weight, even more preferably 1% to 4% by weight, and most preferably 1% to 2.5% by weight of the water-soluble film.

[0035] Preferably, the water-soluble film according to the present invention has a residual water content in the range of at least 4% by weight, more preferably 4% to 15% by weight, and even more preferably 5% to 10% by weight, as measured by Karl Fischer titration.

[0036] A preferred film is one that exhibits good solubility in cold water, i.e., unheated distilled water. Preferably, such a film exhibits good solubility at a temperature of 24°C, and more preferably at 10°C. Good solubility means that, when measured by the method described herein after using the glass filter with a maximum pore size of 20 micrometers as described above, the film exhibits water solubility of at least 50%, preferably at least 75%, or even more than 95%.

[0037] Preferred films include those supplied by Monosol under product reference numbers M8630, M8900, M8779, and M8310.

[0038] The film may be opaque, transparent, or translucent. The film may include printed areas. The printed areas can be obtained using standard techniques such as flexographic printing or inkjet printing. Preferably, the ink used for the printed areas contains 0 ppm to 20 ppm, preferably 0 ppm to 15 ppm, more preferably 0 ppm to 10 ppm, even more preferably 0 ppm to 5 ppm, even more preferably 0 ppm to 1 ppm, even more preferably 0 ppb to 100 ppb, and most preferably 0 ppb of dioxane. Those skilled in the art will recognize known methods and techniques for determining the dioxane level in an ink formulation.

[0039] The film may contain an aversive agent, such as a bittering agent. Suitable bittering agents include, but are not limited to, naringin, sucrose octaacetate, quinine hydrochloride, denatonium benzoate, or mixtures thereof. Any suitable concentration of the aversive agent may be used in the film. Suitable concentrations include, but are not limited to, 1 to 5000 ppm, or even 100 to 2500 ppm, or even 250 to 2000 rpm.

[0040] Preferably, a water-soluble film, or a water-soluble unit-dose article, or both, is coated with a lubricant, which is preferably selected from talc, zinc oxide, silica, siloxane, zeolite, silicic acid, alumina, sodium sulfate, potassium sulfate, calcium carbonate, magnesium carbonate, sodium citrate, sodium tripolyphosphate, potassium citrate, potassium tripolyphosphate, calcium stearate, zinc stearate, magnesium stearate, starch, modified starch, clay, kaolin, gypsum, cyclodextrin, or mixtures thereof.

[0041] Preferably, the water-soluble film and each of its individual components independently contain 0 ppm to 20 ppm, preferably 0 ppm to 15 ppm, more preferably 0 ppm to 10 ppm, even more preferably 0 ppm to 5 ppm, even more preferably 0 ppm to 1 ppm, even more preferably 0 ppb to 100 ppb, and most preferably 0 ppb of dioxane. Those skilled in the art will recognize known methods and techniques for determining the dioxane levels in the water-soluble film and its components.

[0042] Liquid laundry treatment composition The present invention relates to a liquid laundry treatment composition. The term "liquid laundry treatment composition" refers to, but is not limited to, any laundry treatment composition that contains a liquid capable of wetting and treating fabrics, such as liquids, gels, pastes, and dispersions. A liquid composition may contain preferably subdivided forms of solids or gases, but a liquid composition excludes forms that are non-flowing as a whole, such as tablets or granules.

[0043] The liquid laundry treatment composition contains a cation-modified poly-α-1,6-glucan ether compound. The poly-α-1,6-glucan ether compound is described in more detail below.

[0044] Preferably, the liquid laundry treatment composition according to the present invention, or any component thereof, independently contains 0 ppm to 20 ppm, preferably 0 ppm to 15 ppm, more preferably 0 ppm to 10 ppm, even more preferably 0 ppm to 5 ppm, even more preferably 0 ppm to 1 ppm, even more preferably 0 ppm to 100 ppb, and most preferably 0 ppm of dioxane. Those skilled in the art will recognize known methods and techniques for determining the dioxane level in a liquid detergent composition.

[0045] Preferably, the liquid laundry treatment composition contains 1% to 20% by weight, preferably 5% to 15% by weight, of the liquid laundry detergent composition.

[0046] Preferably, the liquid laundry treatment composition contains a non-soap surfactant, which preferably includes an anionic surfactant, a nonionic surfactant, a cationic surfactant, an amphoteric surfactant, a zwitterionic surfactant, or a mixture thereof, and preferably the liquid treatment composition contains 20% to 60% by weight, preferably 25% to 55% by weight, and more preferably 30% to 50% by weight of the non-soap surfactant of the liquid laundry treatment composition.

[0047] Preferably, the non-soap surfactant includes a non-soap anionic surfactant. Preferably, the laundry treatment composition contains 10% to 50% by weight, 15% to 45% by weight, 20% to 40% by weight, or 30% to 40% by weight of a non-soap anionic surfactant.

[0048] Preferably, the non-soap anionic surfactant contains a linear alkylbenzene sulfonate. Preferably, the linear alkylbenzene sulfonate is C 10 ~C 16 Alkylbenzene sulfonate, C 11 ~C 14 The liquid laundry treatment composition contains alkylbenzene sulfonates or mixtures thereof. Preferably, the alkylbenzene sulfonates are amine-neutralized alkylbenzene sulfonates, alkali metal-neutralized alkylbenzene sulfonates, or mixtures thereof. The amine may preferably be selected from monoethanolamine, triethanolamine, or mixtures thereof. The alkali metal may preferably be selected from sodium, potassium, magnesium, or mixtures thereof. Preferably, the liquid laundry treatment composition contains 5% to 40% by weight, preferably 10% to 35% by weight, more preferably 15% to 30% by weight of a linear alkylbenzene sulfonate anionic surfactant.

[0049] Preferably, the non-soap anionic surfactant includes an alkyl sulfate anionic surfactant, and the alkyl sulfate anionic surfactant is selected from alkyl sulfates, alkoxylated alkyl sulfates, or mixtures thereof. The alkyl sulfate anionic surfactant may be a primary or secondary alkyl sulfate anionic surfactant, or a mixture thereof, preferably a primary alkyl sulfate anionic surfactant. Preferably, the alkoxylated alkyl sulfate includes ethoxylated alkyl sulfate, propoxylated alkyl sulfate, mixed ethoxylated / propoxylated alkyl sulfate, or a mixture thereof, more preferably ethoxylated alkyl sulfate. Preferably, the ethoxylated alkyl sulfate has an average degree of ethoxylation of 0.1 to 5, preferably 0.5 to 3. Preferably, the ethoxylated alkyl sulfate has an average alkyl chain length of 8 to 18, more preferably 10 to 16, most preferably 12 to 15. Preferably, the alkyl chain of the alkyl sulfate anionic surfactant may be linear, branched, or a mixture thereof. Preferably, the branched alkyl sulfate anionic surfactant is a branched primary alkyl sulfate, a branched secondary alkyl sulfate, or a mixture thereof, preferably a branched primary alkyl sulfate, where the branching is preferably at the 2-position, or may be located further down the alkyl chain, or the branching may be polybranched, spreading over the alkyl chain. The weight-average degree of polymerization of the alkyl sulfate anionic surfactant may be 0% to 100%, preferably 0% to 95%, more preferably 0% to 60%, and most preferably 0% to 20%. Alternatively, the weight-average degree of polymerization of the alkyl sulfate anionic surfactant may be 70% to 100%, preferably 80% to 90%. Preferably, the alkyl chain is selected from naturally derived materials, synthetically derived materials, or a mixture thereof. Preferably, the synthetic material includes oxo-synthetic materials, Ziegler-synthetic materials, Guerbet-synthetic materials, Fischer-Tropsch-synthetic materials, iso-alkyl-synthetic materials, or mixtures thereof, preferably oxo-synthetic materials.Preferably, the liquid laundry detergent composition contains 1% to 35% by weight, preferably 3% to 30% by weight, and more preferably 6% to 20% by weight of an alkyl sulfate anionic surfactant.

[0050] Preferably, the non-soap anionic surfactant comprises a linear alkylbenzene sulfonate and an alkoxylated alkyl sulfate, with the weight ratio of linear alkylbenzene sulfonate to alkoxylated alkyl sulfate being 1:2 to 9:1, preferably 1:1 to 7:1, more preferably 1:1 to 5:1, and most preferably 1:1 to 4:1. While we do not wish to be bound by theory, these anionic surfactant ratios offer the advantage of providing excellent stain removal and cleaning across a wide range of stains.

[0051] Preferably, the non-soap surfactant includes a nonionic surfactant, and the nonionic surfactant preferably includes an alkoxylated alcohol, which is derived from a synthetic alcohol, a natural alcohol, or a mixture thereof. The alkoxylated alcohol may be a primary alkoxylated alcohol, a secondary alkoxylated alcohol, or a mixture thereof, preferably a primary alkoxylated alcohol. Preferably, the alkoxylated alcohol includes an ethoxylated alcohol, a propoxylated alcohol, a mixed ethoxylated / propoxylated alcohol, or a mixture thereof, more preferably an ethoxylated alcohol. Alternatively, the alkoxylated alcohol may also include a higher alkoxy group, such as a butoxy group. In the case of mixed alkoxy groups, the alkoxy groups may be arranged randomly or exist in blocks, preferably in blocks. For example, mixed ethoxy (EO) / propoxy (PO) groups may be arranged in EO / PO blocks, PO / EO blocks, EO / PO / EO blocks, or PO / EO / PO blocks. Preferably, the ethoxylated alcohol has an average degree of ethoxylation of 0.1 to 20, preferably 5 to 15, and most preferably 6 to 10. If propoxylation is present, preferably the average degree of propoxylation is 0.1 to 25, more preferably 2 to 20, and most preferably 5 to 10. Preferably, the alkoxylated, preferably ethoxylated, alcohol has an average alkyl chain length of 8 to 18, more preferably 10 to 16, and most preferably 12 to 15. Preferably, the alkyl chain of the alkoxylated alcohol is linear, branched, or a mixture thereof, and the branched alkoxylated alcohol is a branched primary alkoxylated alcohol, a branched secondary alkoxylated alcohol, or a mixture thereof, preferably a branched primary alkoxylated alcohol. Preferably, the weight-average degree of polymerization of the alkoxylated alcohol is 0% to 100%, preferably 0% to 95%, more preferably 0% to 60%, and most preferably 0% to 20%. The branching may be at the 2-alkyl position, or further down the alkyl chain, or it may be polybranched with individual branches extending along the alkyl chain.Preferably, the synthetic-derived material includes oxo-synthetic materials, Ziegler-synthetic materials, Guerbet-synthetic materials, Fischer-Tropsch-synthetic materials, iso-alkyl branched materials, or mixtures thereof, preferably oxo-synthetic materials. Preferably, the liquid laundry detergent composition contains 0.5% to 20% by weight, preferably 1% to 15% by weight, more preferably 3% to 12% by weight of a nonionic surfactant, wherein the nonionic surfactant is preferably an alkoxylated alcohol. Although we do not wish to be bound by theory, nonionic surfactants, particularly alkoxylated alcohol nonionic surfactants, offer the advantages of excellent body stain cleaning and stain suspension. Preferably, the laundry treatment composition contains 0.01% to 10% by weight, 0.01% to 8% by weight, 0.1% to 6% by weight, or 0.15% to 5% by weight of a nonionic surfactant.

[0052] Preferably, the weight ratio of non-soap anionic surfactant to nonionic surfactant is 1:1 to 20:1, 1.5:1 to 17.5:1, 2:1 to 15:1, or 2.5:1 to 13:1.

[0053] Preferably, the liquid laundry treatment composition contains a fatty acid, more preferably a neutralized fatty acid soap. Preferably, the liquid laundry treatment composition contains 1.5% to 20% by weight, more preferably 2% to 15% by weight, even more preferably 3% to 10% by weight, or most preferably 4% to 8% by weight of fatty acids in the liquid treatment composition. Preferably, the fatty acid is in molecular chain or linear form, alkoxylated or unalkoxylated, and preferably selected from palm kernel fatty acid, coconut fatty acid, rapeseed fatty acid, neutralized palm kernel fatty acid, neutralized coconut fatty acid, neutralized rapeseed fatty acid, or a mixture thereof, most preferably neutralized palm kernel fatty acid. Preferably, the fatty acid soap is neutralized with an alkali metal, an amine, or a mixture thereof. Preferably, the amine is selected from monoethanolamine, triethanolamine, or a mixture thereof, and the alkali metal is selected from sodium, potassium, magnesium, or a mixture thereof. Although we do not wish to be bound by theory, fatty acids, preferably neutralized fatty acids, offer the advantage of protecting anionic non-soap surfactants from precipitation. Furthermore, these offer the advantages of removing clay stains from fabrics and cleaning body stains.

[0054] Preferably, the liquid laundry treatment composition contains fragrance raw materials. The fragrance raw materials may include fragrance raw materials selected from the group consisting of fragrance raw materials having a boiling point (BP) lower than about 250°C and a ClogP lower than about 3, fragrance raw materials having a BP higher than about 250°C and a ClogP higher than about 3, fragrance raw materials having a BP higher than about 250°C and a ClogP lower than about 3, fragrance raw materials having a BP lower than about 250°C and a ClogP higher than about 3, and mixtures thereof. Fragrance raw materials having a boiling point BP lower than about 250°C and a ClogP lower than about 3 are known as Quadrant I fragrance raw materials. Preferably, Quadrant I fragrance raw materials are limited to less than 30% of the fragrance composition. Fragrance raw materials having a BP higher than approximately 250°C and a ClogP higher than approximately 3 are known as Quadrant IV fragrance raw materials, fragrance raw materials having a BP higher than approximately 250°C and a ClogP lower than approximately 3 are known as Quadrant II fragrance raw materials, and fragrance raw materials having a BP lower than approximately 250°C and a ClogP higher than approximately 3 are known as Quadrant III fragrance raw materials.

[0055] Preferred fragrance raw materials include ketones and aldehydes. Those skilled in the art will know how to prepare appropriate fragrance raw materials.

[0056] Preferably, the liquid laundry treatment composition comprises one or more auxiliary components, the auxiliary components being amphiphilic graft polymers, ethoxylated polyethyleneimines, amphiphilic alkoxylated polyalkyleneimines, ethylene oxide (EO)-propylene oxide (PO)-ethylene oxide (EO) triblock copolymers, zwitterionic polyamines, polyester terephthalates, organic solvents, aesthetic dyes, hue dyes, opacifying agents such as those commercially available under the trade name Acusol, glossing agents including FWA49, FWA15, and FWA36, pigment transfer inhibitors including PVNO, PVP, and PVPVI pigment transfer inhibitors, builders including citric acid, chelating agents, enzymes, fragrance capsules, preservatives, sulfites such as potassium sulfite or potassium bisulfite salts, antioxidants including those commercially available under the brand name Ralox, and Tinosan available from BASF. Antimicrobial and antiviral agents containing 4,4'-dichloro-2-hydroxydiphenyl ether such as HP100; anti-mite active substances such as benzyl benzoate; structuring agents containing hydrogenated castor oil; silicone-based defoamers; inorganic electrolytes such as sodium chloride, potassium chloride, magnesium chloride, and calcium chloride, as well as related electrolytes containing sodium sulfate, potassium, magnesium, and calcium salts; and organic electrolytes such as carbonates, bicarbonates, carboxylates, formate, citrate, and acetate. pH adjusters selected from sodium hydroxide, hydrogen chloride, and alkanolamines including monoethanolamine, diethanolamine, and triethanolamine, or mixtures thereof. Preferably, the organic solvent is selected from alcohols including ethanol, propanol, isopropanol, and mixtures thereof, sugar alcohols, glycols, glycol ethers, and mixtures thereof, polyols, preferably polyethylene glycol, in particular low molecular weight polyethylene glycols such as PEG200 and PEG400, diethylene glycol, glycerol, 1,2-propanediol, dipolypropylene glycol, and tripolypropylene glycol, and low molecular weight polypropylene glycols such as PPG400, sorbitol, or mixtures thereof.Preferably, the chelating agent is selected from EDDS, HEDP, GLDA, DTPA, DTPMP, DETA, or a mixture thereof. Preferably, the enzyme is selected from protease, amylase, cellulase, mannanase, lipase, xyloglucanase, pectinate lyase, nuclease enzyme, or a mixture thereof.

[0057] Preferably, the liquid laundry treatment composition has a pH of 6-10, 6.5-8.9, or 7-8, and the pH of the liquid laundry treatment composition is measured as the 10% product concentration in the desalinated water at 20°C.

[0058] The liquid laundry treatment composition may be Newtonian or non-Newtonian. Preferably, the liquid laundry treatment composition is non-Newtonian. Although we do not wish to be bound by theory, non-Newtonian liquids have different properties from Newtonian liquids; more specifically, the viscosity of non-Newtonian liquids does not depend on the shear rate, whereas Newtonian liquids have a constant viscosity regardless of the shear rate at which they are applied. The decrease in viscosity of non-Newtonian liquids during shear application is thought to further promote the dissolution of liquid detergents. The liquid laundry treatment compositions described herein may have any preferred viscosity depending on factors such as the components they contain and the purpose of the composition.

[0059] Cationic modified poly-α-1,6-glucan ether compounds The liquid laundry treatment composition comprises a cationic modified poly-α-1,6-glucan ether compound. Preferably, the cationic modified poly-α-1,6-glucan ether compound comprises poly-α-1,6-glucan substituted with at least one positively charged organic group, the poly-α-1,6-glucan comprising a glucose monomer unit backbone, where at least 65% of the glucose monomer units are linked via α-1,6-glycosidic bonds, the poly-α-1,6-glucan ether compound having a degree of substitution of about 0.001 to about 3, and characterized by at least one of the following i-iv: i) At least 5 weight-average degrees of polymerization, ii) Weight-average molecular weight of approximately 1,000 to 500,000 Daltons, iii) Derived from poly-α-1,6-glucan having a weight-average molecular weight of about 900 to about 450,000 daltons, determined before substitution with at least one positively charged organic group, iv) A mixture of these.

[0060] As used herein, the term "polysaccharide" refers to a polymer carbohydrate molecule consisting of long chains of monosaccharide units linked together by glycosidic bonds, and which can be obtained by hydrolysis to yield constituent monosaccharides or oligosaccharides.

[0061] As used herein, the term “polysaccharide derivative” means a chemically modified polysaccharide in which at least some of the hydroxyl groups of a glucose monomer unit are 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.”

[0062] The term "hydrophobic" refers to a molecule or substituent that is nonpolar, has little or no affinity for water, and does not tend to repel water.

[0063] The term "hydrophilic" refers to a molecule or substituent that is polar and has an affinity to interact with polar solvents, particularly water, or other polar groups. Hydrophilic molecules or substituents tend to attract water.

[0064] The "molecular weight" of poly-α-1,6-glucan or poly-α-1,6-glucan ether is the number-average molecular weight (M) of the statistically averaged molecular weight distribution. n ) or weight-average molecular weight (M w) can be expressed as such, and both of these are generally indicated in the unit of Dalton (Da), that is, grams / mole. Alternatively, the molecular weight can also be expressed as DPw (weight-average degree of polymerization) or DPn (number-average degree of polymerization). Various means for calculating these molecular weights are known in the art from techniques such as high-performance liquid chromatography (HPLC), size-exclusion chromatography (SEC), or gel-permeation chromatography (GPC), and gel-filtration chromatography (GFC).

[0065] As used herein, "weight-average molecular weight" or "M w " is M w =ΣN i M i 2 / ΣN i M i calculated as, where M i is the molecular weight of an individual chain i, and N i is the number of chains of that molecular weight. In addition to using SEC, the weight-average molecular weight can be determined by other techniques such as static light scattering, mass spectrometry, particularly MALDI-TOF (matrix-assisted laser desorption / ionization time-of-flight), small-angle X-ray or neutron scattering, and ultracentrifugation.

[0066] As used herein, "number-average molecular weight" or "M n " refers to the statistical average molecular weight of all polymer chains in a sample. The number-average molecular weight is M n =ΣN i M i / ΣN i calculated as, where M i is the molecular weight of the chain, and N i is the number of chains of that molecular weight. In addition to using SEC, the number-average molecular weight of a polymer can be determined by methods such as vapor pressure osmometry or by various absolute methods such as spectroscopy using proton NMR, FTIR, or UV-vis, or end-group determination.

[0067] As used herein, the number-average degree of polymerization (DPn) and the weight-average degree of polymerization (DPw) are calculated from the corresponding average molecular weight Mw or Mn by dividing by the molar mass of one monomer unit M1. For unsubstituted glucan polymers, M1 = 162. For substituted glucan polymers, M1 = 162 + M f ×DoS, and in the formula, M f is the molar mass of the substituent, and DoS is the degree of substitution for that substituent (average number of substituents per glucose unit).

[0068] The glucose carbon positions 1, 2, 3, 4, 5, and 6 as referred to herein are known in the art and are shown in Structure I.

[0069] [ka]

[0070] The terms "glycosidic bond" and "glycosidic linkage" are used interchangeably herein and refer to a 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-glucosidic bond" refers to a covalent bond that links α-D-glucose molecules to each other via carbon atoms 1 and 6 in adjacent α-D-glucose rings. As used herein, the term "α-1,3-glucosidic bond" refers to a covalent bond that links α-D-glucose molecules to each other via carbon atoms 1 and 3 in adjacent α-D-glucose rings. As used herein, the term "α-1,2-glucosidic bond" refers to a covalent bond that links α-D-glucose molecules to each other via carbon atoms 1 and 2 in adjacent α-D-glucose rings. As used herein, the term "α-1,4-glucosidic bond" refers to a covalent bond that links α-D-glucose molecules to each other via carbon atoms 1 and 4 in adjacent α-D-glucose rings. In this specification, "α-D-glucose" is referred to as "glucose."

[0071] The glycosidic bond profiles of glucans, dextrans, substituted glucans, or substituted dextrans can be determined using any method known in the art. For example, the bond profile can be determined by nuclear magnetic resonance (NMR) spectroscopy (e.g., 13 1C NMR or 1 This can be determined using methods employing 1H NMR. These and other methods are disclosed in Food Carbohydrates: Chemistry, Physical Properties, and Applications (SWCui, Ed., Chapter 3, SWCui, Structural Analysis of Polysaccharides, Taylor & Francis Group LLC, Boca Raton, FL, 2005), which are incorporated herein by reference.

[0072] The structure, molecular weight, and degree of substitution of polysaccharides or polysaccharide derivatives can be determined using various physiological and chemical analyses known in the art, such as NMR spectroscopy and size exclusion chromatography (SEC).

[0073] As used herein, the term “alkyl group” refers to a linear, branched, aralkyl (such as benzyl), or cyclic ("cycloalkyl") hydrocarbon group that does not contain 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 in the hydrocarbon chain.

[0074] As used herein, the term “aryl” means an aromatic carbocyclic group having a single ring (e.g., phenyl), multiple rings (e.g., biphenyl), or multiple fused rings (e.g., 1,2,3,4-tetrahydronaphthyl, naphthyl, anthuryl, or phenanthryl) in which at least one is aromatic, which may optionally be monosubstituted, disubstituted, or trisubstituted with alkyl groups. “Aryl” also means a heteroaryl group, defined as a five-membered, six-membered, or seven-membered aromatic ring system having at least one heteroatom selected from the group consisting of nitrogen, oxygen, and sulfur. Examples of heteroaryl groups include pyridyl, pyrimidinyl, pyrrolyl, pyrazolyl, pyrazinyl, pyridadinyl, oxazolyl, furanyl, imidazole, quinolinyl, isoquinolinyl, thiazolyl, and thienyl, which may optionally be substituted with alkyl groups.

[0075] Poly-α-1,6-glucan ether compounds comprise poly-α-1,6-glucan substituted with at least one positively charged organic group, wherein the poly-α-1,6-glucan comprises a glucose monomer unit backbone, and at least 65% of the glucose monomer units are linked via α-1,6-glycosidic bonds. Poly-α-1,6-glucan ether compounds may be characterized by (a) a weight-average degree of polymerization of at least 5, (b) a weight-average molecular weight of about 1,000 to about 500,000 daltons, and / or (c) being derived from poly-α-1,6-glucan having a weight-average molecular weight of about 900 to about 450,000 daltons, as determined before substitution with at least one positively charged organic group. Poly-α-1,6-glucan ether compounds may be characterized by a degree of substitution of about 0.001 to about 3.0. Optionally, at least 3%, preferably about 5% to about 50%, and more preferably about 5% to about 35%, of the skeletal glucose monomer units have branching via α-1,2 and / or α-1,3-glycosidic bonds. These compounds, groups, and properties are described in more detail below.

[0076] The poly-α-1,6-glucan ether compounds disclosed herein comprise a poly-α-1,6-glucan substituted with at least one positively charged organic group, wherein one or more organic groups are independently bonded via ether (-O-) bonds to the poly-α-1,6-glucan polysaccharide backbone and / or any branch, if present. The at least one positively charged organic group can derivatize the poly-α-1,6-glucan at the 2nd, 3rd, and / or 4th (or more) glucose carbon positions of the glucose monomer on the glucan backbone, and / or at the 1st, 2nd, 3rd, 4th, or 6th (or more) glucose carbon positions of the glucose monomer on the branch, if present. At the unsubstituted positions, hydroxyl groups are present in the glucose monomer.

[0077] The poly-α-1,6-glucan ether compounds disclosed herein are called “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.

[0078] The cationic poly-α-1,6-glucan ether compounds disclosed herein comprise a water-soluble poly-α-1,6-glucan comprising a glucose monomer unit backbone, wherein at least 65% of the glucose monomer units are linked via α-1,6-glycosidic bonds, and optionally, at least 5% of the backbone glucose monomer units have branching via α-1,2 and / or α-1,3-glycosidic bonds. The poly-α-1,6-glucan is substituted with positively charged organic groups on the polysaccharide backbone and / or any branching that may be present, such that the poly-α-1,6-glucan ether compounds contain unsubstituted and substituted α-D-glucose rings. The poly-α-1,6-glucan may be randomly substituted with positively charged organic groups. As used herein, the term “randomly substituted” means that substituents on the glucose ring in a randomly substituted polysaccharide are present non-repeatedly or randomly. In other words, substitutions on a substituted glucose ring may be identical or different from substitutions on a second substituted glucose ring in the polysaccharide (i.e., substituents on different atoms of the glucose ring in the polysaccharide may be identical or different), resulting in no overall pattern of substitutions on the polymer. Furthermore, substituted glucose rings can exist randomly within the polysaccharide (i.e., there is no pattern of substituted and unsubstituted glucose rings within the polysaccharide).

[0079] Depending on the reaction conditions used to derivatize poly-α-1,6-glucan and the specific substituents used, glucose monomers in the polymer backbone may be heterogeneously substituted for glucose monomers in any branch, including branching via α-1,2 and / or α-1,3 bonds, if present. Depending on the reaction conditions and the specific substituents used, substitution of poly-α-1,6-glucan may occur in blocks.

[0080] Depending on the reaction conditions used to derivatize poly-α-1,6-glucan and the specific substituents, hydroxyl groups at specific glucose carbon positions can be heterogeneously substituted. For example, the hydroxyl at carbon position 6 of the branched unit may be substituted more than hydroxyl at other carbon positions. Hydroxyls at carbon positions 2, 3, or 4 may be substituted more than hydroxyl at other carbon positions.

[0081] The poly-α-1,6-glucan ether compounds disclosed herein contain positively charged organic groups and are targeted due to their solubility in water, which can be varied by appropriate selection of substituents and degrees of substitution. Compositions containing poly-α-1,6-glucan ether compounds may be useful in a wide range of applications, including laundry, cleaning, food, cosmetics, industrial, film, and paper manufacturing. Poly-α-1,6-glucan ether compounds having a solubility greater than 0.1% by weight (wt%) in water may be useful as rheological modifiers, emulsion stabilizers, and dispersants in cleaning, detergent, cosmetics, food, cement, film, and paper manufacturing, with the product mainly in water-based formulations where optical transparency is desired. Poly-α-1,6-glucan ether compounds having a solubility less than 0.1% by weight in water may be useful as rheological modifiers, emulsion stabilizers, and dispersants in cleaning, detergent, cosmetics, food, cement, film, and paper manufacturing, with the product in formulations containing organic solvents to solubilize or disperse the poly-α-1,6-glucan derivative. Poly-α-1,6-glucan ether compounds may have a DoS of about 0.001 to about 1.5 and a solubility of 0.1% by weight or more in deionized water at 25°C. Poly-α-1,6-glucan ether compounds may have a DoS of about 0.05 to about 1.5 and a solubility of less than 0.1% by weight in water with a pH of 7 at 25°C. Poly-α-1,6-glucan ether compounds having a solubility of at least 0.1%, or at least 1%, or at least 10%, or at least 25%, or at least 50%, or at least 75%, or at least 90% by weight in deionized water at 25°C may be preferred for use in fabric care compositions or dish care compositions due to their ease of processing and / or increased solubility under aqueous final use conditions.

[0082] The cationic poly-α-1,6-glucan ether compounds disclosed herein may be present in an effective amount, for example, an amount that provides a desired degree of one or more of the following physical properties for a product or end use: thickening, freeze / thaw stability, lubricity, moisture retention and release, texture, consistency, shape retention, emulsification, binding, suspension, dispersion, and / or gelation. The effective amount may also be selected to provide processing advantages in the desired end use of the composition, for example, advantages of deposition, advantages of freshness, flexibility, or other modifying effects, advantages of color, advantages of stain removal, advantages of whiteness or graying prevention.

[0083] Preferably, the treatment composition contains 0.01% to 10% by weight, or 0.1% to 5% by weight, or 0.3% to 3% by weight, or 0.5% to 2.0% by weight of a poly-α-1,6-glucan ether compound.

[0084] The poly-α-1,6-glucan ether compounds of this disclosure include substituted poly-α-1,6-glucans and are typically prepared from poly-α-1,6-glucan starting materials. The terms “poly-α-1,6-glucan” and “dextran” are used interchangeably herein. Dextran refers to a family of complex branched α-glucans that generally contain chains of α-1,6-linked glucose monomers, in which the side chains (branching) are periodically linked to the linear chain by α-1,3-links (Ioan et al., Macromolecules 33:5730-5739) or α-1,2-links. Dextran is typically produced by fermenting sucrose with bacteria (e.g., lactic acid bacteria or streptococcal species), where sucrose serves as a glucose source 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). Poly-α-1,6-glucans can be prepared using glucosyltransferases such as GTF1729, GTF1428, GTF5604, GTF6831, GTF8845, GTF0088, and GTF8117, etc., as described in International Publications 2015 / 183714 and 2017 / 091533, which are incorporated herein by reference.

[0085] The cationic poly-α-1,6-glucan ether compound may contain a glucose monomer unit backbone, with 40% or more of the glucose monomer units, for example, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 90%, or 95% or more of the glucose monomer units being linked via α-1,6-glycosidine bonds. The backbone of the cationic poly-α-1,6-glucan ether compound may contain at least 3%, 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. Cationic poly-α-1,6-glucan ether compounds may contain a glucose monomer unit skeleton, with at least 65% of the glucose monomer units being bonded via α-1,6-glycosidic bonds. Cationic poly-α-1,6-glucan ether compounds may contain a glucose monomer unit skeleton, with at least 70% of the glucose monomer units being bonded via α-1,6-glycosidic bonds. Cationic poly-α-1,6-glucan ether compounds may contain a glucose monomer unit skeleton, with at least 80% of the glucose monomer units being bonded via α-1,6-glycosidic bonds. Cationic poly-α-1,6-glucan ether compounds may contain a glucose monomer unit skeleton, with at least 90% of the glucose monomer units being bonded via α-1,6-glycosidic bonds. Cationic poly-α-1,6-glucan ether compounds may contain a glucose monomer unit skeleton, with at least 95% of the glucose monomer units being bonded via α-1,6-glycosidic bonds. The cationic poly-α-1,6-glucan ether compound may contain a glucose monomer unit backbone, with at least 99.5% of the glucose monomer units being linked via α-1,6-glycosidic bonds. The poly-α-1,6-glucan ether compound may be mainly linear in structure.

[0086] The dextran “long chains” may contain “substantially (or largely) α-1,6-glucosidic bonds,” meaning that in some embodiments, they may have at least about 98.0% α-1,6-glucosidic bonds. The dextrans described herein may, in some embodiments, include “branched structures.” In these structures, it is thought that long chains may, perhaps iteratively, branch from other long chains (e.g., a long chain may be a branch from another long chain, and this itself may be a branch from another long chain). The long chains in these structures may be of “similar lengths,” meaning that at least 70% of the lengths of all long chains in the branched structure (e.g., measured by DP / degree of polymerization) are within plus or minus 30% of the average length of all long chains in the branched structure.

[0087] Dextran may further contain “short chains” branching from the polysaccharide backbone, which are typically 1-3 glucose monomer lengths and constitute less than 10% of all glucose monomers in the dextran polymer. Such short chains typically contain α-1,2-, α-1,3-, and / or α-1,4-glucosidic bonds (it is understood that in some embodiments, a low proportion of such non-α-1,6 bonds may be present in the long chains). The amount of α-1,2-branching or α-1,3-branching can be determined by NMR spectroscopy, as disclosed in the test methods.

[0088] Dextrans can be enzymatically generated before modification with α-1,2 branching or α-1,3 branching. In certain embodiments, dextrans can be synthesized using dextranscrases and / or methods as disclosed in International Publication No. 2015 / 183714 or 2017 / 091533 or U.S. Patent Application Publication No. 2018 / 0282385, all of which are incorporated herein by reference. In these references, dextranscrases identified as GTF8117, GTF6831, or GTF5604 (or any dextranscrase containing an amino acid sequence that is at least about 90%, 91%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99% identical to any of these specific dextranscrases) may be used as desired. Such enzymatically produced dextrans are linear (i.e., 100% α-1,6 linked) and water-soluble.

[0089] Branched poly-1,6-glucans can be enzymatically produced according to the procedures of International Publications 2015 / 183714 and 2017 / 091533, in which case an α-1,2-branching enzyme such as "gtfJ18T1" or "GTF9905" can be added during or after the production of the dextran polymer (polysaccharide). Any other enzyme known to produce α-1,2-branching may also be added. For example, poly-1,6-glucans having α-1,3-branching can be prepared as disclosed in Vuillemin et al. (2016, J. Biol Chem. 291:7687-7702) or U.S. Patent Application No. 62 / 871,796, which are incorporated herein by reference. The degree of branching of poly-α-1,6-glucan or its derivatives is short branching of 50%, 40%, 30%, 20%, 10%, or 5% or less (or any value between 5% and 50%), for example, α-1,2-branching, 1,3-branching, or both α-1,2-branching and α-1,3-branching. The degree of branching in the poly-α-1,6-glucan starting material is maintained in the branched poly-α-1,6-glucan ether formed by the etherification of branched poly-α-1,6-glucan. The amount of α-1,2-branching or α-1,3-branching can be determined by NMR spectroscopy, as disclosed in the following test methods.

[0090] While we do not wish to be constrained by theory, it is thought that branching can increase the solubility of poly-α-1,6-glucan ether compounds, which may lead to more convenient processability and / or transport. Limiting the degree of branching may also lead to improved performance in the final processed composition.

[0091] Poly-α-1,6-glucan ether compounds may have a degree of α-1,2-branching of less than 50%. Poly-α-1,6-glucan ether compounds may have a degree of α-1,2-branching of at least 5%. Approximately 5% to 50% of the glucose monomer units in the backbone of poly-α-1,6-glucan ether compounds may have branching via α-1,2 or α-1,3 glycosidic bonds. Approximately 5% to 35% of the glucose monomer units in the backbone of poly-α-1,6-glucan ether compounds may have branching via α-1,2 or α-1,3 glycosidic bonds.

[0092] At least about 3%, preferably at least about 5%, of the glucose monomer units in the poly-α-1,6-glucan ether compound's skeleton may have branching via α-1,2- or α-1,3-glycosidic bonds. The poly-α-1,6-glucan ether compound may contain a skeleton of glucose monomer units, with 65% or more of the glucose monomer units being linked via α-1,6-glycosidic bonds. The poly-α-1,6-glucan ether compound may contain a skeleton of glucose monomer units, with 65% or more of the glucose monomer units being linked via α-1,6-glycosidic bonds, and at least 3%, preferably at least 5%, preferably about 5% to about 30%, more preferably about 5% to about 25%, and even more preferably about 5% to about 20% of the glucose monomer units having branching via α-1,2- or α-1,3-glycosidic bonds. Poly-α-1,6-glucan ether compounds may contain a glucose monomer unit backbone, with 65% or more of the glucose monomer units linked via α-1,6-glycosidic bonds, and at least 5% of the glucose monomer units having branching via α-1,2 bonds. Poly-α-1,6-glucan ether compounds may contain a glucose monomer unit backbone, with 65% or more of the glucose monomer units linked via α-1,6-glycosidic bonds, and at least 5% of the glucose monomer units having branching via α-1,3 bonds. Poly-α-1,6-glucan ether compounds may contain a glucose monomer unit backbone, with 65% or more of the glucose monomer units linked via α-1,6-glycosidic bonds, and approximately 5% to approximately 50% of the glucose monomer units having branching via α-1,2 or α-1,3 glycosidic bonds. The poly-α-1,6-glucan ether compound may contain a glucose monomer unit backbone, with more than 70% of the glucose monomer units being linked via α-1,6-glycosidic bonds, and approximately 5% to 35% of the glucose monomer units having branching via α-1,2 or α-1,3 glycosidic bonds.

[0093] Poly-α-1,6-glucan ether compounds may contain a glucose monomer unit skeleton, with 90% or more of the glucose monomer units being linked via α-1,6-glycosidic bonds. Poly-α-1,6-glucan ether compounds may contain a glucose monomer unit skeleton, with 90% or more of the glucose monomer units being linked via α-1,6-glycosidic bonds, and at least 5% of the glucose monomer units having branching via α-1,2 or α-1,3 glycosidic bonds. Poly-α-1,6-glucan ether compounds may contain a glucose monomer unit skeleton, with 90% or more of the glucose monomer units being linked via α-1,6-glycosidic bonds, and at least 5% of the glucose monomer units having branching via α-1,2-glycosidic bonds. Poly-α-1,6-glucan ether compounds may contain a glucose monomer unit backbone, with more than 90% of the glucose monomer units being linked via α-1,6-glycosidic bonds, and at least 5% of the glucose monomer units having branching via α-1,3 bonds. Poly-α-1,6-glucan ether compounds may contain a glucose monomer unit backbone, with more than 90% of the glucose monomer units being linked via α-1,6-glycosidic bonds, and approximately 5% to 50% of the glucose monomer units having branching via α-1,2 or α-1,3 glycosidic bonds. Poly-α-1,6-glucan ether compounds may contain a glucose monomer unit backbone, with more than 90% of the glucose monomer units being linked via α-1,6-glycosidic bonds, and approximately 5% to 35% of the glucose monomer units having branching via α-1,2 or α-1,3 glycosidic bonds.

[0094] The poly-α-1,6-glucan and poly-α-1,6-glucan ether compounds disclosed herein may have a number-average degree of polymerization (DPn) in the range of 5 to 6000. The DPn may be in the range of 5 to 100, or 5 to 500, or 5 to 1000, or 5 to 1500, or 5 to 2000, or 5 to 2500, or 5 to 3000, or 5 to 4000, or 5 to 5000, or 5 to 6000. The DPn may be in the range of 50 to 500, or 50 to 1000, or 50 to 1500, or 50 to 2000, or 50 to 3000, or 50 to 4000, or 50 to 5000, or 50 to 6000.

[0095] The poly-α-1,6-glucan and poly-α-1,6-glucan ether compounds disclosed herein may have a weight-average degree of polymerization (DPw) in the range of at least 5. DPw may be in the range of 5 to 6000, or 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. DPw may also be in the range of 400 to 6000, or 400 to 5000, or 400 to 4000, or 400 to 3000, or 400 to 2000, or 400 to 1500.

[0096] The poly-α-1,6-glucan ether compounds disclosed herein may have a weight-average molecular weight of about 1,000 to about 500,000 daltons, or 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. Polymers of different sizes may be preferred for different applications and / or intended benefits.

[0097] The poly-α-1,6-glucan ether compounds disclosed herein can be derived from poly-α-1,6-glucans having a weight-average molecular weight of about 900 to about 450,000 daltons, determined before substitution with at least one positively charged organic group. The poly-α-1,6-glucan ether compounds disclosed herein can be derived from poly-α-1,6-glucans having a weight-average molecular weight of about 5,000 to about 400,000 daltons, or 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. Different sizes of feedstock or backbone polymers may be preferred for different applications or depending on the intended degree of substitution.

[0098] As used herein, “degree of substitution” (DoS) refers to the average number of hydroxyl groups substituted on each monomer unit (glucose) of a cationic poly-α-1,6-glucan ether compound, including monomer units within the backbone and in any possible α-1,2 or α-1,3 branching. Since a glucose monomer unit in a poly-α-1,6-glucan polymer or cationic poly-α-1,6-glucan ether compound can have up to three hydroxyl groups, the overall degree of substitution may be 3 or less. Since the cationic poly-α-1,6-glucan ether compounds disclosed herein have degrees of substitution ranging from about 0.001 to about 3.0, it will be understood by those skilled in the art that substituents on the polysaccharide cannot be solely hydrogen. The degree of substitution of a poly-α-1,6-glucan ether compound may be described with respect to a specific substituent or as an overall degree of substitution, i.e., the sum of the DoS of each different substituent of the ether compound as defined herein. As used herein, if the degree of substitution is not described with respect to a specific substituent or substituent, it refers to the overall degree of substitution of the cationic poly-α-1,6-glucan ether compound. The degree of substitution can be a cationic degree of substitution, or even a net cationic degree of substitution. The target DoS can be selected to provide the desired solubility and performance of a composition containing a cationic poly-α-1,6-glucan ether compound in a particular application of interest.

[0099] The cationic poly-α-1,6-glucan ether compounds disclosed herein may have DoS for positively charged organic groups in the range of about 0.001 to about 3. Cationic poly-α-1,6-glucan ethers may have DoS of about 0.01 to about 1.5. Poly-α-1,6-glucan ethers may have DoS of about 0.01 to about 0.7. Poly-α-1,6-glucan ethers may have DoS of about 0.01 to about 0.4. Poly-α-1,6-glucan ethers may have DoS of about 0.01 to about 0.2. The DoS of the poly-α-1,6-glucan ether compound may be at least about 0.001, 0.005, 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, or 3.0. The DoS may be about 0.01 to about 1.5, preferably about 0.01 to about 1.0, more preferably about 0.01 to about 0.8, more preferably about 0.03 to about 0.7, or about 0.04 to about 0.6, or about 0.05 to about 0.5. For performance reasons in washing applications (e.g., laundry detergents used in a washing cycle), the DoS may preferably be about 0.01 to about 0.5, or about 0.01 to about 0.25, or about 0.01 to about 0.2, or about 0.03 to about 0.15, or about 0.04 to about 0.12. For performance reasons in rinsing applications (e.g., liquid fabric conditioners used in a rinsing cycle), the DoS may preferably be about 0.01 to about 1, or about 0.03 to about 0.8, or about 0.04 to about 0.7, or about 0.05 to about 0.6, or about 0.2 to about 0.8, or about 0.2 to about 0.6, or about 0.3 to about 0.6, or about 0.4 to about 0.6. The DoS of poly-α-1,6-glucan may be 0.01 to about 0.6, more preferably 0.02 to about 0.5.

[0100] The cationic poly-α-1,6-glucan ether compounds of this disclosure may be characterized by a cationic charge density. The cationic charge density can be expressed as milliequivalents (meq / mol) of charge per gram of compound and may be determined according to the methods provided in the section on test methods. The cationic poly-α-1,6-glucan ether compounds of this disclosure may be characterized by a cationic charge density (or "CCD") of about 0.05 to about 12 meq / g, or about 0.1 to about 8 meq / g, or about 0.1 to about 4 meq / g, or about 0.1 to about 3 meq / g, or about 0.1 to about 2.6 meq / g.

[0101] 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, where one or more substitutions are positively charged. As used herein, the term "chain" includes linear, branched, and cyclic arrangements of carbon atoms, as well as combinations thereof.

[0102] Poly-α-1,6-glucan derivatives include poly-α-1,6-glucans substituted with at least one positively charged organic group on one or more of the polysaccharide backbone and / or any branches. When the substitution is made on a glucose monomer contained in the backbone, the polysaccharide is derivatized with an organic group as defined herein, which is attached to the polysaccharide via an ether (-O-) bond, in place of the hydroxyl groups originally present in the underivativeed (unsubstituted) poly-α-1,6-glucan at the 2nd, 3rd, and / or 4th glucose carbon positions. When the substitution is made on a glucose monomer contained in a branch, the polysaccharide is derivatized with a positively charged organic group as defined herein, which is attached to the polysaccharide via an ether (-O-) bond, at the 1st, 2nd, 3rd, 4th, or 6th glucose carbon positions.

[0103] The poly-α-1,6-glucan ether compounds disclosed herein are, in this specification, defined as having substructure C G -OC R By containing, it is referred to herein as glucan "ether" and "-C G "-" represents the carbon atom of the glucose monomer unit in the poly-α-1,6-glucan ether compound, and "-C" represents the carbon atom of the glucose monomer unit.R The hyphen "-" is included in 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 can also be used.

[0104] The treatment compositions disclosed herein may comprise, or essentially comprise, one or more cationic poly-α-1,6-glucan ether compounds disclosed herein. A treatment composition may comprise one poly-α-1,6-glucan ether compound. A treatment composition may comprise two or more poly-α-1,6-glucan ether compounds, for example, differing in positively charged organic groups.

[0105] The treatment composition may comprise one or more cationic poly-α-1,6-glucan ether compounds as disclosed herein, and may further comprise or be hydrolyzable unsubstituted and / or non-cationic poly-α-1,6-glucan compounds, which may be unreacted / unsubstituted residual reactants. Typically, low levels of unsubstituted / non-cationic poly-α-1,6-glucan compounds are preferred because they may indicate the integrity of the reaction with respect to substitution and / or chemical stability in the treatment composition. The weight ratio of the cationic poly-α-1,6-glucan ether compound to the unsubstituted / non-cationic poly-α-1,6-glucan compound may be 95:5 or higher, preferably 98:2 or higher, and more preferably 99:1 or higher.

[0106] As used herein, “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, one or more of which substitutions are positively charged groups. Positively charged groups are typically linked to the terminal carbon atoms 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). Organic groups or compounds that are “positively charged” typically have more protons than electrons and are repelled by other positively charged substances but attracted to negatively charged substances. Examples of positively charged groups include substituted ammonium groups. Positively charged organic groups may have further substitutions, for example, one or more hydroxyl groups, oxygen atoms (forming ketone groups), alkyl groups, and / or at least one additional positively charged group.

[0107] Positively charged organic groups may include substituted ammonium groups, which can be represented by structure II.

[0108] [ka]

[0109] In structure II, R2, R3, and R4 are each independently a hydrogen atom, an alkyl group, or a C6-C6 group. 24 This can represent an aryl group. The carbon atom (C) shown in structure II is part of a carbon chain of a positively charged organic group. The carbon atom is either directly ether-bonded to the glucose monomer of the poly-α-1,6-glucan, or is part of a chain of two or more carbon atoms ether-bonded to the glucose monomer of the poly-α-1,6-glucan. The carbon atom shown in structure II may be -CH2-, -CH- (H is substituted with another group such as a hydroxyl group), or -C- (both H are substituted).

[0110] If R2, R3, and / or R4 represent alkyl groups, then the alkyl groups are C1-C 30Alkyl groups, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, decosyl, tricosyl, tetracosyl, C 25 , C 26 , C 27 , C 28 , C 29 , or C 30 It can be a group. Alkyl groups are C1-C 24 Alkyl alkyl groups, or C1-C 18 , or C6~C 20 Alkyl alkyl group, or C 10 ~C 16 It may be an alkyl group or a C1-C4 alkyl group. If the 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.

[0111] If R2, R3, and / or R4 represent an aryl group, the aryl group is optionally substituted with an alkyl substituent C6-C 24 It may be an aryl group. The aryl group is optionally substituted with an alkyl substituent. 12 ~C 24 C6-C atoms substituted with an aryl group, or optionally with an alkyl substituent. 18 It may be an aryl group.

[0112] A 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 the ammonium group represented in structure II, where R2, R3, and R4 are each hydrogen atoms (i.e., -C-NH3). + ).

[0113] A secondary ammonium group is an ammonium group represented by structure II, where R2 and R3 are hydrogen atoms, and R4 is C1-C30 Alkyl alkyl groups or C6-C 24 It is an aryl 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 ether, for example, monomethyl-, monoethyl-, monopropyl-, monobutyl-, monopentyl-, monohexyl-, monoheptyl-, monooctyl-, monononyl-, monodecyl-, monoundecyl-, monododecyl-, monotridecyl-, monotetradecyl-, monopentadecyl-, monohexadecyl-, monoheptadecyl-, or monooctadecyl-ammonium poly-α-1,6-glucan ether. These poly-α-1,6-glucan ether compounds may also be referred to as methyl, ethyl, propyl-, butyl-, pentyl, hexyl, heptyl-, octyl-, nonyl, decyl-, undecyl-, dodecyl-, tridecyl, tetradecyl, pentadecyl-, hexadecyl-, heptadecyl-, or octadecyl-ammonium poly-α-1,6-glucan ether compounds. The octadecylammonium group is an example of a monoalkylammonium group, where R2 and R3 are hydrogen atoms, and R4 is an octadecyl group. The second member (i.e., R1), implied by "secondary" in this nomenclature, will be understood to be a chain of one or more carbon atoms of a positively charged organic group ether-bonded to the glucose monomer of the poly-α-1,6-glucan.

[0114] A tertiary ammonium group is an ammonium group represented by structure II, where R2 is a hydrogen atom, and R3 and R4 are independently C1-C2. 24 Alkyl alkyl groups, or C6-C 24The alkyl group is an aryl group. The alkyl groups may be the same or different. "Tertiary ammonium poly-α-1,6-glucan ether compounds" include positively charged organic groups having a dialkylammonium group. Tertiary ammonium poly-α-1,6-glucan ether compounds can be abbreviated as dialkylammonium poly-α-1,6-glucan ether, for example, dimethyl-, diethyl-, dipropyl-, dibutyl-, dipentyl-, dihexyl-, diheptyl-, dioctyl-, dinonyl-, didecyl-, diundecyl-, didodecyl-, ditridecyl-, ditetradecyl, dipentadecyl, dihexadecyl-, diheptadecyl, or dioctadecyl-ammonium poly-α-1,6-glucan ether. The didodecylammonium group is an example of a dialkylammonium group, where R2 is a hydrogen atom and R3 and R4 are dodecyl groups, respectively. The third member (i.e., R1) implied by "tertiary" in this nomenclature will be understood to be a chain of one or more carbon atoms of a positively charged organic group ether-bonded to the glucose monomer of poly-α-1,6-glucan.

[0115] The quaternary ammonium group is the ammonium group represented by structure II, where R2, R3, and R4 are each independently C1-C 30 Alkyl alkyl groups or C6-C 24 It is an aryl group (i.e., none of R2, R3, and R4 are hydrogen atoms).

[0116] The quaternary ammonium poly-α-1,6-glucan ether compound may contain a trialkylammonium group, where R2, R3, and R4 are each independently C1-C 30It is an alkyl group. All alkyl groups may be the same, or two alkyl groups may be the same and different from the others, or all three alkyl groups may be different from each other. Quaternary ammonium poly-α-1,6-glucan ether compounds can be abbreviated as trialkylammonium poly-α-1,6-glucan ethers, e.g., trimethyl-, triethyl-, tripropyl-, tributyl-, tripentyl-, trihexyl-, triheptyl-, trioctyl-, trinonyl-, tridecyl-, triundecyl-, tridodecyl-, tritridecyl-, tritetradecyl-, tripendadecyl-, trihexadecyl-, triheptadecyl-, or trioctadecyl-ammonium poly-α-1,6-glucan ethers. The fourth member (i.e., R1) implied by "quaternary" in this nomenclature will be understood to be a chain of one or more carbon atoms of a positively charged organic group ether-bonded to the glucose monomer of the poly-α-1,6-glucan. The trimethylammonium group is an example of a trialkylammonium group, where R2, R3, and R4 are methyl groups, respectively.

[0117] Positively charged organic groups containing substituted ammonium groups are represented by structure II, where R2, R3, and R4 each 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 cyclohexyl or cyclopentyl. Each of R2, R3, and R4 may further contain an amino group or a hydroxyl group.

[0118] The substituted ammonium group of a positively charged organic group is a substituent on a chain of one or more carbon atoms ether-bonded to the glucose monomer of α-1,6-glucan. The carbon chain may contain 1 to 30 carbon atoms. The carbon chain may be linear. Examples of linear carbon chains include -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2(CH2)2CH2-, -CH2(CH2)3CH2-, -CH2(CH2)4CH2-, -CH2(CH2)5CH2-, -CH2(CH2)6CH2-, -CH2(CH2)7CH2-, -CH2(CH2)8CH2-, -CH2(CH2)9CH2-, and -CH2(CH2) 10 CH2- is an example. Longer carbon chains can be used as desired. 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 site 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-, and -CH2CH(CH2CH2CH3)CH2-. Longer branched carbon chains can be used as desired. When the positively charged group is a substituted ammonium group, the first carbon atom in the chain is ether-bonded to the glucose monomer of the poly-α-1,6-glucan, and the last carbon atom in the chain in each of these examples is represented by C in structure II.

[0119] A chain of one or more carbon atoms may be further substituted with one or more hydroxyl groups. Examples of carbon chains having one or more substitutions with 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-bonded to the glucose monomer of the poly-α-1,6-glucan, and the last carbon atom of the chain is bonded to a positively charged group. When 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.

[0120] 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 group of this ether compound can be represented by the following structure.

[0121] [ka] In the formula, R2, R3, and R4 are each methyl groups. The above structure is an example of a quaternary ammonium hydroxypropyl group.

[0122] If the carbon chain of a positively charged organic group has substitutions in addition to those by the positively charged group, such additional substitutions may be one or more hydroxyl groups, oxygen atoms (thereby forming an aldehyde or ketone group), alkyl groups (e.g., methyl, ethyl, propyl, butyl), and / or additional positively charged groups. The positively charged group is typically linked to the terminal carbon atoms of the carbon chain. The positively charged group may also contain one or more imidazoline rings.

[0123] The cationic poly-α-1,6-glucan ether compounds disclosed herein may be salts. The counterions of the positively charged organic groups may be acetates, borates, bromates, bromides, carbonates, chlorates, chlorides, chlorites, dihydrogen phosphates, fluorides, bicarbonates, hydrogen phosphates, bisulfates, hydrogen sulfides, bisulfites, hydroxides, hypochlorites, iodates, iodides, nitrates, nitrites, oxalates, oxides, perchlorates, permanganates, phosphates, phosphides, phosphites, silicates, stanates, stanites, sulfates, sulfides, sulfates, tartrates, or thiocyanate anions, preferably chlorides, and any other suitable anions. In aqueous solution, the poly-α-1,6-glucan ether compounds are in a cationic form. The positively charged organic groups of the cationic poly-α-1,6-glucan ether compounds can interact with salt anions that may be present in aqueous solution.

[0124] Poly-α-1,6-glucan ether compounds may contain positively charged organic groups, and these positively charged organic groups may contain substituted ammonium groups. Approximately 0.5% to 50% of the glucose monomer units in the ether compound skeleton may have branching via α-1,2 glycosidic bonds, and the positively charged organic groups may contain substituted ammonium groups. Approximately 5% to 30% of the glucose monomer units in the ether compound skeleton may have branching via α-1,2 glycosidic bonds, and the substituted ammonium groups may contain substituted ammonium groups. Approximately 0.5% to 50% of the glucose monomer units in the ether compound skeleton may have branching via α-1,2 glycosidic bonds, and the substituted ammonium groups may contain trimethylammonium groups. Approximately 5% to 35% of the glucose monomer units in the ether compound skeleton may have branching via α-1,2 glycosidic bonds, and the substituted ammonium groups may contain trimethylammonium groups.

[0125] Poly-α-1,6-glucan ether compounds may contain positively charged organic groups, and these positively charged organic groups may include trimethylammonium hydroxyalkyl groups. Approximately 0.5% to 50% of the glucose monomer units in the ether compound skeleton may have branching via α-1,2 glycosidic bonds, and these positively charged organic groups may include trimethylammonium hydroxyalkyl groups. Approximately 5% to 30% of the glucose monomer units in the ether compound skeleton may have branching via α-1,2 glycosidic bonds, and these positively charged organic groups may include trimethylammonium hydroxyalkyl groups. Approximately 0.5% to 50% of the glucose monomer units in the ether compound skeleton may have branching via α-1,2 glycosidic bonds, and these trimethylammonium hydroxyalkyl groups may include trimethylammonium hydroxypropyl groups. Approximately 5% to 30% of the glucose monomer units in the ether compound skeleton may have branching via α-1,2 glycosidic bonds, and these trimethylammonium hydroxyalkyl groups may include trimethylammonium hydroxypropyl groups.

[0126] Poly-α-1,6-glucan ether compounds may contain positively charged organic groups, and these positively charged organic groups may contain substituted ammonium groups including quaternary ammonium groups. Approximately 0.5% to 50% of the glucose monomer units in the ether compound skeleton may have branching via α-1,2 glycosidic bonds, and the quaternary ammonium groups may contain at least one C1-C 18 It may contain alkyl groups. Approximately 5% to 30% of the glucose monomer units in the ether compound skeleton may have branching via α-1,2 glycosidic bonds, but the quaternary ammonium group may have at least one C1-C 18 It may contain alkyl groups. About 0.5% to about 50% of the glucose monomer units in the ether compound backbone may have branching via α-1,2 glycosidic bonds, and the quaternary ammonium group may contain at least one C1-C4 alkyl group. About 5% to about 30% of the glucose monomer units in the ether compound backbone may have branching via α-1,2 glycosidic bonds, and the quaternary ammonium group may contain at least one C1-C4 alkyl group. About 0.5% to about 50% of the glucose monomer units in the ether compound backbone may have branching via α-1,2 glycosidic bonds, and the quaternary ammonium group may contain at least one C 10 ~C 16 It may contain alkyl groups. About 5% to about 30% of the glucose monomer units in the ether compound skeleton may have branching via α-1,2 glycosidic bonds, and the quaternary ammonium group may have at least one C 10 ~C 16 It may contain alkyl groups.

[0127] Poly-α-1,6-glucan ether compounds are one C 10 ~C 16 The ether compound may contain a quaternary ammonium group containing an alkyl group, and the quaternary ammonium group may further contain two methyl groups. About 0.5% to about 50% of the glucose monomer units in the ether compound backbone may have branching via α-1,2 glycosidic bonds, and the quaternary ammonium group may contain one C 10 ~C 16It contains an alkyl group and further contains two methyl groups. About 5% to about 30% of the glucose monomer units in the ether compound skeleton may have branching via α-1,2 glycosidic bonds, and the quaternary ammonium group has one C 10 ~C 16 It contains an alkyl group and further contains two methyl groups.

[0128] Approximately 0.5% to 50% of the glucose monomer units in the ether compound skeleton may have branching via α-1,2 glycosidic bonds, and the quaternary ammonium group has one C 10 It may contain an alkyl group and two methyl groups. About 5% to about 30% of the glucose monomer units in the ether compound skeleton may have branching via α-1,2 glycosidic bonds, and the quaternary ammonium group may have one C 10 It may contain an alkyl group and two methyl groups.

[0129] Poly-α-1,6-glucan ether compounds may contain positively charged organic groups, which may include quaternary ammonium hydroxyalkyl groups. Approximately 0.5% to 50% of the glucose monomer units in the ether compound skeleton may have branching via α-1,2 glycosidic bonds, and the positively charged organic groups may include quaternary ammonium hydroxyalkyl groups. Approximately 5% to 30% of the glucose monomer units in the ether compound skeleton may have branching via α-1,2 glycosidic bonds, and the positively charged organic groups may include quaternary ammonium hydroxyalkyl groups. Approximately 0.5% to 50% of the glucose monomer units in the ether compound skeleton may have branching via α-1,2 glycosidic bonds, and the quaternary ammonium hydroxyalkyl groups may include quaternary ammonium hydroxymethyl groups, quaternary ammonium hydroxyethyl groups, or quaternary hydroxypropyl groups. Approximately 5% to 30% of the glucose monomer units in the ether compound's skeleton may have branching via α-1,2 glycosidic bonds, and the quaternary ammonium hydroxyalkyl group may include a quaternary ammonium hydroxymethyl group, a quaternary ammonium hydroxyethyl group, or a quaternary hydroxypropyl group. Approximately 0.5% to 50% of the glucose monomer units in the ether compound's skeleton may have branching via α-1,2 glycosidic bonds, and the quaternary ammonium hydroxyalkyl group may include a quaternary ammonium hydroxymethyl group. Approximately 5% to 30% of the glucose monomer units in the ether compound's skeleton may have branching via α-1,2 glycosidic bonds, and the quaternary ammonium hydroxyalkyl group may include a quaternary ammonium hydroxymethyl group. Approximately 0.5% to 50% of the glucose monomer units in the ether compound's skeleton may have branching via α-1,2 glycosidic bonds, and the quaternary ammonium hydroxyalkyl group may include a quaternary ammonium hydroxyethyl group. Approximately 5% to 30% of the glucose monomer units in the ether compound skeleton may have branching via α-1,2 glycosidic bonds, and the quaternary ammonium hydroxyalkyl group may contain a quaternary ammonium hydroxyethyl group.Approximately 0.5% to 50% of the glucose monomer units in the ether compound's skeleton may have branching via α-1,2 glycosidic bonds, and the quaternary ammonium hydroxyalkyl group may contain a quaternary ammonium hydroxypropyl group. Approximately 5% to 30% of the glucose monomer units in the ether compound's skeleton may have branching via α-1,2 glycosidic bonds, and the quaternary ammonium hydroxyalkyl group may contain a quaternary ammonium hydroxypropyl group.

[0130] 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 U.S. Patent Application Publication 2016 / 0311935, which is incorporated herein in whole by reference. U.S. Patent Application Publication 2016 / 0311935 discloses poly-α-1,3-glucan ether compounds containing positively charged organic groups and having a maximum degree of substitution of about 3.0, as well as 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. For example, alkaline conditions can be prepared by contacting poly-α-1,6-glucan with a solvent and one or more alkali hydroxides to provide a solution or mixture, and then adding at least one etherifying agent. As another example, at least one etherifying agent can be brought into contact with poly-α-1,6-glucan and a solvent, and then an alkali hydroxide can be added. The mixture of poly-α-1,6-glucan, etherifying agent, and alkali hydroxide can be maintained at ambient temperature, or optionally, depending on the etherifying agent and / or solvent used, it can be heated to a temperature of, for example, about 25°C to about 200°C. The reaction time for producing poly-α-1,6-glucan ether is modified in accordance with the reaction temperature, with lower temperatures requiring longer reaction times and higher temperatures requiring shorter reaction times.

[0131] Typically, the solvent contains water. Optionally, additional solvents can be added to alkaline solutions, such as alcohols like isopropanol, acetone, dioxane, and toluene. Alternatively, solvents such as lithium chloride (LiCl) / N,N-dimethylacetamide (DMAc), SO2 / diethylamine (DEA) / dimethyl sulfoxide (DMSO), LiCl / 1,3-dimethyl-2-imidazolidinone (DMI), N,N-dimethylformamide (DMF) / N2O4, DMSO / tetrabutylammonium fluoride trihydrate (TBAF), N-methylmorpholine-N-oxide (NMMO), aqueous solutions of Ni(tren)(OH)2 [trench-tris(2-aminoethyl)amine] and LiClO4·3H2O, aqueous NaOH / urea solution, aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, formic acid, and ionic liquids can be used.

[0132] The etherifying agent may be capable of etherifying poly-α-1,6-glucan with a positively charged organic group, where only the carbon chain of the positively charged organic group has substitution with a positively charged group (e.g., a substituted ammonium group such as trimethylammonium). Examples of such etherifying agents include dialkyl sulfates, alkyl carbonates, alkyl halides (e.g., alkyl chlorides), iodoalkanes, alkyl triflates (alkyltrifluoromethanesulfonates), and alkylfluorosulfonates, where each alkyl group (or more) of these etherifying agents has 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 sulfates, dimethyl carbonates, methyl chlorides, iodomethane, methyl triflates, and methylfluorosulfonates, where each methyl group (or more) of these etherifying agents has substitution 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, ethyl chloride, iodoethane, ethyl triflate, and ethyl fluorosulfonate, where each of the ethyl groups(s) in these etherifying agents has substitution 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, propyl chloride, iodopropane, propyl triflate, and propyl fluorosulfonate, where each of the propyl groups(s) in these etherifying agents has substitution 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, butyl chloride, iodobutane, and butyl triflate, where each of the butyl groups(s) in these etherifying agents has substitution with one or more positively charged groups (e.g., a substituted ammonium group such as trimethylammonium). Other examples of etherifying agents include halides of imidazoline ring-containing compounds.

[0133] The etherifying agent may be one that can etherify poly-α-1,6-glucan with a positively charged organic group, the carbon chain of the positively charged organic group having substitution with a positively charged group, such as a substituted ammonium group such as trimethylammonium, as well as substitution with a hydroxyl group, for example. Examples of such etherifying agents include hydroxyalkyl halides (e.g., hydroxyalkyl chlorides), such as halogenated hydroxypropyl and hydroxybutyl halides, the terminal carbon of each of these etherifying agents having substitution with a positively charged group (e.g., a substituted ammonium group such as trimethylammonium), one example being 3-chloro-2-hydroxypropyl-trimethylammonium. Additional examples of etherifying agents containing positively charged organic groups include quaternary ammonium compounds such as 2,3-epoxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyldodecyldimethylammonium chloride, 3-chloro-2-hydroxypropylcocoalkyldimethylammonium chloride, 3-chloro-2-hydroxypropylstearyldimethylammonium chloride, and halides of imidazoline ring-containing compounds. Other examples of such etherifying agents include propylene oxide (e.g., 1,2-propylene oxide) and butylene oxide (e.g., 1,2-butylene oxide; 2,3-butylene oxide), where the terminal carbon of each of these etherifying agents has substitution with a positively charged group (e.g., a substituted ammonium group such as trimethylammonium).

[0134] When producing poly-α-1,6-glucan ether compounds containing two or more different positively charged organic groups, two or more different etherifying agents are used accordingly. Any combination of the etherifying agents disclosed herein can produce poly-α-1,6-glucan ether compounds having two or more different positively charged organic groups. Such two or more etherifying agents may be used simultaneously in the reaction or sequentially in the reaction. If used sequentially, any of the temperature treatment (e.g., heating) steps may be optionally used between each addition. The sequential introduction of etherifying agents can be used to control the desired DoS of each positively charged organic group. Generally, a particular etherifying agent is used first when the organic group formed in the ether product is desired to have a higher DoS compared to the DoS of another organic group being added.

[0135] The amount of etherifying agent to contact with poly-α-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 substituents on each monomer unit in the poly-α-1,6-glucan ether compound can be determined using nuclear magnetic resonance (NMR) spectroscopy. Generally, the etherifying agent can be used in an amount of at least about 0.05 moles per mole of polyglucan. There may be no upper limit to the amount of etherifying agent that can be used.

[0136] The reactions for producing poly-α-1,6-glucan ether compounds may optionally be carried out in a pressure vessel such as a Parr reactor, autoclave, shaker tube, or any other pressure vessel known in the art. Optionally, the poly-α-1,6-glucan ether compounds may be prepared under an inert atmosphere, with or without heating. As used herein, the term “inert atmosphere” refers to an atmosphere of non-reactive gases such as nitrogen, argon, or helium.

[0137] After contacting poly-α-1,6-glucan, a solvent, an alkali hydroxide, and an etherifying reagent for a reaction time sufficient to produce a poly-α-1,6-glucan ether compound, the reaction mixture can optionally be filtered by any means known in the art that allows for the removal of liquid from solid.

[0138] Following etherification, one or more acids may be optionally added to the reaction mixture to lower the pH to a neutral pH range that is neither substantially acidic nor substantially acidic, for example, about 6–8 as desired, 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 useful 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.

[0139] The poly-α-1,6-glucan ether compound can be optionally washed once or more times with a liquid that does not readily dissolve the compound. For example, the poly-α-1,6-glucan ether can be washed with water, alcohol, isopropanol, acetone, aromatics, or any combination thereof, depending on the solubility of the ether compound therein (lack of solubility is desirable for washing). Generally, solvents containing organic solvents such as alcohol are preferred for washing. The poly-α-1,6-glucan ether product can be washed once or more times with an aqueous solution containing, for example, methanol or ethanol. For example, the product can be washed using 70-95% by weight of ethanol. In another embodiment, the poly-α-1,6-glucan ether product can be washed with a methanol:acetone (e.g., 60:40) solution.

[0140] Poly-α-1,6-glucan ether compounds can be optionally purified by membrane filtration.

[0141] The poly-α-1,6-glucan ether produced using the above method can be isolated. This step can be performed before or after the neutralization and / or washing step using a funnel, centrifuge, press filter, or any other method or apparatus known in the art that allows for the removal of liquid from solid. The isolated 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.

[0142] Any of the above etherification reactions can be repeated using the poly-α-1,6-glucan ether product as a starting material for further modification. This approach may be suitable for increasing the DoS of the positively charged organic group and / or for adding one or more different positively charged organic groups to the ether product. This approach may also be suitable for adding 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 can be used for this purpose even if they are not substituted with positively charged groups.

[0143] As described above, materials derived from sustainable / renewable raw materials are often desirable. Similarly, biodegradable materials are also sometimes preferred. For example, biodegradable cationic poly-α-1,6-glucan ether compounds are preferred over non-biodegradable materials from an environmental footprint standpoint. The biodegradability of a material can be evaluated by methods known in the art, such as those disclosed in the following section on biodegradability test methods of this specification. Cationic poly-α-1,6-glucan ether compounds may be characterized by at least 10% biodegradability at 90 days of the test period, as determined by the following biodegradability test method (i.e., carbon dioxide emission test method - OECD guideline 301B). Cationic poly-α-1,6-glucan ether compounds may be characterized by biodegradability of at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, or 80%, or any value between 5% and 80%, at 90 days of the test period, as determined by the biodegradability test method. Cationic poly-α-1,6-glucan ether compounds may be characterized by biodegradability of at least 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, or 60%, or any value between 5% and 60%, at 60 days of the test period, as determined by the following biodegradability test method. While we do not wish to be bound by theory, the biodegradability profiles of the materials described herein may be influenced by the degree of substitution, molecular weight, degree of branching, and / or solubility of the material. For example, a relatively low degree of substitution (e.g., low cation charge density) and / or increased solubility are thought to be associated with higher biodegradability.

[0144] The water-soluble unit-dose article is a multi-compartment unit-dose article, and the cationic poly-α-1,6-glucan ether compound may be contained in any compartment, any combination of compartments, or even within each compartment.

[0145] Manufacturing method Those skilled in the art will recognize water-soluble unit-dose articles, liquid laundry treatment compositions, and known methods and techniques for producing these components.

[0146] How to use A further aspect of the present invention is a method for washing fabric, comprising the steps of: preparing a washing solution by diluting a water-soluble unit dose article according to the present invention 200 to 3000 times in water; and bringing the fabric to be washed into contact with the washing solution. Preferably, the washing solution contains 5 L to 75 L, preferably 7 L to 40 L, more preferably 10 L to 20 L of water. Preferably, the temperature of the washing solution is about 5°C to about 90°C, preferably about 10°C to about 60°C, more preferably about 12°C to about 45°C, most preferably about 15°C to about 40°C. Preferably, washing the fabric in the washing solution takes 5 to 50 minutes, preferably 5 to 40 minutes, more preferably 5 to 30 minutes, even more preferably 5 to 20 minutes, most preferably 6 to 18 minutes to complete. Preferably, the washing solution contains 1 kg to 20 kg, preferably 3 kg to 15 kg, most preferably 5 to 10 kg of fabric. The cleaning solution may preferably contain water of any hardness ranging from 0 gpg to 40 gpg.

[0147] The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​listed. Instead, unless otherwise indicated, each such dimension is intended to mean both the listed value and the functionally equivalent range encompassing that value. For example, a dimension disclosed as "40 mm" is intended to mean "approximately 40 mm." [Examples]

[0148] The effects of the single, variable addition of the cationic modified poly-α-1,6-glucan ether compound according to the present invention to a water-soluble unit-dose liquid laundry formulation were evaluated in terms of providing fabric care benefits and the potential to mitigate the deterioration of freshness typically observed in the presence of cationic hydroxyethylcellulose and polyvinyl alcohol. Performance effects were evaluated according to the test methods described herein.

[0149] Example 1: Effect of fabric freshness The effect of a single variable addition of the cation-modified poly-α-1,6-glucan ether compound and cation-modified hydroxyethylcellulose according to the present invention on fabric freshness was evaluated both in the presence and absence of a water-soluble polyvinyl alcohol film, according to the test method described herein, for use in soluble unit-dose laundry formulations.

[0150] Test method: Treatment of the test fabric: The fabric treatment method includes the use of a commercially available washing machine such as the Miele Honeycomb Care W1724, or a similar machine using standard machine settings (short cotton cycle at 40°C, long total cycle of 1:38), followed by drying for 24 hours in a room at constant temperature / humidity (70°F / 50%rH). Before analysis, the fabric is treated in multiple cycles (3). The fabric composition in the machine consists of test cloth and standard ballast containing a total of 5.5 pounds of polyester, polycotton, and cotton mixture. Within each treatment cycle, the polymer and detergent treatment is delivered to the machine drum before the fabric at specified levels (26.65 g detergent base, 1 g PVA film, 10-20 ppm polymer in the washing solution). After the washing cycle, the fabric is subjected to one or more rinse cycles.

[0151] Freshness evaluation One of the test designs recommended by ASTM (E1958) for finding differences in measurable attributes uses a trained descriptive analysis panel. Fourteen validated external (non-employee) descriptive analysis panelists grading fragrance intensity were trained on how to grade fabrics for fragrance intensity on dry fabrics using a typical 0-100 scale (higher is better). The grading protocol was pre-rub (smelling different parts of the fabric) and post-rub (rubbing the fabric together five times and smelling once). All samples were labeled with a blinded 3-digit code and the presentation order was randomized. Three copies were tested and the test ratings were averaged.

[0152] Starting materials: Table 1 describes the first liquid laundry-based detergent composition. • A cation-modified poly-α-1,6-glucan ether compound (MW185M, 0.07% cation substitution degree, 5% branching degree) manufactured by DuPont. • Cation-modified hydroxyethylcellulose and polyquaternium-10 (MW300-500M, low cation charge density, e.g., less than 1% nitrogen) manufactured by Dow. • Water-soluble film: Polyvinyl alcohol homopolymer / anionic polyvinyl alcohol copolymer blend manufactured by MonoSol.

[0153] [Table 1]

[0154] Test results: Table 2 summarizes the aroma expert ratings of absolute pre- and post-friction friction and the single-step variable freshness loss effect of polyvinyl alcohol addition for a comparative polymer of polymer-free cationic hydroxyethyl cellulose outside the scope of the present invention and for examples containing cationic polyglucan according to the present invention. As the data clearly shows, cationic polyglucan according to the present invention partially mitigates the adverse effect on freshness by polyvinyl alcohol observed in polymer-free cationic hydroxyethyl cellulose containing the sample (relative PVA effect value). Furthermore, in contrast to the single-step variable addition of cationic hydroxyethyl cellulose (Comparative Example 3), in which a clear concession in fabric freshness performance is observed in polyvinyl alcohol films containing the sample, which is inherent to water-soluble unit-dose articles, the single-step variable addition of cationic polyglucan (Example 1 of the present invention) to the polymer-free standard (Comparative Example 1) does not adversely affect the fabric freshness performance.

[0155] [Table 2]

[0156] Example 2. Fabric retention performance of soluble unit-dose detergent formulations. The effect of a single, variable addition of the cation-modified poly-α-1,6-glucan ether compound and cation-modified hydroxyethylcellulose according to the present invention on fabric retention was evaluated according to the test method described herein, for use in soluble unit-dose laundry formulations.

[0157] Treatment of the test fabric: The fabric treatment method includes the use of a commercially available washing machine such as the Miele Honeycomb Care W1724, or a similar machine using standard machine settings (short cotton cycle at 40°C, long total cycle of 1:38), followed by drying for 24 hours in a room at constant temperature / humidity (70°F / 50%rH). Before analysis, the fabric is treated in multiple cycles (3). The fabric composition in the machine consists of a test cloth and standard ballast containing a total of 5.5 pounds of polyester, polycotton, and cotton mixture. Within each treatment cycle, the polymer and detergent treatment is delivered to the machine drum before the fabric at the specified levels (26.65 g detergent base, 1 g PVA film, 38 ppm polymer in the washing solution). After the washing cycle, the fabric is subjected to one or more rinse cycles.

[0158] Secant coefficient Instron method The secant coefficient is measured using tensile and compression testing equipment such as the Instron Model 5565 (Instron Corp., Norwood, Massachusetts, USA). This equipment is configured according to the fabric by selecting the following settings: mode is Tensile Extension; wave shape is Triangle; maximum strain is 10% for 479 sanforized and 35% for 7422 knitted; speed is 0.83 mm / sec for 479 sanforized and 2.5 mm / sec for 7422 knitted; number of cycles is 4; and holding time is 15 seconds between cycles. 1. Using scissors, cut the entire stitched edge on one side of each sample lengthwise, carefully removing the threads without applying stress to the fabric until an even edge is obtained. 2. Position the fabric press and cut a strip 1 inch wide and at least 4 inches long parallel to a uniform edge and lengthwise. 3. Cut three strips from each of three separate fabric samples: woven test fabric 479 sanforized 100% cotton or knitted test fabric 7422 50:50 polycotton. Before analysis, the fabrics are conditioned in a room at a constant temperature (70°F) and humidity (50%RH) for at least 6 hours. 4. Secure the upper and then lower parts of the cloth strip within the 2.54 cm gripping section of the tensile testing apparatus, set a 2.54 cm gap, and apply a small force (0.0.05 N to 0.2 N) to the sample. 5. During the holding cycle, release and re-secure the lower part of the sample, apply a force of 0.05N to 0.2N to the sample, and then apply the same force again to remove any slack. 6. After four hysteresis cycles are completed for a sample, the secant coefficient is reported in megapascals (MPa). The final result is the average of the modulus results of four individual cycles from all test strips for a given treatment on a given fabric type. The reported secant coefficient is calculated at the maximum strain for each fabric type.

[0159] Starting materials: Table 3 describes the second liquid laundry-based detergent composition. • Cation-modified poly-α-1,6-glucan ether compounds manufactured by DuPont: See Table 4. • Cation-modified hydroxyethylcellulose and polyquaternium-10 (MW300-500M, low cation charge density, e.g., less than 1% nitrogen) manufactured by Dow. • Water-soluble film: Polyvinyl alcohol homopolymer / anionic polyvinyl alcohol copolymer blend manufactured by MonoSol.

[0160] [Table 3]

[0161] Test results: Table 4 summarizes the obtained cross-sectional moduli measured according to the test methods described herein for a polymer-free standard product and a detergent composition containing a single variable amount of the cationic polyglucan polymer according to the present invention. As the data clearly shows, the single variable addition of the cationic polyglucan according to the present invention results in a decrease in the secant coefficient, and together with the tested cationic-modified hydroxyethylcellulose (instron secant coefficient of 3.5), it shows an improved fabric retention effect. In polymers 1-3 listed below, the cationic group is a quaternary ammonium group substituted with three methyl groups (i.e., trimethylammonium quat). The cationic group is bonded to the ether group (and therefore the glucan backbone) by a hydroxypropyl group, but can be bonded using any suitable alkyl group or other hydroxyalkyl group accordingly.

[0162] [Table 4]

[0163] In summary, the one-time variable addition of the cationic polyglucan polymer according to the present invention to a water-soluble unit-dose liquid detergent composition provides improved fabric care benefits while mitigating the adverse effects on freshness observed with alternative cationic polymer fabric care technologies such as cationic modified hydroxyethylcellulose and polyvinyl alcohol water-soluble film technologies.

[0164] Example 3. Fabric retention performance in detergent formulations with different soluble unit doses. The effect of a single, variable addition of a cationic modified poly-α-1,6-glucan ether compound according to the present invention on fabric retention was evaluated according to the test method described herein, for use in soluble unit-dose laundry formulations.

[0165] Treatment of the test fabric: The fabric treatment method includes the use of a commercially available washing machine such as the Miele Honeycomb Care W1724, or a similar machine using standard machine settings (short cotton cycle at 40°C, long total cycle of 1:38), followed by tumbling and drying in a Miele T640 on a normal cotton cycle. Before analysis, the fabric is treated in multiple cycles (6). The fabric composition in the machine consists of a test cloth and standard ballast containing a total of 5.5 pounds of polyester, polycotton, and cotton mixture. Within each treatment cycle, the polymer and detergent treatment is delivered to the machine drum before the fabric at specified levels (26.01 g detergent base, 0.67 g PVA film, 20 ppm polymer in the washing solution). After the washing cycle, the fabric is subjected to one or more rinse cycles.

[0166] Secant coefficient Instron method The secant coefficient is measured using tensile and compression testing equipment such as the Instron Model 3342 (Instron Corp., Norwood, Massachusetts, USA). This equipment is configured according to the fabric by selecting the following settings: mode is Tensile Extension; wave shape is Triangle; maximum strain is 10% for 479 sanforized and 35% for 7422 knitted; speed is 0.83 mm / sec for 479 sanforized and 2.5 mm / sec for 7422 knitted; number of cycles is 4; and holding time is 15 seconds between cycles. 1. Position the fabric press die and cut a strip 1 inch wide and at least 4 inches long parallel to a uniform edge and lengthwise. 2. Cut three strips from each of three separate fabric samples: woven test fabric 479 sanforized 100% cotton or knitted test fabric 7422 50:50 polycotton. Before analysis, the fabrics are conditioned in a room at a constant temperature (70°F) and humidity (50%RH) for at least 6 hours. 3. Secure the upper and then lower parts of the cloth strip within the 2.54 cm gripping section of the tensile testing apparatus, set a 2.54 cm gap, and apply a small force (0.05 N to 0.2 N) to the sample. 4. During the holding cycle, release and re-secure the lower part of the sample, apply a force of 0.05N to 0.2N to the sample, and then apply the same force again to remove any slack. 5. After four hysteresis cycles are completed for a sample, the secant coefficient is reported in megapascals (MPa). The final result is the average of the modulus results of four individual cycles from all test strips for a given treatment on a given fabric type. The reported secant coefficient is calculated at the maximum strain for each fabric type.

[0167] Starting materials: Table 3 describes the second liquid laundry-based detergent composition. • Cation-modified poly-α-1,6-glucan ether compounds manufactured by DuPont: See Table 4. • Water-soluble film: Polyvinyl alcohol homopolymer / anionic polyvinyl alcohol copolymer blend manufactured by MonoSol.

[0168] [Table 5] 1 Lutensit Z96 (BASF's zwitterionic polyaminediamine - zwitterionic hexamethylenediamine by the following formula: 100% quaternization and approximately 40% sulfonated polyethoxy (EO24) groups).

[0169] [ka]

[0170] Test results: Table 6 summarizes the modulus of cross-section obtained for knitted cotton 7422, measured according to the test methods described herein, for a polymer-free standard product and detergent compositions containing a single variable amount of the cationic polyglucan polymer according to the present invention. As the data clearly shows, the single variable addition of the cationic polyglucan according to the present invention results in a decrease in the secant coefficient and an improved fabric retention effect. In polymers 4 and 5 listed below, the cationic group is a quaternary ammonium group substituted with three methyl groups (i.e., trimethylammonium quat). The cationic group is bonded to the ether group (and therefore the glucan backbone) by a hydroxypropyl group, but can be bonded using any suitable alkyl group or other hydroxyalkyl group accordingly. The data also show that the polymers of the present invention have a greater effect in reducing the secant coefficient in compositions 4 and 5, which also suggests a higher AES to LAS ratio or a higher nonionic surfactant to LAS ratio.

[0171] [Table 6]

[0172] The data in Table 6 clearly demonstrates that the cationic polyglucan according to the present invention provides performance across a wide range of surfactant formulations.

[0173] The dimensions and values ​​disclosed herein should not be understood as being strictly limited to the exact numerical values ​​listed. Instead, unless otherwise indicated, each such dimension is intended to mean both the listed value and the functionally equivalent range encompassing that value. For example, a dimension disclosed as "40 mm" is intended to mean "approximately 40 mm".

Claims

1. A water-soluble unit-dose article comprising a water-soluble film and a liquid laundry treatment composition, The water-soluble film contains polyvinyl alcohol and is molded to create an internal compartment, and the liquid laundry treatment composition is contained within the internal compartment. The liquid laundry treatment composition comprises 0.01% to 10% by weight of a cation-modified poly-α-1,6-glucan ether compound, The cation-modified poly-α-1,6-glucan ether compound contains a glucose monomer unit backbone, and at least 70% of the glucose monomer units are linked via poly-α-1,6-glycosidic bonds. A water-soluble unit-dose article wherein the cation-modified poly-α-1,6-glucan ether compound is substituted with at least one positively charged organic group.

2. The cation-modified poly-α-1,6-glucan ether compound has a degree of substitution of about 0.001 to about 3, and the following i to iv: i) A weight-average degree of polymerization of at least 5; ii) Weight-average molecular weight between 1,000 and 500,000 Daltons; iii) derived from poly-α-1,6-glucan having a weight-average molecular weight of 900 to 450,000 daltons, as determined before substitution with at least one positively charged organic group; iv) mixtures thereof; A water-soluble unit-dose article according to claim 1, characterized by at least one of the above.

3. The water-soluble unit-dose article according to claim 1, wherein at least 3% of the skeletal glucose monomer units have branching via α-1,2 and / or α-1,3-glycosidic bonds.

4. The water-soluble unit-dose article according to any one of claims 1 to 3, wherein the positively charged organic group comprises a quaternary ammonium group.

5. The water-soluble unit-dose article according to claim 4, wherein the quaternary ammonium group comprises at least one C10-C16 alkyl group.

6. The water-soluble unit-dose article according to claim 4 or 5, wherein the quaternary ammonium group comprises a trimethylammonium group.

7. The water-soluble unit-dose article according to any one of claims 1 to 6, wherein the positively charged organic group comprises a quaternary ammonium hydroxyalkyl group.

8. The water-soluble unit dose article according to any one of claims 1 to 7, wherein the water-soluble film comprises a polyvinyl alcohol homopolymer or a polyvinyl alcohol copolymer.

9. The water-soluble unit-dose article according to any one of claims 1 to 8, wherein the liquid laundry treatment composition contains a non-soap surfactant.

10. The water-soluble unit dose article according to claim 9, wherein the non-soap surfactant comprises a non-soap anionic surfactant, and the non-soap anionic surfactant is selected from linear alkylbenzene sulfonates, alkoxylated alkyl sulfates, or mixtures thereof.

11. The water-soluble unit-dose article according to any one of claims 1 to 10, wherein the liquid laundry treatment composition contains a fragrance ingredient.

12. The water-soluble unit dose article according to any one of claims 1 to 11, wherein the liquid laundry treatment composition contains 1% to 20% by weight of water in the liquid laundry treatment composition.

13. A method for washing fabric, comprising the steps of: preparing a washing solution by diluting a water-soluble unit-dose article according to any one of claims 1 to 12 200 to 3000 times in water; and bringing a fabric to be washed into contact with the washing solution.

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