Classifications

• • A—HUMAN NECESSITIES
  • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
  • A23L—FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES, NOT OTHERWISE PROVIDED FOR; PREPARATION OR TREATMENT THEREOF
  • A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
  • A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
  • A23L29/206—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents of vegetable origin
  • A23L29/262—Cellulose; Derivatives thereof, e.g. ethers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
  • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
  • A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
  • A61K47/38—Cellulose; Derivatives thereof
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
  • A61K8/04—Dispersions; Emulsions
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/73—Polysaccharides
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K9/00—Medicinal preparations characterised by special physical form
  • A61K9/10—Dispersions; Emulsions
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
  • C08L1/02—Cellulose; Modified cellulose
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere

Definitions

• the present disclosure relates to a viscous composition and the like, and more particularly to a viscous composition containing cellulose nanocrystals.
• the contents of all documents described in this specification are incorporated herein by reference.
• Nano-sized cellulose is called nanocellulose.
• Examples of nanocellulose include cellulose nanocrystals (CNC), cellulose nanofibers (CNF), and bacterial nanocellulose produced by bacteria.
• Nanocellulose is being studied for application to various materials due to its excellent properties.
• the present inventors have conducted studies for the purpose of preparing a viscous composition containing nanocellulose, particularly cellulose nanocrystals, and having excellent viscosity.
• a viscous composition containing a specific hydroxyethyl cellulose (HEC) together with cellulose nanocrystals may have excellent viscosity and viscoelasticity, and further studies have been conducted.
• HEC hydroxyethyl cellulose
• Item 1 Contains cellulose nanocrystals, hydroxyethyl cellulose, and water, The hydroxyethyl cellulose is hydroxyethyl cellulose crosslinked with a cross-linking agent.
• the magnitude relationship between the storage elastic modulus G'and the loss elastic modulus G'' obtained by the frequency dispersion measurement is the storage elastic modulus G'> the loss elastic modulus G'> in the entire frequency range of 0.1 rad / s to 100 rad / s.
• the viscosity at 25 ° C. is 9000 mPa ⁇ s or more (preferably 9000 to 20000 mPa ⁇ s). Viscous composition.
• the viscosity of the 1.33 mass% aqueous solution at 25 ° C. is 4000 mPa ⁇ s or more (preferably 4000 to 18000 mPa ⁇ s).
• Item 2. The viscous composition according to Item 1.
• Item 3. The viscous composition according to Item 1 or 2, wherein the cross-linking agent is a dialdehyde compound.
• Item 4. Item 6. The viscous composition according to any one of Items 1 to 3, wherein the cellulose nanocrystal is a nano-sized cellulose sulfate crystal.
• a viscous composition containing hydroxyethyl cellulose (HEC) together with cellulose nanocrystals and having excellent viscosity and viscoelasticity.
• HEC hydroxyethyl cellulose
• the present disclosure preferably includes, but is not limited to, a viscous composition, a method for producing the same, and the like, and the present disclosure includes all disclosed in the present specification and recognized by those skilled in the art.
• the viscous composition included in the present disclosure contains cellulose nanocrystals, hydroxyethyl cellulose, and water.
• the viscous composition included in the present disclosure may be referred to as "the composition of the present disclosure”.
• Cellulose nanocrystal is a kind of nanocellulose.
• examples of nanocellulose made from wood or the like include cellulose nanofibers (CNF) and cellulose nanocrystals (CNC).
• CNF cellulose nanofibers
• CNC cellulose nanocrystals
• nanocellulose having a length of about 5 to 10 ⁇ m or more is often referred to as cellulose nanofiber (CNF)
• CNC cellulose nanocrystal
• the nanocrystalline cellulose described in Patent Document 1 Japanese Patent Laid-Open No. 2012-531478 can be preferably used.
• Cellulose is a natural polymer material that constitutes woody biomass and agricultural biomass together with hemicellulose and lignin. It is a homopolymer of repeating units of glucose linked by ⁇ -1,4-glycosidic bonds. Cellulose is formed linearly by ⁇ -1,4-glycosidic bonds, and they interact strongly with each other through hydrogen bonds. Due to its regular structure and strong hydrogen bonds, the cellulose polymer is highly crystalline and aggregates to form partial structures and microfibrils. Then, the microfibrils aggregate to form cellulosic fibers.
• Nanocellulose is a rod-shaped fibril with a length / diameter ratio of approximately 20-200.
• nanocellulose can be prepared, for example, from chemical pulp of wood fiber or agricultural fiber by removing the amorphous region mainly by acid hydrolysis to produce nano-sized fibril.
• Cellulose nanocrystals can be formed and stabilized in an aqueous suspension by, for example, sonicating the fibrils or passing them through a high shear microfluidizer.
• the second method is mainly physical processing. Bundles of microfibrils, usually tens of nanometers (nm) to several micrometer ( ⁇ m) in diameter, called cellulose microfibrils or microfibrillated cellulose, are produced by using high pressure homogenization and grinding. .. Steps with high intensity sonication have also been used to isolate fibril from natural cellulose fibers. High-intensity ultrasound can generate very strong mechanical vibration forces, which allows the separation of cellulose fibrils from biomass. This method produces microfibrillated cellulose having a diameter of less than about 60 nm, more preferably about 4 nm to about 15 nm, and a length of less than 1000 nm. Microfibrillated cellulose can also be subjected to, for example, further chemical, enzymatic and / or mechanical treatments. The microfibrillated cellulose can also be used as a cellulose nanocrystal.
• the cellulose nanocrystals used in the compositions of the present disclosure are, for example, by removing amorphous regions from pulp by acid hydrolysis, or by physical treatment such as high pressure treatment, pulverization treatment, and ultrasonic treatment. It can be appropriately prepared by treatment (and even by using these in combination).
• the cellulose portion of the cellulose nanocrystal used in the composition of the present disclosure may be a cellulose sulfate (cellulose sulfate).
• a sodium salt is preferable. That is, the cellulose portion of the cellulose nanocrystal used in the composition of the present disclosure may be cellulose sulfate sodium sulfate.
• cellulose nanocrystal indicates a crystal of nano-sized cellulose
• the cellulose may be an unmodified form or a modified form.
• the cellulose modified product for example, cellulose sulfate (particularly sodium cellulose sulfate) is preferably mentioned.
• examples of the CNC include nanocellulose having a thickness of about 1 to 100 nm and a length of about 50 to 500 nm.
• the upper or lower limit of the thickness range (1 to 100 nm) is, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, and so on.
• the thickness range may be 2 to 99 nm.
• the upper limit or the lower limit of the length range (50 to 500 nm) is, for example, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, or 490 nm May be.
• the length range may be 60 to 490 nm.
• the ratio (length / thickness) of the length (nm) to the thickness (nm) can be, for example, about 1 to 200.
• the upper or lower limit of the range of the ratio is, for example, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21. , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46. , 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71.
• the hydroxyethyl cellulose (HEC) used in the composition of the present disclosure is hydroxyethyl cellulose crosslinked with a cross-linking agent (in the present specification, it may be referred to as cross-linked HEC).
• cross-linking agent examples include polyvalent aldehyde compounds (preferably dialdehyde compounds) such as glutaraldehyde and glioxal, 2,2-bishydroxymethylbutanol-tris [3- (1-aziridinyl) propionate], 1,8-.
• polyvalent aziridin compounds such as hexamethylene diethylene urea
• polyvalent isocyanate compounds such as tolylene diisocyanate and hexamethylene diisocyanate. Of these, dialdehyde compounds are preferred, and glyoxal is particularly preferred.
• the cross-linking agent may be used alone or in combination of two or more.
• Cross-linking of hydroxyethyl cellulose with a cross-linking agent can be carried out by a known method or a method that can be easily conceived from a known method. For example, it can be carried out by the method described in Japanese Patent Publication No. 58-43402.
• the crosslinked HEC preferably has a viscosity of a 1.33% by mass (w / w%) aqueous solution at 25 ° C. of 4000 mPa ⁇ s or more, and more preferably 4000 to 18000 mPa ⁇ s.
• the upper or lower limit of the viscosity range is, for example, 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, 5100, 5200, 5300, 5400, 5500, 5600, 5700, 5800, 5900, 6000.
• the viscosity range may be 4100 to 17900 mPa ⁇ s.
• the crosslinked HEC is not particularly limited, but preferably has a molecular weight of, for example, about 1800000 to 4300000.
• the upper or lower limit of the molecular weight range is, for example, 19000000, 2000000, 210000, 2200, 230000, 2400000, 25, 260000, 2700, 280000, 2900, 3000, 3100, 3200, 3300, 3400, 3500, 3600, 3700, 380000, It may be 3900000, 4000, 410000, or 4200000.
• the molecular weight range may be 1900000 to 4200000.
• the molecular weight is a mass average molecular weight obtained by gel permeation chromatography (GPC) and converted into polyethylene oxide.
• GPC gel permeation chromatography
• Examples of the column for measuring the mass average molecular weight in terms of polyethylene glycol by GPC include Shodex OHpak SB-807HQ, Shodex OHpak SB-806HQ, Shodex OHpak SB-804HQ and the like. Detailed GPC measurement conditions are shown below.
• HEC is a compound in which the OH group of cellulose is OR (R indicates H or CH 2 CH 2 OH), and is contained in the composition of the present disclosure.
• a group other than H or CH 2 CH 2 OH may be present as R of the OR, but it is preferable that no hydrophobic group is present as R.
• R an alkyl group, particularly a linear chain having 6 to 20 carbon atoms (6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20) or Those having a branched chain alkyl group (more specifically, for example, a cetyl group) may be used, but it is preferable not to use them.
• the composition of the present disclosure contains water as a solvent. Further, a solvent other than water may be further contained as long as the effect of the composition of the present disclosure is not impaired.
• the solvent other than water include water-soluble solvents, and for example, water-soluble organic solvents are preferable.
• the water-soluble organic solvent include monohydric or divalent alkyl alcohols having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6), and more specifically, for example. Examples thereof include ethanol and butylene glycol.
• the composition of the present disclosure has a storage elastic modulus (G') larger than a loss elastic modulus (G'') value (that is, storage elastic modulus G'> loss elastic modulus G''). preferable.
• the composition of the present disclosure preferably has a loss tangent (tan ⁇ ) of less than 1 (that is, tan ⁇ ⁇ 1).
• the loss tangent (tan ⁇ ) is the ratio (G ′′ / G ′) of the storage elastic modulus (G ′) and the loss elastic modulus (G ′′), and is used as one of the indexes of the viscoelastic property.
• the larger the value of the loss tangent the smaller the elastic modulus.
• the loss tangent is used as an index of sol and gel, and usually tan ⁇ > 1 is sol and tan ⁇ ⁇ 1 is gel.
• the values of the storage elastic modulus G ′ and the loss elastic modulus G ′′ can be measured at 25 ° C. using a viscoelasticity measuring device (leometer). More specifically, after confirming the linear region by measuring the strain dispersion at 1 Hz, an appropriate distortion is selected within the range of the linear region, and the frequency dispersion at 25 ° C. (frequency: 0.1 rad / s to 100 rad / s). And observe the magnitude relationship between G'and G''.
• the storage elastic modulus G'and the loss elastic modulus G'' obtained by frequency dispersion measurement have a magnitude relationship of the storage elastic modulus G in the entire range of frequency: 0.1 rad / s to 100 rad / s. It is preferable that'> loss elastic modulus G''.
• composition of the present disclosure has a viscosity at 25 ° C. of 9000 mPa ⁇ s or more, preferably 9000 to 20000 mPa ⁇ s.
• the upper or lower limit of the viscosity range is, for example, 9100, 9200, 9300, 9400, 9500, 9600, 9700, 9800, 9900, 10000, 10100, 10200, 10300, 10400, 10500, 10600, 10700, 10800, 10900, 11000.
• the viscosity is a value measured at 25 ° C. using a rotary viscometer manufactured by BrookField (model number: DVE, spindle: LV) at a rotation speed of 20 rpm.
• the spindle used for measurement is spindle LV-1 when it is less than 200 mPa ⁇ s, spindle LV-2 when it is 200 mPa ⁇ s or more and less than 1000 mPa ⁇ s, and 1000 mPa ⁇ s or more and less than 4000 mPa ⁇ s.
• the content ratio of CNC and crosslinked HEC in the composition of the present disclosure is not particularly limited as long as the effect is not impaired, but for example, about 0.05 to 1 part by mass of CNC with respect to 1 part by mass of crosslinked HEC. Is preferable.
• the upper or lower limit of the range is, for example, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, It may be 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, or 0.95.
• the range may be 0.1 to 0.8.
• the CNC content in the composition of the present disclosure is not particularly limited as long as the effect is not impaired, and examples thereof include about 0.1 to 5% by mass.
• the upper or lower limit of the range is, for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2.
• composition of the present disclosure may contain components other than CNC, crosslinked HEC, and water as long as the effect is not impaired.
• examples of such an ingredient include simple substances and ingredients known in the fields of pharmaceuticals, cosmetics, and foods.
• the method for preparing the composition of the present disclosure is not particularly limited.
• it can be prepared by mixing CNC and crosslinked HEC, or by dissolving them in water in order.
• it is dissolved in water, it is preferable to mix it (for example, stirring and mixing).
• composition of the present disclosure has excellent viscosity and viscoelasticity, it is useful in technical fields in which products required to have such properties exist, for example, in the fields of pharmaceuticals, cosmetics, and foods. That is, the composition of the present disclosure can be preferably used, for example, as a pharmaceutical composition, a cosmetic composition, a food composition, or the like.
• Measurement conditions Leometer: TA Instrument AR-2000ex Plate: 60 mm, 1 ° cone plate Measurement temperature: 25 ° C Distortion: 0.1 to 10% (selected within the range of the linear region obtained in the distortion dispersion measurement at 1 Hz) Frequency: 0.1 rad / s to 100 rad / s [Viscosity measurement] The viscosity of each viscous composition was measured at 25 ° C. using a rotary viscometer (model number: DVE, spindle: LV) manufactured by BrookField at a rotation speed of 20 rpm.
• the spindle used for measurement is spindle LV-1 when it is less than 200 mPa ⁇ s, spindle LV-2 when it is 200 mPa ⁇ s or more and less than 1000 mPa ⁇ s, and 1000 mPa ⁇ s or more and less than 4000 mPa ⁇ s.
• Cellulose Nanocrystals manufactured by Alberta-Pacific Forest Industries Inc.
• CEOLUS manufactured by Asahi Kasei
• a part of Cellulose Nanocrystals is sodium cellulose sulfate.
• water-soluble polymers All powders were purchased and used.
• the water-soluble polymers 1, 2, 3, 4, 5, 6 and 7 were obtained from Sumitomo Seika Chemical Co., Ltd., and the water-soluble polymers 8 and 9 were obtained from DSP Gokyo Food & Chemicals (see Table 1).
• the water-soluble polymers 1 to 6 are crosslinked HECs crosslinked by glyoxal, and the water-soluble polymers 7 are uncrosslinked HECs.
• a cellulose powder and a water-soluble polymer powder were mixed, and the mixed powder was stirred and mixed with ion-exchanged water to dissolve the mixture to prepare a viscous composition. Then, the viscoelasticity and viscosity of the viscous composition were measured. The results are also shown in Table 1.

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• 2021
  • 2021-09-30 JP JP2022554078A patent/JPWO2022071461A1/ja active Pending
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