WO2021193674A1 - 分散安定性の向上に優れるカチオン変性ダイユータンガム - Google Patents

分散安定性の向上に優れるカチオン変性ダイユータンガム Download PDF

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WO2021193674A1
WO2021193674A1 PCT/JP2021/012095 JP2021012095W WO2021193674A1 WO 2021193674 A1 WO2021193674 A1 WO 2021193674A1 JP 2021012095 W JP2021012095 W JP 2021012095W WO 2021193674 A1 WO2021193674 A1 WO 2021193674A1
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Prior art keywords
cation
modified
gum
carbon atoms
daiyutan
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English (en)
French (fr)
Japanese (ja)
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陽平 馬場
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MP Gokyo Food and Chemical Co Ltd
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DSP Gokyo Food and Chemical Co Ltd
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Priority to JP2022510574A priority Critical patent/JP7657776B2/ja
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    • 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
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • A61Q19/10—Washing or bathing preparations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof

Definitions

  • the present invention relates to polysaccharides, and more specifically to cation-modified Daiyutan gum.
  • polysaccharides have been used to improve the quality of various products such as foods, cosmetics, and industrial products.
  • examples of such polysaccharides include natural polysaccharides such as xanthan gum, tamarind gum, and fenugreek gum.
  • Patent Documents 1 to 4 propose cation-modified polysaccharides by substituting a part of hydroxyl groups with quaternary nitrogen-containing groups in order to improve the functions of polysaccharides. Further, it is described that when a cation-modified polysaccharide is contained in shampoo or the like, conditioning properties such as suppression of squeaky hair when washing hair are improved.
  • a polysaccharide in a liquid composition containing insoluble solid particles, may be used in order to uniformly disperse the solid particles in the liquid composition.
  • a polysaccharide in the case of a cosmetic composition, may be used to uniformly disperse the scrubbing agent as solid particles in the cosmetic composition.
  • polysaccharides when the liquid composition is an emulsified composition, polysaccharides may be used to uniformly disperse the emulsified particles in the composition.
  • the solid particles and the emulsified particles in the liquid composition may be stably and uniformly dispersed.
  • the solid particles may float or precipitate on the liquid surface of the liquid composition.
  • the oily component and water may undergo phase separation, and the emulsified particles may not be uniformly dispersed. Therefore, the provision of polysaccharides capable of improving the dispersion stability of the liquid composition continues to be sought after.
  • the present inventor has made a diligent study, and found that when the cation-modified daiyutan gum obtained by cation-modifying a polysaccharide called daiyutan gum is adjusted to a specific cation charge amount, the above-mentioned It has been found that the dispersion stability of the liquid composition is improved.
  • the cation-modified beef tongue gum according to the present invention A cation-modified beef tongue gum in which a part of the hydroxyl group is substituted with a quaternary nitrogen-containing group represented by the chemical formula (1).
  • the amount of cation charge derived from the quaternary nitrogen-containing group is 0.3 to 0.8 meq / g.
  • R 1 and R 2 are alkyl groups having 1 to 3 carbon atoms
  • R 3 is an alkyl group having 1 to 24 carbon atoms
  • R 4 and R 5 are alkyl groups having 1 to 3 carbon atoms or hydrogen.
  • an atom, X - represents a monovalent anion
  • R 4 and R 5 are hydrogen atoms.
  • R 3 is an alkyl group having 1 to 3 carbon atoms.
  • R 1 , R 2 and R 3 are methyl groups.
  • dispersion stabilizer according to the present invention contains the above-mentioned cation-modified daiyutan gum.
  • the cosmetic composition according to the present invention contains the above-mentioned cation-modified beef tongue gum.
  • FIG. 1 compares the IR spectra of the cation-modified daiyutan gum (solid line) of Example 2 and the unmodified daiyutan gum (broken line) of Comparative Example 3.
  • the cation-modified daiyutan gum of the present embodiment is preferably contained in a liquid composition and used in order to exert its function.
  • the liquid composition is composed of a dispersion liquid in which solid particles are dispersed, and is contained in a state in which the cation-modified Daiyutan gum is dissolved in a dispersion medium of the dispersion liquid.
  • the solid particles can be stably and uniformly dispersed in the liquid composition.
  • the dispersion medium may be emulsified containing an oily component and water. In other words, the liquid composition may be an emulsified composition.
  • the emulsified particles contained therein become minute and stably and uniformly dispersed.
  • the degree of the state in which the solid particles and / or the emulsified particles are uniformly and stably dispersed in the liquid composition may be referred to as dispersion stability.
  • the aqueous solution containing the cation-modified daiyutan gum has a specific viscosity.
  • the viscosity (temperature 25 ° C.) of the 0.25% by mass aqueous solution of the cation-modified daiyutan gum is 10,000 to 100,000 mPa ⁇ s at a shear rate of 0.01 s-1. It is preferably 30,000 to 60,000 mPa ⁇ s, more preferably 30,000 to 60,000 mPa ⁇ s.
  • the viscosity means a value measured by the method described in Examples.
  • the emulsified composition may be an oil-in-water (O / W) type or a water-in-oil (W / O) type.
  • the emulsified particle size (median diameter) is preferably 50 ⁇ m or less, and more preferably 40 ⁇ m or less. This can improve the emulsification stability of the emulsified composition.
  • the emulsified particle size means a value measured by the measuring method described in the examples.
  • the cation-modified daiyutan gum according to the present embodiment is a cation-modified daiyutan gum in which a part of the hydroxyl groups contained in the daiyutan gum is replaced with a quaternary nitrogen-containing group represented by the chemical formula (1).
  • the cationically modified Dyutan gum has a cationic charge.
  • the Daiyutan gum is a polysaccharide in which the genus Alcaligenes accumulates outside the cells during the fermentation process.
  • the repeating unit of Daiyutan gum has a main chain composed of glucose, glucuronic acid, glucose and rhamnose, and a side chain composed of rhamnose disaccharide. That is, the Daiyutan gum is an anionic polysaccharide having a repeating unit of these 6 sugars.
  • a commercially available product can be used as the die-utan gum. Examples of the commercially available product include KELCO-VIS DG (manufactured by CP Kelco US, Inc.).
  • R 1 and R 2 represent an alkyl group having 1 to 3 carbon atoms.
  • R 1 and R 2 include a methyl group, an ethyl group, and a propyl group, and among these, a methyl group is preferable.
  • R 1 and R 2 are preferably functional groups of the same type.
  • the propyl group may be an n-propyl group or an iso-propyl group.
  • R 3 represents an alkyl group having 1 to 24 carbon atoms.
  • R 3 a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, heptyl group, octyl group, nonyl group, and decyl group.
  • a methyl group or an ethyl group is preferable, and a methyl group is more preferable.
  • R 3 is preferably a functional group of the same type as R 1 and R 2.
  • These alkyl groups may be linear, branched or cyclic.
  • R 4 and R 5 represent an alkyl group or a hydrogen atom having 1 to 3 carbon atoms.
  • Examples of R 4 and R 5 in the case of an alkyl group include a methyl group, an ethyl group, and a propyl group.
  • R 4 and R 5 a methyl group or a hydrogen atom is preferable, and a hydrogen atom is more preferable.
  • the propyl group may be an n-propyl group or an iso-propyl group.
  • X - represents a monovalent anion.
  • X ⁇ include halide ions such as chloride ion, bromide ion, and iodide ion, methyl sulfate ion, ethyl sulfate ion, and the like. Of these, halide ions are preferable, and chloride ions are more preferable.
  • the cation-modified daiyutan gum is synthesized by reacting the cation-modified daiyutan gum with a glycidyl trialkylammonium salt having a corresponding structure, a 3-halogeno-2-hydroxypropyltrialkylammonium salt, or the like.
  • the reaction is carried out in the presence of alkali in a suitable solvent, preferably hydrous alcohol.
  • a suitable solvent preferably hydrous alcohol.
  • the introduction of such a quaternary nitrogen-containing group can be carried out according to a conventionally known method, but is not necessarily limited thereto.
  • the amount of cation charge of the cation-modified Daiyutan gum is 0.3 to 0.8 meq / g, preferably 0.30 to 0.85 meq / g, and 0.44 to 0. It is more preferably 7 meq / g, and even more preferably 0.44 to 0.62 meq / g.
  • the amount of cation charge is in the above numerical range, the dispersion stability of the liquid composition becomes excellent. Further, the spinnability of the liquid composition is lowered, and the workability when the liquid composition is filled in a container or the like is improved.
  • the cation charge amount means the equivalent number of nitrogen components derived from the quaternary nitrogen-containing group contained in 1 g of the cation-modified daiyutan gum.
  • the amount of cation charge means a value calculated by the following mathematical formula (1).
  • the nitrogen content derived from the quaternary nitrogen-containing group in the mathematical formula (1) means a value measured by the Kjeldahl method (former cosmetic raw material standard, general test method, nitrogen quantification method, second method). .. Since the diet tan gum usually contains a nitrogen content derived from a protein, it is necessary to remove the nitrogen content derived from the protein when measuring the nitrogen content of the cation-modified daiyu tan gum.
  • the nitrogen content derived from the quaternary nitrogen-containing group in the cation-modified Daiyutan gum measured by the Kjeldahl method is based on the measured value of the nitrogen content of the cation-modified Daiyutan gum before the cation-modification.
  • the value obtained by subtracting the measured value of the nitrogen content of the gum is adopted. This will be specifically described with reference to the measurement examples of Example 2 and Comparative Example 3 shown in Table 1 below.
  • the measured value of the nitrogen content of the cation-modified Daiyutan gum (Example 2) was 1.66%
  • the measured value of the nitrogen content of the cation-modified Daiyutan gum (Comparative Example 3) was 0.88%. Therefore, by substituting these measured values into the following mathematical formula (1), the amount of cation charge of the cation-modified Daiyutan gum of Example 2 is calculated to be 0.557 (meq / g).
  • the cation-modified daiyutan gum of the present embodiment shows an IR spectrum different from that of the cation-modified daiyutan gum (FIG. 1). Specifically, in the IR spectrum of the cation-modified daiyutan gum, a decrease in peak intensity (peak height) is observed at some peaks as compared with the IR spectrum of the cation-modified daiyutan gum. In particular, a significant decrease in peak intensity is observed at the first peak P1 near 1730 cm -1. On the other hand, no significant decrease in peak intensity is observed at the second peak P2 near 1600 cm -1 adjacent to the first peak P1.
  • the ratio of the peak intensity of the first peak P1 to the peak intensity of the second peak P2 in the IR spectrum is 0.1 to 0.4.
  • the ratio of the peak intensity of the first peak P1 to the peak intensity of the second peak P2 in the IR spectrum is 0.5 to 1.0.
  • the cation-modified beef tongue gum has a smaller ratio than the beef tongue gum.
  • the IR spectrum shall be measured by the method described in Examples. Further, the ratio of the peak intensities means a value calculated by the method described in the examples.
  • the cation-modified daiyutan gum of the present embodiment can be used as a dispersion stabilizer for imparting excellent dispersion stability to the liquid composition as described above.
  • the dispersion stabilizer can be suitably used for products such as foods, cosmetics, and industrial products, which contain the solid particles and / or the emulsified particles.
  • the dosage form of the dispersion stabilizer is not particularly limited, but may be in the form of a solid such as powder or granules, or in the form of a liquid such as an aqueous solution.
  • the content of the cation-modified daiyutan gum with respect to the total mass of the dispersion stabilizer is usually 0.1 to 100% by mass.
  • the concentration of the cation-modified daiyutan gum in the dispersion stabilizer is usually 0.1 to 10% by mass.
  • the dispersion stabilizer may contain an additive other than the cation-modified beef tongue gum as long as it exerts its function.
  • the additive include thickeners such as xanthan gum and locust bean gum, lubricants such as magnesium stearate, metal salts such as sodium chloride and potassium chloride, and dispersants (viscosity adjusters) such as glucose and dextrin. Be done.
  • the liquid composition is preferably a cosmetic composition containing the cation-modified beef tongue gum.
  • the dosage form of the cosmetic composition is not particularly limited, and any one can be adopted. Specific dosage forms include lotions, milky lotions, beauty essences, gels, creams, facial cleansers, oil-in lotions, sunscreens, shampoos, treatments, body soaps and the like. Among these uses, the cosmetic composition is preferably used as a cleanser for facial cleansers, shampoos, body soaps and the like. In other words, the cosmetic composition is preferably a cleansing cosmetic composition used for facial cleansers, shampoos, body soaps and the like.
  • the content of the cation-modified daiyutan gum with respect to the total mass of the cosmetic composition is usually 0.05 to 5% by mass, more preferably 0.1 to 3% by mass.
  • the cosmetic composition has excellent dispersion stability, suppresses a slimy feeling and a sticky feeling at the time of use, and has a good feeling of use.
  • the density of the liquid component contained in the cosmetic composition is usually 0.70 to 1.30 (g / mL).
  • the oily component that can be contained in the cosmetic composition is preferably an oily component that is easily adapted to hair, skin, nails, and the like.
  • oily components include fatty acids, fatty acid esters, hydrocarbon oils, and silicone oils.
  • the fatty acid is preferably a fatty acid having 8 to 22 carbon atoms, more preferably a fatty acid having 12 to 18 carbon atoms, and further preferably a fatty acid having 16 to 18 carbon atoms.
  • the fatty acid having such a carbon number include capric acid (8 carbon atoms), undecylenic acid (11 carbon atoms), capric acid (10 carbon atoms), lauric acid (12 carbon atoms), and myristic acid (14 carbon atoms).
  • Examples thereof include icosapentaenoic acid (20 carbon atoms), behenic acid (22 carbon atoms), and docosahexaenoic acid (22 carbon atoms).
  • the fatty acid ester is preferably a fatty acid ester having 12 to 54 carbon atoms, more preferably a fatty acid ester having 14 to 50 carbon atoms, and further preferably a fatty acid ester having 16 to 46 carbon atoms.
  • Examples of the fatty acid ester having such a carbon number include cetyl octanate (24 carbon atoms), ethyl laurate (14 carbon atoms), hexyl laurate (18 carbon atoms), isopropyl myristate (17 carbon atoms), and myristic acid.
  • Octyldodecyl (34 carbon atoms), myristyl myristate (28 carbon atoms), -2-hexyldecyl myristate (30 carbon atoms), glycerin trimyristate (45 carbon atoms), isopropyl palmitate (19 carbon atoms), palmitin 2-Ethylhexyl acid (24 carbons), -2-heptylundecyl palmitate (36 carbons), -2-hexyldecyl palmitate (34 carbons), butyl stearate (22 carbons), isocetyl stearate (22 carbons) 34 carbon atoms), isocetyl isostearate (34 carbon atoms), cholesteryl 12-hydroxystearate (45 carbon atoms), trimethylolpropane triisostearate (54 carbon atoms), decyl oleate (28 carbon atoms), cetyl lactate (28 carbon atoms) 19 carbon atoms),
  • a natural oily component can be used as the oily component containing a plurality of the fatty acid and / or the fatty acid ester.
  • Examples of the natural oily component include olive oil, jojoba oil, castor oil, mink oil, tall oil, palm oil, palm oil and the like.
  • hydrocarbon oil examples include liquid paraffin, squalane, ⁇ -olefin oligomer, petrolatum and the like.
  • silicone oil examples include dimethylpolysiloxane, tristrimethylsiloxymethylsilane, caprylylmethicone, phenyltrimethicone, tetraxtrimethylsiloxysilane, methylphenylpolysiloxane, methylhexylpolysiloxane, methylhydrogenpolysiloxane, and dimethylsiloxane.
  • organopolysiloxanes such as methylphenylsiloxane copolymers, octamethylcyclotetrasiloxanes, decamethylcyclopentasiloxanes, dodecamethylcyclohexasiloxanes, tetramethyltetrahydrogencyclotetrasiloxanes , Tetramethyltetraphenylcyclotetrasiloxane and other cyclic organopolysiloxanes, amino-modified organopolysiloxanes, pyrrolidone-modified organopolysiloxanes, pyrrolidone carboxylic acid-modified organopolysiloxanes, high-polymerization gum-like dimethylpolysiloxanes, gum-like amino-modified organoxanes.
  • organopolysiloxanes such as methylphenylsiloxane copolymers, octamethylcyclotetrasiloxa
  • Silicone rubber such as polysiloxane, gum-like dimethylsiloxane / methylphenylsiloxane copolymer, cyclic organopolysiloxane solution of silicone gum and rubber, higher alkoxy-modified silicone such as stearoki silicone, higher fatty acid-modified silicone, alkyl-modified silicone , Long-chain alkyl-modified silicone, amino acid-modified silicone, fluorine-modified silicone and the like.
  • the content of the oily component is usually 0.1 to 90% by mass, preferably 4 to 40% by mass, based on the total mass of the cosmetic composition.
  • the water content is usually 10 to 99% by mass, preferably 50 to 95% by mass, based on the total mass of the cosmetic composition.
  • the solid particles include low-density solid particles having a specific gravity of less than 1 with respect to the liquid component and high-density solid particles having a specific gravity of 1 or more with respect to the liquid component.
  • the specific gravity of the low specific density solid particles is preferably 0.01 to 0.99, and more preferably 0.20 to 0.95.
  • the specific gravity of the high-density solid particles is preferably 1.01 to 20, more preferably 1.05 to 10, and even more preferably 1.05 to 1.25.
  • the solid particles that can be contained in the cosmetic composition may be organic solid particles or inorganic solid particles.
  • organic solid particles examples include solid paraffin, selecin, synthetic wax, solid fat such as carnauba wax, polylactic acid, polyhydroxybutyric acid, polyester such as polyacrylic acid / acrylic acid ester, polyamide such as nylon, polyethylene, and the like.
  • Polymer particles such as polypropylene, polyurethane, vinyl resins, tetrafluoroethylene, polymethylmethacrylate, cellulose, silk, and polymethylsilsesquioxane can be mentioned.
  • the inorganic solid particles include magnesium oxide, barium sulfate, calcium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, talc, mica, kaolin, sericite, silica, aluminum silicate, magnesium silicate, and aluminum silicate.
  • Particles such as magnesium, calcium silicate, hydroxyapatite, zeolite, calcium dibasic phosphate, alumina, aluminum hydroxide, and boron silicate can be mentioned.
  • the inorganic solid component is an ultraviolet scattering agent, zinc oxide, zirconium oxide, titanium oxide and the like can be mentioned.
  • the inorganic solid component is a pigment, an inorganic red pigment such as iron oxide and iron titanate, an inorganic brown pigment such as ⁇ -iron oxide, an inorganic yellow pigment such as yellow iron oxide and ocher, and black Inorganic black pigments such as iron oxide and carbon black, inorganic purple pigments such as manganese violet and cobalt violet, inorganic green pigments such as chromium hydroxide, chromium oxide, cobalt oxide and cobalt titanate, and inorganic pigments such as dark blue and ultramarine. Examples thereof include bluish pigments, white pigments such as mica titanium, pigment-coated mica titanium, and titanium oxide, and pearl pigments such as synthetic gold mica.
  • an inorganic red pigment such as iron oxide and iron titanate
  • an inorganic brown pigment such as ⁇ -iron oxide
  • an inorganic yellow pigment such as yellow iron oxide and ocher
  • black Inorganic black pigments such as iron oxide and carbon black
  • inorganic purple pigments such as manganese violet
  • the content of the solid particles is usually 0.1 to 50% by mass, preferably 0.5 to 30% by mass, based on the total mass of the cosmetic composition.
  • the cosmetic composition may contain a surfactant, but since the cosmetic composition contains the cation-modified Daiyutan gum, the emulsification stability is improved, so that the interface
  • the content of the activator may be less than usual.
  • the content of the surfactant is 0.1 to 50% by mass with respect to the total mass of the cosmetic composition.
  • the content of the surfactant is 0.1 to 50% by mass.
  • the content of the surfactant may be, for example, 0.1% by mass or less, 0.01% by mass or less, and may not substantially contain the surfactant. good.
  • the content of the surfactant is preferably 10 to 40% by mass, preferably 10 to 20% by mass. Is more preferable.
  • the surfactant examples include a cationic surfactant, an anionic surfactant, a nonionic surfactant, and an amphoteric surfactant.
  • the surfactant may contain either an anionic surfactant, a nonionic surfactant, or an amphoteric surfactant. preferable. Further, it is more preferable that the surfactant contains a plurality of these types.
  • the combination of the cation-modified beef tongue gum and the surfactant makes the cosmetic composition even more excellent in dispersion stability.
  • the cosmetic composition has a function peculiar to the surfactant.
  • the composition has functions such as improvement of conditioning property for hair and improvement of foam quality.
  • cationic surfactant examples include alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkylpyridium salt, alkyldimethylbenzylammonium salt, benzethonium chloride, and benzalkonium chloride.
  • anionic surfactant examples include alkyl (8 to 24 carbon atoms) sulfate, alkyl (8 to 24 carbon atoms) ether sulfate, alkyl (8 to 24 carbon atoms) benzene sulfonate, and alkyl (8 carbon atoms).
  • nonionic surfactant examples include alkanolamide, glycerin fatty acid ester, polyoxyalkylene alkyl ether, polyoxyalkylene glycol ether, polyoxyalkylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene sorbit fatty acid ester, and sorbit fatty acid ester.
  • examples thereof include castor oil derivatives, polyoxyalkylene-cured castor oil derivatives, alkyl polyglycosides, and polyglycerin fatty acid esters.
  • amphoteric surfactant examples include alkyl (8 to 24 carbon atoms) amidopropyl betaine, alkyl (8 to 24 carbon atoms) carboxybetaine, alkyl (8 to 24 carbon atoms) sulfobetaine, and alkyl (8 to 24 carbon atoms).
  • Hydroxysulfobetaine alkyl (8 to 24 carbons) amidopropyl hydroxysulfobetaine, alkyl (8 to 24 carbons) hydroxyphosphobetaine, alkyl (8 to 24 carbons) aminocarboxylate, alkyl (8 to 24 carbons) ) AmphoNa, alkyl (8 to 24 carbon atoms) amine oxide, alkyl (8 to 24 carbon atoms) phosphate ester containing tertiary nitrogen and quaternary nitrogen, and the like.
  • the cosmetic composition may contain other additives.
  • the additive include polyhydric alcohols that function as moisturizers such as glycerin and 1,3-butylene glycol, thickeners such as xanthan gum, antioxidants such as tocopherol and BHT, benzophenone derivatives, and paraaminobenzoic acid derivatives.
  • Ultraviolet absorbers such as methoxycinnamic acid derivatives, chelating agents such as edetates, amino acids such as arginine and glutamate, pH regulators, bactericides, preservatives, vitamins, anti-inflammatory agents, pigments, fragrances, foaming enhancement Examples include agents.
  • the cation-modified beef tongue gum according to the present embodiment is A cation-modified beef tongue gum in which a part of the hydroxyl group is substituted with a quaternary nitrogen-containing group represented by the chemical formula (1).
  • the amount of cation charge derived from the quaternary nitrogen-containing group is 0.3 to 0.8 meq / g.
  • R 1 and R 2 are alkyl groups having 1 to 3 carbon atoms
  • R 3 is an alkyl group having 1 to 24 carbon atoms
  • R 4 and R 5 are alkyl groups having 1 to 3 carbon atoms or hydrogen.
  • an atom, X - represents a monovalent anion
  • the dispersion stability of the liquid composition can be improved when the amount of cation charge is 0.3 to 0.8 meq / g.
  • R 4 and R 5 are hydrogen atoms.
  • the dispersion stability of the liquid composition can be further improved by making R 4 and R 5 hydrogen atoms.
  • R 3 is an alkyl group having 1 to 3 carbon atoms.
  • R 1 , R 2 and R 3 are methyl groups.
  • the dispersion stability of the liquid composition can be further improved by having R 1 , R 2 and R 3 being methyl groups.
  • dispersion stabilizer according to the present embodiment contains the above-mentioned cation-modified beef tongue gum.
  • the cosmetic composition according to the present embodiment contains the above-mentioned cation-modified beef tongue gum.
  • the cosmetic composition according to the present embodiment preferably contains a surfactant, and the surfactant contains either an anionic surfactant, an amphoteric surfactant, or a nonionic surfactant. ..
  • the surfactant contains any of an anionic surfactant, an amphoteric surfactant, or a nonionic surfactant, whereby the phase of the surfactant and the cationically modified dietangum. It has excellent solubility.
  • the cosmetic composition according to the present embodiment is preferably a cleaning cosmetic composition.
  • the cosmetic is excellent in quality when used as a cosmetic for cleaning.
  • the cation-modified daiyutan gum according to the present invention is not limited to the configuration of the above embodiment. Further, the cation-modified beef tongue gum according to the present invention is not limited by the above-mentioned effects.
  • the cation-modified daiyutan gum according to the present invention can be modified in various ways without departing from the gist of the present invention.
  • Example 1 1.55 g of sodium hydroxide was dissolved in 49.44 g of water, and 74.88 g of isopropanol was uniformly dissolved. Then, 30 g of Daiyu tan gum (KELCO-VIS DG, CP Kelco US, Inc.) was added while being dispersed. 6.0 g of glycidyltrimethylammonium chloride (hereinafter sometimes referred to as GTA, SY-GTA80, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) was added, and the mixture was reacted at 50 to 55 ° C. for 4 hours. After completion of the reaction, the reaction was neutralized with 1.52 g of 50 mass% sulfuric acid.
  • GTA glycidyltrimethylammonium chloride
  • the reaction was filtered, washed by dispersing in 131.52 g of 60% isopropanol, and then filtered. The reaction was then washed by dispersing in 101.76 g of 75% isopropanol and then filtered. Further, by washing by dispersing in 72 g of 90% methanol, excess GTA was removed, and after drying, the desired cation-modified daiyutan gum was obtained. The amount of cation charge of the obtained cation-modified daiyutan gum was 0.443 meq / g. The results are shown in Table 1.
  • Examples 2 to 3 and Comparative Examples 1 to 2 Cationic-modified Daiyutan gums having different cation charge amounts were produced in the same manner as in Example 1 except that the GTA amount used for cation modification was set to the value shown in Table 1, and the cation charge amount was measured.
  • Example 3 The beef tongue gum used in Example 1 was used as Comparative Example 3, and its nitrogen content was measured.
  • the cation-modified daiyutan gum of Example 2 has a remarkable peak intensity around 1730 cm -1 as the first peak P1 as compared with the unmodified daiyutan gum of Comparative Example 3. A decrease was observed. In addition, a decrease in peak intensity was also observed in the peaks near 1250 cm -1 and the peaks near 1400 cm -1. On the other hand, no significant change was observed in the peak intensity of the peak near 1600 cm -1 as the second peak P2.
  • the ratio of the peak intensity of the first peak P1 to the peak intensity of the second peak P2 in the IR spectrum was calculated.
  • the measurement of the peak intensity ratio is based on a straight line passing through the high wavenumber side end (near 1770 cm -1 ) of the first peak and the low wavenumber side end ( near 1500 cm -1) of the second peak in the IR spectrum. As a line, the distance from the baseline to the peak top of each peak was compared.
  • the ratio of the peak intensities of Example 2 was 0.20.
  • the ratio of the peak intensities of Comparative Example 3 was 0.73.
  • Stable The scrubbing agent does not float near the liquid surface, and no scrubbing agent layer is observed on the liquid surface.
  • Unstable A scrubbing agent is floating near the liquid surface, and a layer of scrubbing agent is observed on the liquid surface.
  • Viscosity measurement conditions Subjecting the 0.25 mass% aqueous solution prior to addition of scrubbing agent to the rheometer (DHR-2, TA Instruments Japan Ltd.), flow curve measurement (temperature: 25 ° C.) 0.01s at - The viscosity at the shear rate of 1 was measured.
  • the aqueous solution containing Examples 1 to 3 had a high viscosity.
  • the viscosity of the aqueous solution containing Examples 1 to 3 was lower than the viscosity of the aqueous solution containing Comparative Example 3 (unmodified Daiyutan gum), which had insufficient dispersion stability. ..
  • the aqueous solution containing Example 3 had better dispersion stability than any of the aqueous solutions containing Comparative Examples 1 to 3.
  • the emulsified particle size (median size) of the obtained emulsion was measured with a laser diffraction / scattering type particle size distribution measuring device (Partica mini LA-350, manufactured by HORIBA, Ltd.) (dispersion medium: water). The results are shown in Table 3.
  • the cation-modified daiyutan gum having a cation charge amount of 0.3 to 0.8 meq / g in Examples 1 to 3 is a polysaccharide having very excellent dispersion stability. It turned out. Therefore, the cation-modified daiyutan gums of Examples 1 to 3 contribute to the dispersion stability of scrubbing agents, pigments, emulsified particles and the like in the field of cosmetics, for example, and contribute to the stabilization of dispersion of cosmetics, emulsions, beauty essences, gels, creams and facial cleansers. , Sunscreen, shampoo, treatment, body soap, etc. have been found to be useful.
  • the component (3) was placed in a 100 mL glass tall beaker, the dispersion liquid was added while stirring with a general-purpose stirrer (BL1200, manufactured by Shinto Kagaku Co., Ltd.), and then the beaker was immersed in a water bath at 85 ° C. After the liquid temperature reached 80 ° C., the mixture was stirred for 15 minutes, and a mixture of components (4) to (6) was further added. Next, the component (7) and the component (8) were added, and the mixture was cooled with water until the temperature reached about room temperature with stirring, and the component (3) was added so as to have a total weight of 50 g to prepare a scrub face wash.
  • BL1200 general-purpose stirrer
  • Stable The scrubbing agent does not settle and no scrubbing agent deposit layer is observed. Unstable: The scrubbing agent settles and a sedimentary layer of the scrubbing agent is observed.
  • the scrub cleanser (E-1 or E-2) containing Example 1 or Example 3 is considered to have high dispersion stability. It showed better dispersion stability than the scrub cleanser (E-3) containing cation-modified xanthan gum.
  • the component (3) was placed in a 200 mL glass tall beaker, the dispersion was added while stirring with a general-purpose stirrer (BL1200, manufactured by Shinto Kagaku Co., Ltd.), and then the mixture was stirred at room temperature for 30 minutes. Then, the components (4) to (6) were added in sequence, and the mixture was stirred for 5 minutes.
  • the component (7) was added to the obtained lotion and stirred at 300 rpm for 5 minutes to prepare a total of 105 g of oil-in lotion. 80 g of the obtained oil-in lotion was transferred to a 100 mL vial and allowed to stand in a thermostat at 50 ° C. (MIR-153, manufactured by Sanyo Electric Co., Ltd. (currently Panasonic Corporation)), and the state was observed 6 days later. Table 6 shows the results of evaluation based on the following evaluation criteria.
  • Stable Olive oil particles do not float and are not separated from the aqueous solution.
  • Unstable Olive oil particles have floated to form a layer separated from the aqueous solution.
  • the oil in lotions (F-1 to F-3) containing Examples 1 to 3 are unmodified Daiyutan gum (F-4) and cation-modified guar gum (F-6).
  • the dispersion stability was superior to that of the oil in lotion (F-5) containing cation-modified xanthan gum, which is said to have high dispersion stability.
  • Stable The scrubbing agent does not float near the liquid surface, and no scrubbing agent layer is observed on the liquid surface. Unstable: A scrubbing agent is floating near the liquid surface, and a layer of scrubbing agent is observed on the liquid surface. (Evaluation criteria for dispersion stability of calcium carbonate) Stable: Calcium carbonate does not settle near the bottom and no calcium carbonate layer is found on the bottom. Instability: Calcium carbonate has settled near the bottom, and a layer of calcium carbonate is observed at the bottom.
  • Stable Liquid paraffin does not float near the liquid surface, and no layer of liquid paraffin is observed on the liquid surface.
  • Unstable Liquid paraffin is floating near the liquid surface, and a layer of liquid paraffin is observed on the liquid surface.
  • the aqueous solutions (G-1 to G-3) containing Examples 1 to 3 are the low-density solid particles even after a long storage period (90 days). No levitation of scrubbing agent and low density oil agent was observed. In addition, no precipitation of calcium carbonate in the high density particles was observed. In other words, the aqueous solutions (G-1 to G-3) containing Examples 1 to 3 maintained a uniformly dispersed state of solid particles and emulsified particles for a long period of time. On the other hand, in the aqueous solutions (G-4 to G-6) containing Comparative Examples 1 to 3, floating of the scrubbing agent and liquid paraffin was observed, and layers of the scrubbing agent and liquid paraffin were observed on the liquid surface. Alternatively, a layer of calcium carbonate formed by sedimentation of calcium carbonate was observed.
  • the mixture was stirred at room temperature for 1 hour to obtain an aqueous solution having a polysaccharide concentration of 2.0% by mass.
  • 5 g of the aqueous solution was dispensed into four 15 mL conical tubes, and sodium lauryl sulfate (alkyl sulfate having 12 carbon atoms, Emar 0 manufactured by Kao Co., Ltd., 10% by mass based on the total mass of the composition) was placed in each conical tube.
  • Lauroyl sarcosine sodium 30% aqueous solution (acylated sarcosate having 12 carbon atoms, sarcosinate LN-30 manufactured by Nikko Chemicals Co., Ltd., 33.4% by mass based on the total mass of the composition), lauroyl methylalanine sodium 30% aqueous solution. (Acylated N-methyl- ⁇ -alanine salt having 12 carbon atoms, Alaninate LN-30 manufactured by Nikko Chemicals Co., Ltd., 33.4% by mass based on the total mass of the composition), or lauric acid, myristic acid, palmitin.
  • a 35% aqueous solution of potassium hydroxide containing an acid and glycerin ie, as an anionic surfactant, a long-chain carboxylic acid salt having 12 carbon atoms, a long-chain carboxylic acid salt having 14 carbon atoms, and a long-chain carboxylic acid salt having 16 carbon atoms.
  • An aqueous solution containing an acid salt Priory B-100 manufactured by Kao Co., Ltd., 28.6% by mass based on the total mass of the composition was added, and deionized water was further added to prepare a composition of 10 g.
  • homogenizer (HG-200, manufactured by Hsiangtai) was used to homogenize at 10,000 rpm for 1 to 2 minutes. The appearance of the obtained aqueous solution was observed and evaluated according to the following evaluation criteria. The results are shown in Table 8.
  • the aqueous solution (H-6) containing Comparative Example 3 was found to have a reduced viscosity when mixed with sodium lauryl sulfate, sodium lauroyl sarcosine, or sodium lauroyl methyl alanine, and sodium lauroyl sarcosine or sodium lauroyl methyl alanine was added. Aggregation was observed when mixed. From these results, it was found that the cation-modified daiyutan gums of Examples 1 to 3 had excellent compatibility with anionic surfactants.
  • the component (4) and the component (5) were added, and the mixture was stirred for 5 minutes. Further, the components (6) to (8) were added, and the mixture was stirred for 10 minutes to prepare a gel shampoo.
  • the appearance of the obtained gel shampoo was observed to confirm the presence or absence of agglomeration. Further, it was subjected to a rheometer (DHR-2, manufactured by TA Instruments Japan Co., Ltd.), and the viscosity at a shear rate of 10s-1 was measured by flow curve measurement (temperature: 25 ° C.).
  • the gel shampoo (I-1) containing Example 1 showed no aggregation and showed a high viscosity value.
  • the gel shampoo (I-2) containing Comparative Example 3 agglomerates when mixed with the components (6) to (8), and has a lower viscosity value than that of Example 1. Indicated. From these results, it was found that the gel shampoo containing Example 1 was more compatible with the anionic surfactant and the amphoteric surfactant than the gel shampoo containing Comparative Example 3. Further, in the scrub gel shampoo containing low specific density solid particles close to water, the scrub gel shampoo (I-1) containing Example 1 is more than the scrub gel shampoo (I-2) containing Comparative Example 3. It was found to be excellent in dispersion stability.
  • the mixture was stirred for 15 minutes, and the components (4) to (7) were further added and stirred for 5 minutes.
  • the body soap was prepared by water-cooling until it became near room temperature, adding the component (8), and then adding the component (1) so as to have a total weight of 50 g. The appearance of the obtained body soap was observed to confirm the presence or absence of aggregation. Further, it was subjected to a rheometer (DHR-2, manufactured by TA Instruments Japan Co., Ltd.), and the viscosity at a shear rate of 10s-1 was measured by flow curve measurement (temperature: 25 ° C.).
  • the body soap (J-1) containing Example 3 showed no aggregation and showed a high viscosity value.
  • the body soap (J-2) containing Comparative Example 3 aggregates when mixed with the components (4) to (7), and has a lower viscosity value than that of Example 3. showed that. From these results, it was found that the body soap containing Example 3 was more compatible with the anionic surfactant and the nonionic surfactant than the body soap containing Comparative Example 3. Further, in the scrub body soap containing high specific density solid particles, the scrub body soap (J-1) containing Example 3 has a higher dispersion stability than the scrub body soap (J-2) containing Comparative Example 3. It turned out to be excellent.

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US20220411590A1 (en) * 2021-06-29 2022-12-29 National Tsing Hua University Nanonetwork with controlled chirality and manufacturing method thereof
JP7454979B2 (ja) 2020-03-25 2024-03-25 Ｍｐ五協フード＆ケミカル株式会社 コアセルベートの形成に優れるカチオン変性ダイユータンガム

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JP7454979B2 (ja) 2020-03-25 2024-03-25 Ｍｐ五協フード＆ケミカル株式会社 コアセルベートの形成に優れるカチオン変性ダイユータンガム
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