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    • 专利摘要:
    The present invention is directed to induced microfibrillated polysaccharides comprising, but not limited to, cellulose induced by steric and / or electrostatic forces by stabilizing and / or microfibrillating the polysaccharide starting material. The electrostatic force is provided by an anionic charge or by a combination of anionic and cationic charges. The present invention also relates to a method for improving the flowability of a composition of matter using derived microfibrillated polysaccharides. In addition, the present invention relates to methods for improving the stability of coatings, paper preparation, and emulsions, dispersions and foams using derived microfibrillated polysaccharides. The present invention also relates to compositions, including emulsions, dispersions and foams, including derived microfibrillated polysaccharides, including paper compositions, edible compositions, non-edible compositions and spreadable compositions.
    公开号:KR20010042551A
    申请号:KR1020007011213
    申请日:2000-02-08
    公开日:2001-05-25
    发明作者:메어리 진 캐쉬；아니타 엔. 찬；허버트 톰프슨 코너；패트릭 조우지프 코완；로버트 앨런 겔만；케이트 마리트 루스바르디；새무얼 안토니 톰프슨；프랭크 페인 티세
    申请人:조이스 엘. 모리슨；허큘레스 인코포레이티드；
    IPC主号:
    专利说明:

    Derivatized Microfibrillar Polysaccharide
    Polysaccharides are often found in nature in a form conforming to fiber morphology. Polysaccharides that are not found in nature in fiber form can often be converted to fiber morphology using fiber spinning techniques. Whether fiber morphology is of natural or artificial origin, polysaccharides will often be present such that the fibers can be reduced to fibrillated and microfibrillated submorphology through energy application.
    Fibrillated and microfibrillated celluloses obtained in this way are contemplated for application uses, including use as additives in aqueous substrate systems to influence fluidity, for example viscosity. The amount of use of these materials in aqueous systems is often on the order of about 2% by weight, below which these materials tend to be poorly bulked and have an uneven overall distribution.
    For microfibrillated cellulose and its preparation, US Pat. Nos. 4,500,546, 4,487,634, 4,483,743, 4,481,077, 4,481,076, 4,464,287, 4,452,722, 4,452,721 4,378,381, 4,374,702 and 4,341,807, the disclosures of which are incorporated herein by reference. Part of the intent of these documents is to describe microfibrillated cellulose in a stable and homogeneous suspension characterized by being useful for end-use products, including food, cosmetics, pharmaceuticals, paints and drilling mud.
    The characteristics of cellulose nanofibrils are described in International Patent Publication Nos. 98/02486 (PCT / FR97 / 01290), 98/02487 (PCT / FR97 / 01291) and 98/02499 (PCT / FR97 / 01297). And the disclosures of which are incorporated herein by reference. Nanofibrils are characterized by having a diameter of about 2 to about 10 nm.
    EP-84584595 discusses cationic cellulose particulates which are insoluble, cationicly charged and used for water treatment, in particular for water treatment in papermaking plants. On papermaking the cationic particulates are described as removing anionic waste from water. The particles are obtained by milling, which is said to uniformly reduce the particle size so that it is typically circular, as the length / diameter ratio is described as approximately 1. The particle size is said to be 0.001 mm (ie 1 μm), preferably 0.01 mm (10 μm).
    EP 859011 ("EP '011") relates to a process for obtaining cationic cellulose microfibrils or soluble derivatives thereof. The method is described as preparing a cationic cellulose derivative and processing the derivative through a high pressure homogenizer to form a transparent gel. The product can be dehydrated and rehydrated. The viscosity measured for the product at 2% concentration in water is reported. EP '011 shows that the degree of substitution (“DS”) of cellulose can be 0.1 to 0.7, preferably 0.2 to 0.7, more preferably 0.3 to 0.6, even more preferably 0.5 to 0.6. Examples show cellulose with a DS in the range of 0.24 to 0.72. Gelling is reported to occur when the concentration of microfibrils in water exceeds 10 g / L or exceeds 1%. EP '011 defines gelation as occurring when G'> G ", where G 'is a dynamic storage modulus and G" is a dynamic loss modulus.
    Microfibrillated chitosan forms a planar oriented sheet upon drying [H. Yokata, J. Polymer Sci., Part C: Polymer Letters, 24: 423-425 (1986). The paper states that when the concentration of chitosan in water is 4%, a gel with a viscosity of 26,600 cps (Brookfield, 20 ° C, rotor number 7, 10 rpm) is formed. Microfibrillated chitosan is prepared by homogenizing commercial chitosan flakes in a Gaulin homogenizer. Sodium hydroxide is used to deacetylate commercial chitosan.
    Japanese Patent No. 59 [1984] -84938 discusses a method for producing a chitosan suspension. Purified commercial chitosan, isolated from crabs and lobsters, is crushed into pieces with a maximum length of about 1 to 2 mm. This piece is then suspended in water with up to 15% chitosan and passed through several high pressure homogenizers of 204.1 to 544.4 atm (3,000 to 8,000 psi).
    It would be desirable to obtain microfibrillated polysaccharides, at least in part due to lack of general suitability of food cationic materials, in which viscosity affecting properties are achieved without the presence of cationic functional groups. It would also be desirable to obtain microfibrillated polysaccharides capable of forming gels at concentrations below 1%, which would provide the economics and ease of formulation while still providing the required flow behavior and uniform distribution. .
    In addition, there is a continuing industrial need to improve the stability of commercial emulsions, such as paper sizing emulsions. Currently, one method of stabilizing such emulsions is to add charged materials such as cationic starch, which may be added in amounts corresponding to 10 to 20% by weight of the size component. Interaction with anionic components such as sulfonates can also improve stability. However, emulsion failure still occurs in such emulsions via density driven separation or gelation, also referred to as creaming. Therefore, it would be desirable to develop materials that can be added to the emulsion to provide long term stability.
    <Summary of invention>
    FIELD OF THE INVENTION The present invention relates to derived microfibrillated polysaccharides, methods for their preparation and their applications. Induced microfibrillary polysaccharides are derived to contain substituents that provide electrostatic and / or steric functionality, and electrostatic functionality includes, but is not necessarily the presence of an anionic charge.
    Suitable polysaccharides for use in the present invention include cellulose, hemicellulose, chitin, chitosan, guar gum, pectin, alginate, daikon radish, xanthan, starch, amylose, amylopectin, alternane, gellan, mutan, dextran , Pullulan, fructan, locust bean gum, carrageenan, glycogen, glycosaminoglycans, murine, capsular polysaccharide of bacteria and derivatives thereof. Mixtures of these can be used. Preferred polysaccharides are cellulose, chitin, chitosan, pectane, daikon, starch, carrageenan and derivatives thereof, used alone or in combination, with cellulose being most preferred. Cellulose is just an example of chemical pulp, mechanical pulp, thermal mechanical pulp, chemical-thermal mechanical pulp, recycled fiber, newsprint, cotton, soybean pods, pea pods, corn pods, flax, hemp, jute, yam, hemp, manila It can be obtained from any available feedstock including, sisal, sugarcane pods, corn, wheat, bamboo, velonia, bacteria, algae, fungi, microcrystalline cellulose, vegetables and fruits. Preferred raw materials of cellulose are tablets, optionally bleached wood pulp, refined cotton linters, fruits and vegetables, produced by a sulfite, kraft or prehydrolysis kraft pulping process.
    Induced microfibrillated polysaccharides obtained using cellulose include hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, carboxymethylhydroxyethyl cellulose, hydroxypropylhydroxyethyl cellulose, methyl cellulose, Methylhydroxypropyl cellulose, methylhydroxyethyl cellulose, carboxymethylmethyl cellulose, hydrophobically modified carboxymethylcellulose, hydrophobically modified hydroxyethyl cellulose, hydrophobically modified hydroxypropyl cellulose, hydrophobically modified ethylhydroxyethyl cellulose, hydrophobically modified carboxymethyl Hydroxyethyl cellulose, hydrophobically modified hydroxypropylhydroxyethyl cellulose, hydrophobic modified methyl cellulose, hydrophobically modified methylhydroxypropyl cellulose, hydrophobically modified methylhydroxyethyl cellulose Rhodes, hydrophobic modified carboxymethylmethyl cellulose, nitrocellulose, cellulose acetate, cellulose sulfate, cellulose vinyl sulphate, cellulose phosphate and cellulose phosphonate.
    Induced microfibrillated cellulose of the present invention has a concentration range of about 0.01% to about 100% in water, or a concentration range of about 0.01% to about 50% in water, or about 0.05% to about 0.99% in water. It is possible to form gels in water at one or more points in the concentration range. In another embodiment, the induced microfibrillated cellulose of the present invention forms a gel in water at a concentration of about 0.95%.
    Derived microfibrillated polysaccharides can be used in the presence of a substantially insoluble solvent. Examples of solvents are water, alcohols and oils.
    When derived using a group that provides electrostatic functionality, the derived microfibrillary polysaccharide of the invention may have a degree of substitution of less than about 0.5, less than about 0.35, less than about 0.2, less than about 0.18, or less than about 0.1. A preferred range of degrees of substitution is about 0.02 to about 0.5, with the range of about 0.05 to about 0.2 being more preferred. If the induced microfibrillary polysaccharide is induced to be characterized by including substituents that provide electrostatic functionality in the form of anionic charges, the degree of substitution of these substituents that provide electrostatic functionality in the form of anionic charges is preferably about 0.05 or greater. Do. Anionic charge can be provided, for example, by carboxyl, sulfate, sulfonate, phosphonate or phosphate groups or combinations thereof. If a cationic charge is also present, the two charges may be provided by the same group or substituent (ie, the substituent may be amphoteric or zwitterionic), or the induced microfibrillary polysaccharide may contain anionic charge It can be derived to contain both substituents and substituents containing cationic charges. In addition, the induced microfibrillated polysaccharides of the present invention are individually derived microfibrillated polysaccharides derived at least one to provide anionic charge and at least the other to provide anionic charge, cationic charge or both. It can be obtained by blending two or more kinds of rides.
    When the derived microfibrillated polysaccharide of the present invention is derived to contain a substituent that provides steric functionality, the molar substitution degree of the derived microfibrillated polysaccharide is less than about 3.0, or less than about 1.5, or about 1.0 Or less than about 0.5. The molar substitution degree may be about 0.5 to about 3.0. Stereofunctionality includes, but is not limited to, hydroxyethyl groups, hydroxypropyl groups, methyl groups, ethyl groups, straight or branched chain alkyl, alkenyl or alkynyl groups having about 4 to about 30 carbon atoms and / or about 4 to about carbon atoms. And aryl, arylalkyl, arylalkenyl, cyclic and heterocyclic hydrocarbons that are about 30.
    In one preferred embodiment, the derived microfibrillated polysaccharide contains carboxymethylcellulose and the degree of substitution is less than about 0.35, or less than about 2.0. The degree of substitution can range from about 0.02 to about 0.2, with a range of about 0.10 to about 0.2 being preferred.
    Induced microfibrillated cellulose of the present invention can form a gel at a concentration of less than about 1% in water.
    In a further embodiment, the invention relates to an edible composition of matter containing the derived microfibrillated polysaccharide of the invention. Edible compositions of matter may be, but are not limited to, low fat, reduced fat or fat free food spreads such as mayonnaise or salad dressings. In addition, the edible composition may contain a pharmaceutically active ingredient. Induced microfibrillary polysaccharides can be used to provide or enhance the control, maintenance or delay of the release of the components of an edible composition, particularly including pharmaceutically active ingredients.
    In another embodiment, the derived microfibrillated polysaccharides of the present invention can be used in non-edible developing compositions of matter, such as skin protection lotions or creams, or sunscreen lotions or creams.
    The present invention also relates to paper compositions containing derived microfibrillated cellulose, in particular but not exclusively, microfibrillated carboxymethylcellulose.
    Derived microfibrillated polysaccharides can be prepared by using a derivatization step of treating microfibrillated polysaccharides to obtain derived microfibrillated polysaccharides. In addition, microfibrillation of the derived polysaccharide may be performed to prepare the induced microfibrillated polysaccharide. Alternatively, the microfibrillation and derivatization steps can be performed substantially simultaneously. In one preferred embodiment, the cellulose is first led to monochloroacetic acid or a salt thereof under alkaline conditions to produce carboxymethylcellulose, the carboxymethylcellulose is suspended in water and the resulting suspension is homogenized to microfibrillated carboxymethyl Prepare cellulose.
    The derivatization step may include contacting a swelling agent, such as an anionic reagent, with the non-microfibrid phase polysaccharide, and may occur under alkaline conditions. These alkaline conditions are anionic reagents in the presence of alkali reagents which are oxides or hydroxides of sodium hydroxide, alkali metals or alkaline earth metals, alkali silicates, alkali aluminates, alkali carbonates, amines, ammonium hydroxide, tetramethylammonium hydroxide or combinations thereof. And contacting cellulose with the cellulose. Induction can occur at high solids.
    Microfibrillation can be achieved by applying energy to non-microfibrillated polysaccharides under conditions sufficient to produce microfibrillated polysaccharides. The non-microfibrillated phase may optionally be enzymatically treated prior to microfibrillation. More specifically, microfibrillation can be achieved using homogenization, pumping, mixing, heating, steam explosion, pressure-decompression cycles, impact, grinding, ultrasonic waves, microwave explosion, milling, and combinations thereof. In one preferred embodiment, the non-microfibrillated polysaccharide is passed through a homogenizer under conditions sufficient to produce microfibrillated cellulose, which conditions may include a pressure difference of at least about 204.1 atm (3,000 psi). And pass through the homogenizer three or more times.
    The process should be carried out to produce a derived microfibrillated polysaccharide that is substantially insoluble in the solvent used. Water is the preferred solvent of use, but other solvents, including but not limited to alcohols and oils, are also contemplated in various applications.
    The present invention relates to a derived microfibrillated polysaccharide prepared by the above method.
    In another embodiment, the present invention relates to a method for modifying the fluidity of a liquid composition of a substance by incorporating the derived microfibrillated polysaccharide of the invention in a liquid composition of the substance.
    This can be accomplished by incorporating the derived microfibrillated polysaccharide into the water containing system and can be used, for example, to provide scale inhibition and / or corrosion inhibition. Fluidity that can be modified by induced microfibrillated polysaccharides includes viscosity, suspension stability, gel insensitivity to temperature, shear reversible gelling, yield stress and liquid retention.
    Liquid compositions that can be fluidly modified include, but are not limited to, food, pharmaceuticals, neutraceuticals, personal care products, fibers, paper, paints, coatings, and building compositions. These include oral protective products, creams or lotions (e.g. moisturizers, knights, anti-aging or sunscreen creams or lotions) for epithelial application, reduced fat, low fat or fat free food spreads (e.g. mayonnaise) and Same food spreads, and drilling fluids.
    The present invention also relates to a method for improving the physical and / or mechanical properties of a coating composition by incorporating an effective amount of the derived microfibrillated polysaccharide in the coating composition. Physical and / or mechanical properties that can be improved in this way include film formability, leveling, sag resistance, strength, durability, dispersibility, water repellency, floatability and sputterability.
    The present invention is particularly useful in the field of paper making and processing. For example, induced microfibrillated cellulose may be used to improve one or more of sizing, strength, scale inhibition, drainage, dehydration, retention, purification, forming ability, adsorption, film forming ability, film forming ability, and polyelectrolyte complexing during paper manufacture. Can be used. As one specific example, induced microfibrillated cellulose may be used as drainage aid and / or sizing agent. Polyelectrolyte complexes containing derived microfibrillated polysaccharides are also within the scope of the present invention.
    Microfibrillated carboxymethylcellulose is a particularly preferred embodiment for use in the paper art. During the papermaking process, induced microfibrillated cellulose is additionally used to increase drainage and / or dehydration rates during paper production, and to retain organic and / or inorganic dispersed particles in the paper sheet during paper sheet production. And to improve the uniform formation of the paper sheet during paper sheet manufacture, and to improve the strength of the paper sheet. Induced microfibrillated cellulose is any additive and performance enhancer commonly used in paper making, such as cationic polyacrylamide, polydiallyldimethyl-ammonium chloride, cationic starch, ammonium or mono-, di- or Cellulose derivatives containing trialkyl ammonium substituents, guar gum derivatives containing ammonium or mono-, di- or trialkyl ammonium substituents, resins, aluminum salts formed by the reaction of amines and / or polyamines with epichlorohydrin At least one polymer of a hydrolyzed or partially hydrolyzed aluminum salt, a hydrolyzed or partially hydrolyzed aluminum salt with an organic or inorganic species, ethylene oxide, ethyleneimine, allylamine or vinylamine, ethylene oxide, ethyleneimine At least one copolymer or terpolymer of allylamine or vinylamine, and The combination can be used in combination. With respect to the retention of organic and / or inorganic dispersed particles, the particles retained as described above may include one or more of pulp fines, fillers, sizing agents, pigments, clays, hazardous organic particulates and hazardous inorganic particulates. .
    In another embodiment, the stability of the emulsified, dispersed or foamed system can be improved by including the derived microfibrillated polysaccharide of the present invention in the system. The derived microfibrillated polysaccharide may be added to an existing system, or may be added to a composition to be processed into such a system, or may be added during processing of such a composition. If the composition is added before the emulsification, dispersion or processing into the foaming system is complete, the processing conditions used to form the emulsion, dispersion or foam can also be used to produce the derived microfibrillated polysaccharides. Thus, derived non-microfibrillated polysaccharides, where “non- microfibrillated” includes incompletely microfibrillated polysaccharides, can be added to the composition before processing is complete. And subsequent processing may be carried out in such a way that the polysaccharide is microfibrillated. In addition, microfibrillated polysaccharides may be added to the composition and subsequent processing may be performed to derive the microfibrillated polysaccharides. In another variation, both derivatization and microfibrillation can occur during processing. Systems that can be treated in this way include water-in-oil and oil-in-water emulsions.
    The present invention also relates to an emulsified, dispersed or expanded system produced by the above process, and an emulsified, dispersed or expanded system containing the derived microfibrillated polysaccharide of the present invention.
    The present invention relates to derived microfibrillated polysaccharides. More specifically, the present invention relates to microfibrillated polysaccharides that are stable by steric and / or electrostatic forces, wherein the electrostatic forces are provided by anionic charges or by a combination of both anion and cation charges.
    1 shows the spectrum of dynamic mechanical properties for Sample 1 of Example 7. FIG.
    2 shows the spectrum of dynamic mechanical properties for Sample 2 of Example 7. FIG.
    3 shows the spectrum of the dynamic mechanical properties for Sample 3 of Example 7. FIG.
    4 shows the spectrum of the dynamic mechanical properties for Sample 4 of Example 7. FIG.
    5 shows the spectrum of the dynamic mechanical properties for Sample 5 of Example 7. FIG.
    6 shows the spectrum of the dynamic mechanical properties of Sample 1 of Example 13. FIG.
    7 shows the spectrum of dynamic mechanical properties for Sample 2 of Example 13. FIG.
    8 shows the spectra of the dynamic mechanical properties for Sample 3 of Example 13. FIG.
    FIG. 9 is a transmission electron micrograph at 10,000 × magnification of a microfibrillated carboxymethylcellulose sample prepared as in Example 3 below with a degree of substitution of about 0.17, negatively stained with uric acid acetate.
    The present invention relates to derived microfibrillated polysaccharides. Suitable polysaccharides for use in the present invention include cellulose, hemicellulose, chitin, chitosan, guar gum, pectin, alginate, daikon radish, xanthan, starch, amylose, amylopectin, alternane, gellan, mutan, dextran , Pullulan, fructan, locust bean gum, carrageenan, glycogen, glycosaminoglycans, murine, capsular polysaccharides of bacteria and derivatives thereof, but are not limited thereto, and cellulose is preferred. The polysaccharides can be used as is, or can be spun to create or enhance fiber structures.
    Cellulose is the preferred polysaccharide for use in the present invention. Cellulose raw materials for use in the present invention include (a) wood fibers, such as chemical pulp, mechanical pulp, thermal mechanical pulp, chemical-thermal mechanical pulp, recycled fibers, newsprint, (b) seed fibers, such as Seed fiber from cotton, (c) seed pod fiber, for example soybean pods, pea pods, seed pod fiber from corn pods, (d) bast fiber, for example flax, hemp, jute, yam, yam Bast fiber, (e) leaf vein fibers such as manilama, leaf vein fibers from sisalma, (f) stem or straw fibers, such as sugarcane pods, corn, stem or straw fibers from wheat, (g) Flower and fiber, for example, flower and fiber from bamboo, (h) cellulose fiber from algae such as bellonia, (i) bacteria or fungi, and (j) oily cells, such as vegetables and fruits, in particular sugar beet, and With lemon, lime, orange, grape There are oily cells from the same citrus fruit. It is also possible to use these cellulose materials in microcrystalline form. Preferred cellulose raw materials are (1) tablets prepared from sulfite, kraft (sulfate) or prehydrolyzed kraft pulping processes, optionally bleached wood pulp, (2) refined cotton linters, and (3) fruits and vegetables It is, especially beets and citrus fruits. The raw material of cellulose is not particularly limited, and any raw material including synthetic cellulose or cellulose analog may be used.
    Cellulose is found in nature at several hierarchical levels of tissue and orientation. Cellulose fibers are characterized by comprising a layered secondary wall structure in which the large fibrils are arranged. Macrofibrils are characterized by including several microfibrils further characterized by cellulose molecules arranged in crystalline and amorphous sites. The diameter of the cellulose microfibrils is about 5 to about 100 nm for various plant species, with diameters of about 25 to about 35 nm being most typical. Microfibrils are present in bundles arranged in parallel in a matrix of amorphous hemicellulose (specifically xyloglucans), pectin polysaccharides, lignin and hydroxyproline rich glycoproteins (including extenes). Microfibrils are spaced approximately 3-4 nm apart in the space occupied by the matrix compound. The specific arrangement and location of matrix materials and how they interact with cellulose microfibrils is not yet fully understood.
    For the purposes of the present invention, polysaccharide microfibrils means a small diameter, a high ratio of length to diameter compared to the diameter, length to diameter ratio of the diameter of the cellulose microfibrils produced in nature. do. As a non-limiting example, the polysaccharide microfibrils may be about 20 to about 100 nm in diameter, with lengths providing high aspect ratios of greater than 100, greater than 500, or greater than 1,000. Although microfibrils and microfibrillation are mentioned in the present specification and claims, the scope of the present invention also includes nanofibrils (cellulose based or otherwise), which may be obtained as microfibrils by practicing the present invention. Flowable modification, stabilization and other properties that can be obtained can also be obtained by using nanofibrils alone or in combination with microfibrils.
    In nature, many polysaccharides do not exist in a microfibril array, but fibers can be made from these polysaccharides by using fiber spinning techniques. In one embodiment of the present invention, it is contemplated that fibers spun from polysaccharides can be derived and microfibrillated into fiber structures with dimensions of the extent found in native cellulose. A background description of the structure, function and spontaneous generation of natural cellulose can be found in Haigler, CH, Cellular Chemistry and Its Applications, Nevell, pages 30-83 (1985), which is hereby incorporated by reference in its entirety. Can be.
    Induced microfibrillated polysaccharides of the present invention are characterized by the presence of substituents that are in the fine fibrils form and provide steric and / or electrostatic functionality. The amount of substituents present can be quantified by the degree of substitution (DS) for some anionic and cationic substituents and by the degree of molar substitution (MS) for steric substituents. The degree of substitution that will vary depending on the molecular weight of the polysaccharide is the average value of the substituted hydroxyl groups per anhydrous saccharide unit, and the molar substitution is the average value of the substituents added per anhydrous saccharide unit. DS and MS determine the solubility of the derived polysaccharides and can be easily adjusted to yield derived polysaccharides that are substantially insoluble in the environment of use, whether aqueous or non-aqueous. Although the environment of use will be primarily aqueous, the derived microfibrillated polysaccharides of the present invention include paints, coatings, lacquers, oil rich foods, inks (including but not limited to ink-jet inks), personal care products, Useful in applications with other solvents or liquid carriers, such as cosmetics and water-in-oil emulsions.
    Any suitable method may be used to obtain the derived microfibrillated polysaccharide. In particular, the microfibrillation and derivatization steps to impart steric and / or electrostatic functionality to the polysaccharide may be performed separately or together to reach the final result. Thus, the non-microfibrillated polysaccharide starting material is derived with anionic groups, with both anionic and cationic groups, or with a blend or mixture of anionic and cationic groups followed by microfibrillation, or first It may be induced after microfibrillation. In addition, if the starting material is a microfibrillated polysaccharide, only a derivatization step is needed, and if the starting material is a polysaccharide already properly derived with anionic groups, or both anion and cation groups, only microfibrils Only an angry step is necessary.
    The degree of substitution (for electrostatic derivatization) and / or molar substitution (for stereoinduction) of the polysaccharide may be such that the derived microfibrillated polysaccharide is substantially insoluble in the solvent or carrier present in the intended use environment. It must be low enough. In many applications, the solvent or carrier will be water, and in such applications the degree of substitution and / or molar substitution should be such that the derived microfibrillary polysaccharide is substantially insoluble in water. However, in other applications, polar solvents or carriers (eg alcohols) with different dissolution properties can be used, or nonpolar solvents or carriers (eg oils) can be used, in which case degree of substitution and / or) The molar substitution degree should be adjusted so that derived microfibrillated polysaccharides which are substantially insoluble in the solvent or carrier to be used in the intended application, which will be referred to herein as "solvents" for convenience, are obtained. Functionally, the derived microfibrillated polysaccharides must be sufficiently insoluble in the environment of use to provide the desired properties in the intended application.
    The presence of substantial insoluble material can be confirmed by observing 1-5% suspension of the problem material in the solvent or carrier used with an optical microscope at a sufficient magnification to see the insoluble material. The size can be determined by preparing under consideration a suspension of the material at approximately 0.1 to 0.01% in a liquid nonsolvent effective to disperse microfibrils. The suspension is then dried on a transmission electron microscope (TEM) glide and the sample is coated to protect it from electron beam damage and inspected at a magnification and focus sufficient to observe the structure from 1 to 1000 nm. If microfibrillary phase factors are present and they can be detected under these conditions, the combination of insoluble confirmation by light microscopy and identification of microfibrillary structures by TEM indicates that there is a substantially insoluble microfibrillary material. It is shown. Please refer to FIG. 9, an example of a transmission electron micrograph of microfibrillated carboxymethylcellulose prepared as in Example 3 and having a DS of about 0.17.
    For simplicity, the term "substituent" as used herein, unless otherwise indicated, refers to chemical species that provide steric stability to polysaccharides, chemical species to provide electrostatic functionality to polysaccharides through anionic charges, both anion and cation By chemical species that provides electrostatic functionality to polysaccharides through a combination of charges, and combinations thereof. In addition, "electrostatic" means an anionic charge or a combination of both anionic and cationic charges, whether two groups are present on a single substituent or provided on two or more substituents, respectively. "Derivatization" means any method that can include, for example, adsorption, as well as chemical reactions in which covalent bonds are produced, in which substituents are sufficiently associated with polysaccharides to provide the fluidity and other advantages of the present invention. . Finally, reference to the combination of both anionic and cationic charges on polysaccharides includes the use of substituents containing two types of charge (ie, amphoteric and / or zwitterionic substituents), both anionic and cationic groups. The use of a combination of substituents containing only one of anionic charge or cationic charge, and anionically derived polysaccharide and cationic derived polysaccharide, to which a polysaccharide in which a substituent including Two or more derived polys in which at least one of the derived polysaccharides comprises at least one anionic substituent and at least one of the other derived polysaccharides comprises at least one cation substituent, from which both blends are produced Blends of saccharides. However, "derived" does not include naturally occurring inducing polysaccharides in which there are groups which will only provide the steric and / or electrostatic functionality required by the present invention at concentrations higher than those found in nature. For example, naturally occurring cellulose may contain very low amounts of anionic charges that may still be present after microfibrillation. However, such microfibrillated cellulose will not be “derived” as the term is used herein, as its degree of substitution does not change from its natural state, and the amount of charge present in such microfibrillated cellulose is an advantage of the present invention. Because it will not provide.
    The step procedure used to obtain the derived microfibrillated polysaccharide of the present invention is not critical. Thus, the starting materials used to prepare the derived microfibrillated polysaccharides may be in the form of microfibrils or non-microfibrils. Similarly, the starting material may or may not already be derived from steric and / or electrostatic substituents. If the starting material is a non-microfibrillated polysaccharide, the substituents may be microfibrillated after being placed on the polysaccharide, or the substituents on the microfibrils produced after the first microfibrillation is performed. Can be located. It is also possible to process the polysaccharide with fibrils, to place substituents on the fibrils, and then further process the fibrils with microfibrils. Similarly, polysaccharides in the form of non-microfibrils that already contain such substituents can be processed into microfibrils. In addition, induction and microfibrillation can be performed simultaneously.
    Most, but not all, polysaccharides will contain some degree of both microfibrillated and non-microfibrillated structures before and after processing, with the ratio between the two structures being substantially completely microfibrillated. It will be appreciated that they range from polysaccharides that are substantially completely non-microfibrils. As used herein, the terms “microfibrillated phase”, “microfibrillated”, and the like, are substantially sufficient to confer the advantages that the polysaccharides, and polysaccharides, provided by the present invention are substantially fully microfibrillated. As long as they are microfibrillated, they include polysaccharides that can be substantially microfibrillated in small or significant amounts of non-microfibrillated phase structure.
    Preference is given to minimizing the energy required to prepare the non-microfibrid phase starting material and / or reducing the amount of water extracted during or at the end of the process. In this regard, the induced microfibrillated polysaccharides of the present invention can be prepared by inducing microfibrillated polysaccharides, and if the polysaccharides are already derived, the microfibrillation process is generally It should be noted that less energy is needed and / or more efficient. Without being bound by theory, this may be because fibril bundle structures are loosened by the presence of steric and / or electrostatic functionality on the polysaccharide.
    The use of less energy not only saves money, but also reduces the breakdown of polysaccharide microfibrils. Thus, microfibrillation of polysaccharides that are already derived can produce derived microfibrillated polysaccharides with relatively long microfibrils compared to derivatization after microfibrillation. This is particularly important because the energy required for microfibrillation can be significantly reduced by the degree of derivatization which is less than the extent to which the resulting derived microfibrillated polysaccharide can be freely dissolved in water. For example, derivatization of cellulose to produce DS on the order of 0.1 or 0.2 will loosen the fibril bundles in cellulose to allow sufficient microfibrillation using conventional shear devices such as homogenizers, immersion mixers or sonicators. The diameters of these low DS cellulose microfibrils are on the order of 50 nm with lengths of less than 500 microns, with the result that the aspect ratio exceeds 1,000. Such low DS enables microfibrillation, while the resulting material is too low to dissolve completely in the solvent or carrier used at the desired concentration. Without being bound by theory, the presence of insoluble sites in the fibers can explain the data indicating maximum gel formation at low DS values. These gels can be enhanced by weak association of more hydrophobic unsubstituted sites.
    Stabilization or derivatization is achieved by generating or placing substituents on fibrils and / or microfibrils. Substituents appear to associate predominantly with the surface portion of fibrils or microfibrils. Regardless of the exact mechanism, in functional terms, the microfibrils-microfibrils contact is inhibited by steric and / or electrostatic mechanisms or forces. The presence of substituents also makes microfibrils more bulky than when they are not derived, probably because contact is inhibited at least a portion of the microfibrils length. The flowability performance of the resulting derived microfibrillated polysaccharides is enhanced at low concentrations because the volume is better occupied and the material is more homogeneously distributed.
    With regard to the use of steric forces, steric functionality or stabilization is provided by the formation of protective barriers or sheaths around the particles (eg, cellulose fibrils or microfibrils) and prevents aggregation. For example, this can be achieved by a material such as a polymer that is physically adsorbed on the particle surface, thereby preventing the two particles from approaching a distance that is twice the sum of the radius of the particle and the thickness of the adsorption layer. The two particles approach and the distance between them approaches the distance described above, and the adsorption layer on the two particles interacts. Such interactions, which may be polymer-polymer interactions as above, create forces such as osmotic and / or entropy forces to repel the particles. This prevents agglomeration of the two particles and provides stabilization. Since steric forces are generally provided by the size and / or shape of the substituents, the substituents used to provide steric functionality or stability to the polysaccharide may be neutral, anionic, cationic, amphiphilic, amphoteric and ( Or zwitterions.
    Without being bound by theory, the surface of the induced microfibrils seems to have some region without substituents such that some limited interaction between the microfibrils still occurs. Limited interactions may still be necessary to facilitate network formation and may be the cause of desired flow properties such as yield stress, shear reversible gelling, and insensitivity of modulus of elasticity to temperature. In addition, the length / diameter ratio (or aspect ratio) of fibrils and microfibrils also appears to contribute to the performance of the materials of the present invention.
    Any suitable method may be used to generate or place a substituent on the polysaccharide. For convenience, a possible method will be generally referred to herein as "derivation", but in the context of the present invention, derivatization may be accomplished by poly with substituents associated with polysaccharides sufficient to provide the desired benefit (s). By any method of generating saccharides (including fibrillated and microfibrillated polysaccharides), it includes physical adsorption, as well as chemical reactions that produce covalent bonds. In addition, two terms "derivation" and "stabilization" will be mentioned herein. Chemically, both terms mean the same type of method, ie, positioning or generating a substituent on a cellulose support. Functionally, "derivatization" is a broader term generally, and "stabilization" refers to the functionality usually observed exclusively or exclusively when the polysaccharide is in microfibrillary form.
    Possible derivatization methods include any synthetic method (s) that can be used to associate polysaccharides with substituents. More generally, the stabilization or derivatization step may use any method or combination of methods that facilitates or results in locating or generating a substituent. For example, the conditions for treating non-microfibrillated polysaccharides should generally include both alkalizing and swelling of the polysaccharides in order to facilitate the placement or creation of substituents on the fibril surface. Alkalization and swelling can be provided by separate formulations, or the same formulation can provide the alkalinity of polysaccharides and cause swelling of the polysaccharides. In particular, alkaline preparations have several effects in that they can catalyze the reaction between polysaccharides and substituents and optionally allow access of reagents to deprotonate derivatives and open swell the polysaccharide structure to effect derivatization. Contribute.
    Certain chemical methods that may be used to achieve the present invention include the production of anionic groups (eg, carboxyl, sulfate, sulfonate, phosphonate and / or phosphate) on or near the particulate polysaccharide surface, Production of anionic and cationic groups (eg, quaternary amines and / or amines), and production of steric groups. Alkaline conditions are preferably obtained by using sodium hydroxide. Any material that functions as a solvent for the selected polysaccharide can be used, and alternative alkaline agents include alkali metal or alkaline earth metal oxides or hydroxides, alkali silicates, alkali aluminates, alkali carbonates, and aliphatic hydrocarbon amines, In particular, there are amines including tertiary amines, ammonium hydroxide, ammonium hydroxide ammonium hydroxide, lithium chloride, N-methyl morpholine N-oxide and the like. In addition to catalytic amounts of alkaline agents, swelling agents can be added to increase access for derivatization. Pre-fibrillary swelling agents and crystalline swelling agents are preferred, and swelling agents which are used to such an extent as to provide adequately low concentrations of inter-fibril swelling such as sodium hydroxide are preferred.
    These derivatization reactions, when originally performed on fibrous polysaccharide structures, may require certain conditions to maximize the site efficiency of derivatization on the polysaccharide surface. For example, in the case of cellulose from wood pulp, the use concentration of swelling agent appears to affect the performance of the final cellulose. In particular, when using sodium hydroxide, it was determined that the content of sodium hydroxide can have a significant effect on the flow performance.
    Derivatization of these fibrous polysaccharides is preferably carried out in a manner that limits the formation of soluble microfibrils in the desired end use composition (which will not severely affect the desired flowability performance). This typically limits the degree of derivatization when higher degrees of derivatization renders the polysaccharide soluble in the end use composition. Certain thresholds may be readily determined based on the desired application, but with respect to general guidance, substitution degrees of less than about 0.5, or less than about 0.35, or less than about 0.2, or less than about 0.18, or less than about 0.1 ( DS) is preferred.
    Derivatization can be carried out in any suitable manner, including in suspension in water, in an organic solvent alone or in admixture with water, in solution, and at high solids with water alone or at high solids with water and a small amount of organic solvent. However, it is not limited thereto. For the purposes of this application, "high solids" means a content of polysaccharides in excess of about 25%.
    Optional derivatization or functionalization that may also occur on polysaccharides include substituents, oligomers and polymer substituents of short-chain aliphatic and other hydrophobic types, and non-charged substituents such as short-chain ethylene glycol and propylene glycol, other associative functional groups, and surfactant-like functional groups. , Methyl, ethyl, propyl, and combinations thereof, but is not limited thereto. These substituents are optional in that they may not be intended to stabilize polysaccharides, and will instead provide additional functionality such as surface activity, emulsifying power, adsorptivity, and the like.
    Processes for processing polysaccharides in non-microfibrillated form in microfibrillated form can be performed before or after the derivatization reaction. Preferred methods include the use of a dilute suspension of non-microfibrid polysaccharide in an aqueous medium in a homogenizer. The aqueous medium may optionally contain swelling agents, in particular fibril interphase swelling agents and / or intercrystalline swelling agents, for example additives such as sodium hydroxide, to assist in improving the ease of microfibrils production. More preferred microfibrillation methods include the use of mechanical energy in an aqueous suspension of undried derived polysaccharide. Other microfibrillation methods include, but are not limited to, the use of immersion mixers, heating, steam explosions, pressure-decompression cycles, freeze-thaw cycles, impacts, grinding (eg disk mills), pumping, mixing, ultrasonics, microwave explosions. And milling. Combinations of these can also be used, such as homogenizing after milling. While essentially any method of reducing particle size can be used, a method of reducing particle size while maintaining the high aspect ratio of polysaccharide is preferred. As mentioned above, the degree of substitution of polysaccharides also affects the ease of processing of polysaccharides in the microfibrils form.
    The method of producing the particulates may be carried out by the consumer in the final application such that the particulates are produced in situ, or as described above in an aqueous medium, dehydrate the material and dry the resulting particulates. The dry particulates of the invention, which are hereafter referred to as ready-to-gel or RTG, can be easily rehydrated in polar solvents to obtain the desired flow properties. Dehydration can be achieved by replacing water with a less polar solvent and can be promoted by protonating or masking the charge groups, if present.
    In view of general properties, particularly useful applications of the derived microfibrillated polysaccharides of the present invention include those where the desired flow properties are one or more of yield stress, shear reversible gelling, and temperature insensitive elastic modulus. The ability to provide the flowability properties described herein also makes it possible to provide stability of mixtures of liquids and solids of different densities, gel-like properties including granularity, stabilization at elevated temperatures, and control of hydration and diffusion.
    From a more specific use application or field of view, the use of the derived microfibrillated polysaccharides of the present invention may be used in food, personal care products, household products, pharmaceuticals, nutraceuticals, paper manufacturing and processing, coating compositions, water treatment, drilling Liquids, agriculture, construction and leak control and / or recovery.
    In food applications, the like microfibrillated polysaccharides of the present invention can be used as flow modifiers, stabilizers that inhibit the creaming or sedimentation of suspensions, and antidiabetic dietary fibers. They can also be used to control ice crystal growth, for example during ice cream manufacturing and storage.
    In personal care products, derived microfibrillated polysaccharides can be used to stabilize emulsions, dispersions, suspensions and foams and can be used in creams, lotions, gels and pastes, including those intended for epithelial application. Non-exclusive, non-exclusive examples include sunscreens, moisturizing or anti-aging creams and lotions, cleaning soaps or gels, and sticks, pump sprays, aerosols, and ball and pen type limiting and deodorants, fragrance release gels, lipsticks, lip gloss Liquid makeup products, and oral care products including toothpaste, tooth abrasives and chalks, and denture hygiene products including cleaning agents and adhesives, and further use, purpose, in sorbitol, sorbitol-water mixtures and glycerol-water mixtures Wound protection products such as products that control, maintain, or delay the release of constituents, ointments (including anesthesia, disinfection and antibiotic ointments), dressings and products such as ostomy rings where good liquid retention is desired, And absorbent products such as diapers. The invention may be particularly useful for other applications such as personal care products as well as products that are dispersed by a pumping action. The shear reversible gelation exhibited by the induced microfibrillated polysaccharides is well suited for pumping distribution and can be advantageously combined with the ability to stabilize emulsions, dispersions and foams to improve uniform delivery of the product.
    In the area of household products, the flowability of the derived microfibrillated polysaccharides of the present invention and their ability to stabilize emulsions, dispersions and foams make them useful in areas such as detergents, shampoos, detergents and air cleaners. Specific examples include laundry products (including fabric treatment compositions such as detergents, preliminary stain cleaners, and softeners), carpet and furniture shampoos, toilet seat cleaners (particularly dispensed in liquid or gel form), air cleaners, and cleaning and (Or) General cleaners, including, but not limited to, liquids, gels, pastes and foams used in sterile household surfactants.
    In pharmaceutical applications, induced microfibrillated polysaccharides can be used to control, maintain or delay the release of the composition, and as disintegrants, as dietary fibers, for wound protection, in particular liquid retention applications (eg For example anastomotic rings), and rheology modifiers.
    In the area of paper production and processing, the derived microfibrillated polysaccharides of the present invention are used for emulsion modification and / or stabilization and for sizing, retention, purification, absorption, drainage, (e.g., acting as a coagulant aid). Formation, by inhibition of deposits or scale (by formation of inorganic deposits and / or inhibition of growth), water treatment, dehydration, film and film forming ability, polyelectrolyte crosslinking, removal of harmful organic and / or inorganic substances, paper coating It is used to improve water and properties such as stiffness, wet strength, absorbency, flexibility, toughness, tear resistance and wrinkle resistance.
    In paper making, scale inhibition means preventing calcium carbonate and calcium oxalate deposits formed during the pulping process. Scale inhibition can be achieved by dispersing salt crystals in the medium, preventing growth and adhesion, inhibiting nucleation, or improving the crystal growth mechanism to prevent the formation of crystalline forms from which deposits can be induced. The use of induced microfibrillated cellulose with submicron particle size, stabilized with appropriate functional groups, will inhibit scale adhesion as these microcarriers inhibit crystal growth causing adhesion. In addition, the cellulose based material will be more easily recovered from the pulping process by its organic nature. Preferred functional groups will include phosphate / phosphonate groups, carboxylate groups and sulfate / sulfonate groups. Other functional groups and appropriate amounts of use can be readily determined by one of ordinary skill in the art based on the particular use environment.
    Induced microfibrillated cellulose is also used in papermaking to increase the rate of drainage and / or dehydration during paper production, and to reduce organic and / or inorganic dispersed particles (e.g., pulp fines, fillers, sizing agents, pigments and (Or) clay), improve the uniform formation of the paper sheet, and improve the strength of the paper sheet. In particular with regard to drainage, drainage aids are additives that increase the rate at which water is removed from the paper slurry on the paper machine. These additives increase the mechanical performance, thus increasing the profitability as the sheets are formed faster. Anionically charged microfibrillary cellulose derivatives, either alone or in combination with other charge polymers, can greatly increase fold.
    Induced microfibrillated cellulose of the present invention can also be used in coated papers, and cellulose derivatives can be used to control the flowability of colored coatings and to provide water retention, thereby allowing the amount of liquid to permeate into the substrate sheet. Can be controlled.
    In coating compositions such as paints and inks, induced microfibrillated polysaccharides can provide improvements in properties such as flow modification, sputtering, leveling, sag resistance, water repellency and suspension and are particularly useful in gel paints. can do. They can also improve pigment dispersion and / or stabilization and can function as charge control or flow control agents in inks such as ink jet inks.
    In the water treatment region, the induced microfibrillated polysaccharide of the present invention inhibits scale inhibition, i.e., formation and / or growth of inorganic deposits in the aqueous system, and provides purification, flocculation, sedimentation, coagulation, charge transfer and softening. can do.
    In drilling fluids, the derived microfibrillated polysaccharides of the present invention can provide flow modification, reduce or prevent fluid loss and improve recovery of secondary oils.
    In agricultural applications, the derived microfibrillated polysaccharides of the present invention can be used for treating contaminants, can provide wet retention, corrosion resistance, freeze resistance, and can be used for agricultural materials such as fertilizers, insecticides, fungicides and herbicides. Emissions can be controlled or maintained or delayed. They can also be used for grain protection, such as minimizing or preventing freeze damage.
    In the construction area, induced microfibrillated polysaccharides can be used in dry wall mud, coke, water soluble adhesives and board manufacture.
    In other areas, the derived microfibrillated polysaccharides can be used for the control and purification of liquid leaks and as absorbents for oils, generally including but not limited to emulsions, dispersions and foams (oil-in-water and water-in-oil emulsions). May be used as a stabilizer and for emulsification. Stabilization of commercial emulsions, such as paper size emulsions, is an industrially recurring issue. Current commercial emulsions are those that are dispersed in water and generally consist of an oil phase, wax or rosin phase. These dispersions are generally stabilized by the addition of charge materials such as cationic starch, sodium lignin sulfonate and aluminum sulfate. Such materials are generally added in amounts corresponding to about 10-20% by weight of the size component. The resulting dispersions are typically 0.2 to 2 micron particles and are considered to be stabilized with cationic charge starch on the surface of the particles, for example by repulsion, by charge repulsion.
    One cause of emulsion failure is density driven separation. This can be limited by increasing the viscosity or by the internal structure in the fluid. For example, if the viscosity is later increased with time and does not exceed the acceptable limit, an emulsion in which the viscosity remains below about 20 centipoise through standard aging tests may be added to the composition to add a viscosity modifier to maintain the commercially acceptable viscosity. Initially increases by 100 centipoise.
    One way to achieve this result is to use a viscosity modifier that does not substantially increase in viscosity when first added to the emulsion formation, but which increases in viscosity during the general process of the emulsion composition to prepare the emulsion. This can be achieved by including polysaccharides derived as described herein but not yet microfibrillated as additives to the emulsion composition. When the emulsion composition is subsequently exposed to energy, typically high shear, the shear during the process used to convert the emulsion composition into an emulsion also results in microfibrillation of the derived polysaccharide, resulting in the presence of part of the emulsion. The derived microfibrillated polysaccharide of the invention will be produced. The gel produced by the induced microfibrillated polysaccharide will then become thin under shear stress but will return to its original form when the shear is interrupted. Also, the insolubility of such low DS / MS polysaccharides may allow the polysaccharides to be concentrated at the oil / water interface of the oil-in-water emulsion rather than the aqueous bulk phase, which may be desirable.
    The same result can be effectively achieved by adding the derived microfibrillated polysaccharides of the present invention at any point during the emulsion composition or the final emulsion, or the production of the emulsion. Further modifications will include introducing only partially microfibrillated derivative polysaccharides into the emulsion preparation process where the subsequent process provides sufficient energy to complete the microfibrillation. It may also be possible to achieve some or all derivatization as part of an emulsion preparation method, for example an emulsion composition may comprise a charge species to be adsorbed onto polysaccharide microfibrils, or such species It can be added individually or in combination with the polysaccharide during the process of the emulsion composition. Thus, the derived microfibrillated polysaccharides of the present invention can serve as stabilizing additives in emulsions with several process routes that can be useful to achieve the end result.
    While the choice of method can lead to various modifications to the properties of the resulting emulsion, the fundamental benefit of improved emulsion stabilization is its final result, in any procedure where the induced microfibrillated polysaccharide of the present invention is present in the final emulsion. Should be achieved by Commercially derived non- microfibrillated polysacchars as powders that are added to the composition and are microfibrillated when subjected to high shear or other suitable forms of energy and will produce the derived microfibrillated polysaccharides of the present invention. It may be desirable to supply the ride to the consumer.
    Such improved emulsion stabilization may enable the use of emulsion compositions that will not perform satisfactorily in the absence of induced microfibrils on polysaccharides. Other advantages may include improved retention in paper, improved drainage of water from the paper system by association of pulp and filler fines with retention microfibrils, and resistance to emulsion breakdown in the presence of high salt concentrations. .
    It was also finally found that the main electrostatic inducing material of the present invention provides fluidity to the aqueous system for a wide pH range (ie about 2.5 to 10 or more) and ionic strength. Insensitivity to pH and ionic strength allows for ease of use in areas where low pH and high salt conditions exist, such as in personal care creams and lotions, food products, and the like.
    In addition to the above, the induced microfibrillated polysaccharide of the present invention corresponds to a vehicle that provides an electric charge between an anion, a cation or both in a given environment. This is useful as a representative example in water treatment where charged particles are used to aggregate particulates and other contaminants.
    The following examples illustrate various possible preparation methods and uses of the derived microfibrillated cellulose of the present invention. These examples are for illustrative purposes only and should not be considered limiting of the invention to particular compounds, processes, conditions or applications. Throughout this application, "gelling" is defined to occur when G '> G ", where G' is a dynamic storage modulus and G" is a dynamic loss modulus. This is the functional definition used in EP '011, see Ferry, J.D., Viscoelastic Properties of Polymers, John E. Wiley & Sons, NY, 1980, as a general background technique.
    Example 1 (Comparative) Microfibrillated uninduced cellulose.
    The following three components were weighed into 3.79 L (1 gallon) bottles with the following weight percent content.
    weight weight% Basic dry weight Bleached Sulfate Wood Pulp (5.2% Moisture) (Wayerhauser Company) 74.82 g 2.11 2.00 Germaben® Biocide (Sutton Laboratories, New Jersey, USA) 17.50 g 0.49 0.49 Deionized Water 3445.58 g 97.39 97.50
    Cellulose settled quickly at the bottom of the bottle if the slurry was not stirred. The bottle was shaken to disperse the solids. The slurry was then processed in a dual stage Gaulin model 15MR homogenizer. The second stage was set at about 68.0 atm (1000 psi) and the first stage was adjusted so that the total pressure was about 544.4 atm (8000 psi). The slurry was processed for a total of 3.5 hours. The resulting slurry was thicker and the cellulose suspended. When the suspension was diluted to 1.0% solids in DI water, the resulting suspension was a viscous slurry that did not exhibit gel properties. The 1% suspension settled with the free water on the surface with time.
    Example 2 Preparation and Microfibrillation of Carboxymethyl Cellulose I (CMC I).
    Isopropanol (IPA) and DI water were charged to a jacketed resin kettle equipped with an air driven stirrer, a stainless steel stirrer, two pressure equalization funnels, a reflux condenser, a nitrogen injector, a vacuum line and a thermocouple and sparged with nitrogen. Sulfate wood pulp (approximately 400 μm in length) was added to the reactor and the mixed slurry was stirred for 10 minutes, after which the slurry temperature was cooled to 15 ° C. while sparging nitrogen for 1 hour. The reactor was inactivated. Aqueous 50% NaOH was slowly added to the reactor while maintaining the temperature of the mixture slurry at about 15 ° C. After the caustic soda addition was complete, the slurry was stirred for 1 hour. Aqueous monochloroacetic acid (80% MCA) was slowly added to the reactor using a funnel while maintaining the reaction slurry temperature at about 15 ° C. After the MCA addition, the reaction slurry was heated to 70 ° C. and maintained for 1.5 hours. The reaction slurry was cooled to below 30 ° C. and glacial acetic acid was added to the reactor. The reaction mixture was then vacuum filtered through an aspirator to a sintered glass funnel and rubber dam. This wet cake was slurried in 565 g of 80% methanol for 15 minutes using an air driven stirrer and a base stainless steel beaker and vacuum filtered with an aspirator to a sintered glass funnel and rubber dam. This was repeated two more times. The wet cake obtained from the three washes was slurried and dehydrated in 1000 g of pure methanol for 15 minutes using an air driven stirrer and a base stainless steel beaker, followed by vacuum filtration with an aspirator on a sintered glass funnel and rubber dam. It was. The final wet cake was dried for 35 minutes in a laboratory fluidized bed dryer (Model No. 23852) (air drying for 5 minutes, 50 ° C. heat drying for 10 minutes, 70 ° C. heat drying for the remaining 20 minutes). Carboxymethylcellulose (CMC) product was ground using a Retsch Grinding Mill (Model 2M1) with a 1 mm screen. (While washing of the product is shown in the examples herein, the need or amount of wash depends on the desired application.)
    CMC I formulation (all weights are in g) Sample number Cellulose length Cellulose Weight (Dry Weight) IPA weight H 2 O weight 50% NaOH (aqueous) weight 80% MCA (Aqueous) Weight Glacial acetic acid weight DS One 400 μm or less 61.36 729 73.6 60 11.8 32.2 0.16 2 400 μm or less 61.36 729 73.6 60 11.8 32.2 0.18
    Preparation of CMC Slurry: Each sample of Table 1 above was prepared using 800 g of 1% CMC slurry using the following materials.
    weight weight% CMC 8.00g 1.0 ± 0.06% Germaben® II Biocide 4.00g 0.5% Deionized water 788.00g 98.5 ± 0.06% gun 800.00 g
    The vessel was sealed and shaken to wet and disperse the CMC solids. The solids would settle if left to stand, so the container was shaken just before pouring the slurry into the homogenizer.
    Homogenization of CMC Slurry: The suspension was processed in a homogenizer with a stirred feed bottle as follows. The homogenizer was spun before loading the slurry. 800 g of the slurry was processed at about 204.1 atm (3000 psi) for about 20 minutes by recycling the discharged vapor from the homogenizer into the feed bottle. Pressure was monitored and in the first step the handwheel was properly adjusted to maintain the total pressure at about 204.1 atm (3000 psi). After the process was complete, the discharge tube was turned and the sample was collected and stored in a stoppered bottle.
    Fluidity Test of Microfibrillated CMC I: Each microfibrillated CMC sample prepared in Example 2 was then tested for fluidity. Data was collected on a Bolin CS Rheometer (Bohlin Instruments, Cranbury, NJ).
    Dynamic mechanical properties including dynamic storage modulus, dynamic loss modulus, composite viscosity and yield stress were measured.
    <Flowmeter test condition>
    Temperature sweep: measurement system: PP 40; 25 ° C. to 65 ° C .; Shear stress: automatic; Frequency 1 Hz; Rate of temperature rise: 5 ° C./60 seconds; Measuring interval: 20 seconds; Clearance: 1mm.
    Yield stress test: measuring system: CP 4/40; Stress: 6.0E-02 to 1.0E + 02; Variation time: 60 seconds; Number of steps: 30; Temperature: manual (25 ° C.); Number of measurements: 1; Measurement interval: 5 seconds.
    Stress fluctuation test: measuring system: PP 40; Temperature: manual (25 ° C.); Number of measurements: 1; Gap: 1mm; Measuring interval: 5 seconds; Frequency: 1 Hz.
    Flowability of Microfibrillated CMC I Sample number Cellulose length DS of CMC I Yield Stress (Pa) G '(Pa) at 5.75 Pa One 400 μm or less 0.16 8.08 256 2 400 μm or less 0.18 Do not test 192
    A copy of the spectrum of the dynamic mechanical properties (obtained by the stress variation test) of Sample 1 is shown in FIG. 1.
    Example 3 Preparation and Microfibrillation of Carboxymethylcellulose II (CMC II).
    Isopropanol (IPA) and DI water were charged to a jacketed resin kettle equipped with an air driven stirrer, a stainless steel stirrer, two pressure equalization funnels, a reflux condenser, a nitrogen injector, a vacuum line and a thermocouple and sparged with nitrogen. Sulfate wood pulp (approximately 400 μm in length) was added to the reactor and the mixed slurry was stirred for 10 minutes and then the slurry temperature was cooled to 15 ° C. while sparging nitrogen for 1 hour. The reactor was inactivated. Aqueous 50% NaOH was slowly added to the reactor while maintaining the temperature of the mixture slurry at about 15 ° C. After the addition of caustic soda, the slurry was stirred for 1 hour. Aqueous monochloroacetic acid (80% MCA) was slowly added to the reactor with a funnel while maintaining the reaction slurry temperature at about 15 ° C. After the MCA addition, the reaction slurry was heated to about 70 ° C. and maintained for 1.5 hours. The reaction slurry was cooled to below 30 ° C. and then vacuum filtered with an aspirator to the sintered glass funnel and rubber dam. The wet cake was slurried in 565 g of 80% methanol for 15 minutes using an air driven stirrer and a base stainless steel beaker and vacuum filtered with an aspirator to a sintered glass funnel and rubber dam. This was repeated two more times. The wet cake obtained from the three washes was slurried and dehydrated in 1000 g of pure methanol for 15 minutes using an air driven stirrer and a base stainless steel beaker and then vacuum filtered with an aspirator on a sintered glass funnel and rubber dam. . The final wet cake was dried for 35 minutes in a laboratory fluidized bed dryer (Model No. 23852) (air drying for 5 minutes, 50 ° C. heat drying for 10 minutes, 70 ° C. heat drying for the remaining 20 minutes). The carboxymethylcellulose (CMC) product was ground using a Letch grinding mill (model 2M1) with a 1 mm screen.
    CMC II formulation (all weights are in g) Sample number Cellulose length Cellulose Weight (dry weight basis) IPA weight H 2 O weight 50% NaOH (aqueous) weight 80% MCA (Aqueous) Weight DS One 400 μm or less 77.11 937.5 141.64 12.50 8.63 0.04 2 400 μm or less 61.69 750 113.32 10.00 6.90 0.06 3 400 μm or less 77.11 937.5 141.64 25.00 17.25 0.13 4 400 μm or less 61.91 750 113.09 20.00 13.95 0.15 5 400 μm or less 61.30 750 113.71 20.00 13.86 0.16 6 400 μm or less 61.91 750 113.09 20.00 13.79 0.17 7 400 μm or less 61.43 750 113.58 23.60 16.27 0.19 8 400 μm or less 61.62 750 109.38 28.00 19.32 0.23 9 400 μm or less 61.88 750 108.12 30.00 20.70 0.28 10 400 μm or less 61.43 750 106.08 35.00 24.15 0.31 11 400 μm or less 61.43 750 108.58 30.00 20.70 0.34 12 200 μm or less 62.60 750 116.41 12.00 8.28 0.10 13 200 μm or less 62.60 750 112.91 19.00 13.11 0.17
    Slurry preparation and homogenizer processes were performed as in Example 2. The fluidity test was performed as described in Example 2.
    Flowability of Microfibrillated CMC II Sample number Cellulose length CMC II DS Yield Stress (Pa) G '(Pa) at 5.75 Pa G '(Pa) at 25 ° C / 50 ° C One 400 μm or less 0.04 Do not test 125 145/168 2 400 μm or less 0.06 Do not test 139 161/160 3 400 μm or less 0.13 18.0 467 508/493 4 400 μm or less 0.15 Do not test 467 441/429 5 400 μm or less 0.16 18.1 474 436/450 6 400 μm or less 0.17 34.7 436 452/462 7 400 μm or less 0.19 28.1 306 331/352 8 400 μm or less 0.23 21.4 148 137/145 9 400 μm or less 0.28 18.0 114 Do not test 10 400 μm or less 0.31 14.7 12.9 12.3 / 12.6 11 400 μm or less 0.34 11.4 19 23.4 / 24.9 12 200 μm or less 0.10 8.08 339 Do not test 13 200 μm or less 0.17 16.1 354 Do not test
    A copy of the spectrum of the dynamic mechanical properties (obtained by the stress variation test) of Sample 3 is shown in FIG. 2.
    Example 4 Preparation and Microfibrillation of Carboxymethylcellulose III (CMC III).
    Isopropanol and DI water were charged to a jacketed resin kettle equipped with an air driven stirrer, a stainless steel stirrer, two pressure equalization funnels, a reflux condenser, a nitrogen injector, a vacuum line and a thermocouple and sparged with nitrogen. Sulfate wood pulp (approximately 400 μm in length) was added to the reactor and the mixed slurry was stirred for 10 minutes and then the slurry temperature was cooled to 15 ° C. while sparging nitrogen for 1 hour. The reactor was inactivated. Aqueous NaOH (50% NaOH) was slowly added to the reactor while maintaining the temperature of the mixture slurry at about 15 ° C. After the caustic soda addition was complete, the slurry was stirred for 1 hour. Aqueous sodium monochloroacetate was prepared by mixing 80% MCA, aqueous 50% NaOH and DI water. The solution was slowly added to the reactor with an addition funnel while maintaining the reaction slurry temperature at about 15 ° C. After the MCA addition, the reaction slurry was heated to about 70 ° C. and maintained for 1.5 hours. The reaction slurry was cooled to below 30 ° C. and vacuum filtered with an aspirator to the sintered glass funnel and rubber dam. The wet cake was slurried in 565 g of 80% methanol for 15 minutes using an air driven stirrer and a base stainless steel beaker and vacuum filtered with an aspirator to a sintered glass funnel and rubber dam. This was repeated two more times. The wet cake obtained from the three washes was slurried and dehydrated in 1000 g of pure methanol for 15 minutes using an air driven stirrer and a base stainless steel beaker, followed by vacuum filtration with an aspirator on a sintered glass funnel and rubber dam. It was. The final wet cake was broken into small particles using a rubber spatula and then dried for 35 minutes in a fluid bed dryer (air drying for 5 minutes, 50 ° C. heat drying for 10 minutes, 70 ° C. heat drying for the remaining 20 minutes). The product was ground using a letch mill with a 1 mm screen.
    CMC III formulation (all weights are in g) Sample number Cellulose length Cellulose Weight (Dry Weight) IPA weight H 2 O weight 50% NaOH (aqueous) NaMCA Solution DS 80% MCA 50% NaOH H 2 O One 400 μm or less 61.88 750 117.12 6.39 8.28 5.61 3.0 0.06 2 400 μm or less 61.88 750 114.32 9.38 12.14 8.22 5.0 0.12 3 400 μm or less 61.62 750 113.38 12.58 16.27 11.02 10.0 0.16 4 400 μm or less 61.62 750 108.38 15.98 20.70 14.02 10.0 0.24 5 400 μm or less 61.62 750 105.88 18.64 24.15 16.36 10.0 0.29 6 400 μm or less 61.88 750 102.47 21.31 27.60 18.69 10.0 0.31 7 200 μm or less 62.60 750 116.41 6.39 8.28 5.61 10.0 0.08 8 200 μm or less 62.60 750 112.91 10.12 13.11 8.88 10.0 0.16 9 200 μm or less 62.60 750 110.61 12.57 16.28 11.03 10.0 0.21 10 200 μm or less 62.60 750 117.12 15.67 20.30 13.75 10.0 0.26
    The slurry preparation and homogenizer process was performed as in Example 2 except Sample No. 7, which was processed for 30 minutes. The fluidity test was performed as described in Example 2.
    Flowability of Microfibrillated CMC III Sample number Cellulose length CMC III DS Yield Stress (Pa) G '(Pa) at 5.75 Pa G '(Pa) at 25 ° C / 50 ° C One 400 μm or less 0.06 14.7 281 316/310 2 400 μm or less 0.12 51.4 568 520/586 3 400 μm or less 0.16 28.1 564 607/649 4 400 μm or less 0.24 18.1 457 414/474 5 400 μm or less 0.29 21.4 298 292/303 6 400 μm or less 0.31 44.7 288 Do not test 7 1) 200 μm or less 0.08 4.70 238 Do not test 8 200 μm or less 0.16 29.5 483 Do not test 9 200 μm or less 0.21 18.1 339 Do not test 10 200 μm or less 0.26 21.4 288 Do not test1) Homogenizer process time 30 minutes
    A copy of the spectrum of the dynamic mechanical properties (obtained by the stress variation test) of Sample 3 is shown in FIG. 3.
    <Example 5> CMC manufacture using the water washing of a wet cake.
    Isopropanol and DI water were charged to a jacketed resin kettle equipped with an air driven stirrer, a stainless steel stirrer, two pressure equalization funnels, a reflux condenser, a nitrogen injector, a vacuum line and a thermocouple and sparged with nitrogen. Sulfate wood pulp (approximately 400 μm in length) was added to the reactor and the mixture slurry was stirred for 10 minutes, after which the slurry temperature was cooled to 15 ° C. while sparging nitrogen for 1 hour. The reactor was inactivated. Aqueous NaOH (50% NaOH) was slowly added to the reactor while maintaining the temperature of the mixture slurry at about 15 ° C. After the caustic soda addition was complete, the slurry was stirred for 1 hour. Aqueous sodium monochloroacetate was prepared by mixing 80% MCA, aqueous 50% NaOH and DI water. The solution was slowly added to the reactor with an addition funnel while maintaining the reaction slurry temperature at about 15 ° C. After the MCA addition, the reaction slurry was heated to about 70 ° C. and maintained for 1.5 hours. The reaction slurry was cooled to below 30 ° C. and vacuum filtered with an aspirator to the sintered glass funnel and rubber dam. The wet cake was slurried in 650 g DI water for 15 minutes using an air driven stirrer and a base stainless steel beaker and then vacuum filtered with an aspirator on a sintered glass funnel and rubber dam. This was repeated once more. The wet cake obtained from the two washes was slurried in 1000 g DI water for 15 minutes using an air driven stirrer and a base stainless steel beaker and then vacuum filtered with an aspirator on a sintered glass funnel and rubber dam. The final wet cake was dried in a fluid bed dryer for 35 minutes (air drying for 5 minutes, 50 ° C. heat drying for 10 minutes, 70 ° C. heat drying for the remaining 20 minutes). The product was ground using a letch mill with a 1 mm screen.
    Water wash CMC formulation (all weights are in grams) Sample number Cellulose Weight (Dry Weight) IPA weight H 2 O weight 50% NaOH (aqueous) weight NaMCA Solution DS 80% MCA 50% NaOH H 2 O One 61.88 750 110.5 10.12 13.11 8.88 10.0 0.10 2 60.06 750 110.5 10.12 13.11 8.88 10.0 0.13
    Slurry preparation, homogenizer process, and fluidity testing were performed as described in Example 2.
    Flowability of Water Washed CMC Samples sample CMC's DS Yield Stress (Pa) G '(Pa) at 5.75 Pa One 0.10 37.4 724 2 0.13 34.7 855
    A copy of the spectrum of the dynamic mechanical properties (obtained by the stress variation test) of Sample 2 is shown in FIG. 4.
    <Example 6> High solid content reaction.
    Abbey Ribbon Blender (Model 0 RM, Paul O. Abbe, Inc., Little Falls, NJ) equipped with spray nozzles for sulphate wood pulp (approximately 200 μm in length) )). The system was inactivated with nitrogen while the reactor was sealed and stirred slowly. Agitation was increased to approximately 125 rpm and a solution of 50% aqueous NaOH and DI water was sprayed into the reactor. The mixture was mixed at ambient temperature for 1 hour. An aqueous solution of sodium monochloroacetate (NaMCA) was sprayed into the reactor and the reactor temperature was increased to 75 ° C. and maintained for 2 hours. Glacial acetic acid was sprayed into the reactor and the reactor was cooled to approximately 30 ° C. The product was slurried in 3 liters of water for 15 minutes and filtered using a rubber dam. This slurry / filtration process was repeated three more times. The final filter cake was dried in a fluid bed dryer and ground in a leach mill using a 1 mm screen.
    High solids formulation (all weight in g) sample Cellulose Weight (dry weight basis) H 2 O weight 50% NaOH (aqueous) weight NaMCA Weight (NaMCA / H 2 O) Acetic acid DS One 500 93 62.8 105 / 128.3 0 0.10 2 180 64.8 43.2 45.3 / 55.4 8.6 0.17
    Slurry Preparation: Performed as in Example 2 except Sample No. 2 (DS = 0.17) was treated as a 10% solids slurry in water. This slurry was then mixed with additional water and Germanaven® II to prepare a new slurry and processed in a homogenizer.
    weight weight% 10% CMC Slurry 80.07 g 10.00% Germanaben® II biocide 4.01 g 0.50% Deionized water 716.88 g 89.50% gun 800.96 g
    Since the final slurry was 10% by weight of the 10% CMC slurry, the actual CMC content was usually 1% by weight. Homogenization was performed as in Example 2, except that Sample No. 1 was processed for 25 minutes, and the fluidity test was performed as in Example 2.
    Flowability of High Solid Samples sample CMC's DS Yield Stress (Pa) G '(Pa) at 5.75 Pa One 0.10 18.1 248 2 0.17 31.4 427
    A copy of the spectrum of the dynamic mechanical properties (obtained by the stress variation test) of Sample 2 is shown in FIG. 5.
    Example 7 Preparation of Microfibrillated CMCs That Can Be Gelled Immediately.
    Gels were prepared as described in the slurry preparation and homogeneous process steps in Example 2 using CMC II (DS about 0.16) prepared in Example 3. This gel was then processed as follows (the content described below corresponds to sample number 1 in Table 11 below and similar procedures were used for all other samples).
    Approximately 2800 ml of isopropyl alcohol was added to a base 11.4 L (12 quart) stainless steel (SS) beaker. IPA was stirred at the highest speed of the overhead stirrer driven by house air. The IPA was stirred using an SS cowl blade on the SS axis. About 1400 g of 1% CMC II gel was slowly added to the stirred IPA. The material ratio was 1 ml of IPA 2 ml / gel. It took about 5 minutes to add the gel to IPA. The beaker was covered with a plastic film and the slurry was stirred for 10 minutes.
    When 10 minutes had elapsed, the slurry was filtered through a tensioned synthetic cloth. The slurry was filtered using gravity. The slurry was covered with a plastic film during filtration to reduce evaporation of IPA. Occasionally, the gel was agitated with a plastic spatula to help speed up the filtration. When the filtration seemed to reach the limit, the wet cake was transferred back to a 12-quiet SS beaker.
    Approximately 2800 ml of fresh IPA was added to the beaker and the slurry was stirred for another 10 minutes with a cowl blade / air stirrer again. The slurry was then filtered on a 20 cm Buchner funnel with # 415 VWR filter paper. The wet cake was transferred to a glass crystal dish. The dish and the wet cake were placed in an 80 ° C. oven under vacuum to dry overnight. The sample was dried until the weight was constant. The solid was triturated in Waring Blender.
    The dehydrated gel was examined by rehydration as follows. Premixes of DI water and Germanaven® II were prepared.
    weight weight% Deionized water 788.00g 99.49% Germanaben® II biocide 4.00g 0.51%
    The water / germaben II solution was then weighed into a small waring blender cup with a dry CMC that could be gelled directly according to the formulation of Table 11 below. Cover the blender cup and mix until the sample looks homogeneous. The resulting gel was transferred to a glass jar. It was then shaken on a vortex mixer. The fluidity test was performed as described in Example 2.
    Liquidity of RTG CMC sample Water / Germanmaven® II Weight% RTG CMC Weight% Yield Stress (Pa) G '(Pa) at 5.75 Pa One 99.75 0.25 2.4 5.61 2 99.5 0.50 10.7 68.6 3 99.0 1.00 25.7 328 4 98.5 1.50 51.0 731 5 98.0 2.00 95.3 1400
    Copies of the spectra of the dynamic mechanical properties (obtained by the stress swap test) of Samples 1 to 5 are shown in FIGS. 6 to 10, respectively.
    Example 8A A process for producing an acid of microfibrils on CMC that can be gelled immediately.
    The gel prepared in Example 3 was acidified with HCl to adjust the pH to about 2.7. The gel was centrifuged to remove about 60% of the water. The concentrated gel was then mixed with IPA equivalent to twice the weight of the gel to convert to RTG form, then filtered on a Buchner funnel and secondly mixed with another twice the weight of IPA. The wet cake was dried in a vacuum oven.
    The dried solid was rehydrated in 1% in water / germaben® II biocide. A small amount of baking soda was added and the sample mixed on the blender. The viscosity gradually increased with agitation resulting in the sample becoming a gel analog. The pH was about 6.9.
    The fluidity test was performed as described in Example 2. G 'at 5.75 Pa: 226 Pa, Yield stress: 17.4 Pa. A copy of the spectrum of the dynamic mechanical properties (obtained by the stress swap test) is shown in FIG. 11.
    Example 8B A process for preparing an acid of microfibrillated CMC that can be gelled immediately.
    The second batch of gels prepared in Example 3 was adjusted to pH about 2.7 with concentrated HCl. The sample was centrifuged and about 62% of the water was removed. About 97 g of concentrated gel was slurried with 150 ml of IPA. The pH was adjusted to 7.0 by adding a small amount of baking soda while stirring the slurry. The slurry was filtered on a Buchner funnel and weighed in a crystal dish to dry the wetcat half (Sample A). For Sample B, the other half of the wet cake was reslurried at about 75 ml of IPA. This wet cake was filtered on a Buchner funnel and pressurized with a rubber dam to remove as much IPA as possible. Both wet cakes were dried to constant weight under vacuum and the solids were ground in a waring blender.
    Sample A was mixed with water to 1% total solids and gelled rapidly. pH was about 5.8. Sample B gelled rapidly when stirred with water at 1% solids.
    The fluidity test was performed as described in Example 2.
    Sample A: G 'at 5.75 Pa: 471 Pa, yield stress: 34.0 Pa. A copy of the spectrum of dynamic mechanical properties (obtained by the stress variation test) is shown in FIG. 12.
    Sample B: G 'at 5.75 Pa: 403 Pa, yield stress: 35.7 Pa. A copy of the spectrum of the dynamic mechanical properties (obtained by the stress variation test) is shown in FIG. 13.
    Example 9 Induction of Microfibrillated Cellulose.
    Isopropanol (602.8 g) and DI water (86.4 g) were charged with an air-driven stirrer, a stainless steel stirrer, two pressure equalization funnels, a reflux condenser, a nitrogen injector, a vacuum line, and a thermocouple, nitrogen-sprayed jacketed resin kettle Was charged. The microfibrillated cellulose of Example 1 was vacuum filtered with a sintered glass funnel and a rubber dam. The wet cake was slurried in 545 g of 80% isopropanol (IPA) for 15 minutes using an air driven stirrer and a base stainless steel beaker followed by vacuum filtration with an aspirator on a sintered glass funnel and rubber dam. This was repeated two more times. The wet cake obtained from the three washes was slurried and dehydrated in 1000 g of pure IPA for 15 minutes using an air driven stirrer and a base stainless steel beaker, and then vacuum filtered with an aspirator on a sintered glass funnel and rubber dam. It was. The resulting wet cake, consisting of 36 g microfibrillated cellulose, 228 g IPA and 36 g DI water, was added to the reactor, the mixture slurry was stirred for 10 minutes, and then nitrogen was added to the mixture for 1 hour while cooling the slurry temperature to 15 ° C. Sprayed. The reactor was inactivated. Aqueous 50% NaOH (10.52 g) was slowly added to the reactor while maintaining the temperature of the mixture slurry at about 15 ° C. After the caustic soda addition was complete, the slurry was stirred for 1 hour. Aqueous monochloroacetic acid (7.26 g of 80% aqueous MCA) was slowly added to the reactor with a funnel while maintaining the reaction slurry temperature at about 15 ° C. After the MCA addition, the reaction slurry was heated to about 70 ° C. and maintained for 1.5 hours. The reaction slurry was cooled to below 30 ° C. and then vacuum filtered with an aspirator to the sintered glass funnel and rubber dam. The wet cake was slurried in 565 g of 80% methanol for 15 minutes using an air driven stirrer and a base stainless steel beaker followed by vacuum filtration with an aspirator on a sintered glass funnel and rubber dam. This was repeated two more times. The wet cake obtained from the three washes was slurried and dehydrated in 1000 g of pure methanol for 15 minutes using an air driven stirrer and a base stainless steel beaker, followed by vacuum filtration with an aspirator on a sintered glass funnel and rubber dam. . The final wet cake was dried in a fluid bed dryer for 35 minutes (air drying for 5 minutes, 50 ° C. heat drying for 10 minutes, 70 ° C. heat drying for the remaining 20 minutes). The product was ground using a letch mill with a 1 mm screen. The DS of the resulting material was 0.14.
    A 1% aqueous suspension of the product was mixed in a waring blender for 15 minutes. This resulted in a viscous suspension that did not settle over time. Slurry Preparation: same as in Example 2. Homogenization was performed as in Example 2, unless otherwise noted, and the fluidity test was performed as in Example 2.
    Yield stress: 5.75 Pa, G 'at 5.75 Pa: 363 Pa. A copy of the spectrum of dynamic mechanical properties (obtained by the stress variation test) is shown in FIG. 14.
    Example 10 Alternative Cellulose.
    CMC was prepared as in Example 12 using the cellulose raw materials and formulations in Table 12 below.
    Alternative cellulose formulation (all weights are in g) sample Cellulose raw materials Cellulose Weight (dry weight basis) IPA weight H 2 O weight 50% NaOH (aqueous) weight 80% MCA (Aqueous) Weight DS One Avicel® pH-101NF (-90) 62.01 750 113.49 19.00 13.11 0.16 2 Solka® Flock (1) 61.23 750 114.27 19.00 13.11 0.19 3 CTMP (2) 54.5 750 121 19.00 13.11 0.22 (1) Solka Flock (Class 300 FCC) obtained from Fiber Sales & Development Corp., Urbana, Ohio, USA. (2) SCA Graphic Sundsvall AB, Bleached CTMP (chemical thermomechanical pulp) fluff obtained from Timla, Sweden
    Slurry preparation of solka floc samples (Sample 2) was prepared as in Example 2. The homogenizer process was performed as in Example 2 and the fluidity test was performed as in Example 2.
    liquidity sample Cellulose raw materials CMC's DS Yield Stress 1 (Pa) G '(Pa) at 5.75 Pa 2 Solka Flock 0.19 22.4 1411 yield stress test results from stress fluctuation test
    A copy of the spectrum of the dynamic mechanical properties of Sample 2 is shown in FIG. 15.
    Example 11 Microfibrillation of CMC with Dipping Mixer.
    The samples used were 0.5%, 1.0% and 1.5% suspensions of the low DS CMC prepared in Example 3. The weight of each slurry was 100 g in total. No Vermaben® II biocide was used for the samples processed in the immersion mixer. The slurry was prepared by weighing the ingredients in a 113.4 g (4 oz) glass bottle. The bottle was capped and shaken to wet and disperse the CMC solids.
    Sample number 1 (0.5%) Sample number 2 (1.0%) Sample number 3 (1.5%) CMC 0.50 g 1.0 g 1.5 g DI number 99.5 g 99.0 g 98.5g
    Before using the Microfluidics Corporation Model M110 Series Immersion Mixer, it was filled with DI water. The pressure was adjusted to the desired setting when pumping water. The immersion mixer was run so that deionized water was pumped until DI water was just at the bottom of the filling funnel. The heating bath used to control the temperature of the immersion mixer tubing was set to 50 ° C.
    The sample bottle was shaken again just before filling the sample funnel. Samples were charged to the funnel. An electrical overhead stirrer was placed in the sample funnel. This was rotated so that the CMC was homogeneously suspended. After one pass, no stirrer was needed. Samples were pumped into collection bottles through microfluidizers. Initial collection material containing initial DI water residues was discarded. The process was then continued until the entire sample was processed to pass through the device once.
    The 0.5% solids gel was processed at 408.3 atm (6000 psi) and passed four times. 1.0% solids gels were processed under the same conditions. The 1.5% solids gel was processed at 408.3 atm (6000 psi) and passed only three times.
    Flowability of Microfibrillated CMC by Immersion Mixer sample Cellulose length CMC's DS Yield Stress (Pa) G '(Pa) at 5.75 Pa G '(Pa) at 25 ° C / 50 ° C One 400 μm or less (0.5% solids gel) 0.17 4.82 79.3 97/109 2 400 μm or less (1.0% solids gel) 0.17 Do not test 270 222/242 3 400 μm or less (1.5% solids gel) 0.17 Do not test 522 363/434
    Copies of the spectra of the dynamic mechanical properties (obtained by the stress variation test) of Samples 1 to 3 are shown in FIGS. 16 to 18.
    Example 12 Microfibrillated hydrophobically modified carboxymethyl cellulose (HMCMC).
    t-butyl alcohol (TBA, 750 g) and Hercules CMC 7H (approximately 0.7, 100 g) were charged with an air driven stirrer, stainless steel stirrer, two pressure equalizer funnels, reflux condenser, nitrogen injector, vacuum line and thermocouple. The jacketed resin kettle was loaded and sprayed with nitrogen. The mixture was sparged with nitrogen at 25 ° C. for 1 hour. Aqueous NaOH (7.5% NaOH 54 g) was slowly added to the reactor while maintaining the temperature of the mixed slurry at about 25 ° C. The slurry was cooled to about 15 ° C and stirred at about 15 ° C for 1 hour. While maintaining the reaction slurry temperature at about 15 ° C., a 50% solution of cetyl glycidal ether (40 g of solution) was slowly added to the reactor with an addition funnel. The reaction slurry was heated to about 80 ° C. and maintained for 3.25 hours. The reaction slurry was cooled to about 50 ° C. and 9 g of 70% nitric acid was added. The mixture was cooled to about 30 ° C. and then vacuum filtered with an aspirator on a sintered glass funnel and rubber dam. This wet cake was slurried in 1000 g of 85% acetone for 15 minutes using an air driven stirrer and a base stainless steel beaker and then vacuum filtered with an aspirator on a sintered glass funnel and rubber dam. This was repeated two more times. The wet cake obtained from the three washes was slurried in 1000 g of 100% acetone for 15 minutes using an air driven stirrer and a base stainless steel beaker and then vacuum filtered with an aspirator on a sintered glass funnel and rubber dam. The final wet cake was dried in a fluid bed dryer for 35 minutes (air drying for 5 minutes, 50 ° C. heat drying for 10 minutes, 70 ° C. heat drying for the remaining 20 minutes). The product was ground using a letch mill with a 1 mm screen. The cetyl content of the resulting product was <0.03 wt%.
    Slurry preparation, homogenizer process, and fluidity testing were performed as described in Example 2. G 'at 5.75 Pa: 319 Pa, Yield stress: 14 Pa. A copy of the spectrum of dynamic mechanical properties (obtained by the stress variation test) is shown in FIG. 19. Although the use of hydrophobically modified induction microfibrillated cellulose has been demonstrated herein by one particular example, for the purposes of the present invention, the induction microfibrillary cellulose is hydrophobic by carbon groups having from about 4 to about 30 carbon atoms. Can be modified.
    Example 13 Microfibrillated hydroxyethyl cellulose (HEC).
    Sulfate wood pulp, t-butyl alcohol (TBA), acetone, isopropanol (IPA) and DI water were charged to a nitrogen-sprayed stirred Chemco reactor (3-pin reactor, Chemco, Oklahoma, USA). . The reactor was inactivated with nitrogen and the reaction slurry temperature was adjusted to 20 ° C. Aqueous NaOH (50% NaOH) was added to the reactor and the mixture was stirred at 20 ° C. for 45 minutes. While maintaining the reaction slurry at 20 ° C., ethylene oxide (EO) was charged to the reactor for a period of about 5 minutes. After EO addition, the reaction slurry was heated to 50 ° C. and stirred for about 45 minutes while maintaining at 50 ° C. The reaction slurry was then heated to about 90 ° C. and stirred for 30 minutes while maintaining at 90 ° C. The reaction slurry was cooled to about 50 ° C. and 70% nitric acid was added. The reaction slurry was cooled to below 30 ° C. and then vacuum filtered with an aspirator to the sintered glass funnel and rubber dam. The wet cake was slurried in 600 g of 80% acetone for 15 minutes using an air driven stirrer and a base stainless steel beaker followed by vacuum filtration with an aspirator on a sintered glass funnel and rubber dam. This was repeated two more times. The wet cake obtained from the three washes was slurried in 600 g of 100% acetone using an air driven stirrer and a base stainless steel beaker for 15 minutes and then vacuum filtered with an aspirator on a sintered glass funnel and rubber dam. The final wet cake was dried in a fluid bed dryer for 35 minutes (air drying for 5 minutes, 50 ° C. heat drying for 10 minutes, 70 ° C. heat drying for the remaining 20 minutes). The product was ground using a letch mill with a 1 mm screen.
    HEC formulation (all weights are in g) Sample number Cellulose TBA IPA Acetone H 2 O 50% NaOH EO 70% nitric acid MS One 46.0 517.8 8.6 7.9 63.5 13.0 16.1 14.6 0.7 2 49.77 517.8 8.6 7.9 59.73 12.7 10.6 14.6 0.8 3 49.77 517.8 8.6 7.9 59.73 13.0 19.5 14.6 1.3
    The slurry preparation and homogenizer process was performed as in Example 2 except that the number of passes required for the process into the gel was small.
    Flowability of Microfibrillated HECs sample HEC MS Yield Stress (Pa) G '(Pa) at 5.75 Pa One 0.7 1.66 43.6 2 0.8 3.65 10.3 3 1.3 2.98 2.96
    Copies of the spectra of the dynamic mechanical properties (obtained by the stress variation test) of Samples 1-3 are shown in FIGS. 20-22.
    Drainage Formulation in Papermaking: The following example shows the efficiency of the derived microfibrillated polysaccharide as a drainage improvement aid.
    Drainage measurements were performed on a Canadian Standard Prinis (CSF) tester using bleached kraft pulp consisting of 70% hardwood and 30% softwood. All prinis measurements were performed in hard water with a pH of 7.95 to 8.05, alkalinity of 50 ppm (calcium carbonate) and hardness of 100 ppm (calcium carbonate) as measured by TAPPI method T 227 om-92. The pulp concentration used was 0.3%. Higher CSF values mean better (faster) multiples.
    The substitution resulted in about 0.17 charge per anhydroglucose unit, resulting in the following results using the RTG microfibrillated CMC prepared in Example 7. All loads were calculated as percent addition (dry basis) to pulp.
    Example 14 RTG CMC Sample Material Only.
    RTG CMC Substance% by Pulp CSF 0 210 0.025 274 0.050 285 0.100 315 0.200 317
    Example 15 RTG CMC Sample Material and Hercules Reten® 1232 (R-1232).
    % RTG material (pulp) CSF figures 0.1% R-1232 0.2% R-1232 0 380 462 0.1 485 591 0.2 526 608 0.4 587 637 0.6 572 671
    Example 16 RTG CMC Sample Material and Hercules Kymen 557H Resin (K-557H).
    A 2: 1 ratio of K-557H to material was used. (Kymen is a registered trademark of Hercules Incorporated.) One used two different starting pulp, which had a relatively high freeness and a low one.
    % RTG Material% (pulp) K-557H% Pulp 1 CSF Pulp 2 CSF 0 0 184 413 0.1 0.2 281 531 0.2 0.4 321 565 0.4 0.8 382 574
    Example 17 RTG CMC Material and Hercules Kymen 450 Resin (K-450).
    A 2: 1 ratio of K-450 to material was used. Two different starting pulp were used, one with a relatively high freeness and the other with a relatively low freeness.
    % RTG Material% (pulp) K-450% Pulp 1 CSF Pulp 2 CSF 0 0 184 413 0.1 0.2 285 536 0.2 0.4 335 546 0.4 0.8 357 562
    Like normal CMC, the sample material expanded the wet and dry strength activity of additives such as Hercules Chimen 557H or Chimen 450 resin. Thus, an advantage of using the sample material is the provision of combined wet strength / dry strength / drainage / holding aid.
    Use in Paper Sizing Compositions The following examples pertain to the use of CMC II prepared in Example 3 with a DS of about 0.15 in relation to the composition used in paper sizing.
    <Example 18>
    Precis 787 ketene dimer (Hercules Incorporated, Wilmington, Delaware, 600 ml beaker), Presis is a registered trademark of Hercules Incorporated, 66.0 g, CMC II (Prepared as in Example 3, DS about 0.15) 1.5 g and 232.5 g DI water were combined. Two minutes of premix using a Tekmar Ultra-turax SD45 rotor-stator high shear mixer (Tekmar Compony, Cincinnati, OH) at a power setting of 50 Dispersed during. This premix was then rapidly poured into the feed chamber of the immersion mixer. The premix was passed through a immersion mixer at a pressure setting of 340.2 atm (5000 psi) with mechanical agitation of about 250 rpm. The emulsion was collected and passed through twice. The two pass product was collected in a clean bottle, a stir bar was added, the bottle was sealed and then cooled in a 5-15 ° C. water bath.
    <Example 19>
    In the same manner as in Example 18, 66.0 g of presses ketene dimer, 1.5 g of sample material, 66.0 g of a 50% aluminum sulfate (18H 2 O) solution in water, and 166.5 g of DI water were used.
    <Example 20>
    In the same manner as in Example 18, the pH was increased to 4.0 by a sufficient alkalinization using 66.0 g of presses ketene dimer, 1.5 g of sample material, 132.0 g of a solution containing 25% by weight of aluminum sulfate (18H 2 O), and deionized water, followed by deionization. 100.5 g of ionized water was used.
    <Example 21>
    In the same manner as in Example 18, 66.0 g of Pressis ketene dimer, CMC 7M (DS 0.7) in deionized water (Hercules Incorporated, Wilmington, DE) 25.0% solution 75.0 g, aluminum sulfate ( 18H 2 O) 132.0 g of a 25 wt% containing solution and deionized water were used and sufficiently alkaline to increase the pH to 4.0 and 27.0 g of DI water was used.
    <Example 22>
    3.0 g of CMC II (prepared in Example 3, DS approximately 0.15) was dispersed in 465 g of DI water for 5 minutes using a high shear mixer with a power setting of 50 and then immersed in an immersion mixer at 340.2 atm (5000 psi). Passed times. As in Example 18, 66.0 g of presses ketone dimer were combined with 234.0 g of sample material in a DI water gel with stirring using a high shear mixer with a power setting of 50, and then twice into the immersion mixer at 340.2 atm (5000 psi). Passed and cooled.
    <Example 23>
    4.0 g of CMC II (prepared in Example 3, DS approximately 0.15) was dispersed in 400 g of DI water for 5 minutes using a high shear mixer with a power setting of 50, followed by 3 microfluidics at 340.2 atm (5000 psi). Pass through to give a gel.
    In a 226.8 g (8 oz) wide inlet bottle, 176.0 g of Pressis 787 ketene dimer and 224.0 g of DI water were combined. The premix was sheared in a high shear mixer for 5 minutes at a power setting of 50 and then rapidly poured into the feed chamber of the immersion mixer. The premix was passed twice through an immersion mixer set at 340.2 atm (5000 psi) with mechanical agitation of about 250 rpm.
    150.0 g of the gel prepared as above was combined with 150.0 g of Fresis ketene dimer 44% emulsion and stirred for 5 minutes using a high shear mixer with a power setting of 50.
    <Example 24>
    In a 226.8 g (8 oz) wide inlet bottle, 66.0 g of Pressis 787 ketene dimer, 1.5 g of pre-shear solvent exchange dry material (DS about 0.16) and 232.5 g of DI water, as prepared in Example 7, were combined. The premix was sheared in a high shear mixer for 5 minutes at a power setting of 50 and then rapidly poured into the feed chamber of the immersion mixer. The premix was passed through an immersion mixer at 5000 psi at 340.2 atm with mechanical agitation of about 250 rpm. The emulsion was collected and passed through a second time. The two pass product was collected in a clean bottle, a stir bar was added, the bottle was sealed and cooled in a 5-15 ° C. water bath.
    The test results for the sample emulsion are shown below using the TAPPI standard method T560.
    Examples 18-24 Surface Sizing of Emulsions (Composition Weight in g)Preliminary shear MF gel MF gel RTG Example number 18 19 1 20 21 22 23 1 24 Precis 787 66.00 66.00 66.00 66.00 66.00 66.00 66.00 Microfibrillated CMC 1.50 1.50 1.50 1.50 1.50 1.50 50% aluminum sulphate 66.00 25% aluminum sulphate pH 4.0132.0 132.002% CMC 7M 75.00DI number 232.50 166.50 100.50 27.00 232.50 232.50 232.50 gun 300.0 300.0 300.0 300.0 300.0 300.0 300.0 Rotor-stator shear 50 to 2 minutes 50 to 2 minutes 50 to 2 minutes 50 to 2 minutes 50 to 2 minutes 50 to 2 minutes 50 to 2 minutes Immersion mixer shear 2X at 340.2atm (5k psi) 2X at 340.2atm (5k psi) 2X at 340.2atm (5k psi) 2X at 340.2atm (5k psi) 2X at 340.2atm (5k psi) 2X at 340.2atm (5k psi) 2X at 340.2atm (5k psi) Rotor-stator gel shear 50 to 5 minutes 50 to 5 minutes Immersion Mixer Gel Shear 2X at 340.2atm (5k psi) 2X at 340.2atm (5k psi) 1 Examples 19 and 23 had an emulsion broken overnight and were not suitable for surface sizing the next day.
    The failure of Example 19 is most likely due to low pH with 50% aluminum sulphate and can be corrected by raising the pH of the aluminum sulphate. Without being bound by any particular theory, it is known that aluminum can be in the form of a polymer, and thus can form an air community at higher pH. In general, it will be desirable to bring the pH of the aluminum, polyaluminum chloride or other aluminum salt as close as possible to the pKa of the cellulose on the induced microfibrils. Thus, in Example 18, poor stability emulsions were obtained by the addition of a low pH 50% aluminum solution, while in Examples 18 and 20, with aluminum lacking or raising its pH to 4.0 Similar formulation resulted in a good emulsion. In Example 23, the microfibrillated gel without shearing the second immersion mixer as in Example 22 produced an emulsion that was not stable overnight and could not be size tested the next day. The emulsions from Examples 18, 20, 21, 23 and 24 were then tested in sizing compositions and the results are shown in Chart 1 below. The procedure used to obtain this data was as follows. All samples were prepared with 5% by weight of D-150 starch (Grain Processing Corp., Muscatine, Iowa, USA). Three pieces of paper and wet pickup for each experiment were size pressurized using a wet gap size press. Each sheet was pressured dry in a drum dryer at 122.2 ° C. ± 11.1 ° C. (220 ° F. ± 5 ° F.) for 20 seconds. The wet weight of the pickup sheet was measured before and after size pressurization to obtain the wet pickup percentage. Hercules size test (HST) was performed for each paper sheet (5 per experiment) using the TAPPI procedure T560.
    〈Chart 1〉

    <Example 25-27>
    The emulsion series was prepared using an Aquipel® 364 sizing agent rather than the Fresis ketene dimer as the size with the formulations shown in Table 18 below. In each case, the samples were sonicated on a Branson 350 Ultrasonicator at power setting 6. Samples of higher grades were prepared using an emulsion on a continuous Fourdrinier-type machine and sized after 100 hours of natural ripening using a standard HST ink resistance test (TAPPI method T-530) using 1% formic acid ink. Tested. Chart 2 below shows the HST sizing results indicating that the sample is at least as good as or better than three commercial controls using a Hercon® paper sizing agent.
    Example 25 Example 26 Example 27 Aquapel 364 (1) 10 10 10 Carrageenan 2% (2) 50 CMC II (manufactured in Example 3, DS about 0.15) One Ambergum (registered trademark) CMC 2% (3)50 pH 4 aluminum sulphate 20 20 20 Reten® 203 20% (4) 5 5 5 Biocide AMA 415 0.05 0.02 0.02 water 14.98 63.98 14.98 (1) Aquiapel 364 Ketene Dimer Sizing Agent-Hercules Incorporated (2) Carrageenan-Genugel (GenuGel®) Carrageenan Type LC-5, Hercules Incorporated (3) Ambergum-Type 99 -3021, Hercules Incorporated Products (4) Reten 203-Cation Resin, Hercules Incorporated Products (Ambergum, Aquiapel, Hercon, Genugel and Reten are registered trademarks of Hercules Incorporated) )
    〈Chart 2〉

    <restraint>
    The paper used in the sizing example was prepared at pH 7 from hardwood and softwood pulp 75:25 blends hit with Canadian standard Prinis 525 and formed into sheets with a basis weight of 65.1 g / m 2 . Hercon 70, Hercon 79 and Hercon 115 sizing agents were all added at 0.06% based on pulp (corresponding to 0.544 kg (1.2 pounds) per ton). Laboratory water with a water hardness of 50 ppm, an alkalinity of 25 ppm and a pH of 8.1 to 8.4 was used.
    Uses in food and personal care compositions: The following examples relate to derived microfibrillated polysaccharides and their use in food and personal care products.
    <Example 28> Use as a fat substitute and viscosity improvement in food application.

    Procedure 1: RTG microfibrillated CMC prepared in Example 7 (DS about 0.16) was dispersed in water with stirring. Starch and maltodextrin were added with stirring. The mixture was heated to 80-90 ° C. and cooled to 15-20 ° C. Egg yolk and then vinegar were added. The product was then mixed using a colloid mill. One pass through Greerco colloid mill model W250V-B (Greerco Corp., Hudson, NH) with emulsion rotor and stator at clearance setting 0.0254 mm (0.001 inch) The mixture was mixed as described above. The texture of the product was then evaluated after 24 hours.
    Procedure 2: The remaining water was added to a 1% microfibrillated CMC gel (DS about 0.16) prepared as in Example 3 above. Starch and maltodextrin were then added with stirring. The mixture was heated to 80-90 ° C. and then cooled to 15-20 ° C. Egg yolk and then vinegar were added. The product was then mixed using a colloid mill. The texture of the product was then evaluated after 24 hours.
    Procedure 3: Starch and maltodextrin were added to the water with stirring. The mixture was heated to 80-90 ° C. and then cooled to 15-20 ° C. Egg yolk and then vinegar were added. The product was then mixed using a colloid mill. The texture of the product was evaluated after 24 hours.
    Evaluation: Viscosity was measured by Brookfield (Model DV-II +) at 20 ° C., helipath, 5 rpm spindle C, program S93.
    The appearance of the product containing either RTG microfibrillated CMC or microfibrillated CMC was the appearance of the gel which did not merge and retained its shape for a period of time when cut. When part of the product was lifted into the cutlery or spatula, there was no excessive stickiness and the texture was described as short. This is the main texture characteristic of reduced fat dressing and mayonnaise that floats into the cutlery.
    Example 29 Use in Personal Care Product.

    Procedure: Part A ingredients were combined, mixed until the water soluble polymer dissolved and heated to 60-65 ° C. All B minor components except the microfibrillated CMC were combined and heated to 60-65 ° C. until homogeneous. The RTG microfibrillated CMC was then dispersed in part B, and part B was added to part A with vigorous stirring and stirring continued until the mixture was well mixed and homogeneous. It was then cooled to 30 ° C. and C part was added.
    characteristic
    pH 5.7
    Viscosity at 25 ° C * (cP) 16,600
    Appearance milky emulsion
    Stability More than 5 weeks at 50 ° C
    The composite viscosity in the linear viscoelastic region was measured with a controlled stress flow meter.
    This example demonstrates the ability of RTG CMC materials to stabilize oil-in-water emulsions, which play a role typically performed by surfactant / cosurfactant network formation systems.

    Procedure: Part A ingredients were combined and mixed until the water soluble polymer dissolved. Part B ingredients were then combined and B part was added to part A with vigorous stirring and stirring continued until the mixture was well mixed and homogeneous.
    characteristic
    pH 6.0
    Viscosity at 25 ° C * (cP) 30,200
    Appearance creamy white emulsion
    Stability More than 5 weeks at 50 ° C
    * The composite viscosity in the linear viscoelastic region was measured with a flow meter.
    This example demonstrates the ability of RTG CMC materials to stabilize oil-in-water emulsions, which play a role typically performed by surfactant / cosurfactant network formation systems. Typical surfactant / cosurfactant systems require heat, while RTG CMC was also processed at room temperature.

    ("Anti-aging" as used herein refers to the classification of epithelial lotions and lotions for the purpose of giving the user a younger appearance, such as reducing or eliminating wrinkles.)
    Procedure: Part A ingredients were combined and heated to 75 ° C. The B minor components except CMC on RTG microfibrils were then combined and heated to 75 ° C. until homogeneous. The CMC on RTG microfibrils was then dispersed in part B. Part B was then added to part A until the mixture was well mixed and homogeneous. The mixture was then cooled to 40 ° C. and C part was added. This composition was formulated at pH 3.5-4.0 and stabilized with CMC on microfibrils rather than a typical xanthan, clay mixture.
    characteristic
    pH 3.7
    Viscosity at 25 ° C * (cP) 932,000
    Appearance Polish white stiff cream
    Stability More than 5 weeks at 50 ° C
    * The composite viscosity in the linear viscoelastic region was measured with a flow meter.
    This example shows the ability of RTG CMC materials to stabilize oil-in-water emulsions at low pH.

    Procedure: The components of Part A and Part B were combined and heated to 70 ° C. The C parts were then added individually and mixed after the addition of each C part component. Part D was then added with vigorous stirring and stirring continued until the mixture was well mixed and homogeneous. Part E was subsequently added, then cooled to 45 ° C. and part F was added.
    characteristic
    pH 5.9
    Viscosity at 25 ° C * (cP) 613,000
    Appearance grayish white bright cream
    Stability More than 5 weeks at 50 ° C
    * The composite viscosity in the linear viscoelastic region was measured with a flow meter.
    This example illustrates the use of microfibrillated CMC with organic sunscreens.

    Procedure: Part A ingredients were combined and heated to 50 ° C. All B minor components except the microfibrillated CMC were combined and heated to 60-65 ° C. until homogeneous. The microfibrillated CMC was then dispersed in part B, then added to part A with vigorous stirring and stirring continued until the mixture was well mixed and homogeneous. The components of Part D were combined and mixed well. Part C was added to the AB emulsion, then with moderate stirring, part D was added slowly to the emulsion and cooled to 30 ° C.
    characteristic
    pH 7.1
    Viscosity at 25 ° C * (cP) 33,900
    Appearance glossy white emulsion gel
    Stability More than 5 weeks at 50 ° C
    * The composite viscosity in the linear viscoelastic region was measured with a flow meter.
    This example illustrates the use of microfibrillated CMC with inorganic sunscreens. The present invention is inevitably discussed herein with reference to certain specific methods and materials. The enumeration of these methods and materials is for illustration only and is not intended to limit the scope of the invention in any way. Those skilled in the art are contemplated and able to make modifications and alternatives to the specific teachings provided herein without departing from the scope of the invention.
    This example illustrates the use of microfibrillated CMC with inorganic sunscreens. The present invention is inevitably discussed herein with reference to certain specific methods and materials. The enumeration of these methods and materials is for illustration only and is not intended to limit the scope of the invention in any way. Those skilled in the art are contemplated and able to make modifications and alternatives to the specific teachings provided herein without departing from the scope of the invention.
    权利要求:
    Claims (165)
    [1" claim-type="Currently amended] Derived substituents that provide electrostatic and / or steric functionality, wherein the electrostatic functionality comprises anionic charge.
    [2" claim-type="Currently amended] The method according to claim 1, wherein the polysaccharide of the derived microfibrillated polysaccharide is cellulose, hemicellulose, chitin, chitosan, guar gum, pectin, alginate, daikon, xanthan, starch, amylose, amylopectin, Alternan, gellan, mutan, dextran, pullulan, fructan, locust bean gum, carrageenan, glycogen, glycosaminoglycans, murine, bacterial capsular polysaccharides and derivatives thereof Induced microfibrillated polysaccharide, characterized in that.
    [3" claim-type="Currently amended] 3. The derived microfibrillary polysaccharide of claim 2, wherein said polysaccharide is at least one of cellulose, chitin, chitosan, pectin, radish, starch, carrageenan and derivatives thereof.
    [4" claim-type="Currently amended] The derived microfibrillated polysaccharide according to claim 3, characterized in that it comprises derived microfibrillated cellulose.
    [5" claim-type="Currently amended] The method according to claim 4, wherein the cellulose is selected from chemical pulp, mechanical pulp, thermal mechanical pulp, chemical-thermal mechanical pulp, recycled fiber, newsprint, cotton, soybean pods, pea pods, corn pods, flax, hemp, jute, yam, Derived microfibrillated polysaccharides obtained from one or more of sheep, manila, sisal, sugarcane pods, corn, wheat, bamboo, velonia, bacteria, algae, fungi, microcrystalline cellulose, vegetables and fruits .
    [6" claim-type="Currently amended] 6. The derived fine according to claim 5, wherein the cellulose is obtained from at least one of a tablet prepared by a sulfite, kraft or prehydrolysis kraft pulping process, optionally bleached wood pulp, purified cotton linter, fruit and vegetables. Fibrillated polysaccharides.
    [7" claim-type="Currently amended] The method of claim 4, wherein the induced microfibrillated cellulose is hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxypropyl hydroxyethyl cellulose, methyl cellulose, methyl hydroxypropyl Cellulose, methylhydroxyethyl cellulose, carboxymethylmethyl cellulose, hydrophobically modified carboxymethylcellulose, hydrophobically modified hydroxyethyl cellulose, hydrophobically modified hydroxypropyl cellulose, hydrophobically modified hydroxypropyl cellulose, hydrophobically modified ethylhydroxyethyl cellulose, hydrophobically modified carboxyethyl hydroxyethyl Hydrophobically modified hydroxypropylhydroxyethyl cellulose, hydrophobically modified methyl cellulose, hydrophobically modified methylhydroxypropyl cellulose, hydrophobically modified methylhydroxyethyl cellulose, hydrophobically modified carboxy Induced microfibrillated cellulose, characterized in that it comprises at least one of methylmethyl cellulose, nitro cellulose, cellulose acetate, cellulose sulfate, cellulose vinyl sulfate, cellulose phosphate and cellulose phosphonate.
    [8" claim-type="Currently amended] 5. The induced microfibrillated cellulose of claim 4 wherein said induced microfibrillated cellulose forms a gel in a concentration range of about 0.01% to about 100% in water.
    [9" claim-type="Currently amended] The induced microfibrillated cellulose of claim 8, wherein the induced microfibrillated cellulose forms a gel in a concentration range of about 0.01% to about 50% in water.
    [10" claim-type="Currently amended] 5. The induced microfibrillated cellulose of claim 4 wherein said induced microfibrillated cellulose forms a gel at at least one point in a concentration range of about 0.05% to about 0.99% in water.
    [11" claim-type="Currently amended] The derived microfibrillated polysaccharide according to claim 1, wherein the derived microfibrillated polysaccharide further comprises a solvent which is substantially insoluble.
    [12" claim-type="Currently amended] 12. The derived microfibrillary polysaccharide of claim 11 wherein said solvent is water, alcohol or oil.
    [13" claim-type="Currently amended] 13. The derived microfibrillated polysaccharide according to claim 12, wherein the solvent is water.
    [14" claim-type="Currently amended] 15. The derived microfibrillary polysaccharide derived from claim 13, comprising a substituent that provides electrostatic functionality.
    [15" claim-type="Currently amended] The derived microfibrillated polysaccharide of claim 1, wherein the derived microfibrillated polysaccharide is an induced microfibrillated cellulose having a degree of substitution of less than about 0.5.
    [16" claim-type="Currently amended] 16. The derived microfibrillary polysaccharide of claim 15, wherein said degree of substitution is less than about 0.35.
    [17" claim-type="Currently amended] 17. The derived microfibrillary polysaccharide of claim 16, wherein said degree of substitution is less than about 0.2.
    [18" claim-type="Currently amended] 18. The derived microfibrillary polysaccharide of claim 17, wherein said degree of substitution is less than about 0.18.
    [19" claim-type="Currently amended] 19. The derived microfibrillary polysaccharide of claim 18, wherein said degree of substitution is less than about 0.1.
    [20" claim-type="Currently amended] 16. The derived microfibrillary polysaccharide of claim 15, wherein said degree of substitution is from about 0.02 to about 0.5.
    [21" claim-type="Currently amended] 21. The derived microfibrillary polysaccharide of claim 20, wherein said degree of substitution is from about 0.05 to about 0.2.
    [22" claim-type="Currently amended] The induced microfibrillated polysaka of claim 1 comprising a substituent that provides electrostatic functionality in the form of anionic charges and wherein the degree of substitution of the substituents that provide electrostatic functionality in the form of anionic charges is at least about 0.02. Ride.
    [23" claim-type="Currently amended] The derived microfibrillary polysaccharide of claim 1, wherein the anionic charge is provided by carboxyl, sulfate, sulfonate, phosphonate or phosphate groups or a combination thereof.
    [24" claim-type="Currently amended] 15. The induced microfibrillary polysaccharide of claim 14, wherein said electrostatic functionality is provided by both anionic and cationic charges.
    [25" claim-type="Currently amended] 25. The induced microfibrils on cellulose according to claim 24, wherein said electrostatic functionality is provided by substituents containing both anionic and cationic charges.
    [26" claim-type="Currently amended] The induced microfibrillated cellulose of claim 24 wherein said electrostatic functionality is provided by both a substituent of anionic charge and a substituent of cationic charge.
    [27" claim-type="Currently amended] 15. The derived microfibrillary polysaccharide derived from claim 13, comprising a substituent that provides steric functionality.
    [28" claim-type="Currently amended] The derived microfibrillary polysaccharide of claim 27, wherein the molar substitution degree is less than about 3.0.
    [29" claim-type="Currently amended] 29. The derived microfibrillary polysaccharide of claim 28, wherein said molar substitution is less than about 1.5.
    [30" claim-type="Currently amended] 30. The derived microfibrillary polysaccharide of claim 29, wherein said molar substitution is less than about 1.0.
    [31" claim-type="Currently amended] 31. The derived microfibrillary polysaccharide of claim 30, wherein said molar substitution is less than about 0.5.
    [32" claim-type="Currently amended] 29. The derived microfibrillary polysaccharide of claim 28, wherein said molar substitution degree is from about 0.5 to 3.0.
    [33" claim-type="Currently amended] The method of claim 27 wherein the substituent is a hydroxyethyl group, hydroxypropyl group, methyl group, ethyl group, straight or branched chain alkyl, alkenyl or alkynyl group having from about 4 to about 30 carbon atoms, about 4 to about carbon atoms A derived microfibrillated polysaccharide, characterized in that it comprises one or more of 30 aryl, arylalkyl, arylalkenyl, cyclic and heterocyclic hydrocarbons, or combinations thereof.
    [34" claim-type="Currently amended] 34. The derived microfibrillated polysaccharide according to claim 33, which is derived microfibrillated cellulose.
    [35" claim-type="Currently amended] 5. The derived microfibrillated cellulose of claim 4 comprising carboxymethylcellulose.
    [36" claim-type="Currently amended] 35. The derived microfibrillary cellulose of claim 34 wherein the degree of substitution is less than about 0.35.
    [37" claim-type="Currently amended] 37. The derived microfibrillated cellulose of claim 36, wherein said degree of substitution is less than about 2.0.
    [38" claim-type="Currently amended] 38. The derived microfibrillated cellulose of claim 37 wherein said degree of substitution is from about 0.02 to about 0.2.
    [39" claim-type="Currently amended] 39. The derived microfibrillated cellulose of claim 38 wherein said degree of substitution is from about 0.10 to about 0.2.
    [40" claim-type="Currently amended] 5. The induced microfibrillated polysaccharide of claim 4, wherein said induced microfibrillated cellulose forms a gel at a concentration of less than about 1% in water.
    [41" claim-type="Currently amended] Microfibrillated carboxymethylcellulose having a degree of substitution of about 0.10 to about 0.20.
    [42" claim-type="Currently amended] An edible composition of matter, characterized in that it comprises a substituent that provides electrostatic and / or steric functionality, wherein the electrostatic functionality comprises an induced microfibrillated polysaccharide induced to be provided by an anionic charge. .
    [43" claim-type="Currently amended] 43. The edible composition of claim 42, wherein the substance is in the form of low fat, reduced fat or no fat mayonnaise.
    [44" claim-type="Currently amended] 43. The edible composition of claim 42, wherein the substance is in the form of a salad dressing.
    [45" claim-type="Currently amended] 43. The edible composition of claim 42, further comprising a pharmaceutically active ingredient.
    [46" claim-type="Currently amended] 46. The edible composition of claim 45, wherein the derived microfibrillated polysaccharide at least partially controls, maintains or delays the release of the pharmaceutical active ingredient.
    [47" claim-type="Currently amended] Non-edible materials of a material characterized in that it comprises a derived microfibrillated polysaccharide induced to be characterized by being provided by an anionic charge. Composition.
    [48" claim-type="Currently amended] 48. The non-edible composition of claim 47, wherein the substance is in the form of a wound care product.
    [49" claim-type="Currently amended] 49. The non-edible composition of claim 48, wherein the wound care product is a wound dressing.
    [50" claim-type="Currently amended] 49. The non-edible composition of claim 48, wherein the wound care product is an anastomotic ring.
    [51" claim-type="Currently amended] 48. The non-edible composition of claim 47 in the form of a skin protective lotion or cream.
    [52" claim-type="Currently amended] 48. The non-edible composition of claim 47 in the form of a sunscreen lotion or cream.
    [53" claim-type="Currently amended] 48. The non-edible composition of claim 47 in the form of an oral protective composition.
    [54" claim-type="Currently amended] 54. The non-edible composition of claim 53, wherein the oral care product is a toothpaste.
    [55" claim-type="Currently amended] 48. The non-edible composition of claim 47, further comprising a fertilizer, herbicide, fungicide or insecticide.
    [56" claim-type="Currently amended] 56. The non-edible composition of claim 55, wherein the derived microfibrillated polysaccharide at least partially controls, maintains, or delays the release of the fertilizer, herbicide, or pesticide.
    [57" claim-type="Currently amended] 48. The non-edible composition of claim 47 in the form of a drilling fluid.
    [58" claim-type="Currently amended] Paper groups comprising induced microfibrillated cellulose derived to characterize electrostatic and / or steric functionality, said electrostatic functionality comprising the presence of an anionic charge.
    [59" claim-type="Currently amended] 59. The paper composition of claim 58, wherein the derived microfibrillated cellulose is microfibrillated carboxymethylcellulose.
    [60" claim-type="Currently amended] a) derivatization step of treating microfibrillated polysaccharide to obtain an induced microfibrillated polysaccharide,
    b) a microfibrillation step of treating an induced non-microfibrillated polysaccharide to produce an induced microfibrillated polysaccharide, or
    c) substituents that provide electrostatic and / or steric functionality, characterized in that it comprises one or more of the steps of microfibrillating and derivatizing non-microfibrillated polysaccharides substantially simultaneously. A process for preparing induced microfibrillated polysaccharides, wherein the electrostatic functionality is induced to be provided by anionic charges.
    [61" claim-type="Currently amended] 61. The polysaccharide according to claim 60, wherein the polysaccharide is cellulose, hemicellulose, chitin, chitosan, guar gum, pectin, alginate, daikon, xanthan, starch, amylose, amylopectin, alternane, gellan, mutan, dextran , Pullulan, fructan, locust bean gum, carrageenan, glycogen, glycosaminoglycans, murine, capsular polysaccharide of bacteria and derivatives thereof.
    [62" claim-type="Currently amended] 62. The method of claim 61, wherein said polysaccharide is at least one of cellulose, chitin, chitosan, pectin, radish, starch, carrageenan and derivatives thereof.
    [63" claim-type="Currently amended] 63. The method of claim 62, wherein the polysaccharide is cellulose and the derived microfibrillated polysaccharide is derived microfibrillated cellulose.
    [64" claim-type="Currently amended] 64. The method according to claim 63, wherein the cellulose is selected from chemical pulp, mechanical pulp, thermal mechanical pulp, chemical-thermal mechanical pulp, recycled fiber, newsprint, cotton, soybean pods, pea pods, corn pods, flax, hemp, jute, yam A method obtained from one or more of sheep, manila, sisal, sugarcane pods, corn, wheat, bamboo, velonia, bacteria, algae, fungi, microcrystalline cellulose, vegetables and fruits.
    [65" claim-type="Currently amended] 65. The method of claim 64, wherein the cellulose is obtained from at least one of a tablet prepared from a sulfite, kraft, or prehydrolyzed kraft pulping process, optionally bleached wood pulp, purified cotton linter, fruit and vegetables. .
    [66" claim-type="Currently amended] The method of claim 60,
    a) inducing cellulose with monochloroacetic acid or a salt thereof under alkaline conditions to produce carboxymethylcellulose,
    b) suspending this carboxymethylcellulose in water to form a suspension, and
    c) homogenizing the suspension to produce microfibrillated carboxymethylcellulose.
    [67" claim-type="Currently amended] 61. The method of claim 60, wherein the derivatization step comprises contacting the non-microfibrillated polysaccharide with a swelling agent.
    [68" claim-type="Currently amended] 68. The method of claim 67, wherein said contact occurs under alkaline conditions.
    [69" claim-type="Currently amended] 69. The method of claim 68, wherein said swelling agent is an anionic reagent.
    [70" claim-type="Currently amended] The method of claim 69, wherein the polysaccharide is cellulose.
    [71" claim-type="Currently amended] 71. The method of claim 70, wherein the alkali conditions are selected from oxides or hydroxides of sodium hydroxide, alkali metals or alkaline earth metals, alkali silicates, alkali aluminates, alkali carbonates, amines, ammonium hydroxides, ammonium hydroxide, or combinations thereof. Contacting cellulose with said anionic reagent in the presence of at least one alkaline reagent.
    [72" claim-type="Currently amended] 61. The method of claim 60, wherein said derivatization step occurs at high solids.
    [73" claim-type="Currently amended] 61. The method of claim 60, wherein said anionic charge comprises carboxyl, sulfate, sulfonate, phosphonate or phosphate groups or combinations thereof.
    [74" claim-type="Currently amended] 74. The method of claim 73, wherein said derivatization step comprises carboxymethylation of cellulose.
    [75" claim-type="Currently amended] 64. The cellulose of claim 63, wherein the derived microfibrillated cellulose is hydroxyethyl cellulose, ethyl hydroxyethyl cellulose, carboxymethyl cellulose, carboxymethyl hydroxyethyl cellulose, hydroxypropyl hydroxyethyl cellulose, methyl cellulose, methyl hydroxy Propyl cellulose, methylhydroxyethyl cellulose, carboxymethylmethyl cellulose, hydrophobically modified carboxymethylcellulose, hydrophobically modified hydroxyethyl cellulose, hydrophobically modified hydroxypropyl cellulose, hydrophobically modified hydroxypropyl cellulose, hydrophobically modified ethyl hydroxyethyl hydroxymethyl hydroxyethyl hydroxy Hydrophobically modified hydroxypropylhydroxyethyl cellulose, hydrophobically modified methyl cellulose, hydrophobically modified methylhydroxypropyl cellulose, hydrophobically modified methylhydroxyethyl cellulose, hydrophobically modified car Method of double vision methyl cellulose, nitro cellulose, cellulose acetate, cellulose sulfate, cellulose vinyl sulfate, cellulose phosphate, and cellulose phosphonate. Characterized in that it comprises one or more of the.
    [76" claim-type="Currently amended] 61. The method of claim 60, wherein said microfibrillation step comprises applying energy to said polysaccharide under conditions sufficient to produce a microfibrillated polysaccharide.
    [77" claim-type="Currently amended] 77. The method of claim 76, comprising enzymatically treating said non-microfibrid polysaccharide before said microfibrillation step.
    [78" claim-type="Currently amended] 77. The method of claim 76, wherein applying at least one of homogenization, pumping, mixing, heating, steam explosion, pressure-decompression cycles, impact, milling, ultrasonic, microwave explosion, and milling to the non-microfibrillated polysaccharide Including method.
    [79" claim-type="Currently amended] 79. The method of claim 78, comprising passing the non-microfibrid polysaccharide through a homogenizer under conditions sufficient to produce a microfibrillated polysaccharide.
    [80" claim-type="Currently amended] 80. The method of claim 79, wherein said conditions comprise passing said non- microfibrid polysaccharide at a pressure difference of at least about 204.1 atm (3,000 psi).
    [81" claim-type="Currently amended] 81. The method of claim 80, further comprising passing the non- microfibrid polysaccharide through the homogenizer three or more times.
    [82" claim-type="Currently amended] 61. The method of claim 60, wherein said derived microfibrillated polysaccharide forms a gel in a concentration range of about 0.01% to about 100% in water.
    [83" claim-type="Currently amended] 83. The method of claim 82, wherein said derived microfibrillated polysaccharide forms a gel in a concentration range of about 0.01% to about 50% in water.
    [84" claim-type="Currently amended] 61. The method of claim 60, wherein said derived microfibrillated polysaccharide forms a gel at one or more points in the concentration range of about 0.05% to about 0.99% in water.
    [85" claim-type="Currently amended] 85. The method of claim 84, wherein said derived microfibrillated polysaccharide forms a gel at a concentration of about 0.9% in water.
    [86" claim-type="Currently amended] 61. The method of claim 60, wherein said derived microfibrillated polysaccharide is substantially insoluble in the solvent used.
    [87" claim-type="Currently amended] 87. The method of claim 86, wherein the solvent used is water.
    [88" claim-type="Currently amended] 88. The method of claim 87, wherein said derived microfibrillary polysaccharide is derived to include a substituent that provides electrostatic functionality.
    [89" claim-type="Currently amended] 89. The method of claim 88, wherein said derived microfibrillated polysaccharide is derived microfibrillated cellulose having a degree of substitution of less than about 0.5.
    [90" claim-type="Currently amended] 90. The method of claim 89, wherein said degree of substitution is less than about 0.35.
    [91" claim-type="Currently amended] 91. The method of claim 90, wherein said degree of substitution is less than about 0.2.
    [92" claim-type="Currently amended] 92. The method of claim 91, wherein said degree of substitution is less than about 0.18.
    [93" claim-type="Currently amended] 93. The method of claim 92, wherein said degree of substitution is less than about 0.1.
    [94" claim-type="Currently amended] 90. The method of claim 89, wherein the degree of substitution of said induced microfibrils on cellulose is from about 0.02 to about 0.5.
    [95" claim-type="Currently amended] 95. The method of claim 94, wherein said degree of substitution is about 0.05 to about 0.2.
    [96" claim-type="Currently amended] 87. The method of claim 86, wherein said derived microfibrillary polysaccharide is derived to comprise steric substituents.
    [97" claim-type="Currently amended] 97. The method of claim 96, wherein said derived microfibrillated polysaccharide is derived to include a substituent that provides electrostatic functionality.
    [98" claim-type="Currently amended] 97. The method of claim 96, wherein the molar substitution degree of the derived microfibrillary polysaccharide is less than about 3.0.
    [99" claim-type="Currently amended] 99. The method of claim 98, wherein said molar substitution is less than about 1.5.
    [100" claim-type="Currently amended] 105. The method of claim 99, wherein said molar substitution is less than about 1.0.
    [101" claim-type="Currently amended] 101. The method of claim 100, wherein said molar substitution is less than about 0.5.
    [102" claim-type="Currently amended] 99. The method of claim 98, wherein said molar substitution degree is about 0.5 to 3.0.
    [103" claim-type="Currently amended] 64. The method of claim 63, wherein said induced microfibrillated cellulose is carboxymethylcellulose.
    [104" claim-type="Currently amended] 103. The method of claim 103, wherein the degree of substitution of the carboxymethylcellulose is less than about 0.35.
    [105" claim-type="Currently amended] 105. The method of claim 104, wherein said degree of substitution is less than about 2.0.
    [106" claim-type="Currently amended] 107. The method of claim 105, wherein said degree of substitution is from about 0.02 to about 2.0.
    [107" claim-type="Currently amended] 107. The method of claim 106, wherein said degree of substitution is about 0.1 to about 0.2.
    [108" claim-type="Currently amended] A derived microfibrillated polysaccharide prepared by the method of claim 60.
    [109" claim-type="Currently amended] Induced microfibrils on cellulose produced by the method of claim 63.
    [110" claim-type="Currently amended] 64. The derived microfibrillated cellulose of claim 63 which is derived to include a substituent that provides steric functionality.
    [111" claim-type="Currently amended] 113. The method of claim 110, wherein said substituent comprises at least one of a hydroxyethyl group, a hydroxypropyl group, a methyl group, an ethyl group, a straight or branched chain aliphatic group having from about 4 to about 30 carbon atoms, or a combination thereof. Induced microfibrillated cellulose.
    [112" claim-type="Currently amended] 109. The induced microfibrils on cellulose of claim 109, wherein the induced microfibrils are derived from a substituent that provides electrostatic functionality by anionic charge.
    [113" claim-type="Currently amended] 112. The induced microfibrils on cellulose according to claim 112, wherein said anionic charge comprises the presence of a carboxyl, sulfate, sulfonate, phosphonate, or phosphate group or combinations thereof.
    [114" claim-type="Currently amended] 116. The induced microfibrillated cellulose of claim 113, wherein said anionic charge comprises the presence of a carboxyl group.
    [115" claim-type="Currently amended] 112. The induced microfibrils on cellulose according to claim 112, wherein said electrostatic functionality is provided by both anionic and cationic charges.
    [116" claim-type="Currently amended] 118. The induced microfibrils on cellulose according to claim 115, wherein said electrostatic functionality is provided by substituents containing both anionic and cationic charges.
    [117" claim-type="Currently amended] 116. The induced microfibrils on cellulose according to claim 115, wherein said electrostatic functionality is provided by both a substituent having an anionic charge and a substituent having a cationic charge.
    [118" claim-type="Currently amended] Including substituents that provide electrostatic and / or steric functionality, the electrostatic functionality comprising incorporating induced microfibrillated polysaccharides derived from the anion charge into the composition of matter. A method of fluidity modification of a composition of matter characterized in that.
    [119" claim-type="Currently amended] 118. The method of claim 118, wherein the composition comprises a liquid.
    [120" claim-type="Currently amended] 119. The method of claim 119, wherein said liquid is water.
    [121" claim-type="Currently amended] 126. The method of claim 120, comprising using said derived microfibrillated polysaccharide in an amount effective to provide scale inhibition and / or corrosion inhibition.
    [122" claim-type="Currently amended] 118. The method of claim 118, wherein the derived microfibrillated polysaccharide is derived microfibrillated cellulose.
    [123" claim-type="Currently amended] 119. The method of claim 119, wherein said flowability is at least one of viscosity, suspension stability, temperature resistance to gel, shear reversible gelation, yield stress, and liquid retention.
    [124" claim-type="Currently amended] 118. The method of claim 118, wherein the composition of matter is a food, pharmaceutical, nutraceutical, personal protective article, fiber, paper, paint, coating or building composition.
    [125" claim-type="Currently amended] 124. The method of claim 124, wherein the composition of matter is an oral protective product.
    [126" claim-type="Currently amended] 124. The method of claim 124, wherein the composition of matter is a cream or lotion for epithelial application.
    [127" claim-type="Currently amended] 124. The method of claim 124, wherein the composition of matter is a moisturizing, knight, anti-aging or sunscreen cream or lotion.
    [128" claim-type="Currently amended] 124. The method of claim 124, wherein the composition of matter is a food spread.
    [129" claim-type="Currently amended] 129. The method of claim 128, wherein the food spread is reduced fat, low fat or fat free food spread.
    [130" claim-type="Currently amended] 129. The method of claim 129, wherein the food thread is reduced fat, low fat or no fat mayonnaise.
    [131" claim-type="Currently amended] 124. The method of claim 124, wherein the composition of matter is a drilling fluid.
    [132" claim-type="Currently amended] Substituents that provide electrostatic and / or steric functionality, the electrostatic functionality of the coating composition by incorporating an effective amount of the derived microfibrillated polysaccharide derived in the coating composition to be provided by an anionic charge. Methods of improving physical and / or mechanical properties.
    [133" claim-type="Currently amended] 134. The method of claim 132, wherein the physical and / or mechanical properties comprise one or more of film forming ability, leveling property, sag resistance, strength, durability, dispersibility, appendageability, floatability and sputtering property.
    [134" claim-type="Currently amended] The use of induced microfibrillated cellulose during paper production, characterized in that it is induced by electrostatic and / or steric substituents, wherein the electrostatic substituents comprise anionic charges or the presence of both anionic and cationic charges. A method for improving one or more of sizing, strength, scale inhibition, drainage, dehydration, retention, purification, formation, adsorption, film-forming ability, film-forming ability, and polyelectrolyte complexing during paper manufacture.
    [135" claim-type="Currently amended] 134. The method of claim 134, wherein said induced microfibrillated cellulose is used as drainage aid and / or sizing agent.
    [136" claim-type="Currently amended] 134. The method of claim 134, wherein the induced microfibrillated cellulose is microfibrillated carboxymethylcellulose.
    [137" claim-type="Currently amended] 137. The method of claim 136, comprising using the microfibrillated carboxymethylcellulose in a paper machine to increase the rate of drainage and / or dehydration during paper making.
    [138" claim-type="Currently amended] 138. The cellulose derivative of claim 137 wherein the microfibrillated carboxymethylcellulose is cationic polyacrylamide, polydiallyldimethyl-ammonium chloride, cationic starch, ammonium or cellulose derivatives containing mono-, di- or trialkyl ammonium substituents. , Guar gum derivatives containing ammonium or mono-, di- or trialkyl ammonium substituents, resins formed by the reaction of amines and / or polyamines with epichlorohydrin, and combinations thereof How to.
    [139" claim-type="Currently amended] 137. The complex of claim 137, wherein the microfibrillated carboxymethylcellulose is complexed with an aluminum salt, a hydrolyzed or partially hydrolyzed aluminum salt, a hydrolyzed or partially hydrolyzed aluminum salt with an organic or inorganic species, and combinations thereof Method of use in the presence of one or more of the.
    [140" claim-type="Currently amended] 137. The copolymer or terpolymer of claim 137, wherein the microfibrillated carboxymethylcellulose is at least one polymer of ethylene oxide, ethyleneimine, allylamine or vinylamine, ethylene oxide, ethyleneimine, allylamine or vinylamine A method for use in the presence of one or more, and combinations thereof.
    [141" claim-type="Currently amended] 137. The method of claim 136, comprising using the microfibrillated carboxymethylcellulose in a paper machine to retain organic and / or inorganic dispersed particles in the paper sheet during manufacture of the paper sheet.
    [142" claim-type="Currently amended] 143. The method of claim 141, wherein the dispersed particles comprise one or more of pulp fines, fillers, sizing agents, pigments, clays, hazardous organic particulates, hazardous inorganic particulates, and combinations thereof.
    [143" claim-type="Currently amended] 141. The cellulose derivative of claim 141, wherein the microfibrillated carboxymethylcellulose is cationic polyacrylamide, polydiallyldimethyl-ammonium chloride, cationic starch, ammonium or cellulose derivatives containing mono-, di- or trialkyl ammonium substituents, For use in the presence of one or more of guar gum derivatives containing ammonium or mono-, di- or trialkyl ammonium substituents, amines and / or resins formed by the reaction of polyamines with epichlorohydrin, and combinations thereof Way.
    [144" claim-type="Currently amended] 143. The complex of claim 141 wherein the microfibrillated carboxymethylcellulose is an aluminum salt, hydrolyzed or partially hydrolyzed aluminum salt, hydrolyzed or partially hydrolyzed aluminum salt with an organic or inorganic species, or a combination thereof. Use in the presence of more than one species.
    [145" claim-type="Currently amended] 145. The copolymer or terpolymer of claim 141, wherein the microfibrillated carboxymethylcellulose is at least one polymer of ethylene oxide, ethyleneimine, allylamine or vinylamine, ethylene oxide, ethyleneimine, allylamine or vinylamine. A method for use in the presence of one or more, and combinations thereof.
    [146" claim-type="Currently amended] 137. The method of claim 136, comprising using the microfibrillated carboxymethylcellulose in a paper machine to improve uniform formation of the paper sheet during manufacture of the paper sheet.
    [147" claim-type="Currently amended] 148. The cellulose derivative of claim 146, wherein the microfibrillated carboxymethylcellulose is cationic polyacrylamide, polydiallyldimethyl-ammonium chloride, cationic starch, ammonium or cellulose derivatives containing mono-, di- or trialkyl ammonium substituents. , Guar gum derivatives containing ammonium or mono-, di- or trialkyl ammonium substituents, resins formed by the reaction of amines and / or polyamines with epichlorohydrin, and combinations thereof How to.
    [148" claim-type="Currently amended] 145. The complex of claim 146, wherein the microfibrillated carboxymethylcellulose is complexed with an aluminum salt, hydrolyzed or partially hydrolyzed aluminum salt, hydrolyzed or partially hydrolyzed aluminum salt with organic or inorganic species, and combinations thereof Method of use in the presence of one or more of the.
    [149" claim-type="Currently amended] 145. The copolymer or terpolymer of claim 146, wherein the microfibrillated carboxymethylcellulose is at least one polymer of ethylene oxide, ethyleneimine, allylamine or vinylamine, ethylene oxide, ethyleneimine, allylamine or vinylamine A method for use in the presence of one or more, and combinations thereof.
    [150" claim-type="Currently amended] 136. The method of claim 136, comprising using the microfibrillated carboxymethylcellulose in a paper machine to improve the strength of the paper sheet produced in the paper machine.
    [151" claim-type="Currently amended] 151. The cellulose derivative of claim 150, wherein the microfibrillated carboxymethylcellulose is cationic polyacrylamide, polydiallyldimethyl-ammonium chloride, cationic starch, ammonium or cellulose derivatives containing mono-, di- or trialkyl ammonium substituents. , Guar gum derivatives containing ammonium or mono-, di- or trialkyl ammonium substituents, resins formed by the reaction of amines and / or polyamines with epichlorohydrin, and combinations thereof How to.
    [152" claim-type="Currently amended] 161. The complex of claim 150, wherein the microfibrillated carboxymethylcellulose is complexed with an aluminum salt, hydrolyzed or partially hydrolyzed aluminum salt, hydrolyzed or partially hydrolyzed aluminum salt with organic or inorganic species, and combinations thereof Method of use in the presence of one or more of the.
    [153" claim-type="Currently amended] 152. The copolymer or terpolymer of claim 150, wherein the microfibrillated carboxymethylcellulose is at least one polymer of ethylene oxide, ethyleneimine, allylamine or vinylamine, ethylene oxide, ethyleneimine, allylamine or vinylamine. A method for use in the presence of one or more, and combinations thereof.
    [154" claim-type="Currently amended] In the emulsifying, dispersing or foaming system, comprising an induced microfibrillated polysaccharide, wherein the electrostatic substituent is induced by an electrostatic and / or steric substituent and the electrostatic substituent comprises the presence of an anionic charge. Method for improving the stability of the emulsion, dispersion or foaming system characterized in that.
    [155" claim-type="Currently amended] 154. The method of claim 154, wherein said derived microfibrillated polysaccharide is added to the system.
    [156" claim-type="Currently amended] 155. The method of claim 155, wherein the system comprises an emulsion, and wherein the emulsion is prepared by an emulsion forming process.
    [157" claim-type="Currently amended] 162. The method of claim 156, wherein the derived microfibrillated polysaccharide is added before completion of the emulsion formation process.
    [158" claim-type="Currently amended] 161. The method of claim 156, wherein non- microfibrillated polysaccharide is added before completion of the emulsion forming process, and the emulsion formation is under conditions sufficient to microfibrillate the non- microfibrillated polysaccharide. How is it going.
    [159" claim-type="Currently amended] 158. The method of claim 158, wherein the non-microfibrillated or only partially microfibrillated polysaccharide is not induced or only partially induced, and the emulsion formation is such that the non-induced polysaccharide is induced. Further proceeding under conditions sufficient to adequately or sufficiently to fully derive only partially derived polysaccharides above.
    [160" claim-type="Currently amended] 162. The non-derived or only partially derived polysaccharide is added prior to completion of the emulsion forming process, and emulsion formation is sufficient to induce or only partially of the non-derived polysaccharide. Proceeding under conditions sufficient to fully induce the derived polysaccharide.
    [161" claim-type="Currently amended] 161. The method of claim 160, wherein the non-induced or only partially derived polysaccharide is not microfibrillated or only partially microfibrillated, and the emulsion formation microfibers the non-induced polysaccharide. Further proceeding under conditions sufficient to be brylated or sufficient to fully microfibrillate said only partially derived polysaccharide.
    [162" claim-type="Currently amended] 155. The method of claim 155, wherein said system is water-in-oil or oil-in-water emulsion.
    [163" claim-type="Currently amended] A system produced by the method of claim 154.
    [164" claim-type="Currently amended] And substituents that provide electrostatic and / or steric functionality, the electrostatic functionality comprising emulsions, dispersions or foams containing derived microfibrillated polysaccharides induced to be provided by anionic charges. The system characterized by the above.
    [165" claim-type="Currently amended] And a substituent that provides electrostatic and / or steric functionality, wherein the electrostatic functionality comprises an induced microfibrillated polysaccharide, characterized in that it comprises an anionic charge.
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    同族专利:
    公开号 | 公开日
    JP2013064134A|2013-04-11|
    AU3359000A|2000-08-29|
    BR0005116A|2001-01-02|
    EP1078008B1|2012-10-17|
    DK1078008T3|2013-01-21|
    ID28502A|2001-05-31|
    TR200002813T1|2002-06-21|
    NO20005085L|2000-12-07|
    JP2002536507A|2002-10-29|
    ES2396596T3|2013-02-22|
    NZ507250A|2003-08-29|
    US6602994B1|2003-08-05|
    PL344839A1|2001-11-19|
    CA2327482A1|2000-08-17|
    JP5238112B2|2013-07-17|
    EP1078008A2|2001-02-28|
    CN100381469C|2008-04-16|
    NO20005085D0|2000-10-09|
    CN1335856A|2002-02-13|
    WO2000047628A2|2000-08-17|
    CA2327482C|2011-11-22|
    WO2000047628A3|2000-12-07|
    AR025822A1|2002-12-18|
    IL138751D0|2001-10-31|
    HU0102765A2|2001-12-28|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1999-02-10|Priority to US9/248,246
    1999-02-10|Priority to US09/248,246
    2000-02-08|Application filed by 조이스 엘. 모리슨, 허큘레스 인코포레이티드
    2001-05-25|Publication of KR20010042551A
    2013-07-15|First worldwide family litigation filed
    优先权:
    申请号 | 申请日 | 专利标题
    US9/248,246|1999-02-10|
    US09/248,246|US6602994B1|1999-02-10|1999-02-10|Derivatized microfibrillar polysaccharide|
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