WO2020008812A1 - Produit cosmétique capillaire - Google Patents
Produit cosmétique capillaire Download PDFInfo
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- 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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- Prior art keywords
- hair
- group
- component
- hair cosmetic
- mass
- Prior art date
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Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/89—Polysiloxanes
- A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
- A61K8/898—Polysiloxanes 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/02—Preparations for cleaning the hair
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/12—Preparations 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
Ce produit cosmétique capillaire est obtenu en mélangeant ou contient: (A) une silicone modifiée par un amino-polyéther qui a une structure polyoxyalkylène dans une partie de chaîne latérale; et (B) une silicone modifiée par amino-polyéther ayant une structure polyoxyalkylène dans une partie de chaîne principale.
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JP2006008611A (ja) * | 2004-06-28 | 2006-01-12 | Lion Corp | 毛髪化粧料 |
JP2014129242A (ja) * | 2012-12-28 | 2014-07-10 | Kracie Home Products Ltd | 毛髪化粧料 |
WO2017094625A1 (fr) * | 2015-12-02 | 2017-06-08 | 花王株式会社 | Cosmétique capillaire |
JP2018002638A (ja) * | 2016-06-30 | 2018-01-11 | ホーユー株式会社 | 毛髪処理剤組成物 |
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JP2006008611A (ja) * | 2004-06-28 | 2006-01-12 | Lion Corp | 毛髪化粧料 |
JP2014129242A (ja) * | 2012-12-28 | 2014-07-10 | Kracie Home Products Ltd | 毛髪化粧料 |
WO2017094625A1 (fr) * | 2015-12-02 | 2017-06-08 | 花王株式会社 | Cosmétique capillaire |
JP2018002638A (ja) * | 2016-06-30 | 2018-01-11 | ホーユー株式会社 | 毛髪処理剤組成物 |
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