WO2020008812A1 - Hair cosmetic - Google Patents

Hair cosmetic Download PDF

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Publication number
WO2020008812A1
WO2020008812A1 PCT/JP2019/022966 JP2019022966W WO2020008812A1 WO 2020008812 A1 WO2020008812 A1 WO 2020008812A1 JP 2019022966 W JP2019022966 W JP 2019022966W WO 2020008812 A1 WO2020008812 A1 WO 2020008812A1
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WO
WIPO (PCT)
Prior art keywords
hair
group
component
hair cosmetic
mass
Prior art date
Application number
PCT/JP2019/022966
Other languages
French (fr)
Japanese (ja)
Inventor
詩織 上野
直幸 山崎
Original Assignee
花王株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 花王株式会社 filed Critical 花王株式会社
Priority to SG11202012836PA priority Critical patent/SG11202012836PA/en
Publication of WO2020008812A1 publication Critical patent/WO2020008812A1/en

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Classifications

    • 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
    • A61K8/84Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/89Polysiloxanes
    • A61K8/896Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
    • A61K8/898Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00Preparations for care of the hair
    • A61Q5/02Preparations for cleaning the hair
    • 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 a hair cosmetic.
  • Hair is damaged by living environment (ultraviolet light and heat by sunlight), daily hair care behavior (rubbing by hair washing and brushing), and chemical treatment (coloring, perm, etc.).
  • a large frictional force is generated on the surface, which causes entanglement.
  • Air entanglement causes all the stresses in hair care behavior.
  • Teeth of hair is sensed by poor finger passing during operation of lathering a hair cleansing agent such as shampoo at the time of hair washing, poor finger passing of hair when rinsing hair after washing, and the like.
  • hair cosmetics such as conditioners and treatments as a method of untangling hair after washing
  • cationic surfactants, higher alcohols, silicones, and the like are blended in hair cosmetics such as conditioners and treatments for the purpose of improving finger passage and combing of hair.
  • Patent Document 1 discloses that a hair cosmetic using a polyetheramino-modified silicone and a cationic surfactant suppresses the feeling of squeaking of hair in a water stream at the time of rinsing, and improves flexibility and smoothness. It is disclosed that damage due to hair entanglement during rinsing can be prevented.
  • Patent Document 2 discloses a combination of an amino-modified silicone having a specific kinematic viscosity range, an aminopolyether-modified silicone, a dimethylpolysiloxane having a specific kinematic viscosity range, a specific alkyl cation, and a specific higher alcohol.
  • Patent Document 3 discloses that in hair cosmetics which are used after being applied to the hair and then washed away, by using a combination of an aminopolyether co-modified silicone having a specific structure and a volatile silicone, the amount of adsorption of adhesive components on the hair is reduced. And that the bulky adhesive component hardly adheres to the hair, and as a result, wet hair after treatment becomes extremely easy to disperse and the drying speed is improved.
  • the present invention comprises or blends an aminopolyether-modified silicone (A) having a polyoxyalkylene structure in a side chain portion and an aminopolyether-modified silicone (B) having a polyoxyalkylene structure in a main chain portion.
  • A aminopolyether-modified silicone
  • B aminopolyether-modified silicone
  • the hair cosmetic composition of the present invention comprises an aminopolyether-modified silicone (A) having a polyoxyalkylene structure in a side chain portion (hereinafter, also referred to as “component (A)”), and a polyoxyalkylene structure in a main chain portion. Characterized by containing or blending an aminopolyether-modified silicone (B) (hereinafter also referred to as “component (B)”).
  • component (A) and component (B) may be any of primary to tertiary amino groups.
  • the amino group may be present in any of the main chain and the side chain of the component (A) and the component (B), but is preferably present in the side chain.
  • the hair cosmetic composition of the present invention contains or blends the above components (A) and (B) so that when applied to hair, it can be untangled without performing operations such as passing through the hair. it can. Furthermore, it is possible to improve the drying speed of the treated hair and to impart smoothness to the hair upon rinsing.
  • “containing component (A) and component (B)” also means “comprising component (A) and component (B)”.
  • the present inventors have found that a hair cosmetic containing or blending two kinds of aminopolyether-modified silicones having a predetermined structure can solve the above problem.
  • the hair cosmetic composition of the present invention When the hair cosmetic composition of the present invention is applied to hair, the hair can be detangled without performing an operation such as passing through the hair.
  • the hair to which the hair cosmetic has been applied dries quickly, and the smoothness of the hair upon rinsing is good.
  • the reason why the effects of the present invention are exhibited by the hair cosmetic of the present invention having the above configuration is not clear, but is presumed as follows. It is considered that it is important to reduce the frictional force acting between the hairs so that the entanglement of the hairs generated during or after the shampooing is spontaneously released. Silicone is sometimes blended as an active ingredient in hair cosmetics. However, when component (B), which is a highly water-soluble aminopolyether-modified silicone, is used, the frictional force acting between hairs can be reduced. It is thought that the effect of untangling the hair appears. In addition, by using the component (A), the drying speed of the hair after the treatment with the hair cosmetic is improved, and the hair at the time of rinsing can be given smoothness. Furthermore, the present inventors have found that by using the component (A) and the component (B) together, the hair can be more effectively entangled than when the component (B) is blended alone. Things.
  • Examples of the hair cosmetic of the present invention include a rinsing agent, a conditioning agent, a treatment agent (including a type that does not wash away), a styling agent, a hair cleansing agent, a hair dye, and a hair restorer.
  • a rinsing agent, a conditioning agent, a treatment agent, a styling agent or a hair cleansing agent is preferable, and a rinsing agent, a conditioning agent, or a treatment agent is more preferable.
  • any dosage form such as a liquid, a foam, a paste, a cream, a solid, and a powder can be used.
  • the hair cosmetic of the present invention is preferably in the form of a liquid, paste or cream, and more preferably in the form of liquid or cream.
  • the hair cosmetic of the present invention may be diluted with water and used in the form of an aqueous solution, depending on the use form.
  • the hair cosmetic composition of the present invention contains or blends, as the component (A), an aminopolyether-modified silicone having a polyoxyalkylene structure in a side chain portion.
  • the hair cosmetic composition of the present invention can improve the drying speed of the treated hair and impart smoothness to the hair upon rinsing.
  • the component (A) and the component (B) are used in combination, the effect of spontaneously untangling the treated hair can be further improved while maintaining the above effects.
  • the component (A) has a structure represented by the following general formula (1).
  • R 1 represents a monovalent hydrocarbon group having 1 to 6 carbon atoms.
  • R 2 represents either R 1 or E 1 .
  • E 1 is a monovalent group represented by —R 3 —Z 1 (R 3 is a divalent hydrocarbon group having 1 to 6 carbon atoms, and Z 1 is a group containing a primary to tertiary amino group).
  • R 4 represents a divalent hydrocarbon group having 1 to 6 carbon atoms
  • R 5 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms.
  • a is a number from 1 to 50
  • b is a number from 1 to 50
  • c is a number from 1 to 50
  • d is a number from 2 to 100.
  • n shows the number of 2 or more and 10 or less. Regardless of the bonding order of the structural units in parentheses, the bonding form may be block-like or random.
  • d number of OC n H 2n may be the same or different.
  • a plurality of R 1 , R 2 , R 4 , R 5 and E 1 may be the same or different.
  • R 1 is a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group, and a methyl group or an ethyl group And more preferably a methyl group.
  • R 2 represents either R 1 or E 1 , and preferably R 1 .
  • E 1 represents —R 3 —Z 1 (R 3 represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and Z 1 represents a primary to tertiary amino group-containing group. ) Represents a monovalent group.
  • R 3 is preferably a divalent hydrocarbon group having 2 to 4 carbon atoms, and more preferably an ethylene group, a trimethylene group, a propylene group, or a tetramethylene group.
  • Z 1 is a group containing a primary to tertiary amino group, and includes —N (R 6 ) 2 , —NR 6 (CH 2 ) p N (R 6 ) 2 , or —NR 6 (CH 2 ) p N (R 7 ) is preferably a group represented by CO-R 8.
  • R 6 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and is preferably a hydrogen atom, a methyl group or an ethyl group.
  • R 7 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms, and is preferably a methyl group or an ethyl group.
  • R 8 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms.
  • p represents a number of 2 or more and 6 or less, and is preferably a number of 2 or more and 4 or less.
  • preferred E 1 groups are — (CH 2 ) 3 —NH 2 , — (CH 2 ) 3 —N (CH 3 ) 2 , — (CH 2 ) 3 —NH— (CH 2 ) 2- NH 2 or — (CH 2 ) 2 —NH— (CH 2 ) 2 —N (CH 3 ) 2 , more preferably — (CH 2 ) 3 —NH 2 .
  • R 4 represents a divalent hydrocarbon group having 1 to 6 carbon atoms, preferably a divalent hydrocarbon group having 2 to 4 carbon atoms, and ethylene, trimethylene, and propylene groups. Or a tetramethylene group is more preferred.
  • R 5 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and is preferably a methyl group or an ethyl group.
  • the component (A) is more preferably represented by the following general formula (1-1).
  • E 1 , R 4 , R 5 , a, b, and c are the same as described above.
  • R 9 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms or a trimethylsilyl group.
  • e represents a number of 1 to 50
  • f represents a number of 0 to 50, preferably 1 to 50.
  • R 9 is preferably a methyl group, an ethyl group or a trimethylsilyl group, more preferably a trimethylsilyl group.
  • the component (A) may be in any form such as an oil and an emulsion, but is preferably an oil.
  • the kinematic viscosity at 25 ° C. of the component (A) is preferably 4,000 mm 2 / s from the viewpoint of untangling the hair, improving the drying speed of the treated hair, and imparting smoothness to the hair upon rinsing.
  • preferably 3,000 mm 2 / s or less still more preferably 2,000 mm 2 / s or less, still more preferably 1,000 mm 2 / s or less, still more preferably 800 mm 2 / s or less, and still more preferably It is at most 500 mm 2 / s, more preferably at most 400 mm 2 / s, and preferably at least 100 mm 2 / s, more preferably at least 200 mm 2 / s.
  • the component (A) is preferably from 100 to 4,000 mm 2 / s, more preferably from 100 to 3,000 mm 2 / s, and still more preferably from 100 to 2,000 mm 2 / s. , More preferably 100 to 1,000 mm 2 / s, still more preferably 100 to 800 mm 2 / s, still more preferably 100 to 500 mm 2 / s, even more preferably 200 to 500 mm 2 / s, and still more preferably Is 200 to 400 mm 2 / s.
  • the kinematic viscosity at 25 ° C. of the component (A) was determined by measuring the time required for a fixed volume of liquid to flow through the capillary of the viscometer at 25 ° C. and 1013.25 hPa using a capillary viscometer. It is calculated from the viscometer constant using the following equation.
  • a type such as Ubbelohde or Cannon-Fenske is generally used.
  • Kinematic viscosity (mm 2 / s) Outflow time (sec) x Viscometer constant
  • Component (A) can be used alone or in combination of two or more.
  • a commercially available aminopolyether-modified silicone can also be used.
  • “ABIL SOFT AF100” aminopolyether-modified silicone represented by the general formula (1-1) (methoxy PEG / PPG-7 / 3 aminopropyl dimethicone) manufactured by EVONIC INDUSTRY, viscosity: 400 mm 2 / s)
  • X-22-3939A viscosity: 2,800 mm 2 / s
  • Shin-Etsu Chemical Co., Ltd. “Silsense A21” (PEG7-amodimethicone, viscosity: 250 mm 2 / s) manufactured by Lubrizol, and the like. No.
  • the content or compounding amount of the component (A) in the hair cosmetic is preferably 0 from the viewpoint of untangling the hair, improving the drying speed of the treated hair, and imparting smoothness to the hair during rinsing.
  • 0.01% by mass or more more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and a viewpoint of improving the drying speed of the treated hair and imparting smoothness to the hair during rinsing. From 5.0 mass% or less, more preferably 3.0 mass% or less, further preferably 1.0 mass% or less, still more preferably 0.8 mass% or less, and still more preferably 0.6 mass%. % Or less.
  • the specific range of the content or blending amount of the component (A) in the hair cosmetic is preferably 0.01 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and still more preferably 0 to 3.0% by mass. 0.01 to 1.0% by mass, more preferably 0.05 to 0.8% by mass, still more preferably 0.1 to 0.6% by mass.
  • the hair cosmetic composition of the present invention contains or blends, as the component (B), an aminopolyether-modified silicone having a polyoxyalkylene structure in the main chain.
  • the hair cosmetic of the present invention can spontaneously disentangle without applying an operation such as passing through the hair when applied to the hair by the above-mentioned action mechanism. it can.
  • the component (B) includes those having a structure represented by the following general formula (2).
  • R 11 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.
  • R 12 represents either R 11 or E 2 .
  • E 2 is represented by —R 13 —Z 2 (R 13 represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and Z 2 represents a primary-tertiary amino group-containing group).
  • a monovalent group represented by Y represents an alkylene group having 1 to 6 carbon atoms.
  • r is a number of 2 or more
  • s is a number of 1 or more
  • t is a number of 4 or more and 100 or less
  • u is a number of 1 or more.
  • m represents a number of 2 or more and 10 or less. Regardless of the bonding order of the structural units in parentheses, the bonding form may be block-like or random.
  • the t C m H 2m O may be the same or different. Further, a plurality of R 11 , R 12 and E 2 may be the same or different.
  • R 11 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.
  • R 11 is independently preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
  • R 12 represents either R 11 or E 2 .
  • E 2 represents a monovalent group represented by —R 13 —Z 2 (R 13 represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms).
  • R 13 is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 20 carbon atoms, and a linear or branched chain having 1 to 6 carbon atoms.
  • Z 2 is a group containing a primary to tertiary amino group, and includes —N (R 14 ) 2 , —NR 14 (CH 2 ) q N (R 14 ) 2 , or —NR 14 (CH 2 ) q N (R 15 ) is preferably an amino group-containing group represented by CO-R 16.
  • R 14 and R 15 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group.
  • R 16 represents an alkyl group having 1 to 3 carbon atoms.
  • q shows the number of 1 or more and 6 or less, Preferably it is the number of 2 or more and 4 or less.
  • preferred E 2 groups are — (CH 2 ) 3 —NH 2 , — (CH 2 ) 3 —N (CH 3 ) 2 , — (CH 2 ) 3 —NH— (CH 2 ) 2- NH 2 or — (CH 2 ) 2 —NH— (CH 2 ) 2 —N (CH 3 ) 2 , more preferably — (CH 2 ) 3 —NH— (CH 2 ) 2 —NH 2 .
  • Y is an alkylene group having 1 to 6 carbon atoms, preferably an ethylene group, a propylene group, a trimethylene group, an n-butylene group (tetramethylene group) or an isobutylene group, and more preferably an n-butylene group or Isobutylene groups are more preferred.
  • the i-butylene group includes -CH (CH 3 ) CH 2 CH 2- , -CH 2 CH (CH 3 ) CH 2- , and -CH 2 CH 2 CH (CH 3 )-.
  • r represents a number of 2 or more
  • s represents a number of 1 or more
  • t represents a number of 4 or more and 100 or less
  • u represents a number of 1 or more.
  • r is preferably a number from 2 to 1,000, more preferably a number from 2 to 100.
  • s is preferably a number of 1 or more and 50 or less
  • t is preferably a number of 4 or more and 50 or less, more preferably 10 or more and 18 or less
  • u is preferably a number of 1 or more and 100 or less.
  • m represents a number of 2 or more and 10 or less, preferably 2 or more and 6 or less, more preferably 2 or more and 4 or less.
  • the component (B) is more preferably an aminopolyether-modified silicone having a structure represented by the following general formula (2-1). More preferably, it is an aminopolyether-modified silicone having a structure represented by the following general formula (2-1).
  • r, s, t, and u are the same as described above.
  • the component (B) preferably satisfies the following formula (I).
  • the effect of detangling the hair is more excellent because of high water solubility.
  • Si indicates the number of moles of silicon atoms in the component (B)
  • AO indicates the average addition mole number of the oxyalkylene in the component (B).
  • Si / AO is 0.01 or more, preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.3 or more, from the viewpoint of untangling the hair.
  • Si / AO in the formula (I) is represented by (r + s + 1) / t.
  • Si / AO in the formula (I) can be calculated from the integrated value of H of the silicon-bonded hydrogen atom and the hydrocarbon group and the integrated value of H of the oxyalkylene group measured by 1 H-NMR measurement. Specifically, it can be measured by the method described in Examples.
  • Component (B) has a nitrogen content of preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, and still more preferably from the viewpoint of untangling the hair. Is 1.0% by mass or more, preferably 2.5% by mass or less, more preferably 2.0% by mass or less, still more preferably 1.8% by mass or less, and still more preferably 1.5% by mass or less. is there.
  • the specific range of the nitrogen content of the component (B) is preferably from 0.1 to 2.5% by mass, more preferably from 0.2 to 2.0% by mass, and still more preferably from 0.5 to 1.8% by mass. %, And still more preferably 1.0 to 1.5% by mass.
  • the nitrogen content of the component (B) is a value measured according to the potentiometric titration method specified in JIS # K0113: 2005.
  • the component (B) may be in any form such as an oil and an emulsion, but is preferably an oil.
  • component (B) is an oil, kinematic viscosity at 25 ° C., from the viewpoint of exhibiting the effects of the present invention efficiently allowed to remain on the hair or the like, preferably 50 mm 2 / s or more, more preferably 100 mm 2 / s or more, more preferably 300 mm 2 / s or greater, even more preferably 500 mm 2 / s or greater, even more preferably at 700 mm 2 / s or more, from the viewpoint of water-soluble, preferably not more than 50,000 mm 2 / s , More preferably 20,000 mm 2 / s or less, further preferably 10,000 mm 2 / s or less, still more preferably 5,000 mm 2 / s or less, even more preferably 3,000 mm 2 / s or less, and still more preferably Is 1,500 mm 2 / s or less, more
  • the specific range of the kinematic viscosity at 25 ° C. of the component (B) is preferably 50 to 50,000 mm 2 / s, more preferably 100 to 20,000 mm 2 / s, and still more preferably 300 to 10,000 mm 2 / s , More preferably 500 to 5,000 mm 2 / s, still more preferably 500 to 3,000 mm 2 / s, still more preferably 500 to 1,500 mm 2 / s, and still more preferably 700 to 1,400 mm 2. / S.
  • the kinematic viscosity of the component (B) can be measured in the same manner as described above.
  • Component (B) can be used alone or in combination of two or more.
  • a commercially available aminopolyether-modified silicone can also be used.
  • the content or the amount of the component (B) in the hair cosmetic is preferably 0.0001% by mass or more, more preferably 0.1% by mass, from the viewpoint of untangling the hair and improving the drying speed of the treated hair. 0005% by mass or more, more preferably 0.001% by mass or more, and preferably 5.0% by mass or less from the viewpoint of improving the drying speed of the treated hair and imparting smoothness to the hair upon rinsing. , More preferably 3.0% by mass or less, further preferably 1.0% by mass or less, still more preferably 0.7% by mass or less, still more preferably 0.5% by mass or less, and still more preferably 0.3% by mass or less. % By mass or less.
  • the specific range of the content or blending amount of the component (B) in the hair cosmetic is preferably 0.0001 to 5.0% by mass, more preferably 0.0001 to 3.0% by mass, and still more preferably 0% by mass. 0.0001 to 1.0% by mass, more preferably 0.0001 to 0.7% by mass, still more preferably 0.0005 to 0.5% by mass, and still more preferably 0.001 to 0.3% by mass. It is.
  • the mass ratio [(A) / (B)] between the component (A) and the component (B) improves the drying speed of the treated hair and smoothens the hair during rinsing. From the viewpoint of providing, it is preferably 1,000 or less, more preferably 500 or less, still more preferably 300 or less, still more preferably 100 or less, still more preferably 50 or less, and still more preferably 20 or less. Further, from the viewpoint of untangling the hair, improving the drying speed of the treated hair, and imparting smoothness to the hair upon rinsing, preferably 0.01 or more, more preferably 0.1 or more, further more preferably 0.3 or more, more preferably 0.5 or more.
  • the specific range of the mass ratio ((A) / (B)) of the component (A) and the component (B) in the hair cosmetic is preferably 0.01 to 1,000, more preferably 0.1 to 500. , More preferably 0.3 to 300, even more preferably 0.5 to 100. Still more preferably, from 0.5 to 50. Even more preferably, it is 0.5 to 20.
  • the hair cosmetic composition of the present invention may further contain or blend a surfactant as the component (C).
  • a surfactant as the component (C).
  • the hair cosmetic composition of the present invention disperses the components (A) and (B) in the hair cosmetic composition and effectively expresses the function as the hair cosmetic composition.
  • the component (C) preferably contains a cationic surfactant.
  • the component (C) is used. It is preferable to include an anionic surfactant. Further, a nonionic surfactant and an amphoteric surfactant can be used in combination.
  • the cationic surfactant can disperse the components (A) and (B) in the hair cosmetic and can impart a conditioning effect to the washed hair.
  • the cationic surfactant include alkyltrimethylammonium salts, alkoxyalkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylamines and salts thereof, alkoxyalkyldimethylamines and salts thereof, and alkylamidoalkyldimethylamines and salts thereof. Is mentioned.
  • alkyl trimethyl ammonium salt examples include compounds represented by the following general formula (i).
  • R 21 -N + (CH 3) 3 X - (i) [In the formula, R 21 represents an alkyl group having 12 to 22 carbon atoms, and X ⁇ represents a halide ion such as a chloride ion and a bromide ion. ]
  • R 21 is preferably an alkyl group having 16 to 20 carbon atoms.
  • Specific examples of the alkyltrimethylammonium salt include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride (stearyltrimonium chloride), behenyltrimethylammonium chloride, and the like.
  • alkoxyalkyltrimethylammonium salt examples include compounds represented by the following general formula (ii).
  • R 22 represents an alkyl group having 12 or more and 22 or less carbon atoms
  • R 23 represents an ethylene group or a propylene group which may be substituted by a hydroxy group.
  • X - is the same as above.
  • R 22 is preferably an alkyl group having 16 to 20 carbon atoms.
  • alkoxyalkyltrimethylammonium salt examples include stearoxypropyltrimethylammonium chloride, stearoxyethyltrimethylammonium chloride, stearoxyhydroxypropyltrimethylammonium chloride and the like.
  • dialkyldimethylammonium salt examples include compounds represented by the following general formula (iii). (R 24) 2 -N + ( CH 3) 2 X - (iii) [Wherein, R 24 independently represents an alkyl group having 12 to 22 carbon atoms. X - is the same as above. ] R 24 is preferably an alkyl group having 16 to 20 carbon atoms. Specific examples of the dialkyldimethylammonium salt include distearyldimethylammonium chloride.
  • alkyldimethylamine and a salt thereof Alkyldimethylamine reacts with an acid to form a quaternary ammonium salt, which serves as a surfactant. Therefore, here, alkyldimethylamine and its salt are defined as a cationic surfactant. The content is converted by the mass of alkyldimethylamine. Examples of the alkyldimethylamine and a salt thereof include a compound represented by the following general formula (iv) and a salt thereof.
  • R 25 -N (CH 3 ) 2 (iv) [In the formula, R 25 represents an alkyl group having 12 to 22 carbon atoms. ] R 25 is preferably an alkyl group having 16 to 20 carbon atoms.
  • Examples of the salt include a salt with an organic acid or an inorganic acid.
  • Examples of the organic acid include monocarboxylic acids such as acetic acid and propionic acid; dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, and phthalic acid; polycarboxylic acids such as polyglutamic acid; Examples include hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxyacrylic acid, glyceric acid, malic acid, tartaric acid, and citric acid; and acidic amino acids such as glutamic acid and aspartic acid.
  • Examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid and the like.
  • organic acids are preferred, and one or more selected from the group consisting of dicarboxylic acids, hydroxycarboxylic acids, and acidic amino acids are more preferred.
  • dicarboxylic acid one or more selected from the group consisting of maleic acid and succinic acid is more preferable.
  • hydroxycarboxylic acid one or more selected from the group consisting of glycolic acid, lactic acid and malic acid is more preferred. Glutamic acid is more preferred as the acidic amino acid.
  • alkyldimethylamines and salts thereof include N, N-dimethylbehenylamine, N, N-dimethylstearylamine and organic acid salts thereof, and lactate of N, N-dimethylbehenylamine, Preferred are glycolates of N-dimethylstearylamine.
  • alkoxyalkyldimethylamine and its salt Alkoxyalkyldimethylamine reacts with an acid to form a quaternary ammonium salt, which becomes a surfactant. Therefore, here, alkoxyalkyldimethylamine and its salt are defined as a cationic surfactant. Further, the content is converted by the mass of the alkoxyalkyldimethylamine. Examples of the alkoxyalkyldimethylamine and a salt thereof include a compound represented by the following general formula (v) and a salt thereof.
  • R 26 -OR 27 -N (CH 3 ) 2 (v) [In the formula, R 26 represents an alkyl group having 12 or more and 22 or less carbon atoms, and R 27 represents an ethylene group or a propylene group. ] R 26 is preferably an alkyl group having 16 to 20 carbon atoms.
  • the salt include a salt with an organic acid or an inorganic acid. Specific examples of the organic acid and the inorganic acid include those exemplified in (iv) alkyldimethylamine and salts thereof. Of these, organic acids are preferred, and one or more selected from the group consisting of dicarboxylic acids, hydroxycarboxylic acids, and acidic amino acids are more preferred.
  • dicarboxylic acid one or more selected from the group consisting of maleic acid and succinic acid is more preferable.
  • hydroxycarboxylic acid one or more selected from the group consisting of glycolic acid, lactic acid and malic acid is more preferred.
  • Glutamic acid is more preferred as the acidic amino acid.
  • alkoxyalkyldimethylamines and salts thereof include N, N-dimethyl-3-hexadecyloxypropylamine, N, N-dimethyl-3-octadecyloxypropylamine and organic acid salts thereof.
  • a glycolate of an amine is preferred.
  • alkylamidoalkyldimethylamine and its salt Alkylamidoalkyldimethylamine reacts with an acid to form a quaternary ammonium salt, which becomes a surfactant. Therefore, here, alkylamidoalkyldimethylamine and its salt are defined as a cationic surfactant. Further, the content is converted by the mass of the alkylamidoalkyldimethylamine. Examples of the alkylamidoalkyldimethylamine and a salt thereof include a compound represented by the following general formula (vi) and a salt thereof.
  • R 28 —C ( O) NH—R 29 —N (CH 3 ) 2 (vi)
  • R 28 represents an alkyl group having 11 to 21 carbon atoms
  • R 29 represents an ethylene group or a propylene group.
  • R 28 is preferably an alkyl group having 15 to 19 carbon atoms.
  • the salt include a salt with an organic acid or an inorganic acid.
  • Specific examples of the organic acid and the inorganic acid include those exemplified in (iv) alkyldimethylamine and salts thereof. Of these, organic acids are preferred, and one or more selected from the group consisting of dicarboxylic acids, hydroxycarboxylic acids, and acidic amino acids are more preferred.
  • the dicarboxylic acid one or more selected from the group consisting of maleic acid and succinic acid is more preferable.
  • the hydroxycarboxylic acid one or more selected from the group consisting of glycolic acid, lactic acid and malic acid is more preferred.
  • Glutamic acid is more preferred as the acidic amino acid.
  • Specific examples of the alkylamidoalkyldimethylamine and a salt thereof include N- [3- (dimethylamino) propyl] docosanamide, N- [3- (dimethylamino) propyl] stearamide and an organic acid salt thereof. Lactates of-[3- (dimethylamino) propyl] docosanamid and glycolates of N- [3- (dimethylamino) propyl] stearamide are preferred.
  • Examples of the cationic surfactants other than the above (i) to (vi) include lanolin ethyl fatty acid aminopropylethyldimethylammonium (ethyl sulfate of alkanoylaminopropyldimethylethylammonium, alkanoyl group is derived from lanolin), and lanolin fatty acid ethyl sulfate Aminoethyltriethylammonium, lanolin fatty acid aminopropyltriethylammonium ethyl sulfate, lanolin fatty acid aminoethyltrimethylammonium methyl sulfate, lanolin fatty acid aminopropylethyldimethylammonium methyl sulfate, isoalkanoic acid ethyl sulfate (C14-20) aminopropylethyldimethylammonium, ethyl sulfate Isoal
  • the cationic surfactant is preferably an alkyltrimethylammonium salt, an alkoxyalkyltrimethylammonium salt, a dialkyldimethylammonium salt, an alkyldimethylamine and a salt thereof, an alkoxyalkyldimethylamine and a salt thereof, and an alkylamidoalkyl.
  • the anionic surfactant is used for dispersing the components (A) and (B) in the hair cosmetic, and for imparting detergency when the hair cosmetic is a hair cleansing agent.
  • the anionic surfactant include alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, alkyl sulfonate, saturated or unsaturated fatty acid salt, alkyl or alkenyl ether carboxylate, ⁇ - Examples thereof include sulfo fatty acid salts, N-acyl amino acids, phosphoric acid mono- or diesters, and sulfosuccinates, and one or more of these can be used.
  • Examples of the counter ion of the anionic group of the anionic surfactant include an alkali metal ion such as a sodium ion and a potassium ion; an alkaline earth metal ion such as a calcium ion and a magnesium ion; an ammonium ion; an alkanol group having 2 or 3 carbon atoms (Eg, monoethanolammonium, diethanolammonium, triethanolammonium, triisopropanolammonium, etc.) having 1 to 3 amino acids.
  • alkali metal ion such as a sodium ion and a potassium ion
  • an alkaline earth metal ion such as a calcium ion and a magnesium ion
  • an ammonium ion an alkanol group having 2 or 3 carbon atoms (Eg, monoethanolammonium, diethanolammonium, triethanolammonium, triisopropanolammonium, etc.) having 1 to 3 amino acids.
  • alkyl ether sulfate examples include a polyoxyethylene alkyl ether sulfate such as ammonium laureth sulfate
  • alkyl ether carboxylate examples include a polyoxyethylene alkyl ether acetate such as sodium laureth acetate.
  • the anionic surfactant is more preferably one or more selected from the group consisting of alkyl ether sulfates and alkyl ether carboxylate salts, still more preferably polyoxyethylene alkyl ether sulfate and One or more selected from the group consisting of polyoxyethylene alkyl ether acetates, and even more preferably one or more selected from the group consisting of ammonium laureth sulfate and sodium laureth acetate.
  • Nonionic surfactant polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene fatty acid ester, alkyl glucoside, alkyl glyceryl ether, higher fatty acid sucrose ester, polyglycerin fatty acid ester , Polyoxyethylene hydrogenated castor oil, alkyl saccharides, alkyl amine oxides, and alkyl amido amine oxides.
  • polyoxyalkylene alkyl ethers one or more selected from the group consisting of polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene fatty acid esters, alkyl glucosides, and alkyl glyceryl ethers are preferable,
  • One or more selected from the group consisting of alkylene alkyl ethers and alkyl glyceryl ethers is more preferred.
  • the fatty acid in the ester, higher fatty acid sucrose ester and polyglycerin fatty acid ester preferably has 8 to 22 carbon atoms, more preferably 10 to 18 carbon atoms.
  • amphoteric surfactant examples include betaine surfactants such as imidazoline betaine, alkyldimethylaminoacetate betaine, and fatty acid amide propyl betaine; alkyl sultaine, alkylhydroxysultaine, alkylamidosultaine, and alkylamidohydroxysultaine.
  • betaine surfactants such as imidazoline betaine, alkyldimethylaminoacetate betaine, and fatty acid amide propyl betaine
  • alkyl sultaine alkylhydroxysultaine, alkylamidosultaine, and alkylamidohydroxysultaine.
  • a sultaine-based surfactant one or more of these can be used.
  • As the betaine surfactant a fatty acid amidopropyl betaine is preferred.
  • the fatty acid amide propyl betaine preferably has an acyl group having 8 to 22 carbon atoms, more preferably 10 to 18 carbon atoms, amide laurate amide betaine (lauramidopropyl betaine), palm kernel oil fatty acid amide propyl betaine, And at least one selected from the group consisting of coconut oil fatty acid amidopropyl betaine, and lauric acid amidopropyl betaine is more preferred.
  • alkylhydroxysultaine is preferable, alkylhydroxysultaine having an alkyl group having 8 to 22 carbon atoms, and further having 10 to 18 carbon atoms is more preferable, and laurylhydroxysultaine is more preferable.
  • the content or blending amount of the component (C) in the hair cosmetic is preferably 0.3% by mass or more, more preferably 0.5% by mass or more.
  • the content is more preferably 0.8% by mass or more, and from the viewpoint of untangling the hair, it is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.
  • the specific range of the content or the compounding amount of the component (C) in the hair cosmetic is preferably 0.3 to 30% by mass, more preferably 0.5 to 20% by mass, and further preferably 0.8 to 15% by mass. % By mass.
  • the hair cosmetic of the present invention is intended to impart smoothness upon rinsing to the treated hair, and from the viewpoint of stability and viscosity adjustment when the form of the hair cosmetic is liquid, paste or cream. Further, it is preferable that a higher alcohol is contained or blended as the component (D).
  • a higher alcohol is contained or blended as the component (D).
  • an aliphatic primary alcohol having 12 to 22 carbon atoms is preferable, for example, cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol, myristyl alcohol, behenyl alcohol, cetostearyl alcohol and the like. And one or more of these can be used.
  • the content or the amount of the component (D) in the hair cosmetic is preferably 0.1% by mass or more, more preferably 0.2% by mass, from the viewpoint of adjusting the viscosity to be easy to use.
  • % Or more more preferably 1.0% by mass or more, and preferably 10% by mass or less, more preferably 9.% or less, from the viewpoint of improving the drying speed of the treated hair and smoothing the hair upon rinsing.
  • the specific range of the content or the compounding amount of the component (D) in the hair cosmetic is preferably 0.1 to 10% by mass, more preferably 0.2 to 9.0% by mass, and further preferably 0.2 to 9.0% by mass. To 8.0% by mass, more preferably 0.2 to 5.0% by mass, still more preferably 1.0 to 5.0% by mass.
  • the hair cosmetic composition of the present invention has a viewpoint of dissolving the components (A) and (B), and as the component (C), among the cationic surfactants, alkyldimethylamine, alkoxyalkyldimethylamine, alkylamidoalkyldimethylamine and the like.
  • the organic acid or inorganic acid include the organic acids and inorganic acids exemplified in (iv) alkyldimethylamine and salts thereof, which are cationic surfactants, and organic acids are preferable.
  • organic acid examples include monocarboxylic acids such as acetic acid and propionic acid; dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, and phthalic acid; polycarboxylic acids such as polyglutamic acid; glycolic acid , Lactic acid, hydroxyacrylic acid, glyceric acid, malic acid, tartaric acid, hydroxycarboxylic acids such as citric acid; glutamic acid, acidic amino acids such as aspartic acid, and the like; and dicarboxylic acids, hydroxycarboxylic acids, and acidic amino acids. One or more selected ones are preferable.
  • dicarboxylic acid one or more selected from the group consisting of maleic acid and succinic acid is more preferable.
  • hydroxycarboxylic acid one or more selected from the group consisting of glycolic acid, lactic acid and malic acid is more preferred. Glutamic acid is more preferred as the acidic amino acid.
  • the content or blending amount in the hair cosmetic is preferably 0.005% by mass or more, more preferably 0.01% by mass, from the viewpoint of dissolving the components (A) and (B).
  • the specific range of the content or blending amount of the organic acid or the inorganic acid in the hair cosmetic is preferably 0.005 to 10% by mass, more preferably 0.01 to 8.0% by mass, and still more preferably 0.1 to 8.0% by mass. It is preferably from 02 to 5.0% by mass, more preferably from 0.02 to 1.0% by mass, even more preferably from 0.02 to 0.5% by mass.
  • amines such as alkyldimethylamine, alkoxyalkyldimethylamine, and alkylamidoalkyldimethylamine are used as the component (C)
  • a suitable amount of an organic acid or inorganic acid to neutralize these to form a salt Can be appropriately contained or blended.
  • the hair cosmetic of the present invention usually contains or blends an aqueous medium.
  • the aqueous medium is preferably composed mainly of water, and may further contain or be mixed with an aqueous medium other than water.
  • aqueous media other than water include 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, diethylene glycol and dipropylene glycol. No.
  • the content of water in the aqueous medium is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and the upper limit is 100% by mass.
  • the content or blending amount of the aqueous medium in the hair cosmetic can be appropriately selected according to the dosage form of the hair cosmetic, but is usually in the range of 5 to 99% by mass, preferably 30 to 98% by mass. Range.
  • the hair cosmetic of the present invention may appropriately contain or mix other components usually added to the hair cosmetic as long as the object of the present invention is not impaired.
  • the component include polymer compounds such as cationized cellulose, hydroxyalkyl cellulose, and highly polymerized polyethylene oxide; oils; silicones other than the components (A) and (B); antioxidants; zinc pyrithione, benzalkonium chloride Anti-dandruff agents, etc .; Vitamin agents; Disinfectants; Anti-inflammatory agents; Preservatives; Chelating agents; Moisturizing agents, such as panthenol; Pearl agents; Ceramides; Polar solvent extract, proteins or hydrolysates thereof obtained from shells or pearls having a nacreous layer, proteins or hydrolysates thereof obtained from silk, protein-containing extracts obtained from seeds of legumes, Panax ginseng extracts , Rice germ extract, hibamata extract, camellia extract, aloe extract, moon peach leaf extract, chlorella extract, etc.
  • the oil include hydrocarbons such as squalene, squalane, liquid paraffin, liquid isoparaffin, and cycloparaffin; glycerides such as castor oil, cacao oil, mink oil, avocado oil, and olive oil; waxes such as beeswax, whale wax, lanolin, and carnauba wax.
  • Esters such as isopropyl palmitate, isopropyl myristate, octyldodecyl myristate, hexyl laurate, cetyl lactate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate and tridecyl isononanoate; Higher fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, coconut oil fatty acid, lanolin fatty acid, isostearyl acid, and isopalmitic acid; And the like.
  • the method for producing the hair cosmetic of the present invention is not particularly limited. For example, it can be produced by blending the components (A) and (B) and other components used as required by the method described in the examples, and mixing using a known stirring device or the like.
  • the method of using the hair cosmetic of the present invention is not particularly limited, and can be appropriately selected depending on the type, dosage form, and the like.
  • the hair cosmetic is a rinse, a conditioning agent, or a treatment agent, after washing, After washing the hair after application to the hair, and washing it off if necessary; a method of immersing the washed hair in a hair cosmetic or an aqueous solution thereof.
  • the hair cosmetic is a hair cleansing agent
  • a method of washing hair using the hair cleansing agent may be mentioned.
  • the present invention discloses a hair cosmetic and a method for preventing hair entanglement.
  • the mass ratio of the component (A) to the component (B) [(A) / (B)] is from 0.1 to 500,
  • the content of the component (A) is 0.1 to 0.6% by mass,
  • E 1 represents —R 3 —Z 1 (R 3 represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and Z 1 represents a primary to tertiary amino group-containing group. .)).
  • R 4 represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and R 5 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms.
  • R 9 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms or a trimethylsilyl group.
  • a is a number from 1 to 50
  • b is a number from 1 to 50
  • c is a number from 1 to 50
  • e is a number from 1 to 50
  • f is a number from 0 to 50.
  • the bonding form may be block-like or random.
  • a plurality of R 4 , R 5 and E 1 may be the same or different.
  • r is a number from 2 to 100
  • s is a number from 1 to 50
  • t is a number from 10 to 18
  • u is a number from 1 to 100.
  • the bonding form may be block-like or random.
  • ⁇ 2> The hair cosmetic according to ⁇ 1>, wherein the component (C) contains a cationic surfactant.
  • ⁇ 3> The hair cosmetic according to ⁇ 1> or ⁇ 2>, wherein the content or blending amount of the component (C) is 0.8 to 15% by mass.
  • ⁇ 4> The hair cosmetic according to any one of ⁇ 1> to ⁇ 3>, wherein the content or blending amount of the component (B) is 0.001 to 0.3% by mass.
  • ⁇ 5> The hair cosmetic according to any one of ⁇ 1> to ⁇ 4>, wherein the mass ratio [(A) / (B)] between the component (A) and the component (B) is 0.3 to 300.
  • ⁇ 6> The hair cosmetic according to any one of ⁇ 1> to ⁇ 5>, further containing or blending a higher alcohol (D).
  • D a higher alcohol
  • ⁇ 7> The hair cosmetic according to any one of ⁇ 1> to ⁇ 6>, which is a rinse, a conditioning agent, or a treatment agent.
  • ⁇ 8> The hair cosmetic according to any one of ⁇ 1> to ⁇ 6>, which is a hair cleansing agent.
  • a method for preventing hair entanglement comprising a step of applying the hair cosmetic according to any one of ⁇ 1> to ⁇ 7> to hair.
  • a hair entanglement preventing method comprising a step of washing the hair using the hair cosmetic according to ⁇ 8>.
  • the hair tress was rinsed with warm water for 30 seconds without passing through the hand, squeezed by hand, and then immersed in 1 L of the hair cosmetic of each example placed in a 1 L beaker.
  • the hair bundle was shaken left and right five times in a beaker, pulled up, and when the water content of the hair bundle became 20 g, the load applied when the hair bundle was first passed through the hair bundle was measured in the following manner.
  • the above-mentioned bristle bundle was set on a combing force measuring device (“KOT-0303” manufactured by Utsunomiya Seiki Co., Ltd.), and a comb (skeleton brush, 2.5 cm wide, 9.0 cm long) was vertically arranged in 5 rows and 5 mm intervals.
  • a pin having a diameter of 1 mm and a length of 2 cm) were set so as to sandwich the uppermost portion of the hair bundle, and the load (gf) applied when the comb was passed to the hair tip was measured.
  • the load was measured 1.5 mm at a time for a hair bundle having a length of 30 cm, and the maximum value of the measured values at a total of 200 points was taken as a through load.
  • the smaller the value of the combing load the higher the effect of spontaneously untangling the hair.
  • the combing load was the upper limit of measurement, 2055 gf.
  • composition of plain shampoo Ingredients (mass%) Polyoxyethylene (2.0) lauryl ether sulfate Na 15.5 Lauric acid diethanolamide 2.2 Disodium edetate 0.15 Sodium benzoate 0.18 Oxybenzone 0.03 Phosphoric acid 0.07 Sodium chloride 0.8 Fragrance 0.4 Purified water balance Total 100.0
  • Rubberless was prepared by implanting Chinese untreated hair having a length of 20 cm and a mass of about 15 g in an area of 7 cm x 4.5 cm on a 9 cm x 7 cm rubber. This tress was sufficiently moistened with warm water at 35 to 40 ° C., and then washed with the plain shampoo. After squeezing, 2 mL of the hair cosmetic prepared in each example was applied, and the hair was well blended, and then rinsed with warm water at 35 to 40 ° C. for 30 seconds to squeeze the water. The water was wiped off with a towel, and the water content of the hair bundle was adjusted to 4 g.
  • drying time After passing the comb once with a ring comb, measure the weight of the tress while drying the hair by applying a drier (weak / warm air) from a distance of 60 cm while shaking the tress with a shaker at a speed of 200 times / min.
  • Table 1 shows the average scores (rounded to the second decimal place) of the evaluations of the five panelists. If the average score of the five panelists is 3.0 or more, it can be determined that there is no squeaky feeling during rinsing and the feel is good. (Evaluation criteria) 5 "Very smooth” 4 "Smooth” 3 "Smooth without squeaky feeling when rinsing” 2 "I feel squeaky” 1 "Severely squeaks" as well as rinse after plain shampoo
  • Examples 1-5, Comparative Examples 1-2 Preparation and evaluation of hair cosmetics
  • the hair cosmetics (conditioning agents) of each example were prepared in the following manner and evaluated.
  • the component (B) and purified water were charged into a 1 L beaker and stirred. Lactic acid was added dropwise to the resulting suspension to form a transparent solution, and then component (C) was added.
  • the beaker was immersed in a water bath and heated to 75 ° C.
  • the mixture was stirred at 75 ° C. for 10 minutes, removed from the water bath, and started cooling.
  • the component (A) was added, and the mixture was cooled to 40 ° C. or lower while stirring to obtain 1 L of a liquid hair cosmetic.
  • evaluation was performed by the above method. Table 1 shows the results.
  • the compounding quantity described in Table 1 is an active ingredient amount (% by mass) of each component.
  • Table 2 shows a formulation example of a hair cleansing agent (shampoo) which is the hair cosmetic of the present invention.
  • the compounding amount described in Table 2 is the amount (% by mass) of the active ingredient of each component.
  • the hair cosmetic composition of the present invention When the hair cosmetic composition of the present invention is applied to hair, the hair can be detangled without performing an operation such as passing through the hair.
  • the hair to which the hair cosmetic has been applied dries quickly, and the smoothness of the hair upon rinsing is good.

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Abstract

This hair cosmetic is obtained by containing or blending: (A) amino-polyether-modified silicone that has a polyoxyalkylene structure in a side chain portion; and (B) amino-polyether-modified silicone having a polyoxyalkylene structure in a main chain portion.

Description

毛髪化粧料Hair cosmetics
 本発明は、毛髪化粧料に関する。 The present invention relates to a hair cosmetic.
 毛髪は生活環境(太陽光による紫外線や熱)、日常のヘアケア行動(洗髪やブラッシングによる摩擦)、化学処理(カラーリング、パーマ等)によりダメージを受けている。ダメージを受けた毛髪が擦れ合うと、表面に大きな摩擦力が発生し、絡まりが生じる。「毛髪の絡まり」は、ヘアケア行動におけるあらゆるストレスの原因となる。洗髪時にシャンプー等の毛髪洗浄剤を泡立てる操作中の指通りの悪さ、洗髪後の毛髪のすすぎ時の毛髪の指通りの悪さ等で「毛髪の絡まり」は感知される。
 洗髪後の毛髪の絡まりを解く方法として、コンディショナーやトリートメント等の毛髪化粧料を用いる場合は、これら毛髪化粧料を毛髪に塗布し絡まり部位に指を通しながら馴染ませることによって、毛髪表面に潤滑成分を行き渡らせながら毛髪の絡まりを解いている。従来の技術では、毛髪の指通りや櫛通りをよくする目的で、コンディショナーやトリートメント等の毛髪化粧料にカチオン性界面活性剤、高級アルコール、シリコーン等が配合されている。
Hair is damaged by living environment (ultraviolet light and heat by sunlight), daily hair care behavior (rubbing by hair washing and brushing), and chemical treatment (coloring, perm, etc.). When the damaged hair rubs against each other, a large frictional force is generated on the surface, which causes entanglement. "Hair entanglement" causes all the stresses in hair care behavior. "Tangle of hair" is sensed by poor finger passing during operation of lathering a hair cleansing agent such as shampoo at the time of hair washing, poor finger passing of hair when rinsing hair after washing, and the like.
When using hair cosmetics such as conditioners and treatments as a method of untangling hair after washing, apply these hair cosmetics to the hair and let them fit into the entangled area while passing the finger to lubricate the hair surface. Untangling the hair while spreading the hair. In the prior art, cationic surfactants, higher alcohols, silicones, and the like are blended in hair cosmetics such as conditioners and treatments for the purpose of improving finger passage and combing of hair.
 特許文献1には、ポリエーテルアミノ変性シリコーンとカチオン界面活性剤を用いた毛髪化粧料が、濯ぎ時、水流中での毛髪のきしみ感を抑制し、柔軟性や平滑性を向上させることで、濯ぎ時の毛髪の絡みによる損傷を予防できることが開示されている。
 特許文献2には、特定の動粘度範囲にあるアミノ変性シリコーンと、アミノポリエーテル変性シリコーンと、特定の動粘度範囲にあるジメチルポリシロキサンと、特定のアルキル型カチオンと、特定の高級アルコールを組み合わせた毛髪化粧料が毛髪の水分保持力を高めながらも、使用時の指どおりを改善し、しなやかでしっとりとした仕上がり感を与えることができ、かつ、低湿度下でのパサツキ防止とうるおい感を与えられることが開示されている。
 また特許文献3には、毛髪に適用した後洗い流して使用される毛髪化粧料において、特定構造のアミノポリエーテル共変性シリコーンと揮発性シリコーンを併用することによって、毛髪上の粘着成分吸着量が少なくなり、かつ嵩高い粘着成分が毛髪に付着し難くなること、その結果、処理後の濡れ髪が極めてばらけやすくなり、乾燥速度が向上することが開示されている。
Patent Document 1 discloses that a hair cosmetic using a polyetheramino-modified silicone and a cationic surfactant suppresses the feeling of squeaking of hair in a water stream at the time of rinsing, and improves flexibility and smoothness. It is disclosed that damage due to hair entanglement during rinsing can be prevented.
Patent Document 2 discloses a combination of an amino-modified silicone having a specific kinematic viscosity range, an aminopolyether-modified silicone, a dimethylpolysiloxane having a specific kinematic viscosity range, a specific alkyl cation, and a specific higher alcohol. While improving the moisture retention of the hair, the hair cosmetics improve the finger feel during use, can give a supple and moist finish, and have a feeling of moisture prevention and suppleness under low humidity. It is disclosed to be given.
Further, Patent Document 3 discloses that in hair cosmetics which are used after being applied to the hair and then washed away, by using a combination of an aminopolyether co-modified silicone having a specific structure and a volatile silicone, the amount of adsorption of adhesive components on the hair is reduced. And that the bulky adhesive component hardly adheres to the hair, and as a result, wet hair after treatment becomes extremely easy to disperse and the drying speed is improved.
特開2002-249418号公報JP-A-2002-249418 特開2013-43848号公報JP 2013-43848 A 特開2017-105760号公報JP 2017-105760 A
 本発明は、側鎖部分にポリオキシアルキレン構造を有するアミノポリエーテル変性シリコーン(A)、及び、主鎖部分にポリオキシアルキレン構造を有するアミノポリエーテル変性シリコーン(B)を含有又は配合してなる毛髪化粧料に関する。 The present invention comprises or blends an aminopolyether-modified silicone (A) having a polyoxyalkylene structure in a side chain portion and an aminopolyether-modified silicone (B) having a polyoxyalkylene structure in a main chain portion. Related to hair cosmetics.
発明の詳細な説明Detailed description of the invention
[毛髪化粧料]
 本発明の毛髪化粧料は、側鎖部分にポリオキシアルキレン構造を有するアミノポリエーテル変性シリコーン(A)(以下、「成分(A)」ともいう)、及び、主鎖部分にポリオキシアルキレン構造を有するアミノポリエーテル変性シリコーン(B)(以下、「成分(B)」ともいう)を含有又は配合してなることを特徴とする。成分(A)及び成分(B)中のアミノ基は1~3級アミノ基のいずれでもよい。また、該アミノ基は成分(A)及び成分(B)の主鎖部分、側鎖部分のいずれに存在していてもよいが、側鎖部分に存在していることが好ましい。
 本発明の毛髪化粧料は上記成分(A)及び成分(B)を共に含有又は配合することで、毛髪に適用した場合に、毛髪に手を通すなどの操作を行うことなく絡まりを解くことができる。さらに、処理後の毛髪の乾燥速度を向上させ、すすぎ時の毛髪に滑らかさを付与できる。なお、ここで「成分(A)及び成分(B)を含有する」とは「成分(A)及び成分(B)を配合してなる」ことをも意味する。
[Hair cosmetics]
The hair cosmetic composition of the present invention comprises an aminopolyether-modified silicone (A) having a polyoxyalkylene structure in a side chain portion (hereinafter, also referred to as “component (A)”), and a polyoxyalkylene structure in a main chain portion. Characterized by containing or blending an aminopolyether-modified silicone (B) (hereinafter also referred to as “component (B)”). The amino group in component (A) and component (B) may be any of primary to tertiary amino groups. The amino group may be present in any of the main chain and the side chain of the component (A) and the component (B), but is preferably present in the side chain.
The hair cosmetic composition of the present invention contains or blends the above components (A) and (B) so that when applied to hair, it can be untangled without performing operations such as passing through the hair. it can. Furthermore, it is possible to improve the drying speed of the treated hair and to impart smoothness to the hair upon rinsing. Here, “containing component (A) and component (B)” also means “comprising component (A) and component (B)”.
 特許文献1~3に記載の毛髪化粧料では、使用時の毛髪の滑らかさや指通り、乾燥速度等は向上するものの、毛髪に手を通すなどの操作を行うことなく、毛髪の絡まりを自発的に解くには至っていない。
 本発明は、毛髪に適用すると、手を通すなどの操作を行うことなく絡まりを解くことができ、さらに処理後の毛髪の乾燥速度を向上させ、すすぎ時の毛髪に滑らかさを付与できる毛髪化粧料に関する。
In the hair cosmetics described in Patent Documents 1 to 3, although the smoothness of the hair at the time of use, finger passing, drying speed, etc. are improved, spontaneous entanglement of the hair is performed without performing operations such as passing through the hair. Has not been solved.
The present invention, when applied to hair, can remove entanglement without performing an operation such as passing through hands, further improve the drying speed of treated hair, and impart smoothness to hair upon rinsing About charges.
 本発明者らは、所定の構造を有する2種のアミノポリエーテル変性シリコーンを含有又は配合してなる毛髪化粧料が前記課題を解決できることを見出した。
 本発明の毛髪化粧料を毛髪に適用すると、毛髪に手を通すなどの操作を行うことなく絡まりを解くことができる。また、当該毛髪化粧料を適用した毛髪は乾燥が速く、すすぎ時の毛髪の滑らかさも良好である。
The present inventors have found that a hair cosmetic containing or blending two kinds of aminopolyether-modified silicones having a predetermined structure can solve the above problem.
When the hair cosmetic composition of the present invention is applied to hair, the hair can be detangled without performing an operation such as passing through the hair. In addition, the hair to which the hair cosmetic has been applied dries quickly, and the smoothness of the hair upon rinsing is good.
 本発明の毛髪化粧料が前記構成であることにより本発明の効果を奏する理由については定かではないが、以下のように推察される。
 洗髪中に生じる、又は洗髪後に存在する毛髪の絡まりが自発的に解けるような状態にするには、毛髪間に働く摩擦力を低下させることが重要であると考えられる。毛髪化粧料には有効成分としてシリコーンが配合されることがあるが、水溶性の高いアミノポリエーテル変性シリコーンである成分(B)を用いると、毛髪間に働く摩擦力を低下させることができるため、毛髪の絡まりを解く効果が発現すると考えられる。また成分(A)を用いることで、毛髪化粧料による処理後の毛髪の乾燥速度を向上させ、すすぎ時の毛髪に滑らかさも付与できる。
 さらに本発明者らは、成分(A)と成分(B)とを併用することで、成分(B)を単独で配合した場合よりも毛髪の絡まりをより効果的に解くことができることを見出したものである。
The reason why the effects of the present invention are exhibited by the hair cosmetic of the present invention having the above configuration is not clear, but is presumed as follows.
It is considered that it is important to reduce the frictional force acting between the hairs so that the entanglement of the hairs generated during or after the shampooing is spontaneously released. Silicone is sometimes blended as an active ingredient in hair cosmetics. However, when component (B), which is a highly water-soluble aminopolyether-modified silicone, is used, the frictional force acting between hairs can be reduced. It is thought that the effect of untangling the hair appears. In addition, by using the component (A), the drying speed of the hair after the treatment with the hair cosmetic is improved, and the hair at the time of rinsing can be given smoothness.
Furthermore, the present inventors have found that by using the component (A) and the component (B) together, the hair can be more effectively entangled than when the component (B) is blended alone. Things.
 本発明の毛髪化粧料としては、リンス、コンディショニング剤、トリートメント剤(洗い流さないタイプを含む)、スタイリング剤、毛髪洗浄剤、染毛剤、育毛剤等が挙げられる。これらの中でも、リンス、コンディショニング剤、トリートメント剤、スタイリング剤又は毛髪洗浄剤であることが好ましく、リンス、コンディショニング剤、又はトリートメント剤であることがより好ましい。
 毛髪化粧料の剤型には特に制限はなく、例えば液体状、泡状、ペースト状、クリーム状、固形状、粉末状等、任意の剤型とすることが可能である。毛髪への塗布性の観点からは、液体状、ペースト状又はクリーム状とすることが好ましく、液体状又はクリーム状とすることがより好ましい。また本発明の毛髪化粧料は、使用形態に応じて、水で希釈して水溶液の状態で用いてもよい。
Examples of the hair cosmetic of the present invention include a rinsing agent, a conditioning agent, a treatment agent (including a type that does not wash away), a styling agent, a hair cleansing agent, a hair dye, and a hair restorer. Among these, a rinsing agent, a conditioning agent, a treatment agent, a styling agent or a hair cleansing agent is preferable, and a rinsing agent, a conditioning agent, or a treatment agent is more preferable.
There is no particular limitation on the dosage form of the hair cosmetic, and any dosage form such as a liquid, a foam, a paste, a cream, a solid, and a powder can be used. From the viewpoint of applicability to hair, it is preferably in the form of a liquid, paste or cream, and more preferably in the form of liquid or cream. Further, the hair cosmetic of the present invention may be diluted with water and used in the form of an aqueous solution, depending on the use form.
<成分(A)>
 本発明の毛髪化粧料は、成分(A)として、側鎖部分にポリオキシアルキレン構造を有するアミノポリエーテル変性シリコーンを含有又は配合してなる。本発明の毛髪化粧料は成分(A)を含有又は配合することで、処理後の毛髪の乾燥速度を向上させ、すすぎ時の毛髪に滑らかさを付与できる。また、成分(A)と成分(B)とを併用すると、上記効果を維持しつつ、処理後の毛髪の絡まりを自発的に解く効果をより向上させることができる。
<Component (A)>
The hair cosmetic composition of the present invention contains or blends, as the component (A), an aminopolyether-modified silicone having a polyoxyalkylene structure in a side chain portion. By containing or blending the component (A), the hair cosmetic composition of the present invention can improve the drying speed of the treated hair and impart smoothness to the hair upon rinsing. When the component (A) and the component (B) are used in combination, the effect of spontaneously untangling the treated hair can be further improved while maintaining the above effects.
 成分(A)としては、より具体的には下記一般式(1)で表される構造を有するものが挙げられる。
Figure JPOXMLDOC01-appb-C000004

 式(1)中、Rは炭素数1以上6以下の1価の炭化水素基を示す。RはR又はEのいずれかを示す。Eは-R-Z(Rは炭素数1以上6以下の2価の炭化水素基を示し、Zは1~3級アミノ基含有基を示す。)で表される1価の基を示す。Rは炭素数1以上6以下の2価の炭化水素基を示し、Rは水素原子又は炭素数1以上4以下の1価の炭化水素基を示す。
 aは1以上50以下の数、bは1以上50以下の数、cは1以上50以下の数、dは2以上100以下の数を示す。nは2以上10以下の数を示す。括弧内の構造単位同士の結合順序は問わず、結合形態はブロック状でもランダム状でもよい。d個のOC2nは同一でも異なっていてもよい。また、複数個のR、R、R、R及びEは同一でも異なっていてもよい。
More specifically, the component (A) has a structure represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000004

In the formula (1), R 1 represents a monovalent hydrocarbon group having 1 to 6 carbon atoms. R 2 represents either R 1 or E 1 . E 1 is a monovalent group represented by —R 3 —Z 1 (R 3 is a divalent hydrocarbon group having 1 to 6 carbon atoms, and Z 1 is a group containing a primary to tertiary amino group). Represents a group. R 4 represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and R 5 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms.
a is a number from 1 to 50, b is a number from 1 to 50, c is a number from 1 to 50, and d is a number from 2 to 100. n shows the number of 2 or more and 10 or less. Regardless of the bonding order of the structural units in parentheses, the bonding form may be block-like or random. d number of OC n H 2n may be the same or different. A plurality of R 1 , R 2 , R 4 , R 5 and E 1 may be the same or different.
 一般式(1)において、Rは炭素数1以上6以下の1価の炭化水素基であり、炭素数1以上6以下のアルキル基、又はフェニル基であることが好ましく、メチル基又はエチル基であることがより好ましく、メチル基であることが更に好ましい。RはR又はEのいずれかを示し、好ましくはRである。 In the general formula (1), R 1 is a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group, and a methyl group or an ethyl group And more preferably a methyl group. R 2 represents either R 1 or E 1 , and preferably R 1 .
 一般式(1)において、Eは-R-Z(Rは炭素数1以上6以下の2価の炭化水素基を示し、Zは1~3級アミノ基含有基を示す。)で表される1価の基を示す。Rは炭素数2以上4以下の2価の炭化水素基が好ましく、エチレン基、トリメチレン基、プロピレン基、又はテトラメチレン基がより好ましい。
 Zは1~3級アミノ基含有基であり、-N(R、-NR(CHN(R、又は-NR(CHN(R)CO-Rで示される基であることが好ましい。ここで、Rは水素原子又は炭素数1以上4以下の1価の炭化水素基を示し、好ましくは水素原子、メチル基又はエチル基である。Rは炭素数1以上4以下の1価の炭化水素基を示し、好ましくはメチル基又はエチル基である。Rは炭素数1以上4以下の1価の炭化水素基を示す。pは2以上6以下の数を示し、好ましくは2以上4以下の数である。
In the general formula (1), E 1 represents —R 3 —Z 1 (R 3 represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and Z 1 represents a primary to tertiary amino group-containing group. ) Represents a monovalent group. R 3 is preferably a divalent hydrocarbon group having 2 to 4 carbon atoms, and more preferably an ethylene group, a trimethylene group, a propylene group, or a tetramethylene group.
Z 1 is a group containing a primary to tertiary amino group, and includes —N (R 6 ) 2 , —NR 6 (CH 2 ) p N (R 6 ) 2 , or —NR 6 (CH 2 ) p N (R 7 ) is preferably a group represented by CO-R 8. Here, R 6 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and is preferably a hydrogen atom, a methyl group or an ethyl group. R 7 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms, and is preferably a methyl group or an ethyl group. R 8 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms. p represents a number of 2 or more and 6 or less, and is preferably a number of 2 or more and 4 or less.
 一般式(1)において、好ましいE基は、-(CH-NH、-(CH-N(CH、-(CH-NH-(CH-NH、又は-(CH-NH-(CH-N(CHであり、より好ましくは-(CH-NHである。 In the general formula (1), preferred E 1 groups are — (CH 2 ) 3 —NH 2 , — (CH 2 ) 3 —N (CH 3 ) 2 , — (CH 2 ) 3 —NH— (CH 2 ) 2- NH 2 or — (CH 2 ) 2 —NH— (CH 2 ) 2 —N (CH 3 ) 2 , more preferably — (CH 2 ) 3 —NH 2 .
 一般式(1)において、Rは炭素数1以上6以下の2価の炭化水素基を示し、炭素数2以上4以下の2価の炭化水素基が好ましく、エチレン基、トリメチレン基、プロピレン基、又はテトラメチレン基がより好ましい。
 Rは水素原子又は炭素数1以上4以下の1価の炭化水素基を示し、メチル基又はエチル基が好ましい。
In the general formula (1), R 4 represents a divalent hydrocarbon group having 1 to 6 carbon atoms, preferably a divalent hydrocarbon group having 2 to 4 carbon atoms, and ethylene, trimethylene, and propylene groups. Or a tetramethylene group is more preferred.
R 5 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms, and is preferably a methyl group or an ethyl group.
 成分(A)は、下記一般式(1-1)で表されるものであることがより好ましい。
Figure JPOXMLDOC01-appb-C000005

 式(1-1)中、E、R、R、a、b、cは前記と同じである。Rは炭素数1以上4以下の1価の炭化水素基又はトリメチルシリル基を示す。eは1以上50以下の数、fは0以上50以下、好ましくは1以上50以下の数を示す。
 Rは、メチル基、エチル基又はトリメチルシリル基が好ましく、トリメチルシリル基がより好ましい。
The component (A) is more preferably represented by the following general formula (1-1).
Figure JPOXMLDOC01-appb-C000005

In the formula (1-1), E 1 , R 4 , R 5 , a, b, and c are the same as described above. R 9 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms or a trimethylsilyl group. e represents a number of 1 to 50, and f represents a number of 0 to 50, preferably 1 to 50.
R 9 is preferably a methyl group, an ethyl group or a trimethylsilyl group, more preferably a trimethylsilyl group.
 成分(A)は、オイル、エマルション等のいずれの形態のものでもよいが、オイルであることが好ましい。成分(A)の25℃における動粘度は、毛髪の絡まりを解く観点、処理後の毛髪の乾燥速度向上、及びすすぎ時の毛髪に滑らかさを付与する観点から、好ましくは4,000mm/s以下、より好ましくは3,000mm/s以下、更に好ましくは2,000mm/s以下、より更に好ましくは1,000mm/s以下、より更に好ましくは800mm/s以下、より更に好ましくは500mm/s以下、より更に好ましくは400mm/s以下であり、また、好ましくは100mm/s以上、より好ましくは200mm/s以上である。成分(A)の25℃における動粘度の具体的範囲は、好ましくは100~4,000mm2/s、より好ましくは100~3,000mm2/s、更に好ましくは100~2,000mm2/s、より更に好ましくは100~1,000mm2/s、より更に好ましくは100~800mm2/s、より更に好ましくは100~500mm2/s、より更に好ましくは200~500mm2/s、より更に好ましくは200~400mm2/sである。 The component (A) may be in any form such as an oil and an emulsion, but is preferably an oil. The kinematic viscosity at 25 ° C. of the component (A) is preferably 4,000 mm 2 / s from the viewpoint of untangling the hair, improving the drying speed of the treated hair, and imparting smoothness to the hair upon rinsing. Or less, more preferably 3,000 mm 2 / s or less, still more preferably 2,000 mm 2 / s or less, still more preferably 1,000 mm 2 / s or less, still more preferably 800 mm 2 / s or less, and still more preferably It is at most 500 mm 2 / s, more preferably at most 400 mm 2 / s, and preferably at least 100 mm 2 / s, more preferably at least 200 mm 2 / s. The specific range of the kinematic viscosity at 25 ° C. of the component (A) is preferably from 100 to 4,000 mm 2 / s, more preferably from 100 to 3,000 mm 2 / s, and still more preferably from 100 to 2,000 mm 2 / s. , More preferably 100 to 1,000 mm 2 / s, still more preferably 100 to 800 mm 2 / s, still more preferably 100 to 500 mm 2 / s, even more preferably 200 to 500 mm 2 / s, and still more preferably Is 200 to 400 mm 2 / s.
 なお、成分(A)の25℃における動粘度は、毛細管式粘度計を使って、一定容量の液体が25℃、1013.25hPa下で粘度計の毛細管を流れる時間を測定し、この流出時間と粘度計定数から次式を用いて算出される。毛細管式粘度計は、一般にウベローデやキャノン-フェンスケなどの型式が用いられる。
   動粘度(mm/s)=流出時間(秒)×粘度計定数
The kinematic viscosity at 25 ° C. of the component (A) was determined by measuring the time required for a fixed volume of liquid to flow through the capillary of the viscometer at 25 ° C. and 1013.25 hPa using a capillary viscometer. It is calculated from the viscometer constant using the following equation. As the capillary viscometer, a type such as Ubbelohde or Cannon-Fenske is generally used.
Kinematic viscosity (mm 2 / s) = Outflow time (sec) x Viscometer constant
 成分(A)は、1種又は2種以上を組み合わせて用いることができる。
 成分(A)として、市販のアミノポリエーテル変性シリコーンを用いることもできる。例えば、EVONIC INDUSTRY社製の「ABIL SOFT AF100」(一般式(1-1)で表されるアミノポリエーテル変性シリコーン(メトキシPEG/PPG-7/3 アミノプロピルジメチコン)、粘度:400mm/s)、信越化学工業(株)製の「X-22-3939A」(粘度:2,800mm/s)、ルブリゾール社製の「Silsense A21」(PEG7-アモジメチコン、粘度:250mm/s)等が挙げられる。
Component (A) can be used alone or in combination of two or more.
As the component (A), a commercially available aminopolyether-modified silicone can also be used. For example, “ABIL SOFT AF100” (aminopolyether-modified silicone represented by the general formula (1-1) (methoxy PEG / PPG-7 / 3 aminopropyl dimethicone) manufactured by EVONIC INDUSTRY, viscosity: 400 mm 2 / s) “X-22-3939A” (viscosity: 2,800 mm 2 / s) manufactured by Shin-Etsu Chemical Co., Ltd., “Silsense A21” (PEG7-amodimethicone, viscosity: 250 mm 2 / s) manufactured by Lubrizol, and the like. No.
 毛髪化粧料中の成分(A)の含有量又は配合量は、毛髪の絡まりを解く観点、処理後の毛髪の乾燥速度向上、及びすすぎ時の毛髪に滑らかさを付与する観点から、好ましくは0.01質量%以上、より好ましくは0.05質量%以上、更に好ましくは0.1質量%以上であり、また、処理後の毛髪の乾燥速度向上及びすすぎ時の毛髪に滑らかさを付与する観点から、好ましくは5.0質量%以下、より好ましくは3.0質量%以下、更に好ましくは1.0質量%以下、より更に好ましくは0.8質量%以下、より更に好ましくは0.6質量%以下である。毛髪化粧料中の成分(A)の含有量又は配合量の具体的範囲は、好ましくは0.01~5.0質量%、より好ましくは0.01~3.0質量%、更に好ましくは0.01~1.0質量%、より更に好ましくは0.05~0.8質量%、より更に好ましくは0.1~0.6質量%である。 The content or compounding amount of the component (A) in the hair cosmetic is preferably 0 from the viewpoint of untangling the hair, improving the drying speed of the treated hair, and imparting smoothness to the hair during rinsing. 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, and a viewpoint of improving the drying speed of the treated hair and imparting smoothness to the hair during rinsing. From 5.0 mass% or less, more preferably 3.0 mass% or less, further preferably 1.0 mass% or less, still more preferably 0.8 mass% or less, and still more preferably 0.6 mass%. % Or less. The specific range of the content or blending amount of the component (A) in the hair cosmetic is preferably 0.01 to 5.0% by mass, more preferably 0.01 to 3.0% by mass, and still more preferably 0 to 3.0% by mass. 0.01 to 1.0% by mass, more preferably 0.05 to 0.8% by mass, still more preferably 0.1 to 0.6% by mass.
<成分(B)>
 本発明の毛髪化粧料は、成分(B)として、主鎖部分にポリオキシアルキレン構造を有するアミノポリエーテル変性シリコーンを含有又は配合してなる。本発明の毛髪化粧料は成分(B)を含有又は配合することで、前述した作用機構により、毛髪に適用すると、毛髪に手を通すなどの操作を行うことなく絡まりを自発的に解くことができる。
<Component (B)>
The hair cosmetic composition of the present invention contains or blends, as the component (B), an aminopolyether-modified silicone having a polyoxyalkylene structure in the main chain. By containing or blending the component (B), the hair cosmetic of the present invention can spontaneously disentangle without applying an operation such as passing through the hair when applied to the hair by the above-mentioned action mechanism. it can.
 成分(B)としては、より具体的には下記一般式(2)で表される構造を有するものが挙げられる。
Figure JPOXMLDOC01-appb-C000006

 式(2)中、R11は水素原子又は炭素数1以上6以下の1価の炭化水素基を示す。R12はR11又はEのいずれかを示す。Eは-R13-Z(R13は単結合、又は炭素数1以上20以下の2価の炭化水素基を示し、Zは1~3級アミノ基含有基を示す。)で表される1価の基を示す。Yは炭素数1以上6以下のアルキレン基を示す。
 rは2以上の数、sは1以上の数、tは4以上100以下の数、uは1以上の数を示す。mは2以上10以下の数を示す。括弧内の構造単位同士の結合順序は問わず、結合形態はブロック状でもランダム状でもよい。t個のC2mOは同一でも異なっていてもよい。また、複数個のR11、R12、及びEは同一でも異なっていてもよい。
More specifically, the component (B) includes those having a structure represented by the following general formula (2).
Figure JPOXMLDOC01-appb-C000006

In the formula (2), R 11 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R 12 represents either R 11 or E 2 . E 2 is represented by —R 13 —Z 2 (R 13 represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and Z 2 represents a primary-tertiary amino group-containing group). A monovalent group represented by Y represents an alkylene group having 1 to 6 carbon atoms.
r is a number of 2 or more, s is a number of 1 or more, t is a number of 4 or more and 100 or less, and u is a number of 1 or more. m represents a number of 2 or more and 10 or less. Regardless of the bonding order of the structural units in parentheses, the bonding form may be block-like or random. The t C m H 2m O may be the same or different. Further, a plurality of R 11 , R 12 and E 2 may be the same or different.
 一般式(2)において、R11は水素原子又は炭素数1以上6以下の1価の炭化水素基である。R11はそれぞれ独立に、水素原子、炭素数1以上6以下のアルキル基、又はフェニル基であることが好ましく、メチル基又はエチル基であることがより好ましく、メチル基であることが更に好ましい。 In the general formula (2), R 11 is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R 11 is independently preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or a phenyl group, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
 一般式(2)において、R12はR11又はEのいずれかを示す。Eは-R13-Z(R13は単結合、又は炭素数1以上20以下の2価の炭化水素基を示す。)で表される1価の基を示す。
 R13は炭素数1以上20以下の2価の炭化水素基であることが好ましく、炭素数1以上20以下のアルキレン基であることがより好ましく、炭素数1以上6以下の直鎖又は分岐鎖のアルキレン基であることが更に好ましく、メチレン基、エチレン基、トリメチレン基、プロピレン基、テトラメチレン基、又はヘキサメチレン基であることがより更に好ましく、トリメチレン基又はプロピレン基であることがより更に好ましい。
In the general formula (2), R 12 represents either R 11 or E 2 . E 2 represents a monovalent group represented by —R 13 —Z 2 (R 13 represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms).
R 13 is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 20 carbon atoms, and a linear or branched chain having 1 to 6 carbon atoms. Is more preferably an alkylene group, more preferably a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, or a hexamethylene group, and still more preferably a trimethylene group or a propylene group. .
 Zは1~3級アミノ基含有基であり、-N(R14、-NR14(CHN(R14、又は-NR14(CHN(R15)CO-R16で示されるアミノ基含有基であることが好ましい。ここで、R14及びR15はそれぞれ独立に水素原子又は炭素数1以上3以下のアルキル基を示し、好ましくは水素原子又はメチル基である。R16は炭素数1以上3以下のアルキル基を示す。qは1以上6以下の数を示し、好ましくは2以上4以下の数である。 Z 2 is a group containing a primary to tertiary amino group, and includes —N (R 14 ) 2 , —NR 14 (CH 2 ) q N (R 14 ) 2 , or —NR 14 (CH 2 ) q N (R 15 ) is preferably an amino group-containing group represented by CO-R 16. Here, R 14 and R 15 each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group. R 16 represents an alkyl group having 1 to 3 carbon atoms. q shows the number of 1 or more and 6 or less, Preferably it is the number of 2 or more and 4 or less.
 一般式(2)において、好ましいE基は、-(CH-NH、-(CH-N(CH、-(CH-NH-(CH-NH、又は-(CH-NH-(CH-N(CHであり、より好ましくは、-(CH-NH-(CH-NHである。 In the general formula (2), preferred E 2 groups are — (CH 2 ) 3 —NH 2 , — (CH 2 ) 3 —N (CH 3 ) 2 , — (CH 2 ) 3 —NH— (CH 2 ) 2- NH 2 or — (CH 2 ) 2 —NH— (CH 2 ) 2 —N (CH 3 ) 2 , more preferably — (CH 2 ) 3 —NH— (CH 2 ) 2 —NH 2 .
 一般式(2)において、Yは炭素数1以上6以下のアルキレン基であり、エチレン基、プロピレン基、トリメチレン基、n-ブチレン基(テトラメチレン基)又はイソブチレン基が好ましく、n-ブチレン基又はイソブチレン基がより好ましい。ここでいうi-ブチレン基には、-CH(CH)CHCH-、-CHCH(CH)CH-、及び-CHCHCH(CH)-が含まれる。 In the general formula (2), Y is an alkylene group having 1 to 6 carbon atoms, preferably an ethylene group, a propylene group, a trimethylene group, an n-butylene group (tetramethylene group) or an isobutylene group, and more preferably an n-butylene group or Isobutylene groups are more preferred. Here, the i-butylene group includes -CH (CH 3 ) CH 2 CH 2- , -CH 2 CH (CH 3 ) CH 2- , and -CH 2 CH 2 CH (CH 3 )-.
 一般式(2)において、rは2以上の数、sは1以上の数、tは4以上100以下の数、uは1以上の数を示す。rは好ましくは2以上1000以下の数、より好ましくは2以上100以下の数である。sは好ましくは1以上50以下の数であり、tは好ましくは4以上50以下の数、より好ましくは10以上18以下の数であり、uは好ましくは1以上100以下の数である。 In the general formula (2), r represents a number of 2 or more, s represents a number of 1 or more, t represents a number of 4 or more and 100 or less, and u represents a number of 1 or more. r is preferably a number from 2 to 1,000, more preferably a number from 2 to 100. s is preferably a number of 1 or more and 50 or less, t is preferably a number of 4 or more and 50 or less, more preferably 10 or more and 18 or less, and u is preferably a number of 1 or more and 100 or less.
 一般式(2)において、mは2以上10以下の数を示し、好ましくは2以上6以下、より好ましくは2以上4以下の数である。 に お い て In the general formula (2), m represents a number of 2 or more and 10 or less, preferably 2 or more and 6 or less, more preferably 2 or more and 4 or less.
 成分(B)は、下記一般式(2-1)で表される構造を有するアミノポリエーテル変性シリコーンであることがより好ましい。更に好ましくは、下記一般式(2-1)で表される構造からなるアミノポリエーテル変性シリコーンである。
Figure JPOXMLDOC01-appb-C000007

 式(2-1)中、r、s、t、uは前記と同じである。
The component (B) is more preferably an aminopolyether-modified silicone having a structure represented by the following general formula (2-1). More preferably, it is an aminopolyether-modified silicone having a structure represented by the following general formula (2-1).
Figure JPOXMLDOC01-appb-C000007

In the formula (2-1), r, s, t, and u are the same as described above.
 成分(B)は、下記式(I)を満たすものであることが好ましい。成分(B)が下記式(I)を満たすものであると、水溶性が高いことから、毛髪の絡まりを解く効果がより優れる。
  0.01≦Si/AO≦1.6   (I)
 〔式(I)中、Siは成分(B)中のケイ素原子のモル数、AOは成分(B)中のオキシアルキレン平均付加モル数を示す。〕
 式(I)において、Si/AOは、毛髪の絡まりを解く観点から、0.01以上であり、好ましくは0.05以上、より好ましくは0.1以上、更に好ましくは0.3以上、より更に好ましくは0.5以上、より更に好ましくは0.7以上であり、同様の観点から、1.6以下、好ましくは1.4以下、より好ましくは1.2以下、更に好ましくは1.0以下、更に好ましくは0.9以下である。
 成分(B)が一般式(2)又は一般式(2-1)で表される構造からなるものである場合、前記式(I)におけるSi/AOは(r+s+1)/tで表される。
 式(I)におけるSi/AOは、H-NMR測定により測定される、ケイ素に結合した水素原子及び炭化水素基のHの積分値と、オキシアルキレン基のHの積分値とから算出できる。具体的には実施例に記載の方法により測定できる。
The component (B) preferably satisfies the following formula (I). When the component (B) satisfies the following formula (I), the effect of detangling the hair is more excellent because of high water solubility.
0.01 ≦ Si / AO ≦ 1.6 (I)
[In the formula (I), Si indicates the number of moles of silicon atoms in the component (B), and AO indicates the average addition mole number of the oxyalkylene in the component (B). ]
In the formula (I), Si / AO is 0.01 or more, preferably 0.05 or more, more preferably 0.1 or more, still more preferably 0.3 or more, from the viewpoint of untangling the hair. It is still more preferably 0.5 or more, even more preferably 0.7 or more, and from the same viewpoint, it is 1.6 or less, preferably 1.4 or less, more preferably 1.2 or less, and still more preferably 1.0 or less. Or less, more preferably 0.9 or less.
When the component (B) has a structure represented by the general formula (2) or (2-1), Si / AO in the formula (I) is represented by (r + s + 1) / t.
Si / AO in the formula (I) can be calculated from the integrated value of H of the silicon-bonded hydrogen atom and the hydrocarbon group and the integrated value of H of the oxyalkylene group measured by 1 H-NMR measurement. Specifically, it can be measured by the method described in Examples.
 成分(B)は、毛髪の絡まりを解く観点から、窒素含有率が好ましくは0.1質量%以上、より好ましくは0.2質量%以上、更に好ましくは0.5質量%以上、より更に好ましくは1.0質量%以上であり、好ましくは2.5質量%以下、より好ましくは2.0質量%以下、更に好ましくは1.8質量%以下、より更に好ましくは1.5質量%以下である。成分(B)の窒素含有率の具体的範囲は、好ましくは0.1~2.5質量%、より好ましくは0.2~2.0質量%、更に好ましくは0.5~1.8質量%、より更に好ましくは1.0~1.5質量%である。成分(B)の窒素含有率は、JIS K0113:2005に規定されている電位差滴定方法に準拠して測定される値である。 Component (B) has a nitrogen content of preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, and still more preferably from the viewpoint of untangling the hair. Is 1.0% by mass or more, preferably 2.5% by mass or less, more preferably 2.0% by mass or less, still more preferably 1.8% by mass or less, and still more preferably 1.5% by mass or less. is there. The specific range of the nitrogen content of the component (B) is preferably from 0.1 to 2.5% by mass, more preferably from 0.2 to 2.0% by mass, and still more preferably from 0.5 to 1.8% by mass. %, And still more preferably 1.0 to 1.5% by mass. The nitrogen content of the component (B) is a value measured according to the potentiometric titration method specified in JIS # K0113: 2005.
 成分(B)は、オイル、エマルション等のいずれの形態のものでもよいが、オイルであることが好ましい。
 成分(B)がオイルである場合、その25℃における動粘度は、毛髪等に効率よく残留させて本発明の効果を発揮させる観点から、好ましくは50mm/s以上、より好ましくは100mm/s以上、更に好ましくは300mm/s以上、より更に好ましくは500mm2/s以上、より更に好ましくは700mm2/s以上であり、水溶性の観点からは、好ましくは50,000mm/s以下、より好ましくは20,000mm/s以下、更に好ましくは10,000mm/s以下、より更に好ましくは5,000mm/s以下、より更に好ましくは3,000mm2/s以下、より更に好ましくは1,500mm2/s以下、より更に好ましくは1,400mm2/s以下である。成分(B)の25℃における動粘度の具体的範囲は、好ましくは50~50,000mm2/s、より好ましくは100~20,000mm2/s、更に好ましくは300~10,000mm2/s、より更に好ましくは500~5,000mm2/s、より更に好ましくは500~3,000mm2/s、より更に好ましくは500~1,500mm2/s、より更に好ましくは700~1,400mm2/sである。成分(B)の動粘度は、前記と同様の方法で測定できる。
The component (B) may be in any form such as an oil and an emulsion, but is preferably an oil.
When component (B) is an oil, kinematic viscosity at 25 ° C., from the viewpoint of exhibiting the effects of the present invention efficiently allowed to remain on the hair or the like, preferably 50 mm 2 / s or more, more preferably 100 mm 2 / s or more, more preferably 300 mm 2 / s or greater, even more preferably 500 mm 2 / s or greater, even more preferably at 700 mm 2 / s or more, from the viewpoint of water-soluble, preferably not more than 50,000 mm 2 / s , More preferably 20,000 mm 2 / s or less, further preferably 10,000 mm 2 / s or less, still more preferably 5,000 mm 2 / s or less, even more preferably 3,000 mm 2 / s or less, and still more preferably Is 1,500 mm 2 / s or less, more preferably 1,400 mm 2 / s or less. The specific range of the kinematic viscosity at 25 ° C. of the component (B) is preferably 50 to 50,000 mm 2 / s, more preferably 100 to 20,000 mm 2 / s, and still more preferably 300 to 10,000 mm 2 / s , More preferably 500 to 5,000 mm 2 / s, still more preferably 500 to 3,000 mm 2 / s, still more preferably 500 to 1,500 mm 2 / s, and still more preferably 700 to 1,400 mm 2. / S. The kinematic viscosity of the component (B) can be measured in the same manner as described above.
 成分(B)は、1種又は2種以上を組み合わせて用いることができる。
 成分(B)として、市販のアミノポリエーテル変性シリコーンを用いることもできる。例えば、一般式(2-1)で表される構造を有するアミノポリエーテル変性シリコーンとして、東レ・ダウコーニング(株)製の「SILSTYLE 201」((ビスイソブチルPEG-14/アモジメチコン)コポリマー、窒素含有率:1.2質量%、粘度:1,000mm/s、Si/AO=0.80)等が挙げられる。
Component (B) can be used alone or in combination of two or more.
As the component (B), a commercially available aminopolyether-modified silicone can also be used. For example, as an aminopolyether-modified silicone having a structure represented by the general formula (2-1), “SILTYLE 201” ((bisisobutyl PEG-14 / amodimethicone) copolymer manufactured by Dow Corning Toray Co., Ltd., nitrogen Content: 1.2% by mass, viscosity: 1,000 mm 2 / s, Si / AO = 0.80).
 毛髪化粧料中の成分(B)の含有量又は配合量は、毛髪の絡まりを解く観点、処理後の毛髪の乾燥速度向上の観点から、好ましくは0.0001質量%以上、より好ましくは0.0005質量%以上、更に好ましくは0.001質量%以上であり、また、処理後の毛髪の乾燥速度向上、及びすすぎ時の毛髪に滑らかさを付与する観点から、好ましくは5.0質量%以下、より好ましくは3.0質量%以下、更に好ましくは1.0質量%以下、より更に好ましくは0.7質量%以下、より更に好ましくは0.5質量%以下、より更に好ましくは0.3質量%以下である。毛髪化粧料中の成分(B)の含有量又は配合量の具体的範囲は、好ましくは0.0001~5.0質量%、より好ましくは0.0001~3.0質量%、更に好ましくは0.0001~1.0質量%、より更に好ましくは0.0001~0.7質量%、より更に好ましくは0.0005~0.5質量%、より更に好ましくは0.001~0.3質量%である。 The content or the amount of the component (B) in the hair cosmetic is preferably 0.0001% by mass or more, more preferably 0.1% by mass, from the viewpoint of untangling the hair and improving the drying speed of the treated hair. 0005% by mass or more, more preferably 0.001% by mass or more, and preferably 5.0% by mass or less from the viewpoint of improving the drying speed of the treated hair and imparting smoothness to the hair upon rinsing. , More preferably 3.0% by mass or less, further preferably 1.0% by mass or less, still more preferably 0.7% by mass or less, still more preferably 0.5% by mass or less, and still more preferably 0.3% by mass or less. % By mass or less. The specific range of the content or blending amount of the component (B) in the hair cosmetic is preferably 0.0001 to 5.0% by mass, more preferably 0.0001 to 3.0% by mass, and still more preferably 0% by mass. 0.0001 to 1.0% by mass, more preferably 0.0001 to 0.7% by mass, still more preferably 0.0005 to 0.5% by mass, and still more preferably 0.001 to 0.3% by mass. It is.
 本発明の毛髪化粧料において、成分(A)と成分(B)との質量比[(A)/(B)]は、処理後の毛髪の乾燥速度向上、及びすすぎ時の毛髪に滑らかさを付与する観点から、好ましくは1,000以下、より好ましくは500以下、更に好ましくは300以下、より更に好ましくは100以下、より更に好ましくは50以下、より更に好ましくは20以下である。また、毛髪の絡まりを解く観点、処理後の毛髪の乾燥速度向上、及びすすぎ時の毛髪に滑らかさを付与する観点から、好ましくは0.01以上、より好ましくは0.1以上、更に好ましくは0.3以上、より更に好ましくは0.5以上である。毛髪化粧料における成分(A)と成分(B)との質量比[(A)/(B)]の具体的範囲は、好ましくは0.01~1,000、より好ましくは0.1~500、更に好ましくは0.3~300、より更に好ましくは0.5~100.より更に好ましくは0.5~50.より更に好ましくは0.5~20である。 In the hair cosmetic composition of the present invention, the mass ratio [(A) / (B)] between the component (A) and the component (B) improves the drying speed of the treated hair and smoothens the hair during rinsing. From the viewpoint of providing, it is preferably 1,000 or less, more preferably 500 or less, still more preferably 300 or less, still more preferably 100 or less, still more preferably 50 or less, and still more preferably 20 or less. Further, from the viewpoint of untangling the hair, improving the drying speed of the treated hair, and imparting smoothness to the hair upon rinsing, preferably 0.01 or more, more preferably 0.1 or more, further more preferably 0.3 or more, more preferably 0.5 or more. The specific range of the mass ratio ((A) / (B)) of the component (A) and the component (B) in the hair cosmetic is preferably 0.01 to 1,000, more preferably 0.1 to 500. , More preferably 0.3 to 300, even more preferably 0.5 to 100. Still more preferably, from 0.5 to 50. Even more preferably, it is 0.5 to 20.
<成分(C):界面活性剤>
 本発明の毛髪化粧料は、成分(C)として、さらに界面活性剤を含有又は配合することができる。本発明の毛髪化粧料は成分(C)を含有又は配合することで、毛髪化粧料に成分(A)、(B)を分散させるとともに、毛髪化粧料としての機能を効果的に発現する。
 毛髪化粧料がリンス、コンディショニング剤、又はトリートメント剤である場合は、成分(C)がカチオン性界面活性剤を含むことが好ましく、毛髪化粧料が毛髪洗浄剤である場合は、成分(C)がアニオン性界面活性剤を含むことが好ましい。さらに、ノニオン性界面活性剤、両性界面活性剤を併用することもできる。
<Component (C): surfactant>
The hair cosmetic composition of the present invention may further contain or blend a surfactant as the component (C). By containing or blending the component (C), the hair cosmetic composition of the present invention disperses the components (A) and (B) in the hair cosmetic composition and effectively expresses the function as the hair cosmetic composition.
When the hair cosmetic is a rinse, a conditioning agent, or a treatment, the component (C) preferably contains a cationic surfactant. When the hair cosmetic is a hair cleanser, the component (C) is used. It is preferable to include an anionic surfactant. Further, a nonionic surfactant and an amphoteric surfactant can be used in combination.
(カチオン性界面活性剤)
 カチオン性界面活性剤は、毛髪化粧料に成分(A)、(B)を分散させるとともに、洗浄後の毛髪に対しコンディショニング効果を付与することができる。
 カチオン性界面活性剤としては、アルキルトリメチルアンモニウム塩、アルコキシアルキルトリメチルアンモニウム塩、ジアルキルジメチルアンモニウム塩、アルキルジメチルアミン及びその塩、アルコキシアルキルジメチルアミン及びその塩、並びに、アルキルアミドアルキルジメチルアミン及びその塩等が挙げられる。
(Cationic surfactant)
The cationic surfactant can disperse the components (A) and (B) in the hair cosmetic and can impart a conditioning effect to the washed hair.
Examples of the cationic surfactant include alkyltrimethylammonium salts, alkoxyalkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylamines and salts thereof, alkoxyalkyldimethylamines and salts thereof, and alkylamidoalkyldimethylamines and salts thereof. Is mentioned.
(i)アルキルトリメチルアンモニウム塩
 アルキルトリメチルアンモニウム塩としては、例えば下記一般式(i)で表される化合物が挙げられる。
  R21-N(CH  X    (i)
〔式中、R21は炭素数12以上22以下のアルキル基を示し、Xは塩化物イオン、臭化物イオン等のハロゲン化物イオンを示す。〕
 R21は、好ましくは炭素数16以上20以下のアルキル基である。アルキルトリメチルアンモニウム塩として、具体的には、セチルトリメチルアンモニウムクロリド、ステアリルトリメチルアンモニウムクロリド(ステアリルトリモニウムクロリド)、ベヘニルトリメチルアンモニウムクロリド等が挙げられる。
(I) Alkyl trimethyl ammonium salt Examples of the alkyl trimethyl ammonium salt include compounds represented by the following general formula (i).
R 21 -N + (CH 3) 3 X - (i)
[In the formula, R 21 represents an alkyl group having 12 to 22 carbon atoms, and X represents a halide ion such as a chloride ion and a bromide ion. ]
R 21 is preferably an alkyl group having 16 to 20 carbon atoms. Specific examples of the alkyltrimethylammonium salt include cetyltrimethylammonium chloride, stearyltrimethylammonium chloride (stearyltrimonium chloride), behenyltrimethylammonium chloride, and the like.
(ii)アルコキシアルキルトリメチルアンモニウム塩
 アルコキシアルキルトリメチルアンモニウム塩としては、例えば下記一般式(ii)で表される化合物が挙げられる。
  R22-O-R23-N(CH  X    (ii)
〔式中、R22は炭素数12以上22以下のアルキル基を示し、R23はヒドロキシ基が置換していてもよいエチレン基又はプロピレン基を示す。Xは上記と同じである。〕
 R22は、好ましくは炭素数16以上20以下のアルキル基である。アルコキシアルキルトリメチルアンモニウム塩として、具体的には、ステアロキシプロピルトリメチルアンモニウムクロリド、ステアロキシエチルトリメチルアンモニウムクロリド、ステアロキシヒドロキシプロピルトリメチルアンモニウムクロリド等が挙げられる。
(Ii) Alkoxyalkyltrimethylammonium salt Examples of the alkoxyalkyltrimethylammonium salt include compounds represented by the following general formula (ii).
R 22 -O-R 23 -N + (CH 3) 3 X - (ii)
[Wherein, R 22 represents an alkyl group having 12 or more and 22 or less carbon atoms, and R 23 represents an ethylene group or a propylene group which may be substituted by a hydroxy group. X - is the same as above. ]
R 22 is preferably an alkyl group having 16 to 20 carbon atoms. Specific examples of the alkoxyalkyltrimethylammonium salt include stearoxypropyltrimethylammonium chloride, stearoxyethyltrimethylammonium chloride, stearoxyhydroxypropyltrimethylammonium chloride and the like.
(iii)ジアルキルジメチルアンモニウム塩
 ジアルキルジメチルアンモニウム塩としては、例えば下記一般式(iii)で表される化合物が挙げられる。
  (R24-N(CH  X    (iii)
〔式中、R24はそれぞれ独立に炭素数12以上22以下のアルキル基を示す。Xは上記と同じである。〕
 R24は、好ましくは炭素数16以上20以下のアルキル基である。ジアルキルジメチルアンモニウム塩として、具体的には、ジステアリルジメチルアンモニウムクロリド等が挙げられる。
(Iii) Dialkyldimethylammonium salt Examples of the dialkyldimethylammonium salt include compounds represented by the following general formula (iii).
(R 24) 2 -N + ( CH 3) 2 X - (iii)
[Wherein, R 24 independently represents an alkyl group having 12 to 22 carbon atoms. X - is the same as above. ]
R 24 is preferably an alkyl group having 16 to 20 carbon atoms. Specific examples of the dialkyldimethylammonium salt include distearyldimethylammonium chloride.
(iv)アルキルジメチルアミン及びその塩
 アルキルジメチルアミンは、酸と反応して第4級アンモニウム塩となり、界面活性剤となる。従って、ここでは、アルキルジメチルアミン及びその塩をカチオン性界面活性剤と定義する。また、その含有量は、アルキルジメチルアミンの質量で換算する。アルキルジメチルアミン及びその塩としては、例えば下記一般式(iv)で表される化合物及びその塩が挙げられる。
  R25-N(CH    (iv)
〔式中、R25は炭素数12以上22以下のアルキル基を示す。〕
 R25は、好ましくは炭素数16以上20以下のアルキル基である。
 塩としては、有機酸又は無機酸による塩が挙げられる。有機酸としては、例えば、酢酸、プロピオン酸等のモノカルボン酸;マロン酸、コハク酸、グルタル酸、アジピン酸、マレイン酸、フマル酸、フタル酸等のジカルボン酸;ポリグルタミン酸等のポリカルボン酸;グリコール酸、乳酸、ヒドロキシアクリル酸、グリセリン酸、リンゴ酸、酒石酸、クエン酸等のヒドロキシカルボン酸;グルタミン酸、アスパラギン酸等の酸性アミノ酸等が挙げられる。無機酸としては、例えば、塩酸、硫酸、リン酸等が挙げられる。これらの中では、有機酸が好ましく、ジカルボン酸、ヒドロキシカルボン酸、及び酸性アミノ酸からなる群から選ばれる1種以上がより好ましい。ジカルボン酸としてはマレイン酸及びコハク酸からなる群から選ばれる1種以上がより好ましい。ヒドロキシカルボン酸としてはグリコール酸、乳酸及びリンゴ酸からなる群から選ばれる1種以上がより好ましい。酸性アミノ酸としてはグルタミン酸がより好ましい。
 具体的なアルキルジメチルアミン及びその塩としては、N,N-ジメチルベヘニルアミン、N,N-ジメチルステアリルアミン及びそれらの有機酸塩が挙げられ、N,N-ジメチルベヘニルアミンの乳酸塩、N,N-ジメチルステアリルアミンのグリコール酸塩などが好ましい。
(Iv) Alkyldimethylamine and a salt thereof Alkyldimethylamine reacts with an acid to form a quaternary ammonium salt, which serves as a surfactant. Therefore, here, alkyldimethylamine and its salt are defined as a cationic surfactant. The content is converted by the mass of alkyldimethylamine. Examples of the alkyldimethylamine and a salt thereof include a compound represented by the following general formula (iv) and a salt thereof.
R 25 -N (CH 3 ) 2 (iv)
[In the formula, R 25 represents an alkyl group having 12 to 22 carbon atoms. ]
R 25 is preferably an alkyl group having 16 to 20 carbon atoms.
Examples of the salt include a salt with an organic acid or an inorganic acid. Examples of the organic acid include monocarboxylic acids such as acetic acid and propionic acid; dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, and phthalic acid; polycarboxylic acids such as polyglutamic acid; Examples include hydroxycarboxylic acids such as glycolic acid, lactic acid, hydroxyacrylic acid, glyceric acid, malic acid, tartaric acid, and citric acid; and acidic amino acids such as glutamic acid and aspartic acid. Examples of the inorganic acid include hydrochloric acid, sulfuric acid, phosphoric acid and the like. Of these, organic acids are preferred, and one or more selected from the group consisting of dicarboxylic acids, hydroxycarboxylic acids, and acidic amino acids are more preferred. As the dicarboxylic acid, one or more selected from the group consisting of maleic acid and succinic acid is more preferable. As the hydroxycarboxylic acid, one or more selected from the group consisting of glycolic acid, lactic acid and malic acid is more preferred. Glutamic acid is more preferred as the acidic amino acid.
Specific examples of alkyldimethylamines and salts thereof include N, N-dimethylbehenylamine, N, N-dimethylstearylamine and organic acid salts thereof, and lactate of N, N-dimethylbehenylamine, Preferred are glycolates of N-dimethylstearylamine.
(v)アルコキシアルキルジメチルアミン及びその塩
 アルコキシアルキルジメチルアミンは、酸と反応して第4級アンモニウム塩となり、界面活性剤となる。従って、ここでは、アルコキシアルキルジメチルアミン及びその塩をカチオン性界面活性剤と定義する。また、その含有量は、アルコキシアルキルジメチルアミンの質量で換算する。アルコキシアルキルジメチルアミン及びその塩としては、例えば下記一般式(v)で表される化合物及びその塩が挙げられる。
  R26-O-R27-N(CH    (v)
〔式中、R26は炭素数12以上22以下のアルキル基を示し、R27はエチレン基又はプロピレン基を示す。〕
 R26は、好ましくは炭素数16以上20以下のアルキル基である。
 塩としては、有機酸又は無機酸による塩が挙げられる。当該有機酸及び無機酸の具体例としては、(iv)アルキルジメチルアミン及びその塩において例示したものが挙げられる。これらの中では、有機酸が好ましく、ジカルボン酸、ヒドロキシカルボン酸、及び酸性アミノ酸からなる群から選ばれる1種以上がより好ましい。ジカルボン酸としてはマレイン酸及びコハク酸からなる群から選ばれる1種以上がより好ましい。ヒドロキシカルボン酸としてはグリコール酸、乳酸及びリンゴ酸からなる群から選ばれる1種以上がより好ましい。酸性アミノ酸としてはグルタミン酸がより好ましい。
 具体的なアルコキシアルキルジメチルアミン及びその塩としては、N,N-ジメチル-3-ヘキサデシルオキシプロピルアミン、N,N-ジメチル-3-オクタデシルオキシプロピルアミン及びそれらの有機酸塩が挙げられ、N,N-ジメチル-3-ヘキサデシルオキシプロピルアミンの乳酸塩、N,N-ジメチル-3-オクタデシルオキシプロピルアミン(ステアロキシプロピルジメチルアミン)の乳酸塩、N,N-ジメチル-3-オクタデシルオキシプロピルアミンのグリコール酸塩が好ましい。
(V) Alkoxyalkyldimethylamine and its salt Alkoxyalkyldimethylamine reacts with an acid to form a quaternary ammonium salt, which becomes a surfactant. Therefore, here, alkoxyalkyldimethylamine and its salt are defined as a cationic surfactant. Further, the content is converted by the mass of the alkoxyalkyldimethylamine. Examples of the alkoxyalkyldimethylamine and a salt thereof include a compound represented by the following general formula (v) and a salt thereof.
R 26 -OR 27 -N (CH 3 ) 2 (v)
[In the formula, R 26 represents an alkyl group having 12 or more and 22 or less carbon atoms, and R 27 represents an ethylene group or a propylene group. ]
R 26 is preferably an alkyl group having 16 to 20 carbon atoms.
Examples of the salt include a salt with an organic acid or an inorganic acid. Specific examples of the organic acid and the inorganic acid include those exemplified in (iv) alkyldimethylamine and salts thereof. Of these, organic acids are preferred, and one or more selected from the group consisting of dicarboxylic acids, hydroxycarboxylic acids, and acidic amino acids are more preferred. As the dicarboxylic acid, one or more selected from the group consisting of maleic acid and succinic acid is more preferable. As the hydroxycarboxylic acid, one or more selected from the group consisting of glycolic acid, lactic acid and malic acid is more preferred. Glutamic acid is more preferred as the acidic amino acid.
Specific examples of alkoxyalkyldimethylamines and salts thereof include N, N-dimethyl-3-hexadecyloxypropylamine, N, N-dimethyl-3-octadecyloxypropylamine and organic acid salts thereof. Lactate of N, N-dimethyl-3-hexadecyloxypropylamine, lactate of N, N-dimethyl-3-octadecyloxypropylamine (stearoxypropyldimethylamine), N, N-dimethyl-3-octadecyloxypropyl A glycolate of an amine is preferred.
(vi)アルキルアミドアルキルジメチルアミン及びその塩
 アルキルアミドアルキルジメチルアミンは、酸と反応して第4級アンモニウム塩となり、界面活性剤となる。従って、ここでは、アルキルアミドアルキルジメチルアミン及びその塩をカチオン性界面活性剤と定義する。また、その含有量は、アルキルアミドアルキルジメチルアミンの質量で換算する。アルキルアミドアルキルジメチルアミン及びその塩としては、例えば下記一般式(vi)で表される化合物及びその塩が挙げられる。
  R28-C(=O)NH-R29-N(CH    (vi)
〔式中、R28は炭素数11以上21以下のアルキル基を示し、R29はエチレン基又はプロピレン基を示す。〕
 R28は、好ましくは炭素数15以上19以下のアルキル基である。
 塩としては、有機酸又は無機酸による塩が挙げられる。当該有機酸及び無機酸の具体例としては、(iv)アルキルジメチルアミン及びその塩において例示したものが挙げられる。これらの中では、有機酸が好ましく、ジカルボン酸、ヒドロキシカルボン酸、及び酸性アミノ酸からなる群から選ばれる1種以上がより好ましい。ジカルボン酸としてはマレイン酸及びコハク酸からなる群から選ばれる1種以上がより好ましい。ヒドロキシカルボン酸としてはグリコール酸、乳酸及びリンゴ酸からなる群から選ばれる1種以上がより好ましい。酸性アミノ酸としてはグルタミン酸がより好ましい。
 具体的なアルキルアミドアルキルジメチルアミン及びその塩としては、N-[3-(ジメチルアミノ)プロピル]ドコサナミド、N-[3-(ジメチルアミノ)プロピル]ステアラミド及びそれらの有機酸塩が挙げられ、N-[3-(ジメチルアミノ)プロピル]ドコサナミドの乳酸塩、N-[3-(ジメチルアミノ)プロピル]ステアラミドのグリコール酸塩が好ましい。
(Vi) Alkylamidoalkyldimethylamine and its salt Alkylamidoalkyldimethylamine reacts with an acid to form a quaternary ammonium salt, which becomes a surfactant. Therefore, here, alkylamidoalkyldimethylamine and its salt are defined as a cationic surfactant. Further, the content is converted by the mass of the alkylamidoalkyldimethylamine. Examples of the alkylamidoalkyldimethylamine and a salt thereof include a compound represented by the following general formula (vi) and a salt thereof.
R 28 —C (= O) NH—R 29 —N (CH 3 ) 2 (vi)
[In the formula, R 28 represents an alkyl group having 11 to 21 carbon atoms, and R 29 represents an ethylene group or a propylene group. ]
R 28 is preferably an alkyl group having 15 to 19 carbon atoms.
Examples of the salt include a salt with an organic acid or an inorganic acid. Specific examples of the organic acid and the inorganic acid include those exemplified in (iv) alkyldimethylamine and salts thereof. Of these, organic acids are preferred, and one or more selected from the group consisting of dicarboxylic acids, hydroxycarboxylic acids, and acidic amino acids are more preferred. As the dicarboxylic acid, one or more selected from the group consisting of maleic acid and succinic acid is more preferable. As the hydroxycarboxylic acid, one or more selected from the group consisting of glycolic acid, lactic acid and malic acid is more preferred. Glutamic acid is more preferred as the acidic amino acid.
Specific examples of the alkylamidoalkyldimethylamine and a salt thereof include N- [3- (dimethylamino) propyl] docosanamide, N- [3- (dimethylamino) propyl] stearamide and an organic acid salt thereof. Lactates of-[3- (dimethylamino) propyl] docosanamid and glycolates of N- [3- (dimethylamino) propyl] stearamide are preferred.
 上記(i)~(vi)以外のカチオン性界面活性剤としては、エチル硫酸ラノリン脂肪酸アミノプロピルエチルジメチルアンモニウム(アルカノイルアミノプロピルジメチルエチルアンモニウムのエチル硫酸塩、アルカノイル基はラノリン由来)、エチル硫酸ラノリン脂肪酸アミノエチルトリエチルアンモニウム、エチル硫酸ラノリン脂肪酸アミノプロピルトリエチルアンモニウム、メチル硫酸ラノリン脂肪酸アミノエチルトリメチルアンモニウム、メチル硫酸ラノリン脂肪酸アミノプロピルエチルジメチルアンモニウム、エチル硫酸イソアルカン酸(C14~20)アミノプロピルエチルジメチルアンモニウム、エチル硫酸イソアルカン酸(C18~22)アミノプロピルエチルジメチルアンモニウム、エチル硫酸イソステアリン酸アミノプロピルエチルジメチルアンモニウム、エチル硫酸イソノナン酸アミノプロピルエチルジメチルアンモニウム及びアルキルトリメチルアンモニウムサッカリン等が挙げられる。 Examples of the cationic surfactants other than the above (i) to (vi) include lanolin ethyl fatty acid aminopropylethyldimethylammonium (ethyl sulfate of alkanoylaminopropyldimethylethylammonium, alkanoyl group is derived from lanolin), and lanolin fatty acid ethyl sulfate Aminoethyltriethylammonium, lanolin fatty acid aminopropyltriethylammonium ethyl sulfate, lanolin fatty acid aminoethyltrimethylammonium methyl sulfate, lanolin fatty acid aminopropylethyldimethylammonium methyl sulfate, isoalkanoic acid ethyl sulfate (C14-20) aminopropylethyldimethylammonium, ethyl sulfate Isoalkanoic acid (C18-22) aminopropylethyldimethylammonium, isostearic acid ethylsulfate Propyl ethyl dimethyl ammonium ethyl isononanoate aminopropyl dimethylammonium and alkyltrimethylammonium saccharin sulfate.
 上記の中でも、カチオン性界面活性剤としては、好ましくはアルキルトリメチルアンモニウム塩、アルコキシアルキルトリメチルアンモニウム塩、ジアルキルジメチルアンモニウム塩、アルキルジメチルアミン及びその塩、アルコキシアルキルジメチルアミン及びその塩、並びに、アルキルアミドアルキルジメチルアミン及びその塩からなる群から選ばれる1種以上であり、具体的には、前記一般式(i)~(iii)で表される化合物、並びに前記一般式(iv)~(vi)で表される化合物及びそれらの塩からなる群から選ばれる1種以上である。より好ましくは、アルキルトリメチルアンモニウム塩、並びにアルコキシアルキルジメチルアミン及びその塩からなる群から選ばれる1種以上であり、具体的には、前記一般式(i)で表される化合物、並びに、前記一般式(v)で表される化合物及びその塩からなる群から選ばれる1種以上である。更に好ましくは、アルコキシアルキルジメチルアミン又はその塩であり、より更に好ましくは、前記一般式(v)で表される化合物又はその塩であり、より更に好ましくは、N,N-ジメチル-3-ヘキサデシルオキシプロピルアミン、N,N-ジメチル-3-オクタデシルオキシプロピルアミン(ステアロキシプロピルジメチルアミン)及びそれらの有機酸塩からなる群から選ばれる1種以上である。 Among the above, the cationic surfactant is preferably an alkyltrimethylammonium salt, an alkoxyalkyltrimethylammonium salt, a dialkyldimethylammonium salt, an alkyldimethylamine and a salt thereof, an alkoxyalkyldimethylamine and a salt thereof, and an alkylamidoalkyl. At least one selected from the group consisting of dimethylamine and salts thereof, specifically, compounds represented by the above general formulas (i) to (iii), and compounds represented by the above general formulas (iv) to (vi) It is one or more selected from the group consisting of the compounds represented and their salts. More preferably, it is at least one selected from the group consisting of alkyltrimethylammonium salts, and alkoxyalkyldimethylamines and salts thereof. Specifically, the compound represented by the general formula (i); At least one selected from the group consisting of the compound represented by the formula (v) and a salt thereof. More preferably, it is an alkoxyalkyldimethylamine or a salt thereof, more preferably, the compound represented by the above general formula (v) or a salt thereof, and further more preferably, N, N-dimethyl-3-hexaamine. It is at least one selected from the group consisting of decyloxypropylamine, N, N-dimethyl-3-octadecyloxypropylamine (stearoxypropyldimethylamine) and their organic acid salts.
(アニオン性界面活性剤)
 アニオン性界面活性剤は、毛髪化粧料に成分(A)、(B)を分散させるとともに、毛髪化粧料が毛髪洗浄剤である場合に洗浄性を付与するために用いられる。
 アニオン性界面活性剤としては、例えば、アルキルベンゼンスルホン酸塩、アルキル又はアルケニルエーテル硫酸塩、アルキル又はアルケニル硫酸塩、アルキルスルホン酸塩、飽和又は不飽和脂肪酸塩、アルキル又はアルケニルエーテルカルボン酸塩、α-スルホ脂肪酸塩、N-アシルアミノ酸、リン酸モノ又はジエステル、スルホコハク酸エステル等が挙げられ、これらのうち1種又は2種以上を用いることができる。
 アニオン性界面活性剤のアニオン性基の対イオンとしては、ナトリウムイオン、カリウムイオン等のアルカリ金属イオン;カルシウムイオン、マグネシウムイオン等のアルカリ土類金属イオン;アンモニウムイオン;炭素数2又は3のアルカノール基を1~3個有するアルカノールアンモニウム(例えばモノエタノールアンモニウム、ジエタノールアンモニウム、トリエタノールアンモニウム、トリイソプロパノールアンモニウム等)が挙げられる。
 なかでも、洗浄時の泡立ちの観点から、アルキル硫酸塩、アルキルエーテル硫酸塩及びアルキルエーテルカルボン酸塩からなる群から選ばれる1種以上が好ましい。上記アルキルエーテル硫酸塩としては、例えば、ラウレス硫酸アンモニウム等のポリオキシエチレンアルキルエーテル硫酸塩が挙げられ、アルキルエーテルカルボン酸塩としてはラウレス酢酸ナトリウム等のポリオキシエチレンアルキルエーテル酢酸塩が挙げられる。
 洗浄時の泡立ちの観点から、アニオン性界面活性剤としては、より好ましくはアルキルエーテル硫酸塩及びアルキルエーテルカルボン酸塩からなる群から選ばれる1種以上、更に好ましくはポリオキシエチレンアルキルエーテル硫酸塩及びポリオキシエチレンアルキルエーテル酢酸塩からなる群から選ばれる1種以上、より更に好ましくはラウレス硫酸アンモニウム及びラウレス酢酸ナトリウムからなる群から選ばれる1種以上である。
(Anionic surfactant)
The anionic surfactant is used for dispersing the components (A) and (B) in the hair cosmetic, and for imparting detergency when the hair cosmetic is a hair cleansing agent.
Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, alkyl sulfonate, saturated or unsaturated fatty acid salt, alkyl or alkenyl ether carboxylate, α- Examples thereof include sulfo fatty acid salts, N-acyl amino acids, phosphoric acid mono- or diesters, and sulfosuccinates, and one or more of these can be used.
Examples of the counter ion of the anionic group of the anionic surfactant include an alkali metal ion such as a sodium ion and a potassium ion; an alkaline earth metal ion such as a calcium ion and a magnesium ion; an ammonium ion; an alkanol group having 2 or 3 carbon atoms (Eg, monoethanolammonium, diethanolammonium, triethanolammonium, triisopropanolammonium, etc.) having 1 to 3 amino acids.
Among them, from the viewpoint of foaming during washing, one or more selected from the group consisting of alkyl sulfates, alkyl ether sulfates, and alkyl ether carboxylates are preferred. Examples of the alkyl ether sulfate include a polyoxyethylene alkyl ether sulfate such as ammonium laureth sulfate, and examples of the alkyl ether carboxylate include a polyoxyethylene alkyl ether acetate such as sodium laureth acetate.
From the viewpoint of foaming during washing, the anionic surfactant is more preferably one or more selected from the group consisting of alkyl ether sulfates and alkyl ether carboxylate salts, still more preferably polyoxyethylene alkyl ether sulfate and One or more selected from the group consisting of polyoxyethylene alkyl ether acetates, and even more preferably one or more selected from the group consisting of ammonium laureth sulfate and sodium laureth acetate.
(ノニオン性界面活性剤)
 ノニオン性界面活性剤としては、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルケニルエーテル、ポリオキシアルキレンソルビタン脂肪酸エステル、ポリオキシアルキレン脂肪酸エステル、アルキルグルコシド、アルキルグリセリルエーテル、高級脂肪酸ショ糖エステル、ポリグリセリン脂肪酸エステル、ポリオキシエチレン硬化ヒマシ油、アルキルサッカライド、アルキルアミンオキサイド、及びアルキルアミドアミンオキサイド等が挙げられる。
 これらのうち、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルケニルエーテル、ポリオキシアルキレンソルビタン脂肪酸エステル、ポリオキシアルキレン脂肪酸エステル、アルキルグルコシド、及びアルキルグリセリルエーテルからなる群から選ばれる1種以上が好ましく、ポリオキシアルキレンアルキルエーテル及びアルキルグリセリルエーテルからなる群から選ばれる1種以上がより好ましい。
 ポリオキシアルキレンアルキルエーテル、アルキルグルコシド、アルキルグリセリルエーテル、アルキルサッカライド、アルキルアミンオキサイド、及びアルキルアミドアミンオキサイドにおけるアルキル基、ポリオキシアルキレンアルケニルエーテルにおけるアルケニル基、及び、ポリオキシアルキレンソルビタン脂肪酸エステル、ポリオキシアルキレン脂肪酸エステル、高級脂肪酸ショ糖エステル、ポリグリセリン脂肪酸エステルにおける脂肪酸は、好ましくは炭素数8以上22以下、より好ましくは炭素数10以上18以下である。
(Nonionic surfactant)
As nonionic surfactants, polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene fatty acid ester, alkyl glucoside, alkyl glyceryl ether, higher fatty acid sucrose ester, polyglycerin fatty acid ester , Polyoxyethylene hydrogenated castor oil, alkyl saccharides, alkyl amine oxides, and alkyl amido amine oxides.
Of these, one or more selected from the group consisting of polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyalkylene sorbitan fatty acid esters, polyoxyalkylene fatty acid esters, alkyl glucosides, and alkyl glyceryl ethers are preferable, One or more selected from the group consisting of alkylene alkyl ethers and alkyl glyceryl ethers is more preferred.
Polyoxyalkylene alkyl ether, alkyl glucoside, alkyl glyceryl ether, alkyl saccharide, alkyl amine oxide, alkyl group in alkyl amide amine oxide, alkenyl group in polyoxyalkylene alkenyl ether, and polyoxyalkylene sorbitan fatty acid ester, polyoxyalkylene fatty acid The fatty acid in the ester, higher fatty acid sucrose ester and polyglycerin fatty acid ester preferably has 8 to 22 carbon atoms, more preferably 10 to 18 carbon atoms.
(両性界面活性剤)
 両性界面活性剤としては、イミダゾリン系ベタイン、アルキルジメチルアミノ酢酸ベタイン、脂肪酸アミドプロピルベタイン等のベタイン系界面活性剤;アルキルスルタイン、アルキルヒドロキシスルタイン、アルキルアミドスルタイン、アルキルアミドヒドロキシスルタイン等のスルタイン系界面活性剤;が挙げられ、これらのうち1種又は2種以上を用いることができる。
 ベタイン系界面活性剤としては、脂肪酸アミドプロピルベタインが好ましい。脂肪酸アミドプロピルベタインは、炭素数8以上22以下、さらには炭素数10以上18以下のアシル基を有するものが好ましく、ラウリン酸アミドプロピルベタイン(ラウラミドプロピルベタイン)、パーム核油脂肪酸アミドプロピルベタイン、及びヤシ油脂肪酸アミドプロピルベタインからなる群から選ばれる1種以上が好ましく、ラウリン酸アミドプロピルベタインがより好ましい。
 スルタイン系界面活性剤としては、アルキルヒドロキシスルタインが好ましく、炭素数8以上22以下、さらには炭素数10以上18以下のアルキル基を有するアルキルヒドロキシスルタインがより好ましく、ラウリルヒドロキシスルタインが更に好ましい。
(Amphoteric surfactant)
Examples of the amphoteric surfactant include betaine surfactants such as imidazoline betaine, alkyldimethylaminoacetate betaine, and fatty acid amide propyl betaine; alkyl sultaine, alkylhydroxysultaine, alkylamidosultaine, and alkylamidohydroxysultaine. A sultaine-based surfactant; one or more of these can be used.
As the betaine surfactant, a fatty acid amidopropyl betaine is preferred. The fatty acid amide propyl betaine preferably has an acyl group having 8 to 22 carbon atoms, more preferably 10 to 18 carbon atoms, amide laurate amide betaine (lauramidopropyl betaine), palm kernel oil fatty acid amide propyl betaine, And at least one selected from the group consisting of coconut oil fatty acid amidopropyl betaine, and lauric acid amidopropyl betaine is more preferred.
As the sultaine-based surfactant, alkylhydroxysultaine is preferable, alkylhydroxysultaine having an alkyl group having 8 to 22 carbon atoms, and further having 10 to 18 carbon atoms is more preferable, and laurylhydroxysultaine is more preferable. .
 毛髪化粧料中の成分(C)の含有量又は配合量は、成分(A)、(B)を分散させる観点から、好ましくは0.3質量%以上、より好ましくは0.5質量%以上、更に好ましくは0.8質量%以上であり、また、毛髪の絡まりを解く観点から、好ましくは30質量%以下、より好ましくは20質量%以下、更に好ましくは15質量%以下である。毛髪化粧料中の成分(C)の含有量又は配合量の具体的範囲は、好ましくは0.3~30質量%、より好ましくは0.5~20質量%、更に好ましくは0.8~15質量%である。 From the viewpoint of dispersing the components (A) and (B), the content or blending amount of the component (C) in the hair cosmetic is preferably 0.3% by mass or more, more preferably 0.5% by mass or more. The content is more preferably 0.8% by mass or more, and from the viewpoint of untangling the hair, it is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. The specific range of the content or the compounding amount of the component (C) in the hair cosmetic is preferably 0.3 to 30% by mass, more preferably 0.5 to 20% by mass, and further preferably 0.8 to 15% by mass. % By mass.
<成分(D):高級アルコール>
 本発明の毛髪化粧料は、処理後の毛髪にすすぎ時の滑らかさを付与する観点、毛髪化粧料の剤型が液体状、ペースト状又はクリーム状である場合は安定性、粘度調整の観点から、さらに、成分(D)として高級アルコールを含有又は配合することが好ましい。高級アルコールとしては、炭素数12以上22以下の脂肪族1級アルコールが好ましく、例えば、セチルアルコール、オレイルアルコール、ステアリルアルコール、イソステアリルアルコール、2-オクチルドデカノール、ミリスチルアルコール、ベヘニルアルコール、セトステアリルアルコール等が挙げられ、これらの1種又は2種以上を用いることができる。
<Component (D): Higher alcohol>
The hair cosmetic of the present invention is intended to impart smoothness upon rinsing to the treated hair, and from the viewpoint of stability and viscosity adjustment when the form of the hair cosmetic is liquid, paste or cream. Further, it is preferable that a higher alcohol is contained or blended as the component (D). As the higher alcohol, an aliphatic primary alcohol having 12 to 22 carbon atoms is preferable, for example, cetyl alcohol, oleyl alcohol, stearyl alcohol, isostearyl alcohol, 2-octyldodecanol, myristyl alcohol, behenyl alcohol, cetostearyl alcohol and the like. And one or more of these can be used.
 成分(D)を用いる場合、毛髪化粧料中の成分(D)の含有量又は配合量は、使いやすい粘度に調整する観点から、好ましくは0.1質量%以上、より好ましくは0.2質量%以上、更に好ましくは1.0質量%以上であり、また、処理後の毛髪の乾燥速度向上、及びすすぎ時の毛髪の滑らかさの観点から、好ましくは10質量%以下、より好ましくは9.0質量%以下、更に好ましくは8.0質量%以下、より更に好ましくは5.0質量%以下である。毛髪化粧料中の成分(D)の含有量又は配合量の具体的範囲は、好ましくは0.1~10質量%、より好ましくは0.2~9.0質量%、更に好ましくは0.2~8.0質量%、より更に好ましくは0.2~5.0質量%、より更に好ましくは1.0~5.0質量%である。 When the component (D) is used, the content or the amount of the component (D) in the hair cosmetic is preferably 0.1% by mass or more, more preferably 0.2% by mass, from the viewpoint of adjusting the viscosity to be easy to use. % Or more, more preferably 1.0% by mass or more, and preferably 10% by mass or less, more preferably 9.% or less, from the viewpoint of improving the drying speed of the treated hair and smoothing the hair upon rinsing. 0 mass% or less, more preferably 8.0 mass% or less, still more preferably 5.0 mass% or less. The specific range of the content or the compounding amount of the component (D) in the hair cosmetic is preferably 0.1 to 10% by mass, more preferably 0.2 to 9.0% by mass, and further preferably 0.2 to 9.0% by mass. To 8.0% by mass, more preferably 0.2 to 5.0% by mass, still more preferably 1.0 to 5.0% by mass.
(有機酸又は無機酸)
 本発明の毛髪化粧料は、成分(A)、(B)を溶解させる観点、及び、成分(C)としてカチオン性界面活性剤のうちアルキルジメチルアミン、アルコキシアルキルジメチルアミン、アルキルアミドアルキルジメチルアミン等のアミン類を用いる場合はこれらを中和して塩とする観点から、さらに、有機酸又は無機酸を含有又は配合することが好ましい。
 有機酸又は無機酸としては、カチオン性界面活性剤である、(iv)アルキルジメチルアミン及びその塩において例示した有機酸又は無機酸が挙げられ、有機酸が好ましい。
 有機酸としては、酢酸、プロピオン酸等のモノカルボン酸;マロン酸、コハク酸、グルタル酸、アジピン酸、マレイン酸、フマル酸、フタル酸等のジカルボン酸;ポリグルタミン酸等のポリカルボン酸;グリコール酸、乳酸、ヒドロキシアクリル酸、グリセリン酸、リンゴ酸、酒石酸、クエン酸等のヒドロキシカルボン酸;グルタミン酸、アスパラギン酸等の酸性アミノ酸等が挙げられ、ジカルボン酸、ヒドロキシカルボン酸、及び酸性アミノ酸からなる群から選ばれる1種以上が好ましい。ジカルボン酸としてはマレイン酸及びコハク酸からなる群から選ばれる1種以上がより好ましい。ヒドロキシカルボン酸としてはグリコール酸、乳酸及びリンゴ酸からなる群から選ばれる1種以上がより好ましい。酸性アミノ酸としてはグルタミン酸がより好ましい。
(Organic acid or inorganic acid)
The hair cosmetic composition of the present invention has a viewpoint of dissolving the components (A) and (B), and as the component (C), among the cationic surfactants, alkyldimethylamine, alkoxyalkyldimethylamine, alkylamidoalkyldimethylamine and the like. When amines are used, it is preferable to further contain or blend an organic acid or an inorganic acid from the viewpoint of neutralizing them to form a salt.
Examples of the organic acid or inorganic acid include the organic acids and inorganic acids exemplified in (iv) alkyldimethylamine and salts thereof, which are cationic surfactants, and organic acids are preferable.
Examples of the organic acid include monocarboxylic acids such as acetic acid and propionic acid; dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, and phthalic acid; polycarboxylic acids such as polyglutamic acid; glycolic acid , Lactic acid, hydroxyacrylic acid, glyceric acid, malic acid, tartaric acid, hydroxycarboxylic acids such as citric acid; glutamic acid, acidic amino acids such as aspartic acid, and the like; and dicarboxylic acids, hydroxycarboxylic acids, and acidic amino acids. One or more selected ones are preferable. As the dicarboxylic acid, one or more selected from the group consisting of maleic acid and succinic acid is more preferable. As the hydroxycarboxylic acid, one or more selected from the group consisting of glycolic acid, lactic acid and malic acid is more preferred. Glutamic acid is more preferred as the acidic amino acid.
 有機酸又は無機酸を用いる場合、毛髪化粧料中の含有量又は配合量は、成分(A)、(B)を溶解させる観点から、好ましくは0.005質量%以上、より好ましくは0.01質量%以上、更に好ましくは0.02質量%以上であり、製品の安定性の観点から、好ましくは10質量%以下、より好ましくは8.0質量%以下、更に好ましくは5.0質量%以下、より更に好ましくは1.0質量%以下、より更に好ましくは0.5質量%以下である。
 毛髪化粧料中の有機酸又は無機酸の含有量又は配合量の具体的範囲は、好ましくは0.005~10質量%、より好ましくは0.01~8.0質量%、更に好ましくは0.02~5.0質量%、より更に好ましくは0.02~1.0質量%、より更に好ましくは0.02~0.5質量%である。
 なお、成分(C)としてアルキルジメチルアミン、アルコキシアルキルジメチルアミン、アルキルアミドアルキルジメチルアミン等のアミン類を用いる場合は、これらを中和して塩とするために好適な量の有機酸又は無機酸を適宜含有又は配合させることができる。
When an organic acid or an inorganic acid is used, the content or blending amount in the hair cosmetic is preferably 0.005% by mass or more, more preferably 0.01% by mass, from the viewpoint of dissolving the components (A) and (B). % By mass or more, more preferably 0.02% by mass or more, and from the viewpoint of product stability, preferably 10% by mass or less, more preferably 8.0% by mass or less, and still more preferably 5.0% by mass or less. , More preferably 1.0% by mass or less, even more preferably 0.5% by mass or less.
The specific range of the content or blending amount of the organic acid or the inorganic acid in the hair cosmetic is preferably 0.005 to 10% by mass, more preferably 0.01 to 8.0% by mass, and still more preferably 0.1 to 8.0% by mass. It is preferably from 02 to 5.0% by mass, more preferably from 0.02 to 1.0% by mass, even more preferably from 0.02 to 0.5% by mass.
When amines such as alkyldimethylamine, alkoxyalkyldimethylamine, and alkylamidoalkyldimethylamine are used as the component (C), a suitable amount of an organic acid or inorganic acid to neutralize these to form a salt. Can be appropriately contained or blended.
(水性媒体)
 本発明の毛髪化粧料は、通常、水性媒体を含有又は配合してなる。水性媒体は、水が主成分であることが好ましく、さらに、水以外の水性媒体を含有又は配合してもよい。水以外の水性媒体としては、エタノール、イソプロピルアルコール等の低級アルコール;1,3-ブチレングリコール、グリセリン、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール等の炭素数6以下の低分子ジオール及びトリオールが挙げられる。
 水性媒体中の水の含有量は、好ましくは50質量%以上、より好ましくは70質量%以上、更に好ましくは80質量%以上であり、上限は100質量%である。
 毛髪化粧料中の水性媒体の含有量又は配合量は、毛髪化粧料の剤型により適宜選択することができるが、通常、5~99質量%の範囲であり、好ましくは30~98質量%の範囲である。
(Aqueous medium)
The hair cosmetic of the present invention usually contains or blends an aqueous medium. The aqueous medium is preferably composed mainly of water, and may further contain or be mixed with an aqueous medium other than water. Examples of aqueous media other than water include 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, diethylene glycol and dipropylene glycol. No.
The content of water in the aqueous medium is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and the upper limit is 100% by mass.
The content or blending amount of the aqueous medium in the hair cosmetic can be appropriately selected according to the dosage form of the hair cosmetic, but is usually in the range of 5 to 99% by mass, preferably 30 to 98% by mass. Range.
(その他の成分)
 本発明の毛髪化粧料は、本発明の目的を損なわない範囲で、毛髪化粧料に通常配合されるその他の成分を適宜含有又は配合してもよい。当該成分としては、例えば、カチオン化セルロース、ヒドロキシアルキルセルロース、高重合ポリエチレンオキサイド等の高分子化合物;油剤;成分(A)及び成分(B)以外のシリコーン;酸化防止剤;ジンクピリチオン、塩化ベンザルコニウム等の抗フケ剤;ビタミン剤;殺菌剤;抗炎症剤;防腐剤;キレート剤;パンテノール等の保湿剤;パール剤;セラミド類;香料;紫外線吸収剤;染料、顔料等の着色剤;ユーカリの極性溶媒抽出物、真珠層を有する貝殻又は真珠から得られる蛋白質又はその加水分解物、シルクから得られる蛋白質又はその加水分解物、マメ科植物の種子から得られる蛋白含有抽出物、オタネニンジン抽出物、米胚芽抽出物、ヒバマタ抽出物、ツバキ抽出物、アロエ抽出物、月桃葉抽出物、クロレラ抽出物等のエキス類;メントール等の清涼剤;等が挙げられる。
 油剤としては、スクワレン、スクワラン、流動パラフィン、流動イソパラフィン、シクロパラフィン等の炭化水素;ヒマシ油、カカオ油、ミンク油、アボカド油、オリーブ油等のグリセリド類;ミツロウ、鯨ロウ、ラノリン、カルナウバロウ等のロウ類;パルミチン酸イソプロピル、ミリスチン酸イソプロピル、ミリスチン酸オクチルドデシル、ラウリン酸ヘキシル、乳酸セチル、モノステアリン酸プロピレングリコール、オレイン酸オレイル、2-エチルヘキサン酸ヘキサデシル、イソノナン酸イソノニル、イソノナン酸トリデシル等のエステル;カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘニン酸、オレイン酸、ヤシ油脂肪酸、ラノリン脂肪酸、イソステアリル酸、イソパルミチン酸等の高級脂肪酸;等が挙げられる。
(Other components)
The hair cosmetic of the present invention may appropriately contain or mix other components usually added to the hair cosmetic as long as the object of the present invention is not impaired. Examples of the component include polymer compounds such as cationized cellulose, hydroxyalkyl cellulose, and highly polymerized polyethylene oxide; oils; silicones other than the components (A) and (B); antioxidants; zinc pyrithione, benzalkonium chloride Anti-dandruff agents, etc .; Vitamin agents; Disinfectants; Anti-inflammatory agents; Preservatives; Chelating agents; Moisturizing agents, such as panthenol; Pearl agents; Ceramides; Polar solvent extract, proteins or hydrolysates thereof obtained from shells or pearls having a nacreous layer, proteins or hydrolysates thereof obtained from silk, protein-containing extracts obtained from seeds of legumes, Panax ginseng extracts , Rice germ extract, hibamata extract, camellia extract, aloe extract, moon peach leaf extract, chlorella extract, etc. Scan the like; cooling agents such as menthol; and the like.
Examples of the oil include hydrocarbons such as squalene, squalane, liquid paraffin, liquid isoparaffin, and cycloparaffin; glycerides such as castor oil, cacao oil, mink oil, avocado oil, and olive oil; waxes such as beeswax, whale wax, lanolin, and carnauba wax. Esters such as isopropyl palmitate, isopropyl myristate, octyldodecyl myristate, hexyl laurate, cetyl lactate, propylene glycol monostearate, oleyl oleate, hexadecyl 2-ethylhexanoate, isononyl isononanoate and tridecyl isononanoate; Higher fatty acids such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, coconut oil fatty acid, lanolin fatty acid, isostearyl acid, and isopalmitic acid; And the like.
<毛髪化粧料の製造方法>
 本発明の毛髪化粧料の製造方法は特に限定されない。例えば、成分(A)、(B)、及び必要に応じて用いられるその他の成分を実施例に記載の方法で配合し、公知の攪拌装置等を用いて混合することにより製造できる。
<Production method of hair cosmetics>
The method for producing the hair cosmetic of the present invention is not particularly limited. For example, it can be produced by blending the components (A) and (B) and other components used as required by the method described in the examples, and mixing using a known stirring device or the like.
<使用方法>
 本発明の毛髪化粧料の使用方法も特に限定されず、種類、剤型等に応じて適宜選択することができる
 例えば、毛髪化粧料がリンス、コンディショニング剤、又はトリートメント剤である場合は、洗浄後の毛髪に塗布してなじませた後、必要に応じ洗い流す方法;毛髪化粧料又はその水溶液に洗浄後の毛髪を浸漬させる方法;等が挙げられる。毛髪化粧料が毛髪洗浄剤である場合は、該毛髪洗浄剤を用いて毛髪を洗浄する方法が挙げられる。
 本発明の毛髪化粧料を例えば上記の方法で使用することにより、毛髪に手を通すなどの操作を行うことなく絡まりを解くことができ、処理後の毛髪の乾燥速度を向上させ、すすぎ時の毛髪に滑らかさを付与することができる。
<How to use>
The method of using the hair cosmetic of the present invention is not particularly limited, and can be appropriately selected depending on the type, dosage form, and the like.For example, when the hair cosmetic is a rinse, a conditioning agent, or a treatment agent, after washing, After washing the hair after application to the hair, and washing it off if necessary; a method of immersing the washed hair in a hair cosmetic or an aqueous solution thereof. When the hair cosmetic is a hair cleansing agent, a method of washing hair using the hair cleansing agent may be mentioned.
By using the hair cosmetic composition of the present invention, for example, in the above-described manner, it is possible to remove entanglement without performing operations such as passing through the hair, to improve the drying speed of the treated hair, It can impart smoothness to hair.
 上述の実施形態に関し、本発明は毛髪化粧料、及び、毛髪の絡まり防止方法を開示する。
<1>
 下記一般式(1-1)で表されるアミノポリエーテル変性シリコーン(A)、下記一般式(2-1)で表される構造を有するアミノポリエーテル変性シリコーン(B)、及び界面活性剤(C)を含有又は配合してなり、
 成分(A)と成分(B)との質量比[(A)/(B)]が0.1~500であり、
 成分(A)の含有量が0.1~0.6質量%であり、
 成分(A)の25℃における動粘度が100~500mm/sであり、
 成分(B)の25℃における動粘度が500~1,500mm/sである毛髪化粧料。
Figure JPOXMLDOC01-appb-C000008

 式(1-1)中、Eは-R-Z(Rは炭素数1以上6以下の2価の炭化水素基を示し、Zは1~3級アミノ基含有基を示す。)で表される1価の基を示す。Rは炭素数1以上6以下の2価の炭化水素基を示し、Rは水素原子又は炭素数1以上4以下の1価の炭化水素基を示す。Rは炭素数1以上4以下の1価の炭化水素基又はトリメチルシリル基を示す。
 aは1以上50以下の数、bは1以上50以下の数、cは1以上50以下の数、eは1以上50以下の数、fは0以上50以下の数を示す。括弧内の構造単位同士の結合順序は問わず、結合形態はブロック状でもランダム状でもよい。また、複数個のR、R及びEは同一でも異なっていてもよい。
Figure JPOXMLDOC01-appb-C000009

 式(2-1)中、rは2以上100以下の数、sは1以上50以下の数、tは10以上18以下の数、uは1以上100以下の数を示す。括弧内の構造単位同士の結合順序は問わず、結合形態はブロック状でもランダム状でもよい。
<2>
 成分(C)がカチオン性界面活性剤を含む、<1>に記載の毛髪化粧料。
<3>
 成分(C)の含有量又は配合量が0.8~15質量%である、<1>又は<2>に記載の毛髪化粧料。
<4>
 成分(B)の含有量又は配合量が0.001~0.3質量%である、<1>~<3>のいずれか1に記載の毛髪化粧料。
<5>
 成分(A)と成分(B)との質量比[(A)/(B)]が0.3~300である、<1>~<4>のいずれか1に記載の毛髪化粧料。
<6>
 さらに高級アルコール(D)を含有又は配合してなる、<1>~<5>のいずれか1に記載の毛髪化粧料。
<7>
 リンス、コンディショニング剤、又はトリートメント剤である<1>~<6>のいずれか1に記載の毛髪化粧料。
<8>
 毛髪洗浄剤である<1>~<6>のいずれか1に記載の毛髪化粧料。
<9>
 <1>~<7>のいずれか1に記載の毛髪化粧料を毛髪に塗布する工程を有する、毛髪の絡まり防止方法。
<10>
 <8>に記載の毛髪化粧料を用いて毛髪を洗浄する工程を有する、毛髪の絡まり防止方法。
Regarding the above-described embodiments, the present invention discloses a hair cosmetic and a method for preventing hair entanglement.
<1>
An aminopolyether-modified silicone (A) represented by the following general formula (1-1), an aminopolyether-modified silicone (B) having a structure represented by the following general formula (2-1), and a surfactant ( C) containing or blending,
The mass ratio of the component (A) to the component (B) [(A) / (B)] is from 0.1 to 500,
The content of the component (A) is 0.1 to 0.6% by mass,
The kinematic viscosity at 25 ° C. of the component (A) is 100 to 500 mm 2 / s,
A hair cosmetic wherein the kinematic viscosity at 25 ° C. of the component (B) is from 500 to 1,500 mm 2 / s.
Figure JPOXMLDOC01-appb-C000008

In the formula (1-1), E 1 represents —R 3 —Z 1 (R 3 represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and Z 1 represents a primary to tertiary amino group-containing group. .)). R 4 represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and R 5 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms. R 9 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms or a trimethylsilyl group.
a is a number from 1 to 50, b is a number from 1 to 50, c is a number from 1 to 50, e is a number from 1 to 50, and f is a number from 0 to 50. Regardless of the bonding order of the structural units in parentheses, the bonding form may be block-like or random. Further, a plurality of R 4 , R 5 and E 1 may be the same or different.
Figure JPOXMLDOC01-appb-C000009

In the formula (2-1), r is a number from 2 to 100, s is a number from 1 to 50, t is a number from 10 to 18 and u is a number from 1 to 100. Regardless of the bonding order of the structural units in parentheses, the bonding form may be block-like or random.
<2>
The hair cosmetic according to <1>, wherein the component (C) contains a cationic surfactant.
<3>
The hair cosmetic according to <1> or <2>, wherein the content or blending amount of the component (C) is 0.8 to 15% by mass.
<4>
The hair cosmetic according to any one of <1> to <3>, wherein the content or blending amount of the component (B) is 0.001 to 0.3% by mass.
<5>
The hair cosmetic according to any one of <1> to <4>, wherein the mass ratio [(A) / (B)] between the component (A) and the component (B) is 0.3 to 300.
<6>
The hair cosmetic according to any one of <1> to <5>, further containing or blending a higher alcohol (D).
<7>
The hair cosmetic according to any one of <1> to <6>, which is a rinse, a conditioning agent, or a treatment agent.
<8>
The hair cosmetic according to any one of <1> to <6>, which is a hair cleansing agent.
<9>
A method for preventing hair entanglement, comprising a step of applying the hair cosmetic according to any one of <1> to <7> to hair.
<10>
A hair entanglement preventing method, comprising a step of washing the hair using the hair cosmetic according to <8>.
 以下、本発明を実施例により説明するが、本発明は実施例の範囲に限定されない。なお本実施例において、各種測定及び評価は以下の方法により行った。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to the scope of the examples. In this example, various measurements and evaluations were performed by the following methods.
(成分(B)のSi/AOの測定)
 各例で使用した成分(B)(アミノポリエーテル変性シリコーン3;主鎖部分にポリオキシエチレン構造を有する)10mgをNo.3スクリューバイアルに秤り取り、窒素雰囲気下で一晩乾燥させた。得られた乾燥物に重クロロホルム(和光純薬工業(株)製:クロロホルム-d、99.8%)1mLを添加して溶解させ、H-NMR(BRUKER JAPAN社製、JH074504 AV400)により、ケイ素に結合したジメチルシリル基(6H:-0.3~0.3ppm)の積分値、及びオキシエチレン(EO)鎖(4H:3.3~3.9ppm)の積分値からSi/AOのユニット比を以下の式を用いて算出した。
Figure JPOXMLDOC01-appb-M000010
(Measurement of Si / AO of component (B))
10 mg of the component (B) (aminopolyether-modified silicone 3 having a polyoxyethylene structure in the main chain portion) used in each example was Weighed into a three screw vial and dried overnight under a nitrogen atmosphere. To the obtained dried product, 1 mL of heavy chloroform (manufactured by Wako Pure Chemical Industries, Ltd .: chloroform-d, 99.8%) was added and dissolved, and 1 H-NMR (JH07504 AV400, manufactured by BRUKER JAPAN) was used. From the integrated value of the dimethylsilyl group bonded to silicon (6H: -0.3 to 0.3 ppm) and the integrated value of the oxyethylene (EO) chain (4H: 3.3 to 3.9 ppm), a unit of Si / AO is used. The ratio was calculated using the following equation.
Figure JPOXMLDOC01-appb-M000010
(くし通し荷重測定)
 日本人の直毛を用いて、質量20g、長さ30cm、幅5.5cmの評価用毛束(後述するブリーチ剤でブリーチ処理することによりダメージを与えたもの)を作製した。この毛束を下記のプレーンシャンプーで洗浄し、すすぐ際には手を通すことで絡まりを解き、35~40℃の温水で十分に湿らせた。
 再度プレーンシャンプーを毛束に塗布し、毛先と根本を両手の掌にはさんで、円を描くように擦り合わせて毛髪が絡むように泡立てた。その毛束を、一切手を通さずに、温水で30秒間すすぎ、水気を手で絞った後、1Lビーカーに入れた各例の毛髪化粧料1Lに浸漬させた。ビーカー中で毛束を5回左右に振った後に引き上げ、毛束の含水量が20gとなったところで、下記要領で、毛束に最初にくしを通した時にかかる荷重を測定した。
 コーミングフォース測定装置(宇都宮精機(株)製「KOT-0303」)に上記毛束をセットし、くし(スケルトンブラシ、横2.5cm、縦9.0cmの面に縦に5列、5mm間隔で、直径1mm、長さ2cmのピンが並んでいるもの)2本で毛束の最上部を挟み込むようにセットし、くしを毛先まで通した時にかかる荷重(gf)を測定した。荷重は長さ30cmの毛束に対して1.5mmずつ測定し、計200点の測定値の最大値をくし通し荷重とした。くし通し荷重の値が小さいほど、毛髪の絡まりを自発的に解く効果が高いことを意味する。
 なお、毛髪化粧料に代えて精製水を用いた場合には、くし通し荷重は測定上限の2055gfであった。
(Mechanical load measurement)
Using Japanese straight hair, a hair bundle for evaluation having a mass of 20 g, a length of 30 cm, and a width of 5.5 cm (which was damaged by a bleaching treatment with a bleaching agent described later) was produced. The hair tress was washed with the following plain shampoo, and when it was rinsed, it was hand-tied to remove the entanglement and was sufficiently moistened with warm water at 35 to 40 ° C.
Plain shampoo was applied to the hair bundle again, and the tip of the hair and the root were sandwiched between palms of both hands and rubbed in a circle to lather and lather hair. The hair tress was rinsed with warm water for 30 seconds without passing through the hand, squeezed by hand, and then immersed in 1 L of the hair cosmetic of each example placed in a 1 L beaker. The hair bundle was shaken left and right five times in a beaker, pulled up, and when the water content of the hair bundle became 20 g, the load applied when the hair bundle was first passed through the hair bundle was measured in the following manner.
The above-mentioned bristle bundle was set on a combing force measuring device (“KOT-0303” manufactured by Utsunomiya Seiki Co., Ltd.), and a comb (skeleton brush, 2.5 cm wide, 9.0 cm long) was vertically arranged in 5 rows and 5 mm intervals. , A pin having a diameter of 1 mm and a length of 2 cm) were set so as to sandwich the uppermost portion of the hair bundle, and the load (gf) applied when the comb was passed to the hair tip was measured. The load was measured 1.5 mm at a time for a hair bundle having a length of 30 cm, and the maximum value of the measured values at a total of 200 points was taken as a through load. The smaller the value of the combing load, the higher the effect of spontaneously untangling the hair.
In addition, when purified water was used instead of hair cosmetics, the combing load was the upper limit of measurement, 2055 gf.
〔プレーンシャンプーの組成〕
   成分                     (質 量%)
ポリオキシエチレン(2.0)ラウリルエーテル硫酸Na 15.5
ラウリン酸ジエタノールアミド              2.2
エデト酸二ナトリウム                  0.15
安息香酸ナトリウム                   0.18
オキシベンゾン                     0.03
リン酸                         0.07
塩化ナトリウム                     0.8
香料                          0.4
精製水                         残 量 
   計                      100.0
(Composition of plain shampoo)
Ingredients (mass%)
Polyoxyethylene (2.0) lauryl ether sulfate Na 15.5
Lauric acid diethanolamide 2.2
Disodium edetate 0.15
Sodium benzoate 0.18
Oxybenzone 0.03
Phosphoric acid 0.07
Sodium chloride 0.8
Fragrance 0.4
Purified water balance
Total 100.0
〔ブリーチ処理方法〕
 花王泡ヘアブリーチL(1液)7mL、花王泡ヘアカラー(2液)14mLを混合し、質量20gの毛束に塗布して20分静置後、35~40℃の温水で十分にすすいだ。この操作を2回繰り返し、評価用毛束を作製した。
[Bleach processing method]
A mixture of 7 mL of Kao Bubble Hair Bleach L (1 solution) and 14 mL of Kao Bubble Hair Color (2 solutions) was applied to a hair bundle having a mass of 20 g, allowed to stand for 20 minutes, and then thoroughly rinsed with warm water at 35 to 40 ° C. . This operation was repeated twice to produce a hair bundle for evaluation.
(乾燥時間)
 9cm×7cmのラバーに、長さ20cm、質量約15gの中国人未処理毛を7cm×4.5cmの面積に植え込んだラバートレスを準備した。
 このトレスを35~40℃の温水で十分に湿らせた後、前記プレーンシャンプーで洗浄した。水気を絞った後、各例で調製した毛髪化粧料2mLを塗布し、毛髪によく馴染ませた後、35~40℃の温水で30秒間すすぎ、水気を絞った。タオルで水を拭き取り、毛束の含水量を4gとした。リングコームで1回櫛を通した後、200回/分の速さでトレスを振盪機で振盪させながらドライヤー(弱・温風)を60cmの距離から当てて毛髪を乾燥させながらトレス重量を測定し、毛髪の含水率が1%(含水量として0.15g)となるまでの時間を「乾燥時間」とした。
(Drying time)
Rubberless was prepared by implanting Chinese untreated hair having a length of 20 cm and a mass of about 15 g in an area of 7 cm x 4.5 cm on a 9 cm x 7 cm rubber.
This tress was sufficiently moistened with warm water at 35 to 40 ° C., and then washed with the plain shampoo. After squeezing, 2 mL of the hair cosmetic prepared in each example was applied, and the hair was well blended, and then rinsed with warm water at 35 to 40 ° C. for 30 seconds to squeeze the water. The water was wiped off with a towel, and the water content of the hair bundle was adjusted to 4 g. After passing the comb once with a ring comb, measure the weight of the tress while drying the hair by applying a drier (weak / warm air) from a distance of 60 cm while shaking the tress with a shaker at a speed of 200 times / min. The time required for the water content of the hair to reach 1% (0.15 g as the water content) was defined as "drying time".
(すすぎ時の毛髪の感触評価)
 乾燥時間評価で準備したラバートレスを35~40℃の温水で十分に湿らせた後、前記プレーンシャンプーで洗浄した。水気を絞った後、各例で調製した毛髪化粧料2mLを塗布し、毛髪によく馴染ませた後、35~40℃の温水ですすぎながら、すすぎ時の毛髪の感触評価を5人のパネラーにより行った。
 「非常に滑らか」を5、「すすぎ時のきしみ感がなく滑らか」を3、プレーンシャンプー後のすすぎと同等に「ひどくきしむ」を1とし、5段階評価とした。5人のパネラーの評価の平均評点(小数第2位を四捨五入)を表1に示した。5人のパネラーの平均評点が3.0以上であれば、すすぎ時のきしみ感がなく感触が良好であると判断できる。
(評価基準)
5 「非常に滑らか」
4 「滑らか」
3 「すすぎ時のきしみ感がなく滑らか」
2 「きしみ感を感じる」
1 プレーンシャンプー後のすすぎと同等に「ひどくきしむ」
(Evaluation of the feel of hair during rinsing)
The rubberless prepared in the evaluation of the drying time was sufficiently moistened with warm water at 35 to 40 ° C., and then washed with the plain shampoo. After squeezing the water, apply 2 mL of the hair cosmetic prepared in each example, and after familiarizing the hair, rinse the hair with warm water of 35 to 40 ° C., and evaluate the feel of the hair at the time of rinsing by five panelists. went.
"Very smooth" was 5, "Smooth without squeaky feeling during rinsing" was 3, and "Severely squeaky" was 1 as in the case of rinsing after plain shampoo. Table 1 shows the average scores (rounded to the second decimal place) of the evaluations of the five panelists. If the average score of the five panelists is 3.0 or more, it can be determined that there is no squeaky feeling during rinsing and the feel is good.
(Evaluation criteria)
5 "Very smooth"
4 "Smooth"
3 "Smooth without squeaky feeling when rinsing"
2 "I feel squeaky"
1 "Severely squeaks" as well as rinse after plain shampoo
実施例1~5、比較例1~2(毛髪化粧料の調製及び評価)
 表1に示す配合に従って下記の要領で各例の毛髪化粧料(コンディショニング剤)を調製し、評価を行った。
 1Lビーカーに成分(B)、及び精製水を投入して攪拌した。得られた懸濁液に乳酸を滴下して透明な溶液とした後に成分(C)を添加し、ビーカーをウォーターバスに浸して75℃まで昇温した。次いで、あらかじめ混合しておいた成分(D)とジプロピレングリコールを添加した後、75℃で10分攪拌し、ウォーターバスから外して冷却を開始した。成分(A)を添加し、攪拌しながら40℃以下になるまで冷却して、1Lの液体状の毛髪化粧料を得た。
 この毛髪化粧料を用いて、前記方法で評価を実施した。結果を表1に示す。なお、表1に記載した配合量は各成分の有効成分量(質量%)である。
Examples 1-5, Comparative Examples 1-2 (Preparation and evaluation of hair cosmetics)
According to the composition shown in Table 1, the hair cosmetics (conditioning agents) of each example were prepared in the following manner and evaluated.
The component (B) and purified water were charged into a 1 L beaker and stirred. Lactic acid was added dropwise to the resulting suspension to form a transparent solution, and then component (C) was added. The beaker was immersed in a water bath and heated to 75 ° C. Next, after the previously mixed component (D) and dipropylene glycol were added, the mixture was stirred at 75 ° C. for 10 minutes, removed from the water bath, and started cooling. The component (A) was added, and the mixture was cooled to 40 ° C. or lower while stirring to obtain 1 L of a liquid hair cosmetic.
Using this hair cosmetic, evaluation was performed by the above method. Table 1 shows the results. In addition, the compounding quantity described in Table 1 is an active ingredient amount (% by mass) of each component.
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
 表1に示すように、アミノポリエーテル変性シリコーンとして成分(B)のみを含有する比較例1、及びアミノポリエーテル変性シリコーンとして成分(A)のみを含有する比較例2の毛髪化粧料と対比して、実施例1~5の毛髪化粧料を毛髪に適用した場合には、毛髪の絡まり改善効果が高いことがわかる。また、実施例1~5の毛髪化粧料を適用した毛髪は、乾燥が速く、すすぎ時のきしみ感もなく良好な感触が得られた。 As shown in Table 1, the hair cosmetics of Comparative Example 1 containing only the component (B) as the aminopolyether-modified silicone and Comparative Example 2 containing only the component (A) as the aminopolyether-modified silicone were compared. Thus, when the hair cosmetics of Examples 1 to 5 were applied to hair, it was found that the effect of improving hair entanglement was high. In addition, the hairs to which the hair cosmetics of Examples 1 to 5 were applied dried quickly and had a good feel without squeaky feeling during rinsing.
 表2に、本発明の毛髪化粧料である毛髪洗浄剤(シャンプー)の処方例を示す。なお、表2に記載した配合量は各成分の有効成分量(質量%)である。 Table 2 shows a formulation example of a hair cleansing agent (shampoo) which is the hair cosmetic of the present invention. In addition, the compounding amount described in Table 2 is the amount (% by mass) of the active ingredient of each component.
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
 本発明の毛髪化粧料を毛髪に適用すると、毛髪に手を通すなどの操作を行うことなく絡まりを解くことができる。また、当該毛髪化粧料を適用した毛髪は乾燥が速く、すすぎ時の毛髪の滑らかさも良好である。
 
When the hair cosmetic composition of the present invention is applied to hair, the hair can be detangled without performing an operation such as passing through the hair. In addition, the hair to which the hair cosmetic has been applied dries quickly, and the smoothness of the hair upon rinsing is good.

Claims (14)

  1.  側鎖部分にポリオキシアルキレン構造を有するアミノポリエーテル変性シリコーン(A)、及び、主鎖部分にポリオキシアルキレン構造を有するアミノポリエーテル変性シリコーン(B)を含有する毛髪化粧料。 (4) A hair cosmetic containing an aminopolyether-modified silicone (A) having a polyoxyalkylene structure in a side chain portion and an aminopolyether-modified silicone (B) having a polyoxyalkylene structure in a main chain portion.
  2.  側鎖部分にポリオキシアルキレン構造を有するアミノポリエーテル変性シリコーン(A)、及び、主鎖部分にポリオキシアルキレン構造を有するアミノポリエーテル変性シリコーン(B)を配合してなる毛髪化粧料。 (4) A hair cosmetic comprising an aminopolyether-modified silicone (A) having a polyoxyalkylene structure in a side chain portion and an aminopolyether-modified silicone (B) having a polyoxyalkylene structure in a main chain portion.
  3.  前記成分(A)が下記一般式(1)で表される構造を有するものである、請求項1又は2に記載の毛髪化粧料。
    Figure JPOXMLDOC01-appb-C000001

     式(1)中、Rは炭素数1以上6以下の1価の炭化水素基を示す。RはR又はEのいずれかを示す。Eは-R-Z(Rは炭素数1以上6以下の2価の炭化水素基を示し、Zは1~3級アミノ基含有基を示す。)で表される1価の基を示す。Rは炭素数1以上6以下の2価の炭化水素基を示し、Rは水素原子又は炭素数1以上4以下の1価の炭化水素基を示す。
     aは1以上50以下の数、bは1以上50以下の数、cは1以上50以下の数、dは2以上100以下の数を示す。nは2以上10以下の数を示す。括弧内の構造単位同士の結合順序は問わず、結合形態はブロック状でもランダム状でもよい。d個のOC2nは同一でも異なっていてもよい。また、複数個のR、R、R、R及びEは同一でも異なっていてもよい。
    The hair cosmetic according to claim 1 or 2, wherein the component (A) has a structure represented by the following general formula (1).
    Figure JPOXMLDOC01-appb-C000001

    In the formula (1), R 1 represents a monovalent hydrocarbon group having 1 to 6 carbon atoms. R 2 represents either R 1 or E 1 . E 1 is a monovalent group represented by —R 3 —Z 1 (R 3 is a divalent hydrocarbon group having 1 to 6 carbon atoms, and Z 1 is a group containing a primary to tertiary amino group). Represents a group. R 4 represents a divalent hydrocarbon group having 1 to 6 carbon atoms, and R 5 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 4 carbon atoms.
    a is a number from 1 to 50, b is a number from 1 to 50, c is a number from 1 to 50, and d is a number from 2 to 100. n shows the number of 2 or more and 10 or less. Regardless of the bonding order of the structural units in parentheses, the bonding form may be block-like or random. d number of OC n H 2n may be the same or different. A plurality of R 1 , R 2 , R 4 , R 5 and E 1 may be the same or different.
  4.  前記成分(A)が下記一般式(1-1)で表されるものである、請求項3に記載の毛髪化粧料。
    Figure JPOXMLDOC01-appb-C000002

     式(1-1)中、E、R、R、a、b、cは前記と同じである。Rは炭素数1以上4以下の1価の炭化水素基又はトリメチルシリル基を示す。eは1以上50以下の数、fは0以上50以下の数を示す。
    The hair cosmetic according to claim 3, wherein the component (A) is represented by the following general formula (1-1).
    Figure JPOXMLDOC01-appb-C000002

    In the formula (1-1), E 1 , R 4 , R 5 , a, b, and c are the same as described above. R 9 represents a monovalent hydrocarbon group having 1 to 4 carbon atoms or a trimethylsilyl group. e indicates a number of 1 to 50, and f indicates a number of 0 to 50.
  5.  前記成分(A)の25℃における動粘度が4,000mm/s以下である、請求項1~4のいずれか1項に記載の毛髪化粧料。 The hair cosmetic according to any one of claims 1 to 4, wherein the kinematic viscosity at 25 ° C of the component (A) is 4,000 mm 2 / s or less.
  6.  前記成分(B)が下記一般式(2)で表される構造を有するものである、請求項1~5のいずれか1項に記載の毛髪化粧料。
    Figure JPOXMLDOC01-appb-C000003

     式(2)中、R11は水素原子又は炭素数1以上6以下の1価の炭化水素基を示す。R12はR11又はEのいずれかを示す。Eは-R13-Z(R13は単結合、又は炭素数1以上20以下の2価の炭化水素基を示し、Zは1~3級アミノ基含有基を示す。)で表される1価の基を示す。Yは炭素数1以上6以下のアルキレン基を示す。
     rは2以上の数、sは1以上の数、tは4以上100以下の数、uは1以上の数を示す。mは2以上10以下の数を示す。括弧内の構造単位同士の結合順序は問わず、結合形態はブロック状でもランダム状でもよい。t個のC2mOは同一でも異なっていてもよい。また、複数個のR11、R12、及びEは同一でも異なっていてもよい。
    The hair cosmetic according to any one of claims 1 to 5, wherein the component (B) has a structure represented by the following general formula (2).
    Figure JPOXMLDOC01-appb-C000003

    In the formula (2), R 11 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R 12 represents either R 11 or E 2 . E 2 is represented by —R 13 —Z 2 (R 13 represents a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms, and Z 2 represents a primary-tertiary amino group-containing group). A monovalent group represented by Y represents an alkylene group having 1 to 6 carbon atoms.
    r is a number of 2 or more, s is a number of 1 or more, t is a number of 4 or more and 100 or less, and u is a number of 1 or more. m represents a number of 2 or more and 10 or less. Regardless of the bonding order of the structural units in parentheses, the bonding form may be block-like or random. The t C m H 2m O may be the same or different. Further, a plurality of R 11 , R 12 and E 2 may be the same or different.
  7.  前記成分(B)が下記式(I)を満たす、請求項1~6のいずれか1項に記載の毛髪化粧料。
      0.01≦Si/AO≦1.6   (I)
     式(I)中、Siは成分(B)中のケイ素原子のモル数、AOは成分(B)中のオキシアルキレン平均付加モル数を示す。
    The hair cosmetic according to any one of claims 1 to 6, wherein the component (B) satisfies the following formula (I).
    0.01 ≦ Si / AO ≦ 1.6 (I)
    In the formula (I), Si represents the number of moles of silicon atoms in the component (B), and AO represents the average addition mole number of oxyalkylene in the component (B).
  8.  前記成分(A)と前記成分(B)との質量比[(A)/(B)]が0.01以上、1,000以下である、請求項1~7のいずれか1項に記載の毛髪化粧料。 8. The method according to claim 1, wherein a mass ratio [(A) / (B)] between the component (A) and the component (B) is 0.01 or more and 1,000 or less. Hair cosmetics.
  9.  さらに界面活性剤(C)を含有又は配合してなる、請求項1~8のいずれか1項に記載の毛髪化粧料。 毛 The hair cosmetic according to any one of claims 1 to 8, further comprising or blending a surfactant (C).
  10.  前記成分(C)がカチオン性界面活性剤を含む、請求項9に記載の毛髪化粧料。 毛 The hair cosmetic according to claim 9, wherein the component (C) contains a cationic surfactant.
  11.  さらに高級アルコール(D)を含有又は配合してなる、請求項1~10のいずれか1項に記載の毛髪化粧料。 The hair cosmetic according to any one of claims 1 to 10, further comprising or blending a higher alcohol (D).
  12.  前記成分(A)の含有量又は配合量が0.01質量%以上、5.0質量%以下である、請求項1~11のいずれか1項に記載の毛髪化粧料。 The hair cosmetic according to any one of claims 1 to 11, wherein the content or blending amount of the component (A) is 0.01% by mass or more and 5.0% by mass or less.
  13.  前記成分(B)の含有量又は配合量が0.0001質量%以上、5.0質量%以下である、請求項1~12のいずれか1項に記載の毛髪化粧料。 The hair cosmetic according to any one of claims 1 to 12, wherein the content or blending amount of the component (B) is 0.0001% by mass or more and 5.0% by mass or less.
  14.  リンス、コンディショニング剤、又はトリートメント剤である、請求項1~13のいずれか1項に記載の毛髪化粧料。
     
    The hair cosmetic according to any one of claims 1 to 13, which is a rinse, a conditioning agent, or a treatment agent.
PCT/JP2019/022966 2018-07-02 2019-06-10 Hair cosmetic WO2020008812A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006008611A (en) * 2004-06-28 2006-01-12 Lion Corp Hair cosmetic
JP2014129242A (en) * 2012-12-28 2014-07-10 Kracie Home Products Ltd Hair cosmetic
WO2017094625A1 (en) * 2015-12-02 2017-06-08 花王株式会社 Hair cosmetic
JP2018002638A (en) * 2016-06-30 2018-01-11 ホーユー株式会社 Hair-treating agent composition

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Publication number Priority date Publication date Assignee Title
TWI468186B (en) * 2012-12-28 2015-01-11 Kao Corp Hair cosmetic composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006008611A (en) * 2004-06-28 2006-01-12 Lion Corp Hair cosmetic
JP2014129242A (en) * 2012-12-28 2014-07-10 Kracie Home Products Ltd Hair cosmetic
WO2017094625A1 (en) * 2015-12-02 2017-06-08 花王株式会社 Hair cosmetic
JP2018002638A (en) * 2016-06-30 2018-01-11 ホーユー株式会社 Hair-treating agent composition

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