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    • 专利摘要:
    The present invention relates to compositions comprising a polysaccharide derivative, wherein the polysaccharide derivative comprises a polysaccharide substituted by (a) at least one hydrophobic group and (b) at least one hydrophilic group, wherein the polysaccharide is. poly alpha-1,3-glucan, poly alpha-1,6-glucan or poly alpha-1,3-1,6-glucan.
    公开号:BR112019012235A2
    申请号:R112019012235-4
    申请日:2017-12-14
    公开日:2019-11-05
    发明作者:S M Lu Helen；Lynn FLITER Kristi；Robert Sivik Mark；C Shah Mukesh；W Shuey Steven；Qiu Weiming；Huang Zhengzheng
    申请人:Du Pont；
    IPC主号:
    专利说明:

    “COMPOSITION AND METHOD FOR THE TREATMENT OF A SUBSTRATE
    Cross Reference to Related Patent Application [001] This application claims the priority and benefit of provisional application 1962/435158, entitled Amphiphilic polysaccharide derivatives and compositions comprising the same, filed on December 16, 2016, the description of which is incorporated present as a reference in its entirety.
    Field of the Invention [002] The present invention relates to a composition comprising a polysaccharide derivative, wherein the polysaccharide derivative comprises a polysaccharide substituted by at least one hydrophobic group and at least one hydrophilic group.
    Background of the Invention [003] Driven by the desire to find new structural polysaccharides using enzymatic or genetic engineering syntheses of microorganisms, Depositors have discovered that oligosaccharides and polysaccharides are biodegradable and can be produced economically from renewable raw materials.
    [004] Modern detergent compositions, including laundry, fabric, dishwashing or other cleaning compositions, comprise common detergent ingredients, such as anionic, non-ionic, cationic, amphoteric, zwitterionic and / or semi surfactants -polar; as well as enzymes such as proteinases, cellulases, lipases, amylases and / or peroxidases. The laundry detergent and / or fabric treatment compositions can still comprise several detergent ingredients that have one or more purposes in obtaining fabrics that are not only clean, fresh and sanitized, but also have the retained appearance and integrity. Therefore, agents
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    2/135 beneficial ones such as perfumes, hygiene agents, insect control agents, bleaching agents, fabric softeners, dye fixers, dirt release agents and fabric bleaching agents have been incorporated into laundry detergents and / or tissue treatment compositions. When using these detergent components, it is important that some of these compounds are deposited on the fabrics in order to be effective during or after the washing process and / or care of the fabric.
    [005] Many of the ingredients that are part of a detergent composition are produced from non-renewable petroleum raw materials. There remains a need to formulate detergent compositions providing improved cleaning performance that are produced from renewable resources.
    Brief Description of the Invention [006] The compositions comprising:
    - a polysaccharide derivative, wherein the polysaccharide derivative comprises a polysaccharide substituted by (a) at least one hydrophobic group; and (b) at least one hydrophilic group;
    - where the polysaccharide is poly alpha-1,3-glucan, poly alpha-1,6glucan or poly alpha-1,3-1,6-glucan.
    [007] In one embodiment, the poly alpha-1,3-glucan comprises a main chain of glucose monomer units in which greater than or equal to 50% of the glucose monomer units are linked by means of alpha-1 bonds , 3-glycosides. In another embodiment, the poly alpha-1,3-glucan comprises a backbone of glucose monomer units in which greater than or equal to 90% of the glucose monomer units are linked by means of alpha-1,3- glycosidics. In another realization,
    Petition 870190055067, of 6/14/2019, p. 269/408
    3/135 the poly alpha-1,6-glucan comprises a structure of glucose monomer units in which greater than or equal to 40% of the glucose monomer units are linked by means of alpha-1,6-glycosidic bonds. In one embodiment, the poly alpha-1,6-glucan has a degree of branching of alpha-1,2 that is less than 50%.
    [008] In one embodiment, at least one hydrophobic group comprises a C1-C18 alkyl, a C2-C18 alkene, a C2-C18 alkene, a polyether comprising (-CH 2 CH 2 O-) repeating units , (CH 2 CH (CH3) O-) or a mixture thereof, where the total number of repeat units is in the range from 3 to 100, a C6-C 2 o aryl group, a benzyl, a C1 alkylsulfonyl group -C18, a C6-C 2 o arylsulfonyl, a ptoluenesulfonyl or one of its combinations. In another embodiment, at least one hydrophobic group comprises a C1-C18 alkyl group, a benzyl, a p-toluenesulfonyl or one of its combinations. In yet another embodiment, at least one hydrophobic group comprises a benzyl group, and the benzyl group is still replaced by one or more of a halogen, a cyano, an ester, an amide, an ether group, a Ci-Ce alkyl group , an aryl group, a C 2 -C 6 alkene group, an alkyne group C2 -C6 alkyl, or combinations thereof.
    [009] In one embodiment, at least one hydrophilic group comprises a carboxylic acid, salt of carboxylic acid, derived from sulfonic acid, salt derived from sulfonic acid, salt derived from sulfuric acid, salt derived from sulfuric acid, thiosulfate, thiosulfate salt , derived from phosphoric acid, salt derived from phosphoric acid, alkyl amine, alkyl substituted ammonium salt, quaternized pyridine salt, quaternized imidazole salt or one of its combinations. In another embodiment, at least one hydrophilic group comprises a carboxylic acid, an alkyl substituted ammonium salt, a sulfonate, an alkyl sulfonate, a sulfate, a thiosulfate or one of its combinations.
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    4/135 [010] In another embodiment, at least one hydrophobic group comprises a C1-C18 alkyl, a C2-C18 alkene, a C2-C18 alkene, a polyether comprising (-CH 2 CH 2 repeat units) O-), (CH 2 CH (CH3) O-) or mixtures thereof, where the total number of repeat units is in the range from 3 to 100, a C6-C 2 o aryl, a benzyl, an alkylsulfonyl C1-C18, a C6-C 2 o arylsulfonyl group, a ptoluenesulfonyl group, or one of its combinations and at least one hydrophilic group comprises a carboxylic acid, carboxylic acid salt, a sulfonic acid derivative, a salt derived from acid sulfonic acid, a sulfuric acid derivative, a sulfuric acid derived salt, thiosulfate, a thiosulfate salt, a phosphoric acid derivative, a phosphoric acid derived salt, an alkyl amine, an alkyl substituted ammonium salt, a salt of quaternized pyridine, a quaternized imidazole salt or one of its combinations . In another embodiment, at least one hydrophobic group comprises a C1-C18 alkyl group, a benzyl, a p-toluenesulfonyl, or one of its combinations, and at least one hydrophilic group comprises a carboxylic acid, a substituted ammonium salt by alkyl, a sulfonate, an alkyl sulfonate, a sulfate, a thiosulfate or one of its combinations. In yet another embodiment, at least one hydrophobic group comprises a C1-C18 alkyl, benzyl, or p-toluenesulfonyl group and at least one hydrophilic group comprises a thiosulfate or carboxymethyl group.
    [011] In one embodiment, the polysaccharide derivative has a degree of polymerization in the range from about 5 to about 1,400. In another embodiment, the polysaccharide derivative has a degree of substitution of about 0.001 to about 3.0. In another embodiment, the 2 wt.% Polysaccharide derivative has a surface tension of 65 mN / m or less, as determined according to ASTM Standard D1331,2015.
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    5/135 [012] In another embodiment, the composition is in the form of a liquid, a gel, a powder, a hydrocolloid, an aqueous solution, a granule, a tablet, a capsule, a single compartment sachet, a sachet of multiple compartments, a single compartment bag or a multiple compartment bag.
    [013] In yet another embodiment, the composition still comprises at least one surfactant, an enzyme, a detergent adjuvant, a complexing agent, a polymer, a dirt release polymer, a surfactant enhancing polymer, a surfactant agent bleach, a bleach activator, a bleach catalyst, a fabric conditioner, a clay, a foam enhancer, a soap foam suppressor, an anti-corrosion agent, a dirt suspending agent, an anti-dust redeposition agent , a dye, a bactericide, a stain inhibitor, an optical brightener, a perfume, a saturated or unsaturated fatty acid, a dye transfer inhibitor, a chelating agent, a colored dye, a calcium cation, a cation of magnesium, a visual signaling ingredient, an antifoam, a structuring agent, a thickening agent, an anti-caking agent, a starch, sand, gelling agent or one of its combinations s.
    [014] In one embodiment, the enzyme is a cellulase, a proteinase, an amylase, a lipase or one of its combinations. In one embodiment, the enzyme is a cellulase. In another embodiment, the enzyme is a proteinase. In another embodiment, the enzyme is an amylase. In yet another embodiment, the enzyme is a lipase.
    [015] Also described in the present is a method for the treatment of a substrate, the method comprises the steps:
    (A) to provide a composition comprising a polysaccharide derivative, wherein the polysaccharide derivative comprises a
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    6/135 polysaccharide replaced by:
    (a) at least one hydrophobic group; and (b) at least one hydrophilic group;
    - wherein the polysaccharide is poly alpha-1,3-glucan, poly alpha-1,6glucan or poly alpha-1,3,6-glucan;
    (B) placing the substrate in contact with the composition; and (C) optionally, rinsing the substrate;
    - where the substrate is the carpet, upholstery or surface.
    [016] A product is also described in the present, the product comprises:
    - from about 1% to about 60% by weight of a surfactant; and
    - from about 0.1% to about 10% by weight of a polysaccharide derivative, wherein the polysaccharide derivative comprises a polysaccharide substituted by (a) at least one hydrophobic group; and (b) at least one hydrophilic group;
    - wherein the polysaccharide is poly alpha-1,3-glucan, poly alpha-1,6glucan or poly alpha-1,3,6-glucan; where said product is a household product.
    [017] In one embodiment, the product is in the form of a liquid, a gel, a powder, a hydrocolloid, an aqueous solution, a granule, a tablet, a capsule, a single compartment sachet, a multiple compartment sachet, a single compartment bag or a multiple compartment bag.
    [018] In another embodiment, the product still comprises at least one of an enzyme, a detergent adjuvant, a complexing agent, a polymer, a dirt release polymer, a polymer
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    7/135 surfactant enhancer, bleaching agent, bleaching activator, bleaching catalyst, fabric conditioner, clay, foam enhancer, soap foam suppressant, anti-corrosion agent, dirt suspension, an anti-dust redeposition agent, dye, bactericide, stain inhibitor, an optical brightener, perfume, a saturated or unsaturated fatty acid, a dye transfer inhibiting agent, a chelating agent, a colored dye, a cation of calcium, a magnesium cation, a visual signaling ingredient, an antifoam, a structuring agent, a thickening agent, an anti-caking agent, a starch, sand, gelling agent or one of its combinations.
    [019] In one embodiment of the product, the enzyme is a cellulase, a proteinase, an amylase, a lipase or one of its combinations.
    [020] In another product embodiment, the 2% by weight polysaccharide derivative has a surface tension of less than 65 mN / m.
    [021] Also described herein is a water-soluble unit dose article comprising a water-soluble film and a composition comprising from about 1% to about 60% by weight of a surfactant; and from about 0.1% to about 10% by weight of a polysaccharide derivative, wherein the polysaccharide derivative comprises a polysaccharide substituted by (a) at least one hydrophobic group; and (b) at least one hydrophilic group;
    - wherein the polysaccharide is poly alpha-1,3-glucan, poly alpha-1,6glucan or poly alpha-1,3,6-glucan; where said water-soluble unit dose article is a household product.
    [022] In one embodiment, the water-soluble unit dose article
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    8/135 comprises at least two compartments. In another embodiment, the water-soluble unit dose article comprises at least two compartments in which the compartments are arranged in an overlapping orientation or in a side-by-side orientation. In another embodiment, the water-soluble unit dose article comprises at least three compartments.
    [023] Also described herein is a method for treating a substrate, in which the method includes the step of putting the substrate in contact with the household product in the presence of water, where the substrate is a fabric or a rigid surface . In addition, a method for treating a fabric with the product is described herein, wherein the treated fabric has a change in WICIE of +1.5 or more units versus the fabric prior to treatment, as determined according to the L * a * b * WICIE method.
    [024] A product that comprises:
    - from about 1% to about 60% by weight of a non-oil derived surfactant;
    - from about 0.1% to about 10% by weight of a polysaccharide derivative, wherein the polysaccharide derivative comprises a polysaccharide substituted by (a) at least one hydrophobic group; and (b) at least one hydrophilic group;
    - wherein the polysaccharide is poly alpha-1,3-glucan, poly alpha-1,6glucan or poly alpha-1,3,6-glucan; where said product is a household product.
    [025] In one embodiment, the product is substantially free of dye and bleach.
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    9/135
    Detailed Description of the Invention [026] The descriptions of all cited patent and non-patent publications are hereby incorporated by reference in their entirety.
    [027] As used herein, the term "embodiment" or "present invention" is not intended to be limiting, but in general applies to any of the embodiments defined in the claims or described herein. These terms are used interchangeably in this document.
    [028] In the present invention, several terms and abbreviations are used. The following definitions apply, unless specifically stated otherwise.
    [029] The articles “one”, “one” and “a / o” that precede an element or component are intended to be non-restrictive in relation to the number of cases (that is, occurrences) of the element or component. Therefore, the articles “one”, “one” and “a / o” should be read to include one or at least one, and the singular word form of the element or component also includes the plural, unless the number obviously means the singular.
    [030] The term “comprising” means the presence of the declared resources, whole numbers, steps or components, as mentioned in the claims, but that does not exclude the presence or addition of one or more other resources, whole numbers, steps, components or their groups. The term it comprises is intended to include the achievements covered by the terms essentially consisting of and consisting of, similarly, the term "essentially consists of" is intended to include the achievements encompassed by the term "consisting of".
    [031] When present, all ranges are inclusive and combinable. For example, when a range from 1 to 5 is recited, the range recited should be interpreted as including ranges 1 to 4,
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    10/135 to 3, 1 to 2.1 to 2 and 4 to 5, Ί to 3 and 5 ”and so on.
    [032] As used herein in relation to a numerical value, the term about refers to a range from +/- 0.5 of the numerical value, unless the term is specifically defined otherwise in context. For example, the phrase "pH value of about 6" refers to pH values of 5.5 to 6.5, unless the pH value is specifically defined otherwise.
    [033] Each maximum numerical limitation provided throughout this Specification is expected to include all lower numerical limitations, as if such lower numerical limitations were expressly written in the present. Each minimum numerical limitation provided throughout this Specification will include all upper numerical limitations, as if such upper numerical limitations were expressly written in the present. Each numeric range provided throughout this Specification will include all the narrowest numeric ranges that fall within a broader numeric range, as if such narrower numeric ranges were all expressly written in the present.
    [034] The characteristics and advantages of the present invention will be more easily understood by those skilled in the art by reading the following Detailed Description of the Invention. It should be considered that certain features of the present invention, which, for clarity, are described above and below in the context of separate embodiments, can also be provided in combination in a single element. Conversely, several characteristics of the description, which, for brevity, are described in the context of a single realization, can also be provided separately or in any subcombination. In addition, references to the singular may also include the plural (for example, "a / o" and "one / an" may refer to one or more), unless the context specifies otherwise.
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    11/135 [035] The use of numerical values in the various ranges specified in the present invention, unless expressly stated otherwise, are expressed as approximations, as if the minimum and maximum values within the declared ranges were both proceeded by the term “ about". In this way, small variations above and below the established ranges can be used to achieve substantially the same results as the values within the ranges. In addition, the description of these ranges is intended as a continuous range, including all values between the minimum and maximum values.
    [036] As used in the present:
    The terms "c entual by weight", "weight percent (wt%)" and "weight percentage weight (wt%)" are used interchangeably in this. The percentage by weight refers to the percentage of a material on a mass basis, as understood in a composition, mixture or solution;
    The term "non-water-soluble" means that an amount less than 5 grams of the substance, for example, the alpha polymer (1.3glucan), dissolves in 100 milliliters of water at 23 ° C. In other embodiments, the term "non-water-soluble" ”Means that less than 4 grams or 3 grams or 2 grams or 1 gram of the substance is dissolved in water at 23 ° C;
    The term “water-soluble” means that the polysaccharide derivative or polysaccharide is soluble at 1% by weight or higher at pH 7 in water at 25- C. The weight percentage is based on the total weight of the water-soluble polysaccharide, for example, 1 gram of polysaccharide in 100 grams of water; and
    The term “dispersible in water” is defined as a compound with the capacity, at 1% by weight or higher at pH 7 at 25- C, of being
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    12/135 distributed through a solution in finite particles or droplets. The weight percentage is based on the total weight of the compound in water, for example, 1 gram of polysaccharide or polysaccharide derivative in 100 grams of water.
    [037] As used herein, the term "weighted average molecular weight" or "Mw" is calculated as,
    Mw = ZNíMÍ2 / ZNíMí; where Mi is the molecular weight of a chain and Ni is the number of chains of that molecular weight. The weighted average molecular weight can be determined using techniques such as static light scattering, gas chromatography (GC), high pressure liquid chromatography (HPLC), gel permeation chromatography (GPC), small angle neutron scattering, X-ray scattering and sedimentation speed.
    [038] As used herein, the term numerical average molecular weight or M n refers to the statistical average molecular weight of all polymer chains in a sample. The numerical average molecular weight is calculated as Mn = ZNiMi / ZNi, where Mi is the molecular weight of a chain and Ni is the number of chains of that molecular weight. The numerical average molecular weight of a polymer can be determined using techniques such as gel permeation chromatography, viscometry using (Mark-Houwink equation) and colligative methods such as vapor pressure osmometry, end group determination or proton NMR.
    [039] The term "hydrophobic" refers to a molecule or substituent that is supporting and has little or no affinity for water and that tends to repel water.
    [040] The term hydrophilic refers to a molecule or a substituent that is polar and has an affinity for interacting with solvents
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    13/135 polar, in particular with water, or with other polar groups. A hydrophilic molecule or substituent tends to attract water.
    [041] The term "amphiphilic" means to contain both hydrophobic and hydrophilic groups.
    [042] The carbon positions 1, 2, 3, 4, 5 and 6 of glucose, as referred to in the present, are known in the state of the art and are represented in Structure I:
    Structure I [043] The terms glycosidic bond and glycosidic bond are used interchangeably in the present and refer to the type of covalent bond that links a carbohydrate (sugar) molecule to another group, such as another carbohydrate. The term "alpha-1,6-glucosidic bond", as used herein, refers to the covalent bond that bonds the alphaD-glucose molecules together through carbons 1 and 6 in the adjacent alpha-D-glucose rings. The term alpha-1,3-glucoside bond, as used herein, refers to the covalent bond that bonds the alpha-D-glucose molecules together through carbons 1 and 3 in adjacent alpha-D-glucose rings. The term alpha-1,2-glucoside bond, as used herein, refers to the covalent bond that bonds the alpha-D-glucose molecules together through carbons 1 and 2 in the adjacent alpha-D-glucose rings. The term alpha-1,4glucosidic bond, as used herein, refers to the covalent bond that bonds the alpha-D-glucose molecules together through carbons 1 and 4 in the adjacent alpha-D-glucose rings. In the present, alpha-D-glucose will be referred to as glucose.
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    14/135 [044] The glycosidic binding profile of a glucan or dextran can be determined using any method known in the art. For example, a binding profile can be determined using methods using nuclear magnetic resonance (NMR) spectroscopy (for example, NMR 13 c or NMR 1 H). These and other methods that can be used are described in Food Carbohydrates: Chemistry, Physical Properties, and Applications (SW Cui, Ed., Chapter 3, SW Cui, Structural Analysis of Polysaccharides, Taylor & Francis LLC Group, Boca Raton, FL, 2005), which is incorporated herein as a reference.
    [045] The term polyglucan, as used herein, refers to poly alpha-1,3-glucan, poly alpha-1,6-glucan and / or poly alpha-1,3-1,6glucan. The plural “polyglucans” refers to the three polysaccharides.
    [046] The term alkyl group, as used herein, refers to linear, branched or cyclic (cycloalkyl) hydrocarbon groups that do not contain any unsaturation. As used herein, the term alkyl group encompasses substituted alkyls, for example, alkyl groups substituted by at least one hydroxyalkyl group or dihydroxyalkyl group, as well as alkyl groups containing one or more heteroatoms such as oxygen, sulfur and / or nitrogen within the hydrocarbon chain.
    [047] As used herein, the term alkene refers to linear, branched or cyclic hydrocarbon groups containing at least one carbon-carbon double bond. As used herein, the term alkene encompasses substituted alkenes, for example, alkenes substituted by at least one alkyl group, hydroxyalkyl group, or dihydroxyalkyl group, as well as alkenes containing one or more heteroatoms such as oxygen, sulfur and / or nitrogen in the hydrocarbon chain.
    [048] As used herein, the term alkino refers to
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    15/135 to linear and branched hydrocarbon groups containing at least one carbon-carbon triple bond. As used herein, the term alkyne encompasses substituted alkaline groups, for example, alkynes substituted by at least one alkyl group, a hydroxyalkyl group, or dihydroxy group, as well as alkines containing one or more heteroatoms such as oxygen , sulfur and / or nitrogen in the hydrocarbon chain.
    [049] As used herein, the term aryl means an aromatic carbocyclic group that has a single ring (eg, phenyl), multiple rings (eg, biphenyl), or condensed multiple rings in which at least one it is aromatic (e.g. 1,2, 3,4 tetrahydronaphthyl, naphthyl, anthryl or phenanthryl), which optionally is mono, di or tri-substituted by alkyl groups. The term "aryl" also means heteroaryl groups in which heteroaryl is defined as aromatic ring systems with 5, 6 or 7 members containing at least one heteroatom selected from the group consisting of nitrogen, oxygen and sulfur. Examples of heteroaryl groups include pyridyl, pyrimidinyl, pyrrolyl, pyrazolyl, pyrazinyl, pyridazinyl, oxazolyl, furanyl, quinolinyl, isoquinolinyl, thiazolyl and thienyl, which can optionally be substituted by alkyl groups.
    [050] The term “molar substitution” (M.S), as used herein, refers to the mol of an organic group per monomeric unit of the polysaccharide or its derivative. Note that the molar substitution value for a poly alpha-1,3-glucan derivative, for example, can have a very high upper limit, for example, in the hundreds or even thousands. For example, if the organic group is an alkyl group containing the hydroxyl, by adding ethylene oxide to one of the hydroxyl groups of poly alpha1,3-glucan, therefore, the hydroxyl group thus formed from ethylene oxide then it can be etherified further to form a polyether.
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    16/135 [051] The present invention relates to a composition comprising a polysaccharide derivative, wherein the polysaccharide derivative comprises a polysaccharide substituted by:
    (a) at least one hydrophobic group; and (b) at least one hydrophilic group;
    - where the polysaccharide is poly alpha-1,3-glucan, poly alpha-1,6glucan or poly alpha-1,3-1,6-glucan.
    [052] The polysaccharide derivatives described herein are referred to as amphiphilic polysaccharide derivatives, that is, polysaccharides containing hydrophobic and hydrophilic groups. Amphiphilic polysaccharide derivatives are of interest due to their enhanced adsorption characteristics at the interfaces, which can cause a reduction in surface stresses. These features are useful in a wide range of applications, including the production of laundry, cleaning, food, cosmetics, industrial, film and paper. For laundry applications, amphiphilic polysaccharide derivatives can function as dirt releasing agents, where hydrophobic groups adsorb to the surface of the hydrophobic substrate and the hydrophilic group repels dirt. Amphiphilic polysaccharide derivatives can also be useful as a surface coating for films and papers, to enable good adhesion to hydrophobic substrates and to provide a hydrophilic surface. Amphiphilic polysaccharide derivatives can orient themselves at the interface of water and oil droplets when the oil is dispersed in water. For an oil-in-water dispersion, the hydrophobic groups of the amphiphilic polysaccharide derivatives are dissolved in the oil phase while the hydrophilic groups are dissolved in the aqueous phase. The amphiphilic polysaccharide derivative therefore forms a film around the oil droplet and stabilizes the emulsion. Thus, amphiphilic polysaccharide derivatives, due to their surface activity,
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    17/135 can be used as emulsion stabilizers and / or foaming agents in cleaning, food and cosmetic applications. Typically, for use in such applications, amphiphilic polysaccharide derivatives are water-soluble or dispersible in water.
    [053] In one embodiment, the polysaccharide derivative comprises a polysaccharide that has the hydrophobic groups and hydrophilic groups randomly substituted along the polysaccharide backbone, such that the polysaccharide backbone comprises the non-D-glucose rings replaced and replaced. As used herein, the term "randomly substituted" means that the substituents on the glucose rings in the randomly substituted polysaccharide occur in a non-repetitive or random manner. That is, the substitution on a substituted glucose ring can be identical or different [that is, the substituents (which can be identical or different) on different atoms in the glucose rings on the polysaccharide] of the substitution on a second substituted glucose ring in the polysaccharide, so that the global substitution in the polymer has no standard. In addition, the substituted glucose rings occur randomly within the polysaccharide (that is, there is no pattern with the substituted and unsubstituted glucose rings within the polysaccharide).
    [054] In one embodiment, the polysaccharide derivative comprises a polysaccharide substituted by (a) at least one hydrophobic group and (b) at least one hydrophilic group, and the polysaccharide is poly alpha-1,3-glucan. In another embodiment, the polysaccharide derivative comprises a polysaccharide substituted by (a) at least one hydrophobic group and (b) at least one hydrophilic group, and the polysaccharide is poly alpha-1,6-glucan. In another embodiment, the derivative of
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    18/135 polysaccharide comprises a polysaccharide substituted by (a) at least one hydrophobic group and (b) at least one hydrophilic group, and the polysaccharide is poly alpha-1,3-1,6-glucan. Mixtures of amphiphilic polysaccharide derivatives can also be used.
    [055] The substituted polysaccharide can also comprise mixtures of the polysaccharides described in the present above.
    [056] The polysaccharide derivative comprises poly alpha-1,3-glucan, poly alpha-1,6-glucan or poly alpha-1,3-1,6-glucan substituted in one or more positions with (a) at least, a hydrophobic group and (b) at least one hydrophilic group. Suitable hydrophobic groups include a C1-C18 alkyl, a C2-C18 alkene, a C2-C18 alkaline, a polyether comprising (-CH 2 CH 2 O-), (-CH 2 CH (CH3) repeat units O-), or mixtures thereof, in which the total number of repeat units is in the range from 3 to 100, a C6-C 2 o aryl, a benzyl group, a C1-C18 alkylsulfonyl group, a C6- arylsulfonyl group C 2 o, a ptoluenesulfonyl group and one of its combinations. Suitable hydrophilic groups include carboxylic acids, carboxylic acid salts, sulfonic acid derivatives, salts derived from sulfonic acid, salts derived from sulfuric acid, thiosulfate, salts of thiosulfate, salts derived from phosphoric acid, salts derived from phosphoric acid phosphoric acid, alkyl amine, alkyl substituted ammonium salts, quaternized pyridine salts, quaternized imidazole salts and one of their combinations.
    [057] At least one hydrophobic group and at least one hydrophilic group can each independently derive the polysaccharide at the hydroxyl position 2, 3, 4 and / or 6 of a glucose monomer, as appropriate for the specific polysaccharide. Hydrophobic and hydrophilic groups, independently, are linked to the
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    19/135 polysaccharide through a chemical bond such as alkylene, ester (COO-, -OOC), amide (-CONH-), carbamate (-NHCO-), ether (-O-), thioether (S-), sulfonate (-OSO 2), sulfate (-OSO2O-), thiosulfate (-SSO 2)), carbonate (-OCOO-), urethane (-NHCOO-, -OOCNH), urea (-NHCONH-), amino (- NH-), phosphate (-OPO 2 (OR) or phosphonate (-PO 2 (OR) -.
    [058] Structures II and III below show two generalized embodiments representing the derivatization of a poly alpha-1,3-glucan glucose repeat unit and a poly alpha-1,6-glucan glucose repeat unit, respectively , to more clearly illustrate the positions at which the glucose unit can be derivatized and the chemical bond (shown as Z) between the glucan polymer and the substituent group R shown on the structures. The number of hydrophobic groups (where R = R ') and hydrophilic groups (where R = R ”) present in the derivatized polysaccharide is reflected in the degree of substitution of the derivatized polysaccharide; in the unsubstituted positions, the Z-R portion would be a hydroxyl group.
    Derivatization of a glucose unit within poly alpha-1,3-glucan
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    20/135
    Structure III
    Derivatization of a glucose unit within poly alpha-1,6-glucan [059] In the case where the hydrophobic group is a C1-C18 alkyl, a C2-C18 alkene, a C2-C18 alkene, a polyether comprising repeat units of (-CH 2 CH 2 O-), (-CH 2 CH (CH3) O-), or mixtures thereof, where the total number of repetition units is in the range from 3 to 100, one aryl C6-C 2 o, or a benzyl group (Aryl-CH 2 -), the hydrophobic group is chemically bonded to the glucan polymer via an ether bond.
    When the hydrophobic group is a p-toluenesulfonyl group (CH3-C6H4-SO 2 -), the hydrophobic group is joined as shown in Structure IV below for a glucose unit within poly alpha-1,3-glucan, where the group ptoluenesulfonyl is shown at position 6:
    Structure IV [060] In the case where the poly alpha-1,3-glucan is oxidized to contain a hydrophilic group comprising a portion of carboxylic acid (-COO-) at position 6 of the glucose ring, the carboxylic acid group (or salt) joins the glucan through a carbon-carbon bond, as shown below in
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    Structure V:
    Structure V [061] Structure VI is a generalized embodiment that represents the derivatization of a poly alpha-1,3-glucan glucose repeating unit with a hydrophobic benzyl group at position 2 of the glucose ring and a hydrophilic alkylsulfonate group (shown as an anion) at position 6:
    [062] The polysaccharide derivative has a degree of substitution from about 0.001 to about 3.0. The term "degree of substitution" DoS, as used herein, refers to the average number of hydroxyl groups substituted in each monomeric unit (glucose) of the polysaccharide. Since there are a maximum of three hydroxyl groups in a monomeric glucose unit in a glucan polymer, the overall degree of substitution cannot be greater than 3. In other embodiments, the degree of substitution may be in the range from 0, 02 to 2.5, or from 0.02 to 2.0, or from 0.2 to 2, or from 0.2 to 1. Alternatively, the DoS can be from about 0.001, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.2, 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,
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    2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3.0, or any value between 0.001 and 3. Must be It is understood by those skilled in the art that, since a polysaccharide derivative as described herein has a degree of substitution between about 0.001 and about 3.0, the substituents on the polysaccharide cannot just be hydrogen. The degree of substitution of an amphiphilic polysaccharide derivative described herein can be established with reference to at least one hydrophobic group, with reference to at least one hydrophilic group, or with reference to the overall degree of substitution, that is, the sum of DoS of the hydrophobic and hydrophilic groups. As used herein, when the degree of substitution is not indicated with reference to the hydrophobic or hydrophilic group, it means the overall degree of substitution. As the polysaccharide derivative comprises a polysaccharide substituted by at least one hydrophobic group and at least one hydrophilic group, the DoS with reference only to the hydrophobic group, or with reference to the isolated hydrophilic group, is necessarily less than 3.
    [063] In one embodiment, the DoS of the polysaccharide derivative relative to the hydrophobic group (s) can be in the range from about 0.02 to about 1.5, or for example, the from about 0.1 to about 1, and the DoS of the polysaccharide derivative with respect to the hydrophilic group (s) can be in the range from about 0.1 to about 2 , 5, or for example, from about 0.2 to about 1.5, with the proviso that the global DoS of the polysaccharide derivative is not greater than 3.
    [064] The polysaccharide derivative has a degree of polymerization in the range from about 5 to about 1,400, for example, in the range from about 5 to about 100, or from about 5 to about 500, or from about 5 to about 1,000, or from about 5 to about 1,100, or from about 5 to about 1,200, or from
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    23/135 about 5 to about 1,300, or from about 5 to about 1,400.
    [065] The structure, molecular weight and degree of substitution of a polysaccharide derivative can be confirmed using various physico-chemical analyzes known in the art, such as NMR spectroscopy and size exclusion chromatography (SEC).
    [066] The molecular weight of a polysaccharide or polysaccharide derivative can be represented as the numerical average molecular weight (Mn) or as the weighted average molecular weight (Mw). Alternatively, the molecular weight can be represented as Daltons, grams / mol, DPw (weighted average degree of polymerization), or DPn (average degree of polymerization). Various means are known in the art to calculate these molecular weight measurements, such as with high pressure liquid chromatography (HPLC), size exclusion chromatography (SEC) or gel permeation chromatography (GPC).
    [067] The terms poly alpha-1,3-glucan, alpha-1,3-glucan polymer and glucan polymer are used interchangeably in the present. Poly alpha-1,3-glucan means a polymer comprising units of glucose monomers linked together by glycosidic bonds, where at least about 50% of the glycosidic bonds are the alpha-1,3- glycosidics. Poly alpha-1,3-glucan is a type of polysaccharide. The alpha-1,3-glycosodic bond of poly alpha-1,3-glucan can be illustrated by Structure VII as follows:
    [068] Poly alpha-1,3-glucan can be prepared using the
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    24/135 chemical methods. Alternatively, it can be prepared by extracting it from several organisms, such as fungi, which produce poly alpha-
    1,3-glucan. Alternatively, poly alpha-1,3-glucan can be produced enzymatically from sucrose using one or more glucosyltransferase (gtf) enzymes (e.g., gtfJ), as described in U.S. patents 7,000,000; 8,642,757; and 9,080,195 (all of which are incorporated herein as a reference), for example. Using the procedures indicated in the present, the polymer is produced directly in a single-step enzymatic reaction using a recombinant glucosyltransferase enzyme, for example, the enzyme gtfJ, as a catalyst and sucrose as a substrate. Poly alpha-1,3-glucan is produced with fructose as a by-product. As the reaction progresses, poly alpha-1,3-glucan precipitates out of solution. Produced using the gtfJ enzyme, poly alpha-1,3-glucan can have an average degree of polymerization (DPn) in the range from 4 to 500. In other embodiments, DPn can be in the range from 30 to 500 or from 40 to 500 or from 50 to 400. In some embodiments, poly alpha-1,3-glucan has a DPw from about 10 to about 400, from 10 to about 300, from 10 to about 200, 10 to about 100, 10 to about 50, 400 to about 1,400, or from about 400 to about 1,000, or from about 500 to about 900.
    [069] In some embodiments, the percentage of glycosidic bonds between the units of glucose monomers of poly alpha-1,3glucan which are alpha-1,3 is greater than or equal to 50%, 60%, 70%, 80% , 90%, 95%, 96%, 97%, 98%, 99% or 100% (or any integer between 50% and 100%). In such embodiments, therefore, poly alpha-1,3-glucan has less than or equal to 50%, 40%, 30%, 20%, 10%, 5%, 4%, 3%, 2%, 1%, or 0% (or any integer between 0% and 50%) of glycosidic bonds other than alpha-1,3. Poly alpha-1,3-glucan can have relatively low percentages of glucose monomers that are linked at positions 1,2, 1,4 and / or
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    I, 6. In some embodiments, poly alpha-1,3-glucan comprises greater than or equal to 93 to 97% of alpha-1,3-glycosidic bonds and less than 3% of alpha-1,6- glycosidics. In other embodiments, poly alpha-1,3-glucan comprises greater than or equal to 95% of alpha-1,3-glycosidic bonds and about 1% of alpha-1,6-glycosidic bonds. In another embodiment, the poly alpha-1,3-glucan comprises less than or equal to 1 to 3% of alpha-1,3,6-glycosidic bonds.
    [070] The poly alpha-1,3-glucan insoluble in some embodiments may be in the form of a copolymer (for example, the grafted copolymer) which has (i) a backbone comprising dextran (for example, with at least least 95%, 96%, 97%, 98%, 99% or 100% of alpha-1,6 bonds) with a molecular weight of at least about 100,000 Daltons, and (ii) the chains secondary alpha-1,3-glucan comprising at least about 95%, 96%, 97%, 98%, 99% or 100% of alpha-1,3-glucoside bonds. Such copolymers can be as described in the international patent publication WO 2017/079595, which is incorporated herein by reference.
    [071] The terms poly alpha-1,6-glucan and dextran are used interchangeably in the present. Dextrans represent a family of branched and complex alpha-glucans that, in general, comprise the chains of glucose monomers linked by alpha-1,6, with the periodic secondary chains (branches) linked to the linear chains by alpha-1 bond, 3 (loan et al., Macromolecules 33: 5730-5739). Dextrans are normally produced by fermenting sucrose with bacteria (for example, Leuconostoc or Streptococcus species), where sucrose serves as a glucose source for the polymerization of dextran (Naessens et al., J. Chem Technol. Biotechnol. 80: 845-60; Sarwat et al., Int.
    J. Biol. Know. 4: 379-386; Onilude etal., Int. Food Res. J. 20: 1.645-1.651). The poly
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    26/135 alpha-1,6-glucan can be prepared using glucosyltransferases such as (but not limited to) GTF1729, GTF1428, GTF5604, GTF6831, GTF8845, GTF0088 and GTF8117 as described in publications WO 2015/183714 and WO 2017/091533, incorporated herein as a reference.
    [072] Poly alpha-1,6-glucan can have a degree of average numerical polymerization (DPn) in the range from 4 to 1,400. In other embodiments, DPn can be in the range from 4 to 100, or from 4 to 500 or from 40 to 500 or from 50 to 400. In some embodiments, poly alpha-1,6glucan has a DPw from about 10 to about 400, 10 to about 300, 10 to about 200, 10 to about 100, 10 to about 50, 400 to about 1,400, or from about 400 to about 1,000, or from about 500 to about 900.
    [073] In some embodiments, poly alpha-1,6-glucan comprises a main chain of glucose monomer units in which greater than or equal to 40% of the glucose monomer units are linked by means of alpha-1 bonds , 6-glycosides, for example, greater than or equal to 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or 90% of the glucose monomer units.
    [074] Long dextran chains can comprise substantially [or mainly] alpha-1,6-glucoside bonds, meaning that they can have at least about 98.0% alpha-1.6 bonds -glucoside in some ways. Dextran at present can comprise a branching structure (branched structure) in some aspects. It is contemplated that in this structure, long chains branch off from other long chains, probably in an iterative manner (for example, a long chain can be a branch of another long chain, which in turn can be a branch of another long chain, and coming soon). It is contemplated that the long chains in this structure can be “similar in length”,
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    27/135 meaning that the length (DP [degree of polymerization]) of at least 70% of all long chains in a branch structure is within plus / minus 30% of the average length of all long chains in the structure branched.
    [075] Dextran in some embodiments may also comprise short branched chains from long chains, usually one to three glucose monomers in length and normally comprising less than about 10% of all glucose monomers in a polymer dextran. Such short chains usually comprise the alpha-1,2-, alpha-1,3- and / or alpha-1,4-glucoside bonds (it is also understood that there may be a small percentage of such non-alpha-1 bonds in 6 long chains in some ways). In certain embodiments, the branched poly alpha-1,6-glucan is produced enzymatically according to the procedures in the publications WO 2015/183714 and WO 2017/091533 in which, for example, the branched alpha-1,2 enzymes such as “GtfJ18T1” or “GTFg905 '' can be added during or after the production of the dextran polymer (polysaccharide). In other embodiments, any other enzyme known to produce alpha-1,2 branching can be added. The degree of branching of poly alpha-1,6glucan in such embodiments is less than or equal to 50%, 40%, 30%, 20%, 10%, 5%, 4%, 3%, 2%, 1%, or 0% (or any integer between 0% and 50%) of short branches, for example, the alpha-1,2 branch. In one embodiment, the poly alpha-1,6-glucan has a degree of branching of alpha-1,2 that is less than 50%. In one embodiment, the poly alpha-1,6-glucan is predominantly linear.
    [076] In one embodiment, the polysaccharide is poly alpha-1,3-1,6glucan. Poly alpha-1,3-1,6-glucan is a product of a glucosyltransferase enzyme, as described in the US patent application publication
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    2015 / 0.232.785 A1. In some embodiments, an insoluble alpha-glucan may comprise at least about 30% of alpha-1,3 bonds and a percentage of alpha-1,6 bonds that total the total of both alpha-1 bonds , 3 and -1.6 in 100% alpha-glucan. For example, the percentage of alpha-1.3 and -1.6 bonds can be about 30 to 40% and 60 to 70%, respectively. In some respects, an insoluble alpha-glucan comprising at least about 30% of alpha-1,3 bonds is linear. Glycosyltransferases for the production of insoluble alpha-glucan comprising at least about 30% of alpha-1,3 bonds are described in patent application publication 2015 / 0.232.819, which is incorporated herein by reference .
    [077] In one embodiment, the polysaccharide comprises poly alpha-
    1.3- 1,6-glucan, where (i) at least 30% of the poly alpha-1,3-1,6-glucan glycosidic bonds are alpha-1,3 bonds, (ii) at least 30 % of the glycosidic bonds of poly alpha-1,3-1,6-glucan are alpha-1,6 bonds, (iii) to poly alpha-
    1.3- 1,6 -glucan has an average degree of polymerization (DPw) of at least 10; and (iv) the alpha-1,3 bonds and alpha-1,6 bonds of poly alpha-1,3-1,6glucan do not alternate consecutively with each other. In another embodiment, at least 60% of the poly alpha-1,3-1,6glucan glycosidic bonds are alpha-1,6 bonds.
    [078] At least 30% of the poly alpha-1, ΟΙ, 6-glucan glycosidic bonds are the alpha-1,3 bonds and at least 30% of the poly alpha-1,3-1 glycosidic bonds, 6 -glucan are the alpha-1,6 bonds. Alternatively, the percentage of alpha-1,3 bonds in poly alpha-1,3-1,6glucan at present may be at least 31%, 32%, 33%, 34%, 35%,
    36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%,
    49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%,
    62%, 63% or 64%. Alternatively, the percentage of calls
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    29/135 of alpha-1,6 in poly alpha-1,3-1,6-glucan at present can be at least 31%, 32%, 33%, 34%, 35%, 36%, 37 %, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58%, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68% or 69%.
    [079] A poly alpha-1,3-1,6-glucan can have any of the percentages mentioned above for alpha-1,3 bonds and any of the percentages mentioned above for alpha-1,6 bonds, just as long as that the total call percentages does not exceed 100%. For example, the poly alpha-1,3-1,6-glucan at present can have (i) any of 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, or 40% (30% -40%) of alpha-1,3 bonds and (ii) any of 60%, 61%, 62%, 63%, 64%, 65%, 66 %, 67%, 68%, or 69% (from 60% to 69%) of alpha-1.6 bonds, provided that the total percentages do not exceed 100%. Non-limiting examples include poly alpha-1,3-1,6-glucan with 31% alpha-1,3 bonds and 67% alpha-1,6 bonds. In certain embodiments, at least 60% of the poly alpha-1,3-1,6-glucan glycosidic bonds are alpha-1,6 bonds.
    [080] A poly alpha-1,3-1,6-glucan can have, for example, less than 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2% or 1% of glycosidic bonds other than alpha-1,3 and alpha-1,6. In another embodiment, a poly alpha-
    1,3-1,6-glucan only has the alpha-1,3 and alpha-1,6 bonds.
    [081] The main chain of a poly alpha-1,3-1,6-glucan described herein can be linear / unbranched. Alternatively, there may be branches on poly alpha-1,3-1,6-glucan. A poly alpha-1,3-1,6-glucan in certain embodiments therefore, may not have the branch points or less than about 30%, 29%, 28%, 27%, 26%, 25%, 24 %, 23%, 22%, 21%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2% or 1% of branch points as a percentage of glycosidic bonds in the polymer.
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    30/135 [082] The alpha-1,3 bonds and alpha-1,6 bonds of a poly alpha-
    1,3-1,6-glucan do not alternate consecutively. For the following discussion, consider that. G-1,3-G-1,6-G-1,3-G-1,6-G-1,3-G -. (where G represents glucose) represents a segment of six units of glucose monomers linked by alternating consecutive alpha-1,3 bonds and alpha-1,6 bonds. Poly alpha-1,3-1,6-glucan in certain embodiments now comprises less than 2, 3, 4, 5, 6, 7, 8, 9, 10 or more units of glucose monomers that are consecutively linked with the alpha-1,3 and alpha-1,6 bonds.
    [083] The molecular weight of a poly alpha-1,3-1,6-glucan can be measured as DPw (weighted average degree of polymerization) or DPn (degree of numerical average of polymerization). Alternatively, the molecular weight can be measured in Daltons or grams / mol. It may also be useful to refer to the numerical average molecular weight (M n ) or the weighted average molecular weight (Mw) of poly alpha-1,3-1,6-glucan.
    [084] A poly alpha-1,3-1,6-glucan at present can have an Mw of at least about 1,600, 3,000, 4,000, 5,000, 8,000, 10,000, 15,000, 20,000, 25,000, 30,000, 35,000 , 40,000, 50,000, 100,000, 200,000, 300,000, 400,000, 500,000, 600,000, 700,000, 800,000, 900,000, 1,000,000, 1,100,000, 1,200,000, 1,300,000, 1,400,000, 1,500,000 or 1,600,000 (or any integer between 50,000 and 1600,000), for example. The Mw in certain realizations is at least about 100.0000. Alternatively, poly alpha-1,3-1,6-glucan can have an Mw of at least about 1,600, 3,000, 4,000, 5,000, 10,000, 20,000, 30,000 or 40,000, for example.
    [085] A poly alpha-1,3-1,6-glucan can comprise at least 10 units of glucose monomers, for example. Alternatively, the number of glucose monomer units can be at least 10, 25, 50, 100, 500, 1,000, 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000 or
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    9,000 (or any integer between 10 and 9,000), for example.
    [086] The polysaccharide derivative comprises poly alpha-1,3-glucan, poly alpha-1,6-glucan or poly alpha-1,3-1,6-glucan substituted in one or more positions with (a) at least, a hydrophobic group and (b) at least one hydrophilic group. Suitable hydrophobic groups include straight or branched C1-8 alkyl, straight or branched C2-C18 alkene, straight or branched C2-C18 alkynes, polyethers comprising (-CH2CH2O-), (-CH2CH (CH3) O-) repeat units ), or a mixture thereof, wherein the total number of repeating units is in the range from 3 to 100, C6-C20 aryl, benzyl, C1-C18 alkylsulfonyl, C6-C20 arylsulfonyl or ptoluenesulfonyl groups.
    [087] The term alkyl group, as used herein, refers to linear, branched or cyclic (cycloalkyl) hydrocarbon groups that do not contain any unsaturation. The alkyl group can be replaced, for example, by another alkyl group or by at least one hydroxyalkyl group or dihydroxyalkyl group. In one embodiment, the hydrophobic group is a C1-C18 alkyl group and the alkyl group, for example, may be methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyla, octyl, nonyl, decila, undecyl, dodecyl, group tridecanila, tetradecanila, pentadecanila, hexadecanila, heptadecanila or octadecanila. In another embodiment, the alkyl group is a C4-C18 alkyl group. One or more carbons from an alkyl group can be substituted by another alkyl group, making the alkyl group branched. Examples of branched chain isomers of linear alkyl groups include isopropyl, iso-butyl, tert-butyl, sec-butyl, isopentyl, neopentyl, isohexyl, neohexyl, 2-ethylhexyl and isooctyl. One or more carbons of an alkyl group can be substituted by at least one hydroxyalkyl group. Suitable hydroxyalkyl groups are hydroxymethyl (-CH2OH), hydroxyethyl (for example, 0 CH2CH2OH, CH (OH) CH3), hydroxypropyl (for example, 0
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    CH2CH2CH2OH, CH 2 CH (OH) CH3, CH (OH) CH 2 CH3), hydroxybutyl and hydroxypentyl. Other examples include dihydroxyalkyl groups (diols) such as dihydroxymethyl, dihydroxyethyl, dihydroxypropyl, dihydroxybutyl and dihydroxypentyl. In another embodiment, the alkyl group is a cycloalkyl group and the cycloalkyl group, for example, can be a cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl group. In one embodiment, the cycloalkyl group is a C5-C10 cycloalkyl group.
    [088] A substitution on an alkyl group in certain embodiments may be attached to the terminal carbon atom of the alkyl group, where the terminal carbon group is opposite the carbon atom that is attached to the oxygen ether of the glucan polymer. An example of this terminal substitution is in the hydroxypropyl group CH2CH2CH2OH. Alternatively, a substitution may be on an internal carbon atom of an alkyl group. An example of an internal substitution is in the hydroxypropyl group CH2CH (OH) CH3.
    [089] Optionally, an alkyl group may contain one or more heteroatoms such as oxygen, sulfur and / or nitrogen within the hydrocarbon chain. Examples include alkyl groups containing an alkylglycerol alkoxylate (-alkylene-OCH2CH (OH) CH20H) portion or a portion derived from the opening of the 2-ethylhexylglycidyl ether ring.
    [090] In another embodiment, the hydrophobic group is a C2-C18 alkene group and the alkene group can be linear, branched or cyclic. As used herein, the term "alkene group" refers to hydrocarbon groups containing at least one carbon-carbon double bond. Examples of alken groups include the groups ethylene, propenyl, butenyl, pentenyl, hexenyl, cyclohexyl and allyl. In other embodiments, one or more carbons of the alkene group may have a substitution (s) with an alkyl group, or with a hydroxyalkyl or dihydroxyalkyl group. Examples of such
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    33/135 alkyl substituent groups include methyl, ethyl and propyl groups. To illustrate, an R group can be CH (CH3) CH2CH3 or CH 2 CH (CH3) CH3, which are both propyl groups that have a methyl substitution. In one embodiment, the alkene group is a C4-C18 alkene group.
    [091] Optionally, an alkene group may contain one or more heteroatoms such as oxygen, sulfur and / or nitrogen within the hydrocarbon chain, for example, an alkene group may contain a portion derived from the ring opening of an allylglycidyl ether .
    [092] In another embodiment, the hydrophobic group is a C 2 -C 8 alkaline group and the alkaline group, for example, can be the bribe, butine, pentine or hexine. The alkaline group can be linear or branched and can be substituted, for example, by alkyl, hydroxyalkyl or dihydroxyalkyl groups. Optionally, an alkaline group can contain one or more heteroatoms, such as oxygen, sulfur and / or nitrogen within the hydrocarbon chain.
    [093] In another embodiment, the hydrophobic group is a polyether comprising the (-CH 2 CH 2 O-), (-CH 2 CH (CH3) O-) repeating units, or a mixture thereof, where 0 total number of repeat units is in the range from 3 to 100. In one embodiment, the hydrophobic group is a polyether group comprising 0 (-CH 2 CH 2 0-) 4-ion. In another embodiment, the hydrophobic group is a polyether group comprising 0 (-CH 2 CH (CH3) 0-) 4 -oyl. As used herein, the subscript designating a range of values will be used to designate the potential number of repetition units, for example, 0 (CH 2 CH 2 0) 4-io means a polyether group containing in the range from 3 to 100 repeat units.
    [094] In yet another embodiment, the hydrophobic group is an aryl group, and the aryl group, for example, can be phenyl or biphenyl, optionally substituted by an alkyl group, such as a methyl, ethyl or propyl group. In one embodiment, the aryl group is a C6-C 2 o aryl group. In another realization, 0
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    34/135 aryl group is an aryl group substituted by methyl.
    [095] In yet another embodiment, the hydrophobic group is a benzyl group. The benzyl group optionally can still be replaced by one or more of a halogen, a cyano, an ester, an amide, an ether group, a C1-C6 alkyl group, an aryl group, a C2-C6 alkene group, an alkaline group C 2 -C 6 , or one of its combinations.
    [096] In another embodiment, the hydrophobic group is a C1-C18 alkylsulfonyl group or a C6-C 2 o arylsulfonyl group, optionally substituted by alkyl groups. An example of an alkylsulfonyl is the methanesulfonyl group. An example of a Ce-C 2 o arylsulfonyl group is a ptoluenesulfonyl group, which can be represented as CH3-aryl-SO 2 -. As a substituent on a derived polysaccharide, the alkylsulfonyl or arylsulfonyl moiety joins the polysaccharide through a sulfuroxygen bond. The C1-C18 alkylsulfonyl, Ce-C 2 or arylsulfonyl and ptoluenesulfonyl groups are not ionizable.
    [097] The polysaccharide derivative comprises 0 poly alpha-1,3-glucan, poly alpha-1,6-glucan or poly alpha-1,3-1,6-glucan which is also substituted by at least one hydrophilic group. Suitable hydrophilic groups include carboxylic acids, carboxylic acid salts, sulfonic acid derivatives, salts derived from sulfonic acid, salts derived from sulfuric acid, thiosulfate, salts of thiosulfate, salts derived from phosphoric acid, salts derived from phosphoric acid phosphoric acid, alkyl amine, alkyl substituted ammonium salts, quaternized pyridine salts and quaternized imidazole salts. These hydrophilic groups are ionizable. Hydrophilic groups can exist in an ionic or neutral form as a solid or in an aqueous formulation or solution, depending on the pH at which they are isolated or used.
    [098] In one embodiment, the hydrophilic group is an acidic group
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    35/135 carboxylic. Examples of suitable carboxylic groups are carboxy (CO2H), carboxymethyl (CH 2 COOH), carboxyethyl (eg 0 CH 2 CH 2 COOH, CH (COOH) CH3), carboxypropyl (eg 0 CH 2 CH 2 CH 2 COOH, CH 2 CH (COOH) CH 3, CH (COOH) CH 2 CH 3), carboxybutyl and carboxypentyl groups. In one embodiment, the hydrophilic group is carboxymethyl. In another embodiment, the hydrophilic group is carboxyethyl. In yet another embodiment, the hydrophilic group is carboxypropyl. The carboxylic acid portion can reside at any substitution site on an alkyl chain.
    [099] In another embodiment, the hydrophilic group is a salt of carboxylic acid, and the salt may comprise a carboxylate anion of the carboxylic groups described hereinabove and an inorganic cation, for example, any one of Li, Na, K, Rb , Cs, Mg., Ca or Ba; an organic cation, for example, an ammonium ion, ammonium (NH4 + ), tetralkyl ammonium cations or one of their combinations.
    [0100] In another embodiment, the hydrophilic group is a sulfuric acid derivative, a sulfuric acid derivative or a thiosulfate (-SO 2 ) OH). As used herein, the term "sulfuric acid derivative" embraces 0 sulfate (-OS (O 2 ) OH) and alkyl sulfates (-alkylene-OS (0 2 ) OH), where the alkyl group can be a group C1-C4. As used herein, the term derived from sulfonic acid encompasses sulfonate (-S (O 2 ) OH) and alkyl sulfonates (-alkylene-S (0 2 ) OH), where the alkyl group may be a C1- group C4. Examples of alkyl sulfonates include ethyl sulfonate, propyl sulfonate and butyl sulfonate.
    [0101] In another embodiment, the hydrophilic group is a salt of a sulfuric acid derivative or a salt of a sulfuric acid derivative, for example, a sulfate salt, an alkyl sulfate salt, a sulfonate salt, a salt alkyl sulfonate or a thiosulfate salt. The salt may comprise an anion of the sulfate, alkylsulfonate and thiosulfate groups described herein.
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    36/135 above and an inorganic cation, for example, any one of Li, Na, K, Rb, Cs, Mg, Ca or Ba; an organic cation, for example, an ammonium ion, ammonium (NH4 + ), tetralkyl ammonium cations or one of their combinations.
    [0102] In one embodiment, the hydrophilic group is a sulfate or a sulfate salt. In another embodiment, the hydrophilic group is an alkyl sulfonate or an alkyl sulfonate salt. In yet another embodiment, the hydrophilic group is a thiosulfate or a thiosulfate salt.
    [0103] In another embodiment, the hydrophilic group is a derivative of phosphoric acid, for example, phosphate (-OPC> 2 (OR ') where R'éo H, alkyl or aryl) or phosphonate (-PC> 2 ( OR ') - where R' is H, alkyl or aryl). In yet another embodiment, the hydrophilic group is a salt of a phosphoric acid derivative, for example, a phosphate salt in which the anion is -OPOs 2 ', or a phosphonate salt in which the anion is -POs 2 - , and the salt further comprises an inorganic cation, for example, any one of Li, Na, K, Rb, Cs, Mg, Ca or Ba; an organic cation, for example, an ammonium ion, ammonium (NH4 + ), tetralkyl ammonium cations or one of their combinations.
    [0104] In one embodiment, the hydrophilic group is a phosphate. In another embodiment, the hydrophilic group is a phosphate salt. In another embodiment, the hydrophilic group is a phosphonate. In yet another embodiment, the hydrophilic group is a phosphonate salt.
    [0105] In one embodiment, the hydrophilic group is an alkyl amine group. The alkyl amine groups can be represented by -NR1R2 where R1 and R2, independently, are 0 hydrogen and C1-C12 alkyl. Examples of alkyl amine include diethylamine, ethylamine, dimethylamine, methylamine, ethylenediamine, propylamine, dipropylamine, butylamine, dibutylamine. In one embodiment, the alkyl amine group is a derivative of ethylenediamine.
    [0106] In another embodiment, the hydrophilic group is an ammonium salt substituted by alkyl. The ammonium salts substituted by alkyl can be
    Petition 870190055067, of 6/14/2019, p. 303/408
    37/135 represented by the following structure:
    - wherein each of R2, R3 and R4 independently represents a hydrogen atom or an alkyl, aryl, cycloalkyl, aralkyl or alkylaryl group. The carbon atom (C) in the structure is part of the chain of one or more carbons ("carbon chain") of the positively charged organic group. The carbon atom is directly attached to the ether with a glucose monomer of poly alpha-1,3-glucan, poly alpha-1,6-glucan, or poly alpha-1,3-1,6-glucan, or is part of of a chain of two or more carbon atoms linked to ether to a glucose monomer of poly alpha-1,3-glucan, poly alpha-1,3-glucan or poly alpha-1,3-1,6-glucan. The carbon atom in the structure can be 0 -CH2-, -CH- (where one H is replaced by another group, such as a hydroxy group), or C (where both H are substituted).
    [0107] A substituted ammonium group can be a "primary ammonium group", "secondary ammonium group", "tertiary ammonium group" or "quaternary ammonium group", depending on the composition of R2, R3 and R4 in the above structure. A primary ammonium group referred to herein refers to the previous structure in which each of R2, R3 and R4 is a hydrogen atom (ie, 0 CNHs + ). A secondary ammonium group referred to herein refers to the above structure in which each of R2 and R3 is a hydrogen atom and R4 an alkyl, aryl or cycloalkyl group. A tertiary ammonium group refers at present to the above structure in which R2 is a hydrogen atom and each of R3 and R4 is an alkyl, aryl or cycloalkyl group. A quaternary ammonium group refers to the previous structure in which each of R2, R3 and R4 is an alkyl, aryl or cycloalkyl group (that is, none of R2, R3 and R4 is a hydrogen atom).
    Petition 870190055067, of 6/14/2019, p. 304/408
    38/135 [0108] A quaternary ammonium poly alpha-1,3-glucan, poly alpha1,6-glucan or poly alpha-1,3-1,6-glucan ether at present can comprise a trialkyl ammonium group ( wherein each of the groups R 2 , Rs and R 4 is an alkyl group), for example. An ammonium group of trimethyl is an example of an ammonium group of trialkyl, where each of R 2 , Rs and R 4 is a methyl group. It should be understood that a fourth member (i.e., Ri) implicated by quaternary in this nomenclature is the chain of one or more carbons of the positively charged organic group that is attached to the ether for a polyglycan glucose monomer.
    [0109] An example of a quaternary ammonium alpha-1,3-polyglucano acid ether compound is poly alpha-1,3-glucan hydroxypropyl trimethylammonium. The positively charged organic group of this ether compound can be represented by the following structure:
    OH R, i i;
    - ch 2 —ch-ch 2 - n —r 3 r 4
    - where each of R 2 , Rs and R4 is a methyl group. The above structure is an example of a quaternary ammonium hydroxypropyl group.
    [0110] A hydroxyalkyl group referred to herein refers to a substituted alkyl group in which one or more hydrogen atoms in the alkyl group are replaced by a hydroxyl group.
    [0111] In one embodiment, the hydrophilic group is a quaternized pyridine salt. In another embodiment, the hydrophilic group is a quaternized imidazole salt.
    [0112] In one embodiment, the polysaccharide derivative comprises a polysaccharide substituted by at least one hydrophobic group and at least one hydrophilic group, wherein at least one hydrophobic group comprises a C1-C18 alkyl, a C2 alkene -C18, a C2 alkaline
    Petition 870190055067, of 6/14/2019, p. 305/408
    39/135
    Cie, a polyether comprising the (-CH2CH2O-), (CH 2 CH (CH3) O-) repeat units, or mixtures thereof, where the total number of repeat units is in the range 3 to 100, a C6-C 2 o aryl, benzyl, C1-C18 alkylsulfonyl, C6-C 2 o arylsulfonyl, p-toluenesulfonyl group, or one of its combinations and at least one hydrophilic group comprises a carboxylic acid, salt of carboxylic acid, a sulfuric acid derivative, a sulfuric acid derived salt, thiosulfate, a sulfonic acid derivative, a sulfonic acid derived salt, thiosulfate, a thiosulfate salt, a phosphoric acid derivative, a phosphoric acid derived salt , an alkyl amine, an alkyl substituted ammonium salt, a quaternized pyridine salt, a quaternized imidazole salt or one of its combinations.
    [0113] In one embodiment, the polysaccharide derivative comprises a polysaccharide substituted by at least one hydrophobic group and at least one hydrophilic group, wherein at least one hydrophobic group comprises a C1-C18 alkyl group, and at least At least, a hydrophilic group comprises a carboxylic acid, salt of carboxylic acid, a derivative of sulfonic acid, a salt derived from sulfonic acid, a derivative of sulfonic acid, a salt derived from sulfonic acid, thiosulfate, a salt of thiosulfate, a derivative phosphoric acid, a salt derived from phosphoric acid, an alkyl amine, an ammonium salt substituted by alkyl, a quaternized pyridine salt, a quaternized imidazole salt or one of its combinations. In another embodiment, at least one hydrophobic group comprises a C1-C18 alkyl group and at least one hydrophilic group comprises a carboxylic acid, an alkyl substituted ammonium salt, a sulfonate, an alkyl sulfonate, a sulfate, a group thiosulfate. or one of its combinations.
    [0114] In another embodiment, the polysaccharide derivative comprises a polysaccharide substituted by at least one group
    Petition 870190055067, of 6/14/2019, p. 306/408
    40/135 hydrophobic and at least one hydrophilic group, wherein at least one hydrophobic group comprises a C2-C18 alkene group, and at least one hydrophilic group comprises a carboxylic acid, salt of carboxylic acid, a derivative of sulfonic acid, a salt derived from sulfonic acid, a derivative of sulfuric acid, a salt derived from sulfuric acid, thiosulfate, a salt of thiosulfate, a derivative of phosphoric acid, a salt derived from phosphoric acid, an alkyl amine, a salt substituted ammonium salt, a quaternized pyridine salt, a quaternized imidazole salt or one of its combinations. In another embodiment, at least one hydrophobic group comprises a C2-C18 alkene group and at least one hydrophilic group comprises a carboxylic acid, an alkyl substituted ammonium salt, a sulfonate, an alkyl sulfonate, a sulfate, a group thiosulfate, or one of its combinations.
    [0115] In yet another embodiment, the polysaccharide derivative comprises a polysaccharide substituted by at least one hydrophobic group and at least one hydrophilic group, wherein at least one hydrophobic group comprises a C2-C18 alkaline group, and at least one hydrophilic group comprises a carboxylic acid, carboxylic acid salt, a sulfonic acid derivative, a sulfonic acid derivative salt, a sulfuric acid derivative, a sulfuric acid derivative salt, thiosulfate, a thiosulfate salt, a derived from phosphoric acid, a salt derived from phosphoric acid, an alkyl amine, an ammonium salt substituted by alkyl, a quaternized pyridine salt, a quaternized imidazole salt or one of its combinations. In another embodiment, at least one hydrophobic group comprises a C2-C18 alkaline group and at least one hydrophilic group comprises a carboxylic acid, an alkyl substituted ammonium salt, a sulfonate, an alkyl sulfonate, a sulfate, a group thiosulfate, or one of its combinations.
    Petition 870190055067, of 6/14/2019, p. 307/408
    41/135 [0116] In a further embodiment, the polysaccharide derivative comprises a polysaccharide substituted by at least one hydrophobic group and at least one hydrophilic group, wherein at least one hydrophobic group comprises a polyether comprising repeat units of (-CH2CH2O-), (-CH2CH (CH3)) O-), or mixtures thereof, where the total number of repeat units is in the range from 3 to 100, and at least one group hydrophilic acid comprises a carboxylic acid, carboxylic acid salt, a sulfonic acid derivative, a sulfonic acid derivative salt, a sulfuric acid derivative, a salt derived from sulfuric acid, thiosulfate, a thiosulfate salt, a phosphoric acid derivative, a salt derived from phosphoric acid, an alkyl amine, an ammonium salt substituted by alkyl, a quaternized pyridine salt, a quaternized imidazole salt or one of its combinations. In another embodiment, at least one hydrophobic group comprises a polyether comprising the (CH2CH2O-), (-CH2CH (CH3) O-) repeat units, or mixtures thereof, wherein the total number of repeat units is in the range from 3 to 100, and at least one hydrophilic group comprises a carboxylic acid, an alkyl substituted ammonium salt, a sulfonate, an alkyl sulfonate, a sulfate, a thiosulfate group or one of its combinations.
    [0117] In a further embodiment, the polysaccharide derivative comprises a polysaccharide substituted by at least one hydrophobic group and at least one hydrophilic group, wherein at least one hydrophobic group comprises a C6-C20 aryl group, and at least one hydrophilic group comprises a carboxylic acid, carboxylic acid salt, a sulfonic acid derivative, a sulfonic acid derivative salt, a sulfuric acid derivative, a sulfuric acid derivative salt, thiosulfate, a thiosulfate salt, a derived from phosphoric acid, a salt derived from phosphoric acid, an alkyl amine, an ammonium salt substituted by alkyl, a salt of
    Petition 870190055067, of 6/14/2019, p. 308/408
    42/135 quaternized pyridine, a quaternized imidazole salt or one of its combinations. In another embodiment, at least one hydrophobic group comprises a C6-C20 aryl group and at least one hydrophilic group comprises a carboxylic acid, an alkyl substituted ammonium salt, a sulfonate, an alkyl sulfonate, a sulfate, a group thiosulfate, or one of its combinations.
    [0118] In a further embodiment, the polysaccharide derivative comprises a polysaccharide substituted by at least one hydrophobic group and at least one hydrophilic group, wherein at least one hydrophobic group comprises a benzyl group, and at least, a hydrophilic group comprises a carboxylic acid, a carboxylic acid salt, a sulfonic acid derivative, a sulfonic acid derivative salt, a sulfuric acid derivative, a sulfuric acid derivative salt, thiosulfate, a thiosulfate salt, an acid derivative phosphoric, a salt derived from phosphoric acid, an alkyl amine, an ammonium salt substituted by alkyl, a quaternized pyridine salt, a quaternized imidazole salt or one of its combinations. In another embodiment, at least one hydrophobic group comprises a benzyl group and at least one hydrophilic group comprises a carboxylic acid group, an alkyl substituted ammonium salt, a sulfonate, an alkyl sulfonate, a sulfate or a thiosulfate group.
    [0119] In a further embodiment, the polysaccharide derivative comprises a polysaccharide substituted by at least one hydrophobic group and at least one hydrophilic group, wherein at least one hydrophobic group comprises a benzyl group substituted by one or more of a halogen, a cyano, an ether, an amide, an ether group, a C1 to C6 alkyl group, an aryl group, a C2-C6 alkene group, a C2-C6 alkaline group, or one of its combinations and at least , a hydrophilic group comprises a carboxylic acid, carboxylic acid salt, a sulfonic acid derivative, a salt
    Petition 870190055067, of 6/14/2019, p. 309/408
    43/135 derivative of sulfonic acid, a derivative of sulfuric acid, a salt derived from sulfuric acid, thiosulfate, a salt of thiosulfate, a derivative of phosphoric acid, a salt derived from phosphoric acid, an alkyl amine, an ammonium salt substituted by alkyl, a quaternized pyridine salt, a quaternized imidazole salt or one of its combinations. In another embodiment, at least one hydrophobic group comprises a benzyl group substituted by one or more of a halogen, a cyano, an ether, an amide, an ether group, a C1-C6 alkyl group, an aryl group, an alkene group C2-C6, a C2-C6 alkaline group, or one of its combinations and at least one hydrophilic group comprises a carboxylic acid, an alkyl substituted ammonium salt, a sulfonate, an alkyl sulfonate, a sulfate or a group thiosulfate.
    [0120] In a further embodiment, the polysaccharide derivative comprises a polysaccharide substituted by at least one hydrophobic group and at least one hydrophilic group, wherein at least one hydrophobic group comprises a C1-C18 alkylsulfonyl or arylsulfonyl group CeC20, and at least one hydrophilic group comprises a carboxylic acid, carboxylic acid salt, a sulfonic acid derivative, a sulfonic acid derivative salt, a sulfuric acid derivative, a salt derived from sulfuric acid, thiosulfate, a salt of thiosulfate, a phosphoric acid derivative, a phosphoric acid derived salt, an alkyl amine, an alkyl substituted ammonium salt, a quaternized pyridine salt, a quaternized imidazole salt or one of its combinations. In another embodiment, at least one hydrophobic group comprises a C1-C18 alkylsulfonyl or CeC20 arylsulfonyl group and at least one hydrophilic group comprises a carboxylic acid, an alkyl substituted ammonium salt, a sulfonate, an alkyl sulfonate, a sulfate or a thiosulfate group.
    [0121] In an additional embodiment, the polysaccharide derivative comprises a polysaccharide substituted by at least one group
    Petition 870190055067, of 6/14/2019, p. 310/408
    44/135 hydrophobic and at least one hydrophilic group, wherein at least one hydrophobic group comprises a p-toluenesulfonyl group and at least one hydrophilic group comprises a carboxylic acid, carboxylic acid salt, a sulfonic acid derivative , a salt derived from sulfonic acid, a derivative of sulfuric acid, a salt derived from sulfuric acid, thiosulfate, a salt from thiosulfate, a phosphoric acid derivative, a salt derived from phosphoric acid, an alkyl amine, an ammonium salt substituted by alkyl, a quaternized pyridine salt, a quaternized imidazole salt or one of its combinations. In another embodiment, at least one hydrophobic group comprises a p-toluenesulfonyl group and at least one hydrophilic group comprises a carboxylic acid, an alkyl substituted ammonium salt, a sulfonate, an alkyl sulfonate, a sulfate or a group thiosulfate.
    [0122] In one embodiment, the polysaccharide derivative comprises a polysaccharide substituted by at least one hydrophobic group and at least one hydrophilic group, wherein at least one hydrophobic group comprises a C1-C18 alkyl, a benzyl, a ptoluenesulfonyl group or a combination and at least one hydrophilic group comprises a carboxylic acid, an alkyl substituted ammonium salt, a sulfonate, an alkyl sulfonate, a sulfate, a thiosulfate or one of its combinations.
    [0123] In one embodiment, the polysaccharide derivative comprises a polysaccharide substituted by at least one hydrophobic group and at least one hydrophilic group, wherein at least one hydrophobic group comprises a C1-C18 alkyl, a benzyl, a ptoluenesulfonyl group or a combination and at least one hydrophilic group comprises a thiosulfate or carboxymethyl group.
    [0124] In another embodiment, at least one hydrophobic group comprises a benzyl or p-toluenesulfonyl group and at least
    Petition 870190055067, of 6/14/2019, p. 311/408
    45/135 less, a hydrophilic group comprises a thiosulfate or carboxymethyl group. In yet another embodiment, at least one hydrophobic group comprises a C1-C18 alkyl or p-toluenesulfonyl group and at least one hydrophilic group comprises a thiosulfate or carboxymethyl group. In another embodiment, at least one hydrophobic group comprises a C1-C18 alkyl or benzyl group and at least one hydrophilic group comprises a thiosulfate or carboxymethyl group.
    [0125] Poly alpha-1,3-glucan, poly alpha-1,6-glucan, or poly alpha-
    I, 3-1,6-glucan can be hydrophobically modified by contacting the polysaccharide with at least one etherifying agent comprising a hydrophobic organic group under alkaline conditions. This step can be carried out, for example, by first preparing the alkaline conditions by contacting the polysaccharide with a solvent and one or more alkali hydroxides to provide a solution or mixture. The alkaline conditions of the reaction, therefore, can comprise an alkaline hydroxide solution. The pH of alkaline conditions can be at least about 11.0,
    II, 2, 11.4, 11.6, 11.8, 12.0, 12.2, 12.4, 12.6, 12.8 or 13.0.
    [0126] Etherification agents comprising a hydrophobic organic group, for example, include dialkyl sulfates, dialkyl carbonates, alkyl halides (eg, alkyl chloride), iodoalkanes, alkyl triflates (alkyl trifluoromethanesulfonates) , alkyl fluorosulfonates, 1,2-epoxyalkyls and epoxides. Therefore, examples of etherifying agents for the production of methyl poly alpha-1,3-glucan ethers, methyl poly alpha-1,6-glucan ethers or poly alpha-1,3-1 ethers, Methyl 6-glucan include dimethyl sulfate, dimethyl carbonate, methyl chloride, iodomethane, methyl triflate, methyl fluorosulfonate. Examples of etherifying agents for the production of ethyl polyglycan ethers include diethyl sulfate, diethyl carbonate, ethyl chloride, iodoethane,
    Petition 870190055067, of 6/14/2019, p. 312/408
    46/135 ethyl triflate and ethyl fluorosulfonate. Examples of etherifying agents for the production of propyl polyglucan ethers include dipropyl sulfate, dipropyl carbonate, propyl chloride, iodopropane, propyl triflate and propyl fluorosulfonate. Examples of etherifying agents for the production of butyl and polyglucan ethers include dibutyl sulfate, dibutyl carbonate, butyl chloride, iodobutane, butyl triflate and 1,2-epoxybutane. Examples of etherifying agents for the production of benzyl polyglycan ethers include benzyl chloride and benzyl bromide.
    [0127] Polysaccharide polyethers, for example polyethylene glycol (PEG), polypropylene glycol (PPG) derivatives, or mixtures thereof, can also be obtained by contacting the polysaccharide with an epoxide, for example, oxide ethylene, propylene oxide, or a mixture thereof in the presence of a base. The hydroxyl group can undergo more reactions with an epoxide, producing a polyether with two or more repeating ether units. Depending on the molar amounts of the epoxide or polysaccharide, one or more of the hydroxyl groups on the polysaccharide may be monoalkoxylated or polyalkoxylated. The polysaccharide can have one or more polyether repeating units, according to Formula (-CH2CH20-) 4-yo, (-CH2CH (CH3) 0-) 4-yo, or one of its combinations. If used in combination, the repeating units can be in a random configuration or in a block configuration. As used herein, the subscript designating a range of values will be used to designate the potential number of repetition units, for example, (CH2CH20) 4-ioo means a polyether group containing in the range from 3 to 100 repetition units .
    [0128] Hydrophilic anionic derivatives of polyglucans can be prepared from reactions known in the art. For example, the
    Petition 870190055067, of 6/14/2019, p. 313/408
    47/135 glucan can be derivatized with a carboxymethyl group by contacting poly alpha-1,3-glucan, poly alpha-1,6-glucan or poly alpha-1,3-1,6-glucan with monochloroacetic acid in alkaline conditions. Suitable etherifying agents for the preparation of a carboxyalkyl polyglucan ether compound can include haloalkylates (e.g., chloroalkylate). Examples of haloalkylates include haloacetate (for example, chloroacetate), 3-halopropionate (for example, 3-chloropropionate) and 4halobutyrate (for example, 4-chlorobutyrate). For example, chloroacetate (monochloroacetate) (for example, sodium chloroacetate) can be used as an etherifying agent for the preparation of carboxymethyl poly alpha-1,3-glucan or poly alpha-1,6-glucan carboxymethyl.
    [0129] The polyglucan phosphate, phosphonate, sulfonates and sulfate derivatives can be produced in a similar manner, as described in Solarek, D.B., Phosphoryated Starches and Miscellaneous Inorganic Esters in Modified Starches: Properties and Uses, Wurzburg, Ο. B., Ed., CRC Press, Inc. Boca Raton, Fla, 1986, pages 97-108. Inorganic glucan esters, such as phosphate and sulfate, can be formed using methods known in the art. For example, phosphate groups can be introduced by reacting the polysaccharide with sodium tripolyphosphate or with alkyl phosphates and pyrophosphate diester, as described in Modified Starches: Properties and Uses, by Ο. B. Wurzburg, CRC Press, 2000). Polysaccharides can be sulfated using a variety of methods, including sulfation with sulfuric acid, chlorosulfonic acid in organic solvents or sulfur trioxide complexes, as described in Modified Starches: properties and Uses, by Ο. B. Wurzburg, CRC Press, 2000).
    [0130] Polyglucan alkylsulfonate ethers can be prepared from Michael's addition of alkaline polyglucan with the acid
    Petition 870190055067, of 6/14/2019, p. 314/408
    48/135 vinyl sulfonic or with chloroalkane sulfonate. Alternatively, the polyglucan can react with the propane sultone or butane sultone to provide the corresponding sulfoalkyl polyglucan. Sulfation of polyglucan can be carried out with chlorosulfonic acid or with sulfur trioxide complexes. Examples of sulfur trioxide complexes include sulfur trioxide-nitrogen based complexes, such as SOs-DMF, SOs-triethylamine, SOs-pyridine.
    [0131] Hydrophilic cationic derivatives of polyglucans can be prepared from reactions known in the art. For example, polyglucan derivatives can be produced in a similar manner, as described in Solarek, D.B., Cationic Starches: Properties and Uses, Wurzburg, Ο. B., Ed., CRC Press, Inc. Boca Raton, Fla, 1986, pages 113148. Some common reagents used for the preparation of cationic polyglucan derivatives include: 2-diethylaminoethyl chloride (DEC); ο 2-dimethylaminoethyl chloride; 2-diisopropylaminoethyl chloride; 2-diethylaminoethyl bromide, N-alkyl-N- (2-haloethyl) -aminomethylphosphoric acid; and 0, 2,3-epoxypropyltrimethylammonium chloride.
    [0132] Methods for the preparation of compositions comprising a poly alpha-1,3-glucan ether compound, poly alpha-1,6glucan or poly alpha-1,3-1,6-glucan containing a positively organic group charged, such as a trimethyl ammonium group, a substituted ammonium group or a quaternary ammonium group, are described in published patent application US 2016 / 0.311.935, which is incorporated herein by reference in its entirety.
    [0133] Suitable etherifying agents for the preparation of a poly alpha-1,3-glucan ether compound, poly alpha-1,6-glucan or dihydroxyalkyl poly alpha-1,3,1,6-glucan are dihydroxyalkyl halides (e.g., dihydroxyalkyl chloride) such as dihydroxyethyl halide, halide
    Petition 870190055067, of 6/14/2019, p. 315/408
    49/135 of dihydroxypropyl (for example, 2,3-dihydroxypropyl chloride [ie, 3-chloro-
    1,2-propanediol]), or dihydroxybutyl halide, for example. The 2,3-dihydroxypropyl chloride can be used for the preparation of poly alpha-1,3-glucan, poly alpha-1,6-glucan or dihydroxypropyl poly alpha-1,3-1,6-glucan, for example.
    [0134] When producing a poly alpha-1,3-glucan ether compound, poly alpha-1,6-glucan or poly alpha-1,3-1,6-glucan with two or more different organic groups, two or more different etherification agents would be used accordingly. For example, an alkylene acid or an alkyl chloride can be used as etherifying agents for the production of an alkyl hydroxyalkyl poly alpha-1,3-glucan ether, a poly alpha-1,6-glucan ether alkyl hydroxyalkyl, or an alkyl hydroxyalkyl poly alpha-1,3-1,6-glucan. Any of the etherifying agents described herein, therefore, can be combined to produce polyglucan ether compounds with two or more different organic groups. These two or more etherification agents can be used in the reaction at the same time, or can be used sequentially in the reaction. When used sequentially, any of the temperature treatment steps (for example, heating) described below can optionally be used between each addition. The sequential introduction of etherification agents can be selected to control the desired DoS of each organic group. In general, a special etherifying agent would be used first if the organic group forming in the ether product was desired at a higher DoS value compared to the DoS of another organic group to be added.
    [0135] The amount of etherifying agent to be brought into contact with poly alpha-1,3-glucan, poly alpha-1,6-glucan or poly alpha-1,3-1,6glucan in a reaction under alkaline conditions can be determined with
    Petition 870190055067, of 6/14/2019, p. 316/408
    50/135 basis on the degree of substitution required in the ether compound being produced. The amount of ether substitution groups in each monomeric unit in poly alpha-1,3-glucan, poly alpha-1,6glucan or poly alpha-1,3-1,6-glucan ether compounds produced herein can be determined using nuclear magnetic resonance (NMR) spectroscopy. The molar substitution (MS) value for poly alpha-1,3-glucan, poly alpha-1,6-glucan or poly alpha-1,3-1,6-glucan has no upper limit. In general, an etherifying agent can be used in an amount of at least about 0.05 mol per mole of polyglucan. There is no upper limit to the amount of etherifying agent that can be used.
    [0136] The reactions for the production of poly alpha-1,3-glucan ether compounds, poly alpha-1,6-glucan or poly alpha-1,3-1,6-glucan in the present optionally can be carried out in a pressure vessel, such as a Parr reactor, an autoclave, an agitator tube or any other pressure vessel well known in the art. A stirring tube is used to carry out the reaction in certain embodiments.
    [0137] A reaction in the present, optionally, can be heated in the next step of putting the polyglycan in contact with an etherifying agent under alkaline conditions. The reaction temperatures and the time of application of such temperatures can vary within wide limits. For example, a reaction can optionally be kept at room temperature for up to 14 days. Alternatively, a reaction can be heated with or without reflux of between about 25- 200 C and C Q (or any integer between 25 and 200 Q C). The reaction time can be varied accordingly: more time at a low temperature and less time at a high temperature.
    [0138] In certain production embodiments of carboxymethyl poly alpha-1,3-glucan, carboxymethyl poly alpha-1,6-glucan, or poly alphaPetition 870190055067, of 6/14/2019, p. 317/408
    51/135
    1.3- 1.6 carboxymethyl-glucan, a reaction may be heated to around 55 Q C for about 3 hours. Therefore, a reaction for preparing a polyglucan of carboxialquila herein may be heated to about 50 Q C to about 60 Q C (or any integer between 50 and 60 Q C) for about 2 hours to about 5 hours, for example.
    [0139] Optionally, a reaction in the present can be maintained under an inert gas, with or without heating. As used in the present, the term inert gas refers to a gas that does not undergo chemical reactions under a set of conditions provided, such as those described for the preparation of a reaction in the present.
    [0140] All the components of the reactions described herein can be mixed together at the same time and brought to the desired reaction temperature, where the temperature is maintained with or without stirring until the desired polyglycan ether compound is formed. Alternatively, the mixed components can be left at room temperature, as described above.
    [0141] After etherification, the pH of a reaction can be neutralized. The neutralization of a reaction can be carried out using one or more acids. The term "neutral pH", as used herein, refers to a pH that is not substantially acidic or basic (for example, a pH of about 6 to 8, or about 6.0, 6.2, 6, 4, 6.6, 6.8, 7.0, 7.2, 7.4, 7.6, 7.8 or 8.0). Various acids that can be used for this purpose include, but are not limited to, sulfuric, acetic, hydrochloric, nitric acid, any mineral (inorganic) acid, any organic acid, or any combination of acids.
    [0142] A polyglucan ether compound is produced in a reaction at present, optionally it can be washed one or more times with a liquid that does not easily dissolve the compound. For example, a poly alpha ether
    1.3- glucan, poly alpha-1,6-glucan, or poly alpha-1,3-1,6-glucan can be washed with
    Petition 870190055067, of 6/14/2019, p. 318/408
    52/135 water, alcohol, acetone, aromatics or any of its combinations, depending on the solubility of the ether compound (where the lack of solubility is desired for washing). In general, a solvent that comprises an organic solvent, such as alcohol is preferably for washing. A polyglycan ether product can be washed one or more times with an aqueous solution containing methanol or ethanol, for example. For example, 70 to 95% by weight of ethanol can be used to wash the product. A polyglycan ether product can be washed with a methanol: acetone solution (eg, 60:40) in another embodiment. Hot water (about 95 to 100 Q C) can be used in certain embodiments, such as for washing ethers of poly alpha-1,3glucan or poly alpha-1,6-glucan of alkyl (for example, poly alpha -1,3-ethyl glucan) and alkyl hydroxyalkyl poly alpha-1,3-glucan ethers (e.g. ethyl hydroxyethyl poly alpha-1,3-glucan).
    [0143] Poly alpha-1,3-glucan, poly alpha-1,6-glucan, or poly alpha-1,3-
    1,6-glucan can also be modified with one or more benzyl groups. The polyglucan can be benzylated by deprotonation of one or more of the hydroxyl groups, using a base, for example, sodium hydroxide, potassium hydroxide, sodium alkoxide, potassium alkoxide, sodium hydride followed by treatment with an benzylation, for example, a benzyl halide. The benzyl group of the benzylating agent can optionally be replaced by one or more halogen, a cyano, an ester, an amide, an ether group, a C1-C6 alkyl group, an aryl group, a C2-C6 alkene group, a alkaline group C2-C6, or one of its combinations. In some embodiments, the benzylating agent can be:
    - where LG is a leaving group, for example, 0 chloride,
    Petition 870190055067, of 6/14/2019, p. 319/408
    53/135 bromide, iodide; R 3 is halogen, cyano, ester, amide, ether, C 1 -C 6 alkyl, aryl, C 2 -C 6 alkene, C 2 -C 6 alkene; and n is 1, 2, 3, 4 or 5. Halogen can be 0 fluorine, chloride, bromide or iodide. The ester can be 0 benzyl-C (O) O-R ', or the ester can be 0 benzyl-OC (O) -R', where the group R 'is a C 1 -C 6 alkyl or an aryl group. The ether can be a C1-C6 alkyl ether or an aryl ether. The amide can be 0 benzyl-C (O) N (R ") 2 or benzyl-N (R") (O) C-, where each R ',' independently, is 0 hydrogen or C 1 -C 6 alkyl. In each of the above examples, the term benzyl refers to the benzylating agent.
    [0144] Poly alpha-1,3-glucan, poly alpha-1,6-glucan, or poly alpha-
    1,3-1,6-glucan has 3 hydroxyl groups per repeating unit. Therefore, the amount of benzylating agent that can be used is sufficient to produce a degree of substitution that has a maximum value of 3.0. The term degree of substitution means the average number of substituting groups, for example benzyl groups, attached per polyglucan repeat unit. For example, a degree of substitution of 0.5 means that, on average, a hydroxyl group for 2 repeat units is replaced by a benzyl group. A degree of substitution of 3 means that all hydroxyl groups of poly alpha-1,3-glucan, poly alpha-1,6-glucan, or poly alpha-1,3-
    1,6-glucan are replaced. In some embodiments, the degree of substitution is in the range from 0.1 to 0.6. In other embodiments, the degree of substitution is in the range from 0.1 to 0.5, or from 0.01 to 1.0, or from 0.2 to 0.45, or from 0.4 to 0.6. One method of determining the degree of substitution may be by integrating the peaks of a carbon-13 NMR spectrum. Proton NMR analysis can also be used.
    [0145] Deprotonation can occur in the presence of an aqueous base and solvent, an organic base and solvent, or an aqueous and organic solvent base and mixture. Suitable organic solvents
    Petition 870190055067, of 6/14/2019, p. 320/408
    54/135 can include, for example, dimethyl sulfoxide, dimethyl acetamide, dimethyl formamide, pyridine, from 1 to methyl-2-pyrrolidinone or one of their combinations. In some embodiments, the polyglucan can be added to a mixture of the base and the solvent. Optionally, the mixture can be heated. The benzylating agent, for example, benzyl chloride, can then be added. In an aqueous system, as the degree of benzylation increases, the benzyl polygene precipitates out of solution and can be removed by filtration. Using organic solvents, or varying the temperature or concentration, the degree of substitution can be increased above 0.4. The benzyl polyglycan can be isolated using known techniques.
    [0146] Any of the etherification reactions mentioned above can be repeated using a poly alpha-1,3-glucan ether, the poly alpha-ether
    1,6-glucan or poly alpha-1,3-1,6-glucan ether as the starting material for further modification. This approach may be suitable for increasing the DoS of an organic group and / or adding one or more different organic groups to the ether product. For example, a benzyl poly alpha-1,3glucan ether product can be used as a substrate for further modification with the carboxymethyl groups.
    [0147] Poly alpha-1,3-glucan, poly alpha-1,6-glucan or poly alpha-
    1,3-1,6-glucan can be hydrophobically modified by contacting the polysaccharide with a C1-C18 alkylsulfonyl chloride, C6-C20OU aryl sulfonyl chloride in the presence of p-toluenesulfonyl chloride. This hydrophobic modification can be carried out, for example, by first preparing the alkaline conditions by contacting the polysaccharide with a solvent and one or more alkali hydroxides to provide a solution or mixture. The alkaline conditions of the reaction, therefore, can comprise an alkaline hydroxide solution. The pH of alkaline conditions
    Petition 870190055067, of 6/14/2019, p. 321/408
    55/135 can be at least about 11.0, 11.2, 11.4, 11.6, 11.8, 12.0, 12.2, 12.4, 12.6, 12.8 or 13.0. To the basic solution, then C1-C18 alkyl sulfonyl chloride, C6-C20 aryl sulfonyl chloride or ptoluenesulfonyl chloride was added and the mixture was reacted at room temperature or with heating.
    [0148] Depending on the desired application, the polysaccharide derivatives described herein can be formulated, for example, mixed, mixed or incorporated into, with one or more other materials and / or active ingredients suitable for use in various compositions, for example , compositions for use in laundry care, textile / fabric products and / or personal care products. The term composition comprising the polysaccharide derivative in this context may include, for example, aqueous formulations, rheology modifying compositions, fabric treatment / care compositions, laundry care formulations / compositions, fabric softeners or care compositions (hair, skin and oral hygiene), each comprising 0 poly alpha-1,3-glucan, poly alpha-1,6-glucan, or poly alpha-1,3-1,6-glucan replaced by (a ) at least one hydrophobic group and (b) at least one hydrophilic group.
    [0149] As used herein, the term effective amount refers to the amount of the substance used or administered that is adequate to achieve the desired effect. The effective amount of material may vary depending on the application. A person skilled in the art will normally be able to determine an effective amount for an application or special subject without undoing the experiment.
    [0150] The term "resistance to enzymatic hydrolysis" refers to the relative stability of the polysaccharide derivative to enzymatic hydrolysis. Having a resistance to hydrolysis is important for the use of these
    Petition 870190055067, of 6/14/2019, p. 322/408
    56/135 materials in applications where enzymes are present, such as detergent applications, tissue care and / or laundry care. In some embodiments, the polysaccharide derivative is resistant to cellulases. In other embodiments, the polysaccharide derivative is resistant to proteinases. In still other embodiments, the polysaccharide derivative is resistant to amylases. In still other embodiments, the polysaccharide derivative is resistant to lipases. In other embodiments, the polysaccharide derivative is resistant to mannanases. In other embodiments, the polysaccharide derivative resistant to multiple classes of enzymes, for example, two or more cellulases, proteinases, amylases, lipases, mannases or combinations thereof. Resistance to any special enzyme will be defined as having at least 10, 20, 30, 40, 50, 60, 70, 80, 90, 95 or 100% of the remaining materials after treatment with the respective enzyme. The remaining percentage can be determined by measuring the supernatant after treatment with the enzyme using SEC-HPLC. The assay for measuring enzyme resistance can be determined using the following procedure: A sample of the polysaccharide derivative is added to the water in a flask and mixed using a PTFE magnetic stir bar to create a 1 weight percent aqueous solution. The aqueous mixture is produced at pH 7.0 and 20- C. After its polysaccharide derivative is completely dissolved, 1.0 milliliter (mL) (1 percent by weight of the enzymatic formulation) of cellulase (PURADEX® EGL), amylase (PURASTAR® ST L) proteinase (SAVINASE® 16.0 L), or lipase (Lipex® 100 L) is added and mixed for 72 hours (h) at 20 ° C. After 72 hours of stirring, the reaction mixture it is heated to 70 ° C for 10 minutes to inactivate the added enzyme and the resulting mixture is cooled to room temperature and centrifuged to remove any precipitate. The supernatant is analyzed using SEC-HPLC for the recovered polysaccharide derivative and
    Petition 870190055067, of 6/14/2019, p. 323/408
    57/135 compared to a control in which no enzyme was added to the reaction mixture. The percentage changes in area counts for the respective polysaccharide derivative can be used to test the relative resistance of the materials to the respective enzymatic treatment. Percentage changes in area versus total will be used to assess the relative amount of materials remaining after treatment with a specific enzyme. Materials that have a percentage recovery of at least 10%, preferably at least 50, 60, 70, 80, 90, 95 or 100% will be considered "resistant" to the respective enzymatic treatment.
    [0151] The term "aqueous composition" refers herein to a solution or mixture in which the solvent is at least about 1% by weight of water and which comprises the polysaccharide derivative.
    [0152] The terms "hydrocolloid" and "hydrogel" are used interchangeably in the present. A hydrocolloid refers to a colloid system in which water is the medium of dispersion. A colloid, at present, refers to a substance that is microscopically dispersed through every other substance. Therefore, a hydrocolloid at present can also refer to a dispersion, emulsion, mixture or solution of the polysaccharide derivative in water or aqueous solution.
    [0153] The term aqueous solution, at present, refers to a solution in which the solvent is water. The polysaccharide derivative can be dispersed, mixed and / or dissolved in an aqueous solution. An aqueous solution can serve as a means of dispersing a hydrocolloid at present.
    [0154] The terms dispersant and dispersing agent are used interchangeably to refer to a material that promotes the formation and stabilization of a dispersion of one substance in another. A dispersion, at present, refers to an aqueous composition that comprises one or more particles, for example, any ingredient of a
    Petition 870190055067, of 6/14/2019, p. 324/408
    58/135 personal care product, pharmaceutical product, food product, household product or industrial product that are spread, or evenly distributed, throughout the aqueous composition. It is believed that the polysaccharide derivative can act as dispersants in the aqueous compositions described herein.
    [0155] The term viscosity, as used herein, refers to the extent to which a fluid or an aqueous composition, such as a hydrocolloid, resists a force that tends to cause it to flow. Several units of viscosity that can be used at present include centipoise (cPs) and Pascal-seconds (Pa s). A centipoise is a hundredth of a poise; one poise is equal to 0.100 kg nr 1 s -1 . Therefore, the terms viscosity modifier and viscosity modifying agent, as used herein, refer to anything that can alter / modify the viscosity of an aqueous fluid or composition.
    [0156] The terms "fabric", "textile" and "cloth" are used interchangeably to refer to a woven or non-woven material that has a network of natural and / or artificial fibers. Such fibers can be the thread or yarn, for example.
    [0157] A "tissue treatment composition" at present is any composition suitable for treating the tissue in some way. Suitable examples of such a composition include non-washable fiber treatments (for peeling, scrubbing, mercerizing, bleaching, coloring, dyeing, printing, biopolishing, antimicrobial treatments, anti-wrinkle treatments, stain resistance treatments and the like), care compositions laundry (for example, laundry care detergents) and fabric softeners.
    [0158] The terms “detergent composition”, “heavy-duty detergent” and “detergent for all purposes” are used in
    Petition 870190055067, of 6/14/2019, p. 325/408
    59/135 interchangeable way to refer to a composition useful for the regular washing of a substrate, for example, crockery, cutlery, vehicles, fabrics, carpets, clothing, white and colored textiles at any temperature. Detergent compositions for the treatment of fabrics, hard surfaces and any other surfaces in the fabric and home care area include: laundry detergents, fabric conditioners (including fabric softeners), washing and rinse additives and care compositions, refreshing fabric compositions, laundry pre-wash, laundry pretreatment, compositions for the treatment of rigid surfaces, compositions for car treatment, compositions for washing dishes (manual dishwashing products and automatic dishwashing products ), air cleaning products, detergent contained or in a porous substrate or non-woven sheet, and other cleaning products for institutional or consumer use.
    [0159] The terms “cellulase” and “cellulase enzyme” are used interchangeably to refer to an enzyme that hydrolyzes the β-1,4-D-glucoside bonds in cellulose, therefore, partially or completely degrading cellulose. Cellulase, alternatively, can be called “β-1,4-glucanose”, for example, and can have endocellulase activity (EC 3.2.1.4), exocellulase activity (EC 3.2.1.91) or celobiase (EC 3.2.1.21). A cellulase in certain embodiments at present can also hydrolyze β1,4-D-glucosidic bonds in cellulose ether derivatives, such as carboxymethyl cellulose. “Cellulose” refers to an insoluble polysaccharide that has a linear chain of D-glucose monomer units linked to β-1,4.
    [0160] As used in the present, the term hand for tissue or handling means people's tactile sensory response to tissue that may be physical, physiological, psychological, social or any of its
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    60/135 combinations. In some embodiments, the fabric hand can be measured using a PHABROMETER® system (available from Nu Cybertek, Inc. Davis, California) to measure the relative hand value provided by the American Textile Chemists and Colorists Association (AATCC test method “ 2022012, Relative Hand Value of Textiles: Instrumental Method ').
    [0161] The composition may be in the form of a liquid, a gel, a powder, a hydrocolloid, an aqueous solution, a granule, a tablet, a capsule, a single compartment sachet, a multiple compartment sachet, a pouch single compartment or a multiple compartment bag. In some embodiments, the composition is in the form of a liquid, a gel, a powder, a single compartment sachet or a multiple compartment sachet.
    [0162] In some embodiments, compositions comprising the polysaccharide derivative may be in the form of a composition for treating fabrics. A fabric treatment composition can be used for manual washing, machine washing and / or other purposes, such as soaking and / or pre-treatment of fabrics, for example. A fabric treatment composition can take the form of, for example, a laundry detergent; tissue conditioner; any wash, rinse or dryer product added; unit or spray dose. The tissue treatment compositions in a liquid form can be in the form of an aqueous composition. In other embodiments, a fabric treatment composition may be in a dry form, such as a granular detergent or a fabric softener sheet added by a dryer. Other non-limiting examples of fabric treatment compositions may include: granular or powder washing agents for all purposes or for heavy duty; liquid washing agents, gels or pastes for all purposes or services
    Petition 870190055067, of 6/14/2019, p. 327/408
    61/135 heavy; thin liquid or dry detergents (for example, delicate); cleaning aids, such as bleaching additives, “stain stick”, or pre-treatments; substrate laden products, such as dry or wet wipes, pillows, or sponges; sprayers and vapors; water-soluble unit dose articles.
    [0163] In some embodiments, compositions comprising the polysaccharide derivative may be in the form of a personal care product. Personal care products include, but are not limited to, hair care compositions, skin care compositions, sun care compositions, body cleansing compositions, oral care compositions, wipes, cosmetic compositions, antifungal compositions and antibacterial compositions. Personal care products can include cleaning, cleaning, protection, deposit, hydration, conditioning, occlusive barrier and emollient compositions.
    [0164] As used herein, personal care products also include products used for cleaning, bleaching and / or disinfecting hair, skin, scalp and teeth, including, but not limited to, shampoos, body lotions, shower gels , topical moisturizers, toothpaste, tooth gels, mouthwashes, mouthwashes, anti-plaque washes and / or other topical cleaning products. In some embodiments, these products are used in humans, while in other embodiments, these products find use in non-human animals (for example, in veterinary applications). In one respect, “personal care products” includes hair care products. The hair care product can be in the form of a powder, paste, gel, liquid, oil, ointment, spray, foam, tablet, a hair shampoo, a hair rinse or any combination thereof.
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    62/135 [0165] The product formulation comprising the polysaccharide derivative described herein can optionally be diluted with water, or a solution predominantly composed of water, to produce a formulation with the desired polysaccharide derivative concentration for the target application. It is evident that a person skilled in the art can adjust the reaction components and / or dilution amounts to obtain the desired polysaccharide derivative concentration for the selected personal care product.
    [0166] The personal care compositions described herein may further comprise one or more dermatologically or cosmetically acceptable components known or otherwise effective for use in hair care products or other personal care products, provided the optional components are physically and chemically compatible with the essential components described herein, or do not otherwise unduly impair the stability, aesthetics or performance of the product. Non-limiting examples of such optional components are described in the International Cosmetic Ingredient Dictionary, Ninth Edition, 2002, and in the CTFA Cosmetic Ingredient Handbook, Tenth Edition, 2004.
    [0167] In one embodiment, the dermatologically acceptable carrier may comprise from about 10% by weight to about 99.9% by weight, alternatively, from about 50% by weight to about 95% by weight, and alternatively, from about 75% by weight to about 95% by weight of a dermatologically acceptable carrier. Suitable vehicles for use with the composition (s) may include, for example, those used in the formulation of hair sprayers, mousses, tonics, gels, skin moisturizers, lotions and conditioners without rinsing. The vehicle can understand water; organic oils; the
    Petition 870190055067, of 6/14/2019, p. 329/408
    63/135 silicones, such as volatile silicones, silicone gums or amino or non-amino oils, and mixtures thereof; mineral oils; vegetable oils, such as olive oil, castor oil, rapeseed oil, coconut oil, peanut oil, avocado oil, macadamia oil, apricot oil, safflower oil, flax oil, tamanu oil, oil lemon and mixtures; the waxes; and organic compounds, such as C2-C10 alkanes, acetone, methyl ethyl ketone, volatile organic C1-C12 alcohols, esters (with the understanding that the selection of the ester (s) may be dependent on whether whether or not it functions as a carboxylic acid ester substrates for the perhydrolases) of C1C20 acids and Ci-Ce alcohols, such as methyl acetate, butyl acetate, ethyl acetate and isopropyl myristate, dimethoxyethane, diethoxyethane, C10 fatty alcohols -C30, such as lauryl alcohol, cetyl alcohol, stearyl alcohol and beenila alcohol; C10-C30 fatty acids, such as lauric acid and stearic acid; fatty amides C10-C30, such as lauric diethanolamide; C10-C30 alkyl fatty esters, such as C10-C30 alkyl fatty benzoates; hydroxypropylcellulose and mixtures thereof. In one embodiment, the vehicle comprises water, fatty alcohols, volatile organic alcohols and mixtures thereof.
    [0168] The composition (s) of the present invention can still comprise from about 0.1% to about 10% and, alternatively, from about 0.2 % to about 5.0% of a gelling agent to assist in providing the desired viscosity to the composition (s). Non-limiting examples of suitable optional gelling agents include cross-linked carboxylic acid polymers; non-neutralized cross-linked carboxylic acid polymers; non-neutralized modified cross-linked carboxylic acid polymers; the crosslinked ethylene / maleic anhydride copolymers; non-neutralized cross-linked ethylene / maleic anhydride copolymers (for example, commercially available EMA 81 from Monsanto); non-neutralized cross-linked alkyl ether / acrylate copolymers (eg
    Petition 870190055067, of 6/14/2019, p. 330/408
    64/135 example, SALCARE ™ SC90 commercially available from Allied Colloids); the non-neutralized cross-linked copolymers of sodium polyacrylate, mineral oil, and PEG-1 tridecet-6 (for example, SALCARE ™ SC91 commercially available from Allied Colloids); the non-neutralized cross-linked copolymers of methyl vinyl ether and maleic anhydride (for example, the commercially available STABILEZE ™ QM-PVM / MA copolymer from International Specialty Products); hydrophobically modified non-ionic cellulose polymers; hydrophobically modified ethoxylated urethane polymers (e.g., Polyphobe UCARE ™ Series of commercially available alkaline swellable polymers from Union Carbide); and their combinations. In this context, the term "non-neutralized" means that the optional polymer and copolymer gelling agent materials contain the non-neutralized acid monomers. Gelling agents preferably include cross-linked non-neutralized water-soluble ethylene / maleic anhydride copolymers, cross-linked non-neutralized water-soluble carboxylic acid polymers, water-soluble hydrophobically modified non-ionic cellulose polymers and surfactant / fatty alcohol gel networks those that are suitable for use in hair conditioner products.
    [0169] The polysaccharide derivatives described herein can be incorporated into hair care products and compositions, such as, but not limited to, hair conditioning agents. Hair conditioning agents are well known in the art, see for example Green et al. (WO 2001/07009), and are commercially available from several sources. Suitable examples of hair conditioning agents include, but are not limited to, cationic polymers, such as guar cationized gum, copolymers of quaternary ammonium salt of diallyl / acrylamide, polyvinylpyrrolidone
    Petition 870190055067, of 6/14/2019, p. 331/408
    65/135 quaternized and its derivatives and several polyquaternary compounds; cationic surfactants, such as stearalkonium chloride, centrimony chloride and sapamine hydrochloride; fatty alcohols, such as beenila alcohol; fatty amines, such as stearyl amine; the waxes; esters; nonionic polymers, such as polyvinylpyrrolidone, polyvinyl alcohol and polyethylene glycol; silicones; siloxanes, such as decamethylcyclopentasiloxane; polymer emulsions, such as amodimethicone; and nanoparticles, such as silica nanoparticles and polymer nanoparticles.
    [0170] Hair care products may also include additional components normally found in cosmetically acceptable media. Non-limiting examples of such components are described in the International Cosmetic Ingredient Dictionary, Ninth Edition, 2002, and in CTFA Cosmetic Ingredient Handbook, Tenth Edition, 2004. A non-limiting list of components often included in a cosmetically acceptable medium for hair care it is also described by Philippe et al. in US patent 6,280,747, and by Omura et al. in US patent 6,139,851 and Cannell et al. in US patent 6,013,250, all of which are hereby incorporated by reference. For example, compositions for the treatment of hair may be aqueous, alcoholic or aqueous alcoholic solutions, alcohol, preferably being ethanol or isopropanol, in a proportion from about 1 to about 75% by weight in total weight, for aqueous alcoholic solutions. In addition, hair treatment compositions may contain one or more conventional cosmetic or dermatological additives or adjuvants including, but not limited to antioxidants, preservatives, fillers, surfactants, UVA and / or UVB sunscreens, fragrances, thickeners, gelling agents, wetting agents and anionic, non-ionic or amphoteric polymers, and
    Petition 870190055067, of 6/14/2019, p. 332/408
    66/135 dyes or pigments.
    [0171] Compositions and methods for hair care can also include at least one coloring agent such as any dye, hairspray, pigment and the like that can be used to change the color of hair, skin or nails. Hair coloring agents are well known in the art (see, for example Green et al., Above, CFTA International Color Handbook, 2nd edition, Micelle Press, England (1992) and Cosmetic Handbook, US Food and Drug Administration, FDA / IAS Booklet (1992)), and are commercially available from a variety of sources (for example Bayer, Pittsburgh, PA; Ciba-Geigy, Tarrytown, NY; ICI, Bridgewater, NJ; Sandoz, Vienna, Austria; BASF, Mount Olive, NJ; and Hoechst, Frankfurt, Germany). Suitable hair coloring agents include, but are not limited to dyes, such as 4-hydroxypropylamino-3-nitrophenol, 4 amino-3- nitrophenol, 2-amino-6-chloro-4-nitrophenol, 2-nitro-paraphenylenediamine , N, N-hydroxyethyl-2-nitro-phenylenediamine, 4-nitro-indole, Henna, HC Blue 1, HC Blue 2, HC Yellow 4, HC Red 3, HC Red 5, Dispersed Violet 4, Dispersed Black 9, HC Blue 7, HC Blue 12, HC Yellow 2, HC Yellow 6, HC Yellow 8, HC Yellow 12, HC Brown 2, D&C Yellow 1, D&C Yellow 3, D&C Blue 1, Scattered Blue 3, Scattered Violet 1, eosin derivatives such as D&C Red 21 and halogenated fluorescein derivatives, such as D&C Red 27, D&C Red Orange 5 in combination with D&C Red 21 and D&C Orange 10; and pigments, such as D&C Red 36 and D&C Orange 17, the calcium lacquers of D&C Red 7, 11,31 and 34, the barium lacquer of D&C Red 12, the strontium lacquer of D&C Red 13, aluminum lacquers of FD&C Yellow 5, FD&C Yellow 6, D&C Red 27, D&C Red 21, and FD&C Blue 1, iron oxides, manganese violet, chromium oxide, titanium dioxide, titanium dioxide nanoparticles, zinc oxide, zinc oxide barium, ultramarine blue, bismuth citrate and carbon black particles. In a
    Petition 870190055067, of 6/14/2019, p. 333/408
    67/135 realization, the hair coloring agents are D&C Yellow 1 and 3, HC Yellow 6 and 8, D&C Blue 1, HC Blue 1, HC Brown 2, HC Red 5, 2-nitroparaphenylenediamine, N, N-hydroxyethyl- 2-nitro-phenylenediamine, 4-nitro-indole and carbon black. Metallic and semiconductor nanoparticles can also be used as hair coloring agents due to their strong light emission (US Patent Application Publication 2004 / 0.010.864 by Vic et a /).
    [0172] Hair treatment compositions may include, but are not limited to, shampoos, conditioners, lotions, aerosols, gels, mousses and hair dyes.
    [0173] Personal care products can be in the form of lotions, creams, pastes, ointments, ointments, ointments, gels, liquids or their combinations. A personal care product can also be in the form of makeup, lipstick, mascara, foundation, blush, eyeliner, lip liner, lip gloss, other cosmetics, sunscreen, sunscreen, nail polish, mousse, hair spray, styling gel, conditioner nail, shower gel, shower gel, liquid soap, facial wash, shampoo, hair conditioner (without rinsing or rinsing), washing cream, hair dye, hair coloring product, hair shine product , hair serum, anti-frizz hair product, hair parting repair product, lip balm, skin conditioner, cold cream, moisturizer, body spray, soap, body scrub, exfoliating, astringent, mouth lotion, depilatory, permanent wavy solution, anti dandruff formulation, antiperspirant composition, deodorant, shaving product, pre-shave product, aftershave product, cleanser, skin gel, rinse, den composition tifrice, toothpaste or mouthwash, for example.
    [0174] Personal care products may include polysaccharide derivatives as described herein, and may also
    Petition 870190055067, of 6/14/2019, p. 334/408
    68/135 understand personal care active ingredient materials including sunscreen agents, moisturizers, humidifiers, beneficial agents for hair, skin, nails and mouth, depositing agents such as surfactants, occlusive agents, moisture barriers, lubricants, emollients, anti-aging agents, antistatic, abrasive, antimicrobial agents, conditioners, exfoliants, fragrances, viscosifying agents, salts, lipids, phospholipids, vitamins, foam stabilizers, pH modifiers, preservatives, suspending agents, silicone oils, silicone derivatives , essential oils, oils, fats, fatty acids, fatty acid esters, fatty alcohols, waxes, polyols, hydrocarbons and their mixtures.
    [0175] In certain embodiments, a skin care product may include at least one active ingredient for the treatment or prevention of skin diseases, providing a cosmetic effect or to provide a moisturizing benefit to the skin, such as oxide. zinc, petrolatum, white petrolatum, mineral oil, cod liver oil, lanolin, dimethicone, hard fat, vitamin A, allantoin, calamine, kaolin, glycerin or colloidal oats and their combinations. A skin care product can include one or more natural moisturizing factors, such as ceramides, hyaluronic acid, glycerin, squalane, amino acids, cholesterol, fatty acids, triglycerides, phospholipids, glycosphingolipids, urea, linoleic acid, glycosaminoglycans, mucopolysaccharides , sodium lactate or sodium pyrrolidone carboxylate, for example. Other ingredients that can be included in a skin care product include, without limitation, glycerides, apricot kernel oil, canola oil, squalane, squalene, coconut oil, jojoba oil, jojoba wax, lecithin, olive oil , safflower oil, sesame oil, shea butter, soy oil, sweet almond oil, sunflower oil, tea tree oil, shea butter, palm oil, cholesterol, cholesterol esters, wax esters, fatty acids and orange oil.
    Petition 870190055067, of 6/14/2019, p. 335/408
    69/135 [0176] The composition can be in any useful form, for example, such as powders, granules, pastes, bars, unit dose or liquid.
    [0177] The unit dose form may be water-soluble, for example, a water-soluble unit-dose article comprising a water-soluble film and a liquid or solid laundry detergent composition, also referred to as a pouch. A water-soluble unit dose pouch comprises a water-soluble film that fully encloses the liquid or solid detergent composition in at least one compartment. The water-soluble unit dose article may comprise a single compartment or multiple compartments. The water-soluble unit dose article may comprise at least two compartments or at least three compartments. The compartments can be arranged in an overlapping orientation or in a side-by-side orientation.
    [0178] A unit dose article is normally a closed structure, produced from water-soluble film that encloses an internal volume that comprises the liquid or solid laundry detergent composition. The bag can have any shape and shape that is adequate to maintain and protect the composition, for example, without allowing the composition of the bag to be released before the bag comes in contact with water.
    [0179] A liquid detergent composition can be aqueous, normally containing up to about 70% by weight of water and from 0% to about 30% by weight of organic solvent. It can also be in the form of a compact gel type containing less than or equal to 30% by weight of water.
    [0180] The polysaccharide derivative comprising a polysaccharide substituted by (a) at least one hydrophobic group and (b) at least one hydrophilic group, wherein the polysaccharide poly alpha-1,3-glucan, poly alpha-1 , 6-glucan, or poly alpha 1,3-1,6-glucan, can be used as an ingredient in the desired product or can be mixed with one or more
    Petition 870190055067, of 6/14/2019, p. 336/408
    70/135 additional suitable ingredients and used as, for example, fabric care applications, laundry care applications, and / or personal care applications. Any of the disclosed compositions, for example, a fabric care, laundry care or personal care composition can comprise in the range from 0.01 to 99 weight percent of the polysaccharide derivative, based on dry weight total composition (dry solids basis). The term "total dry weight" means the weight of the composition excluding any solvent, for example, any water that may be present. In other embodiments, the composition comprises 0.1 to 10% or 0.1 to 9% or 0.5 to 8% or 1 to 7% or 1 to 6% or 1 to 5% or 1 to 4% or 1 to 3% or 5 to 10% or 10 to 15% or 15 to 20% or 20 to 25% or 25 to 30% or 30 to 35% or 35 to 40% or 40 to 45% or 45 to 50% or 50 to 55% or 55 to 60% or 60 to 65% or 65 to 70% or 70 to 75% or 75 to 80% or from 80 to 85% or from 85 to 90% or from 90 to 95% or from 95 to 99% by weight of the polysaccharide derivative, where the weight percentages are based on the total dry weight of the composition.
    [0181] The composition may further comprise at least one surfactant, an enzyme, a detergent adjuvant, a complexing agent, a polymer, a dirt release polymer, a surfactant enhancing polymer, a bleaching agent, bleaching agent bleach, a bleach activator, a bleach catalyst, a fabric conditioner, a clay, a foam enhancer, a soap foam suppressant, anti-corrosion agent, a dirt suspending agent, an anti-dust redeposition agent, dye, bactericide, stain inhibitor, an optical brightener, perfume, a saturated or unsaturated fatty acid, a dye transfer inhibitor, a chelating agent, a colored dye, a calcium cation, a cation of
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    71/135 magnesium, a visual signaling ingredient, a defoamer, a structurant, a thickening agent, an anti-caking agent, a starch, sand, gelling agent or one of its combinations. In one embodiment, the enzyme is a cellulase. In another embodiment, the enzyme is a proteinase. In yet another embodiment, the enzyme is an amylase. In another embodiment, the enzyme is a lipase.
    [0182] The composition may be a detergent composition useful for, for example, tissue care, laundry care and / or personal care and may also contain one or more active enzymes. Non-limiting examples of suitable enzymes include proteinases, cellulases, hemicellulases, peroxidases, lipolytic enzymes (eg, metallolipolytic enzymes), xylanases, lipases, phospholipases, esterases (eg, arylesterase, polyesterase), perhydrolases, cutinases, pectinases , pectate lyases, mannanases, keratinases, reductases, oxidases (for example, choline oxidase), phenoloxidases, lipoxygenases, ligninases, pululanases, tanases, pentosanases, malanases, beta-glucanoses, arabinosidases, hyaluronidases, metallinases, chondrosinases, Amadoriasis, glycoamylases, arabinofuranosidases, phytases, isomerases, transferases, amylases or one of their combinations. If an enzyme (s) is (are) included, it may be present in the composition at about 0.0001 to 0.1% by weight of the active enzyme, based on the weight total composition. In other embodiments, the enzyme may be present in about 0.01 to 0.03% by weight of the active enzyme (for example, calculated as the pure enzyme protein) based on the total weight of the composition. In some embodiments, a combination of two or more enzymes can be used in the composition. In some embodiments, the two or more enzymes are cellulase and one or more proteinases, hemicellulases, peroxidases, lipolytic enzymes, xylanases, lipases, phospholipases, esterases, perhydrolases, cutinases,
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    72/135 pectinases, pectate lyases, mannanases, keratinases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pululanases, tanases, pentosanases, malanases, beta-glucanoses, arabinosidases, hyaluronidases, chondroitinases, laccases, metalloproteinases, glazes, metalloprote , phytases, isomerases, transferases, amylases or one of their combinations.
    [0183] In some embodiments, the composition may comprise one or more enzymes, each enzyme present from about 0.00001% to about 10% by weight, based on the total weight of the composition. In some embodiments, the composition can also comprise each enzyme at a level from about 0.0001% to about 10%, about 0.001% to about 5%, about 0.001% to about 2% or about from 0.005% to about 0.5% by weight in the total weight of the composition.
    [0184] A cellulase may have endocellulase activity (EC 3.2.1.4), exocellulase activity (EC 3.2.1.91) or cellobiase activity (EC 3.2.1.21). A cellulase is an “active cellulase” that has activity under the right conditions to maintain cellulase activity; it is within the skill of the art to determine such suitable conditions. In addition to being able to degrade cellulose, a cellulase in certain embodiments can also degrade cellulose ether derivatives, such as carboxymethyl cellulose.
    [0185] Cellulase can be derived from any microbial source, such as a bacterium or fungus. Chemically modified cellulases or protein engineered mutant cellulases are included. Suitable cellulases, for example, include cellulases of the genera Bacillus, Pseudomonas, Streptomyces, Trichoderma, Humicola, Fusarium, Thielavia and Acremonium. As other examples, cellulase can be derived from Humicola insolens, Myceliophthora thermophile, Fusarium oxysporum, Trichoderma reesei or one of its combinations. Cellulase, as
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    73/135 any of the above, can be in a mature form without an N-terminal signal peptide. Commercially available cellulases useful in the present include CELLUSOFT®, CELLUCLEAN®, CELLUZYME® and CAREZYME® (Novozymes A / S); CLAZINASE® and PURADAX® HA and REVITALENZ ™ (DuPont Industrial Biosciences), BIOTOUCH® (Enzymes AB); and KAC-500 (B) ® (Kao Corporation).
    [0186] Alternatively, a cellulase in the present can be produced by any means known in the art, for example, a cellulase can be produced recombinantly in a heterologous expression system, such as a microbial or heterologous expression system fungal. Examples of heterologous expression systems include bacterial (e.g., E. coli, Bacillus sp.) And eukaryotic systems. Eukaryotic systems can employ yeast (for example, Pichia sp., Saccharomyces sp.) Or fungal (for example, Trichoderma sp., Such as T. reesei, Aspergillus species, such as A. niger) expression systems, for example .
    [0187] Cellulase in certain embodiments can be thermostable. Cellulase thermostability refers to the enzyme's ability to retain activity after exposure to an elevated temperature (for example, about 60 to 70 ° C) for a period of time (for example, for 30 to 60 minutes). The thermostability of a cellulase can be measured through its half-life (t1 / 2) given in minutes, hours or days, during which half of the cellulase activity is lost under defined conditions.
    [0188] Cellulase in certain embodiments can be stable over a wide range of pH values (for example, neutral or alkaline pH, such as a pH of about 7.0 to about 11.0). Such enzymes can remain stable for a predetermined period of time (for example, at
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    74/135 min, for about 15 min, 30 min or 1 hour) under such pH conditions.
    [0189] At least one, two or more cellulases can be included in the composition. The total amount of cellulase in a composition at present is usually an amount that is suitable for using cellulase in the composition (an effective amount). For example, an effective amount of cellulase in a composition designed to enhance the feel and / or appearance of a tissue containing cellulose is an amount that produces measurable improvements in the feel of the tissue (for example, enhancing the softness and / or appearance of the tissue. removing the pills and fibrils that tend to reduce the sharpness of the tissue's appearance). As another example, an effective amount of cellulase in a fabric stone wash composition is that amount that will provide the desired effect (for example, to produce a worn and faded look at seams and fabric panels). The amount of cellulase in a composition at present can also depend on the parameters of the process in which the composition is employed (for example, the equipment, temperature, time and the like) and cellulase activity, for example. The effective concentration of cellulase in an aqueous composition in which a treated tissue can be easily determined by a person skilled in the art. In tissue treatment processes, cellulase can be present in an aqueous composition (for example, washing liquor) in which a tissue treated in a concentration that is minimally about 0.01 to 0.1 ppm of total cellulase protein or about 0.1 to 10 ppb of total cellulase protein (for example, less than 1 ppm), to a maximum of about 100, 200, 500, 1,000, 2,000, 3,000, 4,000 or 5,000 ppm of total cellulase protein, for example example.
    [0190] Suitable enzymes are known in the art and may include, for example, MAXATASE®, MAXACAL ™, MAXAPEM ™, OPTICLEAN®, OPTIMASE®, PROPERASE® proteinases,
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    75/135
    PURAFECT®, PURAFECT® OXP, PURAMAX ™, EXCELLASE ™, PREFERENZ ™ (eg P100, P110, P280), EFFECTENZ ™ proteinases (eg P1000, P1050, P2000), EXCELLENZ ™ proteinases (eg , P1000), ULTIMASE® and PURAFAST ™ (Genencor); ALCALASE®, SAVINASE®, PRIMASE®, DURAZYM ™, POLARZYME®, OVOZYME®, KANNASE®, LIQUANASE®, NEUTRASE®, RELASE® and ESPERASE® (Novozymes); the BLAP ™ proteinases and BLAP ™ variants (Henkel Kommanditgesellschaft auf Aktien, Duesseldorf, Germany) and KAP (B. alkalophilus · subtilisin, Kao Corp., Tokyo, Japan); the mannanases of MANNASTAR®, PURABRITE ™ and MANNAWAY®; M1 LIPASE ™, LUMA FAST ™ and LIPOMAX ™ (Genencor); LIPEX®, LIPOLASE® and LIPOLASE® ULTRA (Novozymes); and LIPASE P ™ Amano lipases (Amano Pharmaceutical Co. Ltd., Japan); STAINZYME®, STAINZYME PLUS®, NATALASE®, DURAMYL®, TERMAMYL®, TERMAMYL ULTRA®, FUNGAMYL® and BAN ™ (Novo Nordisk A / S and Novozymes A / S); the amylases of RAPIDASE®, POWERASE®, PURASTAR® and PREFERENZ ™ (DuPont Industrial Biosciences); the peroxidases of GUARDZYME ™ (Novo Nordisk A / S and Novozymes A / S) or a combination thereof.
    [0191] In some embodiments, the enzymes in the composition can be stabilized using conventional stabilizing agents, for example, a polyol, such as propylene glycol or glycerol; a sugar or sugar alcohol; lactic acid; boric acid or a boric acid derivative (for example, an aromatic borate ester).
    [0192] At present, a detergent composition typically comprises one or more surfactants, in which the surfactant is selected from nonionic surfactants, anionic surfactants, cationic surfactants, ampholytic surfactants, zwiterionic surfactants, semi-nonionic surfactants -polar and their mixtures. THE
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    76/135 surfactant can be derived from petroleum (also called synthetic) or non-petroleum (also called natural). In some embodiments, the surfactant is present at a level from about 0.1% to about 60%, while in alternative embodiments the level is from about 1% to about 50%, while in other embodiments the level is about 5% to about 40% by weight of the cleaning composition. A detergent will normally contain from 0% to about 50% by weight of an anionic surfactant, such as linear alkylbenzenesulfonate (LAS), alpha-olefinsulfonate (AOS), alkyl sulfate (fatty alcohol sulfate) (AS) , alcohol ethoxysulfate (AEOS or AES), secondary alkanesulfonates (SAS), alpha-sulfo fatty acid methyl esters, alkyl- or alkenylsuccinic acid, or soap.
    [0193] The detergent composition may comprise an alcohol ethoxysulfate of Formula R 1 - (OCH2CH2) xO-SO3M, where R 1 is a straight or branched fatty alcohol not derived from petroleum, consisting of carbon chain lengths of even number from about Cs to about C 2 o, and where x is from about 0.5 to about 8 and where M is an alkali metal or ammonium cation. The fatty alcohol portion of the alcohol ethoxysulfate (R 1 ) is derived from a renewable source (for example, derived from animals or plants) rather than geologically derived (for example, derived from petroleum). Fatty alcohols derived from a renewable source can be referred to as natural fatty alcohols. Natural fatty alcohols have an even number of carbon atoms with a single alcohol (-OH) attached to the terminal carbon. The fatty alcohol portion of the surfactant (R 1 ) can comprise the distributions of even-numbered carbon chains, for example, C12, C14, C16, C18, and so on.
    [0194] In addition, a detergent composition may optionally contain 0% by weight to about 40% by weight of a nonionic surfactant such as ethoxylated alcohol (AEO or AE), ethoxylates of
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    77/135 carboxylated alcohol, nonylphenol ethoxylate, alkyl polyglycoside, alkyldimethylamine oxide, ethoxylated fatty acid monoethanolamide, fatty acid monoethanolamide or polyhydroxyalkyl fatty acid amide. The detergent composition may comprise an ethoxylated alcohol of Formula R 2 - (OCH2CH2) y -OH, where R 2 is a non-linear petroleum fatty alcohol, linear or branched, consisting of even-numbered carbon chain lengths from about C10 to about Cie, and y is from about 0.5 to about 15. The fatty alcohol portion of ethoxylated alcohol (R 2 ) is derived from a renewable source (for example, derived from plants or animals) instead of geologically derived (for example, petroleum derived). The fatty alcohol portion of the surfactant (R 2 ) can comprise even-numbered carbon chain distributions, for example, C12, C14, C16, C18 and so on.
    [0195] The composition may further comprise one or more detergent adjuvants or adjuvant systems. In some embodiments incorporating at least one adjuvant, the compositions comprise at least about 1%, from about 3% to about 60% or from about 5% to about 40% by weight of the adjuvant, based on the total weight of the composition. Adjuvants, for example, include the alkali metal, ammonium and / or alkanolammonium salts of polyphosphates, alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicates, polycarboxylate compounds, ether hydroxypolycarboxylates, ethylene maleic anhydride copolymers with ethylene maleic anhydride. or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethylxysuccinic acid, the various alkali metal, ammonium and ammonium salts substituted by polyacetic acids, such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well like polycarboxylates like melitic acid, succinic acid, citric acid, oxidisuccinic acid, polymalleic acid, benzene-1,3,5
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    78/135 tricarboxylic acid, carboxymethylxysuccinic acid and its soluble salts. Examples of a detergent adjuvant or complexing agent include zeolite, diphosphate, triphosphate, phosphonate, citrate, nitrilotriacetic acid (NTA), ethylene diaminetetraacetic acid (EDTA), diethylenetriamineapentacetic acid (DTMPA), alkyl- or alkenyl-succinic acid, or stratified silicates (for example, Hoechst SKS-6). A detergent can also be undeveloped, that is, essentially free of detergent adjuvant.
    [0196] The composition may still comprise at least one chelating agent. Suitable chelating agents, for example, include copper, iron and / or manganese chelating agents and mixtures thereof. In some embodiments in which at least one chelating agent is used, the compositions comprise from about 0.1% to about 15% or even from about 3.0% to about 10% by weight of the chelating agent, based on the total weight of the composition.
    [0197] The composition can still comprise at least one deposition aid. Suitable deposition aids, for example, include polyethylene glycol, polypropylene glycol, polycarboxylate, dirt release polymers such as polyetheletic acid, clays such as kaolinite, montmorillonite, atapulgite, illite, bentonite, halosite, or one of their combinations.
    [0198] The composition may further comprise one or more dye transfer inhibiting agents. Suitable dye transfer inhibiting agents, for example, include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, Nvinylpyrrolidone and N-vinylimidazole copolymers, polyvinyloxazolidones, polyvinylimidazoles, manganese acid phthalocyanines, peroxides ethylene-diamine-tetraacetic (EDTA); diethylene triamine penta methylene phosphonic acid (DTPMP); hydroxyethane-diphosphonic acid (HEDP); acid
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    79/135
    Ν, ethylenediamine Ν'-disuccinic (EDDS); diacetic methylglycine acid (MGDA); diethylene triamine penta acetic acid (DTPA); propylene diamine tetraacetic acid (PDT A); 2-hydroxypyridine-N-oxide (HPNO); or methyl glycine diacetic acid (MGDA); Ν, Ν-diacetic glutamic acid (tetrasodium salt of Ν glutamic acid, Ν-dicarboxymethyl (GLDA)); nitrilotriacetic acid (NTA), 4,5-dihydroxy-m-benzenedisulfonic acid; citric acid and any of its salts, N-hydroxyethylethylenediaminetetraacetic acid (HEDTA), triethylene tetraaminehexaacetiocic acid (TTHA), Nhydroxyethyliminodiacetic acid (HEIDA), dihydroxyethylglycine (DHEG), ethylenediaminetetrapropionic acid and its derivatives (EDTP) and its derivatives, or combinations thereof, and its derivatives. In embodiments, where at least one dye transfer inhibiting agent is used, the compositions can comprise from about 0.0001% to about 10%, from about 0.01% to about 5% , or even, from about 0.1% to about 3% by weight of the dye transfer inhibiting agent, based on the total weight of the composition.
    [0199] The composition may still contain silicates. Suitable silicates can include, for example, sodium silicates, sodium disilicate, sodium metasilicate, crystalline phyllosilicates or one of their combinations. In some embodiments, silicates can be present at a level from about 1% to about 20% by weight, based on the total weight of the composition. In other embodiments, silicates can be present at a level from about 5% to about 15% by weight, based on the total weight of the composition.
    [0200] The composition can still comprise dispersants. Suitable water-soluble organic materials can include, for example, homo- or copolymeric acids or their salts, in which the polycarboxylic acid comprises at least two separate carboxyl radicals
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    80/135 on the other for no more than two carbon atoms.
    [0201] The composition may further comprise one or more other types of polymers in addition to the present derivatives of poly alpha-1,3-glucan, poly alpha-1,6-glucan or poly alpha-1,3-1,6-glucan . Examples of other types of polymers useful in the present invention include carboxymethyl cellulose (CMC), poly (vinylpyrrolidone) (PVP), polyethylene glycol (PEG), poly (vinyl alcohol) (PVA), polycarboxylates, such as polyacrylates , maleic acid / acrylic copolymers and lauryl maleic acid / acrylic copolymers.
    [0202] The composition may still comprise a bleaching system. For example, the bleaching system may comprise a source of H2O2, such as perborate, percarbonate, perhydrate salts, perborate mono or tetrahydrate sodium salt, persulfate, perphosphate, persilicate, percarboxylic acids and salts, percarbonic acids and salts, perimeric acids and salts, peroxymonosulfuric acids and salts, sulphonated zinc phthalocyanines, sulphonated aluminum phthalocyanines, xanthene dyes, which can be combined with a perishing bleach activator, such as, for example, oxybenzene sulfonate dodecanoyl, decanoyl oxybenzene sulfonate, decanoyl oxybenzoic acid or its salts, tetraacetylethylenediamine (TAED) or nonanoyloxybenzenesulfonate (NOBS). Alternatively, a bleaching system may comprise peroxyacids (for example, peroxyacids of the amide, imide or sulfone type). In other embodiments, the bleaching system may be an enzymatic bleaching system that comprises perhydrolase. Combinations of any of the above can also be used.
    [0203] The composition may also comprise conventional detergent ingredients, such as fabric conditioners, clays, foam reinforcements, soap foam suppressants, anti-corrosion agents, dirt suspending agents, anti-dust redeposition agents, dyes ,
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    81/135 bactericides, stain inhibitors, optical brighteners or perfumes. The pH of a detergent composition in the present (measured in aqueous solution at the concentration of use) can be neutral or alkaline (for example, pH from about 7.0 to about 11.0).
    [0204] The composition can be a detergent composition and, optionally, a heavy-duty laundry detergent composition (for all purposes). In some embodiments, the detergent composition may comprise a detersive surfactant (from 10% to 40% w / w), including a detersive anionic surfactant (selected from a linear or branched or random chain group, substituted alkyl sulfates or unsubstituted, alkyl sulfonates, alkoxylated alkyl sulfate, alkyl phosphates, alkyl phosphonates, alkyl carboxylates, and / or mixtures thereof, and optionally nonionic surfactant (selected from a group of linear or alkoxylated alkyl alcohol branched or random, substituted or unsubstituted, for example, Cs-C-iso ethoxylated alcohols and / or C6-C12 alkyl phenol alkoxylates), where the weight ratio of anionic detersive surfactant (with a hydrophilic index (Hlc) from 6.0 to 9) the non-ionic detersive surfactant is greater than 1: 1. Suitable detersive surfactants also include cationic detersive surfactants (selected from a group of alkyl pyridinium compounds, alkyl quaternary ammonium compounds, alkyl quaternary phosphorus compounds, tertiary alkyl sulfonium compounds and / or their mixtures); zwitterionic and / or amphoteric detersive surfactants (selected from a group of alkanolamine sulfo-betaines); ampholytic surfactants; semi-polar non-ionic surfactants and their mixtures.
    [0205] The composition may be a detergent composition, optionally including, for example, a surfactant enhancer polymer consisting of alkoxylated fat cleaning polymers
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    82/135 amphiphiles. Suitable amphiphilic alkoxylated fat cleaning polymers may include, for example, alkoxylated polymers that have branched hydrophilic and hydrophobic properties, such as alkoxylated polyalkylenimines, random graft polymers comprising a hydrophilic backbone comprising monomers, for example, monomers unsaturated Ci-Ce carboxylic acids, ethers, alcohols, aldehydes, ketones, esters, sugar units, alkoxy units, maleic anhydride, saturated polyalcohols, such as glycerol, and mixtures thereof; and hydrophobic side chain (s), for example, one or more C4C25 alkyl, polypropylene, polybutylene groups, vinyl esters of saturated C1-C monocarboxylic acids, C1-C6 alkyl esters of acrylic or methacrylic acid and mixtures thereof .
    [0206] Suitable heavy-duty laundry detergent compositions may optionally include additional polymers such as dirt-release polymers (include anionic-tipped polyesters, for example, SRP1, polymers comprising at least one unit monomeric material selected from saccharide, dicarboxylic acid, polyol and their combinations, in random or block configuration, polymers based on ethylene terephthalate and their copolymers in random or block configuration, for example, REPEL-O-TEX SF, SF- 2 E SRP6, TEXCARE SR A1o O, SR A3 00, SRN100, SRN170, SRN240, SRN300 AND SRN325, MARLOQUEST SL), anti-deposition polymers, include carboxylate polymers, such as polymers that comprise at least one monomer selected to from acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, m ethylenomalonic. and any mixture of these, vinylpyrrolidone homopolymer and / or polyethylene glycol, molecular weight in the range from 500 to 100,000 Daltons (Da); and polymeric carboxylate (as
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    83/135 as the random maleate copolymer! acrylate or polyacrylate homopolymer). If present, dirt release polymers can be included at 0.1 to 10% by weight, based on the total weight of the composition.
    [0207] The heavy-duty laundry detergent composition may optionally still include saturated or unsaturated fatty acids, preferably saturated or unsaturated fatty acids C12-C24; deposition aids, for example, polysaccharides, cellulosic polymers, diallyldimethylammonium halides (DADMAC) and DADMAC copolymers with avinylpyrrolidone, acrylamides, imidazoles, imidazolinium halides and their mixtures, in random or block configuration, cationic starch , cationic polyacylamides or one of their combinations. If present, the fatty acids and / or deposition aids can each be present at 0.1% to 10% by weight, based on the total weight of the composition.
    [0208] The detergent composition may optionally include silicone or fatty acid based soap suppressors; coloring inks, calcium and magnesium cations, visual signaling ingredients, antifoam (from 0.001% to about 4.0% by weight, based on the total weight of the composition) and / or a structuring / thickening agent (from 0, 01% to 5% by weight, based on the total weight of the composition) selected from the group consisting of diglycerides and triglycerides, ethylene glycol distearate, microcrystalline cellulose, microfiber cellulose, biopolymers, xanthan gum, gellan gum and their mixtures).
    [0209] The compositions described herein can be in the form of a dishwashing detergent composition. Examples of dishwashing detergents include automatic dishwashing detergents (typically used in dishwashers) and manual dishwashing detergents. A detergent composition for washing
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    84/135 dishes can be in any dry or liquid form! aqueous as described herein, for example. Components that can be included in certain embodiments of a dishwashing detergent composition, for example, include one or more of a phosphate; bleaching agent based on oxygen or chlorine; nonionic surfactant; alkaline salt (for example, metasilicates, alkali metal hydroxides, sodium carbonate); any active enzyme described herein; anti-corrosive agent (for example, sodium silicate); defoaming agent; additives to delay the removal of enamel and ceramic patterns; perfume; anti-caking agent (in granular detergent); starch (in tablet-based detergents); gelling agent (in liquid / gel based detergents); and / or sand (powder detergents).
    [0210] In addition to the polysaccharide derivative, dishwashing detergent compositions may comprise (i) a nonionic surfactant, including any ethoxylated nonionic surfactant, alcohol alkoxylated surfactant, epoxy coated poly (oxyalkylated) alcohol or an amine oxide surfactant present in an amount, from 0 to 10% by weight; (ii) an adjuvant, in the range from about 5 to 60% by weight, including any phosphate adjuvant (eg monophosphates, phosphates, tripolyphosphates, other oligomeric polyphosphates, sodium tripolyphosphate - STPP), any phosphate without adjuvant (for example, compounds based on amino acids including methyl-glycine-diacetic acid [MGDA] and its salts or derivatives, glutamic-N, N-diacetic acid [GLDA] and its salts or derivatives, iminodisuccinic acid (IDS ) and salts or their derivatives, carboxylmethylinulin and their salts or derivatives, nitrilotriacetic acid [NTA], diethylene triamine pentacetic acid [DTPA], B-alaninadiacetic acid [B-ADA] and their salts), homopolymers and copolymers of acidic polycarboxylics and their partially salts or completely neutralized, polycarboxylic acids
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    85/135 monomeric and hydroxycarboxylic acids and their salts in the range from 0.5 to 50% by weight, or sulfonated / carboxylated polymers in the range from about 0.1% to about 50% by weight; (iii) a drying aid in the range from about 0.1% to about 10% by weight (for example, polyesters, especially anionic polyesters, optionally in conjunction with other monomers with 3 to 6 functionalities, for example example, the acid, alcohol or ester functionalities that are conducive to polycondensation, polycarbonate, polyurethane and / or polyurea-polyorganosiloxane compounds or their precursor compounds, especially the reactive type of cyclic carbonate and urea); (iv) a silicate in the range from about 1% to about 20% by weight (for example, sodium or potassium silicates such as sodium disilicate, sodium meta-silicate and crystalline phyllosilicates); (v) an inorganic bleach (for example, perhydrated salts such as perborate, percarbonate, perphosphate, persulfate and persilicate salts) and / or an organic bleach, for example, organic peroxyacids such as diacila and tetraacil peroxide, especially diperoxydecanedioic acid, diperoxytetradecanedioic acid, and diperoxyhexadecanedic acid; (vi) a bleach activator, for example, organic peracid precursors in the range from about 0.1% to about 10% by weight and / or bleaching catalyst (eg manganese triazacyclononane and complexes Co, Cu, Mn and Fe bispyridylamine and related complexes and pentamine (III) pentate and acetate and related complexes); (vii) a metal treatment agent in the range from about 0.1% to 5% by weight, for example, benzatriazoles, metal salts and complexes, and / or silicates; and / or (viii) any active enzyme described herein in the range from about 0.01 to 5.0 mg of active enzyme per gram of automatic dishwashing detergent composition and an enzyme stabilizing component. At
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    86/135 weight percentages are based on the total weight of the composition.
    [0211] Several examples of detergent formulations that comprise at least one polysaccharide derivative are described below (from 1 to 21):
    (1) A detergent composition formulated as a granulate having a bulk density of at least 600 g / L comprising: linear alkylbenzenesulfonate (calculated as acid) at about 7 to 12% by weight; ethoxysulfate alcohol (for example, C12-C18 alcohol, from 1 to 2 ethylene oxide [EO]) or alkyl sulfate (for example, 0 C16-C18) at about 1 to 4% by weight; ethoxylated alcohol (for example, C14-C15 alcohol) at about 5 to 9% by weight; sodium carbonate at about 14 to 20% by weight; soluble silicate (for example, 0 Na2O2SiO2) at about 2 to 6% by weight; zeolite (for example, 0 NaAISiCU) at about 15 to 22% by weight; sodium sulfate at about 0 to 6% by weight; sodium citrate / citric acid at about 0 to 15% by weight; sodium perborate at about 11 to 18% by weight; TAED at about 2 to 6% by weight; polysaccharide derivative up to about 2% by weight; other polymers (for example, maleic / acrylic acid copolymer, PVP, PEG) at about 0 to 3% by weight; optionally, an enzyme (s) (calculated as the pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (for example, suds suppressors, perfumes, optical brightener, photobleacher) at about 0 to 5% by weight;
    (2) A detergent composition formulated as a granulate having a bulk density of at least 600 g / L comprising: 0 linear alkylbenzenesulfonate (calculated as acid) at about 6 to 11% by weight; ethoxysulfate alcohol (for example, C12-C18 alcohol, from 1 to 2 EO) or alkyl sulfate (for example, 0 C16-C18) at about 1 to 3% by weight; ethoxylated alcohol (for example, C14-C15 alcohol) at about 5 to 9% by weight; sodium carbonate at about 15 to 21% by weight; soluble silicate (for
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    87/135 example, Na 2 O 2 SiO 2 ) at about 1 to 4% by weight; zeolite (eg ο NaAISiCU) at about 24 to 34% by weight; sodium sulfate at about 4 to 10% by weight; sodium citrate I citric acid at about 0 to 15% by weight; sodium perborate at about 11 to 18% by weight; TAED at about 2 to 6% by weight; polysaccharide derivative up to about 2% by weight; other polymers (for example, the maleic acid acrylic copolymer I, PVP, PEG) at about 1 to 6% by weight; optionally, an enzyme (s) (calculated as the pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (for example, suds suppressors, perfumes, optical brightener, photobleacher) at about 0 to 5% by weight;
    (3) A detergent composition formulated as a granulate having a bulk density of at least 600 g / L comprising: linear alkylbenzenesulfonate (calculated as acid) at about 5 to 9% by weight; ethoxysulfate alcohol (for example, C12-C18, 7 EO alcohol) at about 7 to 14% by weight; soap such as 0 fatty acid (for example, C 6 -C 22 fatty acid) at about 1 to 3% by weight; sodium carbonate at about 10 to 17% by weight; soluble silicate (for example, 0 Na 2 O 2 SiO 2 ) at about 3 to 9% by weight; zeolite (for example, 0 NaAISiCU) at about 23 to 33% by weight; sodium sulfate at about 0 to 4% by weight; sodium perborate at about 8 to 16% by weight; TAED at about 2 to 8% by weight; phosphonate (for example, 0 EDTMPA) at about 0 to 1% by weight; polysaccharide derivative up to about 2% by weight; other polymers (for example, maleic / acrylic acid copolymer, PVP, PEG) at about 0 to 3% by weight; optionally, an enzyme (s) (calculated as the pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (for example, suds suppressors, perfumes, optical brightener) at about 0 to 5% by weight;
    (4) A detergent composition formulated as a granulate that has a bulk density of at least 600 g / L which
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    88/135 comprises: linear alkylbenzenesulfonate (calculated as acid) at about 8 to 12% by weight; ethoxylated alcohol (for example, C12-C18, 7 EO alcohol) at about 10 to 25% by weight; sodium carbonate at about 14 to 22% by weight; soluble silicate (for example, 0 Na2O2SIO2) at about 1 to 5% by weight; zeolite (for example, 0 NaAISICU) at about 25 to 35% by weight; sodium sulfate at about 0 to 10% by weight; sodium perborate at about 8 to 16% by weight; TAED at about 2 to 8% by weight; phosphonate (for example, 0 EDTMPA) at about 0 to 1% by weight; polysaccharide derivative up to about 2% by weight; other polymers (for example, maleic / acrylic acid copolymer, PVP, PEG) at about 1 to 3% by weight; optionally, an enzyme (s) (calculated as the pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (for example, suds suppressors, perfumes) at about 0 to 5% by weight;
    (5) An aqueous liquid detergent composition comprising: 0 linear alkylbenzenesulfonate (calculated as acid) at about 15 to 21% by weight; ethoxylated alcohol (for example, C12-C18, 7 EO alcohol; or C12-C15, 5 EO alcohol) at about 12 to 18% by weight; soap such as fatty acid (e.g., oleic acid) at about 3 to 13% by weight; alkenylsuccinic acid (C12-C14) at about 0 to 13% by weight; aminoethanol at about 8 to 18% by weight; citric acid at about 2 to 8% by weight; phosphonate at about 0 to 3% by weight; polysaccharide derivative up to about 2% by weight; other polymers (for example, 0 PVP, PEG) at about 0 to 3% by weight; borate at about 0 to 2% by weight; about 0 to 3% by weight ethanol; propylene glycol at about 8 to 14% by weight; optionally, an enzyme (s) (calculated as the pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (for example, dispersants, suds suppressors, perfume, optical brightener) at about 0 to 5% by weight;
    (6) A structured aqueous liquid detergent composition
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    89/135 comprising: linear alkylbenzenesulfonate (calculated as acid) at about 15 to 21% by weight; ethoxylated alcohol (for example, C12-C18, 7 EO alcohol; or C12-C15, 5 EO alcohol) at about 3 to 9% by weight; soap such as fatty acid (e.g., oleic acid) at about 3 to 10% by weight; zeolite (for example, 0 NaAISiCU) at about 14 to 22% by weight; potassium citrate from 9 to 18% by weight; borate at about 0 to 2% by weight; polysaccharide derivative up to about 2% by weight; other polymers (for example, 0 PVP, PEG) at about 0 to 3% by weight; about 0 to 3% by weight ethanol; anchoring polymers (e.g., lauryl methacrylate / acrylic acid copolymer, 25: 1 molar ratio, PM 3800) at about 0 to 3% by weight; glycerol at about 0 to 5% by weight; optionally, an enzyme (s) (calculated as the pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (for example, dispersants, suds suppressors, perfume, optical brightener) at about 0 to 5% by weight;
    (7) A detergent composition formulated as a granulate having a bulk density of at least 600 g / L comprising: 0 to 5 to 10% by weight fatty alcohol sulfate, ethoxylated fatty acid monoethanolamide to about 3 to 9% by weight; soap such as 0 to 3 wt.% fatty acid; sodium carbonate at about 5 to 10% by weight; soluble silicate (for example, 0 Na 2 O 2 SiO 2 ) at about 1 to 4% by weight; zeolite (for example, 0 NaAISiCU) at about 20 to 40% by weight; sodium sulfate at about 2 to 8% by weight; sodium perborate at about 12 to 18% by weight; TAED at about 2 to 7% by weight; polysaccharide derivative up to about 2% by weight; other polymers (for example, maleic / acrylic acid copolymer, PEG) at about 1 to 5% by weight; optionally, an enzyme (s) (calculated as the pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (for example, 0 optical brightener, suds suppressors, perfumes) at about 0 to
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    5% by weight;
    (8) A detergent composition formulated as a granulate comprising: linear alkylbenzenesulfonate (calculated as acid) at about 8 to 14% by weight; ethoxylated fatty acid monoethanolamide at about 5 to 11% by weight; soap such as fatty acid at about 0 to 3% by weight; sodium carbonate at about 4 to 10% by weight; soluble silicate (for example, Na 2 O 2 SiO 2 ) at about 1 to 4% by weight; zeolite (for example, NaAISiCU) at about 30 to 50% by weight; sodium sulfate at about 3 to 11% by weight; sodium citrate at about 5 to 12% by weight; polysaccharide derivative up to about 2% by weight; other polymers (for example, PVP, maleic / acrylic acid copolymer, PEG) at about 1 to 5% by weight; optionally, an enzyme (s) (calculated as the pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (for example, suds suppressors, perfumes) at about 0 to 5% by weight;
    (9) A detergent composition formulated as a granulate comprising: linear alkylbenzenesulfonate (calculated as acid) at about 6 to 12% by weight; nonionic surfactant at about 1 to 4% by weight; soap such as fatty acid at about 2 to 6% by weight; sodium carbonate at about 14 to 22% by weight; zeolite (for example, NaAISiO4) at about 18 to 32% by weight; sodium sulfate at about 5 to 20% by weight; sodium citrate at about 3 to 8% by weight; sodium perborate at about 4 to 9% by weight; bleach activator (for example, NOBS or TAED) at about 1 to 5% by weight; polysaccharide derivative up to about 2% by weight; other polymers (for example, polycarboxylate or PEG) at about 1 to 5% by weight; optionally, an enzyme (s) (calculated as the pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (for example, the optical brightener, perfume) at about 0 to 5% by weight;
    (10) An aqueous liquid detergent composition that
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    91/135 comprises: linear alkylbenzenesulfonate (calculated as acid) at about 15 to 23% by weight; ethoxysulfate alcohol (for example, C12-C15 alcohol, 2-3 EO) at about 8 to 15% by weight; ethoxylated alcohol (for example, C12C15, 7 EO alcohol; or C12-C15, 5 EO alcohol) at about 3 to 9% by weight; soap such as fatty acid (for example, lauric acid) at about 0 to 3% by weight; aminoethanol at about 1 to 5% by weight; sodium citrate at about 5 to 10% by weight; hydrotrope (eg sodium cumene sulfonate) at about 2 to 6% by weight; borate at about 0 to 2% by weight; polysaccharide derivative up to about 1% by weight; about 1 to 3% by weight ethanol; propylene glycol at about 2 to 5% by weight; optionally, an enzyme (s) (calculated as the pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (for example, dispersants, perfume, optical brighteners) at about 0 to 5% by weight;
    (11) An aqueous liquid detergent composition comprising: 0 linear alkylbenzenesulfonate (calculated as acid) at about 20 to 32% by weight; ethoxylated alcohol (for example, C12-C15, 7 EO alcohol; or C12-C15, 5 EO alcohol) at about 6 to 12% by weight; aminoethanol at about 2 to 6% by weight; citric acid at about 8 to 14% by weight; borate about 1 to 3% by weight; polysaccharide derivative up to about 2% by weight; about 1 to 3% by weight ethanol; propylene glycol at about 2 to 5% by weight; other polymers (for example, maleic acid / acrylic copolymer, anchoring polymer, such as lauryl methacrylate / acrylic acid copolymer) at about 0 to 3% by weight; glycerol at about 3 to 8% by weight; optionally, an enzyme (s) (calculated as the pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (for example, hydrotropes, dispersants, perfume, optical brighteners) at about 0 to 5% by weight;
    (12) A detergent composition formulated as a granulate that has a bulk density of at least 600 g / L which
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    92/135 comprises: anionic surfactant (for example, linear alkylbenzenesulfonate, alkyl sulfate, alpha-olefinsulfonate, alpha-sulfo fatty acid methyl esters, alkanesulphonates, soap) in about 25 to 40% by weight; nonionic surfactant (eg ethoxylated alcohol) at about 1 to 10% by weight; sodium carbonate at about 8 to 25% by weight; soluble silicate (for example, Na2O2SIO2) at about 5 to 15% by weight; sodium sulfate at about 0 to 5% by weight; zeolite (NaAISiCU) at about 15 to 28% by weight; sodium perborate at about 0 to 20% by weight; bleach activator (for example, TAED or NOBS) at about 0 to 5% by weight; polysaccharide derivative up to about 2% by weight; optionally, an enzyme (s) (calculated as the pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (for example, perfume, optical brighteners) at about 0 to 3% by weight;
    (13) The detergent compositions as described in (1) to (12) above, but in which all or part of the linear alkylbenzenesulfonate is replaced by C12-C18 alkylsulfate;
    (14) A detergent composition formulated as a granulate having a bulk density of at least 600 g / L comprising: 0 C12-C18 alkyl sulfate at about 9 to 15% by weight; alcohol ethoxylate at about 3 to 6% by weight; polyhydroxy-alkyl fatty acid amide at about 1 to 5% by weight; zeolite (for example, 0 NaAISICU) at about 10 to 20% by weight; layered disilicate (e.g., Hoechst's SK56) at about 10 to 20% by weight; sodium carbonate at about 3 to 12% by weight; soluble silicate (eg 0 Na2O2SIC> 2) at 0 to 6% by weight; sodium citrate at about 4 to 8% by weight; sodium percarbonate at about 13 to 22% by weight; TAED at about 3 to 8% by weight; polysaccharide derivative up to about 2% by weight; other polymers (for example, polycarboxylates and PVP) at about 0 to 5% by weight; optionally, an enzyme (s) (calculated
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    93/135 as the pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (for example, the optical brightener, photobleacher, perfume, suds suppressors) at about 0 to 5% by weight;
    (15) A detergent composition formulated as a granulate having a bulk density of at least 600 g / L comprising: C12-C18 alkyl sulfate at about 4 to 8% by weight; alcohol ethoxylate at about 11 to 15% by weight; soap about 1 to 4% by weight; MAP zeolite or zeolite A at about 35 to 45% by weight; sodium carbonate at about 2 to 8% by weight; soluble silicate (for example, 0 Na2O2SiO2) at 0 to 4% by weight; sodium percarbonate at about 13 to 22% by weight; TAED at about 1 to 8% by weight; polysaccharide derivative up to about 3% by weight; other polymers (for example, polycarboxylates and PVP) at about 0 to 3% by weight; optionally, an enzyme (s) (calculated as the pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (e.g., optical brightener, phosphonate, perfume) at about 0 to 3% by weight;
    (16) Detergent formulations as described in (1) to (15) above, but which contain a stabilized or encapsulated peracid, as an additional component or as a substitute for a bleaching system (s) specified above;
    (17) The detergent compositions as described in (1), (3), (7), (9) and (12) above, but in which the perborate is replaced by percarbonate;
    (18) The detergent compositions as described in (1), (3), (7), (9), (12), (14) and (15) above, but which additionally contain a manganese catalyst. A manganese catalyst, for example, is one of the compounds described by Hage et al. (1994, Nature 369: 637-639), which is incorporated herein by reference;
    (19) Detergent compositions formulated as a non-aqueous detergent liquid comprising a liquid non-ionic surfactant, for example
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    94/135 example, a linear alkoxylated primary alcohol, an adjuvant system (eg, phosphate), derived from polysaccharide, optionally an enzyme (s), and alkali. The detergent can also comprise an anionic surfactant and / or bleaching system;
    (20) An aqueous liquid detergent composition comprising: non-petroleum alcohol ethoxysulfate sodium sulphate (for example, C12, 1 EO alcohol) about 30 to 45% by weight sodium sulfate; non-petroleum-derived alcohol ethoxylate (e.g., C12-C14, 9 EO alcohol) at about 3 to 10% by weight; soap such as 0 fatty acid (e.g. 0 C12-C18) at about 1 to 5% by weight; propylene glycol about 512% by weight; C12-C14 alkylamineoxide, at about 4 to 8% by weight; citric acid at about 2 to 8% by weight; polysaccharide derivative up to about 4% by weight; other polymers (for example, 0 PVP, PEG) at about 0 to 3% by weight; borate at about 0 to 4% by weight; about 0 to 3% by weight ethanol; optionally, an enzyme (s) (calculated as the pure enzyme protein) at about 0.0001 to 0.3% by weight; and minor ingredients (for example, dispersants, suds suppressors, perfume, optical brighteners, stabilizers) at about 0 to 5% by weight and the balance being water; and (21) A water-soluble unit dose detergent composition comprising: 0 ethoxysulfate sodium sulfate (for example, C12-C15 alcohol, 2-3 EO) at about 10 to 25% by weight; linear alkylbenzenesulfonate (calculated as acid) at about 15 to 25% by weight; ethoxylated alcohol (e.g., C12-C14, 9 EO alcohol) at about 0.5 to 10% by weight; ethoxylated alcohol (for example, C12-C15, 7 EO alcohol) at about 0.5 to 10% by weight; soap such as 0 fatty acid (for example 0 C12-C18) at about 1 to 8% by weight; propylene glycol at about 6 to 15% by weight; citric acid at about 0.5 to 8% by weight; polysaccharide derivative up to about 4% by weight; monoethanolamine at about 5 to 10% by weight, other polymers (for example,
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    95/135 the PVP, PEG, PVOH) at about 0 to 3% by weight; dipropylene glycol about 2 to 6%, glycerin about 2 to 5% by weight; optionally, an enzyme (s) (calculated as the pure enzyme protein) at about 0.0001 to 0.3% by weight; and minor ingredients (for example, dispersants, suds suppressors, perfume, optical brighteners, stabilizers) at about 0 to 5% by weight and the balance being water.
    [0212] Several examples of personal care formulations that comprise at least one polysaccharide derivative are described below (from 22 to 24):
    (22) A hair conditioning composition comprising: cetyl alcohol (from 1 to 3%), isopropyl myristate (from 1 to 3%), hydroxyethyl cellulose (Natrosol® 250 HHR), from 0.1 to 1 %, derived from polysaccharide of the present invention (from 0.1 to 2%), potassium salt (from 0.1 to 0.5%), preservative, Germaben® II (0.5%) available from International Specialty Products) and balance being water;
    (23) A hair shampoo composition comprising: from 5 to 20% sodium sulphate and lauret, from 1 to 2% cocamidopropyl betane, from 1 to 2% sodium chloride, from 0.1 to 2 % of polysaccharide derivative of the present invention and preservative (from 0.1 to 0.5%) and the balance being water; and (24) A skin lotion composition comprising: 1 to 5% glycerin, 1 to 5% glycol stearate, 1 to 5% stearic acid, 1 to 5% mineral oil, from 0.5 to 1% acetylated lanolin (Lipolan® 98), from 0.1 to 0.5 cetyl alcohol, from 0.2 to 1% triethanolamine, from 0.1 to 1% by weight of Germaben preservative ® II, from 0.5 to 2% by weight of polysaccharide derivatives of the present invention, and the balance being water.
    [0213] In other embodiments, the present invention relates to a method for treating a substrate, the method comprises the steps:
    (A) to provide a composition comprising a derivative
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    96/135 polysaccharide, wherein the polysaccharide derivative comprises a polysaccharide replaced by:
    (a) at least one hydrophobic group; and (b) at least one hydrophilic group;
    - wherein the polysaccharide is poly alpha-1,3-glucan, poly alpha-1,6-glucan, poly alpha-1,6-glucan or a mixture thereof;
    (B) placing the substrate in contact with the composition; and (C) optionally, rinsing the substrate.
    [0214] In one embodiment, the substrate can be a fabric, cloth, rug or clothing. In another embodiment, the substrate can be carpet, upholstery or a surface. The term "upholstery" means the soft, quilted textile cover that is attached to furniture such as armchairs and sofas. The treatment provides a benefit to the substrate, for example, one or more improved fabrics, improved resistance to dirt deposition, improved color resistance, improved wear resistance, improved wrinkle resistance, better antifungal activity, improved stain resistance, performance improved cleanliness when washed, improved drying rates, improved dye, pigment or lacquer update, improved whiteness retention or one of its combinations. In another embodiment, the substrate can be a surface, for example, a wall, a floor, a door or a panel, or paper, or the substrate can be a surface of an object, such as a table. The treatment provides a benefit for the substrate, for example, improved resistance to dirt deposition, improved stain resistance, improved cleaning performance or one of its combinations.
    [0215] A fabric in the present can comprise natural fibers, synthetic fibers, semi-synthetic fibers or any of their combinations. A semi-synthetic fiber is produced using the material of
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    97/135 natural occurrence that has been chemically derived, an example of which is rayon. Non-limiting examples of types of fabric include fabrics produced from: (i) cellulosic fibers such as cotton (for example, cashmere, canvas, cambric, chenille, chintz, cotton velvet, cretonne, apricot, denim, flannel, gingham, jaquard, knit, matelasse, oxford, percale, poplin, pleat, satin, anarruga, fine fabric, terry fabric, twill, velvet), rayon (for example, viscose, modal, lyocell), linen and Tencel®; (ii) protein fibers, such as silk, wool and related mammalian fibers; (iii) synthetic fibers such as polyester, acrylic, nylon, and the like; (iv) the long fibers of jute, flax, ramie, coconut, kapok, sisal, henequén, abaca, hemp and crotalaria vegetables; and (v) any combination of a fabric from (i) to (iv). The fabric comprising a combination of fiber types (for example, natural and synthetic) includes those with a cotton and polyester fiber, for example. The materials / articles that contain one or more fabrics in the present invention, for example, include clothes, curtains, curtains, upholstery, carpets, bedding, bath towels, table linen, bags, tents, car interiors, and the like. Other materials that comprise natural and / or synthetic fibers, for example, include nonwovens, fillers, paper and foams. The fabrics are usually wool or knitted.
    [0216] The contact step can be performed in a variety of conditions, for example, times, temperatures, wash / rinse volumes. Methods for contacting a textile fabric or substrate, for example, a fabric treatment method or washing method, in general, are well known. For example, a material comprising the fabric can be contacted with the disclosed composition: (i) for at least about 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110 or 120 minutes; (ii) at a minimum temperature of 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80,
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    85, 90 or 95 Q C (for example, washing or rinsing laundry: a "cold" temperature from about 15 to 30 ° C, a "hot" temperature from about 30 to 50 ° C, a temperature “Hot” from about 50 to 95 ° C); (iii) at a pH of about 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 (for example, the pH range of about 2 to 12, or about 3 to 11); (iv) at a salt concentration (for example, NaCI) of at least about 0.5, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5 or 4.0% by weight; or any combination of (i) to (iv). The contact step in a fabric treatment method or washing method can comprise any of the washing, soaking and / or rinsing steps, for example. In some embodiments, the rinse step is a rinse step with water.
    [0217] Also described herein is a method for treating a fabric to provide enhanced whiteness maintenance. The maintenance of whiteness is the ability of a detergent to maintain white items from loss of whiteness when washed in the presence of dirt, which can again deposit on white items, making them less white each time they are washed. In one embodiment, the method comprises the steps:
    (A) to provide a composition comprising a polysaccharide derivative, wherein the polysaccharide derivative comprises a polysaccharide substituted by:
    (a) at least one hydrophobic group; and (b) at least one hydrophilic group;
    - wherein the polysaccharide is poly alpha-1,3-glucan, poly alpha-1,6glucan or poly alpha-1,3,6-glucan;
    (B) placing the fabric in contact with the composition; and (C) optionally, rinsing the substrate;
    - in which the fabric obtained in step (B) or step (C) has a
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    99/135 WICIE change of +1.5 or more units in relation to the tissue prior to treatment, as determined according to the L * a * b * WICIE method.
    [0218] The hydrophobic and hydrophilic groups are as described herein. In one embodiment, the composition comprising a polysaccharide derivative, or the polysaccharide derivative itself, at 2% by weight has a surface tension of 70 nM / m or less, as determined according to the ASTM Standard D1331,2015 method . In another embodiment, the composition comprises a polysaccharide derivative, or the polysaccharide derivative itself, at 2% by weight has a surface tension of 65 nM / m or less, as determined according to the ASTM Standard D1331, 2015 method. In yet another embodiment, the composition comprises a polysaccharide derivative or the 2% by weight polysaccharide derivative has a surface tension of 54 mN / m or less, as determined according to the ASTM Standard D1331, 2015 method. In another embodiment, the composition comprising a polysaccharide derivative, or the polysaccharide derivative itself, at 1% by weight has a surface tension of 70 mN / m or less, as determined according to the ASTM Standard D1331 method, 2015.
    [0219] Other substrates that can be contacted, for example, include surfaces that can be treated with dishwashing detergent (for example, automatic dishwashing detergent or manual dishwashing detergent). Examples of such materials include the surfaces of dishes, glasses, pots, pans, baking dishes, utensils and cutlery made of ceramic material, porcelain, metal, glass, plastic (for example, polyethylene, polypropylene and polystyrene) and wood (collectively referred to as present as “cutlery”). Examples of conditions (e.g., time, temperature, washing volume) for conducting a dishwashing or cutlery washing method are known in the art. In
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    100/135 other examples, a cutlery article can be brought into contact with the present composition presented under a suitable set of conditions, such as any of those described above with respect to the contact of a material comprising the fabric.
    [0220] Certain embodiments of a method for treating a substrate still comprise a drying step, in which a material is dried after being brought into contact with the composition. The drying step can be performed directly after the contact step, or by following one or more additional steps that can follow the contact step, for example, drying a fabric after rinsing, in water for example, following a wash in a aqueous composition. Drying can be carried out by any of the various means known in the art, such as air drying at a temperature of at least about 30, 40, 50, 60, 70, 80, 90, 100, 120 , 140, 160, 170, 175. 180 or 200, for example. A material that has been dried in the present normally has less than 3, 2, 1.0.5 or 0.1% by weight of water included in the present.
    [0221] In another embodiment, the substrate can be a surface, for example, a wall, a floor, a door or a panel, or the substrate can be a surface of an object, such as a table. The treatment provides a benefit to the substrate, for example, improved resistance to dirt deposition, improved stain resistance, improved cleaning performance or one of its combinations. The contact step can include cleaning or spraying the substrate with the composition.
    [0222] Non-limiting examples of the achievements described herein include:
    (1) A composition comprising:
    - a polysaccharide derivative, wherein the polysaccharide derivative comprises a polysaccharide substituted by
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    101/135 (a) at least one hydrophobic group; and (b) at least one hydrophilic group;
    - wherein the polysaccharide is poly alpha-1,3-glucan, poly alpha-1,6glucan or poly alpha-1,3-1,6-glucan;
    (2) The composition according to embodiment 1, wherein the poly alpha-1,3-glucan comprises a structure of glucose monomer units, in which greater than or equal to 50% of the glucose monomer units are attached through alpha-1,3-glycosidic bonds;
    (3) The composition, according to embodiment 1 or 2, wherein the poly alpha-1,3-glucan comprises a structure of glucose monomer units, in which greater than or equal to 90% of the glucose monomer units they are linked by means of alpha-1,3-glycosidic bonds;
    (4) The composition according to embodiment 1, wherein the poly alpha-1,6-glucan comprises a structure of glucose monomer units, in which greater than or equal to 40% of the glucose monomer units are attached through alpha-1,6-glycosidic bonds;
    (5) The composition, according to embodiment 1 or 4, wherein the poly alpha-1,6-glucan has a degree of branching of alpha-1,2 that is less than 50%;
    (6) The composition, according to embodiments 1, 2, 3, 4 or 5, wherein at least one hydrophobic group comprises a C1-C18 alkyl, a C2-C18 alkene, a C2-C18 alkene, a polyether comprising the (-CH2CH2O-), (-CH2CH (CH3) O-) repeat units, or mixtures thereof, where the total number of repeat units is in the range from 3 to 100, a C6 aryl -C20, a benzyl, a C-C18 alkylsulfonyl, a CeC20 arylsulfonyl, a p-toluenesulfonyl group, or one of its combinations;
    (7) The composition according to embodiments 1, 2, 3, 4 or 5, wherein at least one hydrophobic group comprises a C1 alkyl group
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    Cyl, benzyl, p-toluenesulfonyl or one of its combinations;
    (8) The composition, according to embodiments 6 or 7, in which at least one hydrophobic group comprises a benzyl group, and the benzyl group is still replaced by one or more of a halogen, a cyano, an ester, an amide, an ether group, a C1-C6 alkyl group, an aryl group, a C2-C6 alkene group, a C2-C6 alkaline group, or one of their combinations;
    (9) The composition according to embodiments 1, 2, 3, 4 or 5, in which at least one hydrophilic group comprises a carboxylic acid, salt of carboxylic acid, derived from sulfonic acid, salt derived from sulfonic acid , sulfuric acid derivative, sulfuric acid derivative salt, thiosulfate, a thiosulfate salt, phosphoric acid derivative, phosphoric acid derivative salt, alkyl amine, alkyl substituted ammonium salt, quaternized pyridine salt, quaternized imidazole salt or one of its combinations;
    (10) The composition according to embodiments 1,2, 3, 4 or 5, in which at least one hydrophilic group comprises a carboxylic acid, an alkyl substituted ammonium salt, a sulfonate, an alkyl sulfonate , a sulfate, thiosulfate, or one of its combinations;
    (11) The composition, according to achievements 1,2, 3, 4, 5 or
    8, wherein at least one hydrophobic group comprises a C1-C18 alkyl, a C2-C18 alkene, a C2-C18 alkene, a polyether comprising the (-CH2CH2O-), (-CH2CH (CH3) repeat units ) O-), or mixtures thereof, in which the total number of repeat units is in the range from 3 to 100, a C6-C20 aryl, a benzyl, a C1-C18 alkylsulfonyl, a C6-C20 arylsulfonyl, a p-toluenesulfonyl group, or one of its combinations, and at least one hydrophilic group comprises a carboxylic acid, carboxylic acid salt, a sulfonic acid derivative, a sulfonic acid derivative salt, a sulfuric acid derivative, a salt derivative sulfuric acid, thiosulfate,
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    103/135 a thiosulfate salt, a phosphoric acid derivative, a phosphoric acid derivative salt, an alkyl amine, an alkyl substituted ammonium salt, a quaternized pyridine salt, a quaternized imidazole salt or one of its combinations ;
    (12) The composition, according to achievements 1,2, 3, 4, 5 or
    8, wherein at least one hydrophobic group comprises a C1-8 alkyl group, a benzyl, a p-toluenesulfonyl or one of its combinations, and at least one hydrophilic group comprises a carboxylic acid, an alkyl substituted ammonium salt, a sulfonate, an alkyl sulfonate, a sulfate, thiosulfate or one of its combinations;
    (13) The composition, according to achievements 1,2, 3, 4, 5 or
    8, wherein at least one hydrophobic group comprises a C1-8 alkyl, benzyl, or p-toluenesulfonyl group and at least one hydrophilic group comprises a thiosulfate or carboxymethyl group;
    (14) The composition, according to achievements 1,2, 3, 4, 5, 6,
    7, 8, 9, 10, 11, 12 or 13, wherein the polysaccharide derivative has a degree of polymerization in the range from about 5 to about 1,400;
    (15) The composition, according to embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, in which the polysaccharide derivative has a degree of substitution from about 0.001 to about 3.0;
    (16) The composition, according to embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15, in which the 2% polysaccharide derivative by weight it has a surface tension of 65 mN / m or less, as determined according to the ASTM Standard D1331,2015 method;
    (17) The composition, according to embodiments 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16, in which the composition is in the form of a liquid, a gel, a powder, a hydrocolloid, an aqueous solution, a granule, a tablet, a capsule, a single compartment sachet, a sachet
    Petition 870190055067, of 6/14/2019, p. 370/408
    104/135 multiple compartments, a single compartment bag or a multiple compartment bag;
    (18) The composition, according to achievements 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16 or 17, which still comprises at least least one of a surfactant, an enzyme, a detergent adjuvant, a complexing agent, a polymer, a dirt release polymer, a surfactant enhancing polymer, a bleaching agent, a bleach activator, a bleach catalyst, a tissue conditioner, a clay, a foam enhancer, a suds suppressor, an anti-corrosion agent, a dirt suspending agent, an anti-dust redposition agent, a dye, a bactericide, a stain inhibitor, an optical brightener, a perfume, a saturated or unsaturated fatty acid, a dye transfer inhibitor, a chelating agent, a colored dye, a calcium cation, a magnesium cation, a visual signaling ingredient, a defoamer, a structuring agent, a thickening agent, an anti-caking agent action, a starch, sand, gelling agent or one of its combinations;
    (19) The composition, according to realization
    18, where the enzyme is a cellulase;
    (20) The composition, according to realization
    18, where the enzyme is a proteinase;
    (21) The composition, according to realization
    18, where the enzyme is an amylase;
    (22) The composition, according to realization
    18, where the enzyme is a lipase;
    (23) The composition, according to realization
    18, in which the enzyme is a cellulase, a proteinase, an amylase, a lipase or one of its combinations;
    Petition 870190055067, of 6/14/2019, p. 371/408
    105/135 (24) A method for the treatment of a substrate, the method comprising the steps:
    (A) to provide a composition comprising a polysaccharide derivative, wherein the polysaccharide derivative comprises a polysaccharide substituted by:
    (a) at least one hydrophobic group; and (b) at least one hydrophilic group;
    - wherein the polysaccharide is poly alpha-1,3-glucan, poly alpha-1,6glucan or poly alpha-1,3,6-glucan;
    (B) placing the substrate in contact with the composition; and (C) optionally, rinsing the substrate;
    - where the substrate is the carpet, upholstery or surface;
    (25) The method, according to embodiment 24, wherein the composition comprising a polysaccharide derivative is a composition, according to embodiment 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22 or 23;
    (26) A product comprising:
    - from about 1% to about 60% by weight of a surfactant; and
    - from about 0.1% to about 10% by weight of a polysaccharide derivative, wherein the polysaccharide derivative comprises a polysaccharide substituted by (a) at least one hydrophobic group; and (b) at least one hydrophilic group;
    - wherein the polysaccharide is poly alpha-1,3-glucan, poly alpha-1,6glucan or poly alpha-1,3,6-glucan; wherein said product is a household product;
    (27) The product, according to embodiment 26, in the form of a
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    106/135 liquid, gel, powder, hydrocolloid, aqueous solution, granule, tablet, capsule, single compartment sachet, multiple compartment sachet, single compartment pouch or multiple compartment pouch ;
    (28) The product, according to embodiment 26 or 27, which still comprises at least one of an enzyme, a detergent adjuvant, a complexing agent, a polymer, a dirt-releasing polymer, a potentiating polymer surfactance, a bleaching agent, a bleaching activator, a bleaching catalyst, a tissue conditioner, a clay, a foam enhancer, a soap foam suppressor, an anti-corrosion agent, a dirt suspending agent, an anti-dust redeposition agent, a dye, a bactericide, a stain inhibitor, optical brightener, a perfume, a saturated or unsaturated fatty acid, a dye transfer inhibitor, a chelating agent, a colored dye, a calcium cation , a magnesium cation, a visual signaling ingredient, an antifoam, a structurant, a thickening agent, an anti-caking agent, a starch, sand, gelling agent or one of its combinations;
    (29) The product, according to embodiment 28, in which the enzyme is a cellulase, a proteinase, an amylase, a lipase or one of its combinations;
    (30) The product of any of embodiments 26, 27, 28 or 29, in which the 2% by weight polysaccharide derivative has a surface tension of less than 65 mN / m;
    (31) The product, according to embodiments 26, 27, 28, 29 or 30, in which at least one hydrophobic group comprises a C1-C18 alkyl, a C2-C18 alkene, a C2-C18 alkaline, a polyether comprising the (-CH 2 CH 2 O-), (-CH 2 CH (CH3) O-) repeating units, or mixtures thereof, where 0
    Petition 870190055067, of 6/14/2019, p. 373/408
    107/135 total number of repeat units is in the range from 3 to 100, a C6-C20 aryl, a benzyl, a C1-C18 alkylsulfonyl, a C6-C 2 o arylsulfonyl, a p-toluenesulfonyl, or one of their combinations and at least one hydrophilic group comprises a carboxylic acid, salt of carboxylic acid, a derivative of sulfonic acid, a salt derived from sulfonic acid, a derivative of sulfuric acid, a salt derived from sulfuric acid, thiosulfate, a salt of thiosulfate, a derivative of phosphoric acid, a salt derived from phosphoric acid, an alkyl amine, an ammonium salt substituted by alkyl, a quaternized pyridine salt, a quaternized imidazole salt or one of its combinations;
    (32) A water-soluble unit dose article comprising a water-soluble film and a composition comprising from about 1% to about 60% by weight of a surfactant; and from about 0.1% to about 10% by weight of a polysaccharide derivative, wherein the polysaccharide derivative comprises a polysaccharide substituted by (a) at least one hydrophobic group; and (b) at least one hydrophilic group;
    - wherein the polysaccharide is poly alpha-1,3-glucan, poly alpha-1,6glucan or poly alpha-1,3,6-glucan; where said water-soluble unit dose article is a household product;
    (33) The water-soluble unit dose article, according to embodiment 32, which comprises at least two compartments;
    (34) The water-soluble unit dose article, according to embodiment 33, in which the compartments are arranged in an overlapping orientation or in a side-by-side orientation;
    (35) The water-soluble unit dose article, according to embodiment 32, which comprises at least three compartments;
    (36) The water-soluble unit dose article, according to the
    Petition 870190055067, of 6/14/2019, p. 374/408
    108/135 embodiments 32, 33, 34 or 35, wherein at least one hydrophobic group comprises a C1-C18 alkyl, a C2-C18 alkene, a C2-C18 alkene, a polyether comprising the repeating units of ( -CH 2 CH 2 O-), (CH 2 CH (CH3) O-), or mixtures thereof, where the total number of repeating units is in the range from 3 to 100, a C6-C 2 o , a benzyl, a C1-C18 alkylsulfonyl, a C6-C 2 o arylsulfonyl, a ptoluenesulfonyl group, or one of its combinations, and at least one hydrophilic group comprises a carboxylic acid, carboxylic acid salt, a sulfonic acid derivative , a salt derived from sulfonic acid, a derivative of sulfuric acid, a salt derived from sulfuric acid, thiosulfate, a derivative of phosphoric acid, a salt derived from phosphoric acid, an alkyl amine, an ammonium salt substituted by alkyl, a quaternized pyridine salt, a quaternized imidazole salt or one of its combinations;
    (37) A method for the treatment of a substrate, in which the method includes the step of putting the substrate in contact with the household product, according to embodiments 26, 27, 28, 29, 30 or 31, in the presence of water, where the substrate is a fabric or a rigid surface;
    (38) A method for 0 treating a fabric with 0 product, according to embodiments 26, 27, 28, 29, 30 or 31, in which the treated fabric has a change in WICIE of +1.5 or more units versus tissue prior to treatment, as determined according to the L * a * b * WICIE method;
    (39) A product comprising:
    - from about 1% to about 60% by weight of a non-oil derived surfactant;
    - from about 0.1% to about 10% by weight of a polysaccharide derivative, where 0 polysaccharide derivative
    Petition 870190055067, of 6/14/2019, p. 375/408
    109/135 comprises a polysaccharide substituted by (a) at least one hydrophobic group; and (b) at least one hydrophilic group;
    - wherein the polysaccharide is poly alpha-1,3-glucan, poly alpha1,6-glucan or poly alpha-1,3,6-glucan; wherein said product is a household product;
    (40) The product, according to embodiment 39, wherein the product is substantially free of dye and bleach; and (41) The product, according to embodiment 39 or 40, wherein at least one hydrophobic group comprises a C1-C18 alkyl, a C2-C18 alkene, a C2-C18 alkene, a polyether comprising the units (-CH2CH2O-), -CH2CH (CH3) O-), or mixtures thereof, where the total number of repetition units is in the range from 3 to 100, a C6-C20, a benzyl, a C1-C18 alkylsulfonyl, a C6-C20 arylsulfonyl, a p-toluenesulfonyl group, or one of its combinations, and at least one hydrophilic group comprises a carboxylic acid, carboxylic acid salt, a sulfonic acid derivative, a salt derived sulfonic acid, a sulfuric acid derivative, a sulfuric acid derived salt, thiosulfate, a thiosulfate salt, a phosphoric acid derivative, a phosphoric acid derived salt, an alkyl amine, an alkyl substituted ammonium salt, a quaternized pyridine salt, a quaternized imidazole salt or one of their combinations.
    Examples [0223] Unless otherwise noted, all ingredients are available from Sigma Aldrich, St. Louis, Missouri and have been used as received.
    [0224] As used herein, the term “Ex. Comp. ” refers to the Comparative Example; the term "Ex." refers to the Example.
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    110/135
    Representative Preparation of Poly Alpha-1, 3-Glucan [0225] Poly alpha-1,3-glucan can be prepared using a gtfJ enzyme preparation as described in US patent 7,000,000; US patent application 2013/0244288, at present, US patent 9,080,195; and US patent application 2013/0244287, hereby, US patent 8,642,757 (all of which are incorporated herein by reference in their entirety).
    [0226] Poly alpha-1,3-glucan polymer can be synthesized and its wet cake prepared, following the procedures described in US patent application 2014/0179913, in the present US patent 9,139,718 (see Example 12, for example), both are incorporated herein as a reference in their entirety.
    Preparation of Poly Alpha-1, 6-Glucan [0227] Two samples of poly alpha-1,6-glucan were prepared according to the procedures below. Sample # 1 contained 10.2% alpha1.2-branching. Sample # 2 contained 23.7% alpha-1,2-branching.
    Sample # 1 [0228] Soluble a-1,2-branched poly alpha-1,6-glucan was prepared using the stepwise combination of the GTF8117 glucosyltransferase and the a- (1,2) GTFJ18T1 branching enzyme, from according to the following procedure.
    [0229] A reaction mixture (2 L) comprising sucrose (450 g / L), GTF8117 (9.4 U / mL) and 50 mM sodium acetate was adjusted to pH 5.5 and stirred at 47 Q C . aliquots (from 0.5 to 1 mL) were removed at predetermined times and suddenly cooled by heating at 90 Q C for 15 min. The resulting heat-treated aliquots were passed through a 0.45 filter. The flow was analyzed using HPLC to determine the concentration of sucrose, glucose, fructose, leukrose, oligosaccharides and polysaccharides. After 23.5 h, the reaction mixture was
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    Q 111/135 heated at 90 C for 30 minutes. An aliquot of the heat-treated reaction mixture was passed through a 0.45 filter and the flow was analyzed for soluble mono / disaccharides, oligosaccharides and polysaccharides (Table 1). A major product was linear dextran with a DPw of 93.
    Table
    - HPLC analysis of mono / disaccharides, oligosaccharides and soluble polysaccharides produced through the reaction
    GTF8117.
    Mono / Disassaccharide, Oligosaccharide, Soluble Polysaccharide Quantity (g / L) DP8 + 171.3 DP7 0.5 DP6 0.9 DP5 1.6 DP4 1.8 DP3 2.2 DP2 10.4 Sucrose 0.0 Leukrose 31.2 Glucose 4.6 Fructose 241.1
    [0230] A second reaction mixture was prepared by adding 95.3 g of sucrose and 210 mL of a (1.2) GTFJ18T1 branching enzyme (5.0 U / mL) to the treated residual reaction mixture thermally obtained from the sucrose and GTF8117 reaction described immediately above. The mixture was stirred at 30 Q C in a volume of about 2.2 L. The rates (from 0.5 to 1 mL) were removed at predetermined times and suddenly cooled by heating at 90 for 15 min. The resulting heat-treated aliquots were passed through a 0.45 filter. The flow was analyzed using HPLC to determine the concentration of sucrose, glucose, fructose, leukrose, oligosaccharides and polysaccharides. After 95 h, the mixture of
    Petition 870190055067, of 6/14/2019, p. 378/408
    112/135 reaction was heated at 90 Q C for 30 minutes. An aliquot of the heat-treated reaction mixture was passed through a 0.45 filter and the flow was analyzed for soluble mono / disaccharides, oligosaccharides and polysaccharides (Table 2). The remaining heat-treated mixture was centrifuged using the 1 L centrifuge bottles. The supernatant was collected and cleaned more than 200 times using the ultrafiltration system (Pellicon Mini with 1 or 5 KDa MWCO cassettes) with deionized water. . The clean oligo / polysaccharide product solution was dried. The dry sample was then analyzed using 1 H NMR spectroscopy to determine the anomeric bonds of oligosaccharides and polysaccharides (Table 3).
    Table 2
    - HPLC analysis of mono / disaccharides, oligosaccharides and soluble polysaccharides produced through the a- (1,2) branching reaction.
    Mono / Disassaccharide, Oligosaccharide, Soluble Polysaccharide Quantity (g / L) DP8 + 170.0 DP7 0.0 DP6 1.2 DP5 1.8 DP4 1.8 DP3 2.0 DP2 8.4 Sucrose 0.0 Leukrose 30.3 Glucose 5.5 Fructose 218.1
    Table 3
    - Analysis of anomeric binding of soluble oligosaccharides and polysaccharides using 1 H NMR spectroscopy.
    a- (°, 4) a- (í, 3) %a- (1,3,6) %a- (1,2,6) a- (6 °) % a- (1,2) branching 0.0 0.2 0.2 9.2 80.7 10.2
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    113/135
    Sample # 2 [0231] Soluble a-1,2-branched poly alpha-1,6-glucan was prepared using the step combination of the glucosyltransferase GTF8117 and the a- (1,2) GTFJ18T1 branching enzyme, from according to the following procedure.
    [0232] A reaction mixture (2 L) comprising sucrose (450 g / L), GTF8117 (9.4 U / mL) and 50 mM sodium acetate was adjusted to pH 5.5 and stirred at 47 Q C . aliquots (0.2 to 1 mL) were removed at predetermined times and suddenly cooled by heating at 90 Q C for 15 min. The resulting heat-treated aliquots were passed through a 0.45 filter. The flow was analyzed using HPLC to determine the concentration of sucrose, glucose, fructose, leukrose, oligosaccharides and polysaccharides. After 23.5 h, the reaction mixture was heated at 90 Q C for 30 minutes. An aliquot of the heat-treated reaction mixture was passed through a 0.45 filter and the flow was analyzed for soluble mono / disaccharides, oligosaccharides and polysaccharides (Table 4). A major product was linear dextran with a DPw of 93.
    Table 4
    - HPLC analysis of mono / disaccharides, oligosaccharides and soluble polysaccharides produced through the reaction
    GTF8117.
    Mono / Disassaccharide, Oligosaccharide, Soluble Polysaccharide Quantity (g / L) DP8 + 173.2 DP7 2.2 DP6 0.3 DP5 0.7 DP4 1.1 DP3 1.5 DP2 9.4 Sucrose 0.0
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    114/135
    Mono / Disassaccharide, Oligosaccharide, Soluble Polysaccharide Quantity (g / L) Leukrose 30.7 Glucose 5.6 Fructose 240.2
    [0233] A second reaction mixture was prepared by adding 238.2 g of sucrose and 210 mL of a (1.2) GTFJ18T1 branching enzyme (5.0 U / mL) to the thermally treated residual reaction mixture that was obtained from the sucrose and GTF8117 reaction described immediately above. The mixture was stirred at 30 Q C in a volume of about 2.2 L. The rates (from 0.2 to 1 mL) were removed at predetermined times and suddenly cooled by heating at 90 for 15 min. The resulting heat-treated aliquots were passed through a 0.45 filter. The flow was analyzed using HPLC to determine the concentration of sucrose, glucose, fructose, leukrose, oligosaccharides and polysaccharides. After 95 h, the reaction mixture was heated at 90 Q C for 30 minutes. An aliquot of the heat-treated reaction mixture was passed through a 0.45 filter and the flow was analyzed for soluble mono / disaccharides, oligosaccharides and polysaccharides (Table 5). The remaining mixture, thermally treated, was centrifuged using the 1 L centrifuge bottles. The supernatant was collected and cleaned more than 200 times using the ultrafiltration system with the 1 or 5 KDa MWCO cassettes and deionized water. The clean oligo / polysaccharide product solution was dried. The dry sample was then analyzed using 1 H NMR spectroscopy to determine the anomeric bonds of oligosaccharides and polysaccharides (Table 6).
    Table 5
    - HPLC analysis of soluble mono / disaccharides, oligosaccharides and polysaccharides produced through the reaction branch of Appetition 870190055067, of 06/14/2019, p. 381/408
    115/135 (1.2).
    Mono / Disassaccharide, Oligosaccharide, Soluble Polysaccharide Quantity (g / L) DP8 + 188.2 DP7 0.0 DP6 1.2 DP5 2.0 DP4 1.9 DP3 1.7 DP2 7.7 Sucrose 0.0 Leukrose 45.4 Glucose 0.0 Fructose 233.8
    Table 6
    - Analysis of anomeric binding of soluble oligosaccharides and polysaccharides using 1 H NMR spectroscopy.
    % of a- (1,4) % of ct- (1.3) % of a- (1,3,6) % dea- (1,2,6) % of ct- (1.6) % branching ct- (1,2) 0.0 0.1 0.2 19.2 61.8 23.7
    Example 1A
    Benzylation of Poly-1, 3-Glucan [0234] Poly alpha-1,3-glucan (180 g of wet cake containing 27.5% by weight of glucan, balanced water) was loaded into a 3-neck reactor of 1 L. To this mixture, 110 ml of water were added. This mixture was cooled from 18 to 21 Q C with an ice water bath. To this mixture, 63 g of 50% by weight sodium hydroxide solution was added, and the mixture was stirred for 30 minutes. Water (150 ml) was added to the mixture. The reaction mixture was heated to 48 Q Ceo benzyl chloride (89 g) was added over 40 minutes. The reaction mixture, therefore, was heated to 78 ° C for 3 hours. The mixture was cooled, neutralized to pH 7.0 and filtered. The solid was washed 3X with 20% aqueous cold methanol and dried in vacuum oven at 40 Q C to produce 53 g of yellow solid. The degree of benzyl substitution was determined by 1 H NMR to be 0.57.
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    116/135
    Example 1B
    Preparation of Carboxymethyl Benzyl Glucan [0235] Benzyl glucan (obtained from Example 1A), 53 g, was suspended in 410 ml of 92% by weight of aqueous ethanol and stirred at room temperature. The mixture was cooled from 15 to 19 Q C with an ice water bath. To the stirred, cooled suspension, 48 g of 50 wt% sodium hydroxide solution was added over 20 minutes. The ice-water bath was removed and the mixture was stirred for 25 minutes. The mixture was cooled in an ice-water bath and 30.9 g of chloroacetic acid (in 30 g of 92% by weight of ethanol) were added in two portions, the first two thirds were added and then stirred at 15 Q C for 15 min, followed by the last third. The ice-water bath was removed and the reaction mixture was stirred at room temperature for 15 minutes at 300 rpm. The mixture then was immersed in an oil bath preheated at 90 Q C. The reaction mixture then was heated for 3 hours at 74 Q C (internal temperature). The reaction mixture, therefore, was cooled, diluted with 53 g of water and neutralized to pH 6.7 with 10% by weight of HCI. The reaction mixture was filtered and the solid was washed with 70% aqueous methanol to provide a brown solid. The solid was dissolved in 200 ml of water, adjusted to pH 8 with 0.1 N NaOH and then added to cold methanol. The suspension was stirred at 10 Q C for 1 hour. The solution was decanted and more cold methanol was added to the residual solid, followed by decantation. This process was repeated 2 times. The final fraction was obtained by adding 2-propanol to the residue to lead to an almost white solid that was isolated through filtration. The solids were combined to provide 40 g. The degree of substitution of the carboxymethyl group was determined by 1 H NMR to be 0.59. The degree of benzyl substitution was 0.57.
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    Example 2A
    Preparation of Benzyl Glucan [0236] To a 2 L 2-neck flask was added with the stirring of 980 mL of water and poly alpha-1,3-glucan (270 g of wet cake containing 40% by weight of glucan and 60% water), in portions. Sodium hydroxide (55 g of 50% by weight of aqueous solution) was added dropwise over a period of 10 minutes while the reaction mixture was stirred at 20 to 25 ° C, then at room temperature for 2 hours . The reaction mixture was heated at 75- C. The benzyl chloride (77 g) was added at 75- C. The reaction mixture was heated to 85 C and maintained at Q 85 Q C for 3.5 hours. The reaction mixture was cooled and filtered. The wet cake was washed with water (3 x 700 ml), ethanol (50% by weight, 800 ml), methanol (80% by weight, 800 ml), acetone (800 ml) and hexanes (2 x 500 ml) . The resulting wet cake was dried on a vacuum frit and purged with N 2 for 3 hours to provide a white solid. The solid was dried in a vacuum oven at 80 Q C overnight with nitrogen sweep to give a white solid, 96 g. The degree of benzyl substitution was determined by NMR 1 H to be 0.17.
    Example 2B
    Benzyl Glucan Carboxymethylation for the Preparation of Carboxymethyl Benzyl Glucan [0237] A 4-neck 250 ml round-bottom flask was equipped with an upper mechanical stirrer, a thermocouple and an N 2 inlet. Benzyl glucan (from Example 2A, 20 g) and ethanol (92% by weight) was added to the flask. The mixture was stirred at room temperature for 30 minutes. Sodium hydroxide (40 g of 50% by weight of aqueous solution) was added dropwise over a period of 10 minutes, with stirring. The suspension was stirred at room temperature for 15 minutes. Chloroacetic acid (11.6 g in
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    118/135 g of 92 wt% ethanol) was added in 5 minutes. The suspension was stirred at 63-65 Q C for 3 hours. After being cooled to 30 Q C, the pH of the reaction mixture was adjusted to about 7 by adding 18.5% by weight HCl solution. The solid was collected by filtration and resuspension with hot methanol (90% by weight, 150 mL), then filtered to provide a moist cake. The wet cake was washed with methanol (90% by weight, 3 x 150 mL) using the resuspension / filtration method, then vacuum dried to provide a solid, 22.3 g, which additionally, it was purified through TFF (nanofiltration: Membrane: PES, 5K MWCO), with about 5L of water exchange, then purified through the 10K MWCO membrane. The retentate was concentrated and dried to provide the carboxymethyl benzyl glucan as 18.1 g of solid. The degree of substitution of the carboxymethyl group was determined by NMR 1 H to be 1.75. The degree of benzyl substitution was 0.17.
    Example 3A
    Preparation of Benzyl Glucan [0238] Poly alpha-1,3-glucan (53 kg of wet cake containing 89% glucan and 11% water) was loaded into a 150-gallon reactor, followed by water (2,216 kg) under nitrogen. To this mixture, the sodium hydroxide solution (10% solid, 202 kg) was added, and the mixture was stirred at room temperature under nitrogen for 2 hours. The reactor was heated to 65 Q Ceo benzyl chloride (58.5 kg) was added to the reactor. The reactor temperature was increased 80 to 85 Q Cea reaction was heated for 3.5 hours. The reactor was cooled to 70 ° C and the pH of the reaction mixture was adjusted to pH 3 using 3M sulfuric acid. The reaction mixture was washed with methanol / water (5: 1), acetone (2 X), methanol and dried. The degree of substitution of the benzyl group was determined
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    119/135 per 1 H NMR to be 0.5.
    Example 3B Benzyl Glucan Carboxymethylation [0239] A 4-neck, 250 mL round-bottom flask was equipped with an upper mechanical stirrer, a thermocouple and an N2 inlet. Benzyl glucan (from Example 3A, 20 g) and ethanol (92% by weight, 120 ml) was added to the flask. The mixture was stirred at room temperature for 30 min. Sodium hydroxide (20 g, 50% by weight of aqueous solution) was added dropwise over a period of 10 minutes, while stirring. The suspension was stirred at room temperature for 15 minutes. Chloroacetic acid (11.6 g in 5 g of 92% by weight of ethanol) was added in 5 minutes. The suspension was stirred at 60-62 Q C for 4 hours. The solid was not completely water-soluble. After being cooled to 35 Q C, 0 sodium hydroxide (11.5 g, 50% by weight aqueous solution) and 6.8 g of chloroacetic acid (3 g of 92% by weight of ethanol) were added. The resulting mixture was stirred at 60 Q C. After 1.5 hours at 60 Q C, a large lump was formed. The heating was turned off. The liquid from the upper layer was decanted and 0 50 wt% methanol, 150 ml), The pH of the resulting mixture was adjusted to about 7 by adding 18.5% HCI solution. The mixture was slowly stirred at room temperature overnight to form a gel. Methanol (50 ml) was added slowly while the gel was stirred. A soft solid was precipitated. The liquid from the upper layer was decanted. Methanol (90% by weight, 150 ml) was added. The solid was collected by filtration and washed with 0 methanol (90% by weight, 3 x 100 ml), then dried in vacuo to provide 20.5 g of solid. The solid was then purified by ultrafiltration. The brown solid was dissolved in about 1.5 L of water. The solution was purified using TFF (nanofiltration, membrane: regenerated cellulose, 10K MWCO), with about 5L of water exchange. The retentate was concentrated and dried to obtain 0
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    120/135 carboxymethyl benzyl glucan as 16.8 g of solid. The degree of substitution of the carboxymethyl group was determined by 1 H NMR to be 0.95. The degree of substitution of the benzyl group was 0.5.
    Example 4 Preparation of Quaternary Ammonium Benzyl Glucan [0240] A 4-neck, 250 mL round-bottom flask was equipped with an upper mechanical stirrer, a thermocouple and an N 2 inlet. Benzyl glucan (from Example 2A, 20 g) and isopropyl alcohol (120 ml) were added to the flask. The mixture was stirred at room temperature, sodium hydroxide (18.64 g of 50% by weight of aqueous solution) was added dropwise over a period of 10 minutes, with stirring. The reaction mixture was heated at 50 Q C in a preheated oil bath (60 C Q). 3-chloro-2-hydroxypropyl trimethylammonium chloride (52.3 g of 60% by weight aqueous solution) was added in 5 minutes. The suspension was stirred at 55 to 60 Q C for 3 hours. A large lump was formed. The liquid (about 100 mL) was decanted. Methanol (100 ml) was added and the lump was manually broken. The pH of this mixture was adjusted to about 7 by adding 18.5% by weight of HCI solution. The solid was collected by filtration and washed with 90 wt% methanol (2 x 150 mL) then filtered to provide a wet cake, which was dried under vacuum at 80 Q C to provide a solid. This solid was suspended in water (700 ml) and centrifuged. The top layer solution was poured into methanol to precipitate the product which was dried to provide a white solid, 14.5 g. The degree of quaternary ammonium substitution was determined by NMR 1 H to be 0.25. The degree of substitution of the benzyl group was 0.17.
    Example 5A
    Hydroxypentyl glucan [0241] Poly alpha-1,3-glucan (50 g of wet cake containing
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    27.5% by weight of glucan, 0.085 mol) was added to a 1 L 3-neck reactor. To this is added 30 ml_ of water. This mixture is cooled from 18 to 21 - C with a batch of ice water. To this mixture, 18 g of 50% by weight sodium hydroxide solution was added and the mixture is stirred for 30 minutes. Water is added (50 ml) to the mixture. The reaction mixture is heated at 48 Q C and 1,2-epoxypentane (17 g) was added in 40 minutes. The reaction mixture is then heated to 75 ° C for 3 hours. The mixture is cooled, neutralized to pH 7.0 and filtered. The solid is washed 3 X with 20% cold aqueous methanol and dried in a vacuum oven. The degree of substitution of the -CH2-CH (OH) CH2CH2CH3 group is determined by 1 H NMR.
    Example 5B
    Hydroxypentyl Glucan Carboxymethylation [0242] Hydroxypentyl glucan (from Example 5A), 25 g, is suspended in 200 ml of 92% by weight of aqueous ethanol and stirred at room temperature. The mixture is cooled from 15 to 19 Q C with an ice water bath. To the stirred, cooled suspension is added 24 g of 50% by weight sodium hydroxide solution over 20 minutes. The ice-water bath is removed and the mixture is stirred for 25 minutes. To the mixture is added 15 g of chloroacetic acid (in 15 g of 92% by weight of ethanol) dropwise. The ice water bath is removed and the reaction flask is heated to 70 ° C for 3 hours. The reaction mixture is then cooled, diluted with 25 g of water and neutralized to pH 7 with 10% by weight of HCI. The reaction mixture is filtered and the solid is washed with 70% aqueous methanol. The degree of substitution of the carboxymethyl group is determined by NMR 1 H.
    Example 6A
    Preparation of Poly Alpha-1,6-Glucan Tosylate [0243] | NaOH (35 g, 50% concentration), urea (30 g) and water (160.5 ml) were mixed and stirred to obtain a solution
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    122/135 clear. The poly-1,6-glucan (17K, 10% branch, 35 g, 31.4%) prepared as described in the above was added with stirring. The mixture was cooled to -12 Q C for 1 hour with the dry ice acetone bath, since Q warmed to 0 C, the solution was vigorously stirred to obtain a clear solution of poly-glucan alfa1,6.
    [0244] To the above ice bath-cooled glucan solution, p-toluenesulfonyl chloride (53 grams) and Imbentin AGS / 35 (20 ml) were added. The mixture was vigorously stirred at 0 Q C for at least 3 hours and warmed to room temperature overnight. The mixture was separated into two layers. The pale pale yellow top liquid layer was removed. The lower gel-like layer was precipitated in isopropanol as a white powder. The product was carefully washed with isopropanol (200 ml / each, 5 times) to obtain the desired glucan-tosylate in quantitative yield. The degree of tosyl substitution was determined by NMR to be 1.0.
    Example 6B
    Preparation of Poly Alpha-1,6-Glucan-Tosylate-Ethylene [0245] To glucan-tosylate from Example 6A (15 g) in DMSO (45 ml), N-ethylethylenediamine (31.6 ml) was added at room temperature. AN, N-diisopropylethylamine (7.8 ml) was added. The reaction was stirred at 100 C for 6 hours Q. The mixture was cooled and acidified to pH 7 using 5M aqueous HCI solution (40 ml). The crude mixture was further diluted 5 times with deionized water and purified with dialysis using the membrane tubing (3K MWCO) to provide the desired water-soluble poly alpha-1,6-glucan-tosylate-amine. The degree of tosyl substitution was determined by elementary analysis to be 0.5. The degree of amine substitution was determined by
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    123/135 elementary analysis to be 0.3.
    Example 7 A
    Preparation of Poly Alpha-1,6-Glucan Tosylate [0246] NaOH (30 g, 50% concentration), urea (25 g) and water (154 ml) were mixed and stirred to obtain a clear solution. Poly alpha-1,6-glucan (17K, 25% branch, 20 g) prepared as described in the present above was added with stirring. The mixture was cooled to -12 Q C for 1 hour with the dry ice acetone bath, since Q warmed to 0 C, the solution was vigorously stirred to obtain a clear solution of poly-alpha - 1,6-glucan.
    [0247] To the above ice bath-cooled glucan solution, p-toluenesulfonyl chloride (47 grams) and Imbentin AGS / 35 (5 ml) were added. The mixture was vigorously stirred at 0 Q C for at least 3 hours and warmed to room temperature overnight. The product was precipitated in isopropanol and carefully washed with isopropanol (200 ml / each, 5 times) to provide the desired glucan-tosylate in quantitative yield. The degree of tosyl substitution was determined through elementary analysis to be 0.7.
    Example 7B
    Preparation of Poly Alpha-1,6-Glucan-Tosylate-Ethylene [0248] To a glucan-tosylate of a preparation similar to that of the Examples in the present (15 g, DoS (Ts) = 0.9) in DMSO (30 ml_) and CHsCN (15 ml_), N-ethylethylenediamine (30 ml_) was added at room temperature. N, N-diisopropylethylamine (45 ml) was added. The reaction was stirred at 70 ° C for 20 hours. The mixture was cooled and acidified to pH 7 using a 5 M aqueous solution of HCI. The crude mixture was further diluted 5 times with deionized water and purified with dialysis using the membrane tubing (3K MWCO) to provide 10.5 grams of the poly alpha-1,6-glucan-tosylate-amine
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    124/135 water soluble desired. The degree of tosyl substitution was determined by elementary analysis to be 0.5. The degree of amine substitution was determined by elemental analysis to be 0.3.
    Example 8
    Preparation of Glucan Tosylate-Thiosulfate [0249] To the glucan tosylate of Example 7A (18 g) in DMSO (160 ml), Na2S2C> 3 (36 grams) and water (40 ml) were added at room temperature. The reaction was stirred at 85 Q C (external temperature) for 18 hours. After this procedure, the reaction mixture was cooled to room temperature. Saturated NaHCOs (100 ml) and water (100 ml) were added. The resulting clear solution was further purified with spectra / Por® 6 dialysis membrane (3.5 K) and dried to produce 13 g of the desired product. The degree of tosyl substitution was determined by elementary analysis to be 0.2. The degree of substitution of thiosulfate was determined by elementary analysis to be 0.5. The degree of substitution of tosylate was 0.7.
    Example 9A
    Preparation of Poly alpha-1, 3-Glucan [0250] carboxylate Nitric acid (69%, 500 ml) and phosphoric acid (85%, 250 ml) were mixed at room temperature. To this solution, glucan (jet-ground powder, 130 g) was added at room temperature. The mixture was stirred for 15 min, then sodium nitrite (6 g) was added in one go while the reactor was cooled with an ice bath. The reaction mixture was slowly stirred for 4 hours. The reaction mixture was cooled with a water bath and the internal temperature was controlled not to exceed 35 to 40 Q C. The resulting mixture was adjusted to ambient temperature for 44 hours adicinais. Ice water (500 mL) was added and the resulting mixture was poured into ice water to a total volume of about
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    125/135 of 6 L and treated with NaOH at a pH of about 7 to 8. The resulting solution was purified with ultrafiltration (5K membrane). Retentate was concentrated to provide a residue that was dried in a lyophilizer to provide a solid product (58 g). Analysis by NMR indicated that the glucan was about 96% oxidized in the carboxylate group (-COOH) at the C6 position. The DoS was from about 1.
    Example 9B
    Preparation of Benzyl Derivative of Poly alpha-1 Carboxylate, 3Glucan [0251] The product of Example 9A (20 g) was dissolved in water (70 ml) at room temperature. To this solution, NaOH (12 g, 0.15 mol of 50% solution) was added at room temperature. A homogeneous solution was formed. The mixture was heated at 65 Q C. benzyl chloride (15.6 g, 0.123 mol) was added to the reaction mixture. The reaction mixture therefore was heated at 85 Q C and Q maintained at 85 C for 3 hours. After being cooled to room temperature, the reaction mixture was poured into water (500 ml) and treated with HCI (18.5% by weight of solution) until pH about 7 to 8, then extracted with chloride methylene to remove as much organic as possible. This aqueous solution was then diluted with water to about 3 L and then purified with ultrafiltration (5K membrane). The retentate was concentrated to provide a residue that was lyophilized to provide a solid product (9.0 g). The benzyl group DoS was from about 1 based on NMR analysis.
    Example 10A
    Preparation of Alila Poly-Alpha-1, 6-Glucan [0252] Poly alpha-1,6-glucan (17K, 10% branch, 41 g) prepared as described in the above was dissolved in 100 ml of deionized water in a 3-necked flask equipped with a funnel
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    126/135 additional, suspended stirrer and nitrogen inlet. The mixture was cooled to 0 to 5 Q C. To this mixture was added 50% sodium hydroxide (21 g) through the dropping funnel, followed by allyl glycidyl ether (90 g). The mixture was heated at 65 Q C and stirred under nitrogen for 6 hours. The amber solution was cooled and neutralized with 18 wt% HCI. The solution was diluted to 3 L and purified by ultrafiltration (MWCO 5K, PES). The product was freeze dried to produce white powder. Analysis through NMR showed that the degree of substitution of the allyl group was 1.3.
    Example 10B
    CarboxyMetiLation of Alila Poly-1, 6-Allyl-Glucan [0253] The polyalpha-1,6-allyl-allyl of Example 10A (20 g) was dissolved in 50 ml of deionized water in a 3-necked flask equipped with a additional funnel, suspended stirrer and nitrogen inlet. The mixture was cooled to 0 to 5 Q C. To this mixture was added 50% sodium hydroxide (21 g) via addition funnel and the mixture was stirred for 10 min to obtain an orange slurry . To this mixture, chloroacetic acid (5.2 g dissolved in 3.5 g of water) was added through the addition funnel. The mixture was heated at 65 Q C and stirred under nitrogen for 3 hours. The amber solution was cooled and neutralized with 18 wt% HCI. The product was purified by ultrafiltration (MWCO 5K, PES). The product was freeze dried to produce white powder. The analysis through NMR showed that the degree of substitution of the ally group was 1.3 and the degree of substitution of the carboxymethyl group was 0.1.
    Example 11 Preparation of Tosylate-Alkyl Sulfonate Glucan [0254] To the poly alpha-1,6-glucan-tosylate of Example 7A (10 g) in DMSO (50 ml) is added to 1,3-propanosultone (10 g) , followed by
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    127/135 trimethylamine (3 g) under nitrogen. The reaction mixture is stirred at 60 Q C. for 6 hours. The mixture is cooled to room temperature and diluted with 500 ml of water. The product is purified by dialysis (dialysis membrane spectra / Por® 6 (3.5 K) and dried by freezing.
    Example 12
    Preparation of Poly Alpha-1, 6-Glucan-Tosylate-Carboxymethyl Derivatives [0255] A 4-neck, 250 mL round-bottom flask is equipped with an upper mechanical stirrer, thermocouple and N 2 inlet. The poly alpha-1,6-glucan-tosylate from Example 7A (10 g) and ethanol (92% by weight, 60 ml) is added to the vial. The mixture is stirred at room temperature for 30 min. Sodium hydroxide (10 g, 50% by weight of aqueous solution) was added dropwise over a period of 10 minutes, while stirring. The suspension is stirred at room temperature for 15 minutes. Chloroacetic acid (5.8 g in 3 g of 92% by weight ethanol) was added in 5 minutes. The suspension is stirred at 60-62 Q C for 4 hours. The mixture is cooled to room temperature and neutralized with 18.5% by weight of HCI solution. The mixture is dissolved and purified by ultrafiltration (MWCO 5kD, PES membrane).
    Example 13A
    Preparation of Benzyl Glucan [0256] 610 mL of water and 270 g of wet cake of poly alpha-1,3-glucan (containing about 100 g of dry glucan) were added to a 2 L 4-necked flask. The mixture was stirred at room temperature for 30 min. The sodium hydroxide solution (50%, 129 g) was added. The reaction mixture was heated at 65 Q C. The benzyl chloride (155 g) was added and the resulting reaction mixture was heated to 84 C and maintained Q 80 to 85 Q C for 3 hours. The reaction mixture was cooled to around 35 Q C and treated with hydrochloric acid (18.5 wt%) at about pH 7. The reaction suspension was filtered and washed with water (500 mL) solution of methanol (1: 1 with water, 500 mL) and then acetone
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    128/135 (3 x 500 mL). The resulting wet cake was dried in a vacuum oven at 40 Q C with intermittent N2 overnight to provide the benzyl glucan (68 g). Based on the NMR analysis, the benzyl group DoS was determined to be 0.6.
    Example 13B
    Benzyl Glucan Carboxymethylation [0257] To a 1 L 4-neck flask, 400 ml of ethanol (92% by weight) and benzyl glucan from Example 13A (57.7 g) were added. The mixture was stirred at room temperature for 30 min. The sodium hydroxide solution (50%, 51.5 g) was added. The mixture was stirred at room temperature for 15 min. Monochloroacetic acid (30.5 g) was added in ethanol (23 g) to the reaction mixture. The reaction mixture was heated to 72-75 Q C for 3 hours. The reaction mixture was cooled to around 35 Q C and treated with hydrochloric acid (18.5 wt%) to a pH of about 7 to 8. The reaction suspension was filtered. The wet cake was dissolved in water (4 L) and filtered. The filtrate was purified by ultrafiltration (5K membrane). The retentate was concentrated and dried in a lyophilizer to provide the carboxymethyl benzyl glucan (60.7 g). Based on the NMR analysis, the DoS for the benzyl group was 0.7 and the DoS for the carboxymethyl group was 0.5.
    Example 14
    Preparation of Hydroxyethyl Carboxymethyl Glucan [0258] Hydroxyethyl glucan, with an OE MS substitution of 3.5 was prepared, as described in US patent 9,139,718. The carboxymethylation reaction was performed as follows.
    [0259] A 250 mL 4-neck round-bottom flask was loaded with 20 g of hydroxyethyl glucan and water (80 g). The mixture was stirred and sodium hydroxide (28.5 g, 50% by weight of solution) was added over a period of 20 minutes. The mixture was stirred for an additional 60 minutes. A solution containing 16.8 g of monochloroacetic acid in 5 g of water was added.
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    The resulting mixture was heated for 3 hours 60-63 C. The Q water (100 ml) was added and the pH of the mixture was adjusted to about 7 by addition of HCl (18.5 wt%). The mixture was poured into water (1.2 L) and then purified by ultrafiltration. The retentate was concentrated and dried in a lyophilizer to provide a solid product (12.6 g). The analysis through NMR indicated the DoS (carboxymethyl) = 0.4 and MS (EO) of 3.5.
    Example 15 Benzyl-Carboxymethyl Glucan Dirt Release Test [0260] The benzyl-carboxymethyl glucan of Example 1B was used. The fabric samples (JoAnn's Fabric Symphony Broadcloth: 65% polyester: 35% cotton) were cleaned in 400 ppm non-ionic surfactant before use. The tissue was cut into 4 ”X4” and 3 samples were used per test. The samples were dipped in 100 ppm of aqueous benzylcarboxymethyl glucan solution, squeezed to a consistent liquid mass and placed flat to air dry. Vegetable oil dyed with red solvent 27 was used to dirty each sample (about 0.13 g of dirt was applied to each sample). The samples were dried overnight before washing. Washing conditions: 1L of tap water, 60 ppm hardness. 80 rpm agitation, 38 Q C washing temperature, 10 minute wash with 3 minute rinse. The detergent used: Arms & Hammer Clean Burst 0.68 g / L; the order of addition: water, detergent, cloth. The samples were squeezed into a solid mass before and after the rinse cycle and air dried.
    [0261] A control experiment was carried out in a similar manner, but without the benzyl-carboxymethyl glucan in the aqueous solution. Comparative Examples A and B were also performed in a similar manner, but with Repel-O-Tex Crystal and Fisher LSD, respectively, they substituted benzyl-carboxymethyl glucan.
    [0262] The reflectance readings (x, y, z color space) were
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    130/135 taken in quadruplicate for each sample using a Hunter colorimeter after soiling and after washing. The y values were used to determine the effectiveness of the cleaning. Differences between the two values are reported (Delta R, the higher value indicates more dirt removal). The results shown below in Table 7 illustrate that benzyl carboxymethyl glucan is effective in releasing oily dirt.
    Table7
    - Dirt release test results
    Sample Delta R Control (without the glucan polymer) 0.8 Benzyl-carboxymethyl glucan (Example 1B) 14.6 Repel-O-Tex (Solvay) Crystal (Comparative Example A) 12.3 Fisher's 95% LSD (Comparative Example B) 1.1
    Example 16 Benzyl-Carboxymethyl Glucan and Tosylate-Thiosulfate Glucan Test [0263] Benzyl-carboxymethyl glucan is produced in a similar manner to that described in Example 13B and the tosylate-thiosulfate glycan obtained in Example 8 was used. Whiteness maintenance, also known as whiteness preservation, is the ability of a detergent to maintain white items from loss of whiteness when they are washed in the presence of soiling. White clothes can become dirty / faded over time, when the dirt is removed from the dirty clothes and deposited in the washing water, therefore, these dirt can deposit again on the clothes, making the clothes less white every time they are washed.
    - Whiteness calculation: CIELab b * and Ganz and CIE whiteness index [0264] The whiteness index (IB) is an evaluation of color quality calculated using a Formula that includes three color measurement components - hue, saturation and luminosity - which are therefore indexed to a standard white value. Various whiteness formulas can be used to
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    131/135 measure whiteness on cellulose-based substrates. Two common formulas are the Ganz Whiteness Index and CIE Whiteness Index. The Ganz Whiteness index is expressed by the formula: IB = (D * Y) + (P * x) + (Q * y) + C, where Y, x and y are the colorimetric values and D, P, Q and C are the parameters of the formula. CIE whiteness is expressed using the formula: IB = Y - (800 * x) - (1,700 * x * y) + 813.7, where Y, x and y are the colorimetric values. More information is available in Riba Griesser's publication, Ciba-Geigy Ltd, “Whiteness and Tint ', June 1993.
    [0265] The color of the surface of an article can be quantified using a series of measurements - L *, a * and b * - generated by measuring the samples using a spectrophotometer. The equipment used for this test is a Konica Minolta CM-3610D spectrophotometer. The software program used is the SpectraMagic NX software. L is a measure of the amount of white or black in a sample; higher L values indicate a lighter colored sample. A measure of the amount of red or green in a sample is determined using the “a *” values. A measure of the amount of blue or yellow in a sample is determined using the “b *” values; lower (more negative) values of b * indicate more blue in a sample.
    [0266] This method measures the ability of product formulations to suspend background dirt in the washing water and prevent it from settling on clothes. Due to the multi-cycle nature of this test and the ability to read the change in tissue over the cycles, the data reported below after 3 wash cycles.
    [0267] The average wash load contains about 40 g of dirt. Of this washing dirt, 70% is body dirt, 10% is environmental dirt (soil, grass), 10% is accidental food stains and the final 10% is diverse / unidentified. The strips of
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    132/135 test dirt SBL2004 (artificial dirt, available from WFK Testgewebe GmbH) reproduce this diversity of food, body mass and clay and pigments. SBL2004 test dirt strips are added to simulate consumer dirt levels. An SBL2004 sheet is, on average, loaded with 8 g of dirt. WFK: WFK Testgewebe GmbH, European supplier of test materials (ECE-2 detergent, artificial dirt SBL2004 and whiteness tracers. WFK Testgewebe GmbH.
    [0268] This method is performed under type III washing conditions, using 0.31% dirt / wash cycle and 5 automatic mini-washers (AMW). The product concentration, washing time and temperature in the mini-washer are identical to the product concentration, washing time and temperature in the equivalent condition of complete washing.
    Table 8
    Standard Washing Conditions
    Condition Water filling (1) Wash Time (min) Wash Temperature ( to C) Full Scale Example Type 1 60 35 30 Top loader Type II 30 45 25 NA Loader HE & Asia Bottom Water Type III 16 30 30 Front Loader NA HE and Japan Type IV 16 110 48 WE Front Loader
    - Hardness (in grains per gallon, gpg): US 7 gpg (3: 1 Ca: Mg),
    Western Europe 15 gpg (3: 1 Ca: Mg), Japan 3 gpg (3: 1 Ca: Mg), China 15 gpg (4: 1 Ca: Mg) [0269] Table 8 above shows the appropriate product concentration, the hardness and the load of dirt for the automatic mini-washers of 5 pots of 7.57 liters, under the respective washing conditions. At
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    133/135 tissue samples used in the whiteness test are provided in the
    Table 9.
    Table 9
    Tissue Samples
    Code % Fiber Content Fiber Construction Fabric Density (g / m) Whiteness index (IB) A * Whiteness index (IB) D65 ** Size CT 1 100 Fabrics -540 -93 -163 8x8 (20x20 cm) CK 2 100 Mesh weft -220 -96 -165 8x8 (20x20 cm) PC 3 65/35 Plain Fabric -125 -98 -156 8x8 (20x20 cm) PE 4 100 Mesh weft -200 -95 -156 8x8 (20x20 cm) CS 5 98/2 Woven twill -180 -86 -158 8x8 (20x20 cm)
    - Grades:
    * IB (A) - illuminant A (internal lighting) ** IB (D65) - illuminant D65 (external lighting) 1 Terry cotton 2 Cotton mesh 3 Polyester / Cotton 4 Polyester 5 Cotton / Elastane
    To test the mini-washer, strips of 3.5 SBL are used per washed step (about 28 g of dirt) per cycle. Per test step, there are 3 of each type of tissue that remain through 3 treatment cycles. The SBL dirt strips are replaced after each wash. Whiteness readings are taken before and after treatment using the L * a * b * WICIE method (Hunter Labs). The data reported in Table 10 are after the third wash cycle.
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    Table 10
    Mesh Whiteness Measurement Results
    Glucan Tissue Sample (under Type III conditions) PE PRAÇA CK CS CT none 0.00 0.00 0.00 0.00 0.00 Benzyl carboxymethyl glucan (Ex. 13B) 28.65 5.03 5.48 3.03 3.41 Tosylate Glucan-Thiosulfate (Ex. 8) 14.88 7.52 7.08 6.13 3.93
    Example 17
    Surface Tension Measurements [0270] The surface activity of amphiphilic glucan polymers was determined by measuring the surface tension using the ring method of Nuoy, using a CAHN DCA-312 force tensometer, according to the ASTM method Standard D1331,2015. The data in Table 11 show that amphiphilic polysaccharide derivatives have surface activity, as demonstrated by reducing surface tension. The results for Comparative Example C show that the carboxymethylated poly alpha-1,3-glucan does not exhibit surface activity. Carboxymethylated glucan was prepared as described in US patent 9,139,718 and had a DoS carboxymethylation of 0.6 based on NMR analysis.
    Table 11
    Surface Tension Measurements
    Polymer Description ST (mN / m) 1% by weight ST (mN / m) 2% by weight Water72 Carboxymethylated glucan (Comparative Example C)71 Benzyl carboxymethyl glucan (Example1b) 68 51 Benzyl carboxymethyl glucan (Example 2b) 54 37 Benzyl carboxymethyl glucan (Example 3b) 64 54 Quaternary ammonium benzyl glucan (Example 4) 69 54
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    Polymer Description ST (mN / m) 1% by weight ST (mN / m) 2% by weight Tosylate ethylene diamine glucan (Example 7B) 42 - Tosylate thiosulfate glucan (Example 8) 53 52 Ally carboxymethyl glucan (Example10B) 46 46 Hydroxyethyl carboxymethyl glucan (Example 14) 65 65
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    权利要求:
    Claims (20)
    [1]
    Claims
    1. COMPOSITION characterized by the fact that it comprises:
    - a polysaccharide derivative, wherein the polysaccharide derivative comprises a polysaccharide substituted by (a) at least one hydrophobic group; and (b) at least one hydrophilic group;
    - where the polysaccharide is poly alpha-1,3-glucan, poly alpha-1,6glucan or poly alpha-1,3-1,6-glucan.
    [2]
    2. COMPOSITION, according to claim 1, characterized by the fact that poly alpha-1,3-glucan comprises a main chain of glucose monomer units in which greater than or equal to 50% of the glucose monomer units are linked through alpha1,3-glycosidic bonds.
    [3]
    3. COMPOSITION, according to claim 1, characterized by the fact that the poly alpha-1,3-glucan comprises a main chain of glucose monomer units in which greater than or equal to 90% of the glucose monomer units are linked through alpha1,3-glycosidic bonds.
    [4]
    4. COMPOSITION, according to claim 1, characterized by the fact that poly alpha-1,6-glucan comprises a main chain of glucose monomer units in which greater than or equal to 40% of the glucose monomer units are linked through alpha1,6-glycosodic bonds.
    [5]
    5. COMPOSITION, according to claim 1, characterized by the fact that poly alpha-1,6-glucan has a branching degree of alpha-1,2 that is less than 50%.
    [6]
    6. COMPOSITION, according to claim 1, characterized by the fact that at least one hydrophobic group comprises
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    2/5 a C1-C18 alkyl, a C2-C18 alkene, a C2-C18 alkene, a polyether comprising the (-CH 2 CH 2 O-), (-CH 2 CH (CH3) O-) repeat units ), or mixtures thereof, in which the total number of repetition units is in the range from 3 to 100, a C6-C 2 o aryl, a benzyl, a C1-C18 alkylsulfonyl, a C6-C 2 o arylsulfonyl , a p-toluenesulfonyl group, or one of its combinations.
    [7]
    7. COMPOSITION according to claim 6, characterized by the fact that at least one hydrophobic group comprises a C1-C18 alkyl, a benzyl group, a p-toluenesulfonyl group or one of its combinations.
    [8]
    8. COMPOSITION, according to claim 6, characterized by the fact that at least one hydrophobic group comprises a benzyl group, and the benzyl group is still replaced by one or more of a halogen, a cyano, an ester, an amide an ether group, an alkyl group C1Ce, an aryl group, a C 2 -C 6 alkene group, an alkyne group C2 -C6 alkyl, or combinations thereof.
    [9]
    9. COMPOSITION, according to claim 1, characterized by the fact that at least one hydrophilic group comprises a carboxylic acid, carboxylic acid salt, derived from sulfonic acid, salt derived from sulfonic acid, derived from sulfuric acid, salt derived sulfuric acid, thiosulfate, thiosulfate salt, derived from phosphoric acid, salt derived from phosphoric acid, alkyl amine, alkyl substituted ammonium salt, quaternized pyridine salt, quaternized imidazole salt or one of its combinations.
    [10]
    10. COMPOSITION according to claim 1, characterized by the fact that at least one hydrophilic group comprises a carboxylic acid, an alkyl substituted ammonium salt, a sulfonate, an alkyl sulfonate, a sulfate, a thiosulfate or a of your combinations.
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    [11]
    11. COMPOSITION according to claim 1, characterized by the fact that at least one hydrophobic group comprises a C1-C18 alkyl, a C2-C18 alkene, a C2-C18 alkaline, a polyether comprising the repeating units of (-CH 2 CH 2 O-), (-CH 2 CH (CH3) O-), or mixtures thereof, where the total number of repeat units is in the range from 3 to 100, a C6-C aryl 2 o, a benzyl, a C1-C18 alkylsulfonyl, a C6-C 2 o arylsulfonyl, a p-toluenesulfonyl group, or one of its combinations, and at least one hydrophilic group comprises a carboxylic acid, carboxylic acid salt, a sulfonic acid derivative, a sulfonic acid derived salt, a sulfuric acid derivative, a sulfuric acid derived salt, thiosulfate, a thiosulfate salt, a phosphoric acid derivative, a salt derived from phosphoric acid, an alkyl amine , an ammonium salt substituted by alkyl, a quaternized pyridine salt, a salt of quaternized imidazole or one of its combinations.
    [12]
    12. COMPOSITION according to claim 1, characterized by the fact that at least one hydrophobic group comprises a C1-C18 alkyl group, a benzyl, a p-toluenesulfonyl group, or one of its combinations and at least one group hydrophilic comprises a carboxylic acid, an alkyl substituted ammonium salt, a sulfonate, an alkyl sulfonate, a sulfate, a thiosulfate or one of its combinations.
    [13]
    13. COMPOSITION, according to claim 1, characterized in that at least one hydrophobic group comprises a C1-C18 alkyl, benzyl, or p-toluenesulfonyl group and at least one hydrophilic group comprises a thiosulfate or carboxymethyl group .
    [14]
    14. COMPOSITION, according to claim 1, characterized by the fact that the polysaccharide derivative has a degree of polymerization in the range from about 5 to about 1,400.
    Petition 870190055067, of 6/14/2019, p. 405/408
    4/5
    [15]
    15. COMPOSITION, according to claim 1, characterized by the fact that the polysaccharide derivative has a degree of substitution from about 0.001 to about 3.0.
    [16]
    16. COMPOSITION, according to claim 1, characterized by the fact that the 2% by weight polysaccharide derivative has a surface tension of 65 mN / m or less, as determined according to the ASTM Standard D1331,2015 method .
    [17]
    17. COMPOSITION, according to claim 1, characterized by the fact that in the form of a liquid, a gel, a powder, a hydrocolloid, an aqueous solution, a granule, a tablet, a capsule, a single compartment sachet, a multi-compartment sachet, a single-compartment pouch or a multi-compartment pouch.
    [18]
    18. COMPOSITION, according to claim 1, characterized by the fact that it still comprises at least one surfactant, an enzyme, a detergent adjuvant, a complexing agent, a polymer, a dirt release polymer, an enhancer polymer surfactant, a bleaching agent, a bleaching activator, a bleaching catalyst, a tissue conditioner, a clay, a foam enhancer, a soap foam suppressor, an anti-corrosion agent, a dirt suspending agent , an anti-dust redeposition agent, a dye, a bactericide, a stain inhibitor, an optical brightener, a perfume, a saturated or unsaturated fatty acid, a dye transfer inhibitor, a chelating agent, a colored dye, a cation calcium, a magnesium cation, a visual signaling ingredient, an antifoam, a structurant, a thickening agent, an anti-caking agent, a starch, sand, geli agent or one of its combinations.
    Petition 870190055067, of 6/14/2019, p. 406/408
    5/5
    [19]
    19. COMPOSITION, according to claim 18, characterized by the fact that the enzyme is a cellulase, a proteinase, an amylase, a lipase or one of its combinations.
    [20]
    20. METHOD FOR THE TREATMENT OF A SUBSTRATE, the method characterized by the fact that it comprises the steps:
    (A) to provide a composition comprising a polysaccharide derivative, wherein the polysaccharide derivative comprises a polysaccharide substituted by:
    (a) at least one hydrophobic group; and (b) at least one hydrophilic group;
    - wherein the polysaccharide is poly alpha-1,3-glucan, poly alpha-1,6-glucan, poly alpha-1,6-glucan or a mixture thereof;
    (B) placing the substrate in contact with the composition; and (C) optionally, rinsing the substrate;
    - where the substrate is the carpet, upholstery or surface.
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    同族专利:
    公开号 | 公开日
    EP3555142A1|2019-10-23|
    CA3046223A1|2018-06-21|
    AU2017376773A1|2019-06-20|
    US11066626B2|2021-07-20|
    CN110382553A|2019-10-25|
    EP3628691B1|2021-07-21|
    AU2017376773B2|2021-08-19|
    JP2020041150A|2020-03-19|
    KR20190091553A|2019-08-06|
    HUE055838T2|2021-12-28|
    EP3555142B1|2020-11-18|
    WO2018112187A1|2018-06-21|
    US20220041960A1|2022-02-10|
    US20200002646A1|2020-01-02|
    US20220056375A1|2022-02-24|
    CN111196863A|2020-05-26|
    PL3628691T3|2021-11-22|
    MX2019006868A|2019-09-23|
    ES2887376T3|2021-12-22|
    JP2020501568A|2020-01-23|
    EP3628691A1|2020-04-01|
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    法律状态:
    2020-02-11| B25A| Requested transfer of rights approved|Owner name: DUPONT INDUSTRIAL BIOSCIENCES USA, LLC (US) |
    2021-01-26| B25A| Requested transfer of rights approved|Owner name: NUTRITION AND BIOSCIENCES USA 4, INC. (US) |
    2021-08-31| B06W| Patent application suspended after preliminary examination (for patents with searches from other patent authorities) chapter 6.23 patent gazette]|
    2021-10-13| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    优先权:
    申请号 | 申请日 | 专利标题
    US201662435158P| true| 2016-12-16|2016-12-16|
    PCT/US2017/066395|WO2018112187A1|2016-12-16|2017-12-14|Amphiphilic polysaccharide derivatives and compositions comprising same|
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