COMPOSITION, METHOD FOR THE PRODUCTION OF A COMPOUND AND METHOD FOR THE TREATMENT OF A MATERIAL

专利摘要:
COMPOSITION, METHOD FOR THE PRODUCTION OF A COMPOUND, AQUEOUS OR HYDROCOLOID SOLUTION, METHOD FOR INCREASING THE VISCOSITY OF AN AQUEOUS COMPOSITION AND METHOD FOR THE TREATMENT OF A MATERIAL. The present invention relates to polyethylene alpha-1,3-glucan ether compounds which comprise the positively charged organic groups. The degree of substitution of the ether compounds is from about 0.05 to about 3.0. The present invention also relates to methods for producing the poly alpha-1,3-glucan ether compounds that have the positively charged organic groups, as well as methods for using these ether compounds to increase the viscosity of a composition. aqueous. The present invention also relates to aqueous and hydrocolloid solutions comprising the ether compounds.
公开号:BR112016014014B1
申请号:R112016014014-1
申请日:2014-12-17
公开日:2021-08-10
发明作者:T. Joseph Dennes；Andrea M. Perticone；Jayme L. Paullin
申请人:Nutrition & Biosciences USA 4, Inc.；
IPC主号:

专利说明:

[001] The present patent application claims the benefit of provisional applications US 1961/917,507 (filed on December 18, 2013) and 1962/014,273 (filed on June 19, 2014), both of which are incorporated herein by reference. in your totality. FIELD OF THE INVENTION
[002] The present invention relates to poly alpha-1,3-glucan derivatives. Specifically, the present invention relates to cationic poly alpha-1,3-glucan ethers and methods for their preparation and use as viscosity modifiers. BACKGROUND OF THE INVENTION
[003] Driven by a desire to find new polysaccharides structure is using the enzymatic or genetic engineering syntheses of microorganisms or plant hosts, Depositors discovered that polysaccharides are biodegradable, and can be economically produced from resource-based raw materials renewables. This polysaccharide is poly alpha-1,3-glucan, a glucan polymer characterized by having alpha-1,3-glycosidic bonds. This polymer was isolated by contacting an aqueous solution of sucrose with a glycosyltransferase enzyme isolated from Streptococcus salivarius (Simpson et al., Microbiology 141:1.451-1.460, 1995).
[004] The US patent 7,000,000 describes the preparation of a polysaccharide fiber comprising the hexose units, in which at least 50% of the hexose units within the polymer were linked by means of alpha-1,3 bonds -glycosidic using an enzyme from S. salivarius gtfJ. This enzyme uses sucrose as a substrate in a polymerization reaction producing a poly alpha-1,3-glucan and fructose as end products (Simpson et al., 1995). The polymer described forms a liquid crystalline solution when dissolved above a critical concentration in a solvent or a mixture comprising a solvent. From this solution, strong continuous fibers of the cotton type, highly suitable for use in textiles, were spun and used.
[005] Kiho et al., (Carb Res 189: 273-270, 1989) described the alkaline extraction and isolation of poly alpha-1,3-glucan from the fungus, Agrocybe cylindracea, which was further derivatized to the sodium carboxymethylglucan (CMG). This ether derivative exhibited anti-tumor properties against sarcoma. Similarly, Zhang et al., (international publication CN1283633) described the extraction of poly alpha-1,3-glucan from the medicinal fungus, Ganoderma lucidum, and its derivatization to CMG. BRIEF DESCRIPTION OF THE INVENTION
[006] In one embodiment, the present invention relates to a composition comprising a poly alpha-1,3-glucan ether compound represented by the structure:
- where (i) n is at least 6, (ii) each R, independently, is an H or a positively charged organic group, and (iii) the compound has a degree of substitution from about 0.05 to about 3.0.
[007] In a second embodiment, at least one positively charged organic group comprises a substituted ammonium group. This positively charged organic group may comprise a trimethyl ammonium group of a third embodiment. In a fourth embodiment, the positively charged organic group can be a quaternary ammonium group.
[008] In a fifth embodiment, at least one positively charged organic group comprises an alkyl group or hydroxyalkyl group. The compound in this embodiment can contain one type of positively charged organic group, or two or more types of positively charged organic group. At least one positively charged organic group can be a quaternary ammonium hydroxypropyl group, for example.
[009] In a sixth embodiment, the present invention relates to a method for producing a poly alpha-1,3-glucan ether compound. This method comprises contacting poly alpha-1,3-glucan, in a reaction under alkaline conditions, with at least one etherification agent comprising a positively charged organic group. At least one positively charged organic group is etherified with the poly alpha-1,3-glucan in this contact step, thereby producing a poly alpha-1,3-glucan ether compound represented by the structure:
- where (i) n is at least 6, (ii) each R independently is H or a positively charged organic group, and (iii) the compound has a degree of substitution from about 0.05 to about 3.0. A poly alpha-1,3-glucan ether compound produced by this method optionally can be isolated.
[010] In a seventh embodiment, the alkaline conditions of the reaction comprise an alkali hydroxide solution.
[011] In an eighth embodiment, the reaction comprises an organic solvent. The organic solvent is isopropanol in a ninth embodiment.
[012] In a tenth embodiment, the contact step of the method further comprises heating the reaction, and/or neutralizing the pH of the reaction.
[013] In an eleventh embodiment of the method, at least one positively charged organic group comprises a substituted ammonium group. At least one positively charged organic group comprises a trimethyl ammonium group in a twelfth embodiment.
[014] In a thirteenth embodiment, the present invention relates to an aqueous solution or hydrocolloid comprising a poly alpha-1,3-glucan ether compound represented by the structure:
- wherein (i) n is at least 6, (ii) each R, independently, is an H or a positively charged organic group, (iii) the compound has a degree of substitution from about 0.05 to about of 3.0, and (iv) the aqueous or hydrocolloid solution has a viscosity of at least about 10 cPs.
[015] In a fourteenth embodiment, the present invention relates to a method for increasing the viscosity of an aqueous composition. This method comprises contacting a poly alpha-1,3-glucan ether compound, as described herein, with an aqueous composition, thereby increasing the viscosity of the aqueous composition.
[016] In a fifteenth embodiment, the present invention relates to a method for treating a material. This method comprises contacting a material with an aqueous composition comprising a poly alpha-1,3-glucan ether compound as described herein. The poly alpha-1,3-glucan ether compound absorbs the surface of the material in certain embodiments of this method. DETAILED DESCRIPTION OF THE INVENTION
[017] Descriptions of all patent and non-patent literature cited in the present invention are incorporated herein by reference in their entirety.
[018] As used herein, the term "present invention" or "described invention" is not intended to be limiting, but generally applies to any of the inventions defined in the claims or described in the present invention. These terms are used interchangeably in the present invention.
[019] The terms "poly alpha-1,3-glucan", "alpha-1,3-glucan polymer" and "glucan polymer" are used interchangeably in the present invention. Poly alpha-1,3-glucan is a polymer comprising glucose monomeric units linked together by glycosidic bonds (i.e., glycosidic bonds), where at least about 50% of the glycosidic bonds are bonds. alpha-1,3-glycosidic. Poly alpha-1,3-glucan is a type of polysaccharide. The structure of poly alpha-1,3-glucan can be illustrated as follows:

[020] The poly alpha-1,3-glucan which can be used for the preparation of the poly alpha-1,3-glucan ester compounds of the present invention can be prepared using the chemical methods. Alternatively, it can be prepared by extraction from various organisms that, such as fungi, produce poly alpha-1,3-glucan. Alternatively, poly alpha-1,3-glucan can be enzymatically produced from sucrose using one or more glycosyltransferase (gtf) enzymes (e.g., gtfJ), as described in US Patent 7,000,000, and in US patent publications 2013/0.244,288 and 2013/0.244,287 (all of which are incorporated herein by reference), for example.
[021] The terms "glycosyltransferase enzyme", "gtf enzyme", "gtf enzyme catalyst", "gtf", and "glucansucrase" are used interchangeably in the present invention. The activity of a gtf enzyme in the present invention catalyzes the reaction of the sucrose substrate to produce the poly alpha-1,3-glucans and fructose products. Other products (by-products) of a gtf reaction can include glucose (results in which glucose is hydrolyzed from the intermediate complex of the glucosyl-gtf enzyme), various soluble oligosaccharides (eg, DP2-DP7), and leucrose (results in that glucose from the intermediate complex of the glucosyl-gtf enzyme is linked to fructose). Leukrose is a disaccharide consisting of glucose and fructose linked by an alpha-1.5 bond. Wild-type forms of glucosyltransferase enzymes generally contain (in the N-terminal to C-terminal direction) a signal peptide, a variable domain, a catalytic domain, and a glucan binding domain. The gtf in the present invention is classified under the family glycoside hydrolases 70 (GH70) according to the CAZy (active carbohydrate enzymes) database (Cantarel et al., Nucleic Acids Res. 37: D233-238, 2009).
[022] The percentage of glycosidic bonds between the poly alpha-1,3-glucan glucose monomer units used for the preparation of the poly alpha-1,3-glucan ester compounds of the present invention, which are alpha- 1.3 is at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, or 100% (or any integer in between 50% and 100%). In such embodiments, therefore, the poly alpha-1,3-glucan has an amount of less than about 50%, 40%, 30%, 20%, 10%, 5%, 4%, 3%, 2%, 1 %, or 0% (or any integer value between 0% and 50%) of non-alpha-1,3 glycosidic bonds.
[023] The poly alpha-1,3-glucan used for the production of the poly alpha-1,3-glucan ester compounds of the present invention is preferably linear / unbranched. In certain embodiments, the poly alpha-1,3-glucan does not have branch points less than or equal to about 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2% , or 1% of the branch points as a percentage of the glycosidic bonds in the polymer. Examples of branch points include alpha-1,6 branch points, such as those present in the mutant polymer.
[024] The terms "glycosidic bond" and "glycosidic bond" are used interchangeably in the present invention and refer to the type of covalent bond that joins a carbohydrate molecule (sugar) to another group such as another carbohydrate. The term "alpha-1,3-glucose bond" as used herein refers to the type of covalent bond that joins alpha-D-glucose molecules together through carbon atoms 1 and 3 in alpha rings. Adjacent D-glucose. This binding is illustrated in the poly alpha-1,3-glucan structure provided above. Herein, the term "alpha-D-glucose" will be referred to as "glucose".
[025] The terms "poly alpha-1,3-glucan ester compound", "poly alpha-1,3-glucan ester", and "poly alpha-1,3-glucan ester derivative" are used alternately in the present invention. A poly alpha-1,3-glucan ester compound of the present invention can be represented by the structure:

[026] In relation to the Formula of this structure, n can be at least 6, and each R, independently, can be a hydrogen atom (H) or a positively charged organic group. A poly alpha-1,3-glucan ether compound of the present invention has a degree of substitution from about 0.05 to about 3.0. Since the poly alpha-1,3-glucan ether compounds of the present invention possess one or more types of positively charged organic groups, these compounds can be considered "cationic".
[027] A poly alpha-1,3-glucan ether compound is termed an "ester" in the present invention, by virtue of which it comprises the substructure -CG-O-CO-C-, wherein "-CG-" represents 2, 4, or 6 carbons of a monomeric glucose unit of a poly alpha-1,3-glucan ester compound, and wherein "-C-" is comprised in the positively charged organic group.
[028] The poly alpha-1,3-glucan ester compounds described in the present invention are synthetic, artificial compounds.
[029] The term "positively charged organic group" as used herein, refers to a chain of one or more carbons ("carbon chain"), which has one or more hydrogens replaced by another atom or functional group (ie , a "substituted alkyl group"), wherein one or more of the substitutions is for a positively charged group. Whenever a positively charged organic group has a substitution in addition to a substitution by a positively charged group, such additional substitution may be by one or more hydroxyl groups, oxygen atoms (thereby forming an aldehyde or ketone group), alkyl groups , and/or additional positively charged groups. A positively charged organic group has a net positive charge since it comprises one or more positively charged groups.
[030] The terms "positively charged group", "positively charged ionic group" and "cationic group" are used interchangeably in the present invention. A positively charged group comprises a cation (a positively charged ion). Examples of positively charged groups include substituted ammonium groups, carbocation groups and acyl cation groups.
[031] A composition that is "positively charged" in the present invention, typically, that has more protons than electrons is repelled by other positively charged substances, but attracted to negatively charged substances.
[032] The terms "substituted ammonium group", "substituted ammonium ion" and "substituted ammonium cation" are used interchangeably in the present invention. A substituted ammonium group, in the present invention, comprises structure I:
- R2, R3 and R4 in the structure each independently represent a hydrogen atom or an alkyl, aryl, cycloalkyl, aralkyl or alkaryl group. The carbon atom (C) in structure I is part of the chain of one or more carbon atoms ("carbon chain") of the positively charged organic group. The carbon atom is either directly ether-bonded to an alpha-1,3-glucan polyglucan monomer, or is part of a chain of two or more ether-bonded carbon atoms to a poly alpha-glucan monomer. 1,3-glucan. The carbon atom in structure I can be -CH 2 , -CH- (wherein one H is replaced by another group, such as a hydroxy group), or -C (where both H's are replaced).
[033] A substituted ammonium group can be a "primary ammonium group", "secondary ammonium group", "tertiary ammonium group", or a "quaternary ammonium group", depending on the composition of R2, R3 and R4 in structure I. A primary ammonium group, in the present invention, refers to structure I where each of R2, R3 and R4 is a hydrogen atom (ie, -C-NH3+). A secondary ammonium group, in the present invention, refers to structure I where each of R2 and R3 is a hydrogen atom and R4 is an alkyl, aryl, or cycloalkyl group. A tertiary ammonium group herein refers to structure I where R2 is a hydrogen atom and each of R3 and R4 is an alkyl, aryl, or cycloalkyl group. A quaternary ammonium group, in the present invention, refers to structure I wherein each of R2, R3 and R4 is an alkyl, aryl, or cycloalkyl group (i.e., none of R2, R3 and R4 is a hydrogen atom) .
[034] A quaternary ammonium poly alpha-1,3-glucan ether, in the present invention, may comprise a trialkyl ammonium group (where each of R2, R3 and R4 is an alkyl group), for example. A trimethyl ammonium group is an example of a trialkyl ammonium group, where each of R2, R3 and R4 is a methyl group. It should be understood that a fourth member (ie, R1) implied by "quaternary" in this nomenclature is the chain of one or more carbon atoms of the positively charged organic group which is the ether linked to a poly alpha-1 glucose monomer ,3-glucan.
[035] An example of a quaternary ammonium poly alpha-1,3-glucan ether compound is hydroxypropyl trimethyl ammonium poly alpha-1,3-glucan. The positively charged organic group of this ether compound can be represented as structure II:
- wherein each of R2, R3 and R4 is a methyl group. Structure II is an example of a quaternary ammonium hydroxypropyl group.
[036] A "hydroxy alkyl" group refers to a substituted alkyl group in which one or more hydrogen atoms of the alkyl group are replaced by a hydroxy group. An example of a hydroxy group is a hydroxypropyl group; structure II comprises a hydroxypropyl group.
[037] A "halide" refers to a compound that comprises one or more halogen atoms (eg, fluorine, chlorine, bromine, iodine). A halide, in the present invention, can refer to a compound that comprises one or more halide groups such as fluoride, chloride, bromide, or iodide. A halide group can serve as a reactive group of an etherification agent.
[038] The term "reaction", "reaction composition", and "etherification reaction" are used interchangeably in the present invention and refer to a reaction comprising at least one poly alpha-1,3-glucan and one etherification agent. These components are usually dissolved and/or mixed in an aqueous alkaline hydroxide. The reaction is placed under suitable conditions (eg time, temperature) for the etherification agent to etherify one or more hydroxyl groups of the poly alpha-1,3-glucan glucose units with a positively charged organic group, therefore , obtaining a poly alpha 1,3-glucan ether compound.
[039] The term "alkaline conditions" in the present invention refers to a solution or mixture with a pH of at least 11 or 12. The alkaline conditions can be prepared by any means known in the art, such as by dissolving an alkali metal hydroxide in a solution or mixture.
[040] The terms "etherification agent" and "alkylating agent" are used interchangeably in the present invention. An etherifying agent, in the present invention, refers to an agent that can be used to etherify one or more hydroxyl groups of the glucose units of poly alpha-1,3-glucans with a positively charged organic group. An etherification agent therefore comprises a positively charged organic group.
[041] The term "poly alpha-1,3-glucan slurry" refers to an aqueous mixture that comprises the components of an enzymatic glycosyltransferase reaction such as poly alpha-1,3-glucan, sucrose, one or more enzymes glucosyltransferase, glucose and fructose. This composition is a fluid slurry as the poly alpha-1,3-glucan is not dissolved in it.
[042] The term "poly alpha-1,3-glucan wet cake" refers to poly alpha-1,3-glucan that has been separated from a slurry and washed with water or an aqueous solution. Poly alpha-1,3-glucan is not dried when making a wet cake.
[043] The term "degree of substitution" (DoS), as used herein, refers to the average number of substituted hydroxyl groups in each monomeric unit (glucose) of a poly alpha-1,3-glucan ether compound. Since there are three hydroxyl groups on each poly alpha-1,3-glucan monomer unit, the degree of substitution of a poly alpha-1,3-glucan ether compound of the present invention can be greater than 3.
[044] The term "molar substitution" (M.S), as used herein, refers to the number of moles of a positively charged organic group per monomeric unit of a poly alpha-1,3-glucan ether compound. Alternatively, MS can refer to the average number of moles of etherification agent used to react with each monomeric unit in the poly alpha-1,3-glucan (MS therefore can describe the degree of derivatization of an etherification agent ). It is noted that the M.S. value for poly alpha-1,3-glucan may have no upper limit. For example, when a positively charged organic group containing a hydroxyl group (eg, hydroxyethyl or hydroxypropyl) has been etherified with poly alpha-1,3-glucan, the hydroxyl group of the organic group may undergo a reaction, therefore, coupling more of the positively charged organic group to the poly alpha-1,3-glucan.
[045] The term "crosslink" refers to a chemical bond, atom, or group of atoms that connects two adjacent atoms in one or more polymer molecules. It should be understood that, in a composition comprising the cross-linked poly alpha-1,3-glucan ether, the cross-links may be between at least two poly alpha-1,3-glucan ether molecules (i.e. is, intermolecular crosslinks); it can also be intramolecular crosslinking. A "cross-linking agent", as used herein, is an atom or compound that can create cross-links.
[046] An "aqueous composition" refers to a solution or mixture, in which the solvent at least is about 20% by weight of water, for example, and which comprises the poly alpha-1,3-glucan and/or a poly alpha-1,3-glucan ether compound. Examples of aqueous compositions in the present invention are aqueous solutions and hydrocolloids.
[047] The terms "hydrocolloid" and "hydrogel" are used interchangeably in the present invention. A hydrocolloid refers to a colloidal system in which water is the dispersing medium. A "colloid" in the present invention refers to a substance that is microscopically dispersed throughout another substance. Therefore, a hydrocolloid in the present invention may also refer to a dispersion, emulsion, mixture, or solution of poly alpha-1,3-glucan and/or one or more poly alpha-1,3 ether compounds. -glucan in water or aqueous solution.
[048] The term "aqueous solution" in the present invention refers to a solution in which the solvent is water. The poly alpha-1,3-glucan and/or one or more poly alpha-1,3-glucan ether compounds of the present invention can be dispersed, mixed, and/or dissolved in an aqueous solution. An aqueous solution can serve as the dispersion medium for a hydrocolloid in the present invention.
[049] The terms "dispersant" and "dispersing agent" are used interchangeably in the present invention to refer to a material that promotes the formation and stabilization of a dispersion of one substance in another. A "dispersion" in the present invention refers to an aqueous composition comprising one or more particles (for example, any ingredient of a personal care product, pharmaceutical, food product, household product, or industrial product described herein. invention) which are dispersed, or evenly dispersed, throughout the aqueous composition. It is believed that the poly alpha-1,3-glucan ether compounds and/or the poly alpha-1,3-glucan ether compounds can act as dispersants in the aqueous compositions described in the present invention.
[050] The term "viscosity", as used herein, refers to the measure of the degree to which a fluid or an aqueous composition such as a hydrocolloid resists a force that tends to cause its fluidity. Various viscosity units that can be used in the present invention include centipoise (cPs) and Pascal-second (Pa.s). A centipoise is a hundredth of a poise; a poise is equal to 0.100 kg m-1.s-1. Therefore, the terms "viscosity modifier" and "viscosity modifying agent" as used in the present invention refer to anything that can change/modify the viscosity of an aqueous or fluid composition.
[051] The term "shear thinning behavior" as used herein refers to a reduction in the viscosity of the aqueous solution or hydrocolloid with increasing shear rate. The term "shear thickening behavior", as used herein, refers to an increase in the viscosity of the aqueous solution or hydrocolloid with an increase in the shear rate. The term "shear rate" in the present invention refers to the rate at which a progressive shear strain is applied to the aqueous solution or hydrocolloid. A shear strain can be applied rotationally.
[052] The term "contact" as used herein in connection with methods of increasing the viscosity of an aqueous composition refers to any action that results in bringing together an aqueous composition with the poly alpha-1,3-glucan and/ or a poly alpha-1,3-glucan ether compound. Contacting can be carried out by any means known in the state of the art, such as dissolving, mixing, stirring or homogenizing, for example.
[053] The terms "fabric", "textile", and "cloth" are used interchangeably in the present invention to refer to a woven material that has a network of natural and/or artificial fibers. Such fibers can be a thread or thread, for example.
[054] The term "fabric treatment composition" used herein is any composition suitable for fabric treatment in any way. Examples of such a composition include laundry detergents and fabric softeners.
[055] The terms "heavy duty detergents" and "all-purpose detergents" are used interchangeably in the present invention to refer to a detergent useful for the regular washing of white and colored fabrics at any temperature. The terms "light duty detergents" or "fine fabric detergents" are used interchangeably in the present invention to refer to a detergent useful for the care of delicate fabrics such as viscose, wool, silk, microfiber or other fabric that requires special cares. The term “special care” can include conditions of use of excess water, low agitation, and/or no bleach, for example.
[056] The term "composition for oral care" used herein is any composition suitable for treating a hard or soft surface in the oral cavity, such as the dental (teeth) and/or gingival surfaces.
[057] The term "absorption" in the present invention refers to the adhesion of a compound (eg the poly alpha-1,3-glucan ether) to the surface of a material.
[058] The "molecular weight" of the poly alpha-1,3-glucan and poly alpha-1,3-glucan ether compounds of the present invention can be represented as number average molecular weight (Mn) or as molecular weight weighted average (Mw). Alternatively, molecular weight can be represented as Daltons, grams/mol, DPw (Weighted Average Degree of Polymerization), or DPn (Number Average Degree of Polymerization). Various means are known in the state of the art to calculate these molecular weight parameters, such as high pressure liquid chromatography (HPLC), size exclusion chromatography (SEC), or gel permeation chromatography (GPC).
[059] The terms "percent by volume", "percent by volume", "% by vol" and "%v/v" are used interchangeably in the present invention. The percentage, by volume, of a solute in a solution can be determined using the Formula: [(volume of solute) / (volume of solution)] x 100%.
[060] The terms "percent by weight", "percent by weight (% by weight)" and "percent by weight (% w/w)" are used interchangeably in the present invention. Percent by weight refers to the percentage of material, on a mass basis, as it is composed of a composition, mixture or solution.
[061] The terms "increase", "intensify" and "enhance" are used interchangeably in the present invention. These terms refer to a greater quantity or activity, such as a quantity or activity slightly greater than the original quantity or activity, or an activity or quantity in large excess of the initial quantity or activity, including all quantities or activities in between. Alternatively, these terms can refer, for example, to an amount or activity that is at least 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% , 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, 125%, 150%, 175%, or 200% (or any whole number between 1 % and 20% higher than the amount or activity to which the increased amount or activity is being compared.
[062] The development of new poly alpha-1,3-glucan ether derivatives and methods for the preparation of such derivatives is desired due to its potential utility in various applications. There is great interest in understanding the applicability of poly alpha-1,3-glucan ether derivatives as viscosity and rheology modifiers of aqueous or hydrocolloid compositions.
[063] The embodiments of the present invention relate to a composition comprising a poly alpha-1,3-glucan ether compound represented by the structure:

[064] In relation to the Formula of this structure, n can be at least 6, and each R, independently, can be an H or a positively charged organic group. In addition, the poly alpha-1,3-glucan ether compound has a degree of substitution from about 0.05 to about 3.0.
[065] Significantly, a poly alpha-1,3-glucan ether compound of the present invention can modify the viscosity of an aqueous solution to which it is added. This viscosity modifying effect is often associated with a rheology modifying effect. Furthermore, when contacting an aqueous solution or hydrocolloid in the present invention with a surface (e.g., the fabric surface), one or more poly alpha-1,3-glucan ether compounds adsorbs to the surface.
[066] The degree of substitution (DoS) of a poly alpha-1,3-glucan ether compound described in the present invention, alternatively, can be from about 0.2 to about 2.0. Alternatively, the DoS can be at least about 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 , 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2 .3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or 3.0. It should be understood by those skilled in the art that since a poly alpha-1,3-glucan ether compound of the present invention has a degree of substitution between about 0.05 to about 3.0, and in because it is an ether, the R groups of the compound cannot only be hydrogen.
[067] The percentage of glycosidic bonds between the glucose monomer units of the poly alpha-1,3-glucan ether compounds of the present invention that is alpha-1,3 is at least about 50%. %, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, or 100% (or any whole number between 50% and 100%). In such embodiments, accordingly, the compound has less than about 50%, 40%, 30%, 20%, 10%, 5%, 4%, 3%, 2%, 1% or 0% (or any value integer between 0% and 50%) of the glycosidic bonds that are not alpha-1,3.
[068] The backbone of a poly alpha-1,3-glucan ether compound described in the present invention is preferably linear/unbranched. In certain embodiments, the composite does not have branch points less than or equal to about 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1% of branching as a percentage of the glycosidic bonds in the polymer. Examples of branch points include the alpha-1.6 branch points.
[069] The Formula of a poly alpha-1,3-glucan ether compound in certain embodiments may have an n value of at least 6. Alternatively, it may have an n value of at least 25, 50 75, 100, 150, 200, 250, 300, 350, 400, 450, 500, 600, 700, 800, 900, 1,000, 1,1.00, 1,200, 1,300, 1,400, 1,500, 1,600, 1,700, 1,800, 1,900 , 2,000, 2,100, 2,200, 2,300, 2,400, 2,500, 2,600, 2,700, 2,800, 2,900, 3,000, 3,100, 3,200, 3,300, 3,400, 3,500, 3,600, 3,700, 3,800, 3,900, or 4,000 (or any whole number between 25 and 4,000), for example. The value of n in other examples may still be in a range from 25 to 250, from 50 to 250, from 75 to 250, from 100 to 250, from 150 to 250, from 200 to 250, from 25 to 200, from 50 to 200, from 75 to 200, from 100 to 200, from 150 to 200, from 25 to 150, from 50 to 150, from 75 to 150, from 100 to 150, from 25 to 100, from 50 to 100, from 75 to 100, from 25 to 75, from 50 to 75, or from 25 to 50.
[070] The molecular weight of a poly alpha-1,3-glucan ether compound, described in the present invention, can be measured as the number average molecular weight (Mn) or as the weight average molecular weight (Mw). Alternatively, molecular weight can be measured in Daltons or grams/mol. It may also be useful to refer to the (weighted average degree of polymerization) DPw or DPn (number average degree of polymerization) of the poly alpha-1,3-glucan polymer component of the compound.
[071] The Mn or Mw of a poly alpha-1,3-glucan ether compound described in the present invention can be at least about 1,000. Alternatively, Mn or Mw can be at least about 1,000 to about 60,0000. Alternatively, the Mn or Mw can be at least about 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000, 75,000, 100,000, 150,000, 200,000, 250,000, 300,000, 350,000, 400,000, 450,000, 500,000, 550,000, 600,000 or (or any whole number between 2,000 and 600,000), for example.
[072] Each R group in the Formula of the poly alpha-1,3-glucan ether compound, independently, can be an H or a positively charged organic group. As defined above, a positively charged organic group comprises a chain of one or more carbon atoms that have one or more hydrogens replaced by another atom or functional group, wherein one or more of the substitutions is by a positively charged group.
[073] A positively charged group can be a substituted ammonium group, for example. Examples of substituted ammonium groups are primary, secondary, tertiary, and quaternary ammonium groups. Structure I represents a primary, secondary, tertiary or quaternary ammonium group, depending on the composition of R2, R3 and R4 in structure I. Each of R2, R3 and R4 in structure I independently represents a hydrogen atom or a group alkyl, aryl, cycloalkyl, aralkyl or alkaryl. Alternatively, each of R2, R3 and R4 independently can represent a hydrogen atom or an alkyl group. An alkyl group herein may be a methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl group, for example. Where two or three of R2, R3 and R4 are an alkyl group, they may be the same or different alkyl groups.
[074] The term "primary ammonium poly alpha-1,3-glucan ether compound" used herein may comprise a positively charged organic group that has an ammonium group. In this example, the positively charged organic group comprises structure I, where each of R2, R3 and R4 is a hydrogen atom. A non-limiting example of a positively charged organic group is represented by structure II where each of R2, R3 and R4 is a hydrogen atom. An example of a primary ammonium poly alpha-1,3-glucan ether compound can be represented in abbreviated form as ammonium poly alpha-1,3-glucan ether. It should be understood that a first member (i.e., R1) implied by "primary" in the nomenclature above is the chain of one or more carbon atoms of the positively charged organic group which is the ether linked to a poly alpha-glucose monomer. 1,3-glucan.
[075] The term "secondary ammonium poly alpha-1,3-glucan ether compound" used herein may comprise a positively charged organic group having a monoalkyl ammonium group, for example. In this example, the positively charged organic group comprises structure I where each of R2 and R3 is a hydrogen atom and R4 is an alkyl group. A non-limiting example of a positively charged organic group is represented by structure II where each of R2 and R3 is a hydrogen atom and R4 is an alkyl group. An example of a secondary ammonium poly alpha-1,3-glucan ether compound may be represented in abbreviated form herein as monoalkyl ammonium poly alpha-1,3-glucan ether (e.g., poly ether ammonium alpha-1,3-glucan from monomethyl, monoethyl, monopropyl, monobutyl, monopentyl, monohexyl, monoeptyl, monooctyl, monononyl or monodecyl). It should be understood that a second member (i.e., R1) implied by "secondary" in the above nomenclature is the chain of one or more carbon atoms of the positively charged organic group which is the ether linked to a poly alpha-glucose monomer. 1,3-glucan.
[076] The term "tertiary ammonium poly alpha-1,3-glucan ether compound" used herein may comprise a positively charged organic group that has a dialkyl ammonium group, for example. In this example, the positively charged organic group comprises structure I where R2 is a hydrogen atom and each of R3 and R4 is an alkyl group. A non-limiting example of a positively charged organic group is represented by structure II when R2 is a hydrogen atom and each of R3 and R4 is an alkyl group. An example of a tertiary ammonium poly alpha-1,3-glucan ether compound may be represented in abbreviated form as a dialkyl ammonium poly alpha-1,3-glucan ether (eg, the poly alpha-ether dimethyl, diethyl, dipropyl, dibutyl, dipentyl, dihexyl, diheptyl, dioctyl, dinonyl or didecyl ammonium 1,3-glucan). It should be understood that a third member (i.e., R1) implied by "tertiary" in the above nomenclature is the chain of one or more carbon atoms of the positively charged organic group which is the ether linked to a poly alpha-glucose monomer. 1,3-glucan.
[077] The term "quaternary ammonium poly alpha-1,3-glucan ether compound" used herein may comprise a positively charged organic group that has a trialkyl ammonium group, for example. In this example, the positively charged organic group comprises structure I where each of R2, R3 and R4 is an alkyl group. A non-limiting example of a positively charged organic group is represented by structure II where each of R2, R3 and R4 is an alkyl group. An example of a quaternary ammonium poly alpha-1,3-glucan ether compound can be represented in abbreviated form as trialkyl ammonium poly alpha-1,3-glucan ether (eg, the poly alpha-ether 1,3-ammonium glucan (trimethyl, triethyl, tripropyl, tributyl, tripentyl, trihexyl, triepyl, trioctyl, trinonyl or tridecyl). It should be understood that a fourth member (i.e., R1) implied by "quaternary" in the above nomenclature is the chain of one or more carbon atoms of the positively charged organic group which is the ether linked to a poly alpha-glucose monomer. 1,3-glucan.
[078] Additional non-limiting examples of substituted ammonium groups that can serve as a positively charged group in the present are depicted in structure I, when each of R2, R3 and R4 independently represents a hydrogen atom; an alkyl group such as a methyl, ethyl, or propyl group; an aryl group such as a phenyl or naphthyl group; an aralkyl group such as a benzyl group; an alkylaryl group; or a cycloalkyl group. Each of R2, R3 and R4 may further comprise an amino group or a hydroxyl group, for example.
[079] The nitrogen atom of a substituted ammonium group, represented by structure I, is attached to a chain of one or more carbon atoms as comprised in a positively charged organic group. This chain of one or more carbon atoms ("carbon chain") is an ether-linked poly alpha-1,3-glucan glucose monomer, and may have one or more substitutions in addition to the nitrogen atom substitution. substituted ammonium group. There may be 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms, for example, in a carbon chain in the present. To illustrate, the carbon chain of structure II is 3 carbon atoms in length.
[080] Examples of a carbon chain of a positively charged organic group that does not have a substitution other than substitution by a positively charged group include -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2- and -CH2CH2CH2CH2CH2- . In each of these examples, the first carbon atom in the chain is ether bonded to poly alpha-1,3-glucan glucose monomer, and the last carbon atom in the chain is bonded to a positively charged group. Where the positively charged group is a substituted ammonium group, the last carbon atom in the chain in each of these examples is represented by C in structure I.
[081] Where a carbon chain of a positively charged organic group has a substitution in addition to a substitution by a positively charged group, such additional substitution may be by one or more hydroxyl groups, oxygen atoms (hence, forming an aldehyde or ketone group), alkyl groups (eg, methyl, ethyl, propyl, butyl), and/or additional positively charged groups. A positively charged group is usually attached to the terminal carbon of the carbon chain.
[082] Examples of a carbon chain herein having one or more substitutions by a hydroxyl group include hydroxyalkyl groups (eg, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl) and dihydroxyalkyl groups (eg, dihydroxyethyl, dihydroxypropyl) , dihydroxybutyl, dihydroxypentyl). Examples of hydroxyalkyl and dihydroxyalkyl (diol) carbon chains include -CH(OH)-, -CH(OH)CH2-, -C(OH)2CH2-, -CH2CH(OH)CH2-, -CH(OH )CH2CH2-, -CH(OH)CH(OH)CH2-, -CH2CH2CH(OH)CH2-, -CH2CH(OH)CH2CH2-, -CH(OH)CH2CH2CH2-, -CH2CH(OH)CH(OH)CH2 -, -CH(OH)CH(OH)CH2CH2- and -CH(OH)CH2CH(OH)CH2-. In each of these examples, the first carbon atom in the chain is ether bonded to the poly alpha-1,3-glucan glucose monomer, and the last carbon atom in the chain is bonded to a positively charged group. Where the positively charged group is a substituted ammonium group, the last carbon atom in the chain in each of these examples is represented by C in structure I.
[083] Examples of a carbon chain herein that has one or more substitutions by an alkyl group include chains with one or more methyl, ethyl and/or propyl group substituents. Examples of methyl alkyl groups include -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-, which are both propyl groups that have a substitution by methyl. In each of these examples, the first carbon atom in the chain is ether bonded to poly alpha-1,3-glucan glucose monomer, and the last carbon atom in the chain is bonded to a positively charged group. Where the positively charged group is a substituted ammonium group, the last carbon atom in the chain in each of these examples is represented by C in structure I.
[084] Poly alpha-1,3-glucan ether compounds in certain embodiments described herein may contain a type of positively charged organic group such as an R group. For example, one or more ether positively charged organic groups bonded to the alpha-1,3-glucan polyglucan monomer may be hydroxypropyl trimethyl ammonium groups (structure II); the R groups in this particular example would therefore independently be the hydrogen and hydroxypropyl trimethyl ammonium groups.
[085] Alternatively, the poly alpha-1,3-glucan ether compounds described herein may contain two or more different types of positively charged organic groups as R groups.
[086] The poly alpha-1,3-glucan ether compounds of the present invention may comprise at least one nonionic organic group and at least one anionic group, for example. As another example, the poly alpha-1,3-glucan ether compounds of the present invention can comprise at least one nonionic organic group and at least one positively charged organic group.
[087] The present invention also relates to an aqueous solution or hydrocolloid comprising a poly alpha-1,3-glucan ether compound represented by the structure:

[088] In relation to the Formula of this structure, n can be at least 6, and each R, independently, can be an H or a positively charged organic group. In addition, the poly alpha-1,3-glucan ether compound has a degree of substitution from about 0.05 to about 3.0. The aqueous solution or hydrocolloid comprising the poly alpha-1,3-glucan ether compound has a viscosity of at least about 10 centipoise (cPs). The poly alpha-1,3-glucan ether compound in an aqueous or hydrocolloid solution can be any of the ether compounds described herein.
[089] Aqueous solutions or hydrocolloids comprising a poly alpha-1,3-glucan ether compound described in the present invention have a viscosity of at least about 10 cPs. Alternatively, an aqueous solution or hydrocolloid in the present invention has a viscosity of at least about 100, 250, 500, 750, 1,000, 1,500, 2,000, 2,500, 3,000, 3,500, 4,000, 4,500, 5,000, 5,500, 6,000, 6,500, 7,000, 7,500, 8,000, 8,500, 9,000, 9,500, 10,000, 10,500, 11,000, 12,000, 13,000, 14,000, 15,000, 20,000, 30,000, 40,000, 50,000, 60,000, 70,000, 80,000, 90,000, or 100,000 cPs (or any whole number between 100 and 100,000 cPs), for example.
[090] Viscosity can be measured with the aqueous or hydrocolloid solution, at any temperature between about 3°C to about 110°C (or any integer between 3 and 110°C), for example. Alternatively, viscosity can be measured at a temperature between about 4°C to 30°C, or about 20°C to 25°C. Viscosity can be measured at atmospheric pressure (about 760 torr) or whatever. another higher or lower pressure.
[091] The viscosity of an aqueous solution or hydrocolloid, described in the present invention can be measured using a viscometer or rheometer, or using any other means known in the state of the art. It should be understood by those skilled in the art that a rheometer can be used to measure the viscosity of said aqueous solutions and hydrocolloids of the present invention that exhibit shear thinning behavior or shear thickening behavior (i.e., liquids with viscosities that vary with flow conditions). The viscosity of such embodiments can be measured at a shear rotation rate of about 10 to 1000 rpm (revolutions per minute) (or any integer between 10 and 1000 rpm), for example. Alternatively, viscosity can be measured at a shear rotation rate of about 10, 60, 150, 250, or 600 rpm.
[092] The pH of an aqueous or hydrocolloid solution described in the present invention can be between about 2.0 to about 12.0. Alternatively, the pH can be about 2.0, 3.0, 4.0, 5.0, 6.0, 7.0, 8.0, 9.0, 10.0, 11.0 , 12.0; or between 5.0 and about 12.0; or between about 4.0 to about 8.0; or between about 3.0 and 11.0. In certain embodiments, the viscosity of the aqueous or hydrocolloid solution does not fluctuate largely at a pH between about 3.0 and 11.0.
[093] An aqueous composition of the present invention, such as an aqueous solution or hydrocolloid can comprise a solvent that has at least about 20% by weight of water. In other embodiments, at least one solvent is about 30, 40, 50, 60, 70, 80, 90, or 100% by weight water (or any integer value between 20 and 100% by weight), per example.
[094] A poly alpha-1,3-glucan ether compound described in the present invention may be present in an aqueous or hydrocolloid solution at a percentage by weight (% by weight) of at least about 0.01% , 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9% , 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0% , 4.5%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19% , 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, or 30%, for example.
[095] An aqueous solution or hydrocolloid, in the present invention, may comprise other components in addition to one or more poly alpha-1,3-glucan ether compounds. For example, the aqueous or hydrocolloid solution can comprise one or more salts, such as sodium salts (for example, of NaCl, Na2SO4). Other non-limiting examples of salts include those that have (i) a cation of aluminum, ammonium, barium, calcium, chromium (II or III), copper (I or II), iron (II or III), hydrogen, lead (II ), lithium, magnesium, manganese (II or III), mercury (I or II), potassium, silver, sodium strontium, tin (II or IV), or zinc, and (ii) an acetate, borate, bromate anion , bromide, carbonate, chlorate, chloride, chlorite, chromate, cyanamide, cyanide, dichromate, dihydrogen phosphate, ferricyanide, ferrocyanide, fluoride, hydrogen carbonate, hydrogen phosphate, hydrogen sulfate, hydrogen sulfide, hydride, hydroxide, hypochlorite , iodate, iodide, nitrate, nitride, nitrite, oxalate, oxide, perchlorate, permanganate, peroxide, phosphate, phosphite, phosphite, silicate, stannate, stanite, sulfate, sulfide, sulfite, tartrate, or thiocyanate. Therefore, any salt having a cation from (i) above and an anion from (ii) above may be in an aqueous or hydrocolloid solution, for example. A salt may be present in an aqueous or hydrocolloid solution at a percentage (%) by weight of from about 0.01% to about 10.00% (or any hundredth increment between 0.01% and 10.00%), for example.
[096] A poly alpha-1,3-glucan ether compound of the present invention is in a cationic form in the aqueous or hydrocolloid solution. The cationic groups of a poly alpha-1,3-glucan ether compound of the present invention may interact with salt anions that may be present in an aqueous or hydrocolloid solution. Such salt anions may be any of those listed in (II) above (eg the chloride anion).
[097] In alternative embodiments, a composition comprising the poly alpha-1,3-glucan and/or a poly alpha-1,3-glucan ether compound of the present invention may be non-aqueous (e.g., a dry composition). Examples of such embodiments include powders, granules, microcapsules, flakes or any other form of particulate material. Other examples include larger compositions such as pellets, bars, grains, granules, tablets, sticks or other agglomerates. A non-aqueous or dry composition in the present invention typically has an amount of less than 3, 2, 1, 0.5, or 0.1% by weight of water comprised.
[098] A poly alpha-1,3-glucan ether compound comprised in certain embodiments of the described composition may be cross-linked using any means known in the art. Such crosslinks can be borate crosslinks, where the borate is from any borate-containing compound (eg, acids, diborates, tetraborates, pentaborates, polymeric compounds such as Polybor®, polymeric boric acid compounds , alkaline borates), for example. Alternatively, crosslinks can be provided with polyvalent metals such as titanium or zirconium. Titanium crosslinks can be provided, for example, using titanium IV-containing compounds such as titanium ammonium lactate, titanium triethanolamine, titanium acetylacetonate, and titanium polyhydroxy complexes. Zirconium crosslinks can be provided using zirconium IV containing compounds such as zirconium lactate, zirconium carbonate, zirconium acetylacetonate, zirconium triethanolamine, diisopropylamine zirconium lactate and zirconium polyhydroxy complexes, for example. Alternatively, crosslinks can be provided with any crosslinking agent described in US Patents 4,462,917, 4,464,270, 4,477,360 and 4,799,550, all of which are incorporated herein by reference. A cross-linking agent (e.g., borate) may be present in an aqueous composition of the present invention at a concentration of about 0.2% to 20% by weight, or about 0.1, 0.2.0. .3, 0.4, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, or 20% by weight, for example.
[099] A poly alpha-1,3-glucan ether compound described in the present invention that is cross-linked typically has a higher viscosity in an aqueous solution compared to its non-cross-linked counterpart. Furthermore, a cross-linked poly alpha-1,3-glucan ether compound may have increased shear thickening behavior compared to its non-cross-linked counterpart.
[0100] The composition, in the present invention, optionally may contain one or more active enzymes. Non-limiting examples of suitable enzymes include proteases, cellulases, hemicellulases, peroxidases, lipolytic enzymes (e.g., metalolipolitic enzymes), xylanases, lipases, phospholipases, esterases (e.g., arylesterase, polyesterase), perhydrolases, cutinases, pectinases , pectate lyases, mannanases, keratinases, reductases, oxidases (e.g., choline oxidase), phenoloxidases, lipoxygenases, ligninases, pullulanases, tanases, pentosanases, malanases, beta-glucanases, arabinosidases, hyaluronidases, metalases, cholasons amadoriases, glucoamylases, arabinofuranosidases, phytases, isomerases, transferases and amylases. If an enzyme is included, it can be comprised in a composition in the present invention at about 0.0001 to 0.1% by weight (for example, from 0.01 to 0.03% by weight) of active enzyme (for example, , calculated as the pure enzyme protein), for example.
[0101] One or more cellulase enzymes optionally can be composed of a composition described in the present invention. The cellulase, in the present invention, may have endocellulase activity (EC 3.2.1.4), exocellulase activity (EC 3.2.1.91), or cellobiase activity (EC 3.2.1.21). The cellulase in the present invention is an "active cellulase" that has activity under conditions suitable for maintaining cellulase activity; which is within the state of the art to determine the proper conditions. In addition to being able to degrade cellulose, a cellulase, in certain embodiments, can also degrade cellulose ether derivatives such as carboxymethyl cellulose. Examples of cellulose ether derivatives believed to be stable to cellulase are described in US Patents 7,012,053, 7,056,880, 6,579,840, 7,534,759 and 7,576,048.
[0102] The cellulase described in the present invention can be derived from any microbial source, such as a bacteria or fungus. Cellulases, chemically modified or protein engineered mutant cellulases are included. Suitable cellulases include, but are not limited to, cellulases of the genus Bacillus, Pseudomonas, Streptomyces, Trichoderma, Humicola, Fusarium, Thielavia and Acremonium. As other examples, a cellulase can be derived from Humicola insolens, Myceliophthora thermophila or Fusarium oxysporum; these and other cellulases are described in US patents 4,435,307, 5,648,263, 5,691,178, 5,776,757 and 7,604,974, all of which are incorporated herein by reference. Examples of cellulases from Trichoderma reese are described in US patents 4,689,297, 5,814,501, 5,324,649, and international patent applications. WO 1992/06221 and WO 1992/06165, all of which are incorporated herein by reference. Examples of Bacillus cellulases are described in US patent 6,562,612, which is incorporated herein by reference. A cellulase, such as any of the above, preferably is in a mature form lacking an N-terminal signal peptide. Commercially available cellulases useful in the present invention include Celluzyme® and Carezyme® (Novozymes A/S); Clazinase® and Puradax® HA (DuPont Industrial Biosciences), and KAC-500 (B)® (Kao Corporation).
[0103] Alternatively, a cellulase described in the present invention can be produced by any means known in the art, as described in US patents 4,435,307, 5,776,757 and 7,604,974, which are incorporated herein by reference. For example, a cellulase can be produced recombinantly in a heterologous expression system, such as a microbial or fungal heterologous expression system. Examples of heterologous expression systems include bacterial (e.g. E. coli, Bacillus sp.) and eukaryotic systems. Eukaryotic systems may employ yeast (e.g., Pichia sp., Saccharomyces sp.) or fungal (e.g., Trichoderma sp., such as T. reesei, Aspergillus species, such as A. niger) expression systems, for example. example.
[0104] One or more cellulases can be directly added as an ingredient, when preparing the described composition. Alternatively, one or more cellulases can be indirectly (inadvertently) supplied in the described composition. For example, cellulase can be provided in a composition in the present invention by virtue of being present in a non-cellulase enzyme preparation used to prepare the composition. Cellulase in compositions where cellulase is indirectly supplied for that purpose may be present at about 0.1 to 10 ppb (eg, less than 1 ppm), for example. An advantage of a composition in the present invention, by virtue of employing a poly alpha-1,3-glucan ether compound instead of a cellulose ether compound, is that non-cellulase enzyme preparations may have the cellulase background activity can be utilized without the concern that the desired effects of glucan ether will be negated by cellulase background activity.
[0105] A cellulase in certain embodiments may be thermostable. Cellulase thermostability refers to the ability of the enzyme to retain activity after exposure to an elevated temperature (eg, from about 60 to 70°C) for a period of time (eg, from about 30 to 60 minutes ). The thermostability of a cellulase can be measured by its half-life (t1/2) given in minutes, hours or days, during which time half of the cellulase activity is lost under defined conditions.
[0106] A cellulase in certain embodiments may be stable over a wide range of pH values (for example, neutral or alkaline pH, such as pH from about 7.0 to about 11.0). Such enzymes can remain stable for a predetermined period of time (for example, at least about 15 min., 30 min., or one hour) under such pH conditions.
[0107] At least one, two, or more cellulases can be included in the composition, for example. The total amount of cellulase in a composition in the present invention is usually an amount that is suitable for the purpose of using cellulase in the composition (an "effective amount"). For example, an effective amount of cellulase in a composition intended to improve the feel and/or appearance of a fabric containing the cellulose is an amount that produces measurable improvements in fabric feel (eg, improves fabric softness and/or appearance , removing the scales and fibrils that tend to reduce the sharpness of the tissue appearance). As another example, an effective amount of a fabric stonewash cellulase composition of the present invention is that amount that will provide the desired effect (e.g., to produce a worn and faded appearance on seams and on fabric panels ). The amount of cellulase in a composition, in the present invention, may also depend on the process parameters 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 fabric is treated can be easily determined by one skilled in the art. In fabric care processes, cellulase may be present in an aqueous composition (eg, wash liquor), where a fabric is treated at a concentration that minimally is about 0.01 to 0.1 ppm protein total cellulase, or from about 0.1 to 10 ppb of total cellulase protein (e.g., less than 1 ppm), to a maximum of about 100, 200, 500, 1,000, 2,000, 3,000, 4,000, or 5,000 ppm total cellulase protein, for example.
[0108] The poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ethers of the present invention are mostly or completely (resistant) stable to be degraded by cellulase. For example, the percentage of degradation of a poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ether compound by one or more cellulases is less than 10%, 9%, 8%, 7 %, 6%, 5%, 4%, 3%, 2%, or 1%, ie 0%. Such percentage degradation can be determined, for example, by comparing the molecular weight of the polymer before and after treatment with a cellulase over a period of time (eg, about 24 hours).
[0109] The aqueous and hydrocolloid solutions of the present invention may have a shear thinning behavior or shear thickening behavior. The shear thinning behavior is observed as a reduction in the viscosity of the aqueous solution or hydrocolloid with increasing shear rate, while the shear thickening behavior is observed as an increase in the viscosity of the aqueous or hydrocolloid solution with the increase in shear rate. The modification of the shear thinning behavior or the shear thickening behavior of an aqueous solution of the present invention is due to mixing a poly alpha-1,3-glucan ether composition with the aqueous composition. Accordingly, one or more poly alpha-1,3-glucan ether compounds of the present invention can be added to an aqueous liquid composition to modify its rheological profile (i.e., the flow properties of the aqueous liquid, solution, or mixture are modified). In addition, one or more poly alpha-1,3-glucan ether compounds of the present invention can be added to an aqueous composition to modify its viscosity.
[0110] The rheological properties of aqueous solutions and hydrocolloids of the present invention can be observed by measuring the viscosity by increasing the shear rotation rate (for example, from about 10 rpm to about 250 rpm). For example, the shear thinning behavior of an aqueous solution or hydrocolloid described in the present invention can be observed as a reduction in viscosity (cPs) by at least about 5%, 10%, 15%, 20%, %, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95% (or any whole number in between 5% and 95%) as the shear rotation rate increases from about 10 rpm to 60 rpm, 10 rpm to 150 rpm, 10 rpm to 250 rpm, 60 rpm to 150 rpm, 60 rpm to 250 rpm , or 150 rpm to 250 rpm. As another example, the shear thickening behavior of an aqueous solution or hydrocolloid described in the present invention can be observed as an increase in viscosity (cPs) by at least about 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, 125% , 150%, 175%, or 200% (or any whole number between 5% and 200%) as the shear rotation rate increases from about 10 rpm to 60 rpm, 10 rpm to 150 rpm, 10 rpm to 250 rpm, 60 rpm for 150 rpm, 60 rpm for 250 rpm, or 150 rpm for 250 rpm.
[0111] An aqueous or hydrocolloid solution described in the present invention may be in the form of, and/or comprised in, a personal care product, pharmaceutical products, food products, household products, or industrial products. The poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ether compounds of the present invention can be used as thickening agents and/or dispersing agents in each of these products. Such a thickening agent may be used in conjunction with one or more other types of thickening agents, if desired, such as those described in US patent 8,541,041, the disclosure of which is incorporated herein by reference.
The personal care products in the present invention are not especially limited and, for example, include skin care compositions, cosmetic compositions, antifungal compositions, and antibacterial compositions. The personal care products described in the present invention may be in the form of, for example, lotions, creams, muds, balms, ointments, ointments, gels, liquids, combinations thereof and the like. The personal care products described in the present invention can include at least one active ingredient, if desired. An active ingredient is generally recognized as an ingredient that causes an intended pharmacological effect.
[0113] In certain embodiments, a skin care product may be applied to the skin to treat skin damage related to a lack of moisture. A skin care product can also be used to treat the visual appearance of the skin (eg, reduce the appearance of scaly, cracked, and/or red skin) and/or the tactile sensation of the skin (eg, reduce roughness and/or dryness of the skin while enhancing the smoothness and subtlety of the skin). A skin care product usually can include at least one active ingredient for treating or preventing skin conditions, providing a cosmetic effect, or providing a moisturizing benefit to the skin, such as zinc oxide, petroleum jelly. , white petroleum jelly, mineral oil, cod liver oil, lanolin, dimethicone, hard fat, vitamin A, allantoin, calamine, kaolin, glycerin, or colloidal oatmeal, and combinations thereof. A skin care product may include one or more natural moisturizing factors, such as ceramides, hyaluronic acid, glycerin, squalane, amino acids, cholesterol, fatty acids, triglycerides, phospholipids, glycosphingolipids, urea, linoleic acid, glycosaminoglycans, mucopolysaccharides, sodium lactate, or sodium pyrrolidone carboxylate, for example. Other ingredients that may be included in a skin care product include, without limitation, glycerides, apricot seed oil, canola oil, squalane, squalene, coconut oil, corn oil, jojoba oil, jojoba wax, lecithin, olive oil, safflower oil, sesame oil, shea butter, soybean oil, sweet almond oil, sunflower oil, tea tree oil, shea butter, palm oil, cholesterol, cholesterol esters , wax esters, fatty acids, and orange oil.
[0114] A personal care product, in the present invention, may also be in the form of makeup, lipstick, mascara, rouge, foundation, blush, eyeliner, lip pencil, gloss, other cosmetics, sunscreen, sun block, nail polish , mousse, hairspray, styling gel, nail conditioner, shower gel, shower gel, body wash, face wash, shampoo, hair conditioner (with or without rinse), rinse cream, hair dye, hair coloring product, hair shine product, hair serum, hair anti-frizz product, hair end separation repair product, lip balm, skin conditioner, cold cream, moisturizer, body spray, soap, body scrub , exfoliating, astringent, exfoliating lotion, depilatory, permanent waving solution, anti-dandruff formulation, antiperspirant composition, deodorant, shaving product, pre-shave products, after-shave product, cleanser, skin gel, rinse, comp toothpaste, toothpaste, or mouthwash, for example.
[0115] A pharmaceutical product of the present invention may be in the form of an emulsion, liquid, elixir, emulsion, gel, suspension, solution, cream, or ointment, for example. Furthermore, a pharmaceutical product of the present invention may be in the form of any of the personal care products described in the present invention, such as an antibacterial or antifungal composition. A pharmaceutical product may further comprise one or more pharmaceutically acceptable carriers, diluents, and/or pharmaceutically acceptable salts thereof. A poly alpha-1,3-glucan ether compound described in the present invention can also be used in capsules, encapsulants, tablet coatings, and as excipients for drugs and drugs.
[0116] Examples of non-limiting food products in the present invention include vegetables, meat, and soy pies; modified seafood; modified cheese sticks; cream soups; meat sauces and sauces; salad dressing; Mayo; onion rings; jams, jellies, and syrups; pie filling; potato products such as french fries and extruded french fries; pasta for fried foods, pancakes/waffles and cakes; animal feed; drinks; frozen desserts; Ice cream; cultured dairy products such as cottage cheese, yogurt, sour cheeses and creams; icing cake and icings; stirred toppings; fermented and unleavened roasts; and the like.
[0117] The poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ether compounds, aqueous compositions and hydrocolloids described in the present invention can be used to provide one or more of the following physical properties to a food product (or any personal care product, pharmaceutical, or industrial product): thickener, freeze/thaw stability, lubricity, moisture retention and release, texture, consistency, shape retention, emulsification, binding, suspension, dispersion, and gelling, for example. The poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ether compounds described in the present invention typically can be used in a food product at a level of from about 0.01 to about 5% by weight, for example.
[0118] A poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ether compound described in the present invention can be comprised in a food product or any other ingestible material (e.g. pharmaceutical preparation, enteric) in an amount which provides the desired degree of thickening and/or dispersion. For example, the concentration or amount of a poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ether compound in a product, on a weight basis, can be about 0.1 to 3% by weight, from 0.1 to 4% by weight, from 0.1 to 5% by weight, or from 0.1 to 10% by weight.
[0119] A domestic and/or industrial product of the present invention may be in the form of the plaster joint tape compounds; mortars; grouts; cement renders; spray plaster; stucco cement; stickers; muds; wall/ceiling texturizers; binders and technological aids for tape molding, extrusion forming, injection molding and ceramics; spray adhesives and suspension / dispersion aids for pesticides, herbicides and fertilizers; fabric care products such as fabric softeners and laundry detergents; hard surface cleaners; air deodorizers; polymer emulsions; gels such as water-based gels; surfactant solutions; paints, such as water-based paints; protective coatings; stickers; sealants and sealants; dyes, such as water-based dyes; metalworking fluids; emulsion-based metal cleaning fluids used in electroplating, phosphating, plating and/or general metal cleaning operations; hydraulic fluids (for example, those used for weakening in cavity bottom operations); and aqueous mineral suspensions, for example.
[0120] The poly alpha-1,3-glucan and/or a poly alpha-1,3-glucan ether compound described in the present invention may be comprised in a personal care product, pharmaceutical products, household products, or industrial products in an amount that provides a desired degree of thickening or dispersion, for example. Examples of a concentration or amount of a poly alpha-1,3-glucan ether compound in a product, on a weight basis, may be from about 0.1 to 3% by weight, from 1 to 2% by weight, from 1.5 to 2.5% by weight, from 2.0% by weight, from 0.1 to 4% by weight, from 0.1 to 5% by weight, or from 0.1 to 10 % by weight.
[0121] The compositions described in the present invention may be in the form of a composition for the treatment of tissue. A fabric treatment composition of the present invention can be used for hand washing, machine washing and/or for other purposes such as soaking and/or pre-treating fabrics, for example. A fabric treatment composition may take the form of, for example, a laundry detergent; fabric softener; any additional product for washing, rinsing, or drying; unit dose; or spray. Liquid form fabric treatment compositions may be in the form of an aqueous composition as described herein. In other aspects, a fabric treatment composition may be in a dry form such as an added granular detergent or fabric drying softener sheet. Other non-limiting examples of fabric treatment compositions in the present invention include: the heavy-duty and all-purpose washing agents in granules or powder, the heavy-duty and all-purpose washing agents in gel, liquid or mud; liquid or dry detergents for fine (eg delicate) fabrics; cleaning aids, such as bleach additives, “stain stick”, or pre-treatments; substrate loaded products such as dry and wet wipes, pads, or sponges; sprayers and vapors.
[0122] A detergent composition described in the present invention may be in any useful form, for example, as powders, granules, slurries, bars, unit dose, or liquid. A liquid detergent can be aqueous, typically containing up to about 70% by weight of water and 0% by weight to about 30% by weight of organic solvent. They can also be in the form of a compact type gel that only contains about 30% by weight of water.
[0123] A detergent composition usually comprises in the present invention one or more surfactants, wherein the surfactant is selected from nonionic surfactants, anionic surfactants, cationic surfactants, ampholytic surfactants, zwitterionic surfactants, semipolar nonionic surfactants and their mixtures . 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 still others embodiments, the level is from about 5% to about 40% by weight of the detergent composition. A detergent will usually contain from 0% by weight to about 50% by weight of an anionic surfactant, such as linear alkylbenzene sulfonate (LAS), alpha-olefin sulfonate (AOS), alkyl sulfate (fatty alcohol sulfate). ) (AS), alcohol ethoxy sulfate (AEOS or AES), secondary alkane sulfonates (SAS), alpha-sulfo fatty acid methyl esters, alkyl- or alkenylsuccinic acid, or soap. In addition, a detergent composition optionally may contain from 0% by weight to about 40% by weight of a nonionic surfactant such as alcohol ethoxylate (AEO or EA), carboxylated alcohol ethoxylates, nonylphenol ethoxylate, alkylpolyglycoside, ethoxylated alkyldimethylamineoxide, fatty acid monoethanolamide, fatty acid monoethanolamide, or alkyl polyhydroxy fatty acid amide (as described, for example, in WO 1992/06154, which is incorporated herein by reference).
[0124] A detergent composition typically comprises in the present invention one or more detergent adjuvant agents or adjuvant systems. In some embodiments that incorporate at least one adjuvant, the cleaning compositions comprise at least about 1%, between about 3% to about 60%, or even from about 5% to about 40%. %, adjuvant by weight of composition. Adjuvants include, but are not limited to the alkali metal, ammonium and alkanolammonium salts of polyphosphates, alkali metal silicates, alkaline earth and alkali metal carbonates, aluminosilicates, polycarboxylate compounds, hydroxypolycarboxylate ether, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3,5-trihydroxy-benzene-2, 4, 6-trisulfonic acid, and carboxymethylaxissuccinic acid, various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine acid tetraacetic acid and nitrilatriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, citric acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethylaxissuccinic acid, and their soluble salts. Indeed, it is contemplated that any suitable adjuvant will find use in various embodiments of the present invention. Examples of a detergent adjuvant or complexing agent include zeolite, diphosphate, triphosphate, phosphonate, citrate, nitrilatriacetic acid (NTA), ethylene diamine tetraacetic acid (EDTA), diethylene triamine pentaacetic acid (DTMPA), alkyl- or alkenylsuccinic acid , soluble silicates or layered silicates (eg Hoechst's SKS-6). A detergent can also be non-adjuvant, i.e. essentially free of detergent adjuvant.
[0125] In some embodiments, adjuvants form the water-soluble complexes of hardness ions (eg sequestering adjuvants) such as citrates and polyphosphates (eg sodium tripolyphosphate and sodium tripolyphosphate hexahydrate, potassium tripolyphosphate , and mixed potassium and sodium tripolyphosphate, and the like). It is contemplated that any suitable adjuvant will find use in the present invention, including those known in the art (See, for example, EP patent 2,100,949).
[0126] In some embodiments, adjuvants for use in the present invention include phosphate adjuvants and non-phosphate adjuvants. In some embodiments, the adjuvant is a phosphate adjuvant. In some embodiments, the adjuvant is a non-phosphate adjuvant. If present, adjuvants are used at a level from 0.1% to 80%, or from 5% to 60%, or from 10% and 50% by weight of the composition. In some embodiments, the product comprises a mixture of phosphate and non-phosphate adjuvants. Suitable phosphate builders include monophosphates, diphosphates, tripolyphosphates or oligomeric polyphosphates, including the alkali metal salts of these compounds, including sodium salts. In some embodiments, an adjuvant may be sodium tripolyphosphate (STPP). Furthermore, the composition may comprise carbonate and/or citrate, preferably citrate which helps to achieve a pH neutral composition. Other suitable non-phosphate adjuvants include homopolymers and copolymers of polycarboxylic acids and their partially or completely neutralized salts, monomeric polycarboxylic acids and hydroxycarboxylic acids and their salts. In some embodiments, salts of the compounds mentioned above include the ammonium and/or alkali metal salts, i.e., the lithium, sodium, and potassium salts, including the sodium salts. Suitable polycarboxylic acids include acyclic, alicyclic, heterocyclic and aromatic carboxylic acids, which in some embodiments may contain at least two carboxyl groups which in each case are separated from each other; than two carbon atoms.
[0127] The detergent composition of the present invention may comprise at least one chelating agent. Suitable chelating agents include, but are not limited to copper, iron and/or manganese chelating agents and mixtures thereof. In embodiments where at least one chelating agent is used, the composition comprises from about 0.1% to about 15%, or even from about 3.0% to about 10%, of the agent. chelator, by weight of the composition.
[0128] The detergent composition of the present invention may comprise at least one deposition aid. Suitable deposition aids include, but are not limited to, polyethylene glycol, polypropylene glycol, polycarboxylate, soil release polymers such as polyteleftic acid, clays such as kaolinite, montmorillonite, attapulgite, illite, bentonite, halloysite, and their mixtures.
[0129] The detergent composition of the present invention may comprise one or more dye transfer inhibiting agents. Suitable polymeric dye transfer inhibiting agents include, but are not limited to, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, N-vinylpyrrolidone and N-vinylimidazole copolymers, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. Additional dye transfer inhibiting agents include manganese phthalocyanine, peroxidases, polyvinylpyrrolidone polymers, polyamine N-oxide polymers, N-vinylpyrrolidone and N-vinylimidazole copolymers, polyvinyloxazolidones and polyvinylimidazoles and/or mixtures thereof; examples of chelating agents include ethylene diamine tetraacetic acid (EDTA); diethylene triamine pentamethylene phosphonic acid (DTPMP); hydroxy-ethane diphosphonic acid (HEDP); N,N'-disuccinic ethylenediamine acid (EDDS); methyl glycine diacetic acid (MGDA); diethylene triamine pentaacetic acid (DTPA); propylene diamine tetraacetic acid (PDT A); 2-hydroxypyridine-N-oxide (HPNO); or methyl glycine diacetic acid (MGDA); N,N-diacetic acid glutamic acid (N,N-dicarboxymethyl glutamic acid tetrasodium salt (GLDA); nitrilatriacetic acid (NTA), 4,5-dihydroxy-m-benzenedisulfonic acid; citric acid and all its salts, N-hydroxyethylethylenediaminetriacetic acid (HEDTA), triethylentetraminhexacetic acid (TTHA), N-hydroxyethyliminodiacetic acid (HEIDA), dihydroxyethylglycine (DHEG), ethylenediaminetetrapropionic acid (EDTP) and its derivatives, which can be used alone or in combination with any of the above. In embodiments where at least one dye transfer inhibiting agent is used, a composition in the present invention may 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 composition.
[0130] A detergent composition in the present invention may comprise silicates. In some of these embodiments, sodium silicates (e.g., sodium disilicate, sodium metasilicate, and/or crystalline layered silicates) find use. In some embodiments, silicates are present at a level from about 1% to about 20% by weight of the composition. In some embodiments, silicates are present at a level of from about 5% to about 15% by weight of the composition.
[0131] A detergent composition in the present invention may comprise dispersants. Suitable water-soluble organic materials include, but are not limited to homo- or copolymeric acids or their salts, wherein the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by no more than two carbon atoms.
[0132] A detergent composition in the present invention may additionally comprise one or more enzymes. Examples of enzymes include proteases, cellulases, hemicellulases, peroxidases, lipolytic enzymes (e.g., metalolipolitic enzymes), xylanases, lipases, phospholipases, esterases (e.g., arylesterase, polyesterase), perhydrolases, cutinases, pectinases, lyases of pectate, mannanases, keratinases, reductases, oxidases (e.g., choline oxidase, phenoloxidase), phenoloxidases, lipoxygenases, ligninases, pullulanases, tanases, pentosanases, malanases, beta-glucanases, arabinosidases, hyaluronidases, metal chondroases, chondroases , glucoamylases, alpha-amylases, beta-amylases, galactosidases, galactanases, catalases, carageenases, hyaluronidases, keratinases, lactases, ligninases, peroxidases, phosphatases, polygalacturonases, pullulanases, rhamnogalactanases, phytaloses, rhamnogalactanoses, metallurgiases, rhamnogalactanoses, metallamines , isomerases, transferases and/or amylases in any combination.
[0133] Any cellulase described above is contemplated for use in the detergent compositions described. Suitable cellulases include, but are not limited to Humicola insolens cellulases (see, for example, US patent 4,435,307). Examples of cellulases contemplated for use in the present invention are those that have the benefit for color care for a textile. Examples of cellulases that provide a color care benefit are described in EP 0.495,257, EP 0.531,372, EP 531,315, publications WO 1996/11262, WO 1996/29397, WO 1994/07998; WO 1998/12307; WO 1995/24471, WO 1998/08940, US patents 5,457,046, 5,686,593 and 5,763,254, all of which are incorporated herein by reference. Examples of commercially available cellulases useful in a detergent include Cellusoft®, Celluclean®, Celluzyme®, and Carezyme® (Novo Nordisk A/S and from Novozymes A/S); Clazinese®, Puradax HA®, and Revitalenz™ (DuPont Industrial Biosciences); Biotouch® (AB Enzymes); and KAC-500(B)™ (Kao Corporation). Additional cellulases are described, for example, in US patents 7,595,182, US 8,569,033, US 7,138,263, US 3,844,890, US 4,435,307, US 4,435,307 and GB 2,095,275.
[0134] In some embodiments of the present invention, the detergent compositions of the present invention may comprise one or more enzymes, each at a level of from about 0.00001% to about 10% by weight of the composition and material balance cleaning aids by weight of the composition. In some other embodiments of the present invention, the detergent compositions also comprise each of the enzymes at a level of about 0.0001% to about 10%, about 0.001% to about 5%, about 0.001% to about from 2%, about 0.005% to about 0.5%, enzyme by weight of the composition.
[0135] Suitable proteases include those of animal, vegetable or microbial origin. In some embodiments, microbial proteases are used. In some embodiments, chemically or genetically modified mutants are included. In some embodiments, the protease is a serine protease, preferably an alkaline microbial protease or a trypsin-like protease. Examples of alkaline proteases include subtilisins, especially those derived from Bacillus (e.g. subtilisin, lentus, amyloliquefaciens, subtilisin Carlsberg, subtilisin 309, subtilisin 147 and subtilisin 168). Additional examples include the mutant proteases described in US patents RE 34,606, 5,955,340, 5,700,676, 6,312,936 and 6,482,628, all of which are incorporated herein by reference. Additional examples of protease include, but are not limited to, trypsin (e.g., of porcine or bovine origin) and the Fusarium protease described in WO 1989/06270. In some embodiments, commercially available protease enzymes include, but are not limited to Maxatase®, Maxacal™, Maxapem™, Opticlean®, Optimase®, Properase®, Purafect®, Purafect® Oxp, Puramax™, Excellase™, Preferenz™ proteases (for example P100, P110, P280), the Effectenz™ proteases (for example P1000, P1050, P2000), proteases (for example Excellenz™ P1000), Ultimase®, E Purafast™ (Genencor); Alcalase®, Savinase®, Primase®, Durazym™, Polarzyme®, Ovozyme®, Kannase®, Liquanase®, Neutrase®, Relase® and Esperase® (Novozymes); BLAP™ and BLAP™ variants (Henkel Kommanditgesellschaft auf Aktien, Duesseldorf, Germany), and KAP (B. alkalophilus subtilisina; Kao Corp., Tokyo, Japan). Several proteases are described in publications WO 1995/23221, WO 1992/21760, WO 2009/149200, WO 2009/149144, WO 2009/149145, WO 2011/072099, WO 2010/056640, WO 2010/056653, WO 2011/140364 , WO 2012/151534, patent application 2008/0090747, and US patents. 5,801,039, 5,340,735, 5,500,364, 5,855,625, RE 34,606, 5,955,340, 5,700,676, 6,312,936, 6,482,628, 8,530,219, and various other patents. In some other embodiments, neutral metalloproteases find use in the present invention, including, but not limited to, the neutral metalloproteases described in publications WO 1999/014341, WO 1999/033960, WO 1999/014342, WO 1999/034003, WO 2007/044993, WO 2009/058303 and WO 009/058661, all of which are incorporated herein by reference. Examples of metalloproteases include nprE, the recombinant form of the neutral metalloprotease expressed in Bacillus subtilis (See, for example, publication WO 2007/044993), and PMN, the neutral metalloprotease purified from Bacillus amiloliquefaciens.
[0136] Suitable mannanases include, but are not limited to those of bacterial or fungal origin. Chemically or genetically modified mutants are included in some embodiments. Several mannanases are known to find use in the present invention (See, for example, US Patents 6,566,114, 6,602,842, and 6,440,991, all of which are incorporated herein by reference). Commercially available mannanases that can be used in the present invention include, but are not limited to Mannastar®, Purabrite™, and Mannaway®.
[0137] Suitable lipases include those of bacterial or fungal origin. Chemically modified, proteolytically modified, or protein engineered mutants are included. Examples of useful lipases include those from the Humicola genera (for example H. lanuginosa, EP patents 258,068 and EP 305,216; H. insolens, WO 1996/13580), Pseudomonas (for example PP alcaligenes or Pseudomonas, EP patent 218,272; P cepacia, EP patent 331,376; P. stutzeri, GB patent 1,372,034; strain P. fluorescens and Pseudomonas sp SD 705, publications WO 1995/06720 and WO 1996/27002; P. wisconsinensis, publication WO 1996/12012); (for example, B. subtilis, Dartois et al., Biochemica et Biophysica Acta 1131: 253-360; B. stearothermophilus, JP 1964/744992; B. pumilus, publication WO 1991/16422) and Bacillus. Furthermore, a number of cloned lipases find use in some embodiments of the present invention, including but not limited to Penicillium Camemberti lipase (Vide, Yamaguchi et al., Gene. 103: 61-67 [1991]), Geotricum candidum lipase ( See, Schimada et al., J. Biochem, 106: 383-388 [1989]), and various Rhizopus lipases, such as R.delemar lipase ( Vide, Hass et al., Gene 109: 117-113 [1991]) , an R. niveus lipase (Kugimiya et al., Biosci Biotech Biochem 56: 716719 [1992]) and the R. oryzae lipase. Additional lipases useful in the present invention, for example, include those described in publications WO 1992/05249, WO 1994/01541, WO 1995/35381, WO 1996/00292, WO 1995/30744, WO 1994/25578, WO 1995/14783 , WO 1995/22615, WO 1997/04079, WO 1997/07202, EP 407225 and EP 260105. Other types of lipase polypeptide enzymes such as cutinases also find use in some embodiments of the present invention, including but not limited to cutinase derived from Pseudomonas mendocina (See, publication WO 1988/09367), and cutinase derived from Fusarium solani pisi ( See, publication WO 1990/09446). Examples of certain commercially available lipase enzymes useful in the present invention include M1 Lipase™, Luma Fast™, and Lipomax™ (Genencor); Lipex®, Lipolase® and Lipolase® Ultra (Novozymes); and Lipase P™ "Amano" (Amano Pharmaceutical Co. Ltd., Japan).
[0138] Suitable polyesterases, for example, include those described in WO 2001/34899, WO 2001/14629 and US patent 6,933,140.
[0139] The detergent composition of the present invention may also comprise the 2,6-beta-D-fructan hydrolase, which is effective for the removal / cleaning of certain biofilms present in the household appliance and / or industrial textiles / laundry.
[0140] Suitable amylases include, but are not limited to those of bacterial or fungal origin. Chemically or genetically modified mutants are included in some embodiments. Amylases which find use in the present invention include, but are not limited to alpha-amylases obtained from B. licheniformis (see, for example, GB patent 1,296,839). Additional suitable amylases include those described in publications WO 1995/10603, WO 1995/26397, WO 1996/23874, WO 1996/23873, WO 1997/41213, WO 1999/19467, WO 2000/60060, WO 2000/29560, WO 1999/23211, WO 1999/46399, WO 2000/60058, WO 2000/60059, WO 1999/42567, WO 2001/14532, WO 2002/092797, WO 2001/66712, WO 2001/88107, WO 2001/96537, WO 2002/10355, WO 1994/02597, WO 2002/31124, WO 1999/43793, WO 1999/43794, WO 2004/113551, WO 2005/001064, WO 2005/003311, WO 2001/64852, WO 2006/063594, WO 2006/066594, WO 2006/066596, WO 2006/012899, WO 2008/092919, WO 2008/000825, WO 2005/018336, WO 2005/066338, WO 2009/140504, WO 2005/019443, WO 2010/091221, WO 2010/088447, WO 2001/34784, WO 2006/012902, WO 2006/031554, WO 2006/136161, WO 2008/101894, WO 2010/059413, WO 2011/098531, WO 2011/080352, WO 2011/080353, WO 2011/080354, WO 2011/082425, WO 2011/082429, WO 2011/076123, WO 2011/087836, WO 2011/076897, WO 1994/183314, WO 1995/35382, WO 1999/09183, WO 1998/26078, WO 1999/02702, WO 1997/ 43424, WO 1999/29876, WO 1991/00353, WO 1996/05295, WO 1996/30481, WO 1997/10342, WO 2008/088493, WO 2009/149419, WO 2009/061381, WO 2009/100102, WO 2010/ 104675, WO 2010/117511, and WO 2010/115021, all of which are incorporated herein by reference.
Suitable amylases, for example, include commercially available amylases such as Stainzyme®, Stainzyme Plus®, Natalase®, Duramyl®, Termamyl®, Termamyl Ultra®, Fungamyl® and BAN™ (Novo Nordisk A/S and Novozymes A/S); Rapidase®, Powerase®, Purastar® and Preferenz™ (DuPont Industrial Biosciences).
[0142] Suitable peroxidases / oxidases contemplated for use in the compositions include those of plant, bacterial or fungal origin. Chemically modified or protein engineered mutants are included. Examples of peroxidases useful for the present invention include those of the Coprinus genus (for example, C. cinereus, publications WO 1993/24618, WO 1995/10602, and WO 1998/15257), as well as those referenced in publications WO 2005/056782 , WO 2007/106293, WO 2008/063400, WO 2008/106214, and WO 2008/106215. Commercially available peroxidases useful in the present invention, for example, include Guardzyme™ (Novo Nordisk A/S and Novozymes A/S).
[0143] In some embodiments, peroxidases are used in combination with hydrogen peroxide or a source thereof (for example, a percarbonate, perborate or persulfate) in the compositions of the present invention. In some alternative embodiments, oxidases are used in combination with oxygen. Both types of enzymes are used for the "bleaching solution" (ie to prevent the transfer of a textile dye from one dyed fabric to another fabric when the fabrics are washed together in a wash liquor), preferably , together with an enhancing agent (See, for example, publications WO 1994/12621 and WO 1995/01426). Suitable peroxidases / oxidases include, but are not limited to those of plant, bacterial or fungal origin. Chemically or genetically modified mutants are included in some embodiments.
[0144] Enzymes that may be comprised in a detergent composition described in the present invention may 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 derivative of boric acid (eg an aromatic borate ester).
[0145] A detergent composition in the present invention may contain about 1% by weight to about 65% by weight of a detergent adjuvant or complexing agent such as zeolite, diphosphate, triphosphate, phosphonate, citrate, nitrilatriacetic acid ( NTA), ethylene diamine tetraacetic acid (EDTA), diethylenetriamine pentaacetic acid (DTMPA), alkyl alkenylsuccinic acid, soluble silicates or layered silicates (eg SKS-6 from Hoechst). A detergent can also be adjuvant, i.e. essentially free of detergent adjuvant.
[0146] A detergent composition in certain embodiments may comprise one or more other types of polymers in addition to a poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ether compound. 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/acrylic acid copolymers and lauryl methacrylate/acrylic acid copolymers.
[0147] A detergent composition in the present invention may contain a bleaching system. For example, a bleach system can comprise a source of H 2 O 2 such as perborate or percarbonate which can be combined with a peracid forming bleach activator such as tetracetylethylenediamine (TAED) or nonanoyloxybenzene sulfonate (NOBS). Alternatively, a bleach system can contain peracids (for example, the amide, imide, or peroxyacid type sulfone). Still alternatively, a bleaching system may be an enzymatic bleaching system comprising perhydrolase, for example, such as the system described in WO 2005/056783.
[0148] The detergent composition of the present may also contain conventional detergent ingredients such as fabric conditioners, clays, foam boosters, suds suppressors, anti-corrosion agents, soil suspending agents, anti-fouling redeposition agents, dyes, bactericides, stain inhibitors, optical brighteners, or perfumes. The pH of a detergent composition in the present invention (measured in an aqueous solution at the use concentration), in general, is neutral or earth alkaline (eg, pH from about 7.0 to about 11.0).
[0149] The specific forms of detergent compositions that can be adapted for the purposes described in the present invention are described, for example, in patents US 2009/0.209,445 A1, US 2010/0.081,598 A1, US 700,1878 B2, EP 1,504 994 B1, WO 2001/085888 A2 , WO 2003/089562 A1 , WO 2009/098659 A1 , WO 2009/098660 A1 , WO 2009/112992 A1 , WO 2009/124160 A1 , WO 2009/152031 A1 , WO 2010/059483 A1, WO 2010/088112 A1, WO 2010/090915 A1, WO 2010/135238 A1, WO 2011/094687 A1, WO 2011/094690 A1, WO 2011/127102 A1, WO 2011/163428 A1, WO 2008/000567 A1, WO 2006/045391 A1 , WO 2006/007911 A1 , WO 2012/027404 A1 , EP patent 1,740,690 B1 , WO 2012/059336 A1 , US 6,730,646 B1 , WO 2008/087426 A1 , WO 2010/116139 A1 , and WO 2012/104613A1 , all of which are incorporated herein by reference.
[0150] The laundry detergent compositions in the present invention optionally may be heavy duty (multifaceted) laundry detergent compositions. Examples of heavy duty laundry detergent compositions comprise a detersive surfactant (from 10% to 40% by weight/weight), including an anionic detersive surfactant (selected from a straight or branched chain or random chain group, sulfates of substituted or unsubstituted alkyl, alkyl sulfonates, alkoxylated alkyl sulfate, alkyl phosphates, alkyl carboxylates, and/or mixtures thereof), and optionally non-ionic surfactant (selected from a straight or branched chain group or random, substituted or unsubstituted alkyl alkoxylated alkyl alcohol, for example, ethoxylated C8-C18 alkyl alcohols and/or C6-C12 alkyl phenol alkoxylates, wherein the weight ratio of anionic detersive surfactant (with a hydrophilic index ( HIC) from 6.0 to 9) for the nonionic 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 phosphonium compounds, alkyl ternary sulfonium compounds, and/or mixtures thereof ); zwitterionic and/or amphoteric detergent surfactants (selected from a group of alkanolamine sulfo-betaines); ampholytic surfactants; non-ionic semipolar and their mixtures.
[0151] A detergent in the present invention, such as a heavy duty detergent composition, optionally may include a surfactant boosting polymer consisting of amphiphilic alkoxylated grease cleaning polymers (selected from a group of alkoxylated polymers having properties branched hydrophilic and hydrophobic, such as alkoxylated polyalkyleneimines in the range from 0.05 wt% to 10 wt%) and/or random graft polymers (usually comprising hydrophilic backbone comprising the monomers selected from the group consisting of: unsaturated C1-C6 carboxylic acids, ethers, alcohols, aldehydes, ketones, esters, sugar units; and; maleic anhydride, saturated polyalcohols such as glycerol, and mixtures thereof, and secondary chain(s) ) hydrophobic(s) selected from the group consisting of C4-C25 alkyl group, polypropylene, polybutylene, vinyl ester of a mono-carboxylic acid the saturated C1-C6, C1-C6 alkyl ester of acrylic or methacrylic acid, and mixtures thereof.
[0152] A detergent in the present invention, such as a heavy duty detergent composition, optionally may include additional polymers such as soil release polymers (include terminal anionically encapsulated polyesters, eg SRP1, polymers comprising at least one monomer unit selected from saccharide, dicarboxylic acid, polyol and combinations thereof, in random or block configuration, ethylene terephthalate based polymers and copolymers in random or block configuration, for example REPEL -O-TEX SF, SF-2 and SRP6, Texcare SRA100, SRA300, SRN100, SRN170, SRN240, SRN300 and SRN325, Marloquest SL), anti-redeposition polymers (0.1% by weight to 10% by weight), include the carboxylate polymers, such as polymers comprising at least one monomer selected from acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, acid citraconic, methylenemalonic acid, and any mixture thereof, homopolymer of vinylpyrrolidone, and/or polyethylene glycol, with molecular weight in the range from 500 to 100,000 Da); and polymeric carboxylate (such as maleate/random acrylate copolymer or polyacrylate homopolymer).
[0153] A detergent in the present invention, such as a heavy duty laundry detergent composition, optionally may further include saturated or unsaturated fatty acids, preferably saturated or unsaturated C12-C24 fatty acids (0% by weight) 10% by weight); deposition aids in addition to a poly alpha-1,3-glucan ether compound described in the present invention (examples include polysaccharides, cellulosic polymers, poly diallyl dimethyl ammonium halides (DADMAC), and DAD MAC copolymers with vinyl pyrrolidone, acrylamide, imidazoles, imidazolinium halides, and mixtures thereof, in random or block configuration, cationic guar gum, cationic starch, cationic polyacylamides, and mixtures thereof.
[0154] A detergent in the present invention, such as a heavy duty detergent composition, optionally may further include dye transfer inhibiting agents, examples thereof include manganese phthalocyanine, peroxidases, polyvinylpyrrolidone polymers, polyvinylpyrrolidone polymers. polyamine N-oxide, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylaxazolidones and polyvinylimidazoles and/or mixtures thereof; chelating agents, examples thereof include ethylene-diamine-tetraacetic acid (EDTA), diethylene triamine pentamethylene phosphonic acid (DTPMP), hydroxy-ethane diphosphonic acid (HEDP), ethylenediamine N,N'-disuccinic acid (EDDS) , methyl glycine diacetic acid (MGDA), diethylene triamine pentaacetic acid (DTPA), propylene diamine tetraacetic acid (PDT A), 2-hydroxypyridine-N-oxide (HPNO), or methyl glycine diacetic acid (MGDA), N,N-diacetic acid glutamic acid (N,N-dicarboxymethyl glutamic acid tetrasodium salt (GLDA), nitrilatriacetic acid (NTA), 4,5-dihydroxy-m-benzenedisulfonic acid, citric acid and all its salts, N-hydroxyethylethylenediaminetriacetic acid (HEDTA), triethylentetraminehexaacetic acid (TTHA), N-hydroxyethyliminodiacetic acid (HEIDA), dihydroxyethylglycine (DHEG), ethylendiaminetetrapropionic acid (EDTP), and its derivatives.
[0155] A detergent in the present invention, such as a heavy duty laundry detergent composition, optionally may include silicone based or fatty acid suds suppressors; hueing dyes, calcium and magnesium cations, visual signaling ingredients, defoamer (0.001% by weight to about 4.0% by weight), and/or a builder/thickener (0.01% by weight to 5% by weight) ) selected from the group consisting of diglycerides and triglycerides, ethylene glycol distearate, microcrystalline cellulose, microfiber cellulose, biopolymers, xanthan gum, gellan gum, and mixtures thereof). Such a builder/thickener would be in addition to one or more poly alpha-1,3-glucan compounds comprised in the detergent.
[0156] A detergent of the present invention may be in the form of a solid heavy dry/laundry detergent composition, for example. Such detergent may include: (i) a detersive surfactant, such as any anionic detersive surfactant described in the present invention, any nonionic detersive surfactant described in the present invention, any cationic detersive surfactant described in the present invention, any zwitterionic and/or amphoteric detersive surfactant described in the present invention, any described ampholytic surfactant, any semipolar nonionic surfactant, and mixtures thereof; (ii) an adjuvant, such as any phosphate-free adjuvant (eg zeolite adjuvants in the range of 0% by weight to less than 10% by weight), any phosphate adjuvant (eg sodium tri-polyphosphate in the range of 0% by weight to less than 10% by weight), citric acid, citrate salts and nitrilatriacetic acid, any silicate salt (eg sodium or potassium silicate or sodium metasilicate in the 0% range by weight to less than 10% by weight); any carbonate salt (for example, sodium carbonate and/or sodium bicarbonate in the range of 0% by weight to less than 80% by weight), and mixtures thereof; (iii) a bleaching agent, such as any photobleach (for example, the sulfonated zinc phthalocyanines, sulfonated aluminum phthalocyanines, coloring xanthenes, and mixtures thereof), any hydrophobic or hydrophilic bleach activator (for example, the oxybenzene sulfonate dodecanoyl, decanoyl oxybenzene sulfonate, decanoyl oxybenzoic acid or its salts, 3,5,5-trimethyl hexanoyl oxybenzene sulfonate, tetraacetyl ethylene diamine-TAED, nonanoyloxybenzene sulfonate-NOBS, nitrile quats, and mixtures thereof). any source of hydrogen peroxide (e.g., inorganic perhydrate salts, examples of which include the sodium mono- or tetrahydrate salt groups of perborate, percarbonate, persulfate, perphosphate or persilicate), any preformed hydrophilic and/or hydrophobic peracids (for example, percarboxylic acids and salts, percarbonic acids and salts, perimide acids and salts, peroxymonosulfuric acids and salts, and mixtures thereof); and/or (iv) any other components, such as a bleach catalyst (examples of imine bleach activators include iminium cations and polyions, iminium zwitterions, modified amines, modified amine oxides, N-sulfonyl imines , N-phosphonyl imines, N-acyl imines, thiadiazole dioxides, perfluoroimines, cyclic sugar ketones, and mixtures thereof), and a metal-containing bleach catalyst (eg, the cations of copper, iron, titanium, ruthenium, tungsten, molybdenum or manganese, together with auxiliary metal cations such as zinc or aluminum and a sequestrate such as EDTA, ethylenediaminetetra (methylenephosphonic acid).
[0157] The compositions described in the present invention may be in the form of a dishwashing detergent composition. Examples of dishwashing detergents include those automatic dishwashing detergents (commonly used in dishwashers) and manual dishwashing detergents. The detergent composition may be in any dry or liquid/aqueous form as described in the present invention, for example. Components that may be included in certain embodiments of a detergent composition, for example, include one or more of a phosphate-based bleaching agent; oxygen or chlorine; non-ionic surfactant; alkali salt (eg metasilicates, alkali metal hydroxides, sodium carbonate); any active enzyme described in the present invention; anti-corrosion agent (eg sodium silicate); defoaming agent; additives to retard enamel removal 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 (powdered detergents).
[0158] Dishwashing detergents such as an automatic dishwashing detergent or liquid detergent may comprise (i) a nonionic surfactant, including any nonionic surfactant, alkoxylated alcohol surfactant, poly(oxyalkylated), ethoxylated alcohol capped-epoxy, or amine oxide surfactant present in an amount from 0 to 10% by weight; (ii) an adjuvant, in the range of about 5 to 60% by weight, including any phosphate adjuvant (for example, the mono-phosphates, di-phosphates, tri-polyphosphates, other oligomeric polyphosphates, sodium tripolyphosphate (STPP) , any phosphate-free adjuvant (for example, amino acid-based compounds including methyl glycine diacetic acid [MGDA] and its salts or derivatives, N,N-diacetic acid glutamic acid [GLDA] and the its salts or derivatives, iminodisuccinic acid (IDS) and salts or derivatives thereof, carboxy methyl inulin and its salts or derivatives, nitrilatriacetic acid [NTA], diethylene triamine pentaacetic acid [DTPA], B-alanindiacetic acid [B -ADA] and their salts), homopolymers and copolymers of polycarboxylic acids and partially or completely neutralized, their monomeric polycarboxylic acids and hydroxycarboxylic acids and their salts in the range of 0.5% by weight to 50% by weight, or polymers sulfonated / carboxylated in the range of about 0.1% by weight to about 50% by weight; (iii) a drying aid in the range of about 0.1% by weight to about 10% by weight (eg polyesters, especially anionic polyesters, optionally together with other monomers with 3 to 6 functionalities - normally the acid, alcohol or ester functionalities which are conducive to polycondensation, polycarbonate-, polyurethane- and/or polyurea-polyorganosiloxane compounds or their precursor compounds, in particular the reactive cyclic carbonate and urea type); (iv) a silicate in the range of about 1% by weight to about 20% by weight (for example, sodium or potassium silicates such as sodium disilicate, sodium metasilicate and crystalline layered silicates); (v) an inorganic bleach (eg perhydrate salts such as perborate, percarbonate, perphosphate, persulfate and persilicate salts) and/or an organic bleach (eg organic peracids such as diacyl- and tetraacylperoxides, especially diperoxydodecanedioic acid, diperoxytetradecanedioic acid, and diperoxyhexadecanedioic acid); (vi) a bleach activator (e.g. organic peracid precursors in the range of about 0.1 wt% to about 10 wt%) and/or bleach catalyst (e.g. manganese triazacyclononane and related complexes; Co, Cu, Mn, and Fe bispyridylamine and related complexes, and cobalt(III) pentamine acetate and related complexes); (vii) a metal care agent in the range of about 0.1% by weight to 5% by weight (for example, the benztriazoles, metal salts and complexes, and/or silicates); and/or (viii) any active enzyme described in the present invention, in the range of about 0.01 to 5.0 mg of active enzyme per gram of automatic dishwashing detergent composition, and an enzyme stabilizer component (per example, oligosaccharides, polysaccharides, and inorganic divalent metal salts).
[0159] Several examples of detergent formulations comprising at least one poly alpha-1,3-glucan ether compound (for example, a quaternary ammonium poly alpha-1,3-glucan such as poly alpha - hydroxypropyl trimethyl ammonium 1,3-glucan) are described below (from 1 to 19): (1) A detergent composition formulated as a granulate having a bulk density of at least 600 g/L comprising : linear alkylbenzene sulfonate (calculated in terms of acid) by about 7 to 12% by weight; alcohol ethoxy sulfate (eg, C12-C18 alcohol, 1-2 ethylene oxide [EO]) or alkyl sulfate (eg, C16-C18) at about 1 to 4% by weight; alcohol ethoxylate (for example the C14-C15 alcohol) at about 5 to 9% by weight; about 14 to 20% by weight sodium carbonate; soluble silicate (for example, Na2O2SiO2) at about 2 to 6% by weight; zeolite (eg NaAlSiO4) at about 15 to 22% by weight; about 0 to 6% by weight sodium sulfate; sodium citrate/citric acid at about 0 to 15% by weight; about 11 to 18% by weight sodium perborate; TAED at about 2 to 6% by weight; about 2% by weight poly alpha-1,3-glucan ether; other polymers (eg acrylic/maleic acid copolymer, PVP, PEG) at about 0 to 3% by weight; optionally, an enzyme(s) (calculated as pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (eg suds suppressors, perfumes, optical brighteners, photobleach) 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: linear alkylbenzene sulfonate (calculated in terms of acid) at about 6 to 11% by weight; alcohol ethoxysulfate (eg, C12-C18 alcohol, 1-2 EO) or alkyl sulfate (eg, C16-C18) at about 1 to 3% by weight; alcohol ethoxylate (for example the C14-C15 alcohol) at about 5 to 9% by weight; about 15 to 21% by weight sodium carbonate; soluble silicate (eg Na2O2SiO2) at about 1 to 4% by weight; zeolite (eg NaAlSiO4) at about 24 to 34% by weight; sodium sulfate, at about 4 to 10% by weight; sodium citrate/citric acid at about 0 to 15% by weight; about 11 to 18% by weight sodium perborate; TAED at about 2 to 6% by weight; poly alpha-1,3-glucan ether up to about 2% by weight; other polymers (eg acrylic/maleic acid copolymer, PVP, PEG) at about 1 to 6% by weight; optionally, an enzyme(s) (calculated as pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (eg suds suppressors, perfumes, optical brighteners, photobleach) 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 alkylbenzene sulfonate (calculated in terms of acid) at about 5 to 9% by weight; alcohol ethoxysulfate (for example, C12 -C18 alcohol, 7 EO) at about 7 to 14% by weight; soap as a fatty acid (for example, the C16-C22 fatty acid) at about 1 to 3% by weight; about 10 to 17% by weight sodium carbonate; soluble silicate (eg Na2O2SiO2) at about 3 to 9% by weight; zeolite (eg NaAlSiO4) at about 23 to 33% by weight; about 0 to 4% by weight sodium sulfate; about 8 to 16% by weight sodium perborate; TAED at about 2 to 8% by weight; phosphonate (e.g., EDTMPA) at about 0 to 1% by weight; poly alpha-1,3-glucan ether up to about 2% by weight; other polymers (eg acrylic/maleic acid copolymer, PVP, PEG) at about 0 to 3% by weight; optionally, an enzyme(s) (calculated as pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (eg suds suppressors, perfumes, optical brightener) at about 0 to 5% by weight. (4) A detergent composition formulated as a granulate having a bulk density of at least 600 g/L comprising: linear alkylbenzene sulfonate (calculated in terms of acid) at about 8 to 12% by weight; alcohol ethoxylate (eg, C12 -C18 alcohol, 7 EO) at about 10 to 25% by weight; about 14 to 22% by weight sodium carbonate; soluble silicate (for example, Na2O2SiO2) at about 1 to 5% by weight; zeolite (eg NaAlSiO4) at about 25 to 35% by weight; sodium sulfate, at about 0 to 10% by weight; about 8 to 16% by weight sodium perborate; TAED at about 2 to 8% by weight; phosphonate (e.g., EDTMPA) at about 0 to 1% by weight; poly alpha-1,3-glucan ether up to about 2% by weight; other polymers (eg acrylic/maleic acid copolymer, PVP, PEG) at about 1 to 3% by weight; optionally, an enzyme(s) (calculated as pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (eg suds suppressors, perfumes) at about 0 to 5% by weight. (5) An aqueous liquid detergent composition comprising: linear alkylbenzene sulfonate (calculated in terms of acid) at about 15 to 21% by weight; alcohol ethoxylate (e.g., C12-C18 alcohol, 7 EO; or C12-C15 alcohol, 5 OE), at about 12 to 18% by weight; soap as a fatty acid (eg oleic acid) at about 3 to 13% by weight; alkenylsuccinic acid (C12-C14) at about 0 to 13% by weight; about 8 to 18% by weight aminoethanol; citric acid at about 2 to 8% by weight; phosphonate at about 0 to 3% by weight; poly alpha-1,3-glucan ether up to about 2% by weight; other polymers (eg PVP, PEG) at about 0 to 3% by weight; about 0 to 2% by weight borate; ethanol, about 0 to 3% by weight; about 8 to 14% by weight propylene glycol; optionally, an enzyme(s) (calculated as pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (eg, dispersants, suds suppressors, perfume, optical brightener) at about 0 to 5% by weight. (6) An aqueous liquid detergent composition comprising: linear alkylbenzene sulfonate (calculated in terms of acid) at about 15 to 21% by weight; alcohol ethoxylate (e.g., C12-C18 alcohol, 7 EO; or C12-C15 alcohol, 5 OE) at about 3 to 9% by weight; soap as a fatty acid (eg oleic acid) at about 3 to 10% by weight; zeolite (eg NaAlSiO4) at about 14 to 22% by weight; potassium citrate about 9 to 18% by weight; about 0 to 2% by weight borate; poly alpha-1,3-glucan ether up to about 2% by weight; other polymers (eg PVP, PEG) at about 0 to 3% by weight; ethanol, about 0 to 3% by weight; anchor polymers (e.g., methacrylate/lauryl acrylic acid copolymer, 25:1 molar ratio, MW 3800) at about 0 to 3% by weight; about 0 to 5% by weight glycerol; optionally, an enzyme(s) (calculated as pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (eg, 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: fatty alcohol sulfate at about 5 to 10% by weight, fatty acid ethoxylated monoethanolamide at about from 3 to 9% by weight; about 0 to 3% by weight fatty acid soap; sodium carbonate, at about 5 to 10% by weight; soluble silicate (eg Na2O2SiO2) at about 1 to 4% by weight; zeolite (eg NaAlSiO4) at about 20 to 40% by weight; about 2 to 8% by weight sodium sulfate; about 12 to 18% by weight sodium perborate; TAED at about 2 to 7% by weight; poly alpha-1,3-glucan ether up to about 2% by weight; other polymers (eg acrylic/maleic acid copolymer, PEG) at about 1 to 5% by weight; optionally, an enzyme(s) (calculated as pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (eg, optical brightener, suds suppressors, perfumes) at about 0 to 5% by weight. (8) A detergent composition formulated as a granulate comprising: linear alkylbenzene sulfonate (calculated in terms of acid) at about 8 to 14% by weight; about 5 to 11% by weight ethoxylated fatty acid monoethanolamide; from about 0 to 3% by weight fatty acid soap; sodium carbonate, at about 4 to 10% by weight; soluble silicate (eg Na2O2SiO2) at about 1 to 4% by weight; zeolite (eg NaAlSiO4) at about 30-50% by weight; sodium sulfate, at about 3 to 11% by weight; sodium citrate, at about 5 to 12% by weight; poly alpha-1,3-glucan ether up to about 2% by weight; other polymers (eg, PVP, acrylic/maleic acid copolymer, PEG) at about 1 to 5% by weight; optionally, an enzyme(s) (calculated as pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (eg suds suppressors, perfumes) at about 0 to 5% by weight. (9) A detergent composition formulated as a granulate comprising: linear alkylbenzene sulfonate (calculated in terms of acid) at about 6 to 12% by weight; nonionic surfactant at about 1 to 4% by weight; from about 2 to 6% by weight fatty acid soap; about 14 to 22% by weight sodium carbonate; zeolite (eg NaAlSiO4) at about 18-32% by weight; sodium sulfate, at about 5 to 20% by weight; about 3 to 8% by weight sodium citrate; about 4 to 9% by weight sodium perborate; bleach activator (eg NOBS or TAED) at about 1 to 5% by weight; poly alpha-1,3-glucan ether 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 pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (eg, optical brightener, perfume) at about 0 to 5% by weight. (10) An aqueous liquid detergent composition comprising: linear alkylbenzene sulfonate (calculated in terms of acid) at about 15 to 23% by weight; alcohol ethoxysulfate (eg, C12 -C15 alcohol, 2-3 OE) at about 8 to 15% by weight; alcohol ethoxylate (for example, C12 -C15 alcohol, 7 EO; or C12 -C15 alcohol, 5 OE) at about 3 to 9% by weight; soap as a fatty acid (eg lauric acid) at about 0 to 3% by weight; about 1 to 5% by weight aminoethanol; sodium citrate, at about 5 to 10% by weight; hydrotrope (eg, sodium toluenesulfonate) at about 2 to 6% by weight; about 0 to 2% by weight borate; poly alpha-1,3-glucan ether up to about 1% by weight; ethanol, at about 1 to 3% by weight; propylene glycol at about 2 to 5% by weight; optionally, an enzyme(s) (calculated as pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (eg, dispersants, perfume, optical brighteners) at about 0 to 5% by weight. (11) An aqueous liquid detergent composition comprising: linear alkylbenzene sulfonate (calculated in terms of acid) at about 20 to 32% by weight; alcohol ethoxylate (for example, C12 -C15 alcohol, 7 EO; or C12 -C15 alcohol, 5 OE), at about 6 to 12% by weight; about 2 to 6% by weight aminoethanol; citric acid at about 8 to 14% by weight; borate, at about 1 to 3% by weight; poly alpha-1,3-glucan ether up to about 2% by weight; ethanol, at about 1 to 3% by weight; propylene glycol at about 2 to 5% by weight; other polymers (eg acrylic/maleic acid copolymer, anchor polymer such as lauryl acrylic acid/methacrylate copolymer) at about 0 to 3% by weight; about 3 to 8% by weight glycerol; optionally, an enzyme(s) (calculated as pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (eg, hydrotropes, dispersants, perfumes, optical brighteners) at about 0 to 5% by weight. (12) A detergent composition formulated as a granulate having a bulk density of at least 600 g/L comprising: the anionic surfactant (eg linear alkylbenzene sulfonate, alkyl sulfate, alpha-olefin sulfonate , fatty acid alpha-sulfo methyl esters, alkane sulfonates, soap) at about 25 to 40% by weight; nonionic surfactant (eg, ethoxylated alcohol) at about 1 to 10% by weight; about 8 to 25% by weight sodium carbonate; soluble silicate (eg Na2O2SiO2) at about 5 to 15% by weight; about 0 to 5% by weight sodium sulfate; zeolite (NaAlSiO4) at about 15 to 28% by weight; about 0 to 20% by weight sodium perborate; bleach activator (eg TAED or NOBS) at about 0 to 5% by weight; poly alpha-1,3-glucan ether up to about 2% by weight; optionally, an enzyme(s) (calculated as pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (eg 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 alkylbenzene sulphonate is replaced by C12-C18 alkyl sulphate. (14) A detergent composition formulated as a granulate having a bulk density of at least 600 g/L comprising: C12-C18 alkyl sulfate at about 9 to 15% by weight; about 3 to 6% by weight alcohol ethoxylate; about 1 to 5% by weight polyhydroxy fatty acid alkyl amide; zeolite (eg NaAlSiO4) at about 10 to 20% by weight; layered disilicate (eg Hoechst's SK56) at about 10 to 20% by weight; about 3 to 12% by weight sodium carbonate; soluble silicate (eg Na2O2SiO2) at from 0 to 6% by weight; about 4 to 8% by weight sodium citrate; about 13 to 22% by weight sodium percarbonate; TAED at about 3 to 8% by weight; poly alpha-1,3-glucan ether 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 as pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (e.g., optical brightener, perfume, photobleach, suds suppressor) 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; about 11 to 15% by weight alcohol ethoxylate; soap at about 1 to 4% by weight; MAPA zeolite or zeolite A at about 35 to 45% by weight; about 2 to 8% by weight sodium carbonate; soluble silicate (eg Na2O2SiO2) from 0 to 4% by weight; about 13 to 22% by weight sodium percarbonate; TAED at about 1 to 8% by weight; poly alpha-1,3-glucan ether 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 pure enzyme protein) at about 0.0001 to 0.1% by weight; and minor ingredients (eg, 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) Detergent compositions as described in (1), (3), (7), (9) and (12) above, but in which the perborate is replaced by percarbonate. (18) 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 liquid detergent comprising a liquid nonionic surfactant (eg a linear alkoxylated primary alcohol), an adjuvant system (eg phosphate), poly alpha-1 ether ,3-glucan, optionally an enzyme(s), and alkali. The detergent may also comprise an anionic surfactant and/or bleach system.
[0160] It is believed that several commercially available detergent formulations can be adapted to include a poly alpha-1,3-glucan ether compound. Examples include Purex® Ultrapacks (Henkel), Finish® Quantum (Reckitt Benckiser), Clorox™ 2 Packs (Clorox), Oxiclean Max Force Power Paks (Church & Dwight), Tide® Stain Release, Cascade® Actionpacs, and Tide® PODS ™ (Procter & Gamble).
[0161] The compositions described in the present invention may be in the form of a composition for oral care. Examples of oral care compositions include dentifrices, toothpaste, mouthwash, mouthwash, chewing gum, and edible strips that provide some form of oral care (e.g., the treatment or prevention of caries [tooth decay], gingivitis, plaque, tartar, and/or periodontal disease). An oral care composition can also be for the treatment of an "oral surface", which encompasses any soft or hard surface within the oral cavity, including the surfaces of the tongue, hard and soft palate, buccal mucosa, gums and dental surfaces. . The "dental surface" in the present invention is a surface of a natural tooth or a hard surface of artificial dentition including a crown, restoration, filling, bridge, denture or dental implant, for example.
[0162] One or more poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ether compounds comprised in an oral care composition is typically provided in the present invention as a thickening agent and /or dispersing agent, which may be useful in imparting a desired consistency and/or mouthfeel to the composition. An oral care composition of the present invention may comprise about 0.01 to 15.0% by weight (for example, about 0.1 to 10% by weight or about 0.1 to 5.0% by weight, about 0.1 to 2.0% by weight) of one or more poly alpha-1,3-glucan and/or poly alpha-1,3-glucan ether compounds described in the present invention (e.g., an ether of carboxyalkyl poly alpha-1,3-glucan, such as hydroxypropyl trimethyl ammonium poly alpha-1,3-glucan), for example. One or more other thickening agents or dispersing agents may also be provided in an oral care composition of the present invention, such as a carboxyvinyl polymer, carrageenan (e.g., L-carrageenan), natural gum (e.g., karaya gum, xanthan, arabica, tragacanth), colloidal magnesium aluminum silicate or colloidal silica, for example.
[0163] A composition for oral care described in the present invention can be a toothpaste or other toothpaste, for example. Such compositions, as well as any other oral care composition of the present invention, may additionally comprise, without limitation, one or more of an anticaries agent, antimicrobial or antibacterial agent, anticalculus or tartar control agent, surfactant, abrasive, modifying agent pH, foam modulator, humectant, flavoring, sweetening, pigment/dye, bleaching agent, and/or other suitable components. Examples of oral care compositions to which one or more poly alpha-1,3-glucan ether compounds may be added are described in US patent applications 2006/0.134,025, 2002/0.022,006 and 2008/0.057. 007, which are incorporated herein by reference.
[0164] An anticaries agent, in the present invention, can be an orally acceptable source of fluoride ions. Suitable sources of fluoride ions include fluoride, and phosphate salts of monofluoro and fluorosilicate, as well as amine fluorides, including (N'-octadecyltrimethylenediamine-N,N,N'-tris(2-ethanol)-dihydrofluoride ) of olaflur, for example. An anticaries agent can be present in an amount that provides a total of about 100 to 20,000 ppm, about 200 to 5,000 ppm, or about 500 to 2,500 ppm of fluoride ions in the composition, for example. In oral care compositions where sodium fluoride is the only source of fluoride ions, an amount of about 0.01 to 5.0% by weight, about 0.05 to 1.0% by weight, or about 0.1 to 0.5% by weight of sodium fluoride may be present in the composition, for example.
[0165] A suitable antimicrobial or antibacterial agent to be used in an oral care composition of the present invention, for example, includes phenolic compounds (eg 4-allylcatechol; p-hydroxybenzoic acid esters such as benzylparaben, butylparaben , ethylparaben, methylparaben and propylparaben; 2-benzylphenol; butylated hydroxyanisole; butylated hydroxytoluene; capsaicin; carvacrol; creosol, eugenol, guaiacol; halogenated bisphenolics, such as hexachlorophene and bromochlorophene; 4-hexylresorcinoline salts; of alicylic acids, such as menthyl salicylate, methyl salicylate and phenyl salicylate; phenol; pyrocatechol; salicylanilide; thymol; halogenated diphenyl ether compounds such as triclosan and triclosan monophosphate), copper (II) compounds (for example , copper (II) chloride, fluoride, sulfate and hydroxide), zinc ion sources (eg acetate, citrate, gluconate, glycinate, oxide zinc sulfate), phthalic acid and its salts (eg, monopotassium magnesium phthalate), hexetidine, octenidine, sanguinarine, benzalkonium chloride, domiphene bromide, alkylpyridinium chlorides (eg, cetylpyridinium chloride, chloride tetradecylpyridinium, N-tetradecyl-4-ethylpyridinium chloride), iodine, sulfonamides, bisbiguanides (eg alexidine, chlorhexidine, chlorhexidine digluconate), piperidino derivatives (eg delmopinol, octapinol), magnolia extract, extract grape seed, rosemary extract, menthol, geraniol, citral, eucalyptol, antibiotics (eg, augmentin, amoxicillin, tetracycline, doxycycline, minocycline, metronidazole, neomycin, kanamycin, clindamycin), and/or any antibacterial agents described in US patent 5,776,435, which is incorporated herein by reference. One or more antimicrobial agents optionally may be present at about 0.01 to 10% by weight (for example, about 0.1 to 3% by weight), for example, in the oral care composition described.
[0166] An anticalculus or tartar control agent suitable for use in an oral care composition of the present invention, for example, includes phosphates and polyphosphates (eg, pyrophosphates), polyaminopropansulfonic acid (AMPS), citrate trihydrate of zinc, polypeptides (eg polyaspartic and polyglutamic acids), polyolefin sulfonates, polyolefin phosphates, diphosphonates (eg azacycloalkan-2,2-diphosphonates such as azacycloheptan-2,2-diphosphates acid), N acid -methyl-azacyclopentan-2,3-diphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid (EHDP), ethane-1-amino-1,1-diphosphonate, and/or phosphonoalkane carboxylic acids and their salts (eg alkali metal and ammonium salts). Useful inorganic phosphate and polyphosphate salts, for example, include monobasic, dibasic and tribasic sodium phosphate, sodium tripolyphosphate, tetrapolyphosphate, mono-, di-, tri- and tetrasodium pyrophosphates, disodium pyrophosphate dihydrogen phosphate, trimetaphosphate sodium, sodium hexametaphosphate, or any of these, in which sodium is replaced by potassium or ammonium. Other anticalculus agents useful in certain embodiments include anionic polycarboxylate polymers (for example, polymers or copolymers of acrylic, methacrylic acid, and maleic anhydride, such as polyvinyl methyl ether/maleic anhydride copolymers). Still other useful anticalculus agents include sequestering agents such as hydroxycarboxylic acids (eg citric, fumaric, malic, glutaric and oxalic acid and salts thereof) and aminopolycarboxylic acids (eg EDTA). One or more anticalculus or tartar control agents optionally may be present at from about 0.01 to 50% by weight (for example, from about 0.05 to 25% by weight or about 0.1 to 15% by weight), for example in the oral care composition described.
[0167] A suitable surfactant for use in an oral care composition described in the present invention may be anionic, nonionic, or amphoteric, for example. Suitable anionic surfactants include, without limitation, the water-soluble salts of C8-C20 alkyl sulfates, sulfonated monoglycerides of C8-C20 fatty acids, sarcosinates and taurates. Examples of anionic surfactants include sodium lauryl sulfate, sodium coconut monoglyceride sulfonate, sodium lauryl sarcosinate, sodium lauryl isoethionate, sodium laureth carboxylate and sodium dodecyl benzene sulfonate. Suitable nonionic surfactants include, without limitation, poloxamers, polyoxyethylene sorbitan esters, fatty alcohol ethoxylates, alkylphenol ethoxylates, tertiary amine oxides, tertiary phosphine oxides, and dialkyl sulfoxides. Suitable amphoteric surfactants include, without limitation, those derived from aliphatic C8-C20 secondary and tertiary amines containing an anionic group, such as a carboxylate, sulfate, sulfonate, phosphate or phosphonate. An example of a cocoamidopropyl betaine amphoteric surfactant is suitable. One or more surfactants optionally are present in a total amount of from about 0.01 to 10% by weight (for example, from about 0.05 to 5.0% by weight or about 0.1 to 2, 0% by weight), for example in the oral care composition described.
[0168] An abrasive suitable for use in an oral care composition of the present invention, for example, may include silica (eg, silica gel, hydrated silica, precipitated silica), alumina, insoluble phosphates, calcium carbonate , and resinous abrasives (eg, a urea-formaldehyde condensation product). Examples of insoluble phosphates useful as abrasives in the present invention are orthophosphates, pyrophosphates and polymetaphosphates, and include dicalcium orthophosphate dihydrate, calcium pyrophosphate, beta calcium pyrophosphate, tricalcium phosphate, calcium polymetaphosphate, and insoluble sodium polymetaphosphate. One or more abrasives optionally are present in a total amount of from about 5 to 70% by weight (for example from about 10 to 56% by weight or about 15 to 30% by weight), e.g. composition for oral care described. The average particle size of an abrasive, in certain embodiments, is about 0.1 to 30 microns (e.g., about 1 to 20 microns or about 5 to 15 microns).
[0169] An oral care composition in certain embodiments may comprise at least one pH modifying agent. Such agents can be selected to acidify, make more basic, or buffer the pH of a composition to a pH range of about 2 to 10 (for example, a pH in the range of about 2 to 8, from 3 to 3 to 9, 4 to 8, 5 to 7, 6 to 10, or 7 to 9). Examples of pH modifying agents useful in the present invention include, without limitation, carboxylic, phosphoric and sulfonic acids; acid salts (for example, monosodium citrate, disodium citrate, monosodium malate); alkali metal hydroxides (for example, sodium hydroxide, carbonates such as sodium carbonate, bicarbonates, sesquicarbonates); borates; silicates; phosphates (for example the salts of monosodium phosphate, trisodium phosphate, pyrophosphate); and imidazole.
[0170] A foam modulator suitable for use in an oral care composition described in the present invention may be a polyethylene glycol (PEG), for example. High molecular weight PEGs are suitable, including those with an average molecular weight of about 200,000 to 7,000,000 (for example, from about 500,000 to 5,000,000 or about 1 to 2.5 million), for example. One or more PEGs optionally are present in a total amount of from about 0.1 to 10% by weight (for example, from about 0.2 to 5.0% by weight or about 0.25 to 2, 0% by weight), for example in the oral care composition described.
[0171] A composition for oral care in certain embodiments may comprise at least one humectant. A humectant in certain embodiments can be a polyhydric alcohol such as glycerin, sorbitol, xylitol, or a low molecular weight PEG. More suitable humectants can also function as a sweetener in the present invention. One or more humectants optionally are present in a total amount of from about 1.0 to 70% by weight (for example, from about 1.0 to 50% by weight, about 2 to 25% by weight, or about 5 to 15% by weight), for example in the oral care composition described.
[0172] A natural or artificial sweetener optionally can comprise an oral care composition of the present invention. Examples of suitable sweeteners include dextrose, sucrose, maltose, dextrin, invert sugar, mannose, xylose, ribose, fructose, levulose, galactose, corn syrup (e.g. corn syrup and corn syrup solids), starch partially hydrolyzed, hydrolyzed hydrogenated starch, sorbitol, mannitol, xylitol, maltitol, isomalt, aspartame, neotame, saccharin and its salts, intense sweeteners based on dipeptides, and cyclamates. One or more of the sweeteners are optionally present in a total amount of about 0.005 to 5.0% by weight, for example, in the oral care composition described.
[0173] A natural or artificial flavoring optionally can comprise an oral care composition of the present invention. Examples of suitable flavorings include vanillin; saves; marjoram; parsley oil; mint oil; cinnamon oil; oil of wintergreen (methyl salicylate); mint oil; clove oil; laurel oil; aniseed oil; eucalyptus oil; citrus oils; fruit oils; essences, such as those derived from lemon, orange, lime, grapefruit, apricot, banana, grape, apple, strawberry, cherry, pineapple or; flavors derived from nuts and beans, such as coffee, cocoa, cola, peanut, or almond; and absorbed and encapsulated flavors. Also encompassed within flavorings in the present invention are ingredients that provide the fragrance and/or other sensory effect in the mouth, including cooling or warming effects. Such ingredients include, without limitation, menthol, menthyl acetate, menthyl lactate, camphor, eucalyptus oil, eucalyptol, anethole, eugenol, cassia, oxanone, Irisone®, propenyl guayetol, thymol, linalool, benzaldehyde, cinnamic aldehyde, N-ethyl-P-menthan-3-carboxamine, N,2,3-trimethyl-2-isopropylbutanamide, 3-(1-menthoxy)-propane-1,2-diol, glycerol cinnamaldehyde acetal (CGA), and acetal of menthone glycerol (MGA). One or more flavorings are optionally present in a total amount of from about 0.01 to 5.0% by weight (for example from about 0.1 to 2.5% by weight), for example, in the composition. for oral care described.
[0174] An oral care composition in certain embodiments may comprise at least one bicarbonate salt. Any orally acceptable bicarbonate can be used, including alkali metal bicarbonates such as sodium or potassium bicarbonate, and ammonium bicarbonate, for example. One or more bicarbonate salts optionally are present in a total amount of from about 0.1 to 50% by weight (for example from about 1 to 20% by weight), e.g., in the oral care composition described. .
[0175] A composition for oral care in certain embodiments may comprise at least one bleaching agent and/or colorant. A suitable bleaching agent is a peroxide compound, such as any of those described in US patent 8,540,971, which is incorporated herein by reference. Colorants suitable in the present invention include pigments, dyes, lakes and agents which impart a special shine or reflectivity, such as pearlizing agents, for example. Specific examples of dyes useful in the present invention include talc; mica; magnesium carbonate; calcium carbonate; magnesium silicate; magnesium aluminum silicate; silica; titanium dioxide; zinc oxide; red, yellow, brown and black iron oxides; ammonium ferric ferrocyanide; manganese violet; overseas; titaniated mica; and bismuth oxychloride. One or more dyes optionally are present in a total amount of from about 0.001 to 20% by weight (for example, from about 0.01 to 10% by weight or about 0.1 to 5.0% by weight ), for example in the oral care composition described.
[0176] Additional components that may optionally be included in an oral composition in the present invention include one or more enzymes (above), vitamins, and anti-adhesion agents, for example. Examples of vitamins useful in the present invention include vitamin C, vitamin E, vitamin B5, and folic acid. Examples of suitable anti-adhesion agents include the solbrol, ficin, and quorum sesation inhibitors.
[0177] The present invention described also relates to a method to increase the viscosity of an aqueous composition. This method comprises contacting one or more poly alpha-1,3-glucan ether compounds described in the present invention with the aqueous composition. This step results in increasing the viscosity of the aqueous composition. The poly alpha-1,3-glucan ether compound(s) used in this method can be represented by the structure:

[0178] In relation to the Formula of this structure, n can be at least 6, and each R, independently, can be an H or a positively charged organic group. In addition, the poly alpha-1,3-glucan ether compound has a degree of substitution from about 0.05 to about 3.0. Any aqueous and hydrocolloid solution in the present invention described can be produced using this method.
[0179] An aqueous composition, in the present invention, can be water (for example, deionized water), an aqueous solution, or a hydrocolloid, for example. The viscosity of an aqueous composition before the contacting step, measured at about 20 to 25°C, can be about 0 to 10,000 cPs (or any integer between 0 and 10,000 cPs), for example. Since the aqueous composition can be a hydrocolloid or the like in certain embodiments, it should be apparent that the method can be used to increase the viscosity of aqueous compositions that were previously viscous.
[0180] Contacting a poly alpha-1,3-glucan ether compound described in the present invention with an aqueous composition increases the viscosity of the aqueous composition in certain embodiments. This increase in viscosity can be an increase of at least about 1%, 10%, 100%, 1,000%, 100,000%, or 1,000,000% (or any whole number between 1% and 1,000,000%), for example, compared to the viscosity of the aqueous composition before the contacting step. It should be evident that very large percentage increases in viscosity can be obtained with the method described when the aqueous composition has little or no viscosity prior to the contacting step.
[0181] Contacting a poly alpha-1,3-glucan ether compound described in the present invention with an aqueous composition increases the shear thinning behavior or the shear thickening behavior of the aqueous composition in certain embodiments. Therefore, a poly alpha-1,3-glucan ether compound rheologically modifies the aqueous composition in these embodiments. The increase in shear thinning behavior or shear thickening behavior can be an increase of at least about 1%, 10%, 100%, 10.00%, 100,000%, or 1,000,000% (or any whole number between 1% and 1,000,000%), for example, compared to the shear thinning behavior or shear thickening behavior of the aqueous composition before the contact step. It should be evident that very large percentage increases in rheological modification can be obtained with the method described when the aqueous composition has little or no rheological behavior prior to the contact step.
[0182] The contact step can be performed by mixing or dissolving a poly alpha-1,3-glucan ether compound(s) described in the present invention in the aqueous composition by any means known in the state of the art . For example, mixing or dissolving can be carried out manually or with a machine (eg industrial blender or blender, orbital shaker, stir plate, homogenizer, sonicator, ball mill). Mixing or dissolving may comprise a homogenization step, in certain embodiments. Homogenization (as well as any other type of mixing) can be carried out for about 5 to 60, 5 to 30, 10 to 60, 10 to 30, 5 to 15, or 10 to 15 seconds (or any whole number between 5 and 60 seconds), or longer periods of time required to mix a poly alpha-1,3-glucan ether compound with the aqueous composition. A homogenizer can be used at about 5,000 to 30,000 rpm, 10,000 to 30,000 rpm, 15,000 to 30,000 rpm, 15,000 to 25,000 rpm, or 20,000 rpm (or any whole number between 5,000 and 30,000 rpm), for example. The aqueous solutions and hydrocolloids described in the present invention prepared using a homogenization step may be referred to as aqueous solutions and homogenized hydrocolloids.
[0183] After a poly alpha-1,3-glucan ether compound is mixed with, or dissolved in, an aqueous composition, the resulting aqueous composition may be filtered, or it may not be filtered. For example, an aqueous composition prepared with a homogenization step may or may not be filtered.
[0184] Certain embodiments of the method described above can be used to prepare an aqueous composition described in the present invention, such as a product for household use (e.g. washing powder, fabric softener, dishwashing detergents), product personal care (for example, a dentifrice containing water, such as toothpaste), or industrial product.
[0185] The present invention described also refers to a method for treating a material. This method comprises contacting a material with an aqueous composition comprising at least one poly alpha-1,3-glucan ether compound described in the present invention. A poly alpha-1,3-glucan ether compound(s) used in this method is/are represented by the structure:

[0186] In relation to the Formula of this structure, n can be at least 6, and each R, independently, can be an H or a positively charged organic group. In addition, the poly alpha-1,3-glucan ether compound has a degree of substitution from about 0.05 to about 3.0.
[0187] A material contacted with an aqueous composition of a contact method, in the present invention, may comprise a fabric in certain embodiments. A fabric of the present invention can comprise natural fibers, synthetic fibers, semi-synthetic fibers, or any combinations thereof. A semi-synthetic fiber in the present invention is produced using a naturally occurring material that has been chemically derivatized, an example of which is rayon. Examples of non-limiting fabric types in the present invention include fabrics of (i) cellulosic fibers such as cotton (e.g., cashmere, canvas, cambric, chenille, chintz, cotton velvet, cretone, damask, denim, flannel , gingham, jaquard, knit, matelassé, oxford, percale, poplin, plissé, satin, narruga, fine fabric, terry fabric, twill, velvet), rayon (eg, 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, henequen, abaca, hemp and crotalaria vegetables; and (v) any combination of a fabric from (i) to (iv). Fabric comprising a combination of fiber types (for example, natural and synthetic) include those with a cotton and polyester fiber, for example. Materials/articles containing one or more fabrics in the present invention, for example, include clothing, curtains, curtains, upholstery, carpets, bedding, bath towels, tablecloths, bags, tents, car interiors, and similar. Other materials comprising natural and/or synthetic fibers, for example, include nonwovens, fillers, paper and foams.
[0188] An aqueous composition that is brought into contact with a fabric, for example, can be a fabric treatment composition (eg, washing powder, fabric softener). Therefore, a method for treating certain embodiments can be considered a method for treating fabric or a laundry method if it employs a composition for treating fabric. A fabric treatment composition of the present invention can effect one or more of the following fabric treatment effects (i.e., surface background effects): wrinkle removal, wrinkle reduction, wrinkle resistance, reduction fabric wear, fabric wear resistance, fabric fray reduction, fabric color maintenance, fabric color fade reduction, fabric color restoration, fabric soil reduction, fabric soil release, retention fabric shape, fabric softness enhancement, fabric dirt anti-redeposition, garment anti-aging, fabric texture enhancement / fabric handling, and/or fabric shrinkage reduction.
[0189] Examples of conditions (e.g. time, temperature, wash/rinse volumes) for carrying out a fabric treatment method or laundry method of the present invention are described in WO 1997/003161 and in the US Patents 4,794,661, 4,580,421 and 5,945,394, which are incorporated herein by reference. In other examples, a material comprising the fabric may be contacted with an aqueous composition of the present invention: (i) for at least about 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, or 120 minutes; (ii) at a temperature of at least about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, or 95° C (eg for washing or rinsing laundry: a “cold” temperature of about 15 to 30°C, a “warm” temperature of about 30 to 50°C, a “hot” temperature of about 50 at 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 concentration of a salt (eg NaCl) 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).
[0190] The contact step in a method for treating fabric or laundry method can comprise any washing, dipping, and/or rinsing steps, for example. The contact of a material or fabric in still other embodiments can be carried out by any means known in the prior art, such as dissolving, mixing, stirring, spraying, treating, dipping, drawing, pouring on or inside, combining, painting , coating and applying, affixing, and/or communicating an effective amount of a poly alpha-1,3-glucan ether compound of the present invention with the fabric or material. In still other embodiments, contact can be used in treating a fabric to provide a substantive surface effect. As used herein, the term "tissue texture" or "handling" refers to a person's tactile sensory response to tissue which may be physical, physiological, psychological or any combination thereof. In one embodiment, fabric texture can be measured using a PhabrOmeter® system to measure the relative texture value (available from Nu Cybertek, Inc. Davis, CA) (American Association of Textile Chemists and Colorists (AATCC test method) “202-2012, Relative Hand Value of Textiles: Instrumental Method”)).
[0191] In certain treatment embodiments, a material comprising the fabric, a component(s) of the poly alpha-1,3-glucan ether compound of the aqueous composition absorbs into the fabric. This characteristic is believed to process poly alpha-1,3-glucan ether compounds (eg, quaternary ammonium poly alpha-1,3-glucan ether compounds such as poly alpha-1,3 hydroxypropyl trimethyl ammonium glucan) useful as anti-redeposition agents and/or anti-aging agents in the tissue treatment compositions described in the present invention (in addition to their viscosity modifying effect). An anti-redeposition agent or anti-aging agent in the present invention helps to keep soil from redeposition on laundry in wash water after the soil is removed. It is further contemplated that absorption of one or more poly alpha-1,3-glucan ether compounds of the present invention into a fabric enhances the mechanical properties of the fabric.
[0192] The Examples below demonstrate that poly alpha-1,3-glucan ether compounds, such as quaternary ammonium poly alpha-1,3-glucan (eg poly alpha-1,3-glucan from hydroxypropyl trimethyl ammonium) can absorb both natural (cotton, cretone) and synthetic (polyester) fabrics as well as a mixture thereof (polyester/cretone). This noteworthy result is that carboxymethyl cellulose (CMC) does not absorb, or only weakly absorbs, polyester and polyester/cotton blends (see European patent application EP 0.035.478, for example). Accordingly, in certain embodiments of a method for treating, herein, a cationic poly alpha-1,3-glucan ether compound (e.g., quaternary ammonium poly alpha-1,3-glucan such as hydroxypropyl trimethyl ammonium poly alpha-1,3-glucan) absorbs material comprising natural fibers (eg cotton) and/or synthetic fibers (eg polyester). Such absorption may optionally be under conditions of about 1 to 2% by weight of salt (e.g., the NaCl), and/or a pH of about 3.0, 3.5, 4.0, 4, 5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5, 8.0, 8.5, 9.0, or 9.5, for example.
[0193] The absorption of a poly alpha-1,3-glucan ether compound into a tissue, of the present invention, can be measured, following the methodology described in the Examples below, for example. Alternatively, absorption can be measured using a colorimetric technique (eg, Dubois et al., 1956, Anal Chem 28: 350-356; Zemljic et al., 2006, Lenzinger Berichte 85: 68-76; both incorporated in the present by reference) or any other method known in the state of the art.
[0194] Other materials that may be in contact in the above treatment method include surfaces that can be treated with a detergent (eg automatic dishwashing detergent or manual dishwashing detergent). Examples of such materials include the surfaces of plates, cups, pots, pans, molds, utensils and cutlery made from ceramic, porcelain, metal, glass, plastic material (e.g., polyethylene, polypropylene, polystyrene, and the like .) and wood (collectively referred to herein as “tableware”). Therefore, the method for treating certain embodiments can be considered a dishwashing method or tableware washing method, for example. Examples of conditions (e.g., time, temperature, wash volume) for carrying out a dishwashing or tableware washing method of the present invention are described in US patent 8,575,083, which is incorporated herein as reference. In other examples, a tableware article may be contacted with an aqueous composition of the present invention under a set of suitable conditions, such as any of those described above in connection with contacting a material comprising the fabric.
[0195] Other materials that may be in contact in the above method for treatment include oral surfaces, such as any soft or hard surface on the inside of the oral cavity, including the surfaces of the tongue, hard and soft palate, buccal mucosa, gums and dental surfaces (for example, the natural tooth or a hard surface of the artificial dentition, such as a crown, restoration, filling, bridge, denture or dental implant). Therefore, a method for treating certain embodiments can be considered a method for oral care or a method for dental care, for example. Conditions (eg, time, temperature) for contacting an oral surface with an aqueous composition of the present invention should be suitable for the intended purpose of making such contact. Other surfaces that may be contacted in a method of treatment also include an integumentary system surface such as the skin, hair, or nails.
[0196] Accordingly, certain embodiments of the subject material described of the present invention (e.g., tissue) comprising a poly alpha-1,3-glucan ether compound of the present invention. Such material can be produced following a method for treating material as described, for example. A material may comprise a glucan ether compound in certain embodiments, if the compound is adsorbed on, or is in contact with, the surface of the material.
[0197] Certain embodiments of a method for treating a material of the present invention further comprises a drying step, in which a material is dried, after being placed in contact with the aqueous composition. A drying step can be performed directly after the contact step, or following one or more additional steps that can follow the contact step (for example, drying a fabric after being rinsed in water, for example, in the sequence of a wash in an aqueous composition of the present invention). Drying can be carried out by any of the various means known in the prior art, such as drying in air (for example, from about 20 to 25°C), or at a temperature of at least about 30. 40, 50, 60, 70, 80, 90, 100, 120, 140, 160, 170, 175, 180, or 200°C, for example. A material that has been dried in the present invention typically has an amount of less than 3, 2, 1, 0.5, or 0.1% by weight of water comprised. Fabric is a preferred material for carrying out an optional drying step.
[0198] An aqueous composition used in a method for the treatment of the present invention may be any aqueous composition described in the present invention, such as in the above embodiments or in the Examples below. Accordingly, the poly alpha-1,3-glucan ether component(s) of an aqueous composition can be any as described in the present invention. Examples of aqueous compositions include detergents (e.g. laundry detergent or dish detergent) and dentifrices which contain water such as toothpaste.
[0199] The present invention described also relates to a method for producing a poly alpha-1,3-glucan ether compound. This method comprises: contacting poly alpha-1,3-glucan, in a reaction under alkaline conditions with at least one etherification agent comprising a positively charged organic group, wherein the positively charged organic group is etherified to the poly alpha-1,3-glucan, therefore, producing a poly alpha-1,3-glucan ether compound represented by the structure:
- where (i) n is at least 6, (ii) each R independently is H or a positively charged organic group, and (iii) the compound has a degree of substitution from about 0.05 to about 3.0.
[0200] A poly alpha-1,3-glucan ether produced by this method optionally can be isolated. This method can be considered because it comprises an etherification reaction.
[0201] The poly alpha-1,3-glucan comes into contact with in a reaction under alkaline conditions with at least one etherification agent that comprises a positively charged organic group. This step can be carried out, for example, by first preparing alkaline conditions by contacting the poly alpha-1,3-glucan 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, 11.2, 11.4, 11.6, 11.8, 12.0, 12.2, 12.4, 12.6, 12 .8, or 13.0.
[0202] Various alkali hydroxides can be used, such as sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, and/or tetraethylammonium hydroxide. The alkali metal hydroxide concentration in a preparation with the poly alpha-1,3-glucan and a solvent can be from about 1 to 70% by weight, from 5 to 50% by weight, from 10 to 50% by weight , from 10 to 40% by weight, or from 10 to 30% by weight (or any whole number between 1 and 70% by weight). Alternatively, the concentration of alkali metal hydroxide such as sodium hydroxide can be at least about 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30% by weight. An alkali metal hydroxide used to prepare the alkaline conditions can be in a completely aqueous solution or an aqueous solution comprising one or more water-soluble organic solvents such as ethanol or isopropanol. Alternatively, an alkali metal hydroxide can be added as a solid to provide alkaline conditions.
[0203] Various organic solvents that optionally can be included when preparing the reaction include alcohols, acetone, dioxane, isopropanol and toluene, for example; none of these solvents dissolve the poly alpha-1,3-glucan. Toluene or isopropanol can be used in certain embodiments. An organic solvent can be added before or after addition of alkali hydroxide. The concentration of an organic solvent (eg isopropanol or toluene) in a preparation comprising poly alpha-1,3-glucan and an alkali metal hydroxide can be at least about 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, or 90% by weight (or any whole number between 10 and 90% by weight).
[0204] Alternatively, solvents that can dissolve the poly alpha-1,3-glucan can be used when preparing the reaction. These solvents include, but are not limited to lithium chloride (LiCl) / N,N-dimethyl-acetamide (DMAC), SO2 / diethylamine (DEA) / dimethyl sulfoxide (DMSO), LiCl / 1,3-dimethyl-2 -imidazolidinone (DMI), N,N-dimethylformamide (DMF) / N2O4, DMSO / tetrabutylammonium fluoride trihydrate (TBAF), N-methylmorpholine-N-oxide (NMMO), Ni(tren)(OH)2[ tren%tris(-aminoethyl)amine] aqueous solutions and melts LiClO4.3H2O, aqueous NaOH/urea solutions, aqueous sodium hydroxide, aqueous potassium hydroxide, formic acid, and ionic liquids.
[0205] Poly alpha-1,3-glucan may come in contact with a solvent and one or more alkali hydroxides in mixture. Such mixing can be carried out during or after the addition of these components together. Mixing can be carried out by manual mixing, mixing using an overhead mixer, using a magnetic stir bar, or stirrer, for example. In certain embodiments, the poly alpha-1,3-glucan may first be mixed with water or an aqueous solution before being mixed with a solvent and/or alkali hydroxide.
[0206] After contacting alpha-1,3-glucan hydroxides, solvents, and one or more poly alkali with each other, the resulting composition optionally can be kept at room temperature for up to 14 days. The term "ambient temperature" as used herein refers to a temperature between about 15 to 30°C or 20 to 25°C (or any whole number between 15 and 30°C). Alternatively, the composition can be heated, with or without reflux, at a temperature from about 30°C to about 150°C (or any integer between 30 and 150°C) for up to about 48 hours . The composition in certain embodiments can be heated to about 55°C for about 30 minutes or 60 minutes. Therefore, a composition obtained from mixing a poly alpha-1,3-glucan, solvents, and one or more alkali hydroxides with each other can be heated to about 50, 51, 52, 53, 54, 55, 56 , 57, 58, 59, or 60°C for about 30 to 90 minutes.
[0207] After contacting the poly alpha-1,3-glucan, solvents, and one or more alkali hydroxides with each other, the resulting composition can optionally be filtered (with or without the application of a temperature treatment step) . Such filtration can be carried out using a centrifuge funnel, filter press, or any other method and/or equipment known in the state of the art that enables the removal of solids from liquids. Although filtration would remove most of the alkali metal hydroxide, the filtered poly alpha-1,3-glucan would remain alkaline (i.e. mercerized poly alpha-1,3-glucan), therefore providing the conditions alkaline.
[0208] An etherification agent comprising a positively charged organic group can be contacted with poly alpha-1,3-glucan, in a reaction under alkaline conditions in a method of the present invention for producing the poly ether compounds. alpha-1,3-glucan. For example, an etherification agent can be added to a composition prepared by contacting poly alpha-1,3-glucan, solvents, and one or more alkali hydroxides with each other, as described above. Alternatively, an etherification agent can be included in preparing the alkaline conditions (for example, an etherification agent can be mixed with the poly alpha-1,3-glucan and solvent prior to mixing with the alkaline hydroxide).
[0209] An etherification agent of the present invention refers to an agent that can be used to etherify one or more hydroxyl groups of poly alpha-1,3-glucan glucose units with a positively charged organic group as defined above. One or more etherification agents can be used in the reaction.
[0210] An etherification agent can be one that can etherify the poly alpha-1,3-glucan with a positively charged organic group, wherein the carbon chain of the positively charged organic group only has a substitution by a positively charged group ( for example, a substituted ammonium group such as trimethyl ammonium). Examples of such etherifying agents include dialkyl sulfates, dialkyl carbonates, alkyl halides (e.g., the alkyl chloride), iodoalkanes, alkyl triflates (alkyl trifluoromethanesulfonates) and alkyl fluorosulfonates, wherein the( s) alkyl group(s) of each of these agents has(are) one or more substitutions for a positively charged group (for example, a substituted ammonium group, such as trimethyl ammonium). Other examples of such etherifying agents include dimethyl sulfate, dimethyl carbonate, methyl chloride, iodomethane, methyl triflate and methyl fluorosulfonate, wherein the methyl group(s) of each of these agents have (in ) a substitution by a positively charged group (eg, a substituted ammonium group such as trimethyl ammonium). Other examples of such etherifying agents include diethyl sulfate, diethyl carbonate, ethyl chloride, iodoethane, ethyl triflate and ethyl fluorosulfonate, wherein the ethyl group(s) of each of these agents have ( in) a substitution by a positively charged group (eg a substituted ammonium group such as trimethyl ammonium). Other examples of such etherifying agents include dipropyl sulfate, dipropyl carbonate, propyl chloride, iodopropane, propyl triflate and propyl fluorosulfonate, where the propyl group(s) of each of these agents have(are) one or more substitutions for a positively charged group (for example, the substituted ammonium group, such as trimethyl ammonium). Other examples of such etherifying agents include dibutyl sulfate, dibutyl carbonate, butyl chloride, iodobutane and butyl triflate, where the butyl group(s) of each of these agents have one or more substitutions for a positively charged group (eg, a substituted ammonium group such as trimethyl ammonium).
[0211] An etherification agent may be one that can etherify the poly alpha-1,3-glucan with a positively charged organic group, wherein the carbon chain of the positively charged organic group has a substitution (eg, the hydroxyl group ) in addition to a substitution by a positively charged group (eg, a substituted ammonium group such as trimethyl ammonium). Examples of such etherifying agents include hydroxyalkyl halides (e.g., hydroxyalkyl chloride) such as hydroxypropyl halide and hydroxybutyl halide, where a terminal carbon of each of these agents has a positive group substitution charged (for example, a substituted ammonium group such as trimethyl ammonium); an example is trimethyl 3-chloro-2-hydroxypropyl ammonium. Other examples of such etherifying agents include alkylene oxides such as propylene oxide (eg 1,2-propylene oxide) and butylene oxide (eg 1,2-butylene oxide, oxide of 2,3-butylene), in which a terminal carbon of each of these agents has a substitution with a positively charged group (eg, a substituted ammonium group, such as trimethyl ammonium).
[0212] A substituted ammonium group comprised in any of the foregoing examples of etherification agent may be a primary, secondary, tertiary or quaternary ammonium group. Examples of secondary, tertiary, and quaternary ammonium groups are represented in structure I, where R2, R3 and R4 each independently represent a hydrogen atom or an alkyl group such as a methyl, ethyl, propyl, or butyl group .
[0213] Etherifying agents, at present, usually can be supplied as a fluoride, chloride, bromide, or iodide salt (wherein each of the foregoing halides serves as an anion).
[0214] Any of the etherification agents described herein can be combined to produce poly alpha-1,3-glucan ether compounds with two or more different positively charged organic groups. Such two or more etherifying agents can be used in the reaction at the same time, or they can be used sequentially in the reaction. When used sequentially, any temperature treatment step (e.g., heating) described below, optionally, can be used between each addition. Sequential introduction of etherification agents can be selected in order to control the desired DoS of each positively charged organic group. In general, a special etherification agent would be used if the first positively charged organic group that forms in the ether product is desired at a higher DoS compared to the DoS of another positively charged organic group being added.
[0215] The amount of etherification agent to be brought into contact with the poly alpha-1,3-glucan, in a reaction under alkaline conditions that can be determined based on the degree of substitution required in the poly alpha-ether compound. 1,3-glucan being produced. The amount of ether substitution groups on each monomeric unit in the poly alpha-1,3-glucan ether compounds of the present invention produced can be determined using nuclear magnetic resonance (NMR) spectroscopy. The molar substitution value (MS) for poly alpha-1,3-glucan has no upper limit. In general, an etherification agent can be used in an amount of at least about 0.05 mol per mol of poly alpha-1,3-glucan. There is no upper limit on the amount of etherification agent that can be used.
[0216] The reactions for the production of the poly alpha-1,3-glucan ether compounds of the present invention, optionally, can be carried out in a pressure vessel, such as a Parr reactor, an autoclave, a tube. stirring or any other pressure vessel well known in the state of the art. A stir tube is used to carry out the reaction in certain embodiments.
[0217] The reaction of the present invention optionally can be heated after the step of contacting poly alpha-1,3-glucan with an etherification agent under alkaline conditions. Reaction temperatures and application times of such temperatures can vary within wide limits. For example, the reaction can optionally be kept at room temperature for up to 14 days. Alternatively, the reaction can be heated, with or without reflux, to between about 25°C to about 200°C (or any integer between 25 and 200°C). The reaction time can vary correspondingly: longer at low temperature and less time at high temperature.
[0218] In certain embodiments of the production of quaternary ammonium poly alpha-1,3-glucan ether (eg hydroxypropyl trimethyl ammonium poly alpha-1,3-glucan), the reaction may be heated to about of 55°C for about 1.5 hours. Therefore, a reaction for the preparation of a quaternary ammonium poly alpha-1,3-glucan ether such as hydroxypropyl trimethyl ammonium poly alpha-1,3-glucan can optionally be heated to about 50 to 60°C for about 1 to 2 hours, for example. Such a reaction may comprise trimethyl 3-chloro-2-hydroxypropyl ammonium as an etherification agent.
[0219] Optionally, the reaction of the present invention can be maintained under an inert gas, with or without heating. As used herein, 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 preparing a reaction of the present invention.
[0220] All components of the reactions described in the present invention can be mixed together at the same time and brought to the desired reaction temperature, after which the temperature is maintained with or without stirring, until the poly alpha ether compound. Desired 1,3-glucan is formed. Alternatively, the mixed components can be left at room temperature as described above.
[0221] Following etherification, the pH of a reaction can be neutralized. 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 neither 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 acid, acetic acid, hydrochloric acid, nitric acid, any mineral (inorganic) acid, any organic acid, or any combinations thereof.
[0222] A poly alpha-1,3-glucan ether compound produced in a reaction of the present invention optionally can be washed one or more times with a liquid that does not readily dissolve the compound. For example, poly alpha-1,3-glucan ether can be washed with alcohol, acetone, aromatics, or any combination thereof, depending on the solubility of the ether compound (where the desirable lack of solubility is for the wash) . A poly alpha-1,3-glucan ether product can be washed one or more times with an aqueous solution containing methanol or ethanol, for example. For example, from 70 to 95% by weight of ethanol can be used to wash the product. A poly alpha-1,3-glucan ether product can be washed with a mixture of methanol:acetone (eg, 60:40) in a solution in another embodiment.
[0223] A poly alpha-1,3-glucan ether produced in the described reaction can be isolated. This step can be performed before or after the neutralization and/or washing steps, using a centrifuge funnel, filter press, or any other method or equipment known in the state of the art that enables the removal of solids from liquids. For example, a Buchner funnel can be used to isolate a poly alpha-1,3-glucan ether product. An isolated poly alpha-1,3-glucan ether product can be dried using any method known in the art, such as vacuum drying, air drying or freeze drying.
[0224] Any of the etherification reactions above can be repeated using a poly alpha-1,3-glucan ether product as a starting material for further modifications. This approach may be suitable for increasing the DoS of a positively charged organic group, and/or adding one or more different positively charged organic groups to the ether product. Furthermore, this approach may be suitable for the addition of one or more organic groups that are not positively charged, such as an alkyl group (eg methyl, ethyl, propyl, butyl) and/or a hydroxyalkyl group (eg. , hydroxyethyl, hydroxypropyl, hydroxybutyl). Any of the above etherification agents, but without substitution by a positively charged group, can be used for this purpose.
[0225] The structure, molecular weight and degree of substitution of a poly alpha-1,3-glucan ether product can be confirmed using various physicochemical analyzes known in the art, such as size exclusion chromatography and NMR spectroscopy (SEC).
[0226] The percentage of glycosidic linkages between the poly alpha-1,3-glucan glucose monomer units used to prepare the poly alpha-1,3-glucan ether compounds of the present invention that are poly alpha-1, 3 is at least about 50%, 60%, 70%, 80%, 90%, 95%, 96%, 97%, 98%, 99%, or 100% (or any integer value between 50% and 100%). In such embodiments, therefore, the poly alpha-1,3-glucan has less than about 50%, 40%, 30%, 20%, 10%, 5%, 4%, 3%, 2%, 1%, or 0% (or any integer value between 0% and 50%) of glycosidic bonds that are not alpha-1,3.
[0227] The poly alpha-1,3-glucan used to prepare the poly alpha-1,3-glucan ether compounds of the present invention is preferably linear/unbranched. In certain embodiments, the poly alpha-1,3-glucan has no branch points or less than about 10%, 9%, 8%, 7%, 6%, 5%, 4%, 3%, 2%, or 1% of the branch points as a percentage of the glycosidic bonds in the polymer. Examples of branch points include the alpha-1.6 branch points.
[0228] The Mn or Mw of poly alpha-1,3-glucan used to prepare the poly alpha-1,3-glucan ether compounds of the present invention can be at least from about 1,000 to about 600,000. Alternatively still, Mn or Mw can be at least about 2,000, 3,000, 4,000, 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000 , 75,000, 100,000, 150,000, 200,000, 250,000, 300,000, 350,000, 400,000, 450,000, 500,000, 550,000, or 600,000 (or any whole number between 2,000 and 600,000), for example.
[0229] The poly alpha-1,3-glucan used for the preparation of the poly alpha-1,3-glucan ether compounds of the present invention can be produced enzymatically from sucrose using one or more of the glycosyltransferase enzymes (gtf). The poly alpha-1,3-glucan product of this enzymatic reaction can be purified before being used to prepare an ether using the described process. Alternatively, a poly alpha-1,3-glucan product of a gtf reaction can be used with little or no processing to prepare the poly alpha-1,3-glucan ether compounds.
[0230] A poly alpha-1,3-glucan slurry can be directly used in any of the above processes for producing a poly alpha-1,3-glucan ether compound described in the present invention. As used herein, a "poly alpha-1,3-glucan slurry" refers to a mixture comprising the components of an enzymatic gtf reaction. An enzymatic gtf reaction can include, in addition to the poly alpha-1,3-glucan itself, various components such as sucrose, one or more gtf enzymes, glucose, fructose, leucrose, buffer, FermaSure®, soluble oligosaccharides , oligosaccharide primers, bacterial components of enzyme extract, borates, sodium hydroxide, hydrochloric acid, cell lysates, proteins and/or nucleic acids. Minimally, the components of an enzymatic gtf reaction can include, in addition to poly alpha-1,3-glucan, sucrose, one or more gtf enzymes, glucose and fructose, for example. In another example, the components of an enzymatic gtf reaction may include, in addition to the poly alpha-1,3-glucan itself, sucrose, one or more gtf enzymes, glucose, fructose, leucrose, and soluble oligosaccharides (and optionally the components of the bacterial enzyme extract). It should be apparent that the poly alpha-1,3-glucan, when in suspension as described in the present invention, has not been purified or washed away. It should also be evident that a slurry represents an enzymatic gtf reaction that is complete or for which an observable amount of poly alpha-1,3-glucan has been produced, which forms a solid as it is insoluble in the aqueous reaction medium. (it has a pH of 5 to 7, for example). A poly alpha-1,3-glucan slurry can be prepared by creating a gtf reaction as described in US patent 7,000,000 or US patent applications 2013/0.244,288 and 2013/0.244,287, by example, all of which are incorporated herein by reference. A poly alpha-1,3-glucan slurry can be introduced into a reaction to produce any ether compound present, such as a quaternary ammonium poly alpha-1,3-glucan ether (eg the poly hydroxypropyl trimethyl ammonium alpha-1,3-glucan).
[0231] Alternatively, a poly alpha-1,3-glucan wet cake can be directly used in any of the above processes for producing a poly alpha-1,3-glucan ether compound described in the present invention . A "wet cake of poly alpha-1,3-glucan", as used herein, refers to poly alpha-1,3-glucan that has been separated (eg, filtered) from a slurry and washed with water or an aqueous solution. A wet cake can be washed at least 1, 2, 3, 4, 5 or more times, for example. Poly alpha-1,3-glucan is not dried when making a wet cake. A wet cake is termed “wet” due to water retention by the washed poly alpha-1,3-glucan.
[0232] A wet cake of poly alpha-1,3-glucan can be prepared using any device known in the art for separating solids from liquids, such as a filter or a centrifuge. For example, poly alpha-1,3-glucan solids in a slurry can be collected in a Buchner funnel using a mesh screen over filter paper. The filtered wet cake can be resuspended in water (eg, deionized water) and filtered one or more times to remove soluble sludge components such as sucrose, fructose and leucrose. As another example for preparing a wet cake, alpha-1,3-glucan solids from a poly slurry can be collected as a pellet by means of centrifugation, resuspended in water (eg, deionized water) , and repelletized and resuspended one or more additional times. A wet cake of poly alpha-1,3-glucan can be introduced into a reaction to produce an ether compound, in the present. A wet cake of poly alpha-1,3-glucan can be introduced into a reaction to produce any ether compound present, such as a poly alpha-1,3-glucan quaternary ammonium ether (eg, o poly hydroxypropyl trimethyl ammonium alpha-1,3-glucan).
[0233] The poly alpha-1,3-glucan ether compounds described in the present invention may be cross-linked using any means known in the art. Such crosslinking can be between the same poly alpha-1,3-glucan ether compounds, or between two or more different poly alpha-1,3-glucan ether compounds. Furthermore, cross-linking can be intermolecular and/or intramolecular.
[0234] A cross-linked poly alpha-1,3-glucan ether compound can be prepared as follows, for example. One or more poly alpha-1,3-glucan ether compounds can be dissolved in water or an aqueous solution to prepare a 0.2, 0.5, 1, 2, 3, 4, 5, 6, 7 solution. , 8, 9, or 10% by weight of the solution of the ether compound(s). The poly alpha-1,3-glucan ether compound(s) can be dissolved or mixed using any process known in the art, such as by increasing the temperature, mixing manual, and/or homogenization (as described above).
[0235] A cross-linking agent is then dissolved in the poly alpha-1,3-glucan ether solution or mixture. The concentration of cross-linking agent in the resulting solution can be about 0.2 to 20% by weight, or about 0.1, 0.2, 0.3, 0.4, 0.5, 1.2 , 3, 4, 5, 6, 7, 8, 9, 10, 15, or 20% by weight.
[0236] Examples of suitable cross-linking agents are compounds containing boron and polyvalent metals such as titanium or zirconium. Boron-containing compounds include boric acid, diborates, tetraborates, pentaborates, polymeric compounds such as Polybor®, polymeric boric acid compounds, and alkaline borates, for example. These agents can be used to produce borate crosslinks between poly alpha-1,3-glucan ether molecules. Titanium crosslinks can be produced using titanium IV-containing compounds (eg titanium ammonium lactate, titanium triethanolamine, titanium acetylacetonate, titanium polyhydroxy complexes) as crosslinking agents. Zirconium crosslinks can be produced using IV zirconium-containing compounds (eg, zirconium lactate, zirconium carbonate, zirconium acetylacetonate, zirconium triethanolamine, diisopropylamine zirconium lactate, zirconium polyhydroxy complexes) as agents of crosslinking. Other examples of crosslinking agents useful in this context are described in US Patents 4,462,917, 4,464,270, 4,477,360 and 4,799,550, all of which are incorporated herein by reference.
[0237] The pH of the solution or mixture containing a cross-linking agent and a poly alpha-1,3-glucan ether compound(s) can be adjusted to be alkaline (eg pH 8, 8.5, 9 , 9.5, or 10). The pH modification can be carried out by any means known in the art, such as with a concentrated aqueous solution of an alkaline hydroxide such as sodium hydroxide. Dissolving a cross-linking agent in a solution or mixture that contains one or more poly alpha-1,3-glucan ether compounds in a pH alkali results in cross-linking the poly ether compound(s). alpha-1,3-glucan. EXAMPLES
[0238] The present invention is further defined in the following Examples. It is to be understood that these Examples, while indicating certain preferred aspects of the present invention, are given by way of illustration only. From the above discussion and these examples, a person skilled in the art can determine the essential characteristics of the present invention, and without departing from the spirit and scope of the present invention, can make various changes and modifications of the present invention to adapt it to various uses. and conditions. PREPARATION OF POLY ALPHA-1,3-GLUCAN
[0239] Poly alpha-1,3-glucan was prepared using a gtfJ enzyme preparation as described in US patent application 2013/0.244,288, incorporated herein by reference in its entirety. NUCLEAR1H MAGNETIC RESONANCE (NMR) METHOD FOR DETERMINING MOLAR REPLACEMENT OF POLY ALPHA-1,3-GLUCAN ETHER DERIVATIVES
[0240] About 30 mg of the poly alpha-1,3-glucan ether derivative was weighed into a vial on an analytical balance. The vial was removed from the balance and 1.0 mL of deuterium oxide was added to the vial. A magnetic stir bar was added to the flask and the mixture was stirred to suspend the solid. Deuterated sulfuric acid (50% v/v in D2O), 1.0 mL, was then added to the flask and the mixture was heated at 90°C for 1 hour to depolymerize and solubilize the polymer. The solution was allowed to cool to room temperature and then a 0.8 ml portion of the solution was transferred to a 5 mm NMR tube using a glass pipette. A quantitative 1H NMR spectrum was acquired using an Agilent VNMRS 400 MHz NMR spectrometer equipped with a 5 mm Autoswitchable Quad probe. The spectrum was acquired at a spectral frequency of 399.945 MHz, using a spectral window of 6410.3 Hz, an acquisition time of 3.744 seconds, an inter-pulse delay of 10 seconds, and 64 pulses. Time domain data was transformed using 0.50 Hz exponential multiplication. DETERMINATION OF THE DEGREE OF POLYMERIZATION
[0241] The degree of polymerization (DP) was determined by size exclusion chromatography (SEC). For SEC analysis, dry poly alpha-1,3-glucan ether derivative was dissolved in phosphate buffered saline (PBS) (from 0.02 to 0.2 mg/ml). The chromatographic system used was an AllianceTM 2695 liquid chromatograph from Waters Corporation (Milford, MA) along with three in-line detectors: the Waters 410 differential refractometer, a HeleosTM 8+ multi-angle light scattering photometer from Wyatt Technologies ( Santa Barbara, CA), and a ViscoStarTM differential capillary viscometer from Wyatt Technologies. The columns used for the SEC were two Tosoh Bioscience Haas TSK GMPWXL g3K and g4K G3000PW and G4000PW polymeric columns for the aqueous polymers. The mobile phase was PBS. The chromatographic conditions used were 30°C in the column and compartment detector, 30°C in the sample and injector compartments, a flow rate of 0.5 mL/min, and an injection volume of 100 μL. The software packages used for data reduction were Wyatt's Astra version 6 (triple detection method with column calibration). HOMOGENIZATION
[0242] Homogenization was performed using an IKA Ultra Turrax T25 Digital Homogenizer (IKA, Wilmington, NC). EXAMPLE 1 PREPARATION OF POLY ALPHA-1,3-GLUCAN OF QUATERNARY AMMONIUM
[0243] This example describes the production of a quaternary ammonium poly alpha-1,3-glucan ether derivative. Specifically, hydroxypropyl trimethyl ammonium poly alpha-1,3-glucan was produced.
[0244] 10 g of poly alpha-1,3-glucan (Mw [weighted average molecular weight] = 168,000) was added to 100 ml of isopropanol in a 500 ml round bottom flask equipped with a thermocouple for monitoring temperature and a condenser connected to a recirculating bath, and a magnetic stir bar. 30 ml of sodium hydroxide (17.5% solution) was added dropwise to this preparation, which was then heated to 25°C on a hot plate. The preparation was stirred for 1 hour before the temperature was raised to 55°C. Trimethyl 3-chloro-2-hydroxypropyl ammonium chloride (31.25 g) was then added to provide a reaction, which was held at 55°C for 1.5 hours before being neutralized with 90% acetic acid. The solid thus formed (the hydroxypropyl trimethyl ammonium poly alpha-1,3-glucan) was collected by vacuum filtration and washed with ethanol (95%) four times, dried under vacuum at 20 to 25° C, and analyzed by NMR and SEC to determine molecular weight and DoS.
[0245] Additional samples of hydroxypropyl trimethyl ammonium poly alpha-1,3-glucan were synthesized following the procedure described above, but with some process variations. Specifically, samples of poly alpha-1,3-glucan with varying Mw of were used as starting material, and different amounts of etherification agent (3-chloro-2-hydroxypropyl-ammonium trimethyl chloride) were used. Furthermore, the reaction time (starting from the addition of the etherification agent and ending with the neutralization) was varied. Table 1 presents these various process variations and the subsequent DoS measurements of the quaternary ammonium glucan ether products. TABLE 1 OF POLY ALPHA-1,3-GLUCAN OF HYDROXYPROPIL QUATERNARY AMMONIUM PREPARED FROM POLY ALPHA-1,3-GLUCAN

a The reaction time was measured from the time the etherification agent was added to the neutralization reaction time.
[0246] Therefore, the quaternary ammonium glucan ether derivative, the hydroxypropyl trimethyl ammonium poly alpha-1,3-glucan, was prepared and isolated. EXAMPLE 2 EFFECT OF SHEAR RATE ON THE VISCOSITY OF POLY ALPHA-1,3-GLUCAN OF QUATERNARY AMMONIUM
[0247] This example describes the effect of shear rate on the viscosity of hydroxypropyl trimethyl ammonium poly alpha-1,3-glucan. This glucan ether derivative has been shown to exhibit shear thinning behavior. Therefore, the addition of hydroxypropyl trimethyl ammonium poly alpha-1,3-glucan to a liquid can modify the rheological behavior of the liquid.
[0248] Several samples of hydroxypropyl trimethyl ammonium poly alpha-1,3-glucan were prepared as described in Example 1. To prepare a 2% by weight solution of each sample, 1 g of sample was added to 49 g of DI water. Each preparation was then homogenized for 12 to 15 seconds at 20,000 rpm to dissolve the hydroxypropyl trimethyl ammonium poly alpha-1,3-glucan sample in the water.
[0249] To determine the viscosity of each 2% by weight quaternary ammonium glucan solution at different shear rates, each solution was subjected to different shear rates using a Brookfield DV III + Rheometer equipped with a recirculating bath to control the temperature (20°C) and an ULA spindle (ultra low adapter) and adapter assembly. The shear rate was increased using a gradient program that increased from 10 to 250 rpm and the shear rate was increased by 4.9 1/sec every 20 seconds for the ULA spindle and adapter. The results of the experiment are shown in Table 2. TABLE 2 VISCOSITY OF POLY ALPHA-1,3-GLUCAN SOLUTIONS OF HYDROXYPROPYL QUATERNARY AMMONIUM AT VARIOUS SHEAR RATES

a Each sample is described in Table 1.
[0250] The results summarized in Table 2 indicate that the viscosity of each of the quaternary ammonium poly alpha-1,3-glucan solutions is reduced as the shear rate is increased. This observation means that these solutions demonstrate the shear thinning behavior.
[0251] Therefore, hydroxypropyl trimethyl ammonium poly alpha-1,3-glucan when dissolved in an aqueous solution not only modifies the viscosity of the solution, but also the rheological properties of the solution. This quaternary ammonium glucan, therefore, can be added to an aqueous liquid to modify its rheological profile. EXAMPLE 3 CREATING THE CALIBRATION CURVE FOR DIRECT RED 80 STAINING USING UV ABSORPTION
[0252] This example describes the creation of a calibration curve useful for determining the relative level of absorption of poly alpha-1,3-glucan ether derivatives on tissue surfaces.
[0253] The solutions of known concentration (ppm) were performed using the dye Direct Red 80. The absorbance of the solutions was measured using a LAMOTTE SMART2 colorimeter at 520 or 620 nm. The absorption information was plotted so that it could be used to determine the dye concentration of the solutions that were exposed to tissue samples. The concentration and absorbance of each calibration curve are given in Table 3. TABLE 3 DIRECT RED 80 CALIBRATION CURVE DATA

[0254] Therefore, a calibration curve was prepared which is useful to determine the relative level of absorption of the poly alpha-1,3-glucan ether derivatives on the tissue surfaces. This calibration curve was used in Example 4. EXAMPLE4 ADSORPTION OF POLY ALPHA-1,3-GLUCAN ETHER OF QUATERNARY AMMONIUM IN VARIOUS TISSUES
[0255] This example describes the test of the degree of absorption of a quaternary ammonium poly alpha-1,3-glucan (the hydroxypropyl trimethyl ammonium poly alpha-1,3-glucan) in different tissue types.
[0256] A solution of 0.07% by weight of the hydroxypropyl trimethyl ammonium poly alpha-1,3-glucan (Sample 1F, Table 1) was prepared by dissolving 0.105 g of the polymer in 149.89 g of deionized water. This solution was divided into several aliquots with different concentrations of polymer and other components (Table 4). Such other components were acid (diluted hydrochloric acid) or base (sodium hydroxide) to modify the pH, or the NaCl salt. TABLE 4 POLY ALPHA-1,3-GLUCAN QUATERNARY AMMONIUM SOLUTIONS USED IN TISSUE ABSORPTION STUDIES

[0257] Four different types of fabric (cretone, polyester, polyester/cretone 65:35, bleached cotton) were cut into pieces of 0.17 g. Each piece was placed in a 2 ml well in a 48-well cell culture plate. Each tissue sample was exposed to 1 mL of each of the above solutions (Table 4) for a total of 36 samples (a control solution with no polymer was included in each tissue test). Tissue samples were allowed to rest for at least 30 minutes in the polymer solutions. Tissue samples were removed from the polymer solutions and rinsed in deionized water for at least one minute to remove any unbound polymer. The tissue samples were then dried at 60°C for at least 30 minutes until constant dryness was achieved. Tissue samples were weighed after drying and placed individually into 2 ml wells in a clean 48-well cell culture plate. The tissue samples were then exposed to 1 mL of a 250 ppm Direct Red 80 dye solution. Samples were left in the dye solution for at least 15 minutes. Each tissue sample was removed from the dye solution, the dye solution after that time was diluted 10x.
[0258] The absorbance of the diluted solutions was measured in comparison to a control sample. A relative measure of tissue adsorbed glucan polymer was calculated based on the calibration curve created in Example 3 for the Direct Red 80 dye. Specifically, the UV absorbance difference for the tissue samples exposed to the polymer compared to the controls (tissue not exposed to polymer) represents a relative measure of polymer adsorbed to tissue. This UV absorbance difference can also be expressed as the amount of dye bound to the tissue (relative to the amount of dye bound to the control), which was calculated using the calibration curve (ie, UV absorption was converted to ppm dye). Table 5 provides the “dye (ppm)”; a positive value represents the amount of dye that was in excess of the amount of dye bound to the control tissue, while a negative value represents the amount of dye that was less than the amount of dye bound to the control tissue. A positive value reflects that the glucan ether compound has absorbed to the tissue surface. TABLE 5 RELATIVE AMOUNT OF POLY ALPHA-1,3-GLUCAN OF QUATERNARY AMMONIUM BOUNDED TO DIFFERENT TISSUES UNDER DIFFERENT CONDITIONS
the amount of dye bound to the fabric. A positive value represents the amount of dye that was in excess of the amount of dye bound to the control. The amount of positive dye in turn represents the relative amount of glucan ether adsorbed to the tissue. - b pH of binding conditions was about 7 (see Table 4). c binding conditions do not include salt (see Table 4).
[0259] The data in Table 5 indicate that the quaternary ammonium glucan polymer can absorb different types of tissue under different salt and pH conditions. This absorption occurs even if the tissues were rinsed after exposure to the polymer. It is noteworthy that the glucan ether was able to absorb the polyester and the polyester/cretone blend, in addition to absorbing cotton.
[0260] Therefore, a poly alpha-1,3-glucan ether derivative in an aqueous composition can absorb to tissue.

权利要求:
Claims (20)
[0001]
1. COMPOSITION, characterized by comprising a poly alpha-1,3-glucan ether compound represented by the structure:
[0002]
2. COMPOSITION according to claim 1, characterized in that at least one positively charged organic group comprises a substituted ammonium group.
[0003]
3. COMPOSITION according to claim 2, characterized in that the positively charged organic group comprises a trimethyl ammonium group.
[0004]
4. COMPOSITION according to claim 2, characterized in that the positively charged organic group is a quaternary ammonium group.
[0005]
A COMPOSITION according to claim 1, characterized in that at least one positively charged organic group comprises an alkyl group or hydroxy alkyl group.
[0006]
6. COMPOSITION according to claim 5, characterized in that at least one positively charged organic group is a hydroxypropyl quaternary ammonium group.
[0007]
A COMPOSITION according to any one of claims 1 to 6, characterized in that at least 90% of the glycosidic bonds of the poly alpha-1,3-glucan ether compound are alpha-1,3-glycosidic bonds.
[0008]
8. COMPOSITION according to any one of claims 1 to 7, characterized in that the composition is a personal care product, household product or industrial product.
[0009]
9. COMPOSITION, according to claim 8, characterized in that the composition is a product for tissue treatment.
[0010]
10. COMPOSITION according to any one of claims 1 to 9, characterized in that the composition comprises at least one surfactant.
[0011]
11. COMPOSITION according to any one of claims 1 to 10, characterized in that the composition comprises at least one enzyme.
[0012]
12. COMPOSITION according to any one of claims 1 to 11, characterized in that the composition is an aqueous composition.
[0013]
13. COMPOSITION according to any one of claims 1 to 7, characterized in that the composition additionally comprises fiber.
[0014]
A COMPOSITION according to claim 13, characterized in that the poly alpha-1,3-glucan ether compound is on the surface of the composition.
[0015]
15. COMPOSITION according to any one of claims 13 to 14, characterized in that the fiber is a natural fiber, synthetic fiber or semi-synthetic fiber.
[0016]
16. COMPOSITION according to any one of claims 13 to 15, characterized in that the composition is fabric.
[0017]
17. COMPOSITION according to any one of claims 13 to 15, characterized in that the composition is paper.
[0018]
18. METHOD FOR THE PRODUCTION OF A poly alpha-1,3-glucan ether COMPOUND, characterized in that it comprises: (a) contacting poly alpha-1,3-glucan, in a reaction under alkaline conditions, with at least an etherification agent comprising a positively charged organic group, wherein at least one positively charged organic group is etherified to the poly alpha-1,3-glucan, thereby producing a poly alpha-1,3-glucan ether compound as defined in claim 1; and (b) optionally isolating the poly alpha-1,3-glucan ether compound produced in step (a).
[0019]
19. METHOD FOR THE TREATMENT OF A MATERIAL, characterized in that it comprises the contact of a material with a composition as defined in claim 1, in which the composition is an aqueous composition.
[0020]
20. The method according to claim 19, characterized in that the material comprises a fabric, optionally wherein the fabric comprises a natural fiber, synthetic fiber, semi-synthetic fiber or any combination thereof.

类似技术:

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同族专利:

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公开号 | 公开日

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EP3789407A1|2021-03-10|

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AU2014364772B2|2018-07-26|

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ES2835703T3|2021-06-23|

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EP3083705B1|2020-09-30|

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CA2932501A1|2015-06-25|

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US10800860B2|2020-10-13|

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WO2015095358A1|2015-06-25|

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US20160311935A1|2016-10-27|

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EP3083705A1|2016-10-26|

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CN106029700B|2019-04-12|

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JP6559139B2|2019-08-14|

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AU2014364772A1|2016-06-09|

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BR112016014014A2|2017-08-08|

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US10323102B2|2019-06-18|

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JP2017500409A|2017-01-05|

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MX2016007920A|2016-09-13|

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US20180223002A1|2018-08-09|

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US9957334B2|2018-05-01|

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CN106029700A|2016-10-12|

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KR20160101983A|2016-08-26|

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US20190345266A1|2019-11-14|

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法律状态:
2020-01-21| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-01-19| B25A| Requested transfer of rights approved|Owner name: DUPONT INDUSTRIAL BIOSCIENCES USA, LLC (US) |

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2021-02-09| B25A| Requested transfer of rights approved|Owner name: NUTRITION AND BIOSCIENCES USA 4, INC. (US) |

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2021-07-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-08-10| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 17/12/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201361917507P| true| 2013-12-18|2013-12-18|

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US61/917,507|2013-12-18|

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US201462014273P| true| 2014-06-19|2014-06-19|

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