WO2022230986A1 - Produit cosmétique capillaire - Google Patents

Produit cosmétique capillaire Download PDF

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Publication number
WO2022230986A1
WO2022230986A1 PCT/JP2022/019324 JP2022019324W WO2022230986A1 WO 2022230986 A1 WO2022230986 A1 WO 2022230986A1 JP 2022019324 W JP2022019324 W JP 2022019324W WO 2022230986 A1 WO2022230986 A1 WO 2022230986A1
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hair
mass
less
component
hair cosmetic
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PCT/JP2022/019324
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Japanese (ja)
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直幸 山崎
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花王株式会社
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/46Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing sulfur
    • 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
    • A61K8/72Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/06Preparations for styling the hair, e.g. by temporary shaping or colouring
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/12Preparations containing hair conditioners

Definitions

  • the present invention relates to hair cosmetics and hair treatment methods.
  • hair cosmetics are expected to have a conditioning effect that can impart smoothness, softness, manageability, etc. to the hair.
  • Techniques for imparting smoothness, softness, manageability, etc. to hair by blending cationic polymers and anionic polymers have already been reported.
  • JP 2017-210413 A (Patent Document 1) describes (A) a cationic polysaccharide, (B) a specific crosslinked cationic polymer, (C) a fatty acid or a salt thereof, and (D) a cationic A hair treatment agent containing a surfactant not only prevents the hair from becoming prone to sleepiness, but also suppresses stickiness during rinsing, imparts smoothness to the hair, and improves the manageability and smoothness of the hair as follows. It is described that it can be maintained until the hair is washed.
  • Patent Document 2 Japanese Unexamined Patent Application Publication No. 2017-88516 (Patent Document 2) describes a hair cleanser composition containing (A) an anionic surfactant, (B) a crosslinked cationic polymer, a hydrophobic cationized hydroxyethyl cellulose, and water.
  • A an anionic surfactant
  • B a crosslinked cationic polymer
  • hydrophobic cationized hydroxyethyl cellulose a hair cleanser composition containing (A) an anionic surfactant, (B) a crosslinked cationic polymer, a hydrophobic cationized hydroxyethyl cellulose, and water.
  • component (A) an anionic surfactant
  • component (B) cationic polymer
  • component (C) a polymer containing a specific structural unit
  • a hair cleansing composition containing water wherein the mass ratio ((B)/(C)) of the content of component (B) to the content of component (C) in the hair cleansing composition is It is described that a hair cleansing composition within a specific range is less likely to cause bedriddenness and imparts smoothness and softness that are desirable in terms of manageability and feel to the hair.
  • the present invention relates to a hair cosmetic and a hair treatment method with improved ability to fix the shape of hair.
  • the present inventors have found that (A) at least one anionic polymer selected from crosslinked polyacrylic acid and (acrylates/alkyl acrylate (C10-30)) crosspolymer, (B) an anionic surfactant, and The inventors have found that a hair cosmetic containing (C) a cationic polymer having a cellulose skeleton can improve the ability to fix the shape of hair, and completed the present invention.
  • FIG. 10 is a diagram for explaining the fixing of the shape of hair, and is a photograph of a state in which the upper end of a bundle of hair is fixed and hung, as seen from the front.
  • (a) shows an untreated hair bundle for evaluation
  • (b) shows the untreated hair bundle for evaluation of (a) treated with the hair cosmetic of the present invention and straightened with a ring comb. It shows the state of being completely dried with a dryer.
  • the hair cosmetic composition of the present invention contains the following components (A) to (C), and the component (C) contains both the following components (C1) and (C2).
  • "containing component X” means "containing component X. shall be regarded as synonymous with
  • FIG. 1 is a diagram for explaining the fixation of the shape of hair, and shows a front view of a state in which a bundle of hair is hung with its upper end fixed.
  • the "shape fixing power of hair” means, for example, that curly hair as shown in FIG. It is a force that strongly fixes the shape so that the shape is maintained even after drying.
  • "fixing the shape of hair” means a state in which hairs are bound together and a bundle of hair is fixed in a fixed shape, and the hair line is beautifully disordered from the top to the tip. This is a different state from the "hair clump,” which means a state in which the hair is not straightened.
  • the hair cosmetic composition of the present invention comprises at least one anionic polymer selected from crosslinked polyacrylic acid and (acrylates/alkyl acrylate (C10-30)) crosspolymer as component (A), and an anion as component (B).
  • a cationic polymer having a cellulose skeleton as component (C) wherein component (C) comprises (C1) hydrophobic cationized hydroxyethyl cellulose and (C2) a cellulose skeleton other than (C1) above. Includes both cationic polymers.
  • Component (A), which is an anionic polymer, component (B), which is an anionic surfactant, and component (C), which is a cationic polymer, can interact to form a composite gel. Then, when the hair to which the hair cosmetic composition of the present invention is applied is rinsed, the excess anionic surfactant component (B) is washed away, and the composite gel is deposited on the hair surface and bound to the hair surface. It is thought that a composite gel film having properties is formed. It is believed that the hair on which a composite gel film having binding properties is formed is fixed in shape by binding the hairs to each other and supporting each other by the composite gel film.
  • the component (C) since the component (C) has excellent adhesion to the hair, it tends to be uniformly adsorbed on the entire hair.
  • the component (C) contains both the components (C1) and (C2), it is possible to further improve the shape-fixing power of the hair.
  • the reason for this is not clear, but is presumed as follows.
  • Component (C2) forms a highly viscous gel and is excellent in adhesion to hair, so that it is easily uniformly adsorbed on the entire hair.
  • the component (C1) forms a low-viscosity gel with excellent water retention, so that the entire hair can be easily coated with the composite gel film, and the binding force can be further improved.
  • the hair cosmetic composition of the present invention since the component (C) contains both the components (C1) and (C2), it is possible to more uniformly form a film with good binding power over the entire hair. It is considered that the shape fixing force for fixing the shape can be further improved. Furthermore, since the components (A) and (C) are excellent in water retention, the binding force of the composite gel film can be improved. Therefore, by combining the components (A) to (C), the hair cosmetic composition of the present invention can uniformly form a film with good binding strength over the entire hair, and thus the hair can be bundled and given a certain shape. , it is thought that the shape-fixing force for fixing the shape of the bundled hair can be improved.
  • the hair cosmetics of the present invention include hair cleansers such as hair shampoos, hair rinses, hair conditioners, hair treatments, hair packs, and hair styling agents.
  • hair cleansers such as hair shampoos, hair rinses, hair conditioners, hair treatments, hair packs, and hair styling agents.
  • the one that is used after washing the hair is preferable, and the one that is used after being applied to the hair and then rinsed is more preferable.
  • the hair cosmetic of the present invention is preferably a hair rinse, hair conditioner, hair treatment, hair pack or hair styling agent.
  • the dosage form of the hair cosmetic composition of the present invention can be, for example, any dosage form such as liquid, foam, paste or cream. Among these, liquid, paste or cream is preferable, and liquid is more preferable, from the viewpoint of ease of use.
  • composition of the present invention contains at least one anionic polymer selected from crosslinked polyacrylic acid and (acrylates/alkyl acrylate (C10-30)) crosspolymer as component (A).
  • Component (A) is more preferably crosslinked polyacrylic acid.
  • carboxyvinyl polymers ie carbomers by the INCI name
  • Carbomer is a polymer of acrylic acid crosslinked with pentaerythyl allyl ether, sucrose allyl ether or propylene allyl ether.
  • Component (A) forms a composite gel through interaction with component (C), which is a cationic polymer having cationic properties.
  • the ability to fix the shape of hair can be improved due to the effect of improving water retention of hair and the effect of binding hair together by the composite gel.
  • (Acrylates/alkyl acrylate (C10-30)) crosspolymer is a copolymer of one or more monomers consisting of acrylic acid, methacrylic acid or their simple esters and an alkyl acrylate (C10-30) It is crosslinked with an ether or an allyl ether of pentaerythritol and has the INCI name Acrylates/C10-30 Alkyl Acrylate Cross Polymer.
  • Examples of commercial products of carbomer include Carbopol (registered trademark; hereinafter abbreviated) 980 and Carbopol 981 (manufactured by Lubrizol Co., Ltd.).
  • Examples of commercial products of the (acrylates/alkyl acrylate (C10-30)) crosspolymer include Carbopol ETD2020 (manufactured by Lubrizol Co., Ltd.).
  • the component (A) may be used singly or in combination of two or more.
  • the content of component (A) in the hair cosmetic of the present invention is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and further preferably 0.03% by mass or more, from the viewpoint of further improving the shape-fixing power of hair. It is preferably 0.05% by mass or more, more preferably 0.08% by mass or more, still more preferably 0.10% by mass or more, and still more preferably 0.20% by mass or more. It is 0% by mass or less, more preferably 3.0% by mass or less, still more preferably 1.0% by mass or less, and even more preferably 0.80% by mass or less.
  • the content of component (A) in the hair cosmetic composition of the present invention is preferably 0.01% by mass or more and 5.0% by mass or less, more preferably 0.03% by mass or more and 3. 0% by mass or less, more preferably 0.05% by mass or more and 1.0% by mass or less, more preferably 0.08% by mass or more and 0.80% by mass or less, still more preferably 0.10% by mass or more and 0.80% by mass % or less, more preferably 0.20 mass % or more and 0.80 mass % or less.
  • the hair cosmetic composition of the present invention contains an anionic surfactant as component (B).
  • Anionic surfactants include polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, ⁇ -olefin sulfonates, internal olefin sulfonates, alkyl or alkenyl sulfates, alkyl sulfonates, saturated or unsaturated fatty acids.
  • salts alkyl or alkenyl ether carboxylates, ⁇ -sulfo fatty acid salts, N-acyl amino acid salts, phosphoric acid mono- or diester salts, sulfosuccinic acid ester salts, etc., and one or more of these may be used. can be done.
  • Component (B) contains at least one selected from the group consisting of polyoxyethylene alkyl ether sulfate, ⁇ -olefin sulfonate, and internal olefin sulfonate, from the viewpoint of further improving the shape fixing power of hair. is preferred, and it is more preferred to contain a polyoxyethylene alkyl ether sulfate.
  • Polyoxyethylene alkyl ether sulfates include compounds represented by the following formula (I).
  • R 1 represents a linear or branched alkyl group having 8 to 22 carbon atoms.
  • p indicates the average number of added moles and is a number of 0.25 or more and 20 or less.
  • Y represents an alkali metal, alkaline earth metal, ammonium, alkanolamine or basic amino acid.
  • the linear or branched alkyl group in R 1 preferably has 8 or more and 18 or less carbon atoms, more preferably 10 or more and 18 or less carbon atoms, from the viewpoint of further improving the shape-fixing power of hair.
  • R 1 in formula (I) include 2-ethylhexyl group, n-octyl group, nonyl group, n-decyl group, isodecyl group, undecyl group, n-dodecyl group, lauryl group, tridecyl group and myristyl group.
  • R 1 is preferably a linear alkyl group, more preferably one selected from the group consisting of n-octyl group, n-decyl group, lauryl group, myristyl group, cetyl group, and stearyl group. More preferably, one or more selected from the group consisting of n-decyl group, lauryl group, myristyl group, cetyl group and stearyl group, more preferably lauryl group.
  • R 1 may be an alkyl group derived from multiple fatty acids contained in natural products such as coconut oil, palm oil, palm kernel oil, soybean oil, rapeseed oil, beef tallow, lard, or fish oil.
  • the compound represented by formula (I) is obtained as a mixture of a plurality of compounds having different alkyl groups.
  • p in the formula (I) represents the average number of added moles and is a number of 0.25 or more and 20 or less. From the viewpoint of further improving the shape fixing power of hair, p is preferably 0.5 or more, preferably 15 or less, more preferably 10 or less, and even more preferably 5 or less.
  • Y in formula (I) represents an alkali metal, alkaline earth metal, ammonium, alkanolamine or basic amino acid, preferably alkali metal or ammonium. Preferred alkali metals are lithium, sodium, or potassium. Ammonium may be alkylammonium or alkanolammonium. Y is preferably one or more selected from the group consisting of sodium, potassium, and ammonium, more preferably one or more selected from the group consisting of sodium and ammonium, from the viewpoint of further improving the shape fixing power of hair. be.
  • the average addition mole number p of the oxyethylene group is 0.25 or more and 20 or less, preferably 0.5 or more and 15 or less, more preferably is 0.5 to 10, more preferably 1 to 5, sodium laureth sulfate, ammonium laureth sulfate, and the like.
  • sodium laureth sulfate include "Emal 227HP” and “Emal 125HP” manufactured by Kao Corporation, and specific examples of ammonium laureth sulfate include "Emal 170S-A" manufactured by Kao Corporation.
  • the number of carbon atoms in the ⁇ -olefin sulfonate is preferably 8 or more and 22 or less, more preferably 8 or more and 18 or less, and still more preferably 10 or more, from the viewpoint of further improving the shape fixing power of hair. 18 or less.
  • Examples of the counter ion of the ⁇ -olefinsulfonic acid constituting the ⁇ -olefinsulfonate include alkali metal ions such as sodium ion and potassium ion; alkaline earth metal ions such as calcium ion and magnesium ion; ammonium ion; or alkanolammonium having 1 to 3 alkanol groups of 3 (for example, monoethanolammonium, diethanolammonium, triethanolammonium, triisopropanolammonium, etc.).
  • the counter ion of the ⁇ -olefinsulfonic acid is preferably one or more selected from the group consisting of sodium, potassium and ammonium, more preferably sodium, from the viewpoint of further improving the shape fixing power of the hair.
  • Specific examples of ⁇ -olefin sulfonates include sodium sulfonates of ⁇ -olefins having preferably 8 or more and 22 or less carbon atoms, more preferably 10 or more and 18 or less carbon atom
  • the internal olefin sulfonate can be obtained, for example, by sulfonating, neutralizing, and hydrolyzing an internal olefin having a double bond inside the olefin chain (2 or more positions).
  • the number of carbon atoms in the internal olefin sulfonate is preferably from 8 to 22 carbon atoms, more preferably from 8 to 18 carbon atoms, still more preferably from 10 to 18 carbon atoms, from the viewpoint of further improving the shape fixing power of hair. It is below.
  • the internal olefin of the internal olefin sulfonate is an olefin having a double bond inside the olefin chain, and the position of the double bond is present at the 1st position of the carbon chain, so-called ⁇ -olefin When it contains a trace amount It has a broader meaning including Sulfonation of internal olefins produces ⁇ -sultones quantitatively, part of which converts to ⁇ -sultones and olefinsulfonic acids, which are further converted into hydroxyalkanes by the steps of neutralization and hydrolysis. Sulfonate and converted to internal olefin sulfonate.
  • the hydroxy group of the resulting hydroxyalkanesulfonate is inside the alkane chain and the double bond of the internal olefinsulfonate is inside the olefin chain.
  • Counter ions of the internal olefinsulfonic acid constituting the internal olefinsulfonate include alkali metal ions such as sodium ion and potassium ion; alkaline earth metal ions such as calcium ion and magnesium ion; ammonium ion; (eg, monoethanolammonium, diethanolammonium, triethanolammonium, triisopropanolammonium, etc.) having 1 or more and 3 or less alkanol groups.
  • the counter ion of the internal olefin sulfonic acid is preferably one or more selected from the group consisting of sodium, potassium and ammonium, more preferably sodium, from the viewpoint of further improving the shape fixing power of the hair.
  • Anionic surfactants other than polyoxyethylene alkyl ether sulfates, ⁇ -olefinsulfonates and internal olefinsulfonates include, for example, alkylbenzenesulfonates, alkyl or alkenyl sulfates, alkylsulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, ⁇ -sulfo fatty acid salts, N-acylamino acid salts, phosphoric acid mono- or diester salts, sulfosuccinic acid ester salts, etc., one or more of these can be used.
  • Hydrocarbon groups such as alkyl groups and alkenyl groups possessed by the above anionic surfactants other than polyoxyethylene alkyl ether sulfates, ⁇ -olefin sulfonates and internal olefin sulfonates, or constituent fatty acids preferably have a carbon number 8 or more and 22 or less, more preferably 8 or more and 18 or less carbon atoms, and still more preferably 10 or more and 18 or less carbon atoms.
  • Counter ions for the anionic groups of the above anionic surfactants other than polyoxyethylene alkyl ether sulfate, ⁇ -olefin sulfonate and internal olefin sulfonate include alkali metal ions such as sodium ion and potassium ion; calcium alkaline earth metal ions such as ions and magnesium ions; ammonium ions; ).
  • alkyl sulfate examples include sodium lauryl sulfate and the like.
  • alkyl ether carboxylates include polyoxyethylene alkyl ether acetates such as sodium laureth acetate.
  • N-acylamino acid salts examples include cocoyl alanine salts and the like.
  • the component (B) may be used singly or in combination of two or more.
  • the content of component (B) in the hair cosmetic composition of the present invention is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and further preferably 0.2% by mass or more, from the viewpoint of further improving the shape-fixing power of hair. It is preferably 0.3% by mass or more, more preferably 0.4% by mass or more, still more preferably 0.5% by mass or more, and from the same viewpoint, preferably 10% by mass or less, more preferably 8.0% by mass. % or less, more preferably 7.0 mass % or less. Taking these points together, the content of component (B) in the hair cosmetic of the present invention is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.2% by mass or more and 8.0% by mass.
  • % or less more preferably 0.3 mass % or more and 7.0 mass % or less, more preferably 0.4 mass % or more and 7.0 mass % or less, still more preferably 0.5 mass % or more and 7.0 mass % or less is.
  • Component (C) Cationic polymer having a cellulose skeleton>
  • the hair cosmetic composition of the present invention contains a cationic polymer having a cellulose skeleton as a component (C), and the component (C) contains both the following components (C1) and (C2).
  • C1 Hydrophobic cationized hydroxyethyl cellulose (C2)
  • "a cationic polymer having a cellulose skeleton” means a cationic group and a cellulose skeleton. , and an overall cationic charge.
  • the cationic group refers to a cationic group, or a group that can be ionized to become a cationic group, for example, a quaternary ammonium group, or a 3 means a tertiary amino group.
  • the hair cosmetic composition of the present invention contains (C1) hydrophobic cationized hydroxyethyl cellulose from the viewpoint of further improving the shape-fixing power of hair.
  • Hydrophobic cationized hydroxyethyl cellulose preferably has an anhydroglucose-derived main chain represented by the following formula (3), and The average number of moles of cationized ethyleneoxy groups per anhydroglucose unit is 0.01 or more and 3.0 or less, and the average number of moles of ethyleneoxy groups is 0.5 or more and 4.0 or less.
  • R 7 , R 8 and R 9 each independently represent a substituent having a cationized ethyleneoxy group and an ethyleneoxy group represented by the following formula (4), n is anhydroglucose It is an average degree of polymerization and shows a number of 50 or more and 5000 or less.
  • R 7 , R 8 and R 9 in formula (3) are groups represented by formula (4) and may be the same or different.
  • n R 7 s, n R 8 s, and n R 9s may be the same or different.
  • one of Y 2 and Y 3 is a hydrogen atom and the other is a cationic group represented by the following formula (5).
  • p is the number of ethyleneoxy groups contained in formula (4)
  • q is the number of cationized ethyleneoxy groups (-CH(Y 2 )-CH(Y 3 )-O-) contained in formula (4) , each being 0 or a positive integer.
  • p and q is 0, the addition order of the cationized ethyleneoxy group and the ethyleneoxy group does not matter, and when p and/or q is 2 or more, either block bond or random bond.
  • the values of p and q may differ between the substituents, but at least one of them has q of 1 or more.
  • R 10 to R 12 each independently represent a linear or branched alkyl group having 1 to 18 carbon atoms, and X 1 - represents an anionic group. However, at least one of R 12 present in the molecule is a linear or branched alkyl group having 8 to 18 carbon atoms.
  • R 10 to R 12 are methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, n-decyl group, n-dodecyl group, n-tetradecyl group, Examples include n-hexadecyl group and n-octadecyl group.
  • R 10 and R 11 are preferably methyl group, ethyl group, n-propyl group, n-butyl group, n-octyl group, n-decyl group and n-dodecyl group, more preferably methyl group.
  • R 12 is preferably a methyl group, an n-octyl group, an n-decyl group or an n-dodecyl group, more preferably a methyl group or an n-dodecyl group.
  • X 1 - is an anionic group which is a counterion of ammonium, and specific examples thereof include alkyl sulfate ions, sulfate ions, phosphate ions, alkyl carbonate ions, and halide ions.
  • halide ions are preferred from the viewpoint of ease of production.
  • examples of halide ions include fluoride ions, chloride ions, bromide ions and iodide ions. From the viewpoint of the water solubility and chemical stability of component (C1), chloride ions and bromide ions are preferred. Chloride ions are more preferred.
  • component (C1) include a quaternary ammonium salt polymer (INCI name: Polyquaternium-67) obtained by addition reaction of trimethylammonium-substituted epoxide and lauryldimethylammonium-substituted epoxide to hydroxyethyl cellulose;
  • a quaternary ammonium salt polymer (INCI name: Polyquaternium-24) obtained by addition polymerization of glycidyl lauryldimethylammonium chloride, a quaternary ammonium salt obtained by addition reaction of coconut oil alkyldimethylammonium substituted epoxide to hydroxyethyl cellulose.
  • Polymer (INCI name: Polyquaternium-72) and the like. Among these, polyquaternium-67 is preferred.
  • the content of the component (C1) is preferably 0.05% by mass from the viewpoint of further improving the shape-fixing power of the hair.
  • the content of the component (C1) is preferably 0.05% by mass from the viewpoint of further improving the shape-fixing power of the hair.
  • Component (C2) Cationic polymer having a cellulose skeleton other than (C1)
  • Component (C2) includes at least one selected from cationized cellulose, cationized hydroxyethyl cellulose other than component (C1), cationized hydroxypropyl cellulose, and cationized carboxymethyl cellulose.
  • a cationized hydroxyethyl cellulose other than the component (C1) is preferable from the viewpoint of further improving the shape-fixing power of hair, and a polymer of a quaternary ammonium salt obtained by adding glycidyltrimethylammonium chloride to hydroxyethyl cellulose. (INCI name: Polyquaternium-10) is more preferred.
  • the content of component (C2) is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, from the viewpoint of further improving the shape fixing power of hair. preferably 0.20% by mass or more, more preferably 0.25% by mass or more, and preferably 3% by mass or less, more preferably 1% by mass or less, even more preferably 0.40% by mass or less, and more More preferably, it is 0.35% by mass or less.
  • Component (C) is composed of hydrophobic cationized hydroxyethyl cellulose as component (C1) and cationized cellulose as component (C2) from the viewpoint of forming a composite gel film and further improving the shape-fixing power of hair. , It is preferably at least one selected from cationized hydroxyethyl cellulose, cationized hydroxypropyl cellulose, and cationized carboxymethyl cellulose other than component (C1), and component (C1) is hydrophobic represented by the formula (3) It is more preferable that the component (C2) is a cationic hydroxyethyl cellulose other than the component (C1), the component (C1) is polyquaternium-67, and the component (C2) is polyquaternium-10. It is even more preferable to have
  • the mass ratio of component (C2) to component (C1) ((C2)/(C1)) is preferably 0.20 or more from the viewpoint of further improving the shape fixing power of hair. , More preferably 0.30 or more, still more preferably 0.40 or more, still more preferably 0.50 or more, still more preferably 0.70 or more, still more preferably 0.80 or more, from the same viewpoint, preferably It is 2.5 or less, more preferably 2.0 or less, still more preferably 1.5 or less, still more preferably 1.2 or less. Taking these viewpoints together, the mass ratio of component (C2) to component (C1) ((C2)/(C1)) is preferably 0.20 or more and 2.5 or less, more preferably 0.30 or more and 2.5. 0 or less, more preferably 0.40 or more and 1.5 or less, more preferably 0.50 or more and 1.2 or less, still more preferably 0.70 or more and 1.2 or less, still more preferably 0.80 or more and 1.2 or less is.
  • Each of the components (C1) and (C2) may be used alone or in combination of two or more.
  • the content of component (C) in the hair cosmetic of the present invention is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, and further preferably 0.10% by mass or more, from the viewpoint of further improving the shape-fixing power of hair. It is preferably 0.30% by mass or more, more preferably 0.40% by mass or more, still more preferably 0.50% by mass or more, and from the same viewpoint, preferably 10.0% by mass or less, more preferably 5. 0% by mass or less, more preferably 3.0% by mass or less, still more preferably 2.0% by mass or less, even more preferably 1.5% by mass or less, even more preferably 1.2% by mass or less, still more preferably 0.5% by mass or less. It is 90% by mass or less.
  • the content of component (C) in the hair cosmetic of the present invention is preferably 0.05% by mass or more and 10.0% by mass or less, more preferably 0.10% by mass or more5. 0% by mass or less, more preferably 0.30% by mass or more and 3.0% by mass or less, more preferably 0.40% by mass or more and 2.0% by mass or less, still more preferably 0.50% by mass or more and 1.5% by mass %, more preferably 0.50% by mass or more and 1.2% by mass or less, more preferably 0.50% by mass or more and 0.90% by mass or less.
  • the mass ratio of component (A) to component (B) ((A)/(B)) is preferably 0.01 or more from the viewpoint of further improving the shape fixing power of hair. , More preferably 0.03 or more, still more preferably 0.04 or more, still more preferably 0.05 or more, still more preferably 0.06 or more, and from the same viewpoint, preferably 2.0 or less, more preferably It is 1.5 or less, more preferably 1.2 or less.
  • the mass ratio of component (A) to component (B) ((A)/(B)) is preferably 0.01 or more and 2.0 or less, more preferably 0.03 or more and 1.0. 5 or less, more preferably 0.04 or more and 1.2 or less, still more preferably 0.05 or more and 1.2 or less, still more preferably 0.06 or more and 1.2 or less.
  • the mass ratio of component (A) to component (C) ((A)/(C)) is preferably 0.05 or more from the viewpoint of further improving the shape fixing power of hair. , More preferably 0.10 or more, still more preferably 0.20 or more, still more preferably 0.30 or more, still more preferably 0.40 or more, and from the same viewpoint, preferably 2.5 or less, more preferably It is 2.0 or less, more preferably 1.5 or less, still more preferably 1.2 or less, still more preferably 1.0 or less. Taking these viewpoints together, the mass ratio of component (A) to component (C) ((A)/(C)) is preferably 0.05 or more and 2.5 or less, more preferably 0.10 or more and 2.5. It is 0 or less, more preferably 0.20 or more and 1.5 or less, still more preferably 0.30 or more and 1.2 or less, still more preferably 0.40 or more and 1.0 or less.
  • the total content of components (A) to (C) in the hair cosmetic of the present invention is preferably 0.5% by mass or more, more preferably 1.0, from the viewpoint of further improving the shape-fixing power of hair. % by mass or more, more preferably 1.2% by mass or more, more preferably 1.5% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less , more preferably 12% by mass or less, more preferably 10% by mass or less, and still more preferably 8.0% by mass or less. Taking these points together, the total content of components (A) to (C) in the hair cosmetic composition of the present invention is preferably 0.5% by mass or more and 25% by mass or less, more preferably 1.0% by mass.
  • the hair cosmetic composition of the present invention contains an aqueous medium, depending on its mode and dosage form, from the viewpoint of ease of handling and the action and effect of the components (A) to (C). be able to.
  • the aqueous medium include water, lower alcohols such as ethanol and isopropyl alcohol; low-molecular-weight diols and triols having 6 or less carbon atoms such as 1,3-butylene glycol, glycerin, ethylene glycol, propylene glycol and dipropylene glycol. mentioned. Among these, one type may be used alone, or two or more types may be used in combination. Among these, water is preferably included as the aqueous medium.
  • the content of the aqueous medium in the hair cosmetic of the present invention is preferably 60% by mass or more, more preferably 65% by mass or more, and still more preferably 70% by mass, from the viewpoint of adjusting the hair cosmetic to an appropriate concentration and viscosity. % or more, more preferably 75 mass % or more, and from the same viewpoint, preferably 99 mass % or less, more preferably 98 mass % or less, still more preferably 97 mass % or less, and still more preferably 96 mass % or less. .
  • the content of the aqueous medium in the hair cosmetic of the present invention is preferably 60% by mass or more and 99% by mass or less, more preferably 65% by mass or more and 98% by mass or less, and still more preferably 70% by mass. % or more and 97 mass % or less, more preferably 75 mass % or more and 96 mass % or less.
  • the hair cosmetic composition of the present invention may contain other ingredients as appropriate within a range that does not impair the purpose of the present invention.
  • Such components include, for example, nonionic surfactants, amphoteric surfactants, pH adjusters, aromatic alcohols, antioxidants, oil agents, and component (A), which are components normally blended in hair cosmetics.
  • the pH of the hair cosmetic composition of the present invention is not particularly limited as long as it is within a range that can be generally used as a hair cosmetic composition.
  • the addition of an acid or base is preferably 3.0 or more, more preferably 4.0 or more, still more preferably 5.0 or more, and preferably 10.0 or less, more preferably 9.0 or less, More preferably, it is adjusted to 8.0 or less.
  • the pH of the hair cosmetic composition of the present invention is preferably 3.0 or more and 10.0 or less, more preferably 4.0 or more and 9.0 or less, and still more preferably 5.0 or more and 8.0. It is below.
  • pH of hair cosmetics is a measured value in 25 degreeC.
  • the hair cosmetic composition of the present invention can be produced by a conventional method.
  • it can be produced by blending components (A) to (C) and, if necessary, other components, and mixing them using a known stirring device or the like.
  • the hair treatment method of the present invention comprises the steps of applying the hair cosmetic of the present invention to the hair, and rinsing the hair to which the hair cosmetic has been applied with water.
  • Methods for applying the hair cosmetic to the hair include, for example, coating, spraying or casting the hair, and immersing the hair in the hair cosmetic.
  • the hair to be applied may be dry or wet, preferably after being combed with a brush, comb or the like and then washed and wet.
  • the hair cosmetic may be applied by hand or by rubbing, or by using a brush, comb, or the like.
  • the hair to which the hair cosmetic is applied may be all or part of the hair.
  • the amount of the hair cosmetic applied to the hair is preferably 0.01 or more, more preferably 0.03 or more, and still more preferably 0.03 or more, as a bath ratio to the weight of the applied hair (mass of the hair cosmetic/mass of the applied hair). is 0.05 or more, more preferably 0.08 or more, and is preferably 20 or less, more preferably 15 or less, still more preferably 10 or less, still more preferably 5 or less, still more preferably 1 or less, still more preferably 0.5 or less.
  • the amount of the hair cosmetic applied to the hair is preferably 0.01 or more and 20 or less, preferably 0.01 or more and 20 or less, in terms of a bath ratio to the weight of the hair to be applied (mass of hair cosmetic/mass of hair to be applied).
  • a bath ratio to the weight of the hair to be applied mass of hair cosmetic/mass of hair to be applied.
  • 0.03 to 15, more preferably 0.05 to 10, more preferably 0.08 to 5, still more preferably 0.08 to 1, still more preferably 0.08 to 0.5 is.
  • the application time is preferably 15 seconds or longer, more preferably 30 seconds or longer, and preferably 5 minutes or shorter, more preferably 3 minutes or shorter.
  • the coating time is preferably 15 seconds or more and 5 minutes or less, more preferably 30 seconds or more and 3 minutes or less.
  • the step of rinsing with water is sufficient as long as the excess hair cosmetic on the surface of the hair can be removed, and the time for rinsing with water is preferably 5 seconds or more and 3 minutes or less.
  • the temperature of the water may be such that it does not burden the body, preferably 15°C or higher and 50°C or lower, more preferably 25°C or higher and 45°C or lower.
  • the hair After washing with water, the hair is dried naturally by towel drying or the like, or by forced drying using a dryer or the like.
  • the hair cosmetic of the present invention as described above, the hair can be bundled into a fixed shape and the shape of the bundled hair can be fixed. It is possible to improve the shape fixing force for Therefore, in particular, it is possible to reduce the time and effort required for styling curly hair, and it can be suitably applied.
  • a hair cosmetic containing the following components (A) to (C), wherein the component (C) contains both the following components (C1) and (C2).
  • the component (A) preferably contains a crosslinked polyacrylic acid, more preferably a carboxyvinyl polymer, that is, a polymer of acrylic acid crosslinked with pentaerythyl allyl ether, sucrose allyl ether or propylene allyl ether. , the hair cosmetic according to ⁇ 1>.
  • Component (B) is preferably polyoxyethylene alkyl ether sulfate, alkylbenzene sulfonate, ⁇ -olefin sulfonate, internal olefin sulfonate, alkyl or alkenyl sulfate, alkyl sulfonate, saturated or at least one selected from unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, ⁇ -sulfo fatty acid salts, N-acyl amino acid salts, phosphoric acid mono- or diester salts, and sulfosuccinic acid ester salts, more preferably At least one selected from the group consisting of ⁇ -olefin sulfonates, internal olefin sulfonates and polyoxyethylene alkyl ether sulfates, more preferably polyoxyethylene alkyl ether sulfates, more preferably the following formula
  • the hair cosmetic composition according to a
  • R 1 O—(CH 2 CH 2 O) p —SO 3 Y
  • R 1 represents a linear or branched alkyl group having 8 to 22 carbon atoms.
  • p indicates the average number of added moles and is a number of 0.25 or more and 20 or less.
  • Y represents an alkali metal, alkaline earth metal, ammonium, alkanolamine or basic amino acid.
  • the component (C1) is a hydrophobic cationized hydroxyethyl cellulose, preferably has an anhydroglucose-derived main chain represented by the formula (3), and
  • the average number of moles of cationized ethyleneoxy groups is 0.01 or more and 3.0 or less, and the average number of moles of ethyleneoxy groups is 0.5 or more and 4.0 or less, more preferably hydrophobic cationized hydroxyethyl cellulose.
  • quaternary ammonium salt polymer (INCI name: Polyquaternium-67) obtained by addition reaction of trimethylammonium-substituted epoxide and lauryldimethylammonium-substituted epoxide to hydroxyethyl cellulose, addition polymerization of glycidyl lauryl dimethyl ammonium chloride to hydroxyethyl cellulose. and a quaternary ammonium salt polymer (INCI name: Polyquaternium-24) obtained by adding a coconut oil alkyldimethylammonium-substituted epoxide to hydroxyethyl cellulose (INCI name: Polyquaternium-24).
  • the component (C2) preferably contains at least one selected from cationized cellulose, cationized hydroxyethyl cellulose other than component (C1), cationized hydroxypropyl cellulose, and cationized carboxymethyl cellulose, more preferably Contains cationized hydroxyethyl cellulose other than component (C1), more preferably contains a quaternary ammonium salt polymer (INCI name: polyquaternium-10) obtained by adding glycidyltrimethylammonium chloride to hydroxyethyl cellulose, ⁇ 1>
  • the hair cosmetic according to any one of ⁇ 4>.
  • the component (C1) is a hydrophobic cationized hydroxyethyl cellulose
  • the component (C2) is a cationized cellulose, a cationized hydroxyethyl cellulose other than the component (C1), or a cationized hydroxypropyl
  • At least one selected from cellulose and cationized carboxymethyl cellulose preferably component (C1) is hydrophobic cationized hydroxyethyl cellulose represented by the formula (3)
  • component (C2) is component (C1 ), more preferably, component (C1) contains at least one selected from polyquaternium-67, polyquaternium-24, and polyquaternium-72, and component (C2) contains polyquaternium-10 More preferably, component (C1) contains polyquaternium-67, and component (C2) contains polyquaternium-10, according to any one of ⁇ 1> to ⁇ 5>.
  • the mass ratio ((C2)/(C1)) of the component (C2) to the component (C1) is preferably 0.20 or more, more preferably 0.30 or more, and still more preferably 0.40 or more. , more preferably 0.50 or more, more preferably 0.70 or more, still more preferably 0.80 or more, and preferably 2.5 or less, more preferably 2.0 or less, still more preferably 1.5
  • the mass ratio of component (A) to component (B) ((A)/(B)) is preferably 0.01 or more, more preferably 0.03 or more, and still more preferably 0.04 or more.
  • the mass ratio of component (A) to component (C) ((A)/(C)) is preferably 0.05 or more, more preferably 0.10 or more, and still more preferably 0.20 or more. , more preferably 0.30 or more, more preferably 0.40 or more, and preferably 2.5 or less, more preferably 2.0 or less, still more preferably 1.5 or less, still more preferably 1.2
  • the total content of components (A) to (C) is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, still more preferably 1.2% by mass or more, and still more preferably 1.5% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less, even more preferably 15% by mass or less, even more preferably 12% by mass or less, further preferably 10% by mass or less,
  • the content of component (A) is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, still more preferably 0.05% by mass or more, and still more preferably 0.08% by mass. Above, more preferably 0.10% by mass or more, more preferably 0.20% by mass or more, and preferably 5.0% by mass or less, more preferably 3.0% by mass or less, still more preferably 1.0% by mass or less.
  • the content of component (B) is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, and still more preferably 0.4% by mass.
  • the content of component (C) is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, still more preferably 0.30% by mass or more, and still more preferably 0.40% by mass. Above, more preferably 0.50 mass % or more, and preferably 10.0 mass % or less, more preferably 5.0 mass % or less, still more preferably 3.0 mass % or less, still more preferably 2.
  • the content of component (C1) is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, still more preferably 0.20% by mass or more, and even more preferably 0.25% by mass. % or more, and preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 1% by mass or less, even more preferably 0.60% by mass or less, and even more preferably 0.50% by mass.
  • the hair cosmetic composition according to any one of ⁇ 1> to ⁇ 13>, more preferably 0.35% by mass or less.
  • the content of component (C2) is preferably 0.05% by mass or more, more preferably 0.10% by mass or more, still more preferably 0.20% by mass or more, and even more preferably 0.25% by mass. % or more, and preferably 3% by mass or less, more preferably 1% by mass or less, even more preferably 0.40% by mass or less, and even more preferably 0.35% by mass or less, ⁇ 1> to ⁇ 14>
  • the pH of the hair cosmetic is preferably 3.0 or higher, more preferably 4.0 or higher, still more preferably 5.0 or higher, and preferably 10.0 or lower, more preferably 9.0 or lower. , and more preferably 8.0 or less, the hair cosmetic according to any one of ⁇ 1> to ⁇ 15>.
  • the aqueous medium preferably contains at least one selected from water, ethanol, isopropyl alcohol, 1,3-butylene glycol, glycerin, ethylene glycol, propylene glycol and dipropylene glycol, more preferably water. , the hair cosmetic according to ⁇ 17>.
  • the content of the aqueous medium is preferably 60% by mass or more, more preferably 65% by mass or more, still more preferably 70% by mass or more, still more preferably 75% by mass or more, and preferably 99% by mass. % or less, more preferably 98 mass % or less, still more preferably 97 mass % or less, still more preferably 96 mass % or less, the hair cosmetic composition according to ⁇ 17> or ⁇ 18>.
  • ⁇ 21> Preferably liquid, foam, paste or cream, more preferably liquid, paste or cream, still more preferably liquid, any of ⁇ 1> to ⁇ 20> Crab hair cosmetic.
  • a hair treatment method comprising the steps of: applying the hair cosmetic composition according to any one of ⁇ 1> to ⁇ 21> to the hair; and rinsing the hair to which the hair cosmetic composition is applied.
  • a method for fixing the shape of hair comprising applying the hair cosmetic composition according to any one of ⁇ 1> to ⁇ 21>.
  • ⁇ Method of blending hair cosmetics> Components (C1) and (C2) dissolved or uniformly dispersed in water, appropriate amounts of water, and component (B) were placed in a beaker, and these components were uniformly mixed at 80°C.
  • Component (A) uniformly dispersed in water is added to the resulting mixture, cooled to room temperature and uniformly mixed, and the pH is adjusted to 6 using a pH adjuster (sodium hydroxide) (measurement temperature 25 ° C. ), and hair cosmetics were obtained.
  • a pH adjuster sodium hydroxide
  • the length of the obtained hair bundle for evaluation and the bundle width at a point of 20 cm from the root of the hair bundle were measured to evaluate the shape fixing power of the hair.
  • the fixing force in the width direction of the hair bundle was evaluated by the bundle width (cm).
  • “the length of the hair bundle when stretched before treatment” is the length when the curly hair bundle before treatment is lightly stretched by hand and the curled hair bundle is straightened.
  • composition of plain shampoo [Unit: % by mass] Polyoxyethylene (2.5) sodium lauryl ether sulfate 15.5 Lauric acid diethanolamide 2.3 Disodium edetate 0.15 Sodium benzoate 0.5 sodium chloride 0.8 Phosphoric acid appropriate amount (pH adjustment) Perfume Trace amount (less than 0.5) Methylparaben trace amount (less than 0.5) water balance (pH 7.0) Total 100
  • GC apparatus (trade name: HP6890, manufactured by HEWLETT PACKARD), column (trade name: Ultra-Alloy-1HT capillary column 30 m ⁇ 250 ⁇ m ⁇ 0.15 ⁇ m, manufactured by Frontier Lab Co., Ltd.), detector (hydrogen flame ion detector ( FID)), injection temperature 300°C, detector temperature 350°C, He flow rate 4.6 mL/min
  • GC device (trade name: Agilent Technologies 6850, manufactured by Agilent Technologies), column (trade name: Ultra-Alloy-1HT capillary column 15 m ⁇ 250 ⁇ m ⁇ 0.15 ⁇ m, manufactured by Frontier Labs), detector (flame ion detection device (FID)), injection temperature 300 ° C., detector temperature 350 ° C., He flow rate 3.8 mL / min
  • the obtained crude alkene internal olefin was transferred to a distillation flask and distilled at 136 to 160° C./4.0 mmHg to obtain raw material olefin a1 having 16 carbon atoms and olefin purity of 100%.
  • the double bond distribution of the obtained raw material olefin a1 was 1.8% by mass at C1, 21.8% by mass at C2, 18.7% by mass at C3, 18.6% by mass at C4, and 14.3% at C5. % by mass, 11.4% by mass at C6-position, 13.6% by mass in total at C7 and 8-positions, and the average double bond position was 4.17.
  • the raw material olefin thus obtained is placed in a thin-film sulfonation reactor having an external jacket, and the sulfonation reaction is carried out using sulfur trioxide gas under the condition that cooling water at 10°C is passed through the outer jacket of the reactor. rice field.
  • the SO 3 /internal olefin molar ratio during the sulfonation reaction was set at 1.01.
  • the resulting sulfonated product was mixed with an alkaline aqueous solution prepared with 1.04 moles of sodium hydroxide (alkaline agent) relative to the theoretical acid value, and neutralized at 30° C. for 1 hour by a continuous method.
  • the resulting neutralized product was hydrolyzed by heating in an autoclave at 170° C.
  • the content of raw material olefin contained in the obtained sodium internal olefin sulfonate 1 having 16 carbon atoms was 0.4% by mass, and the content of inorganic compounds was 0.39% by mass.
  • Sodium internal olefin sulfonate 2 having 16 carbon atoms was obtained in the same manner as in Production Example 1, except that the obtained raw material olefin a2 was used.
  • the content of raw material olefin contained in the obtained sodium internal olefin sulfonate 2 having 16 carbon atoms was 0.4% by mass, and the content of inorganic compounds was 0.42% by mass.
  • the hair cosmetic of this example had a small bundle width and ⁇ length, and had an improved hair bundle shape-fixing power. That is, according to the hair cosmetic composition of the present invention, it is possible to improve the shape-fixing force for fixing the shape of the bundled hair while bundling the hair to impart a certain shape. It can be understood that curly hair such as hair can be bundled and fixed in a straight shape.

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Abstract

L'invention fournit un produit cosmétique capillaire et un procédé de traitement capillaire dont le pouvoir de fixation de forme des cheveux est amélioré. Plus précisément, l'invention concerne [1] un produit cosmétique capillaire qui comprend (A) au moins une sorte de polymère anionique choisie parmi un acide polyacrylique de type réticulé et un polymère réticulé (acrylate / alkyle d'acide acrylique(C10-30)), (B) un tensio-actif anionique, et (C) un polymère cationique ayant un squelette de cellulose. Ledit composant (C) inclut à la fois (C1) une hydroxyéthyl cellulose cationisé hydrophobe et (C2) un polymère cationique ayant un squelette de cellulose autre que ledit composant (C1). En outre, l'invention concerne [2] un procédé de traitement capillaire qui présente une étape au cours de laquelle ledit produit cosmétique capillaire est appliqué sur les cheveux, et une étape au cours de laquelle les cheveux sur lesquels ledit produit cosmétique capillaire est ainsi appliqué, sont rincés à l'eau.
PCT/JP2022/019324 2021-04-30 2022-04-28 Produit cosmétique capillaire WO2022230986A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009522349A (ja) * 2006-01-09 2009-06-11 ザ プロクター アンド ギャンブル カンパニー カチオン変性デンプン及びアニオン性界面活性剤系を含有しているパーソナルケア組成物
WO2020025275A1 (fr) * 2018-07-30 2020-02-06 Unilever Plc Dépôt d'hydratant amélioré dans des liquides de nettoyage contenant des polymères anioniques modifiés de manière hydrophobe ou non-hydrophobe
JP2020536959A (ja) * 2017-10-10 2020-12-17 ザ プロクター アンド ギャンブル カンパニーThe Procter & Gamble Company コンパクトなシャンプー組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009522349A (ja) * 2006-01-09 2009-06-11 ザ プロクター アンド ギャンブル カンパニー カチオン変性デンプン及びアニオン性界面活性剤系を含有しているパーソナルケア組成物
JP2020536959A (ja) * 2017-10-10 2020-12-17 ザ プロクター アンド ギャンブル カンパニーThe Procter & Gamble Company コンパクトなシャンプー組成物
WO2020025275A1 (fr) * 2018-07-30 2020-02-06 Unilever Plc Dépôt d'hydratant amélioré dans des liquides de nettoyage contenant des polymères anioniques modifiés de manière hydrophobe ou non-hydrophobe

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DATABASE GNPD MINTEL; "Black Recipe Intensive Care Shampoo", XP055981834, Database accession no. 919113 *
DATABASE GNPD MINTEL; "Nourishing & Smoothing Shampoo", XP055981841, Database accession no. 7557555 *
DATABASE GNPD MINTEL; "Shampoo", XP055981837, Database accession no. 3547043 *
DATABASE GNPD MINTEL; "Shampoo", XP055981842, Database accession no. 1777727 *
DATABASE GNPD MINTEL; "Sweet Love You Hair Shampoo", XP055981839, Database accession no. 3699189 *

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