WO2023013536A1 - Composition émulsifiée visqueuse - Google Patents

Composition émulsifiée visqueuse Download PDF

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Publication number
WO2023013536A1
WO2023013536A1 PCT/JP2022/029243 JP2022029243W WO2023013536A1 WO 2023013536 A1 WO2023013536 A1 WO 2023013536A1 JP 2022029243 W JP2022029243 W JP 2022029243W WO 2023013536 A1 WO2023013536 A1 WO 2023013536A1
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Prior art keywords
water
cellulose
composition
ascorbic acid
oil
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PCT/JP2022/029243
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English (en)
Japanese (ja)
Inventor
香澄 茂川
真智子 中川
博史 山口
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住友精化株式会社
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Priority to JP2023540311A priority Critical patent/JPWO2023013536A1/ja
Publication of WO2023013536A1 publication Critical patent/WO2023013536A1/fr

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/67Vitamins
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73Polysaccharides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/92Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/02Cellulose; Modified cellulose
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L1/00Compositions of cellulose, modified cellulose or cellulose derivatives
    • C08L1/08Cellulose derivatives
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00Compositions of unspecified macromolecular compounds
    • C08L101/12Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C08L101/14Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity the macromolecular compounds being water soluble or water swellable, e.g. aqueous gels

Definitions

  • the present disclosure relates to viscous compositions and the like, and more particularly to viscous compositions containing water-soluble cellulose derivatives. It should be noted that the contents of all documents mentioned herein are hereby incorporated by reference.
  • Polymer thickeners are widely used to prepare viscous compositions in various fields, such as cosmetics and food fields.
  • the resulting viscous composition is often extremely sticky and difficult to use.
  • the tackiness may be even more severe.
  • ascorbic acid and its derivatives are ingredients that are preferably contained in cosmetics, but it has been difficult to prepare a stable viscous composition that suppresses stickiness by using it together with a polymer thickener.
  • a viscous composition is prepared using a polymer thickener while ingredients that are preferably contained in cosmetics are blended, and this is used as a composition for external use (especially a cosmetic composition). When it was wet, the stickiness was severe and the feeling of use was impaired.
  • the present inventors conducted studies with the aim of preparing a highly stable viscous composition that contains a polymer thickener and ascorbic acid or a derivative thereof while suppressing stickiness.
  • the present inventors used a water-soluble cellulose derivative as a polymer thickener, combined it with cellulose, and added an oily component to form an emulsified composition containing ascorbic acid or a derivative thereof.
  • the inventors have found the possibility of preparing a stable viscous composition in which the stickiness is suppressed even when the composition is being used, and have conducted further studies.
  • Section 1 A viscous emulsion composition comprising a water-soluble cellulose derivative, a water-insoluble cellulose, ascorbic acid or a derivative thereof, an oily component, and water.
  • Section 2. A composition according to Item 1, wherein the water-soluble cellulose derivative is hydroxyalkylcellulose (preferably HEC).
  • Item 3. Item 3.
  • At least one derivative of ascorbic acid selected from the group consisting of ascorbate, ascorbic acid glycoside, ascorbic acid phosphate, fatty acid ascorbyl, ascorbyl ethyl, ascorbic acid-phosphoric acid-fatty acid, and glyceryloctylascorbic acid
  • Item 4 The composition according to any one of Items 1 to 3, which is a seed.
  • Item 5. The composition according to any one of Items 1 to 4, wherein the oily component is at least one selected from the group consisting of fats, ester oils, and hydrocarbon oils.
  • Item 7. The composition according to any one of Item 6, wherein the oily component is at least one selected from the group consisting of acylglycerols having a structure in which at least capric acid is ester-bonded to glycerin, squalene, and squalane.
  • composition according to any one of 4. Item 9.
  • Item 9. The composition according to any one of Items 1 to 8, which is an O/W emulsion composition.
  • the water-soluble cellulose derivative is hydroxyethyl cellulose
  • the water-insoluble cellulose is a cellulose nanocrystal
  • At least one derivative of ascorbic acid selected from the group consisting of ascorbate, ascorbic acid glycoside, ascorbic acid phosphate, fatty acid ascorbyl, ascorbyl ethyl, ascorbic acid-phosphoric acid-fatty acid, and glyceryloctylascorbic acid is a seed
  • the oily component is at least one selected from the group consisting of acylglycerols and terpenes or saturated compounds thereof
  • Viscosity at 25 ° C. is 4000 to 20000 mPa s, It is an O / W type emulsion composition, Item 1.
  • a viscous composition that contains a polymer thickener (specifically, a water-soluble cellulose derivative) and ascorbic acid or a derivative thereof, while suppressing stickiness and having excellent stability.
  • the viscous composition preferably further contains a water-soluble salt (for example, a pH adjuster) and is stable with less viscosity decrease.
  • the present disclosure preferably includes, but is not limited to, viscous compositions, methods of making the same, and the like, and includes everything disclosed herein and recognized by a person skilled in the art.
  • a viscous composition included in the present disclosure is an emulsified composition containing a water-soluble cellulose derivative, cellulose, ascorbic acid or a derivative thereof, an oily component, and water.
  • the viscous emulsion composition encompassed by the present disclosure is sometimes referred to as the "composition of the present disclosure.”
  • Water-soluble in the present invention means exhibiting a solubility of 0.1% by mass or more in water at 25°C.
  • the term "exhibiting solubility” refers to, for example, a state in which a transparent solution can be visually confirmed after a water-soluble cellulose derivative is added to water and sufficiently stirred, or a state in which precipitation does not occur.
  • a cellulose derivative having a hydroxy group is preferable, and a hydroxyalkyl cellulose is more preferable.
  • the alkyl group of hydroxyalkylcellulose is preferably an alkyl group having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6), more preferably a methyl group, an ethyl group, or a propyl group.
  • Hydroxyalkyl cellulose may have different alkyl groups. More specifically, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose and the like are preferred. Among them, hydroxyethyl cellulose (HEC) is particularly preferred.
  • hydroxyethyl cellulose used in the composition of the present disclosure
  • both hydroxyethyl cellulose not cross-linked with a cross-linking agent (uncross-linked HEC) and hydroxyethyl cellulose cross-linked with a cross-linking agent (cross-linked HEC) can be used in the composition of the present disclosure.
  • Crosslinking agents include polyaldehyde compounds (preferably dialdehyde compounds) such as glutaraldehyde and glyoxal, 2,2-bishydroxymethylbutanol-tris[3-(1-aziridinyl)propionate], 1,8-hexamethylene.
  • polyvalent aziridine compounds such as diethylene urea
  • polyvalent isocyanate compounds such as tolylene diisocyanate and hexamethylene diisocyanate.
  • dialdehyde compounds are preferred, and glyoxal is particularly preferred.
  • a crosslinking agent can be used individually by 1 type or in combination of 2 or more types.
  • the crosslinked HEC preferably has a crosslinker content of 0.05% by mass or more, more preferably about 0.05 to 2% by mass.
  • the upper limit or lower limit of the content ratio range of the cross-linking agent is 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0. 14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, 0.36, 0.37, 0.38, 0.
  • the content ratio range of the cross-linking agent is more preferably 0.1 to 1% by mass. In particular, 0.35% by mass or more is preferable, and 0.35 to 1% by mass is particularly preferable.
  • 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 known methods.
  • the method described in JP-B-58-43402 can be used.
  • HEC (including non-crosslinked HEC and crosslinked HEC) preferably has a viscosity of 4000 mPa s or more at 25°C in a 1.33% by mass (w/w%) aqueous solution, more preferably 4000 to 18000 mPa s. preferable.
  • the upper or lower limit of the viscosity range is 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, 5100, 5200, 5300, 5400, 5500, 5600, 5700, 5800, 5900, 6000, 6100 , 6200, 6300, 6400, 6500, 6600, 6700, 6800, 6900, 7000, 7100, 7200, 7300, 7400, 7500, 7600, 7700, 7800, 7900, 8000, 8100, 8200, 8300, 8400, 8500, 8600 , 8700, 8800, 8900, 9000, 9100, 9200, 9300, 9400, 9500, 9600, 9700, 9800, 9900, 10000, 10100, 10200, 10300, 10400, 10500, 10600, 10700, 10800, 110000, 110000 ⁇ 11200 ⁇ 11300 ⁇ 11400 ⁇ 11500 ⁇ 11600 ⁇ 11700 ⁇ 11800 ⁇ 11900 ⁇ 12000 ⁇ 12
  • HEC (including non-crosslinked HEC and crosslinked HEC) preferably has a molecular weight of about 1,800,000 to 4,300,000. ⁇ 1900000 ⁇ 2000000 ⁇ 2100000 ⁇ 2200000 ⁇ 2300000 ⁇ 2400000 ⁇ 2500000 ⁇ 2600000 ⁇ 2700000 ⁇ 2800000 ⁇ 2900000 ⁇ 3000000 ⁇ 3100000 ⁇ 3200000 ⁇ 3300000 ⁇ 3400000 ⁇ 3500000 ⁇ 3600000 ⁇ 3700000 ⁇ 3800000 ⁇ 3900000 , 4000000, 4100000 or 4200000 are preferred. More preferably, the molecular weight range is from 1,900,000 to 4,200,000.
  • the said molecular weight is a weight average molecular weight calculated
  • GPC gel permeation chromatography
  • a column for measuring the weight average molecular weight by polyethylene glycol conversion by GPC Shodex OHpak SB-807HQ, Shodex OHpak SB-806HQ, Shodex OHpak SB-804HQ and the like are preferable.
  • GPC gel permeation chromatography
  • HEC is a compound in which the OH group of cellulose is OR (R represents H or CH 2 CH 2 OH).
  • R is an alkyl group, especially a linear or branched chain having 6 to 20 carbon atoms (6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20) Those having an alkyl group (more specifically, for example, a cetyl group) may be used, but are preferably not used.
  • Cellulose is a water-insoluble substance, and the cellulose used in the composition of the present disclosure is also water-insoluble cellulose.
  • water-insoluble refers to something that is not “water-soluble”.
  • cellulose crystalline cellulose and nanocellulose are preferable, and nanocellulose is more preferable.
  • nanocelluloses cellulose nanocrystals (CNC) are preferred.
  • cellulose nanocrystals are a type of nanocellulose.
  • cellulose nanofibers (CNF) and cellulose nanocrystals (CNC) are examples of nanocellulose made from wood or the like.
  • CNF cellulose nanofibers
  • CNC cellulose nanocrystals
  • nanocellulose with a length of approximately 5-10 ⁇ m or more is often referred to as cellulose nanofibers (CNF)
  • CNC cellulose nanocrystals
  • the nanocrystalline cellulose described in Patent Document 1 Japanese Patent Publication No. 2012-531478 can be preferably used.
  • Cellulose is a natural polymeric material that together with hemicellulose and lignin constitute woody and agricultural biomass. It is a homopolymer of repeating units of glucose linked by ⁇ -1,4-glycosidic bonds. Cellulose is formed into linear chains by ⁇ -1,4-glycosidic bonds, which interact strongly with each other through hydrogen bonds. Due to their regular structure and strong hydrogen bonding, cellulose polymers are highly crystalline and aggregate to form substructures and microfibrils. The microfibrils then aggregate to form cellulosic fibers.
  • Purified cellulose from woody or agricultural biomass can be degraded or produced on a large scale by bacterial processes.
  • cellulosic materials are composed of nano-sized fibers and the properties of the material are determined by the structure of the nanofibers, these polymers are said to be nanocellulose.
  • nanocellulose is rod-shaped fibrils with a length/diameter ratio of approximately 20-200.
  • nanocellulose can be prepared from chemical pulps, for example wood fibers or agricultural fibers, by removing the amorphous regions, mainly by acid hydrolysis, to produce nano-sized fibrils.
  • Cellulose nanocrystals can be generated and stabilized in aqueous suspension by, for example, sonicating the fibrils or passing them through a high shear microfluidizer.
  • the second method is mainly physical processing.
  • Microfibril bundles usually called cellulose microfibrils or microfibrillated cellulose, with a diameter of several tens of nanometers (nm) to several micrometers ( ⁇ m) are produced by using high-pressure homogenization and pulverization processes. .
  • a process using high intensity sonication has also been used to isolate fibrils from native cellulose fibers.
  • High-intensity ultrasound can produce very strong mechanical vibratory forces, thus enabling the separation of cellulose fibrils from biomass.
  • This method produces microfibrillated cellulose having a diameter of less than about 60 nm, more preferably from about 4 nm to about 15 nm, and a length of less than 1000 nm.
  • the microfibrillated cellulose can, for example, also be subjected to further chemical, enzymatic and/or mechanical treatments.
  • the microfibrillated cellulose can also be used as cellulose nanocrystals.
  • the cellulose nanocrystals can be obtained, for example, from pulp by removing non-crystalline regions by acid hydrolysis, or by high pressure treatment, pulverization treatment. , by physical treatment such as ultrasonic treatment (or by using them in combination).
  • the cellulose portion of the cellulose nanocrystals used in the composition of the present disclosure may be cellulose sulfate (cellulose sulfate).
  • a sodium salt is preferred as the salt. That is, the cellulose portion of the cellulose nanocrystals used in the composition of the present disclosure is preferably sodium cellulose sulfate.
  • cellulose nanocrystals or “CNC” refers to nano-sized cellulose crystals.
  • the cellulose is preferably unmodified or modified.
  • Preferred examples of modified cellulose include cellulose sulfate (especially sodium cellulose sulfate), as described above.
  • nanocellulose with a thickness of about 1 to 100 nm and a length of about 50 to 500 nm is preferable.
  • the upper or lower limit of the thickness range (1 to 100 nm) is 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, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98 or 99 nm are preferred.
  • the thickness range is more preferably 2 to 99 nm.
  • the upper or lower limit of the length range (50 to 500 nm) is 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 are preferred. More preferably, the length range is from 60 to 490 nm.
  • the CNC can have a ratio of length (nm) to thickness (nm) (length/thickness) of about 1 to 200.
  • the upper or lower limits of the range of said ratios are 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, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110
  • ascorbic acid includes ascorbate, ascorbic acid glycoside, ascorbic acid phosphate, fatty acid ascorbyl (ester of fatty acid and ascorbic acid), ethyl ascorbyl, ascorbic acid-phosphoric acid-fatty acid, glyceryl octylascorbic acid etc. are preferred.
  • Preferred ascorbates are sodium ascorbate, calcium ascorbate, and the like.
  • As the ascorbic acid glycoside, ascorbic acid glucoside and the like are preferable, and more specifically, ascorbic acid 2-glucoside, ascorbic acid 6-glucoside and the like are preferable.
  • Ascorbic acid phosphate sodium ascorbyl phosphate and magnesium ascorbyl phosphate are preferable.
  • fatty acid ascorbyl ascorbyl palmitate, ascorbyl stearate, ascorbyl isopalmitate and the like are preferable.
  • Ascorbic acid-phosphoric acid-fatty acid is preferably ascorbic acid-2-phosphate-6-palmitic acid.
  • Ascorbic acid or its derivative can be used individually by 1 type or in combination of 2 or more types. Ascorbic acid or derivatives thereof are preferably ascorbic acid, ascorbic acid glycosides, and ascorbic acid phosphates.
  • the composition of the present disclosure contains an oily component.
  • Fats, ester oils, hydrocarbon oils and the like can be mentioned as the oily component.
  • oils and fats acylglycerol (ester of fatty acid and glycerin) is preferable.
  • ester oils monoesters, diesters, polyol esters, phosphate esters, and the like are preferable.
  • hydrocarbon oils terpenes or saturated products thereof are preferable.
  • an oily component can be used individually by 1 type or in combination of 2 or more types.
  • acylglycerol mono-, di-, or triacylglycerol is preferable, and triacylglycerol is more preferable.
  • Acylglycerol is an ester of glycerin and fatty acid. , or 20) are preferred. The number of carbon atoms is more preferably 8-18, more preferably 8-14. Moreover, it is preferable that it is a linear fatty acid.
  • the fatty acids ester-bonded to glycerin are preferably the same or different. Moreover, it is preferable to ester-bond the OH groups at the 1- and 2-positions of glycerin, or to ester-bond the OH groups at the 1- and 3-positions of glycerin.
  • the fatty acids ester-bonded to glycerin may be the same or different, and preferably all three fatty acids are different, or two out of the three are the same.
  • acylglycerol having a structure in which at least capric acid is ester-bonded to glycerin is preferable.
  • acylglycerols include glyceryl caprate, glyceryl laurate, glyceryl myristate, glyceryl palmitate, glyceryl stearate, glyceryl isostearate, glyceryl oleate, and the like.
  • Triacylglycerols include tri(caprylic/capric) glyceryl, tricaprate glyceryl, tri-2-ethylhexanoate glyceryl, tri(caprylic/capric/myristic/stearic) glyceryl, tri(caprylic) /capric acid/lauric acid) glyceryl, triisopalmitic acid glyceride, triisostearic acid glyceryl and the like are preferable.
  • Vegetable oils containing acylglycerols can also be used, and such vegetable oils are preferably olive fruit oil, castor oil, palm oil, camellia oil, sunflower oil, corn oil, macadamia nut oil, soybean oil, avocado oil, and the like. .
  • Acylglycerol can be used singly or in combination of two or more.
  • a terpene is a compound composed of two or more isoprene units (C5). It is classified into terterpene (C25), triterpene (C30), tetraterpene (C40) and the like. Also, by hydrogenating a terpene, a terpene saturated compound can be obtained. Among them, triterpenes or saturated compounds thereof are preferred, and more specifically, squalene and squalane are more preferred.
  • the terpene or its saturated compound can be used singly or in combination of two or more.
  • composition of the present disclosure contains water as a solvent.
  • a solvent other than water may be further contained within a range that does not impair the effects of the composition of the present disclosure.
  • Solvents other than water include, for example, water-soluble solvents, and water-soluble organic solvents are preferred.
  • Specific examples of water-soluble organic solvents include monohydric alkyl alcohols having 1 to 6 carbon atoms (1, 2, 3, 4, 5, or 6), and more specific examples include ethanol. be done.
  • composition of the present disclosure preferably has a viscosity of 4000 to 20000 mPa ⁇ s at 25°C.
  • the upper or lower limit of the viscosity range is 4100, 4200, 4300, 4400, 4500, 4600, 4700, 4800, 4900, 5000, 5100, 5200, 5300, 5400, 5500, 5600, 5700, 5800, 5900, 6000, 6100 , 6200, 6300, 6400, 6500, 6600, 6700, 6800, 6900, 7000, 7100, 7200, 7300, 7400, 7500, 7600, 7700, 7800, 7900, 8000, 8100, 8200, 8300, 8400, 8500, 8600 , 8700, 8800, 8900, 9000, 9100, 9200, 9300, 9400, 9500, 9600, 9700, 9800, 9900, 10000, 10100, 10200, 10300, 10400, 10500, 10600, 10700, 10800, 11
  • the viscosity is a value measured at 25°C using a rotational viscometer manufactured by BrookField (model number: DV1MRVTJ0) with a rotational speed of 20 revolutions per minute.
  • the spindle used for measurement should be rotor No. when the pressure is less than 2,000 mPa ⁇ s. 3.
  • Rotor No. in the case of 2,000 mPa ⁇ s or more and less than 5,000 mPa ⁇ s. 4, 5,000 mPa ⁇ s or more and less than 15,000 mPa ⁇ s, rotor No. 5, 15,000 mPa ⁇ s or more and less than 40,000 mPa ⁇ s, rotor No. Rotor No. 6, 40,000 mPa ⁇ s or more. 7.
  • the content ratio of the water-soluble cellulose derivative and the water-insoluble cellulose in the composition of the present disclosure is preferably about 0.05 to 1 part by mass of the water-insoluble cellulose relative to 1 part by mass of the water-soluble cellulose derivative.
  • the upper or lower limit of the range is 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.55, 0.25, 0.35, 0.4, 0.45, 0.5, 0.55. 6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9 or 0.95 are preferred. More preferably, the range is 0.1 to 0.8.
  • the water-insoluble cellulose content in the composition of the present disclosure is preferably about 0.05 to 5% by mass.
  • the upper or lower limit of the range is 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8 or 4.9% by weight are preferred. More preferably, the range is 0.1 to 2% by mass.
  • the content of the water-soluble cellulose derivative in the composition of the present disclosure is preferably about 0.1 to 5% by mass.
  • the upper or lower limit of the range is 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8 or 4.9% by weight are preferred. More preferably, the range is 0.2 to 2% by mass.
  • the content of the oil component in the composition of the present disclosure is preferably about 1 to 20% by mass.
  • the upper or lower limit of the range is preferably 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, or 19% by mass.
  • the range is more preferably about 2 to 10% by mass.
  • the composition of the present disclosure has high viscosity stability. More specifically, for example, even if the composition of the present disclosure is stored at 50 ° C. for 30 days immediately after production, the ratio of the viscosity after storage compared to the viscosity before storage (viscosity retention rate) is preferably It is about 80 to 120%.
  • the composition of the present disclosure has a storage modulus (G′) value greater than a loss modulus (G′′) value (i.e., storage modulus G′>loss modulus G′′). things are preferred.
  • the compositions of the present disclosure preferably have a loss tangent (tan ⁇ ) of less than 1 (ie, tan ⁇ 1).
  • the loss tangent (tan ⁇ ) is the ratio (G′′/G′) of the storage elastic modulus (G′) to the loss elastic modulus (G′′), and is used as one index of viscoelastic properties.
  • the larger the value of the loss tangent the smaller the rebound resilience.
  • 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 storage elastic modulus G' and loss elastic modulus G'' can be measured at 25°C using a viscoelasticity measuring device (rheometer). More specifically, by strain dispersion measurement at 1 Hz, after confirming the linear region, select an appropriate strain within the range of the linear region, frequency dispersion at 25 ° C. (frequency: 0.1 rad / s to 100 rad / s) is measured to observe the magnitude relationship between G' and G''.
  • the magnitude relationship between the storage elastic modulus G′ and the loss elastic modulus G′′ obtained by frequency dispersion measurement is in the entire frequency range of 0.1 rad/s to 100 rad/s. It is preferable that '>loss modulus G''.
  • the composition has such properties, it can be said that the composition is a preferable gel composition. preferable. In addition, an improvement in stability can also be expected.
  • composition of the present disclosure may contain ingredients other than the above-described ingredients as long as the effects are not impaired.
  • examples of such components include carriers and components known in the fields of pharmaceuticals, cosmetics, and foods.
  • surfactants known in the above fields can be used.
  • nonionic surfactants and anionic surfactants are preferred, and nonionic surfactants are more preferred.
  • polyoxyethylene sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene hydrogenated castor oil, glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan Fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkyl ethers, polyoxyalkylene derivatives, fatty acid alkanolamides and the like are preferred.
  • Surfactant can be used individually by 1 type or in combination of 2 or more types.
  • the polyoxyethylene in the polyoxyethylene sorbitan fatty acid ester is preferably condensed with about 10 to 100 molecules of ethylene oxide. Those having about 20, 40, 60, 80, or 100 condensations are preferred.
  • the content of the surfactant is preferably about 0.05-5% by mass.
  • the upper or lower limit of the range is preferably 0.1, 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, or 4.5% by mass. More preferably, the range is 0.1 to 2% by mass.
  • the composition of the present disclosure is a viscous emulsified composition (viscous emulsified composition), and is preferably an O/W type (oil-in-water type) emulsified composition.
  • viscous emulsified composition viscous emulsified composition
  • O/W type oil-in-water type
  • emulsified composition when the composition of the present disclosure contains a surfactant, since it contains an oil component, water and a surfactant, it is emulsified by stirring during preparation, and an O / W type (oil-in-water type) emulsion composition. can be obtained.
  • composition of the present disclosure may contain water-soluble salts such as pH adjusters.
  • water-soluble salts such as pH adjusters.
  • the thickening effect of a polymeric thickener generally tends to be reduced by salt. This point is also preferable.
  • a pH adjuster or a buffer is preferable, and more specifically, sodium hydroxide, potassium hydroxide, sodium citrate, potassium citrate and the like are preferable.
  • the composition of the present disclosure preferably has a pH of about 5 to 8.5, more preferably about 5.5 to 8 or 6 to 8.
  • the pH can be adjusted, for example, using a pH adjuster.
  • pH is the value measured with the pH meter at 25 degreeC.
  • composition of the present disclosure can be prepared, for example, by mixing water-soluble cellulose derivatives, water-insoluble cellulose, ascorbic acid or derivatives thereof, oily components, and water.
  • water-soluble cellulose derivatives water-insoluble cellulose, ascorbic acid or derivatives thereof
  • oily components oily components
  • water-soluble cellulose derivatives water-insoluble cellulose, ascorbic acid or derivatives thereof
  • oily components water-insoluble cellulose, and water.
  • Both the water-soluble cellulose derivative and the water-insoluble cellulose used for mixing before adding to water are preferably powder.
  • the mixture is preferably powder.
  • composition of the present disclosure has excellent viscosity and viscoelasticity, it is useful in technical fields where there are products that require such properties, such as pharmaceutical fields, cosmetics fields, and food fields. That is, the composition of the present disclosure can be preferably used as, for example, pharmaceutical compositions, cosmetic compositions, food compositions, and the like. Among others, it is suitable for application to the skin as a cosmetic composition or the like.
  • pH measurement The pH of the composition was measured using a pH meter at 25°C.
  • Viscosity measurement The viscosity of each viscous composition was measured at 25° C. using a rotational viscometer manufactured by BrookField (model number: DV1MRVTJ0) at a rotational speed of 20 revolutions per minute.
  • the spindle used for measurement should be rotor No. when the pressure is less than 2,000 mPa ⁇ s. 3.
  • Rotor No. in the case of 2,000 mPa ⁇ s or more and less than 5,000 mPa ⁇ s. 4, 5,000 mPa ⁇ s or more and less than 15,000 mPa ⁇ s, rotor No. 5, 15,000 mPa ⁇ s or more and less than 40,000 mPa ⁇ s, rotor No. Rotor No. 6, 40,000 mPa ⁇ s or more. 7.
  • Cellulose Nanocrystals manufactured by Alberta-Pacific Forest Industries Inc. was used as crystal nanocellulose.
  • a part of Cellulose Nanocrystals is sodium cellulose sulfate.
  • HEC HEC (CF-Y) (manufactured by Sumitomo Seika Co., Ltd.) was used. This is a crosslinked HEC crosslinked with a crosslinking agent (glyoxal), and the content of the crosslinking agent in HEC (CF-Y) is 0.55% by mass.
  • carboxyvinyl polymer may be referred to as Production Example 2 polymer.
  • a viscous composition was prepared by mixing water-insoluble cellulose (crystal nanocellulose: CNC) powder and water-soluble polymer powder according to the composition in Table 1, and then further mixing various components. More specifically, it was carried out as follows.
  • Example 1 (1) Method for preparing 2% aqueous solution of water-soluble polymer [Examples 1 to 3] 0.5 g of crystal nanocellulose powder and 1.5 g of water-soluble polymer (HEC) powder are mixed, and the mixed powder is dissolved in 98 g of ion-exchanged water with stirring to obtain a 2% water-soluble polymer composition. was prepared. More specifically, the mixture was stirred for 4 hours with a 4-paddle stirring blade at 550 rpm.
  • HEC water-soluble polymer
  • composition preparation method [Examples 1 and 3, and Comparative Examples 1 to 4] Compositions of Examples and Comparative Examples were prepared according to the compositions shown in Table 1 using the resulting 2% water-soluble polymer compositions. Specifically, 22.6 g of ion-exchanged water and 1.0 g of a surfactant (polysorbate 60; POE (20) sorbitan monostearate) were mixed with heating and stirring, and added to 40 g of a 2% water-soluble polymer composition. Stir mixed. 6.9 g of ion-exchanged water, 2 g of ascorbic acid derivative, and 2 g of citrate buffer were added to another container, stirred and mixed at room temperature, added to the aqueous solution, and stirred and mixed. Next, 4 g of a 6% NaOH aqueous solution and 16 g of ion-exchanged water were added to neutralize the pH to 6.5 to 6.8.
  • a surfactant polysorbate 60; POE (20) sorbitan mono
  • Example 2 A composition was prepared according to the composition in Table 1 using each of the obtained 2% water-soluble polymer compositions. Specifically, 51.5 g of ion-exchanged water and 1.0 g of a surfactant (polysorbate 60; POE (20) sorbitan monostearate) were mixed with heating and stirring, and added to 40 g of a 2% water-soluble polymer composition. Stir mixed. Next, 2 g of an ascorbic acid derivative was added and mixed with stirring. Thereafter, 5.0 g of an oily component and 0.5 g of phenoxyethanol were added and emulsified to prepare a composition (O/W type emulsion composition). Specifically, the mixture was stirred at 3000 rpm for about 10 minutes. After defoaming with a centrifuge, viscoelasticity, viscosity and pH were measured, and stickiness was evaluated. The results are also shown in Table 1.
  • a surfactant polysorbate 60; POE (20) sorbitan monostearate

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Abstract

L'invention concerne une composition visqueuse qui contient un épaississant polymère et un acide ascorbique ou un dérivé de celui-ci, tout en ayant une adhésivité supprimée et une excellente stabilité. Spécifiquement, l'invention concerne une composition émulsifiée visqueuse contenant un dérivé de cellulose soluble dans l'eau, une cellulose insoluble dans l'eau, un acide ascorbique ou un dérivé de celui-ci, un composant huileux et de l'eau.
PCT/JP2022/029243 2021-08-06 2022-07-29 Composition émulsifiée visqueuse WO2023013536A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003012498A (ja) * 2001-04-25 2003-01-15 Eisai Co Ltd 外用組成物
JP2007246667A (ja) * 2006-03-15 2007-09-27 Yakult Honsha Co Ltd 増粘組成物およびこれを含有する皮膚外用剤
JP2012126788A (ja) * 2010-12-14 2012-07-05 Dai Ichi Kogyo Seiyaku Co Ltd 粘性水系組成物
JP2013035785A (ja) * 2011-08-09 2013-02-21 Kose Corp 皮膚用水中油型乳化組成物
JP2014169266A (ja) * 2013-03-01 2014-09-18 Daito Kasei Kogyo Kk 水中油型化粧料
WO2022071474A1 (fr) * 2020-10-02 2022-04-07 住友精化株式会社 Composition visqueuse

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003012498A (ja) * 2001-04-25 2003-01-15 Eisai Co Ltd 外用組成物
JP2007246667A (ja) * 2006-03-15 2007-09-27 Yakult Honsha Co Ltd 増粘組成物およびこれを含有する皮膚外用剤
JP2012126788A (ja) * 2010-12-14 2012-07-05 Dai Ichi Kogyo Seiyaku Co Ltd 粘性水系組成物
JP2013035785A (ja) * 2011-08-09 2013-02-21 Kose Corp 皮膚用水中油型乳化組成物
JP2014169266A (ja) * 2013-03-01 2014-09-18 Daito Kasei Kogyo Kk 水中油型化粧料
WO2022071474A1 (fr) * 2020-10-02 2022-04-07 住友精化株式会社 Composition visqueuse

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DATABASE Mintel GNPD; DRUNK ELEPHANT : "Soak + Revive F-Balm Electrolyte Waterfacial.", XP093032475 *
DATABASE Mintel GNPD; SKIN INC : "Refresh & Nourish Hand Serum Duo.", XP093032488 *

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